JPH037392A - Azo color for sublimable transfer recording - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention provides a magenta color dye for sublimation transfer recording using the general formula (I) (the following is a blank) (in the formula, R8 represents a butyl group or a butoxy group, R2, R
1 each independently represents an alkyl group or an alkenyl group,
X represents a hydrogen atom or an alkyl group, and Y represents an alkylcarbonylamino group or a formylamino group.

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

However, few of the conventionally proposed ab dyes completely satisfy the conditions such as heat resistance, light resistance, hue, ribbon stability, etc., and furthermore, for transfer purposes to OHP films, etc., higher density dyes are needed. There has been a demand for dyes that can be transferred, and it has been expected that dyes that meet these conditions will emerge as sublimable dyes.

[Means to solve the problem]

As a result of extensive studies to solve the above problems, the present inventors discovered a compound represented by the general formula (I) that has excellent ribbon stability even in a particularly high concentration state, and completed the present invention.

That is, the present invention relates to the following general formula (I) (wherein, Rt represents a butyl group or a butoxy group, and R8, R
5 each independently represents an alkyl group or an alkenyl group,
X represents a hydrogen atom or an alkyl group, and Y represents an alkylcarbonylamino group or a formylamino group. ] is an azo dye for sublimation transfer recording.

The dye is magenta in color.

The present invention will be explained in detail below.

In the present invention, R7 represents n-butyl group, isobutyl group, ter
Alkyl group such as t-butyl group, n-butoxy group, 1so
Examples thereof include alkoxy groups such as -butoxy group and tert-butoxy group.

Rt and R3 each independently represent a methyl group, an ethyl group, n
Examples include alkyl groups such as -propyl group and 1so-propyl group, and alkenyl groups such as allyl group and butenyl group.

X is a hydrogen atom, methyl group, ethyl group, n-propyl group,
Examples include alkyl groups such as 1so-propyl group, butyl group, and 1so-butyl group.

Examples of Y include alkylcarbonylamino groups such as methylcarbonylamino group, ethylcarbonylamino group, propylcarbonylamino group, butylcarbonylamino group, and cyclohexylcarbonylamino group, and formylamino group.

According to the research conducted by the present inventors, it has been found that the sublimation rate during transfer is related to the interaction between the dye molecules and the interaction between the dye molecules and the binder resin for ink.

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 should also have a low melting point so that interaction with the ink binder resin does not impair storage stability after ribbon production). It has become clear that those having a small value are the best dyes.The general formula (I
The dye represented by ) satisfies the above conditions and has a relatively good sublimation rate.

The dye represented by the general formula (I) of the present invention can be prepared by a conventional method.
It can be obtained by diazotizing -substituted 2,6-dibromoaniline, performing a cambling reaction with various anilines, and then cyanating it.

As a method for producing a thermal transfer recording ink using the dye of the present invention, the dye may be mixed with a suitable resin, solvent, etc. to prepare the recording ink. In addition, as a thermal transfer method,
An example of a method is to apply the ink obtained above onto a suitable base material to create a transfer sheet, overlap the sheet with a recording medium, and then heat and pressurize the sheet from the back side with a heat-sensitive recording head. 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 xylene, 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.

Suitable substrates for applying ink include thin paper such as condenser paper and glassine paper, and films made of plastics with good heat resistance such as polyester, polyamide, and polyimide. In order to improve heat transfer efficiency 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, 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 fine particles such as 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.

[Action and effect]

The azo dye represented by the general formula (I) of the present invention can be used by changing the energy given to the thermal head during thermal transfer.
Since the amount of dye sublimation transfer can be controlled, gradation recording is easy and it is 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.

In addition, the dye of the present invention has particularly excellent solubility in organic solvents, and is compatible with conventionally used anthraquinone color charts,
Moreover, compared to some azo dyes, the dye content on the ribbon could be increased by about 1.5 to 2 times, and the ribbon stability was very excellent.

Therefore, the transfer density increases as the content increases,
This dye makes it possible to achieve a density approximately 1.5 times higher than that of conventional dyes, and is a particularly useful dye in practice.

〔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. Maximum absorption wavelength of the compound in toluene (
λmaχ) was 530 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 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: Apply the above ink to a 98-part thick polyethylene terephthalate film whose back surface has been heat-resistant treated using a gravure proofing machine (rice temperature: 30μII) at a dry coating rate of 1.0 g/rrf.
Apply it and let it dry.

(ij) Preparation of recording material Polyester resin 0.8 part (vy
lon 103 Toyobo Tg=47°C) EVA polymer plasticizer 0.2 parts (Elvaloy 74
1P Mitsui Polychemical Tg-37°C) Amino-modified silicone 0.04 part (KF
-857 Shin-Etsu Chemical Co., Ltd.) Epoxy modified silicone 0.04 part (KF
-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, a coating liquid was adjusted, and a bar was applied to synthetic paper (manufactured by Tamago Yuka Co., Ltd., Yupo ppcitso). Coater (RK Pr1nt
Manufactured by Coat In5truaients,
k 1 ) at a dry rate of 4.5 g/% and dried at 100'C for 15 minutes.

(iv) Transfer recording The above-mentioned transfer sheet and the above-mentioned recording material are overlapped with their respective ink-coated surfaces and coating liquid-coated surfaces facing each other, and a thermal conductor is applied from the back side of the thermal transfer sheet at a voltage of 10 V and a printing time. Recording was performed under conditions of 4.0 milliseconds, and the color density was 2.7.
A magenta color record of 5 was obtained.

The color density was measured using a densitometer R manufactured by Macbeth Co., Ltd. in the United States.
It was measured using D-514 type (filter m: Utsutenma 58).

Color density was calculated using the following formula.

Color density -j! Qg Io (To/r) 1o - Intensity of reflected light from a standard white reflector ■ - Intensity of reflected light from a test object In addition, the light resistance test of the obtained record was performed using a xenon fade meter (Suga Test Instruments Co., Ltd.) The experiment was carried out using a black panel (manufactured by the same company) at a black panel temperature of 63±2°C, and 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 the sharpness of the image and the coloring when the surface was rubbed with white paper after the recorded image was left in an atmosphere at 50°C for 48 hours, and the sharpness of the image did not change. Further, 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 of the compound in toluene (λa+a
x) was 530ns+.

According to the method of Example-1, the dye (B) was increased to 4.5 parts, the ink was adjusted, a transfer sheet and a recording material were prepared, and transfer recording was performed to obtain a magenta color record with a color density of 3.65. Ta.

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 5 7zo dyes shown in Table 1 were produced according to the same method as in Example 2, and 4.5 parts of the dye was used to adjust the ink, prepare a transfer sheet, and prepare a recording material. were prepared and transferred, and each record shown in Table 1 was obtained.

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 at and under high temperatures.

Also, A fastness test was conducted in the same manner as in Example-1, but The sharpness of the image remains unchanged. Also, color the blank paper. figure, The fastness of the recorded image was good.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 represents a butyl group or a butoxy group, and R_2
, R_3 each independently represent an alkyl group or an alkenyl group, X represents a hydrogen atom or an alkyl group, and Y represents an alkylcarbonylamino group or a formylamino group. ] Azo dye for sublimation transfer recording.