JPH037391A - Azo color for sublimable transfer recording - Google Patents

Abstract

PURPOSE:To facilitate recording of a density gradation image so that full-color recording is achieved by using an azo color as shown by a specific chemical structure. CONSTITUTION:An azo color shown by formula I is added is a magenta color for sublimable transfer recording. In the formula, R1 is an alkyl group and an alkoxy group, R2, R3 are an alkyl group, an aralkyl group, an allyl group, an allyl group, an alkoxyalkyl group and a hydroxyalkyl group, X is C2 or more alkyl groups and C5 or more alkoxy groups, Y is an alkyl group, an alkoxy group, an alkylcarbonyl amino group, a holmylamino group, an alkylsulfonylamino group and an alkoxycarbonylamino group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention provides a magenta dye for sublimation transfer recording and [in the formula:
R1 represents an alkyl group, an alkoxy group, and R2 and R1 each independently represent an alkyl group, an aralkyl group, an allyl group,
Indicates an alkoxyalkyl group, a hydroxyalkyl group,
χ represents an alkyl group of C2 or more, an alkoxy group of C5 or more, and Y represents an alkyl group, an alkoxy group, an alkylcarbonylamino group, a formylamino group, an alkylsulfonylamino group, or an alkoxycarbonylamino group. ] is provided.

[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, among the dyes that have been proposed in the past, there are very few that satisfy all the conditions such as heat resistance, light resistance, sublimation speed, hue, ribbon stability, etc., and there are few dyes that meet the optimal conditions as sublimable dyes. has been expected to appear.

[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) and completed the present invention.

That is, the present invention relates to the following general formula (I) (% formula %) [wherein, R represents an alkyl group or an alkoxy group, and Rt
, Rs each independently represents an alkyl group, an aralkyl group,
An allyl group, an alkoxyalkyl group, or a hydroxyalkyl group; , represents an alkoxycarbonylamino group. ] is an ab-based dye for sublimation transfer recording.

The dye is magenta in color.

The present invention will be explained in detail below.

In the present invention, R1 represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 1so-butyl group,
Alkyl groups such as ter-7' tyl group, n-pentyl group, n-hexyl group, β-dimethylbutyl group, n-octyl group, methoxy group, ethoxy group, n-propoxy group, 1s
Examples include alkoxy groups such as o-propoxy group, n-butoxy group, 1so-butoxy group, tert-butoxy group, and n-hexyloxy group, and cyano group.

Rt and Rs each independently represent a methyl group, an ethyl group, n
- Alkyl groups such as propyl group and 1so-propyl group, aralkyl groups such as benzyl group and phenethyl group, allyl group,
Examples include alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, ethoxymethyl group, and ethoxyethyl group, and hydroxyalkyl groups such as hydroxymethyl group and hydroxyethyl group.

X is an ethyl group, a lopropyl group, a 1so-propyl group,
Examples include alkyl groups of 02 or more such as butyl group and 1so-butyl group, pentyloxy group, hexyloxy group and alkoxy groups of ring C3 or more.

Y is a methyl group, ethyl group, n-propyl group, 1so-propyl group, n-butyl group, 1so-butyl group, tert
Alkyl groups such as butyl groups, alkoxy groups such as methoxy groups and ethoxy groups, alkylcarbonylamino groups such as methylcarbonylamino groups, ethylcarbonylamino groups, propylcarbonylamino groups, butylcarbonylamino groups, cyclohexylcarbonylamino groups, and formylamino groups. , alkylsulfonylamino groups such as methylsulfonylamino group and ethylsulfonylamino group, and alkoxycarbonylamino groups such as methoxycarbonylamino group and ethoxycarbonylamino 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 be such that interaction with the ink binder resin does not impair storage stability after ribbon production. It has become clear that the smallest dye is the best dye.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 coupling 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, sheilac, 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 fruit tree nFJ, polyamide resins, copolymer resins of olefins such as ethylene and propylene and other vinyl monomers, ionomers, cellulose diacetate,
Examples include fibers, woven fabrics, films, sheets, and molded products made of cellulose resins such as cellulose triacetate, polycarbonate, polysulfone, polyimide, and the like.

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 at and under high temperatures 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 recording during storage.

[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, 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. Maximum absorption wavelength of the compound in toluene (
λmax) was 535 nm.

(I) Preparation method of ink 3-part pigment of the above formula (A) Polybutyral resin 4.5 Methyl ethyl ketone 46.25 Toluene
46.25 Using a glass piece, mix the pigment mixture with the above composition with paint conditioner for approx.
An 8-year ink was prepared by section processing for 0 minutes.

(I1) How to create a transfer sheet Using Gravure Calibration R (rice temperature: 30 μm), apply the above ink to a 9 μm thick polyethylene terephthalate film whose back side has been heat-resistant treated so that the dry coating amount is 1.0 g/n. Coated and dried.

(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
p Mitsui Polychemical T, -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, the coating liquid was adjusted, and synthetic paper (Yubo FPG1150 manufactured by Tamago Yuka Co., Ltd.) was mixed. Bar coater (RK Pr1nt
Manufactured by Coat Instruments, N
11 l) at a dry rate of 4.5 g/ryf, 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 ink-coated surfaces and coating liquid-coated surfaces facing each other, and a thermal hand applies a voltage of 10 V from the back side of the thermal transfer sheet for a printing time of 4. Recording was performed under conditions of 0 milliseconds, and the color density was 2.70.
A record of magenta color 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: Wratten Nct58).

Color density was calculated using the following formula.

Color density=fog. (io/f) 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±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.

In addition, 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 (λwax) of the compound in toluene
) was 532 nm.

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 magenta recording with a color density of 2.68.

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 the stability of the images under high temperature and high humidity was compromised.

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 6 The azo pigments shown in Table 1 were produced in the same manner as in Example 1, and the ink was adjusted, the transfer sheet was prepared, and
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 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.

Claims (1)

[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R_1 represents an alkyl group or an alkoxy group, and R
_2 and R_3 each independently represent an alkyl group, an aralkyl group, an allyl group, an alkoxyalkyl group, or a hydroxyalkyl group; Alkylcarbonylamino group, formylamino group,
Indicates an alkylsulfonylamino group and an alkoxycarbonylamino group. ] Azo dye for sublimation transfer recording.