JPH02579A - Yellow dye donative element used for heat transfer and heat transfer sheet using the same - Google Patents

Abstract

PURPOSE:To obtain yellow dye donative element for three primary colors for use in heat transfer having suitable sublimation or dispersion, sufficient coloring, excellent inking properties, transfer density or recorded image preservation stability by composing the title element of specific yellow dye. CONSTITUTION:Yellow dye represented by a formula (where R1 is 1-12C alkyl group, aryl group or crotyl group, X is hydrogen atom, halogen atom, 1-4C lower alkyl group or lower alkoxy group, Y is 1-12C alkyl group 5-7C cycloalkyl group, 1-4C alkoxy group, phenyl group, tryl group or phenoxy group, A is -CH2CH2-, -CH2CH2O- or -CH2CH2CH2-) of yellow dye donative element for heat transfer made of yellow dye dispersed or dissolved in resin binder is inked, coated on one side face of a base material, dried to form a dye carrying layer as a heat transfer sheet. The yellow dye represented by the formula used here may be used solely or in mixture of two or more.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a yellow dye donor element used in thermal transfer, and
Thermal transfer sheet used: 2.

<Prior art> The thermal transfer image recording method is a method in which an image is formed by sublimating or scattering dye using heat, and is currently used in televisions,
This method is attracting attention as a method of obtaining color hard copies from CRT color displays, color 7 cameras, magnetic cameras, etc. The heat source can be a heating element such as a thermal head, or a laser, especially a semiconductor laser.The amount of sublimation or evaporation of the dye can be controlled by the applied energy, making continuous tone recording possible. It is characterized by being

For full-color recording, dyes of four colors are usually required: the three primary colors of 777 colors, magenta and yellow, and in some cases black. The conditions that each dye must meet are that it has appropriate sublimation or perishability, good color development by applying dove energy, excellent suitability for ink formation, and excellent storage stability of recorded images. There are many things that can be mentioned. However, a yellow dye that fully satisfies these conditions has been discovered.
) Currently there is no such thing.

<Problems to be Solved by the Invention> For example, Japanese Patent Application Laid-Open No. 1961.85/1985 describes a yellow dye-donor element used for thermal transfer, but this element has an appropriate sublimation property. , has good coloring properties upon application of thermal energy, but has a problem in that storage stability of recorded images is not sufficient.

In addition, JP-A-60-53564 also describes a yellow dye-donor element similar to the present invention, but these have ink-forming properties (such as no precipitation of crystals during ink formation or ink sheet production). Due to problems with the transfer density during thermal transfer using a thermal head, the original power of the dye may not be fully demonstrated, or there may be problems with the storage stability of the recorded image, and improvements are awaited. It was

The present inventors have developed a yellow dye-donor element for the three primary colors used in thermal transfer that has appropriate sublimation or evaporation properties, good color development, and excellent ink forming properties, transfer density, and storage stability of recorded images. As a result of intensive studies to find out, it was discovered that the specific dye defined in the present invention satisfactorily achieves the above object,
The present invention has now been completed.

<Means for Solving the Problems> The present invention provides a yellow dye-donor element for thermal transfer consisting of a yellow dye dispersed or dissolved in a finger binder, wherein the yellow dye is represented by the following -9 formula (I). (In the formula, RI is Cl-C
I2 alkyl group, allyl group or crotyl group, X is a hydrogen atom, group, CI~C
4 alkoxy group, phenyl group, tolyl group or phenoxy group, A is -CLCLCHxCH2D- or -C)I,
CH,C)1. The present invention provides a yellow dye-donor element for use in thermal transfer characterized by the following characters: - and a thermal transfer sheet using the same.

In the formula -9 (f) above, C1 to C1 represented by R3
Specific examples of the alkyl group □ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, Examples include dodecyl groups, among which C3 to C1 lower alkyl groups are preferably used.

Next, examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, or a bromine atom; Methyl group, ethyl group, metquin group,
Examples include ethoxy group, and more preferably, X represents a hydrogen atom or a methyl group. Specific examples of the C5-C alkyl group represented by Y include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, etc. Examples of the 05-C7 cycloalkyl group include a cyclopentyl group, a nclohexyl group, a ncloheptyl group, and a C1-C4 group represented by Y. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and the phenyl group, phenoxy group, and tolyl group represented by Y may further have a substituent. Particularly preferable examples of Y include C3 to C, a cycloalkyl group, and a phenyl group.

A part of the yellow dye represented by the general formula (I) used as the yellow dye donor element used in the thermal transfer of the present invention is a known dye described in Japanese Patent Publication No. 51-20204, and these are the same. It can be easily produced by the method described in the publication.

For example, a compound represented by the -9 formula (II) (wherein R5, x, Y and A each represent the above-mentioned meanings) is formylated by a Willsmeier reaction in a polar solvent such as dimethylformamide. rear,
It is obtained by condensation with IJ.

In the present invention, the yellow dye represented by formula (I) -9 is made into an ink, and this is applied to one side of a substrate and dried to form a dye-carrying layer, thereby producing a thermal transfer sheet.

The yellow dye represented by the general formula (1) used herein may be used alone or in combination of two or more.

Examples of the base material include capacitor paper, cellophane, polyimide resin, polyester resin, and polyethersulfone resin.

This base material is preferably ribbon-like or film-like, usually having a yellow dye-carrying layer formed on one side, and treated on the other side to improve the heat resistance and/or smoothness of the base material. This is illustrated as an example.

The yellow dye can be made into ink using the yellow dye 04 of the above-mentioned tube formula (1),
When using a laser on a resin binder, solvent, and heat source, it is composed of a compound that absorbs at the oscillation wavelength of the laser, and if necessary, is dissolved using a ball mill or paint conditioner with Ike's known 4B additive. Or by being decentralized.

Here, as a resin binder, examples such as dammar, gum arabic, gum tragacanth, destrines or casein are used. A resin or its modified resin, methylcellulose, ethylcellulose, hydroquine ethylcellulose,
Examples include cellulose-based resins such as ethyl hydroxycellulose or nitrocellulose, acrylic acid-based resins, and vinyl-based resins such as polyvinyl alcohol or polyvinyl acetate, and these may be used alone or as a mixture of two or more thereof.

In addition, as a solvent, water, enotal, propatool,
Alcohols such as butanol, ketones such as acetone, methyl bicarbonate, and methyl isobutyl ketone, aromatic hydrocarbons such as toluene, xylene, and monochlorobenzene, and chlorinated solvents such as dichloroethane, trichlorethylene, and perchlorethylene. , acetate esters such as ethyl acetate, butyl acetate, ethoxyethyl acetate, etc., and one or a mixture of two or more of these may be used.

Further, examples of compounds having absorption at the laser oscillation wavelength include carbon black, phthalonanine dyes, dithiol complexes, and naphthoquinones.

Application of the dye ink thus obtained to the base is as follows:
This is carried out using a bar coater, roll coater, knife coater, screen printing, gravure EO printing, etc., and thus a thermal transfer notebook is manufactured.

Any known method may be used for printing using the thermal transfer sheet produced in this manner, and a clear image can be obtained on the print paper.

Printing paper can be paper coated with polyester resin or polyamide resin, synthetic paper such as polypropylene, polyvinyl chloride, or polyester, or synthetic paper that has been treated to improve heat resistance. Up,
Polyester with strong affinity for dyes if necessary! Materials coated with boar, polyamide resin, etc. are used.

<Effects of the Invention> The yellow dye represented by formula (1) according to the present invention has excellent ink-forming properties, and the thermal transfer sheet produced using the ink has appropriate sublimation or vaporization properties. In addition, it has good color development properties such as a high recording rate of 4 degrees on printing paper, and has good aging resistance and storage stability of recorded g images, making it useful as a yellow thermal transfer sheet for three colors.

<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples.

In the examples, parts represent parts by weight.

Example 1) Preparation of dye 323 parts of N-ethyl-N C2 (4-cyclohekynlufenoquine) ethyl] aniline was dissolved in 700 parts of dimethylformamide, cooled to 0 to 10°C, and then converted to oxine salt at the same temperature. Add 230 parts of phosphorus.

Then, at the same temperature, add pyridine 12 (lN) and add 40"
Raise the temperature to C and keep at the same temperature for 1 hour. After cooling to 20°C and adding 400 parts of methanol at 20-30°C,
Add 34G parts of lium acetate.

Next, 66 parts of 70% nitrile dissolved in 20 parts of methanol were added at 40 to 50°C, then the temperature was raised to 70°C and kept at the same temperature for 1 hour. Then, after cooling to room temperature, water 4
000 parts, and the precipitated crystals were separated, washed with water, and dried to obtain a dye of Formula 1 [1].

m, p, 109-110°C (blank below) 11) Ink preparation method Dye obtained in the above 1) 2 parts Ethyl cellulose 6 parts Toluene 44 parts Methyl ethyl ketone 44 parts Total 96 parts A mixture of the above composition was mixed with glass beads. The ink was prepared by thoroughly kneading with a paint conditioner.

111) Method for producing thermal transfer sheet A heat-resistant treated polyester film having a thickness of 6 μm was coated with a wet film thickness of 12 μm using a bar coater, and dried in a hot air dryer at 80° C. to obtain a thermal transfer sheet. Further, the ink-forming properties of this product were good, with no crystal precipitation.

iv) Method for making receiver paper 20% of saturated polyester resin (Toyobo Byron 200)
Heavy! It % toluene/methyl ethyl ketone solution was coated on synthetic paper (Tako Yuka Yubo FPG: 150) using a bar coater to a wet film thickness of 12 μm, and dried in a hot air dryer at 80° C. for 30 minutes.

■) Transfer recording method The ink-coated surface of the thermal transfer sheet is placed on the image-receiving paper-power-coated surface using a thermal head (8V voltage for 21 milliseconds) having a 200Ω heating resistor at a density of 4 dots/mm. A yellow record with a recording density of 1.31 was obtained by thermal transfer recording. The color density was measured using a densitometer RD-914 manufactured by Macbeth, USA. In addition, when the light resistance test of the obtained record was conducted using a carbon arc fade meter (Shimabara Seisakusho), there was almost no discoloration after 40 hours of irradiation, and the image stability was maintained at high temperature and high humidity (60°C, 80%). It was also excellent.

Example 2 N-ethyl~NC2 (4-chlorohexylphenoxy)
After dissolving 33 parts of ethyl c-3-methylani9 in 700 parts of dimethylformamide and cooling to 0 to 10°C,
At the same temperature, 230 parts of phosphorus oxochloride is added. Thereafter, 130 parts of pyridine was added at the same temperature I, the temperature was raised to 40°C, and the mixture was kept at the same temperature for 1 hour.

Cool to 30°C, add 400 parts of methanol at 20-30°C, and then add 346 parts of acetic acid. Next, 66 parts of marroni (IJ) dissolved in 20 ml of methanol were added at 40 to 50°C, the temperature was raised to 70°C, and the mixture was kept at the same temperature for 1 hour. Thereafter, the mixture was cooled to room temperature, and then drained into 4000 parts of water, and the precipitated crystals were filtered off, washed with water, and dried to obtain the dye of formula (2).

m, p, 117 to 118 °C Ink preparation and thermal transfer were carried out in the same manner as in Example 1, except that the dye in (2) above was used and hydroxyethyl cellulose was used in place of ethyl cellulose in 11) of Example 1. A sheet was prepared, an image receiving paper was prepared, and transfer recording was performed to obtain a recorded image with a recording density of 1.35, a yellow color, excellent luminosity, and excellent stability under high temperature and high humidity.

Example 3 317 parts of N-ethyl-N-C2-(2-phenylphenoxy)ethyl]aniline was dissolved in 600 parts of dimethylformamide.
After dissolving in B and cooling to 0 to 10° C., phosphorus oxychloride 230B is added at the same temperature for 4 hours. Thereafter, 130 parts of pyridine was added at the same temperature, the temperature was raised to 40°C, and the mixture was kept at the same temperature for 1 hour. After cooling to 30°C and adding 400 parts of ethanol at 20-30°C, sodium acetate 346B is added. Next, 66 parts of 3M malonitrile was added to 20 parts of ethanol at 40 to 50°C, and the temperature was raised to 70°C.
Keep warm at the same temperature for 1 hour. Thereafter, after cooling to room temperature, the mixture was poured into 4000 B of water, and the precipitated crystals were separated, washed with water, and dried to obtain the dye of formula (3).

m, p, 124 - 125 °C Toluene 4 of Example 1 11) using the dye of (3) above
4. The same method as in Example 1 was used except that 88 parts of isopropyl alcohol was used instead of 44 parts of methyl ethyl ketone to adjust the ink, prepare a thermal transfer sheet, prepare an image receiving paper, and perform transfer recording to obtain a recording density of 1.30. A recorded image of yellow color with excellent light fastness and excellent stability under high temperature and high humidity was obtained.

Examples 4 to 7 Formulas (4) to (7) in Table 1 below were prepared in the same manner as in Example 1.
) were obtained, and thermal transfer sheets were manufactured using the dyes, and transfer tests were conducted. In each case, high-density, clear yellow images were obtained. The obtained image had excellent destination, moisture resistance, and storage stability.

(Left below) Table 1 Example 8 271 parts of N-ethyl-N-(2-(4-methoxyphenoxy)ethyl)aniline was dissolved in 700 parts of dimethylformamide.
After cooling to 0 to 10°C, 230 parts of phosphorus oxychloride is added at the same temperature. Thereafter, 130 parts of pyridine was added at the same temperature, the temperature was raised to 40°C, and the mixture was kept at the same temperature for 1 hour. Cool to 30°C, add 400 parts of methanol at 20-30°C, and then add 346 parts of sodium acetate. Next, malonitrile 66 dissolved in 20 parts of methanol
After adding 1 part at 40 to 50°C, the temperature is raised to 70°C and kept at the same temperature for 1 hour.

Then, after cooling to room temperature, drain into 4000 parts of water,
The precipitated Kisho was separated by filtration, washed with water, and dried to obtain the dye of formula (8).

Add 346 parts of IJum. Next, methanol 2
40 to 50 parts of IJ Le 66 parts
After adding at ℃, the temperature is raised to 70℃ and kept at the same temperature for 1 hour. Thereafter, after cooling to room temperature, it was poured into 4000 parts of water, and the precipitated crystals were filtered off, washed with water, and dried.
dye was obtained.

mp, 119 to 120°C A transfer sheet was produced in the same manner as in Example 1 using the dye described in [8] above, and a transfer test was conducted. As a result, Record 1, Text 1.
A recorded image was obtained which had yellow light fastness of No. 20 and excellent stability under high temperature and high humidity conditions.

Example 9 N-Ethyl-N-C2-(4-phenoxy-phenoquine)ethylcoaniline 333B in dimethylformamide 7
After cooling to 0 to 10°C, 230 parts of phosphorus oxychloride is added at the same temperature. Thereafter, 130 parts of pyridine was added at the same temperature, the temperature was raised to 40°C, and 130 parts of pyridine was added at the same temperature.
Keep warm for hours. After cooling to 30°C and adding 400 parts of methanol at 20 to 30°C, a transfer sheet was produced in the same manner as in Example 1 using vinegar as described in (9) above, and a transfer test was performed. A recorded image with a density of 1.24, yellow color, excellent light fastness, and excellent stability under high temperature and high humidity was obtained.

Example 1O 253 parts of N-ethyl-N-(2-(4-methylphenyl)ethyl]-3-methylaniline was dissolved in 700 parts of dimethylformamide, cooled to 0 to 10°C, and then oxychlorinated at the same temperature. Add 230 parts of phosphorus. Then, add 130 parts of pyridine at the same temperature, raise the temperature to 40°C, and keep at the same temperature for 1 hour. Cool to 30°C, and add 400 parts of methanol at 20-30°C. , add 346 parts of sodium acetate. Next, add 66 parts of malonitrile dissolved in 20 parts of methanol at 40 to 50°C, then raise the temperature to 70°C and keep at the same temperature for 1 hour. Then, warm to room temperature. After cooling, the mixture was poured into 4000 parts of water, and the precipitated crystals were filtered off, washed with water, and dried to obtain a dye of formula αG.

there were.

Table 2 A transfer sheet was manufactured in the same manner as in Example 1 using the dye No. 00 above, and a transfer test was performed. As a result, the recording density was 1.25.
A recorded image was obtained that had a yellow color and was excellent in light resistance and excellent in stability under high temperature and high humidity conditions.

Examples 11 to 14 In the same manner as in Example 1, dyes of 2〇D to 0 in Table 2 below were obtained, and thermal transfer sheets were manufactured using the dyes, and a transfer test was conducted to determine the respective densities. A high, clear yellow image was obtained. The obtained ii@ image had excellent light and moisture resistance, and good storage stability. (4-methylphenyl)phenoxy>ethyl] 3-bromoaniline 436
0 to 10 parts was dissolved in 700 parts of dimethylformamide.
After cooling to ℃, 230 parts of oxine phosphorus chloride is added at the same temperature. After that, 130 parts of pyridine was added at the same temperature, and 40 parts of pyridine was added.
Raise the temperature to ℃ and keep it at the same temperature X for 1 hour. After cooling to 30°C and adding 400 parts of methanol at 20-30°C,
Add 346 parts of sodium acetate. Next, methanol 20
After adding 66 parts of malonitrile dissolved in 1 part at 40 to 50°C, the temperature was raised to 70°C and kept at the same temperature for 1 hour.

Then, after cooling to room temperature, drain into 4000 parts of water,
Separately, the precipitated crystals were washed with water and dried to obtain the formula Q! 9 dyes were obtained.

A transfer notebook was manufactured in the same manner as in Example 1 using the above $0 dye, and a transfer test was conducted. As a result, the recording density was 1.20.
A recorded image with excellent yellow light fastness (!) and excellent stability under high temperature and high humidity conditions was obtained.

The test results of Examples 1 to 15 are summarized in Table 3.

Note that the evaluation of ink-forming properties, light resistance, and image stability in the table below was expressed based on the following criteria.

Ink-forming properties; Those in which dye crystals were precipitated during ink formation or thermal transfer sorting were indicated as △, and those in which no crystal precipitation was observed were indicated as ○.

Light resistance: Those that showed discoloration after 40 hours of irradiation using a fade meter were indicated as △, and those that showed no discoloration were indicated as ◯.

Image stability: When the recorded image and blank paper are placed in a constant temperature and humidity chamber at 60°C and 30% humidity with 3 mouths open, the blank paper remains l
Items that were not dyed were marked with ◎, items that were slightly contaminated were marked with ○, and items that were seriously contaminated were marked with △.

(Hereinafter, blank spaces) The same procedure as in Example 1 was carried out except that A to E below were used as surface dyes, and the results shown in Table 4 were obtained.

(8) Dye ○ ■ ○ In addition, the dyes HA and B used in the comparative example are JP-A-60-5
These are dyes each having the following structural formula described in Japanese Patent No. 3564.

0D dye weight: 1.35 ○ 〇-◎ In addition, dyes C and D used in the comparative example are JP-A-61-1
62396, and Dye E was disclosed in Japanese Patent Application Laid-open No. 62
-196186, and are dyes having the following structural formulas.

C1(3 (Margin below)

Claims (14)

[Claims] (1) A yellow dye-donor element for thermal transfer consisting of a yellow dye dispersed or dissolved in a resin binder, in which the yellow dye has the following general formula (I) ▲Mathematical formula, chemical formula, table, etc. ) (In the formula, R_1 is an alkyl group, allyl group, or crotyl group of C_1 to C_1_2, X is a hydrogen atom, halogen atom, lower alkyl group or lower alkoxy group of C_1 to C_4, and Y is an alkyl group of C_1 to C_1_2. , C_
5 to C_7 cycloalkyl group, C_1 to C_4 alkoxy group, phenyl group, tolyl group or phenoxy group, A
represents -CH_2CH_2-, -CH_2CH_2O-, or -CH_2CH_2CH_2-, respectively. (2) The yellow dye-donor element according to claim (1), wherein in the general formula (I), X is a hydrogen atom or a methyl group. (3) In general formula (I), Y is a phenyl group or C
The yellow dye-donor element according to claim 1, which is a _5 to C_7 cycloalkyl group. (4) In general formula (I), A is -CH_2CH_
The yellow dye-donor element according to claim 1, which is 2O- or -CH_2CH_2-. (5) The yellow dye-donor element according to claim (1), wherein the yellow dye is represented by the following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (6) The yellow dye-donor element according to claim (1), wherein the yellow dye is represented by the following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (7) The yellow dye-donor element according to claim (1), wherein the yellow dye is represented by the following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (8) A support layer comprising a base sheet and a yellow dye dispersed or dissolved in a resin binder on one side of the base sheet, and the yellow dye has the general formula (I) ▲ mathematical formula, chemical formula,
There are tables etc.▼(I) (In the formula, R_1 is an alkyl group, allyl group or crotyl group of C_1 to C_1_2, X is a hydrogen atom, halogen atom, lower alkyl group or lower alkoxy group of C_1 to C_4, Y is an alkyl group of C_1 to C_1_2, C_
5 to C_7 cycloalkyl group, C_1 to C_4 alkoxy group, phenyl group, tolyl group or phenoxy group, A
represents -CH_2CH_2-, -CH_2CH_2O-, or -CH_2CH_2CH_2-, respectively. (9) The thermal transfer sheet according to claim (8), wherein in the general formula (I), X is a hydrogen atom or a methyl group. (10) Claim (8), wherein in general formula (I), Y is a phenyl group or a C_5 to C_7 cycloalkyl group.
Thermal transfer sheet described in . (11) In general formula (I), A is -CH_2CH
Claim (8) which is _2O- or -CH_2CH_2-
Thermal transfer sheet described in . (12) The thermal transfer sheet according to claim (8), wherein the yellow dye is represented by the following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (13) The thermal transfer sheet according to claim (8), wherein the yellow dye is represented by the following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (14) The thermal transfer sheet according to claim (8), wherein the yellow dye is represented by the following general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼.