JP2548218B2 - Red dye for thermal sublimation transfer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a red dye for thermal sublimation transfer.

More specifically, the present invention relates to a red dye which has good dyeability and color developability and is excellent in fastness, particularly in the method of recording by sublimation transfer by heating with a thermal head.

The dye of the present invention is a CRT color display, a color facsimile, which uses a transfer type thermal recording system (Nikkei Electronics February 13, 1984 issue) which is a means of information recording.
It is a dye suitable for obtaining a color hard copy from a magnetic camera or the like.

(Problems to be Solved by Prior Art and Invention) As a red dye for thermal sublimation transfer recording, JP-A-59-78
896 has the following general formula (A) [In the general formula (A), X represents a hydrogen atom or a methyl group, and R and R'represent a methyl group, an ethyl group, a linear or branched propyl group or a butyl group, respectively. ], But the dye of the general formula (A) has a poor light resistance and is a drawback in terms of storage of information records.

Further, JP-A-60-131293 discloses the following general formula (B) (In the formula, -x- represents -0- or -S-, and -A- represents a linear or branched alkylene group or alkylene-.
O-alkylene group, alkylene-S-alkylene group, cyclohexylene group, phenylene group,- Indicates. Although an anthraquinone dye represented by the formula (1) is disclosed, the energy required for transfer is large and the machine cost increases, which is not preferable.

Further, a known 1-amino-2-phenoxy-4-hydroxyanthraquinone (CI. No. Disp Red 60) is also used, but its sublimability is poor, and its dyeing property and fastness are not satisfactory.

(Means for Solving Problems) The inventors of the present invention have conducted extensive studies in order to solve the above problems, have excellent sublimation properties, and have no dye migration and staining properties in the substrate. The present invention was completed by finding a dye.

That is, the present invention has the following general formula (I) (In the formula, R represents an acetylamino group, a propionylamino group, a methanesulfonylamino group, a maleimide group, a succinimide group, an optionally substituted benzoylamino group, a phthalimide group, or a 2,3-naphthalimide group.) Is a red dye for heat-sensitive sublimation transfer.

In formula (I), R represents an acetylamino group, a propionylamino group, a methanesulfonylamino group, a maleimido group, a succinimido group, an optionally substituted benzoylamino group, a phthalimido group or a 2,3-naphthalimido group, Examples of the substituent of the benzoylamino group include a methyl group, an ethyl group, a methoxy group, an ethoxy group and a chlorine atom.

Examples of the substituent of the phthalimido group include a methyl group, an ethoxy group, a nitro group and a chlorine atom.

Moreover, a chlorine atom is mentioned as a substituent of a naphthalimide group.

The synthesis of the dye represented by the general formula (I) is carried out by using tetracyanoethylene and the general formula (II) (In the formula, R represents an acetylamino group, a propionylamino group, a methanesulfonylamino group, a maleimido group, a succinimido group, an optionally substituted benzoylamino group, a phthalimido group and a 2,3-naphthalimido group.) The compound represented in an aprotic polar solvent
It can be easily obtained by heating to 50 ° C and reacting.

As a method for producing a thermal transfer recording ink using the dye of the present invention, the dye is mixed with an appropriate resin, a solvent, etc.,
The recording ink may be used. As a thermal transfer method, the ink obtained above is applied onto a suitable substrate to prepare a transfer sheet, the sheet is superposed on a recording medium, and then the back surface of the sheet is heated and pressed by a thermal recording head. The method can be mentioned.

As the resin for adjusting the above ink, those used in ordinary printing inks may be used, such as rosin-based, phenol-based, xylene-based, petroleum-based, vinyl-based, polyamide-based, alkyd-based, nitrocellulose-based, alkyl. Oily resins such as cellulose and alkyl celluloses, or aqueous resins such as maleic acid, acrylic acid, casein, shellac and glue can be used. Further, as a solvent for ink preparation, methanol, ethanol,
Alcohols such as propanol and butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatics such as benzene, toluene and xylene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone and cyclohexanone, ligroin Hydrocarbons such as cyclohexane and kerotenes, dimethylformamide and the like can be used. When an aqueous resin is used, water or water and a mixture of the above solvents can also be used.

The base material to which the ink is applied is condenser paper, thin paper such as glassine paper, polyester, polyamide,
A film of plastic having good heat resistance such as polyimide is suitable, but a thickness of about 5 to 50 μm is suitable for these substrates in order to improve heat transfer efficiency from the thermal recording head to the dye.

Examples of the recording medium include polyolefin resins such as polyethylene and polypropylene, polyvinyl chloride,
Halogenated polymers such as polyvinylidene chloride, vinyl polymers such as polyvinyl alcohol, polyvinyl acetate and polyacrylic ester, polyethylene terephthalate,
Polyester resin such as polybutylene terephthalate,
Polystyrene resin, polyamide resin, copolymer resin of olefin and other vinyl monomers such as ethylene and propylene, ionomer, cellulose diacetate,
Examples thereof include fibers, woven fabrics, films, sheets, molded products and the like made of cellulose resins such as cellulose triacetate, polycarbonate, polysulfone, polyimide and the like.

Particularly preferred is a woven fabric, sheet or film made of polyethylene terephthalate. Further, in the present invention, by using plain paper coated or impregnated with the above resin to which acidic fine particles such as silica gel are added, or laminated resin film or acetylated special processed paper Good recording with excellent image stability under high temperature and high humidity can be performed. or,
It is also possible to use synthetic paper made from various resins.

Furthermore, after transfer recording, for example, a polyester film may be hot pressed and laminated on the transfer recording surface to improve the coloring of the dye and stabilize the storage of the recording.

(Function and Effect) The tricyanovinyl-based red dye represented by the general formula (I) of the present invention can control the sublimation transfer amount of the dye by changing the energy applied to the thermal head during thermal transfer. Tonal recording is easy and suitable for full color recording.

Further, since it is stable against heat, light, moisture, chemicals, etc., it is not thermally decomposed during transfer recording, and the preservability of the obtained record is excellent.

In addition, since the dye of the present invention has good solubility in organic solvents and good dispersibility in water, it is easy to prepare a high-density ink that is uniformly dissolved or dispersed, and as a result, recording with good color density can be achieved. It is a practically valuable dye that can be obtained.

(Examples) Hereinafter, the present invention will be described in detail with reference to Examples. In the examples, "part" indicates weight.

Example-1 (i) Synthesis of dye Example-1 N-ethyl-N- {2 (acetylamino) ethyl} m
-Dissolve 22 parts of toluidine in 50 parts of dimethylformamide, add 13.4 parts of tetracyanoethylene and raise the temperature to 50 ° C,
The mixture was stirred at the same temperature for 1 hour, the reaction solution was discharged into 500 ml of water, filtered, and the filter cake was washed with water and dried to obtain 19.3 parts (yield 60.1%) of a red dye represented by the following formula.

λmax (in chloroform) was 539 nm.

(Ii) Ink preparation method Dye obtained in (i) above 3 parts Polybutyral resin 4.5 〃 Methyl ethyl ketone 46.25 〃 Toluene 46.25 〃 Mix the dye mixture with the above composition for about 30 minutes with a glass bean conditioner. The ink was prepared by processing.

(Iii) Method for preparing transfer sheet Using a gravure proofing machine (plate depth: 30 μm), apply the above ink to a polyethylene phthalate film with a thickness of 9 μm that has been heat-treated on the back surface so that the dry coating amount is 1.0 g / m ^2. Dried.

(Iv) Preparation of recording material Polyester resin (vylon103 Toyobo Tg = 47 ° C) 0.8 parts EVA polymer plasticizer (Elvalloy 741p Mitsui Polychemical Tg = -32 ° C) 0.2 parts Amino-modified silicone (KF-857 Shin-Etsu) Chemical industry) 0.04 parts Epoxy-modified silicone (KF-103 Shin-Etsu Chemical industry) 0.04 parts Methyl ethyl ketone / toluene / cyclohexane (weight ratio 4: 4: 2) 0.9 parts Mix the above and adjust the coating solution to prepare synthetic paper. (Oji Yuka, Yupo FPG # 150) with a bar coater (RK Print Coat I
It was applied at a rate of 4.5 g / m ² when dried using No. 1 manufactured by Nstruments Co., Ltd. and dried at 100 ° C. for 15 minutes.

(V) Transfer recording The transfer sheet and the recording material are superposed with the ink application surface and the coating liquid application surface facing each other, and the thermal head applied voltage of 10 V from the back surface of the thermal transfer sheet for printing time.
Recording was performed under the condition of 4.0 milliseconds to obtain a red recording with a color density of 0.91.

In addition, the color density is a densitometer manufactured by Masbeth Co.
It was measured using RD-514 type (filter: Ratten No. 58).

 The color density was calculated by the following formula.

Color density = log ₁₀ (Io / I) Io = Intensity of light reflected from a standard white reflector I = Intensity of light reflected from a test object Further, the light resistance test of the obtained recording was performed using a xenon fade meter (suga). The test was carried out at a temperature of 63 ± 2 ° C. using a tester manufactured by Test Machine Co., Ltd., but the color hardly changed after irradiation for 40 hours, and the image stability under high temperature and high humidity was excellent.

In addition, the robustness of the obtained recorded image in an atmosphere of 50 ° C
After leaving for 48 hours, the sharpness of the image and the coloring when the surface was rubbed with a white paper were judged, and the sharpness of the image did not change, and the white paper was not colored, and the fastness of the recorded image was good. It was

Example-2 23.4 parts of N-ethyl-N- {2 (propionylamino) ethyl} m-toluidine were dissolved in 50 parts of dimethylformamide, 13.4 parts of tetracyanoethylene was added and the temperature was raised to 50 ° C., and at the same temperature. Stir for 1 hour and add 500 ml of water to the reaction mixture.
The mixture was discharged to a filter and filtered, and the filter cake was washed with water and dried to obtain 22.5 parts (yield 67.1%) of a red dye represented by the following formula.

λmax (in chloroform) was 539 nm.

Ink preparation, transfer sheet preparation, recording material preparation, and transfer recording were carried out in the same manner as in Example 1 to obtain a red recording having a color density of 0.92.

The sharpness of the recorded image did not change, the white paper was not colored, and the fastness was good.

Example 3 N-ethyl-N- {2 (benzoylamino) ethyl}
16.8 parts of m-toluidine are dissolved in 50 parts of dimethylformamide, 7.1 parts of tetracyanoethylene is added, and the temperature is raised to 50 ° C. After that, the mixture is stirred for 1 hour at temperature, and the reaction solution is mixed with
The mixture was discharged to 1 l, filtered, and the filter cake was washed with water and dried to obtain 12.0 parts (yield 56.4%) of a red dye represented by the following formula.

λmax (in chloroform) was 538 nm.

Ink preparation, transfer sheet preparation, recording material preparation, and transfer recording were carried out in the same manner as in Example 1 to obtain a red recording having a color density of 0.95.

The sharpness of the recorded image did not change, the white paper was not colored, and the fastness was good.

Example 4 17.9 parts of N-ethyl-N- {2 (2,3-naphthalimino) ethyl} m-toluidine are dissolved in 50 parts of dimethylformamide and 7.0 parts of tetracyanoethylene are added. 50 ° C
The temperature is raised to 0 ° C, and the mixture is stirred for 1 hour at the same temperature, and the reaction solution is mixed with water (500 m).
The resulting mixture was discharged to 1 l, filtered, and the filter cake was washed with water and dried to obtain 22.2 parts (yield 96.7%) of a red dye represented by the following formula.

λmax (in chloroform) was 535 nm.

Ink density adjustment, transfer sheet preparation, recording material preparation and transfer recording were performed in the same manner as in Example-1 to obtain color density.
A red record of 0.92 was obtained. The sharpness of the recorded image did not change, the white paper was not colored, and the fastness was good.

Example-5 N-ethyl-N- {2 (phthalimino) ethyl} m-
Toluidine (6.7 parts) was dissolved in dimethylformamide (50 parts), tetracyanoethylene (2.8 parts) was added, the temperature was raised to 50 ° C., the mixture was stirred at the same temperature for 1 hour, the reaction solution was discharged into 500 ml of water, filtered and filtered. The slag was washed with water and dried to obtain 8.5 parts of a red dye represented by the following formula (yield 95.6%).

λmax (in chloroform) was 535 nm.

Ink preparation, transfer sheet preparation, recording material preparation, and transfer recording were carried out in the same manner as in Example 1 to obtain red recording having a color density of 0.90. The sharpness of the recorded image did not change, the white paper was not colored, and the fastness was good.

Example-6 15.6 parts of N-ethyl-N- {2 (metatoluoylamino) ethyl} m-toluidine were dissolved in 50 parts of dimethylformamide, 7.1 parts of tetracyanoethylene was added and the temperature was raised to 50 ° C, and the same temperature was reached. Stir for 1 hour at 500 ml with water.
The mixture was discharged to a filter and filtered, and the filter cake was washed with water and dried to obtain 12.7 parts (yield 60.7%) of a red dye represented by the following formula.

λmax (in chloroform) was 536 nm.

Ink preparation, transfer sheet preparation, recording material preparation, and transfer recording were carried out in the same manner as in Example 1 to obtain red recording having a color density of 0.92.

The sharpness of the recorded image did not change, the white paper was not colored, and the fastness was good.

Example-7 12.8 parts of N-ethyl-N- {2 (methanesulfonylamino) ethyl} m-toluidine was added to 50 parts of dimethylformamide.
It was dissolved in 1 part and 7.1 parts of etracyanoethylene was added. 40
The temperature was raised to 0 ° C., and the mixture was stirred at the same temperature for 2 hours. Drain into 500 ml of water and filter, wash the filter cake with water and dry it.
7.6 parts (yield 98.8%) were obtained.

λmax (in chloroform) was 529 nm.

Ink adjustment, transfer sheet preparation, recording material preparation and transfer recording were carried out in the same manner as in Example 1 to obtain red recording with a color density of 1.0. The sharpness of the recorded image did not change, the white paper was not colored, and the fastness was good.

Example-8 N-Ethyl-N- {2 (maleimido) ethyl} m-toluidine (13 parts) was dissolved in dimethylformamide (50 parts), tetracyanoethylene (7.4 parts) was added, and the mixture was stirred at 40 to 45 ° C for 3 hr. It is discharged into 500 ml of water, stirred and filtered, and the filter cake is washed with water and dried to give 14.4 parts of a red dye represented by the following formula (yield:
79.7%).

λmax (in chloroform) was 538 nm.

Ink preparation, transfer sheet preparation, recording material preparation and transfer recording were carried out in the same manner as in Example-1 to obtain a color density of 0.9.
A red record was obtained. The sharpness of the recorded image did not change, the white paper was not colored, and the fastness was good.

Example-9 N-ethyl-N- {2 (succinimido) ethyl} m
12.9 parts of toluidine were dissolved in 50 parts of dimethylformamide and 7.0 parts of tetracyanoethylene were added. The mixture was stirred at 40 to 45 ° C for 2 hours. Discharge to 500 cc of water, stir and filter, wash the filter cake with water and dry to give 14.7 g of red dye (yield 82.1
%) Was obtained.

λmax (in chloroform) was 532 nm.

Ink adjustment, transfer sheet preparation, recording material preparation, and transfer recording were carried out in the same manner as in Example 1 to obtain a color density of 0.92.
A red record was obtained. The sharpness of the recorded image did not change, the white paper was not colored, and the fastness was good.

Claims (1)

(57) [Claims] 1. A general formula (I) (In the formula, R represents an acetylamino group, a propionylamino group, a methanesulfonylamino group, a maleimido group, a succinimido group, an optionally substituted benzoylamino group, a phthalimido group or a 2,3-naphthalimido group.) The red dye for thermal sublimation transfer represented.