JPH0513076B2 - - Google Patents

Description

[Detailed description of the invention]

OBJECT OF THE INVENTION A. Field of Industrial Application The present invention relates to a dye used in sublimation type heat-sensitive transfer recording and a heat-sensitive transfer recording sheet using the same. B. Prior Art Conventionally, there has been a demand for technology for color recording facsimile printers, copying machines, television images, etc., and color recording technologies using electrophotography, inkjet, thermal transfer, etc. are being considered. The thermal transfer recording method is considered to be advantageous over other methods because the device is easy to maintain and operate, and the device and consumables are inexpensive. Thermal transfer methods include a transfer sheet in which a heat-melting ink layer is formed on a base film, and a melting method in which a transfer sheet is heated with a heat-sensitive head to melt the ink and transferred onto a recording medium, and a transfer sheet is formed on a base film. There is a sublimation method in which a transfer sheet on which an ink layer containing a sublimable dye is formed is heated with a thermal head to sublimate the dye and transfer it onto the recording medium. Since the amount of sublimation transfer of the dye can be controlled by changing the energy, gradation recording becomes easy and it is considered to be particularly advantageous for full color recording. C. Problems to be Solved by the Invention The present invention is characterized in that it sublimates easily under the operating conditions of a thermal recording head, does not thermally decompose under the operating conditions of a thermal recording head, has a hue favorable for color reproduction, and has a molecular extinction coefficient. The purpose is to provide a cyan dye that satisfies the following conditions: large pigmentation, stability against light, moisture, chemicals, etc., easy synthesis, excellent suitability for ink production, and other purposes. relates to a heat-sensitive transfer recording sheet using the dye. Structure of the invention The present invention is based on the general formula [] (In the formula, X represents a hydrogen atom, a methyl group, a methoxy group, a formylamino group, an acetylamino group, a propionylamino group, a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom, and Y represents a hydrogen atom, a methoxy group, Represents an ethoxy group, chlorine atom, bromine atom, iodine atom, fluorine atom or methyl group,
R, R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted C ₁ to C ₈ alkyl group, or an aryl group.
However, N-[3-[{4-(N,N-diethylamino)
-2-methyl}phenyl]imino-6-oxo-
1,4-Cyclohexadien-1-yl]acetamide is excluded. The gist is the dye for thermal transfer recording shown in the following. That is, the dye of the present invention is a dye represented by the above general formula []. In the general formula [], the groups represented by R, R ¹ and R ² include a hydrogen atom, a C ₁ to C ₈ alkyl group, a C ₃ to _{C 8} alkoxyalkyl group, and a C ₂ to _{C 4} hydroxyalkyl group. , a _C1 - _C8 halogenated alkyl group, a -cyanoethyl group, an allyl group, or a tetrahydrofurfuryl group. Other R ¹
and R ² is a benzyl group, a phenylethyl group, a phenoxyethyl group, a C ₄ to C ₈
-acyloxyethyl group, C4 _{- C8} 〓-alkoxycarbonylethyl group, _C4 - _C8 〓-alkoxycarbonyloxyethyl group, and phenyl group are similarly preferred. However, the dye of the present invention is N-[3-
[{4-(N,N-diethylamino)-2-methyl}
Phenyl]imino-6-oxo-1,4-cyclohexadien-1-yl]acetamide dyes represented by the following structural formula are excluded. The dye of the present invention has the following general formula [] (In the formula, R is the same as defined above.) Phenols represented by the following general formula [] (In the formula, X, Y, R ¹ and R ² are the same as defined above.) In the presence of silver nitrate,
It can be manufactured by heating. The thermal transfer recording sheet of the present invention having a coloring material layer containing the dye of the present invention on a base material can be prepared by preparing an ink by dissolving or dispersing the dye in the form of fine particles in a medium together with a binder. A transfer sheet may be prepared by applying ink onto a base film and drying it. Binders for ink preparation include water-soluble resins such as cellulose, acrylic acid, and starch, and organic solvent-soluble resins such as acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyethersulfone, and ethyl cellulose. Examples include resin. In the case of an organic solvent-soluble resin, it is possible to use it not only as an organic solvent solution but also in the form of an aqueous dispersion. In addition to water, media for ink preparation include alcohols such as methyl alcohol, isopropyl alcohol, and isobutyl alcohol, cellosolves such as methyl cellosolve and ethyl cellosolve, aromatics such as toluene, xylene, and chlorobenzene, ethyl acetate, Esters such as butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, chlorinated solvents such as methylene chloride, chloroform, and trichloroethylene, tetrahydrofuran,
Examples include ethers such as dioxane, and organic solvents such as N,N-dimethylformamide and N-methylpyrrolidone. The base film used to apply ink for the production of transfer sheets includes condenser paper, thin paper such as glassine paper, polyester, polyamide,
A plastic film with good heat resistance, such as polyimide, is suitable. Further, the thickness of the base film may be in the range of 3 to 50 m. The ink can be applied to the base film using a reverse roll coater, gravure coater, rod coater, air doctor coater, etc. The thickness of the ink coating layer after drying is 0.1 to 5 mm. (Yuji Harasaki, "Coating method")
(1979) Maki Shoten). Functions and Effects of the Invention Since the dye shown in [] above of the present invention has a clear cyan color, it is suitable for obtaining full-color recording with good color reproducibility by combining it with appropriate magenta and yellow colors. Moreover, since it sublimes easily and has a large molecular extinction coefficient, it is possible to obtain high-speed recording with high color density without placing a large burden on the heat-sensitive head. Furthermore, since it is stable against heat, light, moisture, chemicals, etc., it does not undergo thermal decomposition during transfer recording, and the resulting recording has excellent storage stability. Furthermore, since the dye 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, and by using such ink, , it is possible to obtain a transfer sheet on which the dye is uniformly coated at a high concentration. Therefore, by using these transfer sheets, recording with good uniformity and color density can be obtained. EXAMPLES The present invention will be specifically explained below with reference to Examples, but these Examples are not intended to limit the present invention. Example 1 a Preparation of ink Above dye 10g Polysulfone resin ^* 10g Chlorobenzene 80g Total 100g * Manufactured by Nissan Chemical Industries, Ltd., Udel P-
1700 (trade name) A mixture having the above composition was treated with a paint conditioner for 10 minutes to prepare an ink. The pigment and resin were completely dissolved, and an ink with a uniform solution could be obtained. b Preparation of transfer sheet Apply the above ink using a bar coater (RK Print
Coat Instruments Co., Ltd., No. 1) was used to coat a polyimide film (15 mm thick), and the transfer sheet was air-dried to obtain a transfer sheet. c. Transfer Recording The ink coated surface of the above transfer sheet was overlapped with the recording medium and recording was performed using a thermal head under the following conditions, and it was possible to obtain a clear cyan record with a uniform and high color density of 1.40. Recording conditions Main scanning and sub-scanning linear density: 4 dots/mm Recording power: 0.6 W/dot Head heating time: 10 msec The recording material is 34% by weight saturated polyester.
10 g of aqueous dispersion (manufactured by Toyobo Co., Ltd., Vylonal MD-1200, trade name) and silica (manufactured by Nippon Silica Kogyo Co., Ltd., Nipsil E220A, trade name)
Mix 1g of the prepared liquid with high-quality paper (200〓m thick)
Bar coater (RK Print Coat Instruments)
Co., Ltd., No. 3) was applied and dried. Color density was measured using a densitometer RD-514 model (filter: Ratten No. 25) manufactured by Macbeth, USA.
Measured using A light resistance test of the obtained record was conducted using a carbon arc fade meter (manufactured by Suga Test Instruments Co., Ltd.) at a black panel temperature of 63±2°C.
There was almost no discoloration or fading after irradiation for hours. Example 2 The dyes shown in Table 1 were used instead of the dyes used in Example 1, and ink preparation, transfer sheet production, and transfer recording were carried out according to the method of Example 1. A clear cyan color record with the color density shown in Table 1 could be obtained.

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 General formula [1] (In the formula, X represents a hydrogen atom, a methyl group, a methoxy group, a formylamino group, an acetylamino group, a propionylamino group, a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom, and Y represents a hydrogen atom, a methoxy group, Represents an ethoxy group, chlorine atom, bromine atom, iodine atom, fluorine atom or methyl group,
R, R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted C ₁ to C ₈ alkyl group, or an aryl group. However, N-[3-[{4-(N,N-diethylamino)-2-methyl}phenyl]imino-6-oxo-1,4-cyclohexadien-1-yl]
Excludes acetamide. ) A dye for thermal transfer recording. 2 General formula [1] on the base material (In the formula, X represents a hydrogen atom, a methyl group, a methoxy group, a formylamino group, an acetylamino group, a propionylamino group, a chlorine atom, a bromine atom, an iodine atom, or a fluorine atom, and Y represents a hydrogen atom, a methoxy group, Represents an ethoxy group, chlorine atom, bromine atom, iodine atom, fluorine atom or methyl group,
R, R ¹ and R ² represent a hydrogen atom, a substituted or unsubstituted C ₁ to C ₈ alkyl group, or an aryl group. However, N-[3-[{4-(N,N-diethylamino)-2-methyl}phenyl]imino-6-oxo-1,4-cyclohexadien-1-yl]
Excludes acetamide. ) A heat-sensitive transfer recording sheet comprising a coloring material layer containing a dye represented by: