JPH0815820B2 - Black thermal transfer sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a transfer sheet used for sublimation thermal transfer recording.

(Prior Art) Conventionally, a technology for color recording a facsimile printer, a copying machine, a television image or the like has been demanded, and a color recording technology by electrophotography, ink jet, thermal transfer or the like has been studied.

The thermal transfer recording method is considered to be advantageous as compared with other methods because the apparatus is easy to maintain and operate and the apparatus and consumables are inexpensive.

The thermal transfer system includes a base film, a base film and a transfer sheet having a heat-fusible ink layer formed thereon, which is heated by a thermal head to melt the ink and transfer-record on a recording medium. There is a sublimation method in which a transfer sheet on which an ink layer containing a sublimable dye is formed is heated by a thermal head to sublimate the dye, and transfer recording is performed on a recording medium. Since the sublimation transfer amount of the dye can be controlled by changing the applied energy, gradation recording becomes easy, which is considered to be particularly advantageous for full-color recording.

In order to obtain black recording by sublimation thermal transfer recording, transfer recording may be performed using a transfer sheet in which yellow, magenta and cyan colors are mixed, but conventionally, it is sufficient for black transfer sheet. There is no performance, and its development is desired.

(Problems to be Solved by the Invention) The present invention is preferable because it is easily sublimated under the operating conditions of a thermal recording head, and the sublimation properties of each of the yellow dye, magenta dye, and cyan dye are well matched. It is an object of the present invention to provide a black heat-sensitive transfer sheet which can obtain a recording satisfying conditions such as having a hue and being stable against light, moisture and chemicals.

(Means for Solving the Problems) The present invention provides the following general formulas [I] and [I] on a base film.
A black-type heat-sensitive transfer comprising a coloring material layer containing at least one of the dyes represented by I] or [III], the dye represented by the general formula [IV] and the dye represented by the general formula [V]. The main point is the sheet.

(In the formula [I], X ¹ represents a hydrogen atom or a halogen atom, X ² represents a hydrogen atom, COOR ⁷ or CONR ⁸ R ⁹ , and R ⁷ , R ⁸
And R ⁹ is a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents a cycloalkyl group, an allyl group or a substituted or unsubstituted aryl group.

[II] In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group or a substituted or unsubstituted aryl group, and the ring A is benzene which may have a substituent. Represents a ring.

[III] In the formula, Z represents a hydrogen atom, a chlorine atom or a lower alkyl group, and q ¹ and q ² represent a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group, or a substituted or unsubstituted aryl group. .

[IV] In the formula, X ³ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a formylamino group, a lower alkylcarbonylamino group, a lower alkylsulfonylamino group, a lower alkoxycarbonylamino group, and X ⁴ represents a hydrogen atom,
It represents a lower alkyl group, a lower alkoxy group or a halogen atom, and R ² , R ³ and R ⁴ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group or a substituted or unsubstituted aryl group.

[V] In the formula, X ⁵ and X ⁶ represent a lower alkyl group, a lower alkoxy group or a halogen atom, and X ⁷ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a formylamino group, a lower alkylcarbonylamino group, a lower alkyl group. Represents an alkoxycarbonylamino group or a halogen atom, X ⁸ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom, and X ⁹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted vinyl group Represents a substituted or unsubstituted aryl group or alkoxy group, R ⁵ and
R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group or a substituted or unsubstituted aryl group).

The black transfer sheet of the present invention has the general formula [I],
The yellow dyes represented by [II] and [III], the magenta dye represented by the general formula [IV] and the cyan dye represented by the general formula [V] can be obtained by blending them at an arbitrary ratio, but it is preferable. Can be produced by considering the molecular extinction coefficient and sublimation property of each and blending so as to match the color density of the obtained record.

The mixing ratio (weight) of each dye is 10 to 50% of yellow dye,
A magenta dye of 10 to 50% and a cyan dye of 30 to 80% are suitable, and particularly preferable mixing ratios are a yellow dye of 20 to 30%, a magenta dye of 20 to 30%, and a cyan dye of 40 to 55%.

The general formulas [I], [II] and [II] used in the present invention
The dyes represented by I], [IV] and [V] will be described in detail.

Formulas [I], [II], [III], [IV] and [V]
Examples of the unsubstituted alkyl group of R ^{1 to} R ⁹ , q ¹ , q ² and X ⁹ include a C _{1 to} C ₁₂ linear or branched alkyl group, and the substituted alkyl group is , Alkoxy group, alkoxyalkoxy group, aryloxy group, allyloxy group, aralkyloxy group, aryl group, cyano group, hydroxy group, halogen atom, furyl group, tetrahydrofuryl group, alkoxycarbonyl group, allyloxycarbonyl group, acyloxy group, etc. C ₁ -C replaced with
_{There are 12} linear or branched alkyl groups.

Examples of the alkyl group substituted with an alkoxy group include a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2- (n) propoxyethyl group, a 2- (iso) propoxyethyl group,
2- (n) butoxyethyl group, 2- (iso) butoxyethyl group, 2- (sec) putoxyethyl group, 2- (n) pentyloxyethyl group, 2- (n) hexyloxyethyl group, 2- (n ) Octyloxyethyl group, 2- (2 '
-Ethylhexyloxy) ethyl group, 1-methyl-2-
Methoxyethyl group, 1-methyl-2-ethoxyethyl group, 1-methyl-2- (n) propoxyethyl group, 1-
Methyl-2- (iso) propoxyethyl group, 1-methyl-2- (n) butoxyethyl group, 1-methyl-2- (is
o) Butoxyethyl group, 1-methyl-2- (n) hexyloxyethyl group, 1-methyl-2- (2-ethylhexyloxy) ethyl group, 3-methoxybutyl group, 3-ethoxybutyl group, 1-ethyl -2-methoxyethyl group,
Examples thereof include a 1-ethyl-2ethoxyethyl group, but a C ₃ -C ₈ β-alkoxyethyl group is particularly preferable.

As the alkyl group substituted with an aralkyloxy group, a 2-benzyloxyethyl group, a 1-methyl-2-benzyloxyethyl group, a 1-ethyl-2-benzyloxyethyl group, a 2- (β-phenylethyl) oxyethyl group And so on.

The alkyl group substituted with an allyloxy group is 2-
Examples thereof include an allyloxyethyl group, a 1-methyl-2-allyloxyethyl group, a 1-ethyl-2-allyloxyethyl group and the like.

2 as an alkyl group substituted with an aryloxy group
-Phenoxyethyl group, 1-methyl-2-phenoxyethyl group, 1-ethyl-2-phenoxyethyl group and the like.

Examples of the alkyl group substituted with an alkoxyalkoxy group include a 2- (2′-methoxyethoxy) ethyl group and a 2- (2′-methoxyethoxy) ethyl group.
(2'-Ethoxyethoxy) ethyl group, 2- {2 '
(N) butoxyethoxy} ethyl group, 2- {2'-
(N) Hexyloxyethoxy} ethyl group, 2- {2 '
-(N) octyloxyethoxy} ethyl group, 2-
{2 '-(iso) butoxyethoxy} ethyl group, 1-methyl-2- (2'-methoxyethoxy) ethyl group, 1-
Methyl -2 {2 '- (n) butoxyethoxy} ethyl group, 3- (2'-methoxyethoxy) but a butyl group, especially, a C ₅ ~C ₁₀ β- (β'- alkoxyethoxy) The ethyl group is preferred.

Examples of the alkyl group substituted with a cyano group include 2-cyanoethyl group and cyanomethyl group, and examples of the alkyl group substituted with a hydroxy group include 2-hydroxyethyl group and 3.
-Hydroxy (n) propyl group, 4-hydroxy (n)
Butyl group, 1-methyl-2-hydroxyethyl group, 1-
An ethyl-2-hydroxyethyl group or the like is a 2-chloroethyl group as an alkyl group substituted with a halogen atom,
2-Bromoethyl group, 2,2,2-trifluoroethyl group, etc., furfuryl group as an alkyl group substituted with a furyl group, and tetrahydrofurfuryl group as an aryl group as an alkyl group substituted with a tetrahydrofuryl group Examples of the alkyl group substituted with include a benzyl group, a p-chlorobenzyl group, a 2-phenylethyl group and the like.

Examples of the alkyl group substituted with an alkoxycarbonyl group or an allyloxycarbonyl group include 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-
(Iso) butoxycarbonylethyl group, 2- (n) hexyloxycarbonyl group, 1-methyl-2-methoxycarbonylethyl group, 1-methyl-2- (n) butoxycarbonylethyl group, 2-allyloxycarbonylethyl group , 1-methyl-2-allyloxycarbonylethyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, (iso) butoxycarbonylmethyl group,
(N) Hexyloxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group and the like.

The alkyl group substituted with an acyloxy group is 2-
Acetoxyethyl group, 2-propionyloxyethyl group, 2-benzoyloxyethyl group, 3-acetoxy (n) propyl group, 4-acetoxy (n) butyl group, 1
-Methyl-2-acetoxyethyl group, 1-ethyl-2-
An acetoxyethyl group etc. are mentioned.

Formulas [I], [II], [III], [IV] and [V]
Examples of R ^{1 to} R ⁹ and the cycloalkyl group of q ¹ and q ² include a cyclopentyl group and a cyclohexyl group.

Formulas [I], [II], [III], [IV] and [V]
Examples of the substituted or unsubstituted aryl group of R ^{1 to} R ⁹ , q ¹ , q ² and X ⁹ include a substituted or unsubstituted phenyl group, and the substituent is a C _{1 to} C ₄ lower alkyl group. Group, a C ₁ -C ₄ lower alkoxy group, a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, and a trifluoromethyl group.

Examples of X ^{3 to} X ⁸ lower alkyl groups and lower alkoxy groups in the general formulas [IV] and [V] include C _{1 to} C ₄ linear or branched alkyl groups and alkoxy groups.

Examples of the halogen atom represented by X ¹ and X ^{4 to} X ^{8 in} the general formulas [I], [IV] and [V] include a chlorine atom, a bromine atom and a fluorine atom.

Lower alkylcarbonylamino group, lower alkoxycarbonylamino group of X ³ and X ⁷ of the general formulas [IV] and [V] and lower alkyl group and lower alkoxy group of lower alkylsulfonylamino group of the X ³ of general formula [IV] As C _{1 to} C ₄
And straight-chain or branched alkyl groups and alkoxy groups.

Examples of the alkoxy group represented by X ^{9 in} the general formula [V] include C _{1 to} C ₈ linear and branched alkoxy groups.

Examples of the substituted vinyl group represented by X ^{9 in} the general formula [V] include a 2-methylvinyl group and a 1-methylvinyl group.

As the substituent of the benzene ring A in the general formula [II], a substituted or unsubstituted alkyl group, alkoxy group, nitro group, hydroxy group, halogen atom, cyano group, aryl group, substituted or unsubstituted alkoxycarbonyl group, Allyloxycarbonyl group, aryloxycarbonyl group, cycloalkyloxycarbonyl group, alkoxysulfonyl group,
Examples thereof include an aryloxysulfonyl group, an alkylsulfonyloxy group, and an arylsulfonyloxy group, and particularly, a C _{1 to} C ₈ alkyl group, a C _{1 to} C ₈ alkoxy group, a fluorine atom, a chlorine atom, and C _{1 to} C ₈ Alkoxycarbonyl groups, benzyloxycarbonyl groups, phenoxycarbonyl groups, etc. are suitable.

As the dye used in the heat-sensitive transfer sheet of the present invention, the above-mentioned dyes are used as a main component, but styryl dyes, pyrazolone azo dyes and the like as yellow dyes, anthraquinone dyes, tricyanovinyl dyes, and thiadiazole as magenta dyes. As a cyan dye such as an azo dye, anthraquinone dye, naphthoquinone dye, etc. may be used together with the above dyes, if necessary.

When the coloring material layer is formed on the heat-sensitive transfer sheet of the present invention using the above dye, the method is not particularly limited, and usually, the dye is dissolved or finely dispersed in the medium together with the binder. An ink is prepared, and the ink is applied onto a base film and dried to form a color material layer on the base film.

As a binder for preparing the ink, cellulose-based,
Acrylic acid, starch-based water-soluble resin, acrylic resin, methacrylic resin, polystyrene, polycarbonate, polysulfone, polyether sulfone, polyvinyl butyral, ethyl cellulose, acetyl cellulose,
Examples thereof include resins soluble in organic solvents such as polyester and AS resin.

As a medium for preparing the ink, in addition to water, 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; ethers such as tetrahydrofuran and dioxane; N, N-dimethylformamide; Organic solvents such as methylpyrrolidone can be mentioned.

In the above ink, in addition to the above components, if necessary, organic or inorganic non-sublimable fine particles, a dispersant, an antistatic agent, an anti-blocking agent, an antifoaming agent, an antioxidant, a viscosity modifier, etc. It can be added.

As a base film for applying the ink for producing the transfer sheet, condenser paper, thin paper such as glassine paper, polyester, polycarbonate, polyamide,
Films of plastics having good heat resistance such as polyimide and polyaramid are suitable, and the thickness thereof can be in the range of 3 to 50 μm.

Of the above base films, the polyethylene terephthalate film is particularly advantageous in consideration of mechanical strength, solvent resistance, economy and the like. However, in some cases, the polyethylene terephthalate film does not always have sufficient heat resistance, and the running performance of the thermal head is insufficient. Therefore, heat resistance that includes a surfactant, heat-resistant fine particles with high lubricity, etc. on the opposite surface of the color material layer. By providing a layer of functional resin,
A thermal head having improved running properties can be used.

The ink can be applied to the base film by using a reverse roll coater, a gravure coater, a rod coater, an air doctor coater, etc., and the thickness of the ink coating layer is in the range of 0.1 to 5 μm after drying. It should be applied so that it becomes (Yuji Harasaki, Maki Shoten 19
Issued in 1979 "Coating method").

(Example) Hereinafter, the present invention will be specifically described with reference to examples, but the examples do not limit the present invention.

Examples 1 to 5 a) Preparation of inks The dyes shown in Table 1 were used and their mixtures shown in Table 10
Each ink was prepared by treating each of them with 10 g of cellulose acetate (manufactured by Daicel Chemical Co., Ltd., product name L-30) and 80 g of methyl ethyl ketone in a paint conditioner for 10 minutes. The mixing ratio (weight ratio) of the dyes is shown in Table 2.

b) Preparation of transfer sheet A polyethylene terephthalate film (6 μm) whose back surface was heat-resistant and slip-treated with a wire bar was used.
m) and then dried (dry film thickness: about 1 μm) to obtain a transfer sheet. In addition, the polyethylene terephthalate film is subjected to the heat-resistant lubricity treatment by applying the following formula A liquid consisting of 8 parts by weight of a polycarbonate resin having a repeating structural unit represented by, 1 part by weight of a phosphoric acid ester-based surfactant (trade name: PRYSURF A-208B: Dai-ichi Kogyo Seiyaku Co., Ltd.), and 91 parts by weight of toluene. Was applied and dried (dry film thickness of about 0.5 μm).

c) Preparation of image receptor 10 parts of saturated polyester resin (product name: TP-220, manufactured by Nippon Gosei Co., Ltd.), amino-modified silicone (product name: KF3)
93, Shin-Etsu Chemical Co., Ltd. product) 0.5 part, methyl ethyl ketone 15 parts, xylene 15 parts liquid on synthetic paper (Product name: YUPO FPG150, Oji Yuka Co., Ltd. product) with a wire bar and dry (dry film thickness) An image receptor was prepared by further heat-treating in an oven at 100 ° C. for 30 minutes.

d) Transfer recording The ink-coated surface of the transfer sheet was superposed on a recording medium and a thermal head was used for recording under the following conditions.

Recording conditions Cotton density in main scan and sub-scan: 6 dots / mm Recording power: 0.4 W / dot Head heating time: 0 to 10 ms The recording density characteristics of Example 1 are shown in FIG. In addition, Table 2 shows the color density and chromaticity of the recorded matter when recording was performed with the head heating time of 10 milliseconds.

Color density is densitometer-TR-, manufactured by Macbeth, USA
It was measured using a model 927. The chromaticity was measured with a spectroscopic color difference meter SZ-Σ80 type manufactured by Nippon Denshoku Industries Co., Ltd.
(L ^* a ^* b ^* ) Color system.

e) Light fastness test The light fastness test of the record (with a color density of about 1.0) obtained in d) above was conducted using a carbon arc fade meter (manufactured by Suga Test Co., Ltd.) (black panel temperature 63 ±).
2 degree) and the degree of discoloration and fading after irradiation for 80 hours {ΔE (L ^* a ^*
b ^* )} is shown in Table 2.

Example 6 Y-1 and Y-2 shown in Table 1 as yellow dyes
10% by weight, 15% by weight and 5% by weight, respectively, of the dyes Y-5 and Y-5 in the total amount of the dyes, and the same magenta dye and cyan dye as in Example 1 were used in the same amounts.
Ink preparation, transfer sheet preparation, transfer recording, and light resistance test were conducted in the same manner as in Example 1 to obtain the results shown in Table 2.

(Operation and Effect of the Invention) When the heat-sensitive transfer sheet of the present invention is used, a high density black recorded material can be obtained with low energy, and the obtained recorded material has very good storage stability. .

The heat-sensitive transfer sheet of the present invention can utilize not only a heat-sensitive head but also infrared rays, laser light, etc. as a heating means.

[Brief description of drawings]

FIG. 1 shows recording density characteristics when heat-sensitive transfer recording is performed using the transfer recording sheet manufactured in Example 1 of the present invention. In the figure, the vertical axis represents the color density and the horizontal axis the application time (milliseconds).
Represents

Front page continuation (72) Inventor Yukichi Murata 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Sanryoh Chemical Industry Co., Ltd. (72) Inventor Takao Hirota 1000 Kamoshida-cho, Midori-ku, Yokohama, Kanagawa Sanryo Kasei Kogyo Co., Ltd. (56) References JP-A-60-260060 (JP, A) JP-A-60-260381 (JP, A) JP-A-60-260391 (JP, A)

Claims (2)

[Claims] 1. A base film having the following general formula [I]:
A black-type sensation having a coloring material layer containing at least one of the dyes represented by [II] or [III], the dye represented by the general formula [IV] and the dye represented by the general formula [V]. Thermal transfer sheet. (In the formula [I], X ¹ represents a hydrogen atom or a halogen atom, X ² represents a hydrogen atom, COOR ⁷ or CONR ⁸ R ⁹ , and R ⁷ , R ⁸
And R ⁹ is a hydrogen atom, a substituted or unsubstituted alkyl group,
It represents a cycloalkyl group, an allyl group or a substituted or unsubstituted aryl group. [II] In the formula, R ¹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group or a substituted or unsubstituted aryl group, and the ring A is benzene which may have a substituent. Represents a ring. [III] In the formula, Z represents a hydrogen atom, a chlorine atom or a lower alkyl group, and q ¹ and q ² represent a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group, or a substituted or unsubstituted aryl group. . [IV] In the formula, X ³ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a formylamino group, a lower alkylcarbonylamino group, a lower alkylsulfonylamino group, a lower alkoxycarbonylamino group, and X ⁴ represents a hydrogen atom, It represents a lower alkyl group, a lower alkoxy group or a halogen atom, and R ² , R ³ and R ⁴ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group or a substituted or unsubstituted aryl group. [V] In the formula, X ⁵ and X ⁶ represent a lower alkyl group, a lower alkoxy group or a halogen atom, and X ⁷ represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, a formylamino group, a lower alkylcarbonylamino group, a lower alkyl group. Represents an alkoxycarbonylamino group or a halogen atom, X ⁸ represents a hydrogen atom,
Represents a lower alkyl group, a lower alkoxy group or a halogen atom, X ⁹ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted vinyl group, a substituted or unsubstituted aryl group or an alkoxy group, R ⁵ And R ⁶ represents a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group or a substituted or unsubstituted aryl group). 2. The ratio of the dye in the color material layer is represented by the general formula [I],
At least one dye represented by [II] or [III], 10
Claims (1) to (50)% by weight, a dye represented by the general formula [IV], 10 to 50% by weight, and a dye represented by the general formula [V], 30 to 80% by weight. A black heat-sensitive transfer sheet according to the item 1).