JPH0292686A - Heat sensitive transfer material - Google Patents

Abstract

PURPOSE:To obtain satisfactory spectral absorption and optical rigidity for reproduction by forming a colorant layer containing specific dye on a support. CONSTITUTION:A colorant layer formed on a support contains dye represented by a formula (I), where Q<1> is necessary atom group for forming nitrogen- containing 5-7-membered heterocyclic ring together with at least one nitrogen atom and carbon atom to be coupled, R<1> is acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group or sulfonyl group, R<2> is hydrogen atom or alkyl group, R<3>-R<6> are hydrogen atom, alkyl group, alkoxy group or halogen atom, R<7> is hydrogen atom or alkyl group, R<8>, R<9> are hydrogen atom, alkyl group or aryl group, X is alkyl group, alkoxy group, aryloxy group or amino group.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to thermal transfer materials.

(Prior Art) Currently, thermal transfer methods, electrophotography methods, inkjet methods, and the like are being actively studied as technologies related to color hard copies. The thermal transfer method is easy to maintain and operate the equipment,
It has many advantages over other methods because the equipment and consumables are inexpensive.

Thermal transfer methods include a method in which a heat-sensitive transfer material in which a heat-melting ink layer is formed on a base film is heated with a thermal head to melt the ink and recorded on the transfer sheet, and a method in which the ink is recorded on the transfer sheet, and a method in which the ink is recorded on the transfer sheet by sublimation on the base film. There is a method in which a heat-sensitive transfer material on which a coloring material layer containing a coloring matter is formed is heated by a thermal head to sublime-transfer the coloring material onto a transfer sheet, but the sublimation transfer method in the second step uses energy applied to a thermal head. By changing the dye transfer layer, the dye transfer layer can be changed.
Gradation recording is facilitated, which is particularly advantageous for high-quality full-color recording.

However, there are various restrictions on the sublimable dyes used in this method, and there are very few that do not meet all the required performances.

Required performances include, for example, spectral characteristics favorable for color reproduction, ease of sublimation, resistance to light and heat, resistance to various chemicals, and protection against loss of sharpness (image quality). cyan dyes are difficult to retransfer, are resistant to various chemicals, are easy to synthesize, and are easy to make into heat-sensitive transfer materials, and it has been particularly desired to develop a cyan dye that satisfies these requirements.

(Problems to be Solved by the Invention) Various cyan dyes for thermal transfer have been proposed, among which Japanese Patent Application Laid-open Nos. 60-239,289 and 61-
No. 22,993, No. 61268493, No. 62-19
Indoaniline dyes described in specifications such as No. 1191 and No. 63-91287 have relatively good performance. However, these also had the problem that they were still not at a satisfactory level in terms of spectral absorption and light fastness, which are favorable for color reproduction.

(Object of the Invention) The object of the present invention is to provide a heat-sensitive transfer material containing a cyan dye which overcomes the above-mentioned defects.

(Means for Solving the Problems) The above object of the present invention is to provide the following -1'IQ (I
) was achieved using a heat-sensitive transfer material having a coloring material layer containing a dye represented by:

R″0 FI′ In the formula, Ql contains at least one nitrogen atom and represents an atomic group necessary to form a 5- to 7-membered nitrogen-containing heterocycle with the bonded carbon atom, , represents an alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group or sulfonyl group, R2 represents a hydrogen atom or an alkyl group, R3-R6 represents a hydrogen atom,
represents an alkyl group, an alkoxy group or a halogen atom,
R7 represents a hydrogen atom or an alkyl group, RI, R9
also represents a hydrogen atom, an alkyl group or an aryl group; X represents an alkyl group, an alkoxy group, an aryloxy group or an amino group; may be combined with each other to form a ring.

General formula [1] will be explained in detail below.

Q' contains at least one nitrogen atom and represents an atomic group necessary to form a 5- to 7-membered nitrogen-containing heterocycle with the bonding carbon atom, and represents a divalent group forming the ring excluding the nitrogen atom. Examples include divalent amino groups, ether bonds,
thioether bond, alkylene group, vinylene bond, imino bond, sulfonyl group, carbonyl group, arylene group,
It represents a divalent heterocyclic group, etc., and may be a combination of two or more of these, and may further have a substituent.

Examples of Ql include divalent amino groups, ether bonds,
thioether bond, alkylene group, ethylene bond, imino bond, sulfonyl group, carbonyl group, arylene group,
Examples include divalent heterocyclic groups and groups that combine two or more of these groups.

R16 is a hydrogen atom, an alkyl group (including those having a substituent), preferably having 1 to 10 carbon atoms, such as methyl, ethyl, isopropyl, butyl, cyclohexyl, 2-methoxyethyl, benzyl, allyl), an aryl group (substituent) Including those with.

It preferably represents a carbon number of 6 to 12 degrees (e.g., phenyl, p-tolyl) or a heterocycle (including those having substituents, preferably carbon atoms of 3 to 10 degrees, such as 2-pyridyl, 2-imidazolyl, 2-furyl). 'ijl@' is preferably a hydrogen atom.

In R1, the acyl group is an alkylcarbonyl group (including those having an f substituent, preferably having 1 to 10 carbon atoms; for example, formyl, acetyl, propionyl, isobutyryl, hexahydrobenzoyl, pivaloyl, trifluoroacetyl, heptafluorobutylene). lyl, chloropropionyl, cyanoacetylamino, phenoxyacetylamine)
, vinyl carbonyl group (including those having a substituent, preferably having 3 to 100 carbon atoms, such as acryloyl, methacryloyl, crotonoyl), arylcarbonyl group (including those having a substituent, preferably having 7 to 15 carbon atoms, such as benzoyl) , p-tolyl, pentafluorobenzoyl, q-fluorobenzoyl, m-methoxybenzoyl, p-trifluoromethylbenzoyl, 214-dicOObenzoyl, p-methoxycarbonylbenzoyl, l-naf]-yl) and heterylcarbonyl groups (Including those with substituents. Preferably 5 to 13 carbon atoms, such as picolinoyl, nicotinoyl, pyrrole-2-carbonyl, thiophene-2-carbonyl, furoyl, piperidine-4-carbonyl) The alkoxycarbonyl group of Rl is Including those having a substituent, preferably having 2 to 10 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, methoxyethoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, chloroethoxycarbonyl, Represents cyanoethoxycarbonyl, benzyloxycarbonyl, and allyloxycarbonyl. The aryloxycarbonyl group of No. 11 includes those having a substituent. Preferably carbon atoms having 7 to 16 carbon atoms, such as phenoxycarbonyl, p-tolylcarbonyl,
R1 represents p-methoxyphenoxycarbonyl, m-chlorophenoxycarbonyl, 2,4-dimethylphenoxycarbonyl, p-ethylpheno-1dicarbonyl
The aminocarbonyl group includes those having a substituent, preferably those having 1 to 11 carbon atoms, such as methylaminocarbonyl, dimethylaminocarbonyl, isopropylaminocarbonyl, butylaminocarbonyl, methoxyethylaminocarbonyl, anilinocarbonyl, thiazolyl The sulfonyl group of R-, which represents aminocarbonyl or hendithiazolyl aminocarbonyl, preferably has 1 to 1 carbon atoms.
0, for example methanesulfonyl, ethanesulfonyl, isobutanesulfonyl, phenylsulfonyl, p-methoxyphenylsulfonyl.

Among R1, preferred is an acyl group or alkylcarbonyl group having 2 to 7 carbon atoms.

R1 represents a hydrogen atom or an alkyl group (including those having substituents, preferably having 1 to 12 carbon atoms, such as methyl, ethyl, isopropyl, butyl, cyclohexyl, 2-methoxyethyl, benzyl, allyl).

Preferred among R' is a hydrogen atom.

R1 to R6 are hydrogen atoms, alkyl groups (same as Rz), and alkoxy groups (including those having substituents).

Preferably carbon number 1-12. For example, methoxy, ethoxy, isopropoxy, butoxy, methoxyethoxy, cyclopentyloxy, cyclohexyloxy, benzyloxy, 2-cyanoethoxy, 2-chloroethoxy, allyloxy) or halogen atoms (fluorine atom, chlorine atom,
(bromine atom).

Among R3 to R-, a hydrogen atom is preferred.

R7 represents a hydrogen atom or alkyl W (same as R2).

R? Among them, a hydrogen atom is preferred.

R1 and R9 are a hydrogen atom, an alkyl group (including those having a substituent), preferably having 1 to 12 carbon atoms, such as methyl,
Ethyl, isopropyl, butyl, cyclopentyl, cyclohexyl, 2-methoxyethyl, 2-chloroethyl,
2-hydro-toethyl, 2-cyanoethyl, cyanomethyl, 2-methylsulfamoylethyl, 2-methylsulfonylaminoethyl, 2-methoxycarbonylethyl, 2-acetoxyethyl, methoxycarbonylmethyl,
benzyl, allyl), aryl groups (including those with substituents, preferably having 6 to 12 carbon atoms), e.g. evaphenyl,
p-1lyl, m-chlorophenyl).

Among R1 and RQ, preferred is an alkyl group having 1 to 6 carbon atoms.

X is an alkyl group (same as R1 and R9), an alkoxy group (
R3-R4), aryl A xy group (including those with substituents. Preferably carbon atoms 6 to 15°; for example, phenoxy, p-methylphenoxy, p-methoxyphenoxy, m-chlorophenoxy, 2.4- (dimethylphenoxy, p-ethylphenoxy), amino group (including those with substituents. Preferably carbon number is 0 to 10°. For example, methylamino, dimethylamino, isopropylamino, butylamino, methoxyethylamino, anilino, thiazolyl amino, benzo thiazolyl amino).

Among X, preferred are an alkyl group having 1 to 4 carbon atoms or an alkoxy group.

R1 and R1, R4 and R1, and/or R5 and R9, or R8 and R9 may be bonded to each other to form a 5- or 6-membered ring.

Among the dyes represented by the general formula (I), the dyes represented by the general formula (■) are preferred.

(Here, R', R, R1, Re, X, Q! are the same as above) In the general formula (II), it is preferable that Q2 is an atomic group necessary to form the 5th to 7th rings, Qt represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Specific examples of the dye represented by the general formula (+) used in the present invention are shown below.

evening l evening evening evening evening The dye used in the present invention is R’ Ql’ It can be synthesized by bling.

A synthesis example is shown below.

Synthesis of dye No. 2: Compound represented by the following structural formula: 3.5 g 2-acetamido-4-diethylaminoaniline 3.0 g, ethyl acetate 200 ai! , 90 ml of ethanol and 150 d of an aqueous solution containing 17 g of sodium carbonate were stirred at room temperature. Is this water containing 3.1g of ammonium persulfate? 8 liquid 25rrd
Added l. After reacting for 1 hour, the layers were separated, and the ethyl acetate layer was washed twice with water. After concentrating to 1OI11, 50% of methanol was added for crystallization. By filtration and washing with methanol, 4.5 g of desired crystals were obtained.

The main feature of the heat-sensitive transfer material of the present invention is the use of a specific dye as described above, and in the first embodiment, the heat-sensitive transfer layer containing the above-mentioned dye has a thermal transfer property. This embodiment is a heat-sensitive sublimation transfer layer consisting of a dye and a binder resin. In the heat-sensitive transfer material 1 of the present invention according to this embodiment, a coating solution is prepared by dissolving or dispersing the dye of the present invention and a binder resin in an appropriate solvent, and the coating solution is applied to one side of the support. On the surface, for example, about 0.2 to 5.0 μm1
Preferably 0.4-2. A heat-sensitive transfer layer is obtained by applying the coating amount to give a dry film thickness of 0.4 m and drying.

Furthermore, as the binder resin used with the above dye, any binder resin conventionally known for this purpose can be used, and usually has high heat resistance and does not hinder the transfer of the dye when heated. For example, polyamide resin, polyester resin,
Vinyl resins including epoxy resins, polyurethane resins, polyacrylic resins (e.g. polymethyl methacrylate, polyacrylamide), polyvinylpyrrolidone, etc., polyvinyl chloride resins (e.g. vinyl chloride-vinyl acetate copolymers, etc.) ), polycarbonate resin, polysulfone, polyphenylene oxide, cellulose resin (e.g. methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen chloride, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, cellulose triacetate, etc.), polyvinyl alcohol type resin (e.g. polyvinyl alcohol, partially saponified polyvinyl alcohol such as polyvinyl butyral),
Petroleum resin, rosin derivative, coumaron-indene resin,
Terpene resins, novolanc type phenol resins, polystyrene resins, polyolefin resins (eg, polyethylene, polypropylene), etc. are used.

It is preferable to use such a binder resin in an amount of, for example, about 80 to 600 parts by weight per 100 parts by weight of the dye.

In the present invention, as the ink solvent for dissolving or dispersing the above pigment and binder resin, conventionally known ink solvents can be freely used. Specifically, water, alcohol-based solvents, methanol, ethanol, isopropyl alcohol, etc. , butanol, isobutanol, etc.; as esters, 112 ethyl, butyl acetate, etc. as ketones;
Menal ethyl ketone, methyl isobunal ketone, cyclohexanone, etc.; aromatic systems such as toluene, xylene, chlorobenzene, etc.; halogen systems, such as C dichloromethane,
Examples include trichloroethane, chloroform, etc., N,N dimethylformamide, N-methylpyrrolidone, dioxane, tetrahydrofuran, etc., cellosolve systems such as methyl cellosolve, ethyl cellosolve, and mixtures of the above solvents. It is important to select and use these solvents in such a way that the dye used has a predetermined concentration or higher and the binder resin is sufficiently dissolved or dispersed.

For example, about 9% of the total weight of the dye and binder resin.
Preferably, ~20 times the volume of solvent is used.

The dyes used in the present invention may be used alone or in combination of two or more. Further, the dye used in the present invention may be mixed with a known dye.

The dye used in the present invention may be used in combination with a known anti-fading agent.

The support used in the construction of the heat-sensitive transfer material of the present invention may be any conventionally known support as long as it has a certain degree of heat resistance and strength. For example, 0.5 to 50 μm,
Preferably paper with a thickness of about 3 to 1 OIIm, various processed papers, polyester (for example, polyethylene terephthalate); polyamide; polycarbonate; glassine; condenser paper; cellulose ester; fluorine polymer; polyether; polyacetal; polyolefin; polyimide; polyphenylene sulfide ,polypropylene,
Examples include polystyrene, allophane, polyimide, and the like. Particularly preferred is polyester film.

The ink can be applied to the base film using a reverse throw coater, a gravure coater rod coater, an air doctor coater, or the like.

The heat-sensitive transfer material as described above is useful in the present invention as it is, but an anti-adhesive layer, that is, a release layer may be further provided on the surface of the dye-carrying layer, and by providing such a layer, Prevents adhesion between the thermal transfer material and the recording material during thermal transfer, and uses a higher thermal transfer temperature.
- Capable of forming images of superior temperature.

As this mold release layer, it is quite effective to simply deposit an inorganic powder with anti-adhesive properties, and it is also possible to use resins with excellent mold release properties such as silicone polymers, acrylic polymers, fluorinated polymers, etc. It can be formed by providing a release layer with a thickness of 0.01 to 5 μm, preferably 0.05 to 2 μm.

However, the above-mentioned inorganic powders or release polymers exhibit sufficient effects even if they are contained in the dye blocking layer.

Furthermore, a heat-resistant layer may be provided on the surface of the heat-sensitive transfer material of the present invention in order to prevent the adverse effects of the heat of the thermal head.

A dye-barrier layer consisting of a hydrophilic polymer may also be used in the dye-donor element between the support and the dye layer to improve the dye transfer density.

The heat-sensitive transfer material of the present invention in a preferred embodiment obtained as described above is superimposed on a conventionally known heat-sensitive transfer material, and heated from either side, preferably from the surface of the heat-sensitive transfer material, using a thermal head or the like. By heating according to the image signal by the means, the dye in the heat-sensitive transfer layer is easily transferred and transferred to the receiving layer of the heat-sensitive transfer material with relatively low energy according to the magnitude of the heating energy.1. It is possible to form color images with excellent clarity and resolution and gradation.

According to a preferred embodiment of the present invention, the thermal transfer material is in the form of a sheet or a continuous ribbon or roll.Only a layer of the cyan dye of the present invention may be provided thereon. In addition, layers of known yellow, magenta, and possibly black pigments may be provided in separate parts.

In a preferred embodiment, a colorant layer of each color having yellow-magenta, cyan (and optionally black) sublimable dyes, i.e., yellow, magenta, cyan (and optionally black) regions is provided on the support. A thermal transfer material t-t is constructed by sequentially and repeatedly arranging them.

To perform full-color recording using such a thermal transfer material, for example, when the cyan coloring material layer (cyan dye area) is in pressure contact with the thermal transfer material, the thermal head is activated by a color signal corresponding to cyan. A heating pattern corresponding to a pixel for one scanning line is generated in each head element, and the cyan dye in the coloring material layer is transferred to the receiving layer of the thermal transfer material in accordance with this heating pattern. Transfer the cyan color for one screen by moving the thermal transfer material one scanning line at a time, and then repeat the same transfer process for each color of yellow and magenta (or black in some cases) on the same screen. The apparatus used for this recording is well known and is described, for example, in Japanese Patent Laid-Open No. 1585/1985.

The dye used in the present invention can also be used in heat-sensitive transfer materials other than those using sublimation transfer methods. That is, a second preferred embodiment of the present invention is an embodiment in which the heat-sensitive transfer layer of the heat-sensitive transfer material is a heat-sensitive melting transfer layer comprising the dye of the present invention and wax. The heat-sensitive transfer material of this embodiment is obtained by preparing a heat-sensitive transfer layer-forming ink made of wax containing a dye on one surface of the specific support as described above, and forming a heat-sensitive melt transfer layer from the ink. It will be done. The ink is made of a wax having an appropriate melting point, such as paraffin wax,
microcrystalline wax, carnauba wax,
It is made by using a binder such as urethane-based Wanx, and mixing and dispersing a pigment. The ratio of the dye and wax used is such that the dye in the heat-sensitive melt transfer layer to be formed is about 10 to
A range that accounts for 56% by weight is good, and 1 yen of the layer to be formed.
The thickness is preferably in the range of about 1.5 to 6.0 μm. Their manufacture and application onto a support can be carried out according to known techniques.

When the second preferred embodiment B of the heat-sensitive transfer material of the present invention is used in the same manner as in the first embodiment, the heat-sensitive melt transfer layer is transferred to the transfer material and provides excellent printing.

(Effects of the Invention) Since the dye represented by the formula (N) of the present invention has a clear cyan color, it is possible to obtain a full-color record with good color reproducibility by combining it with appropriate magenta and yellow colors. It is suitable for high-speed recording with high color density without placing a large burden on the thermal head because it sublimes well and has a large molecular extinction coefficient.It is also resistant to heat, light, humidity, chemicals, etc. Because it is stable, it does not undergo thermal decomposition during transfer recording, and the obtained recording has excellent storage stability.Also, the dye of the present invention has good solubility in organic solvents and good dispersibility in water, so it can be coated uniformly. It is easy to prepare high-concentration inks by dissolving or dispersing them, and by using these inks, it is possible to obtain transfer sheets on which pigments are uniformly coated at high concentrations. By using this, it is possible to obtain records with good uniformity and color density.

〔Example〕

In the following Examples and Comparative Examples, the production of thermal transfer materials and thermal transfer materials, printing using both materials, and testing of thermal transfer materials were conducted as follows.

Example 1 (Creation of thermal transfer material (I)) A 6 μm thick polyethylene terephthalate film (Lumirror, manufactured by Toshi), which had been corona treated on one side, was used as a support, and the following composition was applied on the corona treated side of the film. Coating composition (I) for a thermal transfer layer was coated by wire bar coating so that the dry thickness was 1, um, and polyvinyl butyral (Butopearl-76 ■ Monsite) (0) was coated on the back side of the member. A slipping layer of poly(vinyl stearate) (0.3 g/%) in .,45 g/n) was coated from tetrahydrofuran solvent.

1 Dye (So-2) 4g polyvinyl butyral resin (Denki Kagaku Decane Butyral 5000-A) 4g toluene 40al! Methyl ethyl ketone 40ml Polyisocyanate (Takenate DIION manufactured by Kyoyo Yakuhin) 0.2m Replace the pigment with other materials and use the thermal transfer materials (2) to (2) in Table 1.
6) and comparative material 111(a) were created.

(Creation of thermal transfer material) Synthetic paper with a thickness of 150 μm (manufactured by Tamago Yuka Co., Ltd., YU
PO-FPG-150) was used, and a receiving layer coating composition (I) having the following composition was applied to the surface by wire bar coating so that the dry thickness was 5 am to form a thermal transfer material (I). did. After temporarily drying with a hair dryer,
The test was carried out in an open environment at a temperature of 100°C for 30 minutes.

Receiving M] J Old 1ヰ Enclosure 1 Sotsu Y Polyester resin (Toyobo Byron-290) 20g Amino-modified silicone oil (Shin-Etsu Silicone KF-857) 0.5g Methyl ethyl ketone 85m Toluene
85m cyclohexanone
The thermal transfer material and the material to be thermally transferred obtained as described in 30m-F are superimposed so that the thermal transfer layer and the receiving layer are in contact with each other, and a thermal head is used from the support side of the thermal transfer material, and the output of the thermal head is 0°25
W/dot, 0 during pulse. 1'5~15m sec.

Printing was carried out under the conditions of a dot density of 6 dots and 7 m, and the receiving layer of the thermal transfer material was dyed with a cyan colorant in the form of an image, resulting in a clear image recording material with no transfer unevenness.

The reflection spectrum of the recorded thermal transfer material thus obtained was measured using a Hitachi spectrophotometer 340 equipped with an integrating sphere. The difference between the wavelength at the absorption concentration peak position and the wavelength on the shorter wavelength side of the peak wavelength that gives 1/2 the wavelength of the peak wavelength is the half value 11
The clarity of the cyan image was evaluated as follows.

In addition, the obtained recorded thermal transfer material was heated for 7 [] to 600
It was placed in a 0 Lux fluorescent lamp light resistance tester to examine the stability of the color image. Measure Status Eight reflex density before and after the test,
The light resistance during bright storage was evaluated based on the ratio. The results are shown in Table-1.

It is clear that the dye used in the present invention has sharper absorption, better color reproducibility, and better light resistance than the dye (a) of the comparative example.

Claims (1)

[Scope of Claims] A heat-sensitive transfer material having a coloring material layer on a support, wherein the coloring material layer contains a dye represented by general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) In the formula, Q^1 is an atom that contains at least one nitrogen atom and is necessary to form a 5- to 7-membered nitrogen-containing heterocycle with the bonding carbon atom. represents a group, R^1 represents an acyl group, alkoxycarbonyl group, aryloxycarbonyl group, aminocarbonyl group, or sulfonyl group, R^2 represents a hydrogen atom or an alkyl group, and R^3 to R^6 represent hydrogen represents an atom, an alkyl group, an alkoxy group, or a halogen atom, R^7 represents a hydrogen atom or an alkyl group, and R^
8, R^9 represents a hydrogen atom, an alkyl group or an aryl group, and X represents an alkyl group, an alkoxy group, an aryloxy group or an amino group. R^1 and R^3, R^4 and R^5 and/or R^5 and R^9, or R^
8 and R^9 may be combined with each other to form a ring.