JPH07112585A - Thermal transfer dye donating material - Google Patents

Abstract

PURPOSE:To obtain a high density transfer image causing no color shift at the time of transfer at a high transfer speed by adding a cellulose derivative whose specific average mol.wt. is a specific value or greater and poly-fluorinated alkyl (meth)acrylate or a fine granular compd. whose specific average particle is a specific value or greater a dye donating layer. CONSTITUTION:A thermal transfer dye donating material using a thermal transfer dye is fundamentally constituted by providing a dye donating layer containing a thermally sublimable and movable dye and a binder on a support and obtained by applying a coating soln. prepared by dissoving or dispersing the above mentioned dye and the binder in a proper solvent to one surface of the support and drying the coated support to form the dye donating layer. The binder resin of the dye donating layer is composed of a compsn. prepared by adding poly-fluorinated alkyl (meta)acrylate or a fine granular compd. with an average particle size of 0.5-10mum to a cellulose derivative with an average mol.wt. of 70000 or greater.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer dye-donating material for thermal transfer recording, which is particularly excellent in transferability during thermal transfer and enables transfer in a short time. The present invention relates to a thermal transfer dye-donor element with less transfer abnormality.

[0002]

2. Description of the Related Art In recent years, with the rapid development of the information industry, various information processing systems have been developed, and recording methods and apparatuses suitable for the respective information processing systems have also been developed and adopted. As one of such recording methods, the thermal transfer recording method has been widely used recently because the apparatus used is light and compact, noise-free, excellent in operability and maintainability, and easy to colorize. . This thermal transfer recording method is roughly classified into two types, a heat melting type and a heat transfer type. In the latter method, a thermal transfer dye-donor material having a dye-donor layer containing a binder and a heat transferable dye on a support is superposed on a thermal transfer image-receiving material, and heat is applied from the support side of the dye-donor material, and a heat-applied pattern is applied. In this method, a heat transferable dye is transferred to a recording medium (heat transfer image receiving material) in a uniform manner to obtain a transfer image. Here, the heat transferable dye means a dye which can be transferred from the thermal transfer dye-providing material to the thermal transfer image-receiving material by sublimation or diffusion in a medium.

[0003]

However, the thermal transfer dye-providing material used in the thermal transfer type thermal transfer recording method has been required more and more rapidly in the conventional thermal transfer in a short time. This is because one pixel has been made smaller in order to transfer the transferred image at a higher density and to improve the image quality, and a high quality image has been formed by forming more dots, and the image data processing capability. This is because the transfer rate has increased and high-speed transfer has become possible. However, the conventional thermal transfer dye-donating material requires an absolute amount of heat required for transfer, and thus there is a problem that a transferred image having a sufficient density cannot be obtained even if the heating from the thermal head is increased. There is also a method of applying a high voltage to the thermal head to obtain the amount of heat, but this impairs the durability of the thermal head and also causes the dye-donor material and the image-receiving material to be thermally damaged during transfer, causing sticking or fusion. The problem arises. As a method for solving these problems, various binder polymers for thermal transfer dye-donating materials have been studied. Cellulose binders are known to be particularly excellent. Acetate ester derivatives of cellulose and mixed ester derivatives of acetic acid and butyric acid are widely known. As an ether derivative, ethyl ester of cellulose,
Methyl ester and the like are known. However, although these derivatives have high transferability, there are insufficient points in order to obtain the high transferability required for high-speed transfer which is currently required. In order to obtain particularly high transferability, it is necessary to reduce the amount mixed with the thermal transfer dye very much, so that the coating property on the heat-resistant base for producing the thermal transfer dye-providing material becomes poor and a uniform coating surface is obtained. It was difficult to get.
In addition, heat fusion during thermal transfer was also poor, and a good transferred image could not be obtained. In addition, there is a problem that slippage occurs on the surface of the image receiving sheet and the surface of the ink sheet at the time of transfer, causing color shift in the transferred image.

[0004]

The object of the present invention is to provide a thermal transfer dye-donating material having a dye-donor layer on one side of a support, wherein a cellulose derivative having a molecular weight of 70,000 or more and a polyfluorinated alkyl are contained in the dye-donor layer. It was achieved by a (meth) acrylate compound or a thermal transfer dye-donor material characterized by containing fine particles having an average particle size of 0.5 to 10 μm.

The cellulose derivative of the present invention having an average molecular weight of 70,000 or more and a solution viscosity of 80 cs or more will be described. The cellulose derivative is a cellulose ester such as cellulose acetate, acetic acid or butyric acid cellulose, or a cellulose ether such as ethyl cellulose, hydroxyethyl cellulose, propyl cellulose or hydroxypropyl cellulose, and ethyl cellulose is particularly preferable.
The molecular weight is gel filtration chromatography (GPC).
Is used for comparison of molecular weight, and is calculated by using a polystyrene standard sample as a standard for molecular weight conversion. The solution viscosity is measured by dissolving a cellulose derivative in a concentration of 5% by weight in a 1: 1 (weight ratio) solution of ethyl alcohol and toluene and using a B-type viscometer at 25 ° C. The cellulose derivative used in the present invention has an average molecular weight of 70,000 or more and 500,000 or less, preferably 200,000 or less and a viscosity of about 80 cs or more, and gives excellent performance. Commercial products include ethyl cellulose N-100G and the like, which are commercially available from Shin-Etsu Chemical Co., Ltd.

The cellulose derivative used in the present invention is dye 1.
It is preferably used in a ratio of 30 to 200 parts by weight per 00 parts by weight, and particularly preferably 50 to 100 parts by weight. As the solvent for dissolving or dispersing the dye and the binder resin in the present invention, conventionally known ink solvents such as acetone, methyl ethyl cetone, methyl isobutyl ketone, ketones such as cyclohexanone, and aromatic hydrocarbons such as toluene and xylene. Solvents and alcohol solvents such as ethanol and propanol can be used. The following are preferred combinations of the cellulose derivative of the present invention and the polyisocyanate compound. That is, a reaction product of ethyl cellulose and trimethylol propane and toluidine isocyanate, a reaction product of ethyl cellulose and trimethylol propane and hexamethylene diisocyanate, a reaction product of ethyl cellulose and trimethylol propane and isophorone diisocyanate, ethyl cellulose and isocyanurate bonded tolylene diisocyanate, ethyl cellulose and Isocyanurate-bonded hexamethylene diisocyanate, reaction product of propylcellulose and trimethylolpropane and toluidine isocyanate, propylcellulose and trimethylolpropane and hexamethylenediisocyanate reaction product, propylcellulose and isocyanurate-bonded tolylene diisocyanate, hydroxyethylcellulose and trimethylolpropane Truizi Isocyanate reactant, hydroxyethyl cellulose and isocyanurate-bonded hexamethylene diisocyanate, cellulose acetate and trimethylolpropane and hexamethylene diisocyanate reactant, cellulose acetate and isocyanurate-bonded hexamethylene diisocyanate, cellulose acetate butyrate and trimethylolpropane and isophorone diisocyanate A combination of the reaction product, cellulose acetate butyrate and isocyanurate-bonded tolylene diisocyanate is preferable.

The polyisocyanate compound of the present invention is a compound containing two or more isocyanate groups in the molecule,
Preferred is triisocyanate. Examples of triisocyanates include trimethylolpropane, a reaction product of tolylene diisocyanate, a reaction product of trimethylol propane and hexamethylene diisocyanate, a reaction product of trimethylol propane and isophorone diisocyanate, isocyanurate-bonded tolylene diisocyanate,
Examples are isocyanurate-bonded hexamethylene diisocyanate, burette-bonded hexamethylene diisocyanate, and the like. Takenate D manufactured by Takeda Products as a commercial product
-110N, polyisocyanate made by Nippon Polyurethane,
Coronate L, Coronate HL, KP-90 and the like.

The polyfluorinated alkyl (meth) acrylate compound of the present invention will be described. The polyfluorinated alkyl (meth) acrylate means a polyfluorinated alkyl acrylate or a polyfluorinated alkyl methacrylate, and a fluorinated alkyl acrylate, a homopolymer of fluorinated alkyl methacrylate, or a copolymer acrylate having a different alkyl chain length. It may be a copolymer of methacrylate. Further, it may be a copolymer of another acrylate or methacrylate with a fluorinated alkyl acrylate or a fluorinated alkyl methacrylate. The polyfluorinated alkyl (meth) acrylate compound of the present invention is an oligomer type polymer having a relatively low molecular weight, and is 100 as a (meth) acrylate unit.
It is preferably no more than 50 units, more preferably no more than 50 units. It is available as a commercial product and is marketed under the name of Asahi Glass Asahi Guard or NOK Kluver Co. Knox Guard.

Next, the average particle size used in the present invention is 0.5.
The fine particles of μ to 10 μm will be described. The fine particles used in the present invention are usually called matting agents, and the materials are silicon dioxide, polyolefin, polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads,
There are AS resin beads and the like, and benzoguanamine resin beads are particularly effective in the present invention. Commercially available products, Nippon Shokubai Chemical Co., benzoguanamine resin beads,
There are eposters S, eposters M, eposters MS, eposters L and the like. A preferable average particle size is 0.5 to 10 μm.
Particularly preferred is a matting agent of 1 to 5 μm. The preferred amount of the matting agent is particularly preferably at 0.01g / m ² ~0.3g / m ² is 0.05~0.15g / m ^2.

Any conventionally known support can be used as the support of the thermal transfer dye-providing material. Examples thereof include polyethylene terephthalate, polyamide, polycarbonate, glassine paper, condenser paper, cellulose ester, fluoropolymer, polyether, polyacetal, polyolefin, polyimide, polyphenylene sulfide, polypropylene, polysulfone, and cellophane. The thickness of the support of the thermal transfer dye-donor element is generally 2 to
It is 30 μm. Particularly, polyethylene terephthalate having a size of 5 to 6 µ is excellent. An undercoat layer may be provided if necessary.

The thermal transfer dye-donor material using the heat-transferable dye basically has a dye-donor layer containing a dye and a binder which are movable by heat on a support. This thermal transfer dye-donating material is prepared by dissolving or dispersing a conventionally well-known dye that becomes sublimable or becomes mobile and a binder resin in an appropriate solvent to prepare a coating solution, which is prepared by a conventionally known thermal transfer dye-donor. On one side of the support for the material, for example about 0.2-5 μm, preferably 0.4-2 μm.
It can be obtained by coating and drying at a coating amount that results in a dry film thickness of m to form a dye-donor layer. The dye-donor layer may be formed of one layer, but may be formed of two or more layers for use in a method in which the dye-donating layer is repeatedly used many times.
In this case, the dye content and dye / binder ratio in each layer may be different.

As the dye useful for the shape of such a dye-donor layer, any of the dyes conventionally used in thermal transfer dye-donor materials can be used, but a particularly preferred dye in the present invention is about 200 to 600. Has a small molecular weight, and is selected in consideration of transfer temperature, hue, light resistance, solubility in ink and binder resin, dispersibility and the like. Specific examples thereof include disperse dyes, basic dyes, oil-soluble dyes, and the like. Among them, Sumikaron Yellow E4GL, Dianix Yellow H2G-FS,
Miketone Polyelter Yellow 3GSL, Kayaset Yellow 937, Sumikaron Red EFBL, Dyanix Red ACE, Miketone Polyelter Red FB, Kayaset Red 126, Miketone Fast Brilliant Blue B, Kayaset Blue 136, etc. are preferably used. To be Further, it is preferable to use a yellow dye represented by the following general formula (Y).

[0013]

[Chemical 1]

(In the formula, D ¹ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an alkoxycarbonyl group, a cyano group or a carbamoyl group, and D ² represents a hydrogen atom,
It represents an alkyl group or an aryl group, D ³ represents an aryl group or a heteryl group, and D ⁴ and D ⁵ represent a hydrogen atom or an alkyl group. The above groups may be further substituted. ) Specific examples of compounds are shown below.

[0015]

[Chemical 2]

[0016]

[Chemical 3]

[0017]

[Chemical 4]

[0018]

[Chemical 5]

[0019]

[Chemical 6]

[0020]

[Chemical 7]

[0021]

[Chemical 8]

[0022]

[Chemical 9]

[0023]

[Chemical 10]

[0024]

[Chemical 11]

[0025]

[Chemical 12]

As the magenta dye, the dye of the following general formula (M) is preferable.

[0027]

[Chemical 13]

(Wherein D ⁶ and D ¹⁰ are hydrogen atom, halogen atom, alkyl group, alkoxy group, aryl group, aryloxy group, cyano group, acylamino group, sulfonylamino group, ureido group, alkoxycarbonylamino group,
It represents an alkylthio group, an arylthio group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an acyl group or an amino group, and D ¹¹ and D ¹² represent a hydrogen atom, an alkyl group or an aryl group. D ¹¹ ,
D ¹² may combine with each other to form a ring, or D ⁸ and D ¹¹ or / and D ⁹ and D ¹² may combine with each other to form a ring. X, Y and Z represent = C (D ¹³ )-or a nitrogen atom (D ¹³ is a hydrogen atom, an alkyl group, an aryl group,
Represents an alkoxy group, an aryloxy group and an amino group). When X and Y are ═C (D ¹³ ) − or when Y and Z are ═C (D ¹³ ) −, two D ^13's may be bonded to each other to form a saturated or unsaturated carbocycle. . The above groups may be further substituted. ) Specific examples of compounds are shown below.

[0029]

[Chemical 14]

[0030]

[Chemical 15]

[0031]

[Chemical 16]

[0032]

[Chemical 17]

[0033]

[Chemical 18]

[0034]

[Chemical 19]

[0035]

[Chemical 20]

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

[0038]

[Chemical formula 23]

As the cyan dye, the following general formula (C) is used.
Are preferred.

[0040]

[Chemical formula 24]

(In the formula, D ^{14 to} D ²¹ are synonymous with D ^{6 to} D ¹⁰ , and D ²² and D ²³ are synonymous with D ¹¹ and D ^12. ) Specific examples of compounds are shown below.

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

[0044]

[Chemical 27]

[0045]

[Chemical 28]

[0046]

[Chemical 29]

[0047]

[Chemical 30]

[0048]

[Chemical 31]

[0049]

[Chemical 32]

[0050]

[Chemical 33]

It is preferable to introduce the anti-fading group described in Japanese Patent Application No. 1-271078 into the compounds of the above general formulas (Y), (M) and (C) since the light fastness is improved.

The dye-donor layer is formed by selecting a dye so that a desired hue can be transferred when printed, and by arranging two or more dye-donor layers having different hues side by side with one thermal transfer dye-donor material, if necessary. May be. For example, when an image such as a color photograph is formed by repeatedly printing each color according to the color separation signal, it is desirable that the hue when printed is cyan, magenta, and yellow, and such a hue is given. Line up the three dye-donor layers containing the dye. Alternatively, in addition to cyan, magenta, and yellow, a dye-donor layer containing a dye that imparts a black hue may be added. In addition, it is preferable to provide a mark for position detection at the same time when any one of the dye-donor layers is formed during the formation of these dye-donor layers, because an ink or printing step different from the dye-donor layer formation is not required.

In the present invention, the support used for the thermal transfer image-receiving material can withstand the transfer temperature and satisfies the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic property, dent after transfer and the like. Anything that can be used can be used. For example, synthetic paper (synthetic paper such as polyolefin and polystyrene), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin Paper support such as paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene methacrylate, polycarbonate, etc. Films or sheets treated to impart white reflectivity to the plastic, and laminates of any combination of the above may also be used.

The thermal transfer image receiving material is provided with an image receiving layer.
This image-receiving layer contains a substance capable of receiving a heat-transferable dye having a function of dyeing the heat-transferable dye, which receives the heat-transferable dye transferred from the heat-transfer dye-providing material during printing. Or with other binder substances, it is preferable that the film has a thickness of about 0.5 to 50 μm. The following resins are examples of polymers that are typical examples of substances that can receive heat transferable dyes.

(A) those having an ester bond: dicarboxylic acid components such as terephthalic acid, isophthalic acid and succinic acid (these dicarboxylic acid components may be substituted with a sulfonic acid group or a carboxyl group) and ethylene. Polyester resin obtained by condensation of glycol, diethylene glycol, propylene glycol, neopentyl glycol, bisphenol A, etc .: polyacrylic acid ester resin or polymethacrylic acid ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate : Polycarbonate resin: Polyvinyl acetate resin: Styrene acrylate resin: Vinyl toluene acrylate resin, etc. Specifically, JP-A-59-101395
No. 63, No. 63-7971, No. 63-7972, No. 63
No. 7973 and No. 60-294862 can be mentioned. As commercially available products, Toyobo Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-14 are used.
0, Byron GK-130, ATR-200 made by Kao
9, ATR-2010, etc. can be used.

(B) Those having a urethane bond Polyurethane resin and the like. (C) Those having an amide bond Polyamide resin and the like. (D) Urea resin having a urea bond. (E) Those having a sulfone bond Polysulfone resin, etc. (F) Others having a highly polar bond Polycaprolactone resin, styrene-maleic anhydride resin, polyvinyl chloride resin, polyacrylonitrile resin, etc. In addition to the above synthetic resins, mixtures or copolymers of these can also be used.

The thermal transfer image-receiving material, particularly the image-receiving layer, may contain a high-boiling organic solvent or a thermal solvent as a substance capable of receiving the heat-transferable dye or as a diffusion aid of the dye. Specific examples of the high boiling point organic solvent and the heat solvent include JP-A Nos. 62-174754 and 62-24525.
No. 3, No. 61-209444, No. 61-200538
No. 6, No. 62-8145, No. 62-9348, No. 62
The compounds described in Nos. -30247 and 62-136646 can be mentioned.

In the present invention, the image-receiving layer of the thermal transfer image-receiving material may have a structure in which a substance capable of receiving the heat-transferable dye is dispersed in a water-soluble binder to carry it. As the water-soluble binder used in this case, various known water-soluble polymers can be used, but water-soluble polymers having a group capable of undergoing a crosslinking reaction by a hardening agent are preferable, and gelatins are particularly preferable. The image receiving layer may be composed of two or more layers. In that case, a synthetic resin having a low glass transition point is used for the layer closer to the support, or a dye having a high boiling point organic solvent or thermal solvent is used to enhance the dyeing property, and the outermost layer has a glass transition point. Use a synthetic resin with a higher point, reduce the amount of high-boiling organic solvent or thermal solvent to the required minimum amount or do not use it, and make the surface sticky, adhere to other substances, re-transfer to other substances after transfer. It is desirable to have a structure that prevents failures such as transfer and blocking with a thermal transfer dye-donating material. The total thickness of the image receiving layer is 0.5 to 50 μm, especially 3 to 50 μm.
The range of 30 μm is preferable. In the case of a two-layer structure, the outermost layer preferably has a thickness of 0.1 to 2 μm, particularly 0.2 to 1 μm.

In the present invention, the thermal transfer image-receiving material may have an intermediate layer between the support and the image-receiving layer. The intermediate layer is any one of a cushion layer, a porous layer, and a dye diffusion preventing layer or a layer having two or more functions depending on the constituent material, and also serves as an adhesive in some cases. The dye diffusion-preventing layer serves to prevent the heat transferable dye from diffusing into the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable, and examples thereof include the water-soluble binders mentioned above as the binder for the receiving layer, particularly gelatin. The porous layer is
This layer serves to prevent the heat applied during thermal transfer from diffusing from the image receiving layer to the support and to effectively utilize the applied heat.

In the present invention, silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, and the like are used as the image-receiving layer, cushion layer, porous layer, diffusion-preventing layer, adhesive layer and the like which constitute the thermal transfer image-receiving material. Fine powders of aluminum silicate, synthetic zeolite, zinc oxide, lithopone, titanium oxide, alumina and the like may be contained.

A fluorescent whitening agent may be used in the thermal transfer image-receiving material. As an example, K. Veen-kataraman edition `` The C
hemistry of Synthetic Dyes ", Volume V, Chapter 8, and JP-A-61-143752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazolethiophene compounds, etc. Can be mentioned. The fluorescent whitening agent can be used in combination with an anti-fading agent.

The layer constituting the thermal transfer image-receiving material used in the present invention may be cured with a hardener. When curing an organic solvent-based polymer, JP-A-61-11999
Nos. 97 and 58-215398 can be used. It is particularly preferable to use an isocyanate type hardener for the polyester resin. For curing water soluble polymers, US Pat. No. 4,678,739, 4,
Column 1, JP-A-59-116655 and JP-A-64-2452.
The hardeners described in No. 61 and No. 61-18942 are suitable for use. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane, etc.), N-methylol type hardener (dimethylol urea, etc.), or polymer hardener (JP-A-62-23415).
Compounds described in No. 7 and the like).

An anti-fading agent may be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a kind of metal complex. Examples of the antioxidant include chroman compounds, coumarane compounds, phenol compounds (for example, hindered phenols), hydroquinone derivatives, hindered amine derivatives, and spiroindane compounds.
The compounds described in JP-A-61-159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.),
4-thiazolidone compounds (US Pat. No. 3,352,68
No. 1), benzophenone compounds (JP-A-56-2)
No. 784, etc.) and other JP-A-54-48535,
There are compounds described in JP-A-62-136641, JP-A-61-188256 and the like. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective. Examples of the metal complex include U.S. Pat. Nos. 4,241,155 and 4,2.
45,018, columns 3 to 36, ibid., 4,254,195.
Nos. 3-8, JP-A-62-174741, 61-
88256, pages (27) to (29), JP-A-1-755.
68, compounds described in JP-A No. 63-199248 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137). An anti-fading agent for preventing discoloration of the dye transferred to the image-receiving material may be contained in the image-receiving material in advance, or may be supplied to the image-receiving material from the outside by a method such as transferring from the dye-providing material. May be. The above-mentioned antioxidant, ultraviolet absorber, and metal complex may be used in combination.

A releasing agent may be used in the thermal transfer dye-donating material and the thermal transfer image-receiving material in order to prevent fusion during thermal transfer. As the release agent, non-modified or amino-modified,
Examples include modified silicone resins or silicone oils such as epoxy-modified, hydroxy-modified, carboxy-modified, and ether-modified, fluorine compounds such as fluorine-containing surfactants, and waxes.

Various surfactants can be used in the constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material for the purpose of coating aid, improvement of peeling property, improvement of sliding property, prevention of electrostatic charge, acceleration of development and the like. Nonionic surfactants, anionic surfactants, amphoteric surfactants and cationic surfactants can be used. Specific examples of these are disclosed in JP-A-62-1734.
63, 62-183457 and the like.

When a substance capable of accepting a heat transferable dye, a releasing agent, an anti-fading agent, an ultraviolet absorber, a fluorescent brightening agent, and other hydrophobic compounds are dispersed in a water-soluble binder, they are dispersed. It is preferable to use a surfactant as an auxiliary agent.
For this purpose, in addition to the above-mentioned surfactants, the surfactants described on pages 37 to 38 of JP-A-59-157636 are particularly preferably used.

A matting agent can be used in the thermal transfer dye-providing material and the thermal transfer image-receiving material. As the matting agent, in addition to the compounds described in JP-A No. 61-88256, page 29, such as silicon dioxide, polyolefin or polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in JP-A-63-27.
There are compounds described in 4944 and 63-274952.

A releasing agent can be used in the thermal transfer dye-donor material and the thermal transfer image-receiving material in order to prevent fusion due to heat during transfer. As the release agent, unmodified or modified silicone resin having various functional groups introduced, silicone oil, fluorine compound, various waxes, etc. can be used. Particularly, unmodified dimethylsiloxane polymers, amino-modified silicones, epoxy-modified silicones, ether-modified silicones, carboxy-modified silicones, hydroxy-modified silicones and the like are excellent.

As mentioned above, the dye-donor element of the invention comprises
Used to form transfer images. Such a process
Imagewise heating the dye-donor element as described above using a laser and transferring the dye image to the image-receiving material to form the transferred image.

The dye-donor elements of the invention are used in sheet form or in continuous rolls or ribbons. If a continuous roll or ribbon is used, it may have areas of different dyes, such as cyan and / or magenta and / or yellow and / or black and / or other dyes that have only one type of dye or are heat transferable. Have separately. That is, one-color, two-color, three-color, or four-color materials (or even multi-color materials) are included within the scope of the present invention.

[0073]

EXAMPLES The effects of the present invention will be described in more detail below by showing specific examples of the present invention. However, the present invention is not limited to these. In the following, "parts" means "parts by weight" unless otherwise specified.

Example 1 A polyester film having a thickness of 5 μ having a heat-resistant layer made of a thermosetting acrylic resin and silicone oil on one side was used as a support, and the surface of the support opposite to the side provided with the heat-resistant layer was as follows. The dye-donor layer-forming ink having the composition was applied and dried by gravure printing in the order of a black marking layer, a yellow dye-donor layer, a magenta dye-donor layer, and a cyan dye-donor layer to prepare a dye-donor ink sheet. This was designated as Sample 101.

Ink for black marking layer XEL detection mark ink (made by Moroboshi Ink Co., Ltd.) 100 g EXEL curing agent (D) (made by Moroboshi Ink Co., Ltd.) 4 g Methyl ethyl ketone 40 g Toluene 40 g Dry coating amount 1.2 g / m ²

Ink for yellow dye-donating layer Dye Y-1 3.2 parts Dye Y-2 0.8 parts Ethyl cellulose (N-100G Sekisui Chemical Co., Ltd.) 2 parts Polyisocyanate (Takenate D110N, Takeda Yakuhin) 0.1 parts Silicone oil KF96 (manufactured by Shin-Etsu Silicone) 0.2 parts Methyl ethyl ketone 50 parts Toluene 50 parts Dry coating amount 1.2 g / m ²

Ink for magenta dye-donating layer Dye M-2 2 parts Dye M-1 1 part Ethylcellulose (N-100G Sekisui Chemical Co., Ltd.) 1.5 parts Polyisocyanate (Takenate D110N, Takeda Chemical Industries) 0.1 part Silicone oil KF96 (Shin-Etsu Silicone) 0.2 parts Methyl ethyl ketone 50 parts Toluene 50 parts Dry coating amount 1.2 g / m ²

Ink for cyan dye-donating layer Dye C-5 2 parts Dye C-2 1 part Ethyl cellulose (N-100G Sekisui Chemical Co., Ltd.) 1.5 parts Polyisocyanate (Takenate D110N, Takeda Yakuhin) 0.1 part Silicone oil KF96 (Shin-Etsu Silicone) 0.2 parts Methyl ethyl ketone 50 parts Toluene 50 parts Dry coating amount 1.2 g / m ²

(Preparation of Thermal Transfer Image Receiving Material) Low density polyethylene having titanium oxide and ultramarine blue kneaded therein was laminated to a thickness of 33 μm on one surface of a high quality paper having a thickness of 175 μm as a support, and a high density was formed on the opposite surface. Polyethylene thickness 3
Polyethylene coated paper laminated to 2 μm was used. The composition for hydrophilic binder layer (1) was coated on the side of the low-density polyethylene laminate so that the amount of gelatin was 1 g / m ² .

Composition for hydrophilic binder layer (1) Gelatin 60 g Water 3000 g Surfactant (compound represented by the following chemical formula 34) 2.3 g Thickener (polystyrene sulfonate potassium salt) 1.4 g

[0081]

[Chemical 34]

Further, a coating composition (2) for image-receiving layer having the following composition was coated on this hydrophilic binder layer by Giesser coating so that the amount of polyester would be 10 g / m ² .
A thermal transfer image receiving material was prepared. Drying was carried out for 30 minutes in an oven at 100 ° C. after natural drying in a draft.

Coating composition for image receiving layer (2) Polyester resin (1) ^* 20 g Polyisocyanate (KP-90, manufactured by Dainippon Ink) 3 g Amino-modified silicone oil (KF-857, manufactured by Shin-Etsu Silicone) 0.5 g Methyl ethyl ketone 100 cc Toluene 100cc

The composition (mol%) of the above polyester resin (1) ^* is shown in Table A below.

[0085]

[Table 1]

Samples 102 to 108 were prepared by changing the binder and isocyanate of the yellow dye-donor layer ink, the magenta dye-donor layer ink and the cyan dye-donor layer ink in Sample 101 as shown in the table below.

[0087]

[Table 2]

(Measurement of Transfer Density) A thermal head of 12 dots per 1 mm is heated for 13 ms per pixel,
Thermal transfer was performed in the order of Y, M, and C. The black image after transfer was measured for the densities of three colors Y, M, and C with a reflection density measuring Xrite.

Image color shift test Video printer VP9000 (manufactured by Fuji Photo Film)
Then, using a pattern generator, a signal was input so that the transfer density was about 0.50 in a gray uniform image, and five sheets were transferred by continuous transfer, and the color misregistration occurred in the image was measured. It was judged that there was no color misalignment ◯, color misregistration was slightly generated at the edges Δ, and color misregistration was bad. Further, the uniformity of the transferred image was visually judged, and it was judged as uniform ∘, unevenness ∘ was observed, white spots were present and rough surface was formed x.
The results are shown in Table 3.

[0090]

[Table 3]

As is clear from the results in Table 3, by using the high molecular weight ethyl cellulose and the polyfluorinated alkyl (meth) acrylate compound of the present invention, excellent gravure printing suitability and high density at high speed transfer can be obtained. It is also understood that an excellent thermal transfer dye-donor material having no color shift in transfer and no abnormality in surface state can be obtained.

Sample 102 in which a matting agent was added to the yellow dye-donor layer ink, the magenta dye-donor layer ink, and the cyan dye-donor layer ink in Sample 101 as shown in Table 4
~ 109 were created.

[0093]

[Table 4]

Image color shift test Video printer VP9000 (manufactured by Fuji Photo Film)
Then, using a pattern generator, a signal was input so that the transfer density was about 0.50 in a gray uniform image, and five sheets were transferred by continuous transfer, and the color misregistration occurred in the image was measured. It was judged that there was no color misalignment ◯, color misregistration was slightly generated at the edges Δ, and color misregistration was bad. Further, the uniformity of the transferred image was visually judged, and it was judged as uniform ∘, unevenness ∘ was observed, white spots were present and rough surface was formed x.
The results are shown in Table 5.

[0095]

[Table 5]

As is clear from the results in Table 5, the high molecular weight ethyl cellulose of the present invention and the average particle size of 0.5 to 10 are used.
It is understood that by using the fine particles of μ, a high density can be obtained at high speed transfer, and an excellent thermal transfer dye-donor material free from color misregistration at the time of transfer can be obtained. If fine particles were not used, color misregistration occurred at low density transfer, and a normal image could not be obtained. Further, in the case of particles having a large size, the transfer surface was rough and the transfer deviation could not be improved.

[0097]

EFFECT OF THE INVENTION The cellulose derivative of the present invention and polyfluorinated alkyl methacrylate or average particle diameter of 0.5 μ-10
By using the fine particles of μ, a high density can be obtained by high-speed transfer, and a transfer image without color deviation of the image at the time of transfer can be obtained.

Claims (1)

[Claims] 1. A thermal transfer dye-donor material having a dye-donor layer on one surface of a support, wherein the dye-donor layer has a cellulose derivative having an average molecular weight of 70,000 or more, and a polyfluorinated alkyl (meth) acrylate or an average particle diameter. 0.5 ~
A thermal transfer dye-donor element containing 10 µm of a fine particle compound.