JPH03183593A - Sublimable thermally transferable recording - Google Patents

Abstract

PURPOSE:To obtain a satisfactory thermally transferred image even on a plain sheet without any deterioration of transfer density, if a recording sheet is used many times by transferring dye from a sublimable ink layer in a specific sublimable ink layer area to a dye receptive material layer on an image receiving sheet using a sublimating technique. CONSTITUTION:A sublimable thermally transferable recording sheet is used which consists of a sublimable ink layer area 2 of a dye supply layer in which sublimable dye is dispersed in an organic binder and a dye receptive material supply layer area 7 containing a dye receptive substance on a base. Initially an image receiving sheet 3 such as plain sheet is placed over the dye receptive substance layer of the sheet. Then the dye receptive substance is transferred to an image receiving sheet under pressure or under a thermal pressure. Next the image receiving sheet 3 to which the dye receptive substance is transferred is placed over the sublimable ink layer of the sheet. After this procedure, thermal printing is performed on the recording sheet side under conditions [speed is image receiving sheet]/[speed of recording medium]>1 or [feed amount of image receiving sheet]/[feed amount of recording medium]>1. Thus the dye in the sublimable ink layer of the thermally printed part is transferred in a sublimated form to the dye receptive substance layer.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a sublimation type thermal transfer recording method, particularly to a sublimation type thermal transfer recording method for multiple printing.

[Prior Art] In recent years, the demand for full-color printers has increased year by year, and the recording methods for these full-color printers include electrophotography,
There are inkjet methods, thermal transfer methods, etc., but among these, the thermal recording transfer method is often used because it is easy to maintain and has no noise.

This thermal transfer consists of a fixed color ink sheet and an image-receiving paper, and images are formed by transferring the ink to the receiving paper by thermal melting or sublimation using thermal energy controlled by electrical signals from a laser or thermal head. This is a recording method that allows

This thermal transfer recording method can be roughly divided into the above-mentioned heat-melting transfer type and sublimation transfer type. In the latter, in principle, the sublimation dye is sublimated in a monomolecular form in response to thermal energy from a thermal head, etc. This method is considered to be the most suitable for full-color printers, as it has the advantage of easily obtaining halftones and allowing the gradation to be controlled at will.

However, this dye-sublimation transfer recording method uses a color ink sheet as a recording supply and selectively performs heating recording based on image signals. This method has the drawback that running costs are high because one ink sheet is used, and even if there is an unused portion, it is discarded.

Therefore, we are currently focusing on this drawback, and in an attempt to improve this drawback by using the ink sheet many times, we have developed a constant velocity mode method in which the ink sheet and image receptor are moved at a constant speed and used repeatedly, and the traveling speed of the ink sheet. An N-fold mode method has been proposed in which the overlapping portions of the first and second used portions of the coloring material layer are slightly shifted at a slower rate than that of the image receptor.

However, in the sublimation thermal transfer recording method, sublimation and evaporation reactions are basically zero-order reactions, and in constant velocity mode, even though the ink layer contains a sufficient amount of dye to withstand multiple uses, As the number of times of printing increases, the transfer density, especially in high image density areas, rapidly decreases, so there is a drawback that it is virtually impossible to print many times.

The reason why a thick conventional ink layer that uniformly contains a sufficient amount of dye to withstand multiple printings causes a sudden decrease in density after the second printing is because (1) the dye that contributes to transfer is concentrated on a small portion of the free surface of the ink layer; It was found that this is because the dye in the immediate vicinity of the free surface of the ink layer decreases with each printing, because (2) dye transfer follows Fick's law.

Based on this knowledge, the present inventors transferred dye from the dye supply layer to the lower layer of the dye transfer contributing layer in order to replenish the dye already consumed in the upper layer (free surface layer) of the dye transfer contributing layer due to printing. In order to easily compensate for this, it was proposed to design each layer so that the relationship of dye release ability is as follows: dye supply layer>dye transfer contributing layer (see Japanese Patent Application No. 63-62866). Furthermore, there is a method of using this in the N-fold mode method (patent application published in 1983).
3-175147). However, although this method can produce good results when using special photographic paper with a receptor layer formed as the transfer material, it does not necessarily produce good, clear images when thermally transferring to plain paper. That wasn't necessarily the case.

[Problems to be Solved by the Invention] The present invention provides a dye-sublimation thermal transfer for multiple printing, which overcomes the drawbacks of the conventional technology, does not reduce the transfer density even after multiple printing, and provides a good thermal transfer image even on plain paper. The purpose is to provide a recording method.

[Means for Solving the Problems] As a result of intensive research to achieve the above-mentioned objective, the present inventors found that (1) on a substrate, (i) a sublimable dye is dispersed in an organic binder; (ii) A sublimation type thermal transfer recording sheet provided with a sublimation ink layer region formed by laminating a dye supply layer and a dye transfer contributing layer; and (ii) a dye receptive material supply layer region containing a dye receptive material; An image-receiving sheet such as plain paper is placed on the dye-receptive material layer of the sheet, and the dye-receptive material is transferred onto the image-receiving sheet by pressure or heat, and then the dye-receptive material is applied to the sublimation ink layer of the sheet. from the recording sheet side under the conditions of [image-receiving sheet speed]/[recording medium speed]>1 or [image-receiving sheet feed amount]/[recording medium feed amount]>1. After thermal printing, the dye in the sublimation ink layer is applied to the image receiving sheet.
A sublimation thermal transfer recording method in which sublimation transfer is carried out to a dye-receiving material layer (2) (2) A dye supply layer and a dye transfer contribution layer each comprising (i) a sublimable dye dispersed in an organic binder are laminated on a substrate. Using a sublimation type thermal transfer recording sheet, which has a sublimation ink layer area made of 00 dye-receptive material and a dye-receptive material supply layer region containing a 00 dye-receptive material, first, plain paper is applied to the dye-receptive material supply layer of the sheet. Layer image-receiving sheets such as , run both in constant speed mode, thermally print from the recording sheet side to transfer the dye-receiving layer material in that area onto the image-receiving sheet, and then transfer the dye-receiving layer material of the sheet onto the image-receiving sheet. The image-receiving sheet to which the dye-receptive substance has been transferred is placed on the image-receiving sheet, and the conditions of [image-receiving sheet speed]/[recording medium speed]>1 or [image-receiving sheet feed amount]/[recording medium feed amount]>] are applied. A sublimation-type thermal transfer recording method in which the dye in the transfer contribution layer of that part is sublimated and transferred to the dye-receptive material layer on the image-receiving sheet by thermal printing, and 3) organic binding of (i) sublimable dye on the substrate A sublimation type thermal transfer recording comprising an ink layer region formed by laminating a dye supply layer and a dye transfer contribution layer dispersed in a dye, and (ii) a dye receptive material supply layer region containing a dye receptive material. Using a heart, first stack an image receiving sheet such as plain paper on the dye-receptive material supply layer of the sheet, and then set [speed of image receiving sheet]/[speed of recording medium]>1, or [feeding amount of image receiving sheet] /[Recording medium feed ffi]> While both are running under the conditions of 1, thermal printing is performed from the recording sheet side to transfer the dye-receptive material in that area onto the image-receiving sheet, and then the dye transfer contribution of the sheet is Dye-sublimation thermal transfer, in which an image-receiving sheet on which a dye-receptive substance has been transferred is placed on top of the layer, and thermal printing is performed using the same method as described above, and the dye in the transfer-contributing layer in that area is sublimated and transferred to the dye-receptive substance layer on the image-receiving sheet. It has been found that the above object can be achieved by a recording method.

The recording method of the present invention has a configuration as shown in FIG. Next, the above ink sheet will be explained.

The present invention is based on the invention disclosed in Japanese Patent Application No. 6:3-13286t3 filed by the present applicant, namely, dye supply in which sublimable dyes are dispersed in an organic binder on a substrate in order from the base side. In a sublimation thermal transfer medium formed by laminating layers and dye transfer contribution layers, the dye supply layer and the dye transfer contribution layer are each formed as a single layer on the substrate with the same amount of adhesion in each formulation, and each When layered with separate image-receiving layers and applying the same thermal energy to both,
This invention is an improvement on the invention relating to a sublimation type thermal transfer medium characterized in that the amount of dye transferred to each image receiving layer is in the relationship of dye supply layer>dye transfer contributing layer.

That is, in the present invention, a dye-receptive material containing a dye-receptive material is placed on the substrate in parallel with the ink layer region so that the dye can be thermally transferred well even onto plain paper that does not have a special ink-receiving layer. It is characterized by providing a supply layer area. When forming an image, a dye-receptive material is first transferred onto plain paper from the dye-receptive material supply layer area on the recording sheet, and then a dye-receptive material is transferred onto the portion of the dye-receptive material transferred onto the plain paper. Imaging is completed by transferring the sublimable dye from the ink layer areas.

The sublimation ink layer area on the recording sheet of the present invention will be explained.

The thickness of the dye transfer contributing layer forming the ink layer area is 0.05 to 5 .mu.m, preferably 0.1 to 2 .mu.m, and the thickness of the dye supplying layer is generally 0.1 to 5 .mu.m. ~20μ
m is preferably 0.5 to 5 μm.

Known sublimable dyes, binders, etc. can be used in the dye transfer contribution layer and the dye supply layer that form the ink layer region of the present invention.

A specific example of the sublimable dye used in the present invention is 60°C.
Any dye that sublimes or vaporizes and is mainly used in thermal transfer printing such as disperse dyes and oil-soluble dyes may be used. For example, c, 1° disperse yellow 1,3
, 8, 9.1B, 41, 54.60° 77.116, etc., C, 1, 1.4, 6° 11.1 of disper thread
5, 17.55, 59, 80.73.83 etc., C01
, Disperse Blue 3.14.19, 26.5B,
60, 64, 72.99, 108, etc., C, 1, Solvent Yellow, such as 77.116, C, 1, Solvent Red, 23.25.27, etc., C, 1, Solvent Blue, 36, 83, 1.05, etc. are listed, and
5OT as an anthraquinone or azo disperse dye
-Blue G55OT-Blue 2.5OT-Re
d2G.

5OT-Red 200.5OT-Red 300.5
OT-Red 800°SOT-Yellow 5, S
Examples include OT-Yellow 5G (manufactured by Hodogaya Chemical), and these dyes can be used alone, but
It is also possible to use a mixture of several types.

Thermoplastic or thermosetting resins are used as binders for the dye transfer contribution layer and the dye supply layer, and examples of resins having relatively high glass transition points or high softening properties include, for example, vinyl chloride resins. , vinyl acetate resin, polyamide,
Polyethylene, polycarbonate, polystyrene, polypropylene, acrylic resin, phenolic resin, polyester, polyurethane, epoxy resin, silicone resin,
Examples include fluororesin, butyral resin, melamine resin, natural rubber, synthetic rubber, polyvinyl alcohol, and cellulose resin.

These resins can be used alone, but several types may be mixed or a copolymer may be used.

Furthermore, when creating a difference in glass transition or softening temperature between the dye transfer contribution layer and the dye supply layer, a resin or natural resin with a glass transition temperature of 0° C. or less or a softening temperature of 60° C. or less is used.
Synthetic rubber is preferable, specifically syndiotactic 1,2-polybutazinine (JSRRB81 as a commercially available product).
Olefin copolymers and terpolymers containing acids or non-acidic acids (Dexon XEA-7, Dexon Chemical as commercial products); Ethylene-acetate picopolymers (400 & 400A as commercial products)
, 405,430, Allied Fibers and Plastics: P-3307 (EV 150) P-2
so7 (BY250), Mitsui DuPont Polychemicals); low molecular weight polyolefin polyols and derivatives thereof (commercial names: Polytail H, HE Mitsubishi Chemical Industries)
; Brominated epoxy resin (YDB-340, 400, 50
0.

600 Tobu Chemical); Novolac type epoxy resin (YDC
N-701, 702, 703 Tobu Kagaku); Thermoplastic acrylic trusion (Titanal LR1075, 108
0゜1081.1082, 1063.1079 Mitsubishi Rayon); Thermoplastic acrylic emulsion (LX-400
, LX-450, Mitsubishi Rayon); polyethylene oxide (Alcox E-30, 45, Alcox L?
-150,400,10 (ii) Meisei Chemical Industry); caprolactone polyol (praxephor H-1,4,7,
Daicel Chemical Industries); etc. are preferred; polyethylene oxide and polycaprolactone polyols are particularly useful; It is preferable to use

The dye content of the dye transfer contributing layer is usually Preferably, it is about 10 to 60%.

Regarding the dye content of the dye supply layer, a dye content of 5 to 80% is preferable, but when creating a dye concentration gradient between the dye transfer contribution layer and the dye supply layer, the dye concentration of the transfer contribution layer may be On the other hand, it is desirable that it is 1.1 to 5 times, preferably 1.5 to 3 times.

The dye-receptive material supply layer region containing the dye-receptive material is one that can be easily transferred by pressure, heat pressure, or thermal printing with a thermal head, is made of a substance with a relatively low melting point, and is made of a material with a relatively low melting point, and Must have good receptivity. Examples include polyester with a low melting point, vinyl chloride, vinyl acetate, acrylic resin, etc., and those with a melting point of 11.0°C or lower are preferable. These can be dissolved in a solvent, etc. The thickness of the supply layer should be 5 to 80%, preferably 1 to 50 μm, preferably 3 to 20 μm.

Preferably, a release layer made of a silicone-based or Teflon-based binder wax or the like is provided in advance before applying the above-mentioned binder onto the base film, so that pressure or heat-pressure transfer can be carried out more smoothly.

In the present invention, since the sublimable ink layer area allows multiple recordings, the dye-receptive material supply layer area can also be structured to similarly allow multiple transfers. To this end, a relatively low melting point dye-receptive material is held in a microporous structure consisting of a high melting point resin. This low-melting-point dye-receptive material is melted by heating with a thermal head or the like, and oozes out from between the porous structures and gradually oozes onto the plain paper, making it possible to transfer the material multiple times.

The content of the dye-receptive substance in the dye-receptive substance supply layer region is generally 10 to 80% by weight, preferably 3% by weight.
It is 0 to 60% by weight.

The thickness of the dye-receiving material supply layer is generally 1 to 50 μm.
m, preferably 3 to 20 μm.

Although the method for producing the dye-receptive material supply layer having the above-described structure is not particularly limited, the following method is generally adopted. That is, a low-melting-point dye-receptive substance and an oil that serves to form a porous structure in the resin are mixed and dispersed together with an appropriate organic solvent using a dispersion device such as an attritor or a ball mill to form a dispersion. (It may also be a solution). Separately, prepare a molten acid of a thermoplastic resin dissolved in an organic solvent, and mix this with the dispersion liquid,
Uniformly disperse using a mixer such as a ball mill. Next, the resulting dispersion is applied onto a support and dried to obtain a dye-receptive substance supplying layer region having the above-mentioned fine structure. A wetting agent, a dispersing agent, etc. may be added to the dispersion liquid in order to improve the dispersion of the dye-receiving substance and oil described above. If necessary, fillers commonly used in resin coatings of this type can also be added.

Here, the mixing ratio of the dye-receptive substance nioleum to the thermoplastic resin for forming a porous structure is generally (1 to G): (1 to
4):(1-8), preferably (1-3):(1
~2): (1 to 4).

Examples of low melting point dye-receptive materials include polyester,
Vinyl chloride, vinyl acetate, and acrylic resins with a melting point of 110° C. or lower are preferred.

Examples of high melting point resins constituting the microporous resin structure include vinyl chloride, vinyl acetate, vinylidene chloride, acrylic acid, methacrylic acid, cellulose resins, acrylic esters and Thermoplastic resins such as single or copolymers of monomers selected from methacrylic acid esters, phenolic resins, furan resins, formaldehyde resins, urea resins, melamine resins, alkyd resins, unsaturated polyesters 1. Thermosetting resins such as epoxy resins with a melting point of 120° C. or higher are preferred.

Alternatively, a substance that is incompatible with the resin that forms the porous structure and is soluble in a solvent that does not dissolve the resin is kneaded with the resin and coated on a support to form a resin layer. A dye-receptive material having the above-described structure can also be supplied by dissolving the material in the above-mentioned solvent to form a porous resin structure, and then filling the porous structure with the dye-receptive material. A layer area is obtained.

As the oil that serves to form a porous structure in the resin, any liquid or semisolid oil can be used as long as it is incompatible with the above-mentioned thermoplastic resin and is nonvolatile. Examples of liquid oils include animal and vegetable oils such as cottonseed oil, rapeseed oil, and whale fat; and mineral oils such as motor oil, spindle oil, and dynamo oil. Examples of semisolid oils include lanolin, lanolin derivatives, Examples include petrolatum and lard.

In addition, in order to more strongly hold the porous resin structure on the support, it is also possible to provide an intermediate adhesive layer on the support in advance. Examples of the intermediate adhesive layer include so-called plastic resins and plastic resins with fillers added.

In the recording using the ink layer according to the present invention, due to the shift recording due to the difference in speed, the ink layer is likely to peel off or fuse at the interface between the ink layer and the receiving layer, resulting in poor running. Therefore, the ink layer described above may contain a known substance with lubricating properties or mold release properties, and if necessary, it is also possible to use a heat-resistant resin or a resin that is cured by adding a curing agent. be.

Examples of substances with lubricity or mold release properties (lubricity substances) include petroleum-based lubricating oils such as liquid paraffin, synthetic lubricating oils such as hydrogen halides, diester oils, silicone oils, and fluorosilicone oils, and various modified silicones. Oils (epoxy-modified, amino-modified, alkyl-modified, polyether-modified, etc.), silicone-based lubricating substances such as copolymers of silicone and organic compounds such as polyxyalkylene glycol, various fluorine-based surfactants such as fluoroalkyl compounds, Fluorine-based lubricating substances such as trifluorochloroethylene low polymers, waxes such as paraffin wax and polyethylene wax, higher fatty acids, higher fatty alcohols, higher fatty acid amides, higher fatty acid esters, higher fatty acid salts, and the aforementioned lubricants. There are various types of particles listed as particles having heat-release properties or heat-release properties.

Films such as condenser paper polyester film, polystyrene film, polysulfone film, polyimide film, polyamide film, etc. are used as the base sheet, and a conventional adhesive layer or the like is provided between the base sheet and the dye supply layer as necessary. Alternatively, a conventional heat-resistant lubricant layer may be provided on the back surface of the base sheet, if necessary.

Although the above description has been made with reference to a recording method using a thermal head, the transfer medium of the present invention can also be applied to a recording method in which recording thermal energy is applied by a method other than a thermal head, for example.
It can also be used for methods using Joule heat generated in a medium such as a thermal printing plate, laser light, or a support.

Among these, the so-called electrical thermal transfer method, which uses Joule heat generated in the medium, is the most well-known.
4,103. It is described in many documents such as OBB, JP-A-57-14080, JP-A-57-11080, and JP-A-59-9098.

When used in this current transfer method, aluminum, copper, iron, tin, zinc, nickel, Supports in which metal powders such as molybdenum, silver, etc. and/or conductive powders such as carbon black are dispersed to adjust the resistance value to an intermediate value between insulators and good conductors, and conductive metals as described above in these supports. A support on which is vapor-deposited or sputtered may be used. The thickness of these supports is desirably about 2 to 15 microns in consideration of Joule heat conduction efficiency.

Further, when used in a laser beam transfer method, it is sufficient to select an abrasive material that absorbs laser beams and generates heat as a support. For example, a conventional thermal transfer film containing a light absorption conversion material such as carbon, or a film in which an absorption layer is formed on the front and back surfaces of a support is used.

[Examples] Hereinafter, the present invention will be further explained based on the following Examples, but the present invention is not limited thereto.

Example 1 [Formation of dye-receiving material supply layer region] Carnauba wax was coated in advance on an aromatic polyamide film by hot melt coating to a thickness of about 1 μm.

Low melting point polyester resin
60 Next, the above formulation was sufficiently dispersed to prepare a coating agent for supplying a dye-receptive substance.

As shown in FIGS. 2 and 3, the composition of the above formulation was applied to an aromatic polyamide film substrate with a thickness of about 6.5 μm and a width of 210 mm, which had a silicone-based lubricant and heat resistance 0.5 μm thick on the back side ( A release layer made of carnauba wax (manufactured by Toshi ■) 1 with a thickness of about 1 μm was provided, and then coated using a wire bar and dried at 100°C for 1 minute to form a dye-receptive material with a thickness of about 4 μm. A supply layer region 7 was formed.

[Formation of ink layer region] Part by weight Polyvinyl butyral resin BX-1i.

(manufactured by Block Chemical Industry ■) Sublimable dye Kayaset Blue 14 (manufactured by Nippon Kayaku ■) Solvent I. Luene 100 Methyl ethyl ketone 100 In the above formulation, in the formulation for the dye supply layer, 20 parts by weight of the above sublimable dye contributes to dye transfer. In the layer formulation, 10 parts by weight of the above sublimable dye and silicone oil 5P84 were added.
Add 1.5 parts by weight of 17 (manufactured by Torre Silicone),
Disperse each composition in a ball mill for 24 hours7
I met.

Thereafter, 5 parts by weight of Coronate L (manufactured by Nippon Bo 11 Urethane Co., Ltd.) was added to the supply layer formulation, and the mixture was sufficiently stirred.

Next, a sublimation type thermal transfer recording sheet hS having the structure shown in FIG. 1 was prepared as follows.

As mentioned above, as shown in FIG. 2, a wire is inserted directly onto the film in parallel with the dye-receiving material supply layer region 7 formed on the aromatic polyamide film substrate 1 (manufactured by Toshi). After applying the ink composition for the dye supply layer 4 to a film thickness of 3.0 μm using the above-mentioned ink composition, the ink composition for the dye transfer contribution layer 5 having the above formulation was applied on top of the ink composition for the dye transfer contribution layer 5 to a film thickness of 0.8 μm.
The ink layer region 2 was formed by applying the ink layer to a thickness of .mu.m, and a sublimation type thermal transfer recording sheet S was manufactured.

[Print Recording Experiment] First, using a sublimation thermal transfer recording sheet S and plain paper 3 in which the dye-receiving substance supply layer region 7 and the ink layer region 2 are arranged in parallel, the dye-receiving substance supply layer region 7 is The dye-receptive substance was thermally transferred in a solid manner onto the plain paper 3 by pressing the dye-receptive substance over the entire surface with a heated roller from the back side of the sheet (Fig. 1 a).
). As a result, a glossy dye-receiving layer made of resin was formed all over the plain paper. In FIG. 1a, the roller is fixed, and after the thermal transfer recording sheet and the receiver paper are moved together to transfer the dye-receptive material layer onto the receiver paper,
Only the receiver paper returns and comes into contact with the ink layer.

Next, a pressure 442 is applied from the back surface of the sublimable ink layer region 2 adjacent to the dye-receiving layer transferred solidly onto the plain paper 3.
a+W/dot, maximum applied energy 2.21mJ/
Density steps of 16 gradations were printed and recorded under a printing condition where the speed ratio of the dots and the image-receiving sheet (plain paper) to the recording sheet was n=5 (FIG. 1-b). As a result, a good cyan image with 16 gradations was formed on the dye-receiving layer formed on the plain paper as shown in FIG. 4.

Example 2 [Formation of dye-receiving substance supply layer region] A dye-receiving substance supply layer region was formed in exactly the same manner as in Example 1.

[Formation of Ink Layer Region] As shown in FIG. 3, the cyan ink layer region 2C was formed in exactly the same manner as in Example 1.

Next, for the magenta color ink layer region 2M, MS R is used instead of the cyan color color set blue 14.
ed G (manufactured by Mitsui Toatsu) and MaCrOIeXRed
An ink layer region was formed in the same manner as in Example 1, except that a dye mixed with Violet R (manufactured by Bayer) at a mixing ratio of 2:1 was used.

Furthermore, for the yellow ink layer region 2Y, Macro is used instead of the cyan color set blue 14.
The ink layer region was formed in the same manner as in Example 1 except that lex Yellow 6G (manufactured by Bayer) was used.

[Print recording experiment] A dye-receiving layer was first transferred onto plain paper in the same manner as in Example 1, and a color image pattern was recorded in the order of yellow, magenta, and cyan in the same manner as in Example 1. An image was formed under the printing conditions of ratio n-5, and a good color image with almost no decrease in density was formed.

Example 3 [Formation of dye-receiving material supply layer region] Part by weight Low melting point polyester resin XA-7052 (manufactured by Unitika ■, melting point 8
6℃) 30 Silicone oil 5F8417 3 (manufactured by Toray Silicone) Dispersant 2 Solvent Methyl ethyl ketone 60 Toluene
60 The above formulation was sufficiently dispersed to prepare a coating agent for a dye-receptive substance supply layer.

As shown in FIGS. 2 and 3, the composition of the above formulation was applied to an aromatic polyamide film substrate having a thickness of approximately 8.5μ11 and a width of 210+am, with a silicone-based lubricity and heat resistance 0.5μ thickness on the back side ( (manufactured by Toshi Corporation) 1 using a wire bar and dried at 100° C. for 1 minute to form a dye-receiving material supply layer region 7 having a thickness of about 5 μm.

[Formation of ink layer region] Part by weight Polyvinyl butyral resin BX-110 (manufactured by Tsukisui Kagaku Kogyo ■) Sublimable dye Kayaset Blue 14 (manufactured by Nippon Kakami) Solvent Toluene 100 Methyl ethyl ketone 100 In the above formulation, the formulation for the dye supply layer In this case, 20 parts by weight of the above sublimable dye, 10 parts by weight of the above sublimable dye in the dye transfer contributing shoe formulation, and silicone oil 5F84.
Add 1.5 parts by weight of 17 (manufactured by Torre Silicone),
Each composition was dispersed in a ball mill for 24 hours.

Thereafter, 1.5 parts by weight of Coronate L (manufactured by Nippon Polyurethane) was added to the supply layer formulation and thoroughly stirred.

Next, a sublimation type thermal transfer recording sheet S having the structure shown in FIG. 1 was prepared as follows.

As described above, as shown in FIG. 2, the dye supplying layer 4 is placed in parallel with the dye-receptive substance supplying layer region 7 formed on the aromatic polyamide film substrate (manufactured by East Side) 1 using a wire bar. After coating the ink composition for the dye transfer contributing layer 5 to a thickness of 3.0 μm, further coat the ink composition for the dye transfer contributing layer 5 having the above formulation to a thickness of 0.8 μm,
Ink layer region 2 was formed, and a sublimation type thermal transfer recording sheet S was manufactured.

[Print Recording Experiment] First, using a sublimation thermal transfer recording sheet S and plain paper 3 in which the dye-receiving substance supply layer region 7 and the ink layer region 2 are arranged in parallel, the dye-receiving substance supply layer region 7 is The recording density is 6 dots/l using the thermal head 6 from the back side of the sheet.
A solid thermal transfer of the dye-receiving material was performed on plain paper 3 under printing conditions of B11% applied energy of 1.60++ J/dot and constant speed mode. As a result, a glossy dye-receiving layer made of resin was formed all over the plain paper.

Next, a pressure 44 is applied from the back side of the sublimable ink layer region 2 adjacent to the dye-receiving layer 2 that has been solidly transferred onto the plain paper 3.
2mW/dot, maximum applied energy 2.21mJ/
Density steps of 16 gradations were printed and recorded under printing conditions of a speed ratio of n-5 between the dots and the image-receiving sheet (plain paper) and the recording sheet. As a result, a good cyan image with 16 gradations was formed on the dye-receiving layer formed on the plain paper as shown in FIG. 4.

Example 4 [Formation of dye-receiving substance supply layer region] A dye-receiving substance supply layer region was formed in exactly the same manner as in Example 3.

[Formation of Ink Layer Region] Regarding the cyan ink layer region 2C, the ink layer region was formed in exactly the same manner as in Example 1.

Next, for the magenta color ink layer region 2M, 88 R was used instead of the cyan color color set blue 14.
erl G (manufactured by Mitsui Toatsu) and Macrolex Red
An ink layer region was formed in the same manner as in Example 3, except that a dye mixed with Violet R (manufactured by Bayer) at a mixing ratio of 2:1 was used.

Furthermore, for the yellow ink layer region 2Y, Macro is used instead of the cyan color set blue 14.
Ink 1? ! j region was formed.

[Print recording experiment] A dye-receiving layer was first transferred onto plain paper in the same manner as in Example 3, and a color image pattern was recorded in the order of yellow, magenta, and cyan in the same manner as in Example 1. An image was formed under the printing conditions of ratio n-5, and a good color image with almost no decrease in density was formed.

Example 5 "Formation of dye-receiving substance supply layer region" Part by weight Low melting point polyester resin XA-7052 (manufactured by Unitika ■, melting point 8
6℃) 30 Lanolin fatty acid oil 0ES-183 (manufactured by Yoshikawa Oil Co., Ltd.) 15 Silicone oil 5F8417 3 (manufactured by Toray Silicone) Dispersant 2 Solvent Methyl ethyl ketone 70 Toluene
85 The above formulation was dispersed in a ball mill for about 24 hours, and then a solution of the following formulation was added and dispersed in a ball mill for about 15 minutes to prepare a coating agent for a dye-receiving substance supply layer.

Part by weight Cellulose acetate butyrate CA3381-20
(Manufactured by Eastman Kodak, melting point 195-205°C) Coronate L (Japan Polyurethane) 4 Solvents Methyl ethyl ketone 80 Toluene
80 As shown in FIGS. 2 and 3, the composition of the above formulation was applied onto a polyimide film substrate (manufactured by Toshi Dubon ■) 1 with a thickness of approximately 7.5 μm and a width of 210 mm using a wire bar. , dried at 100℃ for 1 minute to a thickness of about 10μm1
A dye-receptive material supply layer region 7 was formed.

[Formation of ink layer region] Part by weight polyvinyl butyral resin BX-1t.

(manufactured by Block Chemical Industry ■) Sublimable dye Kayaset Blue 14 (manufactured by Nippon Kayaku ■) Solvent Toluene 100 Methyl ethyl ketone 100 In the above formulation, in the formulation for the dye supply layer, 20 parts by weight of the above sublimable dye is used for the dye transfer contribution layer. In the recipe, the above sublimable dye is 10 parts by weight, and silicone oil 5P84 is added.
17 ()-manufactured by Resilicone) was added to 1.5 parts by weight,
Each composition was dispersed in a ball mill for 24 hours.

Thereafter, 1.5 parts by weight of Coronate L (manufactured by Nippon Polyurethane) was added to the supply layer formulation and thoroughly stirred.

Next, a sublimation type thermal transfer recording sheet S having the structure shown in FIG. 1 was prepared as follows.

As mentioned above, as shown in FIG. 2, a wire bar is used directly on the film in parallel with the dye-receptive material supply layer region 7 formed on the aromatic polyimide film substrate (manufactured by Toshi) 1. After applying the ink composition for the dye supply layer 4 to a thickness of 3.0 μm, the ink composition for the dye transfer contribution layer 5 having the above formulation was applied thereon to a thickness of 048 μm.
The ink layer area 2 was formed by applying the ink layer in an amount of 100 m, and a sublimation type thermal transfer recording sheet S was manufactured.

[Printing Recording Experiment] Using the dye-receptive substance supply layer area 7 and the ink layer area 2 arranged in parallel, using a sublimation type thermal transfer recording sheet S and plain paper 3, first, the dye-receptive substance supply layer area 7 was Recording density of 6 dots/mm with thermal head 6 from the back side of the sheet.
A solid thermal transfer of the dye-receptive material was carried out on the plain paper 3 under printing conditions of an applied energy of 1.80 aJ/dot and a speed ratio of n-5 between the image receiving sheet (plain paper) and the recording sheet. As a result, a glossy dye-receiving layer made of resin was formed all over the plain paper.

Next, a pressure 442 is applied from the back surface of the sublimable ink layer region 2 adjacent to the dye-receiving layer transferred solidly onto the plain paper 3.
+oV/dot, maximum applied energy 2.21 m'J
A density step of 16 gradations was printed and recorded under the printing conditions of /dot and speed ratio n-5 as above. As a result, a good cyan image with 16 gradations was formed on the dye-receiving layer formed on the plain paper as shown in FIG. 4.

Example 6 [Formation of dye-receiving substance supply layer region] A dye-receiving substance supply layer region was formed in exactly the same manner as in Example 5.

[Formation of Ink Layer Region] Regarding the cyan ink layer region 2C, the ink layer region was formed in exactly the same manner as in Example 5.

Next, for the magenta color ink layer region 2M, MS R is used instead of the cyan color color set blue 14.
ed G (manufactured by Mitsui Toatsu) and Macrolex Red
Violet R (manufactured by Bayer) at 2:1. An ink layer region was formed in exactly the same manner as in Example 5, except that dyes mixed at a mixing ratio of .

Further, for the yellow ink layer area 2Y, Macro
The ink layer region was formed in the same manner as in Example 5 except that lex Yellow 8G (manufactured by Bayer) was used.

[Print recording experiment] A dye-receiving layer was first transferred onto plain paper in the same manner as in Example 5, and a color image pattern was recorded in the order of yellow, magenta and cyan in the same manner as in Example 1. An image was formed under the printing conditions of ratio n-5, and a good color image with almost no decrease in density was formed.

[Effects of the Invention] As described above, by using the sublimation thermal transfer recording method as in the present invention, it is possible to perform multiple recordings without causing a rapid decrease in transfer density even when the speed difference mode increases by a factor of n. , and it is possible to obtain clear images even on plain paper.

[Brief explanation of drawings]

FIGS. 1A and 1B, FIGS. 2 and 3 are explanatory diagrams showing the structure of the sublimation type thermal transfer recording sheet of the present invention. FIG. 4 is a graph showing the multiple printing characteristics of the sublimation type thermal transfer recording sheet of Example 1. l... Support, 2... Ink layer area, 3... Plain paper, 4... Dye supply layer, 5... Dye transfer contributing layer, 6
... Thermal head, 7. Dye-receptive substance supply layer region, 8. Pressure or heat roller. 2Y. Yellow sublimable ink layer region, 2M. Magenta sublimable ink layer region. 2C: Cyan sublimable ink layer area, S: Thermal transfer recording sheet.

Claims (3)

[Claims] (1) On a substrate, (i) a sublimation ink layer region formed by laminating a dye supply layer and a dye transfer contributing layer formed by dispersing a sublimable dye in an organic binder, and (ii) a dye receptive substance. Using a sublimation type thermal transfer recording sheet provided with a dye-receiving material supplying layer region, first, an image-receiving sheet such as plain paper is overlaid on the dye-receiving material layer of the sheet, and the dye is applied by pressure or heat. A receptor material is transferred onto an image-receiving sheet, and then an image-receiving sheet with a dye-receiving material transferred is placed on the sublimation ink layer of the sheet, and [image-receiving sheet speed]/[recording medium speed]>1 or [ Thermal printing is performed from the recording sheet side under the conditions of [Image-receiving sheet feed amount] / [Recording medium feed amount] > 1,
A sublimation thermal transfer recording method characterized by sublimation-transferring the dye in the sublimation ink layer at that portion to a dye-receptive material layer on an image-receiving sheet. (2) A sublimation ink layer region formed by laminating (i) a dye supply layer and a dye transfer contribution layer in which a sublimable dye is dispersed in an organic binder on a substrate, and (ii) a dye receptive substance. Using a sublimation thermal transfer recording sheet provided with a dye-receiving substance supplying layer region, first, an image-receiving sheet such as plain paper is superimposed on the dye-receptive substance supplying layer of the sheet, and in a constant speed mode, Both are run, thermal printing is performed from the recording sheet side to transfer the dye-receiving layer material in that part onto the image-receiving sheet, and then the sublimation ink layer of the sheet is overlaid with the image-receiving sheet on which the dye-receiving material has been transferred, Thermal printing is performed under the conditions of [image-receiving sheet speed]/[recording medium speed]>1 or [image-receiving sheet feed amount]/[recording medium feed amount]>1 to remove the dye in the transfer contributing layer in that area. A sublimation thermal transfer recording method characterized by sublimation transfer onto a dye-receptive material layer on an image-receiving sheet. (3) Contains (i) an ink layer region formed by laminating a dye supply layer and a dye transfer contributing layer formed by dispersing a sublimable dye in an organic binder on a substrate, and (ii) a dye-receptive substance. Using a sublimation type thermal transfer recording heart provided with a dye-receiving material supplying layer region, an image-receiving sheet such as plain paper is first placed on the dye-receiving material supplying layer of the sheet, and the speed of the image-receiving sheet is divided by [speed of image-receiving sheet]/[ Recording medium speed] > 1, or [Image-receiving sheet feed amount] / [Recording medium feed amount] > 1, with both running, thermal printing is performed from the recording sheet side to determine the dye receptivity of that part. The substance is transferred onto an image-receiving sheet, and then the image-receiving sheet to which the dye-receptive substance has been transferred is placed on the dye-transfer contributing layer of the sheet, and thermal printing is performed using the same method as described above to remove the dye in the transfer-contributing layer in that area. A sublimation-type thermal transfer recording method characterized by sublimation transfer to a dye-receptive material layer on an image-receiving sheet.