JPH0867073A - Image-receiving sheet for sublimating dye transfer and recording using the sheet - Google Patents

Abstract

PURPOSE: To obtain an image-receiving sheet for sublimating dye transfer with high surface peelability and at the same time, ensure high concentration even in a mixed color, if a speed difference mode recording method is applied, by increasing a gel dispersion powder for the entire layer of a dye-receiving layer consisting maily of curable resin of a thermosensitive transfer-type image- receiving sheet, to higher than a specific weight %. CONSTITUTION: An image-receiving sheet for sublimating dye transfer is obtained by providing a dye receiving layer directly or through an intermediate layer, on a support. Consequently, no fusion or damage generates, if this sheet is recorded in a speed difference mode. In addition, it is possible to output data in monochrome and high concentration and prevent dye from being reversely transferred by using a transfer sheet and a transfer sheet whose top ink layer is a low dyeable resin layer'.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image receiving sheet for sublimation transfer and a recording method using the speed-difference mode method.

[0002]

2. Description of the Related Art In recent years, the demand for full-color printers has increased year by year, and there are electrophotographic systems, ink jet systems, thermal transfer systems, etc. as recording systems for these full-color printers. Among them, maintenance is easy and there is no noise. For the reason, the thermal transfer method is drawing attention. In this heat-sensitive transfer system, a transfer sheet having an ink layer in which a colorant is dispersed in a heat-fusible substance and an image receiving sheet are superposed, and heat is applied to the transfer sheet in an imagewise manner to heat-melt the ink layer to thereby receive an image. A transfer sheet having an ink layer containing a thermal sublimation dye or a heat transferable dye (hereinafter simply referred to as a sublimation dye) for transfer recording onto a sheet and an image receiving sheet are superposed. There is sublimation transfer recording in which the dye in the ink layer is sublimated or transferred onto the image receiving sheet by imagewise application of heat to the transfer sheet to record the image. Sublimation transfer recording is generally superior in terms of fidelity of color tone for recording full-color images.

In the sublimation transfer recording, the speed of the sublimation transfer image receiving sheet (hereinafter sometimes simply referred to as an image receiving sheet) is set to a sublimation transfer sheet (hereinafter A speed difference mode recording method (n-times mode method) is adopted in which the speed is n times (n> 1) the speed of the transfer sheet, and both sheets are repeatedly printed. .

[0004]

In the conventional sublimation type transfer recording, a dye receiving layer made of a thermoplastic polyester resin showing strong dyeing property to a sublimable dye is used as an image receiving sheet as a substrate (paper, synthetic paper). , Synthetic resin film, etc.) has been used. However, the conventional image-receiving sheet does not have sufficient releasability from the transfer sheet surface,
Particularly when applied to the speed difference mode recording method, a strong frictional force is applied between both sheets, which may cause fusion during recording or damage to the sheet.

Further, in the speed difference mode recording method, when an image receiving sheet having a gel fraction of less than 70% by weight based on the entire layer of the dye receiving layer is used, high energy cannot be imparted due to the occurrence of fusion, resulting in High concentration cannot be obtained. On the other hand, when an image receiving sheet having a gel fraction of 100% by weight based on the entire image receiving layer is used, high energy can be imparted without fusion and the like, so that a high density can be obtained in a single color. Since the obtained dye has a high gel fraction in the receiving layer, the dye is less likely to diffuse inside the receiving layer, and the transferred dye is located near the surface of the receiving layer. Therefore, at the time of color mixing, 1 on the surface of the receiving layer
The next-color dye is reversely transferred to the transfer sheet, and as a result, a high-density image cannot be obtained during color mixing (especially black).

Accordingly, the present invention provides an image-receiving sheet for sublimation transfer having a high surface peeling property, and a recording method capable of obtaining a high density even with mixed colors when a speed difference mode recording method is applied using the image-receiving sheet. The purpose is to provide.

[0007]

According to the present invention, in a sublimation transfer image-receiving sheet in which a dye receiving layer is provided on a substrate directly or via an intermediate layer, the dye receiving layer is mainly composed of a curable resin, And the gel fraction to the whole layer is 7
There is provided an image receiving sheet for sublimation transfer characterized by being 0% by weight or more.

Further, according to the present invention, the sublimation transfer image receiving sheet and the sublimation transfer sheet in which the uppermost layer of the ink layer is a low dyeing resin layer are used, and the sublimation transfer sheet is opposed to the image receiving sheet. There is provided a recording method characterized by recording at a speed of 1 / n (n> 1).

The present inventors have found that when the dyeable resin of the dye receiving layer in the image receiving sheet is cured, the releasability of the surface becomes high, and the gel fraction is set to 70% by weight or more, whereby the speed difference is increased. It was found that fusion or damage does not occur even when applied to mode recording, and by using the above-mentioned image receiving sheet and a transfer sheet in which the uppermost ink layer is a low dyeing resin layer, speed difference mode recording Applied to
The present invention has been accomplished by discovering that high density output is possible with a single color, reverse dye transfer is prevented, and high density can be obtained even when colors are mixed.

The gel fraction in the present invention means a ratio of a portion of the receptor layer which does not elute in the solvent, when a small piece of 50 mm × 100 mm of the image receiving sheet is used as a sample and immersed in 500 g of methyl ethyl ketone solvent for 10 minutes. Is defined.

In the speed difference mode recording method, the gel fraction of the receiving layer is set to 90% by weight or more in order to prevent fusion and breakage even if the speed difference is large (n is large). It is preferable. Further, when the dyeable resin is cured, the releasability of the surface becomes high, but the dyeability tends to decrease, so the upper limit of the gel fraction is preferably about 99% by weight.

The curable resin which constitutes the receiving layer can be obtained by curing a resin having a good dyeing property to a sublimable dye. As the resin having good dyeing property to the sublimable dye, conventionally known materials may be used, for example, vinyl chloride resin, vinyl acetate resin, polyamide, polyethylene,
Examples thereof include polypropylene, polystyrene, acrylic resin, polyester, polycarbonate, polyurethane, epoxy resin, silicone resin, melamine resin, natural rubber, synthetic rubber, polyvinyl alcohol, and cellulose resin. These may be used alone or in combination of two or more, or may be used as a copolymer thereof. Further, of these, it is preferable to use a resin having active hydrogen. Further, among the dyeing resins, those containing an average of 20 or more OH groups per molecule are preferable. OH
In the case of a resin having less than 20 groups per molecule, the resin layer is insufficiently cured and cannot have sufficient heat resistance, so that it is difficult to obtain an original recorded image during printing.

As the curing agent, known curing agents can be used, but when a resin having active hydrogen is selected as the resin capable of being dyed with the sublimable dye, it is suitable to use an isocyanate compound. . As the isocyanate compound, a di- or tri-isocyanate compound is particularly effective, for example, 2,4-tolylene diisocyanate,
Examples include 2.6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, triphenylmethane triisocyanate, isophorone diisocyanate, biscyanate methylcyclohexane and trimethylhexamethylene diisocyanate. -O of resin having active hydrogen and -NCO group of isocyanate compound
It is suitable to mix with the H group in a ratio of 0.1: 1 to 1: 1.

In order to obtain a high gel fraction receiving layer of the present invention by reacting a resin having active hydrogen with an isocyanate compound, it cannot be obtained only by coating and drying the receiving layer. It can be obtained only by leaving it to stand in the atmosphere for a long period of time and aging.

Since aging in a high-temperature atmosphere for a long period of time is disadvantageous in terms of production cost, the high-temperature aging condition can be relaxed by adding a curing catalyst to the receiving layer forming liquid. With such a curing catalyst,
Acids, bases, metal compounds and the like are effective, and it is preferable to use a tin-based catalyst for the reaction between the resin having active hydrogen and the isocyanate compound. Examples of tin catalysts include dibutyltin oxide, dioctyltin oxide, tetrabutyltin, tin tetrachloride, dibutyltin laurate, dibutyltin dilaurate, dioctyltin dilaurate, butyltin trichloride, dibutyltin diacetate and the like.

A lubricant may be mixed in order to improve the lubricity of the receiving layer. Examples of the lubricant include petroleum-based lubricating oil such as liquid paraffin, hydrogen halide, diester oil, silicone oil, fluorosilicone oil, modified (epoxy modified, amino modified, alkyl modified, polyether modified etc.) silicone oil, etc. Silicone lubricating products such as synthetic lubricating oils, copolymers of organic compounds such as polyoxyalkylene glycol and silicone, various fluorine-based lubricants such as fluoroalkyl compounds, paraffin wax,
Examples thereof include waxes such as polyethylene wax, higher fatty acids, higher aliphatic alcohols, higher fatty acid amides, higher fatty acid esters, and higher fatty acid salts. If the amount of these lubricants added to the receiving layer is 5% by weight, the lubricating effect is effectively exhibited, and of course, the amount must be less than 30% by weight.

Further, known additives such as surfactants, ultraviolet absorbers, antioxidants and optical brighteners may be added to the receiving layer, but the total amount of these additives is of course 30.
Must be below wt%.

To produce the image-receiving sheet for sublimation transfer of the present invention, a receptive layer forming liquid is directly formed on a substrate made of paper, synthetic paper or a resin film or through a known intermediate layer such as an adhesive layer or a heat insulating layer. After coating and drying, aging in a high temperature atmosphere or heat curing treatment may be performed. The thickness of the receiving layer is generally preferably about 1 to 20 μm.

Among the base films, it is preferable to use a film having fine air bubbles inside. As a result, elasticity and heat insulation are provided, and it becomes possible to prevent the image from being rough and the sensitivity being lowered, which are problems in the velocity difference mode method.
In particular, a foamed type polyethylene terephthalate film (hereinafter abbreviated as PET film) is preferable in terms of sensitivity, heat resistance, hiding power, whiteness, and gloss. Also,
In order to eliminate curl, it is suitable to stick two or more films together. For example, from the side of the receiving layer PET /
Paper, PET / synthetic paper, PET / paper / PET, PET / P
ET, PET / PET / synthetic paper and the like are preferable. More preferably, it is preferable to use an adhesive agent for lamination in order to prevent curling. Further, among the films having bubbles, a film having a density D satisfying the following formula (1) is particularly preferable in terms of sensitivity and image roughness. (D ₀ −D) / D ₀ > 0.3 (1) (D ₀ represents the density of the plastic film containing the same material as the substrate and containing no bubbles.)

The uppermost layer of the ink layer of the sublimation transfer sheet used in the present invention is composed of a low dyeing resin. The low dyeing resin layer in the present invention is defined as follows. That is, synthetic paper YUPO FPG # 9 as a base
5 (manufactured by Oji Yuka Co., Ltd.), a modified silicone oil SF8417 / SF8411 = 1/1 (manufactured by Toray Silicone Co., Ltd.) having a resin solid content of 5 to 20% by weight dissolved in a resin solution having a resin solid content of 30% by weight. The liquid containing is dried for 1 minute so that the dry film thickness is 10 μm, and then dried at room temperature for 1 day or more. Next, a sheet cassette CK2LB for a Mitsubishi color video copy processor and a cyan ribbon are overlaid on the receiving layer formed above, and a thermal head KMT-85-6MPD4 (manufactured by Kyocera Corp.) having a resolution of 6 dots / mm and an average resistance of 542 ohms. Was recorded at 2.00 mj / dot, and the recording density was evaluated by a reflection densitometer RD-918.
A resin layer showing 1.2 or less, preferably 1.0 or less is defined as a low dyeing resin layer.

As a result, preferred resins are aromatic polyester resins, styrene-butadiene resins, polyvinyl acetate resins, polyamide resins, and particularly preferred resins are methacrylate resins or their copolymers, styrene-maleic acid ester copolymers, polyimides. Resin, acetate resin, silicone resin, styrene acrylonitrile resin, polysulfone resin and the like can be mentioned. Further, a silicone resin as a resin constituting the low-dyeing resin layer has a low dyeing property required for the low-dyeing resin layer and a fusion preventing ability as the uppermost layer of the transfer member in the speed difference mode method, In particular, it is particularly preferable because it has both heat resistance and releasability. Of course, this resin layer may be formed by mixing several kinds of resins.

The sublimable dye used in the ink layer is a dye that sublimes or vaporizes at 60 ° C. or higher, and may be any dye mainly used in thermal transfer printing such as disperse dyes and oil-soluble dyes. I. Disperse Yellow 1,3,8,9,16,41,54,60,77,1
16, etc., C.I. I. Disperse Red 1, 4, 6,
11, 15, 17, 55, 59, 60, 73, 83, C.I. I. Disperse Blue 3,14,19,2
6,56,60,64,72,99,108, etc., C.I.
I. Solvent Hierro 77,116, C.I. I. Solvent Red 23, 25, 27, C.I. I. Solvent blue 36, 105 and the like can be mentioned. One of these dyes can be used, but a mixture of several dyes can also be used.

A thermoplastic or thermosetting resin is used for the binder used in the ink layer, and examples thereof include vinyl chloride resin, vinyl acetate resin, polyamide, polyethylene, polycarbonate, polystyrene, polypropylene, acrylic resin, and phenol resin. , Polyester, polyurethane, epoxy resin, silicone resin, fluorine resin, butyral resin, melamine resin, natural rubber, synthetic rubber, polyvinyl alcohol, cellulose resin and the like. These resins can be used in one kind, but if several kinds are mixed,
Further, a copolymer may be used.

The thickness of the ink layer is preferably 0.5 to 20 μm, and more preferably 1 to 10 μm from the viewpoint of thermal response sensitivity and multi-function of the transfer member. The dye concentration is 5
Is preferably 80% to 80%, more preferably 50% to 80% from the viewpoint of the thermal response sensitivity of the transfer material and the multiplicity.

Further, as the ink layer structure of the thermal transfer member, a dye supply layer containing at least an undissolved particulate sublimable dye is provided in order to stably supply the dye for a long time and maintain good printing characteristics. It is preferable. Here, the undissolved particles mean a dye that cannot be completely dissolved in the organic binder after the ink (organic binder + sublimable dye + solvent) is dried at the time of forming the ink layer and is deposited in the form of particles. Even in the case of the binder and the dye, the presence of the undissolved particulate dye varies depending on the solvent.
The presence or absence of the undissolved particulate dye can be easily identified by an electron microscope after forming the dye supply layer. The particle size of the undissolved particulate dye varies depending on the thickness of the dye supply layer, but is 0.01 μm to
It is 20 μm, preferably 1.0 μm to 5 μm.

Further, as the ink layer constitution of the thermal transfer member, it is preferable to provide a dye transfer contributing layer between the dye supply layer and the low dyeing resin layer as described in JP-A-5-64980. The dye supply layer and the dye transfer contributing layer are formed by forming the same adhesive agent as a single layer on the substrate in each formulation, superposing each of them on different receiving layers, and applying the same thermal energy to both. , The amount of dye transferred to each receiving layer is in the relationship of dye supply layer> dye transfer contributing layer.

From the viewpoint of the present inventors, the diffusion of the dye in the ink layer is Fick's law, that is, the dye amount dn which has passed the cross-sectional area q in a unit time is the concentration of the dye in the diffusion direction. Where dc / dx and D is the average diffusion coefficient of each part in the ink layer when heat is applied, the relationship of dn = −D × (dc / dx) × q × dt is applied. Therefore, as means for facilitating the diffusive supply of the sublimable dye from the dye supply layer to the transfer contribution layer, I) regarding the dye concentration, there is a relationship of dye supply layer> transfer contribution layer, and / or II) respectively. Regarding the diffusion coefficient in the layer (1), there is a means for making the relationship of dye supply layer> transfer contributing layer.

Next, the thickness of the dye transfer contributing layer and the low dyeing resin layer is generally 0.05 to 5 μm, preferably 0.
It is 1 to 2 μm. The thickness of the dye supply layer is generally 0.1 to 20 μm, preferably 0.5 to 10 μm. Known sublimable dyes, binders and the like can be used in the transfer contributing layer and the dye supplying layer of the present invention.

When there is a difference in the glass transition or softening temperature between the dye transfer contributing layer and the dye supplying layer, a resin having a glass transition temperature of 0 ° C. or lower, or a softening temperature of 60 ° C. or lower, or a natural or synthetic rubber, is preferable. Specifically, polyethylene oxide (Alcox E-30, 45, R-15
0,400,1000; manufactured by Meisei Chemical Industry Co., Ltd .; Caplacton Polyol (Plaxel H-1, 4, 7: manufactured by Daicel Chemical Industry Co., Ltd.) and the like are practically useful, and the thermoplastic or thermosetting resin described above. It is preferable to use a mixture of the organic resin and one or more of the above.

The dye concentration of the dye transfer contributing layer and the low dyeing resin layer is usually 0 to 80%, preferably about 10 to 60%. The dye concentration of the dye supply layer is 5-8.
Although a dye concentration of 0% is preferable, when a dye concentration distribution is provided between the dye transfer contributing layer and the dye supplying layer, it is 1.1 to 5 times, preferably 1.5 times the dye concentration of the dye transferring contributing layer. ~
3 times is desirable. In addition, the dye state in the dye transfer contributing layer and the low dyeing resin layer is dispersed in a monomolecular form that actually contributes to the transfer, preventing the occurrence of uneven transfer darkness and contributing to the dye supply layer and the dye transfer. It is desirable because it maintains a stable dye concentration gradient with the layer. Further, each ink layer may contain known additives such as a lubricant, a curing agent, a dispersant and an antioxidant.

As the base sheet, films such as condenser paper, polyester film, polystyrene flume, polysulfone film, polyimide film and polyaramid film are used, and a conventional sheet may be provided between the base sheet and the dye supply layer as required. An adhesive layer or the like may be provided, and if necessary, a conventional heat resistant lubricating layer may be provided on the back surface of the base sheet.

Up to now, an example in which the dye layer is divided into three layers has been described, but if an appropriate difference in dye transfer amount is produced and the functional separation intended by the present invention can be achieved, that is, the concentration gradient and the diffusion coefficient gradient are obtained. If the above condition holds, the dye layer may have two layers, and of course, it may have four or more layers.

Although the recording method using the thermal head described above has been described, the transfer medium of the present invention is recorded by a method other than recording energy, for example, a thermal printing plate, a laser beam, or a support. It can also be used for the method using Joule heat generated in the medium. Among them, the electrothermal transfer method using Joule heat generated in the medium is the most well known, and for example, US Pat.
No. 3,066, JP-A-57-14060, JP-A-57-11080, or JP-A-59-9096, and the like. When used in this energization thermal transfer method, a relatively heat-resistant polyester, polycarbonate, triacetyl cellulose, nylon, polyimide, aromatic polyamide or the like resin as a support, aluminum, copper, iron, tin, zinc, Supports prepared by dispersing metal powders such as nickel, molybdenum, and silver and / or conductive powders such as carbon black so that the resistance value is intermediate between that of an insulator and a good conductor, or these supports have the above-mentioned conductivity. A support obtained by vapor-depositing or sputtering a functional metal may be used. Considering the Joule heat conduction efficiency, the thickness of these supports is preferably about 2 to 15 microns. When used in the laser light transfer method, a material that absorbs laser light and generates heat may be selected as the support. For example, a conventional thermal transfer film containing a light absorption conversion agent such as carbon, or an absorption layer formed on the front and back surfaces of a support is used.

[0034]

[Examples] Specific examples will be described below. The amount (part) of each component in the following description is part by weight.

Example 1 [Receptor layer forming solution] Polyester resin (Vylon 200: manufactured by Toyobo Co., Ltd.) 18 parts Isocyanate compound (Coronate L: manufactured by Nippon Polyurethane Co., Ltd.) 5 parts Silicone oil (SF8417: manufactured by Toray Silicone Co., Ltd.) 1 part Silicone Oil (SF8411: manufactured by Torre Silicone Co., Ltd.) 1 part Toluene 40 parts Methyl ethyl ketone 40 parts The above-prepared solution is applied on synthetic paper (Yupo: Oji Yuka Synthetic Paper Co., Ltd.) and dried to form a 6 μm-thick receiving layer. After that, this was heated at 110 ° C. for 2 hours to prepare an image receiving sheet.

Example 2 In Example 1, the tin catalyst (TK
(IL: manufactured by Takeda Pharmaceutical Co., Ltd.) was added, and an image receiving sheet was prepared in the same manner as in Example 1 except that aging treatment was performed for 4 days in an environment of 60 ° C. without heat treatment. .

Example 3 An image receiving sheet was prepared in the same manner as in Example 2 except that a vinyl chloride resin (VAGH: manufactured by Union Carbide Co.) was used in place of the polyester resin.

Example 4 The same as Example 1 except that the heating treatment was performed in an environment of 80 ° C.
An image-receiving sheet was prepared in the same manner as in Example 1 except that the aging treatment for a day was performed.

Comparative Example 1 An image receiving sheet was prepared in the same manner as in Example 1 except that the isocyanate compound was omitted.

Comparative Example 2 In Example 1, the heat treatment was not performed, and
An image receiving sheet was prepared in the same manner as in Example 1 except that the aging treatment was performed for 0 days.

(Evaluation test) [Transfer sheet] Polyvinyl butyral resin (BX-1: manufactured by Sekisui Jushi Co., Ltd.) 10 parts Sublimation dye (Kayaset Blue 714: manufactured by Nippon Kayaku Co., Ltd.) 25 parts Isocyanate compound (Coronate L: Japan) Polyurethane Co., Ltd.) 10 parts Silicone oil (SF8417: Toray Silicone Co., Ltd.) 1.5 parts Toluene 100 parts Methyl ethyl ketone 100 parts A liquid of the above formulation is applied onto an aromatic polyamide film substrate and dried to a thickness of 4.5 μm. A transfer sheet having a sublimation dye layer was prepared.

(Recording Conditions) The ink layer of the thermal sublimation transfer sheet and the receiving layer of the image receiving sheet were overlapped so as to be in contact with each other, and a recording evaluation test was conducted under the following conditions. Applied power 442 mW / dot Thermal head 6 dot / mm Partial grace (travel speed of image-receiving sheet) / (travel speed of transfer sheet)
= 7 to 30 Maximum applied energy 2.21 mJ / dot

(Results) The recording results are shown in Table 1.

[Table 1]

In Table 1, the fusing property test was carried out by observing the sticking of the image, the fusing to the ink layer, and the presence of wrinkles, when the speed difference between the image receiving sheet and the transfer sheet was increased. The maximum speed difference at which no adhesion was observed was examined. ◎ indicates a speed difference up to 30, a ○ indicates a speed difference of 20, and a △ indicates a speed difference of 20.
In Fig. 5, unevenness in running property was observed, x indicates that fusion was observed at a speed difference of 15, and xx indicates that the transfer sheet was damaged due to a speed difference of 7. Also, the image density in Table 1 is
The gradation test pattern is recorded and the maximum density thereof is measured by a Macbeth densitometer. It can be seen from Table 1 that the image-receiving sheets of the examples do not cause fusion or sticking even when applied to the speed difference mode recording method.

Example 5 In Example 3, a vinyl chloride resin (1000 GKT,
An image receiving sheet was produced in the same manner as in Example 3 except that an average OH group number in one molecule, 34, manufactured by Denki Kagaku Kogyo Co., Ltd. was used.

Example 6 In Example 5, the polyester resin (Vylon 29
No. 0, manufactured by Toyobo Co., Ltd., and having an average number of OH groups in one molecule of 2.6) were used to prepare an image-receiving sheet in the same manner as in Example 5.

(Results) The recording results are shown in Table 2.

[Table 2] From Table 2, it is understood that when the cured resin has a small number of OH groups, a sufficient fusion preventing ability cannot be exhibited.

Example 7 An image-receiving sheet was prepared in the same manner as in Example 3 except that the isocyanate compound (Takenate D218, Tolylene Diisocyanate Trimer) used in Example 3 was used.

Example 8 An image-receiving sheet was prepared in the same manner as in Example 7 except that an isocyanate compound (Takenate D160N, an adduct of hexamethylene diisocyanate with trimethylolpropane) was used in Example 7. It was made.

(Results) Table 3 shows the recording results.

[Table 3] From Table 3, it can be seen that the use of aromatic isocyanate as the isocyanate has higher reactivity and is more effective in preventing fusion.

Example 9 An image-receiving sheet was prepared in the same manner as in Example 3 except that a bubble-containing PET film (Crisper G, manufactured by Toyobo Co., Ltd.) was used as the substrate in Example 3.

Example 10 In Example 9, a bubble-containing PET film (Crisper G), a white PET film (E20, manufactured by Toray) and a synthetic paper (Yupo, manufactured by Oji Yuka Synthetic Paper) were laminated on the substrate. An image-receiving sheet was prepared in the same manner as in Example 9 except that the receiving layer was provided on the side of the bubble-containing PET film.

Example 11 An image-receiving sheet was prepared in the same manner as in Example 10 except that the film on the receiving layer side of the substrate was a bubble-containing PET film (E60, manufactured by Toray Industries, Inc.).

(Results) Table 4 shows the recording results.

[Table 4] Looking at the image density at two points with different applied energies and the curl of the image-receiving sheet after printing, a specific density [(D ₀ −
D) / D ₀ > 0.3] has the effect of improving the sensitivity and reducing the curl due to the laminated substrate, and it can be seen that the substrate is suitable for this printing method.

Example 12 6 μm thick having a 1 μm thick silicone resin heat-resistant layer
m of the aromatic polyamide film using a wire bar, a 1.0 μm thick intermediate adhesive layer and then a dye supply layer were applied so as to have a film thickness of 4.5 μm. Low-dyeing resin layer 0.5μ each
m, 0.7 μm to form an ink layer, which was then heat-cured at 60 ° C. for 12 hours to prepare a recording material (transfer sheet).

However, the compositions of the intermediate adhesive layer forming liquid, the dye supply layer forming liquid and the dye transfer contributing layer liquid of Examples and Comparative Examples were all the same, and the compositions are shown below. [Intermediate adhesive layer] Polyvinyl butyral resin (BX-1: Sekisui Chemical Co., Ltd.) 10 parts Diisocyanate (Coronate L: Nippon Polyurethane Co., Ltd.) 5 parts Toluene 95 parts Methyl ethyl ketone 95 parts

[Dye Supply Layer] Polyvinyl butyral resin (BX-1: Sekisui Chemical Co., Ltd.) 7 parts Polyethylene oxide (Alcox R400: Meisei Chemical Co., Ltd.) 3 parts Diisocyanate (Coronate L: Nippon Polyurethane Co., Ltd.) 3 parts Sublimation Dye 30 parts Toluene 95 parts Methyl ethyl ketone 95 parts

[Dye Transfer Contribution Layer] Polyvinyl butyral resin (BX-1: Sekisui Chemical Co., Ltd.) 10 parts Diisocyanate (Coronate L: Nippon Polyurethane Co., Ltd.) 3 parts Sublimation dye 20 parts Toluene 45 parts Methyl ethyl ketone 45 parts Dioxane 100 parts

[Low Dyeing Resin Layer] Styrene-maleic acid copolymer (Sprapearl AP20: manufactured by BASF) 5 parts Silicone oil (SF8417: manufactured by Torre Silicone) 0.75 parts Silicone oil (SH8411: Torre Silicone) 0.75 parts Toluene 47.5 parts Methyl ethyl ketone 47.5 parts

Sublimation dye for yellow (Foron Brilliant
Yellow S-6GL: Sand Company Sublimation dye for magenta (HM1041 / Hso147 = 6/4: both manufactured by Mitsui Toatsu) Sublimation dye for cyan (Hso271 / Foron Brillant Blue S
R = 9/1: The former is manufactured by Mitsui Toatsu, the latter is manufactured by Sand Co.)

[Accepting Layer] Vinyl Chloride Resin (VAGH: Union Carbide Co., Ltd.) 18 parts Diisocyanate (Coronate L: Nippon Polyurethane Co., Ltd.) 5 parts Silicone oil (SF8417: Toray Silicone Co., Ltd.) 1 part Silicone oil (SF8411: 1 part Toluene Silicone Co., Ltd.) 1 part Toluene 40 parts Methylethylketone 40 parts The above-prepared liquid is applied on a foamed PET film and dried to form a 6 μm-thick receiving layer, followed by aging treatment at 80 ° C. for 5 days. I went and got an image receiving sheet.

Example 13 In Example 12, a tin catalyst (T
KIL: Takeda Yakuhin Co., Ltd.) 0.1 part added, and 60 ° C
An image-receiving sheet was prepared in the same manner as in Example 12, except that the aging treatment was performed for 4 days in the above environment.

Example 14 An image receiving sheet was prepared in the same manner as in Example 13 except that the low dyeing resin layer of the transfer sheet was prepared by the following prescription liquid. (Synthesis of hydrolysis product of silane coupling agent) 15 g of dimethylmethoxysilane and 9 of methyltrimethoxysilane
g was dissolved in a mixed solution of 12 g of toluene and 12 g of methyl ethyl ketone, 13 ml of 3% sulfuric acid was added, and hydrolysis was carried out for 3 hours. This liquid is referred to as Liquid A. [Low-dyeing resin layer] Styrene-malein copolymer (Sprapearl AP20: manufactured by BASF) 5 parts Liquid A 20 parts Ortho-butanol 20 parts

Example 15 An image-receiving sheet was prepared in the same manner as in Example 14 except that the image-receiving sheet was heat-treated at 110 ° C. for 2 hours.

Comparative Example 3 In Example 12, the image-receiving sheet was subjected to 6 without heating.
An image receiving sheet was prepared in the same manner as in Example 12 except that the aging treatment was performed for 10 days in an environment of 0 ° C.

Comparative Example 4 In Example 13, the transfer sheet was prepared by placing silicone oil (SF8417 / SF8411 = 1/1) in the dye transfer contributing layer.
A transfer sheet was prepared in the same manner as in Example 13 except that 5 parts of Toray Silicone Co., Ltd.) was added and the low dyeing resin layer was removed.

Under the conditions that the thermal head resolution is 12 dots / mm, the applied energy is 0.64 mj / dot, and the applied power is 0.16 W / dot, the feeding speed (14 times speed) during recording, the image receiving sheet 8.4 mm / sec, the transfer sheet 0. The speed was set to 6 mm / sec, recording was performed in the order of yellow, magenta, and cyan by the speed difference mode method recording, and the black densities of the respective colors and mixed colors were measured by a reflection type Macbeth densitometer RD-918 (manufactured by Macbeth Co.). It was measured

Recording results are shown in Table 5.

[Table 5] (Note 1) Since sticking occurred at an applied energy of 0.64 mj / dot, the applied energy was recorded at 0.58 mj / dot. (Note 2) Since sticking occurred at an applied energy of 0.64 mj / dot, the applied energy was recorded at 0.60 mj / dot. (Note 3) Since sticking occurred at the applied energy of 0.64 mj / dot, the applied energy was recorded at 0.56 mj / dot.

From Table 5, in Examples 12 to 15,
It can be seen that even in the speed difference mode recording, high energy is not fused and high density output is possible with a single color, and high density can be obtained even when colors are mixed. In particular, it can be seen that the effect is remarkable in Examples 13 to 14 using the image receiving sheet having a gel fraction of the receiving layer of 98%.

[0070]

The image-receiving sheet for sublimation transfer according to claim 1 is excellent in releasability because the gel fraction of the receiving layer is 70% by weight or more, and the image-receiving sheet is applied to speed difference mode recording. However, fusion or sticking does not occur.

In the sublimation transfer image-receiving sheet of claim 2, since the gel fraction of the receptor layer is 90 to 99% by weight, it is possible to suppress the deterioration of dyeing property due to the extreme increase of the gel fraction. The effect is added.

When the image receiving sheet for sublimation transfer of claim 3 is used in the speed difference mode method, the effect of achieving both fusion prevention and dyeing property is remarkably exhibited.

The sublimation transfer image-receiving sheet according to claim 4 is more heat resistant because the receptor layer contains a cured product of a resin having an average of 20 or more OH groups in one molecule and a curing agent having an isocyanate group. And the effect of improving the anti-fusion property is added.

In the image-receiving sheet for sublimation transfer of claim 5, the curable resin forming the receiving layer is made of a reaction product of a vinyl chloride resin containing active hydrogen and an isocyanate compound. The effect of improving sex is added.

In the sublimation transfer image-receiving sheet according to the sixth aspect, the reaction layer contains a reaction product of an aromatic isocyanate, whereby the reactivity is improved and the physical properties (gel fraction) of the present invention are easily obtained. The effect is added.

In the image-receiving sheet for sublimation transfer of claim 7, the tin layer is contained in the receptor layer, so that the curing reaction is catalyzed and the curing temperature can be lowered.

In the sublimation transfer image-receiving sheet of the eighth aspect, by using a film containing bubbles as the substrate, the effect of reducing printing unevenness, which is a particular problem in the speed difference mode method, is added.

In the sublimation transfer image-receiving sheet according to claim 9, by using a substrate in which a film containing bubbles and another film (or the same film) are bonded to the substrate, it is possible to achieve both printing unevenness and curl prevention. Join.

In the sublimation transfer image-receiving sheet of the tenth aspect, by using the bubble-containing plastic film having the density D as the substrate, the effect of improving the image density, particularly the sensitivity in the low applied energy portion, is added.

In the recording method of claim 11, the speed difference mode method recording is carried out using the sublimation transfer image-receiving sheet and the sublimation transfer sheet in which the uppermost ink layer is a low dyeing resin. Therefore, according to the present method, high density output is possible with a single color without fusion with high energy, and the reverse dye transfer is prevented by the sheet of the low dyeing resin layer, and high density can be obtained even when colors are mixed.

According to the recording method of claim 12, since the lowermost layer of the ink layer of the image-receiving sheet for sublimation transfer comprises a dye supply layer in which at least a sublimable dye is dispersed in an organic binder, According to this method, the release and replenishment of the monomolecular dye required for multi by the particulate dye is realized,
Good mulching ability can be obtained and high density can be obtained even if the number of N is increased in the speed difference mode recording.

In the recording method of claim 13, since the low dyeing resin layer of the ink layer uppermost layer of the image receiving sheet for sublimation transfer contains at least a silicone resin, according to the present method, Due to its high heat resistance, releasability, and low dyeing performance, it does not fuse with high energy, reverse transfer is also prevented, and high density can be obtained.

According to the recording method of claim 14, black (not only black) is output by subtractive color mixing of yellow, magenta and cyan. Therefore, the sheet is only yellow, magenta and cyan, and the running cost is low. In addition, high density output becomes possible.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Hiroki Kuboyama 1-3-6 Nakamagome, Ota-ku, Tokyo Stock company Ricoh Co., Ltd. (72) Inventor Yutaka Ariga 1-3-3 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh

Claims (14)

[Claims] 1. A sublimation transfer image-receiving sheet in which a dye-receiving layer is provided on a substrate directly or via an intermediate layer, wherein the dye-receiving layer is mainly composed of a curable resin and has a gel fraction of 70% by weight based on the entire layer. % Or more, an image-receiving sheet for sublimation transfer. 2. The image-receiving sheet for sublimation transfer according to claim 1, wherein the gel fraction of the receiving layer is 90 to 99% by weight. 3. A sublimation transfer sheet to an image receiving sheet,
The image receiving sheet for sublimation transfer according to claim 1, which is used for speed difference mode recording in which a relative speed is 1 / n (n> 1). 4. The receiving layer contains a cured product of a dyeing resin having an average of 20 or more OH groups per molecule and a curing agent having an isocyanate group.
The image-receiving sheet for sublimation transfer according to any one of items 1 to 3. 5. The image-receiving sheet for sublimation transfer according to claim 1, wherein the curable resin is a reaction product of a vinyl chloride resin containing active hydrogen and an isocyanate compound. 6. The image-receiving sheet for sublimation transfer according to claim 4, wherein the isocyanate is an aromatic isocyanate. 7. The image receiving sheet for sublimation transfer according to claim 5, wherein the receiving layer contains a tin compound. 8. The image-receiving sheet for sublimation transfer according to claim 1, wherein the substrate is a film having fine bubbles, and a dye receiving layer is formed directly or through an intermediate layer. 9. The image-receiving sheet for sublimation transfer according to claim 8, wherein the substrate is one obtained by laminating two or more films with an adhesive. 10. The image-receiving sheet for sublimation transfer according to claim 8, wherein the substrate is made of a bubble-containing plastic film having a density D satisfying the following formula (1). (D ₀ −D) / D ₀ > 0.3 (1) (In the above formula, D ₀ represents the density of the plastic film of the same material as the above-mentioned substrate and containing no bubbles.) 11. A sublimation transfer sheet using the sublimation transfer image-receiving sheet according to any one of claims 1 to 10 and a sublimation transfer sheet in which an uppermost ink layer is a low-dyeing resin layer. Relative speed to the image receiving sheet is 1 / n (n> 1)
The recording method is characterized by recording as. 12. The recording method according to claim 11, wherein in the transfer sheet for sublimation, the lowermost layer of the ink layer comprises a dye supply layer in which at least a sublimable dye is dispersed in an organic binder. . 13. The recording method according to claim 11, wherein in the transfer sheet for sublimation, the low-dyeing resin layer as the uppermost ink layer is a layer containing at least a silicone resin. 14. The recording method according to claim 11, wherein black is obtained by subtractive color mixing of yellow, magenta, and cyan in the recording method.