JP3243310B2 - Thermal transfer image receiving sheet and method of manufacturing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer image-receiving sheet, and more particularly, to an object of the present invention is to provide a thermal transfer image-receiving sheet which is excellent in releasability during thermal transfer and excellent in writing.

[0002]

2. Description of the Related Art Conventionally, various thermal transfer methods are known. Among them, a sublimable dye is used as a recording material, and this is carried on a base sheet such as paper or plastic film to form a thermal transfer sheet. Methods for forming various full-color images on paper or plastic film provided with a layer have been proposed. In this case, a thermal head of a printer is used as a heating means, and a large number of color dots of three or four colors are transferred to a thermal transfer image receiving sheet by heating for a very short time, and a full-color image of an original is formed by the multicolored dots. Is to reproduce.

[0003]

In the above-mentioned thermal transfer method, in forming an image, the dye layer of the thermal transfer sheet and the dye receiving layer of the thermal transfer image receiving sheet are superposed on each other, and the dye is heated by a thermal head to transfer the dye. And then peel off both, but when forming a full-color image, these operations must be performed a plurality of times on the same dye-receiving layer surface, and therefore, the surface of the dye-receiving layer It is required to form a release layer which is excellent in release property and strength and is dye-permeable. In the prior art, as these release agents, for example, fluorine compounds, silicone compounds, waxes, higher fatty acids, derivatives thereof and the like have been used (Japanese Patent Application No. 60-212394, Japanese Patent Application Laid-Open No. 4-219286). However, none of the above-mentioned requirements are sufficiently satisfied, and further, if an attempt is made to write on the surface of the release layer with a pencil or various inks after image formation, the release layer may have a liquid repellent property or lubricity. There is a problem that writing is difficult. Therefore, an object of the present invention is to provide a thermal transfer image-receiving sheet having a good release property, strength, and dye permeability even when forming a full-color image, and further having a release layer on the surface thereof, which can be written with various writing tools. To provide.

[0004]

The above object is achieved by the present invention described below. That is, the present invention provides a thermal transfer image-receiving sheet having a dye-receiving layer formed on at least one surface of a base sheet, wherein a polymer or copolymer of a long-chain alkyl group-containing addition polymerizable monomer is formed on the surface of the receptor layer. a united
Reaction product of polyisocyanate with active hydrogen
A thermal transfer image-receiving sheet, characterized in that a release layer composed of a product is formed, a thermal transfer image-receiving sheet having a dye-receiving layer formed on at least one surface of a substrate sheet, wherein the receiving layer has a long-chain alkyl group. Polymers or copolymers of addition-containing monomers containing active hydrogen and polyisomers
Thermal transfer image-receiving sheet, characterized by containing a release agent consisting of a reaction product with cyanate , less of a base sheet
Thermal transfer image receiving system with a dye receiving layer formed on one side
A long-chain alkyl group on the surface of the receptor layer.
A polymer or copolymer of addition polymerizable monomer that is active
A compound having hydrogen, a compound having active hydrogen,
Forming a release layer consisting of the reaction product with the isocyanate
Less heat transfer image-receiving sheet and substrate sheet
Thermal transfer receiver with a dye receiving layer formed on at least one side
In the image sheet, the receiving layer may have a long-chain alkyl group-containing layer.
A polymer or copolymer of a polymerizable monomer,
A compound having an active hydrogen, a compound having an active hydrogen,
Contains a release agent consisting of a reaction product with a cyanate
And a method for producing the same.

[0005]

[Acting] on the surface of the dye receiving layer, the active hydrogen to a polymer or copolymer of a long chain alkyl group-containing addition polymerizable monomers
And (or even a compound having active hydrogen)
And) forming a release layer composed of a reaction product with polyisocyanate , or including the above-mentioned release resin in the dye-receiving layer, so that the long-chain alkyl group has good release properties. The addition polymer which is a main chain gives excellent coating strength and adhesion strength to the receiving layer. Further, these layers have good dye permeability and good writing properties even for oil-based inks and the like.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to preferred embodiments. As the base sheet used in the present invention, synthetic paper (polyolefin, polystyrene, etc.), woodfree paper, art paper, coated paper, cast-coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex Various plastic films or sheets such as impregnated paper, paper with synthetic resin, paperboard, cellulose fiber paper, polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, and polycarbonate can be used. A white opaque film formed by adding a white pigment or a filler to a resin, a foamed foamed sheet, or the like can be used, and is not particularly limited. Also, a laminate formed by any combination of the above base sheets can be used. Examples of typical laminates include synthetic paper of cellulose fiber paper and synthetic paper or cellulose fiber paper and plastic film or sheet. The thickness of these base sheets may be arbitrary, and for example, a thickness of about 10 to 300 μm is generally used. When the substrate sheet as described above has poor adhesion to the dye-receiving layer formed on its surface, it is preferable to apply a primer treatment or a corona discharge treatment to its surface.

The dye-receiving layer formed on the surface of the base sheet is for receiving a sublimable dye transferred from the thermal transfer sheet and maintaining the formed image. Examples of the resin for forming the dye receiving layer include polyolefin resins such as polypropylene, halogenated polymers such as polyvinyl chloride and polyvinylidene chloride, vinyl polymers such as polyvinyl acetate and polyacrylester, polyethylene terephthalate, and poly (ethylene terephthalate). Polyester resins such as butylene terephthalate, polystyrene resins, polyamide resins, copolymer resins of olefins such as ethylene and propylene with other vinyl monomers, ionomers, cellulose resins such as cellulose diacetate, and polycarbonate. Particularly preferred are vinyl resins and polyester resins.

The dye-receiving layer in the thermal transfer image-receiving sheet of the present invention is obtained by dissolving at least one surface of the above-mentioned base sheet with the above-mentioned necessary additives for the resin in an appropriate organic solvent. Alternatively, a dye-receiving layer is formed by applying, drying and heating a dispersion dispersed in an organic solvent or water by a forming means such as a gravure printing method, a screen printing method, or a reverse roll coating method using a gravure plate. Obtained by In the formation of the dye-receiving layer, pigments such as titanium oxide, zinc oxide, kaolin clay, calcium carbonate, and finely powdered silica are used for the purpose of improving the whiteness of the dye-receiving layer to further enhance the sharpness of the transferred image. Agents can be added. The dye-receiving layer formed as described above may have any thickness, but generally has a thickness of 1 to 50.
μm thickness. Further, such a dye receiving layer is preferably a continuous coating, but may be formed as a discontinuous coating using a resin emulsion or a resin dispersion.

In the present invention, a release layer is formed on the surface of the dye-receiving layer or a release resin is contained in the dye-receiving layer in order to impart the releasing property to the dye-receiving layer. Such a release layer or release agent can be formed by the following method. (A) a method of forming a release layer on the surface after forming the dye receiving layer, and (B) a method of including a release agent in the dye receiving layer simultaneously with the formation of the dye receiving layer. The release resin used in the dye layer is included in the interior of the dye layer, as a characteristic of the release resin used, at least a part thereof, particularly a long-chain alkyl group portion is exposed on the surface of the dye receiving layer, Good release properties are exhibited.).

The release layer or release agent in the present invention is mainly formed by homopolymerization of a long-chain alkyl group-containing addition polymerizable monomer or copolymerization with another addition polymerizable monomer. so as to have an active hydrogen i.e. isocyanate-reactive groups, is reacted with a polyisocyanate, or improve the film strength of the release layer to be formed, it is possible to prevent phase separation of the dye-receiving layer resin. The reaction between the polymer and the polyisocyanate may be performed before or during the formation of the release layer, but may be performed before or after the release layer is formed, to such an extent that the polymer does not gel. desirable.

The long-chain alkyl group-containing addition polymerizable monomer used in the present invention includes acrylic acid, methacrylic acid,
Itaconic acid, maleic acid, a reaction product of an addition-polymerizable unsaturated carboxylic acid such as fumaric acid and a long-chain aliphatic alcohol or a long-chain aliphatic amine, esters of vinyl alcohol and a long-chain fatty acid, and the like. Examples of carbon chains of long-chain alcohols, amines, carboxylic acids and the like include, for example, hexyl, isohexyl, heptyl, octyl, decyl, lauryl, tridecyl, tetradecyl, pentadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, docosyl, tricosyl, pentacosyl, hexacosyl And among these long-chain alkyl groups, those having 1 carbon atom
Particularly preferred are those having 5 or more, for example, alcohols, amines or carboxylic acids having a stearyl group which are easily available industrially.

[0012] Also, the long-chain alkyl group-containing addition polymerizable monomers, in order to react the resultant polymer with a polyisocyanate, a monomer having a group reactive with an isocyanate group such as a hydroxyl group, such as 2-hydroxyethyl ( Several moles (1 to 10 moles) of ethylene oxide, propylene oxide or caprolactone at the terminal hydroxyl group of (meth) acrylate, 2-hydroxypropyl (meth) acrylate, or 2-hydroxyethyl (meth) acrylate
The ring-opening addition monomers like Ru is copolymerized. Examples of other copolymerizable monomers include other general monomers such as other (meth) acrylic acid esters, various carboxylic acid esters, styrene, vinyl chloride, and vinylpyridine. When the copolymerization is these other addition polymerizable monomers, preferably the entire 30 mol% to 95 mol long-chain alkyl group-containing addition polymerizable monomers in the copolymer, the active hydrogen-containing monomers over 5 mol % To 70 mol% is preferred. If the amount of the long-chain alkyl group-containing addition polymerizable monomer is less than the above range, the resulting polymer will have insufficient releasability.

[0013] As the polyisocyanate used in the present invention, conventional polyurethane resins, polyurethane coatings, various polyisocyanates which are widely used in polyurethane glue or the like, for example, 2,4-tolylene diisocyanate (2, 4-TDI), 2,5-tolylene diisocyanate (2,5-TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI), isophorone diisocyanate, triphenylmethane triisocyanate, tris (isocyanate Phenyl) thiophosphate, lysine ester triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,6,11
-Undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, urea-bonded HMDI, isocyanate-bonded HMDI, trimethylolpropane-TDI
Examples thereof include a 3-mol adduct or a mixture thereof. The amount of these polyisocyanates used varies depending on the active hydrogen content of the release polymer, the amount of the active hydrogen-containing compound to be added, the conditions for forming a release layer or a release agent, and the like. It is common to use up to 1.5 equivalents per equivalent of active hydrogen of the release polymer or active hydrogen-containing compound.

The following compounds are used as the active hydrogen-containing compound. Further, a terminal polyisocyanate oligomer obtained by previously reacting these active hydrogen compounds with polyisocyanate may be used. The active hydrogen-containing compounds, include conventional low or high molecular weight of the various polyols and various polyamine is used as a raw material for polyurethane resin, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene grayed Li call, Jipuropirengu recall, tripropylene grayed recall, polypropylene grayed recall, glycerol, pentaerythritol,
Bisphenol A or an ethylene oxide and / or propylene oxide adduct thereof, a hydroxyl group-containing polymer, for example, an acrylic polyol, a homo- or copolymer of a hydroxyl-containing acrylic monomer such as hydroxyethyl (meth) acrylate, vinyl acetate alone or A vinyl resin containing a vinyl alcohol unit such as a saponified copolymer,
Examples include polyvinyl acetal resin and cellulose resin, but the present invention is not limited to these polyols.
Examples of the polyamine include low and high molecular weight polyamines such as ethylenediamine, propylenediamine, triethylenediamine, tripropylenediamine, polyethylenepolyamine, polyethyleneimine, and polyacrylamide, but the present invention is not limited to these polyamines.

The above-mentioned releasable polymer is dissolved or dispersed in an appropriate solvent to form a coating solution, and after forming a dye-receiving layer, the surface is coated and dried by an arbitrary coating method. In some cases, a release layer can be formed by aging treatment for crosslinking. The thickness of the release layer thus formed is generally in the range of about 0.01 to 0.5 μm. When forming the release layer or the release agent, a crosslinking (curing) catalyst or the like and other additives can be added as necessary. In forming the release layer, another binder resin may be used together if necessary, as long as the release property of the release layer to be formed is acceptable. These combined to the binder resin, wherein the resin forming the dye receiving layer is preferably not limited to, for example, ultraviolet rays, electron beams, it may be a resin which is cured by heat or the like. Further, in case of incorporating the said release polymer in the dye receiving layer, was added to the polymer to dye charge-receiving layer coating liquid to Po polyisocyanate co, the formation of the dye-receiving layer simultaneously dye Included in the receiving layer. In the case of this method, at least a long-chain alkyl group is exposed on the surface of the dye-receiving layer after the dye-receiving layer is formed, and excellent release properties are exhibited. The release polymer is preferably added at a ratio of 0.5 to 20 parts by weight based on 100 parts by weight of the dye-receiving layer-forming resin.

The thermal transfer image-receiving sheet of the present invention as described above comprises:
By appropriately selecting the base sheet, it can be applied to various uses such as a heat transfer recordable sheet, a card, and a transmission type original creation sheet. Further, the image receiving sheet of the present invention can be provided with a cushion layer between the base sheet and the dye receiving layer, if necessary. By providing such a cushion layer, noise during printing can be reduced and the image information can be handled. The transferred image can be transferred and recorded with good reproducibility. Examples of the material constituting the cushion layer include polyurethane resin, acrylic resin, polyethylene resin, butadiene rubber, and epoxy resin. The thickness of the cushion layer is preferably about 2 to 20 μm. Further, a lubricating layer can be provided on the back surface of the base sheet. Examples of the material of the lubricating layer include a methacrylate resin such as methyl methacrylate or a corresponding acrylate resin, and a vinyl resin such as a vinyl chloride-vinyl acetate copolymer. Furthermore, it is also possible to provide a detection mark on the image receiving sheet. The detection mark is extremely convenient when positioning the thermal transfer sheet and the image receiving sheet. For example, a detection mark that can be detected by a photoelectric tube detection device can be provided on the back surface of the base sheet by printing or the like.

The thermal transfer sheet used when performing thermal transfer using the thermal transfer image-receiving sheet of the present invention as described above is one in which a dye layer containing a sublimable dye is provided on paper or polyester film. Any thermal transfer sheet can be used as it is in the present invention. As a means for applying thermal energy at the time of thermal transfer, any conventionally known applying means can be used. For example, a thermal printer (for example,
By controlling the recording time with a recording device such as a video printer VY-100 manufactured by Hitachi, Ltd., it is possible to sufficiently achieve the intended purpose by applying heat energy of about 5 to 100 mJ / mm ^2. I can do it.

[0018]

EXAMPLES Next, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples. In the following description, parts or% are based on weight unless otherwise specified. Synthesis Example ( Synthesis of Release Polymer) Release Polymer A : Solution polymerization of 32.4 parts of stearyl acrylate and 8.6 parts of methyl methacrylate in methyl ethyl ketone using azobisisobutyronitrile as a polymerization initiator. A copolymer having an average molecular weight of 100,000 was obtained. Releasable polymer B : 31.0 parts of vinyl stearate and 8.6 parts of methyl methacrylate were solution-polymerized in methyl ethyl ketone using azobisisobutyronitrile as a polymerization initiator to give a copolymer having a number average molecular weight of 80,000. Obtained. Releasable polymer C : solution polymerization of 32.4 parts of stearyl acrylate, 8.6 parts of methyl methacrylate and 3.9 parts of 2-hydroxyethyl methacrylate in methyl ethyl ketone using azobisisobutyronitrile as a polymerization initiator. A copolymer having an average molecular weight of 25,000 was obtained. Releasable polymer D : 31.0 parts of vinyl stearate, 1.7 parts of methyl methacrylate and 3.9 parts of 2-hydroxyethyl methacrylate were solution-polymerized in methyl ethyl ketone using azobisisobutyronitrile as a polymerization initiator, A copolymer having a number average molecular weight of 45,000 was obtained. Releasable polymer E : 32.4 parts of stearyl acrylate, 1.2 parts of vinyl chloride and 3.9 parts of 2-hydroxyethyl methacrylate were solution-polymerized in methyl ethyl ketone using benzoyl peroxide as a polymerization initiator, and the number average molecular weight was 4 100,000 copolymers were obtained.

REFERENCE EXAMPLE 1 Synthetic paper (110 μm thick, manufactured by Oji Oil Chemical Co., Ltd.) was used as a base sheet, and a coating solution having the following composition was dried on one surface thereof with a bar coater to 4.0 g / m ² when dried. The dye receiving layer was formed by coating and drying at an appropriate ratio. Dye receiving layer coating liquid composition: polyester resin (Vylon 200, manufactured by Toyobo) 20 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 80 parts 1% methyl ethyl ketone solution containing the following components on the surface of the dye receiving layer is dried. coating so that the ratio of the 0.05 g / m ^2, dried and aged a release layer formed, ginseng
To obtain a thermal transfer image-receiving sheet of Reference Example. Release layer coating liquid composition: Polymer A 0.49 part Polyisocyanate (Takenate XA-14, manufactured by Takeda Pharmaceutical Co.) 2.32 parts Polyol (4-mol adduct of bisphenol A with ethylene oxoside) 1.00 part Dibutyltin Laurate (catalyst) 500ppm

[0020] Instead of the release layer coating solution in Reference Example 2 Reference Example 1 using the coating solution having the following composition (1% methyl ethyl ketone solution) and the other reference
A release layer was formed in the same manner as in Example 1 to obtain a thermal transfer image-receiving sheet of Reference Example . Release layer coating liquid composition: Polymer B 0.50 parts Polyisocyanate (Takenate XA-14, manufactured by Takeda Pharmaceutical Co.) 2.32 parts Polyol (4-mol adduct of bisphenol A with ethylene oxoside) 1.00 part Dibutyltin Laurate (catalyst) 500ppm

[0021] Instead of the release layer coating solution in Example 1 Reference Example 1 using the coating solution having the following composition (1% methyl ethyl ketone solution) and the other reference
A release layer was formed in the same manner as in Example 1 to obtain a thermal transfer image-receiving sheet of the present invention. Release layer coating liquid composition: Polymer C 0.50 part Polyisocyanate (Takenate XA-14, manufactured by Takeda Pharmaceutical Co.) 2.32 parts Polyol (4-mol adduct of bisphenol A with ethylene oxoside) 1.00 part Dibutyltin Laurate (catalyst) 500ppm

[0022] Instead of the release layer coating solution in Example 2 Reference Example 1 using the coating solution having the following composition (1% methyl ethyl ketone solution) and the other reference
A release layer was formed in the same manner as in Example 1 to obtain a thermal transfer image-receiving sheet of the present invention. Release layer coating composition: Polymer D 0.50 parts Polyisocyanate (Takenate XA-14, manufactured by Takeda Pharmaceutical Co.) 2.32 parts Polyol (4-mol adduct of bisphenol A with ethylene oxoside) 1.00 part Dibutyltin Laurate (catalyst) 500ppm

Reference Examples 3 and 4 and Examples 3 and 4 Synthetic paper (thickness: 110 μm, manufactured by Oji Oil Chemical Co., Ltd.) was used as a base sheet, and an aqueous polyester resin dispersion (Vylonal MD-1200, Toyobo, solid content
(35%) was applied by a bar coater at a rate of 4.0 g / m ² when dried, and dried to form a dye receiving layer. The coating liquid for forming a release layer used in Reference Examples 1 to 4 was applied, dried and aged in the same manner as described above to form a release layer on the surface of the dye receiving layer. Reference Examples 3 to 4 and Example 3 To 4 were obtained. Reference Example 5 In place of the coating liquid for the release layer in Reference Example 1,
A release layer was formed in the same manner as in Reference Example 1 except that a% methyl ethyl ketone solution was used, and a thermal transfer image-receiving sheet of Reference Example was obtained.

Reference Example 6 A synthetic paper (thickness: 110 μm, manufactured by Oji Oil Chemical Co., Ltd.) was used as a base sheet, and a coating solution having the following composition was dried on one surface thereof with a bar coater to 4.0 g / m ² when dried. ginseng to form a dye-receiving layer by coating and drying so that the ratio of containing a release agent
To obtain a thermal transfer image-receiving sheet of Reference Example. Dye receiving layer coating liquid composition: polyester resin (Vylon 200, manufactured by Toyobo) 20 parts Polymer A 3 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 77 parts

Reference Example 7 A synthetic paper (thickness: 110 μm, manufactured by Oji Oil Chemical Co., Ltd.) was used as a base sheet, and a coating solution having the following composition was dried on one surface of the base sheet with a bar coater to 4.0 g / m ² when dried. Coating and drying were performed at an appropriate ratio, followed by aging at 60 ° C. for 24 hours to form a dye receiving layer containing a release agent, thereby obtaining a thermal transfer image receiving sheet of Reference Example . Dye receiving layer coating liquid composition: polyester resin (Vylon 200, manufactured by Toyobo) 20 parts Polymer B 4 parts Polyisocyanate (Takenate XA-14, manufactured by Takeda Pharmaceutical Co., Ltd.) 3 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 73 parts

Reference Example 8 1% of the following composition was used in place of the release layer coating solution in Reference Example 1 .
A release layer was formed in the same manner as in Reference Example 1 except that a methyl ethyl ketone solution was used, and a thermal transfer image-receiving sheet of Reference Example was obtained. Release layer coating liquid composition: Polymer A 2.30 parts Polyisocyanate (Takenate XA-14, manufactured by Takeda Pharmaceutical) 1.20 parts Dibutyltin laurate (catalyst) 500 ppm Reference example 9 Release layer coating liquid in Reference example 1 Instead of 1% of the following composition
A release layer was formed in the same manner as in Reference Example 1 except that a methyl ethyl ketone solution was used, and a thermal transfer image-receiving sheet of Reference Example was obtained. Release layer coating liquid composition: Polymer A 5.00 parts Polyester resin (Byron 200, manufactured by Toyobo Co., Ltd.) 5.00 parts

[0027] Instead of the release layer coating solution of Comparative Example 1 Reference Example 1 using the coating solution having the following composition, other forms a release layer in the same manner as in Reference Example 1, the thermal transfer image-receiving Comparative Example I got a sheet. Release layer coating liquid composition: catalyst-curable dimethylpolysiloxane (X-62-1212, manufactured by Shin-Etsu Chemical) 1.5 parts Platinum-based catalyst (CatPL-50T, manufactured by Shin-Etsu Chemical) 0.1 part Comparative Example 2 Reference Example using the coating solution having the following composition in place of the release layer coating solution in 1, the other forms a releasing layer in the same manner as in reference example 1 to obtain a thermal transfer image-receiving sheet of Comparative example. Release layer coating composition: Polyisocyanate (Takenate XA-14, manufactured by Takeda Pharmaceutical Co.) 2.3 parts Polyol (bisphenol A 4-mol ethylene oxoside adduct) 1.5 parts

On the other hand, a coating liquid for forming a dye layer having the following composition was prepared, and a 6 μm-thick polyethylene terephthalate film having a heat-treated back surface was dried at a coating amount of 1.0 g / m 2.
As it becomes ² was coated and dried by gravure printing to obtain a Netsuten transfer paper over you want to use in the present invention. Dye layer coating liquid composition: Kayaset Blue 714 (CI Solvent Blue 63, manufactured by Nippon Kayaku) 5.50 parts Polyvinyl butyral resin (Eslec BX-1, manufactured by Sekisui Chemical Co., Ltd.) 3.00 parts Methyl ethyl ketone 22. 54 parts Toluene 68.18 parts

Thermal transfer test The thermal transfer image-receiving sheet described above and the thermal transfer image-receiving sheets of the present invention and the comparative examples were used in a commercially available video printer (VY-
Using P-1 (manufactured by Hitachi, Ltd.) and a commercially available thermal transfer image-receiving sheet, black solid printing was performed to evaluate the releasability. or,
For the evaluation of the sensitivity, the thermal transfer image-receiving sheet described in the examples was used, the respective dye layers and the dye-receiving surface were superposed on each other, and a thermal head was applied from the back of the thermal transfer image-receiving sheet to a head applied voltage of 12.0 V. , Applied pulse width 1.0m
sec. 1msec./line to 16msec.
The thermal head recording was performed in a step pattern in which the pulse width was sequentially increased every time, and a cyan step image was formed. The following test was performed on this image to obtain the results shown in Table 1 below. (1) Evaluation of releasability: The number of times that the solid black printing can be printed in the same area was evaluated. (2) Writability: Writing with an oil-based felt-tip pen, writing is possible without ink repelling, and writing is possible without any problem.
And (3) Printing sensitivity: Pulse widths required for an image density of 1.0 were compared. Relative sensitivity = Pulse width in Example or Comparative Example / Pulse width in Reference Example 1.

[0030]

[Table 1]

[0031]

According to the present invention as described above, a polymer or copolymer of a long-chain alkyl group-containing addition polymerizable monomer having active hydrogen on the surface of the dye receiving layer (or
Is a compound having active hydrogen), polyisocyanate and
By forming a release layer composed of the reaction product of , or by including the above-mentioned release resin in the dye receiving layer,
The long-chain alkyl group exhibits good releasability, and the main chain addition polymer gives excellent coating strength and adhesion strength to the receiving layer. Further, these layers have good dye permeability and good writing properties even for oil-based inks and the like.

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Masanori Torii 1-1-1 Ichigaya-Kaga-cho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd. (56) References JP-A 1-2229689 (JP, A) JP-A-3-23991 (JP, A) JP-A-1-195092 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (10)

(57) [Claims] 1. A thermal transfer image-receiving sheet having a dye-receiving layer formed on at least one surface of a substrate sheet, wherein a polymer or copolymer of a long-chain alkyl group-containing addition-polymerizable monomer is formed on the surface of the receptor layer. And having active hydrogen
A thermal transfer image-receiving sheet having a release layer formed of a reaction product with polyisocyanate . 2. A thermal transfer image-receiving sheet obtained by forming a dye-receiving layer on at least one surface of the substrate sheet, said receiving layer, encounters polymers or copolymers of long chain alkyl group-containing addition polymerizable monomers With active hydrogen
A thermal transfer image-receiving sheet containing a release agent comprising a reaction product with a cyanate . 3. A dye on at least one surface of a substrate sheet.
A heat transfer image-receiving sheet having a receiving layer formed thereon,
Polymers or copolymers of long-chain alkyl group-containing addition-polymerizable monomers having active hydrogen on the surface of the container
When, to a compound which have a active hydrogen, that the formation of the release layer comprising a reaction product of a polyisocyanate, wherein
That the thermal transfer image-receiving sheet. 4. A dye on at least one surface of a substrate sheet
A heat transfer image-receiving sheet having a receiving layer formed thereon,
Volume layer, and those having an active hydrogen to a polymer or copolymer of a long chain alkyl group-containing addition polymerizable monomer, a compound having an active hydrogen, a release agent comprising a reaction product of a polyisocyanate A thermal transfer image-receiving sheet comprising: 5. The thermal transfer image-receiving sheet according to claim 1 is a long chain alkyl group-containing addition-polymerizable monomer is stearyl (meth) acrylate or vinyl stearate. 6. A method for producing a thermal transfer image-receiving sheet having a dye-receiving layer formed on at least one surface of a substrate sheet, wherein a polymer of a long-chain alkyl group-containing addition polymerizable monomer or Copolymer with active hydrogen
Coating liquid coating, including those with the port polyisocyanate,
A method for producing a thermal transfer image receiving sheet, comprising forming a release layer by drying and forming a film. 7. The method according to claim 1 , wherein at least one surface of the base sheet is dyed.
Which Charge the dyeable resin, a polymer or copolymer of a long chain alkyl group-containing addition polymerizable monomers active hydrogen
And a coating liquid containing polyisocyanate , drying and
It is characterized by forming a dye receiving layer containing a release agent by forming a film.
A method for producing a thermal transfer image receiving sheet. 8. A dye on at least one surface of a substrate sheet
The method for producing a thermal transfer image-receiving sheet having a receptor layer formed thereon
A polymer or copolymer of a long-chain alkyl group-containing addition polymerizable monomer having active hydrogen on the surface of the receptor layer.
And those, a compound having an active hydrogen, coating liquid coating comprising a polyisocyanate, releasing dried and deposited
A method for producing a thermal transfer image-receiving sheet, comprising forming a layer . 9. A polymer or copolymer of a dye-dyeable resin and a long-chain alkyl group-containing addition polymerizable monomer having active hydrogen on at least one surface of a base sheet.
And a coating liquid containing a compound having active hydrogen and a polyisocyanate , and containing a release agent by drying and forming a film.
A method for producing a thermal transfer image receiving sheet, comprising forming a dye receiving layer . 10. An addition-polymerizable monomer containing a long-chain alkyl group.
ー is stearyl (meth) acrylate or stearic acid
The thermal transfer according to any one of claims 6 to 9, which is vinyl.
A method for manufacturing an image receiving sheet.