JP3399603B2 - 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 a thermal transfer image-receiving sheet excellent in releasability during thermal transfer.

[0002]

2. Description of the Related Art Conventionally, various thermal transfer methods have been known. Among them, a sublimable dye is used as a recording material, and this is carried on a base material sheet such as paper or plastic film to form a thermal transfer sheet. Methods have been proposed for forming various full color images on layered paper or plastic films.

In this case, a thermal head of a printer is used as a heating means, and a large number of color dots of three colors or four colors are transferred to a heat transfer image-receiving sheet by heating for an extremely short time, and the original is formed by the multicolor color dots. It reproduces a full-color image.

[0004]

In the above thermal transfer method,
In image formation, the dye layer of the thermal transfer sheet and the dye receiving layer of the thermal transfer image receiving sheet are superposed facing each other and heated by a thermal head to transfer the dye to the dye receiving layer. Since both are made of a thermoplastic resin, there are problems that they are fused and peeled off during thermal transfer, and that the formed image is damaged.

As a method for solving such a problem, a method has been proposed in which a releasing agent is added to the dye receiving layer and the releasing agent is bleed out to the surface of the dye receiving layer to form a releasing layer.

When a liquid or wax-like release agent is used in such a method, there is a problem that these release agents may contaminate other articles or cause discoloration of an image and the like. Methods using mold release agents have been proposed.

According to this method, after forming the dye receiving layer,
The release agent contained in the dye-receiving layer is heat-treated to bleed out to the surface of the dye-receiving layer, and a cross-linked thin film of the release agent is formed on the surface of the dye-receiving layer. It takes a long time and the productivity is low, and the cross-linked film has a weak coating film strength and lacks scratch resistance and the like. Further, as an example of the reactive silicone, there is one described in Japanese Patent Application No. 3-87424, but this is a reaction between vinyl groups, and there is a problem that their reactivity is low.

Further, there is known an image receptor in which a specific silicone cross-linked coating is formed on the surface of the receptor layer (Japanese Patent Laid-Open No. 6-58242).
2-116189) is not always satisfactory.

Therefore, an object of the present invention is to provide a thermal transfer image-receiving sheet having a dye receiving layer which is excellent in the reaction rate of the releasing agent, the coating strength of the releasing layer and the releasing property of the thermal transfer sheet.

[0010]

The above object can be achieved by the present invention described below.

That is, the first aspect of the present invention is a thermal transfer image-receiving sheet in which a dye receiving layer is formed on at least one side of a substrate sheet, and the addition layer contains an addition-polymerizable silicone and a hydrogen-modified silicone. The thermal transfer image-receiving sheet is characterized in that a release agent mixture is added. Further, another embodiment of the first invention is a thermal transfer image-receiving sheet comprising a base sheet and a dye-receiving layer formed on at least one surface of the base sheet, wherein the surface of the receiving layer is composed of an addition-polymerizable silicone and a hydrogen-modified silicone. The present invention relates to a thermal transfer image-receiving sheet having a mold layer formed thereon.

By using a mixture of a specific reactive silicone as a releasing agent, thermal transfer having a dye receiving layer excellent in reaction rate of the releasing agent, coating strength of the releasing layer and releasing property of the thermal transfer sheet. An image receiving sheet can be provided.

A second aspect of the present invention is a release layer composition comprising a reactive silicone, a reaction catalyst and a reaction inhibitor as essential components in a liquid medium, and a dye-receptive resin and a reactive composition. An ink for a dye receiving layer, which comprises silicone, a reaction catalyst and a reaction inhibitor as essential components in a liquid medium, and a method for producing a thermal transfer image receiving sheet using these compositions.

In forming a dye receiving layer or a release layer, a coating liquid is prepared by using an ink characterized by containing a reactive silicone, a reaction catalyst and a reaction inhibitor as essential components in a liquid medium. In this state, the reaction of the release agent is sufficiently suppressed, and the reaction rate is rapidly increased during the heat treatment after the formation of the dye receiving layer or the release layer, and the image receiving sheet can be produced with high productivity. It is possible to provide a thermal transfer image-receiving sheet having a dye receiving layer which is excellent in the coating strength of the releasing layer and the releasing property of the thermal transfer sheet.

A third aspect of the present invention is a method for producing a thermal transfer image-receiving sheet which comprises forming a dye receiving layer on at least one surface of a base sheet and a release layer on the surface of the base sheet, and the release layer is a catalyst curing type. It consists of a release agent and a curing catalyst, and when the dye receiving layer is formed, one of the release agent and the curing catalyst is contained in the dye receiving layer coating liquid, and the dye receiving layer is formed and then cured on the receiving layer surface. A method for producing a thermal transfer image-receiving sheet, which comprises applying one of a catalyst and a releasing agent to form a releasing layer, and a dye receiving layer on at least one side of a base sheet and a releasing layer on the surface thereof. In the method for producing a thermal transfer image-receiving sheet comprising forming a layer, the release layer comprises a catalyst-curable release agent and a curing catalyst, and a coating solution containing the release agent after the formation of the dye receiving layer and the curing Any of the coating liquid containing catalyst Thermal transfer characterized by coating the surface of the dye-receiving layer with a coating liquid, and then applying either a coating liquid containing a curing catalyst or a coating liquid containing a release agent to form a release layer. It is a manufacturing method of an image receiving sheet.

When forming a release layer composed of a catalyst-curable release agent and a curing catalyst on the surface of the dye receiving layer, by separately using the release agent and the curing catalyst, the coating strength of the release layer and the A thermal transfer image-receiving sheet having a dye receiving layer having excellent releasability from the thermal transfer sheet can be produced with good productivity.

The present invention will be described in more detail with reference to the preferred embodiments. 1st present invention As a base material sheet used in the present invention, synthetic paper (polyolefin-based, polystyrene-based, etc.), fine paper, art paper,
Coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, poly Various plastic films or sheets such as methacrylate and polycarbonate can be used, and a white opaque film formed by adding a white pigment or a filler to these synthetic resins or a foamed foamed sheet can also be used. Not done.

Further, a laminated body made of any combination of the above-mentioned substrate sheets can also be used. As an example of a typical laminated body, there is a synthetic paper of cellulose fiber paper and synthetic paper or cellulose fiber paper and plastic film or sheet. The thickness of these base material sheets may be arbitrary, and for example, a thickness of about 10 to 300 μm is common.

The substrate sheet as described above is preferably subjected to a primer treatment or a corona discharge treatment on the surface when the adhesion to the dye receiving layer formed on the surface is poor.

The dye receiving layer formed on the surface of the substrate sheet is for receiving the sublimable dye transferred from the thermal transfer sheet and maintaining the formed image.

As the resin for forming the dye receiving layer,
For example, polyolefin resin such as polypropylene, polyvinyl chloride, halogenated polymer such as polyvinylidene chloride, polyvinyl acetate, vinyl polymer such as polyacrylic ester, polyethylene terephthalate, polyester resin such as polybutylene terephthalate, polystyrene resin, Polyamide resins, copolymer resins of olefins such as ethylene and propylene with other vinyl monomers, ionomers, cellulosic resins such as cellulose diacetate, polycarbonates, and the like. Particularly preferred are vinyl resins and polyester resins. It is a resin.

The thermal transfer image-receiving sheet of the present invention is obtained by adding a mixture of the above-mentioned resin to the following specific reactive silicone release agent and other necessary additives on at least one surface of the above-mentioned substrate sheet. , A dispersion that is dissolved in a suitable organic solvent or dispersed in an organic solvent or water, for example, gravure printing method, screen printing method, coating by a forming means such as a reverse roll coating method using a gravure plate, drying and It is obtained by heating to form a dye receiving layer. At this time, at least a part of the release agent mixture contained in the dye receiving layer bleeds out on the surface of the dye receiving layer due to the drying and heating of the coating liquid, and the release agent mixture does not react to the inside of the dye receiving layer and the surface. And a release layer is formed on the surface of the dye receiving layer.

In forming the dye receiving layer, titanium oxide, zinc oxide, kaolin clay, calcium carbonate, fine powder silica, etc. may be used for the purpose of improving the whiteness of the dye receiving layer to further improve the sharpness of the transferred image. Pigments and fillers can be added.

The dye receiving layer formed as described above may have any thickness, but it is generally 1 to 50 μm thick.
Further, such a dye receiving layer is preferably a continuous coating, but it may be formed as a discontinuous coating by using a resin emulsion or a resin dispersion.

In the present invention, one of the releasing agents for imparting releasability to the dye receiving layer is a silicone compound having an addition-polymerizable group, and the following compounds may be mentioned as examples thereof.

[0026]

[Chemical 1] (In the above formula, R is mainly a methyl group, but is an alkyl group or an aryl group such as a phenyl group or a combination thereof, l + m + n is an integer of 1 or more, and each siloxane unit is randomly arranged. At least one of X, Y and Z is a vinyl group, an allyl (—CH ₂ —CH═CH ₂ ) group, a (meth) acryloyl group or the like and is an addition-polymerizable group, and R ^{1 to} R
³ is a single bond or an alkylene group. Although the molecular weight of the above addition-polymerizable silicone is not particularly limited, a range of 3,500 to 20,000 is generally suitable. These addition-polymerizable silicones are commercially available and can be easily used in the present invention.

In the hydrogen-modified silicone used in combination with the addition-polymerizable silicone in the present invention, at least one of --R ¹ --X, --R ² --Z, and --R ³ --Y in the above general formula is a hydrogen atom. Other substituents, the arrangement of siloxane units, the molecular weight, etc. are the same as in the above general formula. These addition-polymerizable silicones and hydrogen-modified silicones are preferably modified with aryl groups such as phenyl groups.

The introduction of the aryl group generally improves the compatibility with the thermoplastic resin. Therefore, when the aryl group is mixed with the resin and used as a receiving layer or a release layer, the forming ink thereof becomes cloudy or separates. It is hard to cause problems such as
Further, there is little repellency during coating, and it becomes easy to obtain a good coated surface. Further, since the resin is mixed with the resin appropriately, there is an advantage that the strength of the obtained coating film is improved.

Further, since the affinity with the disperse dye is improved,
Dyeing inhibition is unlikely to occur, and particularly when applied on the receiving layer, sufficient releasability and dyeing density can both be achieved.

More preferred general formulas of addition-polymerizable silicone and hydrogen-modified silicone include the following structural formulas.

[0031]

[Chemical 2] Note that l, m, and n are the same as in the above case.

The content of diphenylsiloxane units is preferably 5 to 50 mol% based on the total siloxane units.

If the amount is less than 5 mol%, compatibility with the resin for the receiving layer is insufficient when internally added to the receiving layer, so that the ink for forming the receiving layer is liable to cause clouding, separation, etc., and uniform coating. There are problems that the surface cannot be obtained and the coating strength of the receiving layer is lowered.

Further, since the bleed-out of silicone is too good, the friction coefficient of the surface of the receiving layer is greatly reduced, and problems such as skew during printing and misalignment during three-color printing may occur depending on printing conditions. There is a nature.

On the other hand, if it is 50 mol% or more, the compatibility between the silicone and the resin is too high, and the bleed-out of the silicone to the surface of the receiving layer is hindered, so that there is a problem that the releasability is insufficient.

The addition ratio of the addition-polymerizable silicone and the hydrogen-modified silicone is determined by the molar ratio of the reactive groups possessed by both, and the ratio of the former to the latter is 4: 1 to 1: 4, particularly 1: 1 to 1 The range of 3 is preferable, and if it deviates from this range, satisfactory performance cannot be obtained in terms of reduction of releasability, reduction of coating film strength, deterioration of storage stability due to unreacted reactive groups, and the like.
The release agent mixture is preferably used in the range of about 2 to 20 parts by weight per 100 parts by weight of the dye-receiving layer forming resin.

When using the above releasing agent mixture, it is possible to use a curing catalyst suitable for the employed releasing agent. These curing catalysts are also commercially available, and various radical-generating polymerization catalysts, platinum-based catalysts and the like are used, but platinum-based catalysts are particularly suitable. About 5 to 200 parts by weight of the catalyst is preferably used per 100 parts by weight of the reactive silicone release agent. The use of these catalysts is not essential, and the reaction of the releasing agent can be caused by simply heating depending on the type of the releasing agent. Further, in order to improve the slipperiness of the thermal transfer image-receiving sheet, an epoxy-modified silicone or the like can be further added.

In another embodiment of the present invention, a dye receiving layer is once formed without adding the above releasing agent mixture to the receiving layer coating liquid, and the above releasing agent is formed on the surface of the dye receiving layer. Apply a coating solution containing the mixture (curing catalyst if necessary),
The release layer is formed by drying and heat curing. At this time, in order to enhance the coating suitability such as repellency of the release layer, the adhesiveness to the receiving layer surface after the release layer is formed, and the permeability of the sublimable dye transferred from the thermal transfer sheet during printing, an addition polymerizable silicone is used. And hydrogen-modified silicone
As described above, it must be modified with an aryl group such as a phenyl group. The use of the silicone modified with the aryl group improves the affinity with the resin used in the receiving layer and the sublimable dye that migrates. Further, for the purpose of improving the film-forming property and strength of the release layer to be formed and improving the dye permeability, about 1 to 50 parts by weight of the thermoplastic resin is added to the resin binder per 1 part by weight of the release agent mixture. Can be used together.

The resin used as the binder is not particularly limited, but is preferably selected from the above-mentioned dye-receiving layer forming resins. Further, in consideration of the adhesiveness with the receiving layer and the coated surface, it is preferable that at least one type of resin component used in the receiving layer is used as the binder resin of the release layer. Even if a resin binder is used, it is preferable to use an aryl-modified silicone in consideration of the affinity for the resin used in the receiving layer and the sublimable dye that migrates.

The method of forming the release layer itself may be the same as the formation of the dye receiving layer such as coating of the release layer coating liquid, drying and heating, and aging. The thickness of the release layer formed is 0.01 to 20 μm. Is preferred.

The image-receiving sheet of the present invention can be applied to various applications such as a heat-transferable recording sheet capable of thermal transfer recording, cards, and a transmission type original preparation sheet by appropriately selecting a base 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, and by providing such a cushion layer, there is less noise during printing and the image is reduced. Images corresponding to information can be transferred and recorded with good reproducibility.

Examples of the material forming 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 slipping layer can be provided on the back surface of the base material sheet. Examples of the material of the slippery layer include a methacrylate resin such as methyl methacrylate or a corresponding acrylate resin, a vinyl-based resin such as a vinyl chloride-vinyl acetate copolymer, and the like.

Further, it is 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, and for example, the detection mark that can be detected by the photoelectric tube detection device can be provided on the back surface of the base material 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 a sheet having a dye layer containing a sublimable dye provided on paper or a polyester film, and is conventionally known. Any thermal transfer sheet can be used as it is in the present invention.

Further, as the means for applying the thermal energy at the time of thermal transfer, any conventionally known applying means can be used.
By controlling the recording time with a recording device such as a thermal printer (for example, video printer VY-100 manufactured by Hitachi, Ltd.), 5 to 100 mJ / m
The intended purpose can be sufficiently achieved by applying thermal energy of about m ² . Second invention The second object of the present invention is that the reaction of the release agent is sufficiently suppressed in the state of the coating liquid, and the reaction rate is drastically increased during the heat treatment after the formation of the dye receiving layer or the release layer. A receiving layer ink and a releasing layer ink, which gives rise to a dye receiving layer which is excellent in productivity of an image receiving sheet and excellent in coating strength of a releasing layer and releasing property from a thermal transfer sheet, and the ink are used. A method of manufacturing a thermal transfer image-receiving sheet is provided.

The release layer composition of the present invention is characterized by containing a reactive silicone, a reaction catalyst and a reaction inhibitor as essential components in a liquid medium.

The dye receiving layer composition of the present invention is characterized by containing a dye receiving resin, a reactive silicone, a reaction catalyst and a reaction inhibitor as essential components in a liquid medium.

Preferred reactive silicones used in the present invention are, for example, epoxy-modified, alkyl-modified, amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified, alkylaralkylpolyether-modified, epoxy.
Examples thereof include modified silicone oils such as polyether-modified, polyether-modified, addition-polymerizable silicone, and hydrogen-modified silicone.

These reactive silicone oils can be prepared, for example, by a combination of amino modification and epoxy modification.
Although it is preferable to use compounds which react with each other, they may be used in a mode in which the same compounds are reacted with each other through a crosslinking agent such as polyisocyanate such as amino-modified or alcohol-modified silicone. A particularly preferred combination is a combination of addition-polymerizable silicone and hydrogen-modified silicone.

Particularly preferred addition-polymerizable silicones in the present invention include the following compounds.

[0053]

[Chemical 3] (In the above formula, R is mainly a methyl group, but is an alkyl group or an aryl group such as a phenyl group or a combination thereof, l + m + n is an integer of 1 or more, and each siloxane unit is randomly arranged. At least one of X, Y and Z is a vinyl group, an allyl (—CH ₂ —CH═CH ₂ ) group, a (meth) acryloyl group or the like and is an addition-polymerizable group, and R ^{1 to} R
³ is a single bond or an alkylene group. Although the molecular weight of the above addition-polymerizable silicone is not particularly limited, a range of 3,500 to 20,000 is generally suitable. These addition-polymerizable silicones are commercially available and can be easily used in the present invention.

The hydrogen-modified silicone preferably used in the present invention is represented by the formula-R ^{1 in the} above general formula.
At least one of —X, —R ² —Y—Z, and —R ³ —Y is a hydrogen atom, and other substituents, the arrangement of siloxane units, the molecular weight, etc. are the same as in the above general formula. Is. These addition-polymerizable silicones are commercially available and can be easily used in the present invention.

The ratio of the addition-polymerizable silicone and the hydrogen-modified silicone used is determined by the molar ratio of the reactive groups possessed by both, and the ratio of the former to the latter is 4: 1 to 1: 4, particularly 1: 1 to 1 The range of 3 is preferable, and if it deviates from this range, satisfactory performance cannot be obtained in terms of reduction of releasability, reduction of coating film strength, deterioration of storage stability due to unreacted reactive groups, and the like.
The release agent mixture is preferably used in the range of about 2 to 20 parts by weight per 100 parts by weight of the dye-receiving layer forming resin.

When the above-mentioned reactive silicone alone does not sufficiently react, it is necessary to use a catalyst for sufficiently reacting this. As the curing catalyst used together with the release agent, it is preferable to use a curing catalyst suitable for the selected reactive silicone or a combination thereof, for example, various radical generating polymerization catalysts, platinum-based catalysts and the like are used. Especially, platinum-based catalysts are suitable. The catalyst is about 5 to 200 per 100 parts by weight of the reactive silicone.
About a weight part is a preferable amount to be used.

In the coexisting state of the above-mentioned reactive silicone and catalyst, the reaction proceeds even at room temperature, and the progress of the reaction in the coating solution causes a decrease in releasability, and the storage stability and handling of the coating solution. There is a problem with sex. In the present invention, in order to solve such a problem, a reaction inhibitor is used which has a reaction inhibiting effect on the reactive silicone at room temperature and which eliminates the inhibiting effect during the heat treatment. The reaction inhibitor used in the present invention suppresses the action of the curing catalyst on the above-mentioned reactive silicone in the state of the solution of the solvent, and in the heated state or the state in which the solvent is vaporized, that is, the above-mentioned curing in the heated or dried state. It is a material that does not suppress the action of the catalyst but rather promotes it. Examples of such a curing inhibitor include a silylation product of acetylene alcohol. These reaction inhibitors can be obtained from the market and used. The reaction inhibitor is used in an amount of about 5 per 100 parts by weight of the reactive silicone.
It is preferably used in a proportion of from about 100 parts by weight.

As the liquid medium of the composition for dissolving or dispersing the above-mentioned essential components, any of the organic solvents used in general gravure compositions can be used, for example, methyl ethyl ketone, toluene, xylene, ethyl acetate,
Suitable examples include cellosolves, methyl isobutyl ketone, and mixed solvents thereof.

The ink composition for release layer of the present invention comprises the above-mentioned components as essential components, and the above-mentioned essential components generally have a solid content concentration of about 10 to 40% by weight. The method for producing the ink for the release layer itself can be easily prepared by uniformly mixing and dissolving each component in the ink medium. Hereinafter, the composition for coating is also referred to as "ink" according to the usage in the art.

In the present invention, in order to improve the coating property of the release layer formed in the above ink, a dye-receptive thermoplastic resin as described below is added in an amount of about 4 to 50 per 1 part by weight of the reactive silicone. It can be added in the range of parts by weight. In addition, dye-receptive resin as a binder component in high concentration,
For example, about 100 to 50 per 100 parts by weight of the release agent component.
The ink can be used as an ink for forming a dye-receptive layer by adding it in an amount of 00 parts by weight, and in this case, the dye-receptive layer is provided with good releasing property at the same time when the dye-receptive layer is formed. You can

The base material sheet used in the production of the thermal transfer image-receiving sheet of the present invention includes synthetic paper (polyolefin-based, polystyrene-based, etc.), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic paper. Films or sheets of various plastics such as resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, etc. Can be used,
In addition, a white opaque film formed by adding a white pigment or a filler to these synthetic resins, a foamed foamed sheet, or the like can be used, and there is no particular limitation.

Further, a laminated body made of any combination of the above-mentioned substrate sheets can also be used. As an example of a typical laminated body, there is a synthetic paper of cellulose fiber paper and synthetic paper or cellulose fiber paper and plastic film or sheet. The thickness of these base material sheets may be arbitrary, and for example, a thickness of about 10 to 300 μm is common. The substrate sheet as described above is preferably subjected to a primer treatment or a corona discharge treatment on the surface when the adhesion to the dye receiving layer formed on the surface is poor.

The dye receiving layer formed on the surface of the base sheet is for receiving the sublimable dye transferred from the thermal transfer sheet and maintaining the formed image. As the resin for forming the dye receiving layer, for example, polyophine resin such as polypropylene, polyvinyl chloride, halogenated polymer such as polyvinylidene chloride, polyvinyl acetate, vinyl polymer such as polyacrylic ester, polyethylene terephthalate, Polyester resins such as polybutylene 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, polycarbonates and the like. However, vinyl resins and polyester resins are particularly preferable.

In the method for producing the thermal transfer image-receiving sheet of the present invention, the resin as described above is used as an essential component in the ink for the receiving layer of the present invention, and other necessary additives on at least one surface of the substrate sheet. Of the dispersion prepared by dissolving in an appropriate organic solvent or dispersed in an organic solvent or water, for example, by a gravure printing method, a screen printing method, a forming means such as a reverse roll coating method using a gravure plate. It is obtained by coating, drying and heating to form a dye receiving layer. At this time, at least a part of the release agent contained in the dye receiving layer bleeds out on the surface of the dye receiving layer by drying and heating the coating solution, and the release agent mixture undergoes some reaction inside and on the surface of the dye receiving layer. As a result, a release layer is formed on the surface of the dye receiving layer.

In forming the dye receiving layer, titanium oxide, zinc oxide, kaolin clay, calcium carbonate, fine powdered silica, etc. may be used for the purpose of improving the whiteness of the dye receiving layer to further improve the clarity of the transferred image. Pigments and fillers can be added.

The dye receiving layer formed as described above may have any thickness, but it is generally 1 to 50 μm thick.
Further, such a dye receiving layer is preferably a continuous coating, but it may be formed as a discontinuous coating by using a resin emulsion or a resin dispersion.

In another embodiment of the present invention, the dye-receiving layer is formed once without adding the essential components of the release layer ink to the receiving-layer coating liquid, and the above-mentioned dye-receiving layer is formed on the surface thereof. The release layer can be formed by applying, drying and heating and curing the above release layer ink.

The method of forming the release layer itself may be the same as the formation of the dye receiving layer such as coating of the release layer coating liquid, drying and heating, and aging. The thickness of the release layer formed is 0.01 to 20 μm. Is preferred.

Further, the image-receiving sheet of the present invention can be applied to various applications such as a heat-transferable sheet capable of thermal transfer recording, cards, and a transmission type original preparation sheet by appropriately selecting a substrate sheet.

Further, the image-receiving sheet of the present invention may be provided with a cushion layer between the base sheet and the dye-receiving layer, if necessary. By providing such a cushion layer, there is less noise during printing and the image is reduced. Images corresponding to information can be transferred and recorded with good reproducibility.

Examples of the material forming 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.

A slipping layer may be provided on the back surface of the base sheet. Examples of the material of the slippery layer include a methacrylate resin such as methyl methacrylate or a corresponding acrylate resin, a vinyl-based resin such as a vinyl chloride-vinyl acetate copolymer, and the like.

Furthermore, it is 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, and for example, the detection mark that can be detected by the photoelectric tube detection device can be provided on the back surface of the base material 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 a paper or polyester film provided with a dye layer containing a sublimable dye, and is a conventionally known one. Any thermal transfer sheet can be used as it is in the present invention.

Further, as the means for applying the thermal energy during the thermal transfer, any conventionally known applying means can be used.
By controlling the recording time with a recording device such as a thermal printer (for example, video printer VY-100 manufactured by Hitachi, Ltd.), 5 to 100 mJ / m
The intended purpose can be sufficiently achieved by applying thermal energy of about m ² . Third Invention Next, the present invention according to the third aspect will be described in detail.

The base material sheet used in the production of the thermal transfer image-receiving sheet of the present invention includes synthetic paper (polyolefin type, polystyrene type, etc.), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic paper. Films or sheets of various plastics such as resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, cellulose fiber paper, polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, etc. Can be used,
In addition, a white opaque film formed by adding a white pigment or a filler to these synthetic resins, a foamed foamed sheet, or the like can be used, and there is no particular limitation.

Further, a laminate having any combination of the above-mentioned base sheets can be used. As an example of a typical laminated body, there is a synthetic paper of cellulose fiber paper and synthetic paper or cellulose fiber paper and plastic film or sheet. The thickness of these base material sheets may be arbitrary, and for example, a thickness of about 10 to 300 μm is common. The substrate sheet as described above is preferably subjected to a primer treatment or a corona discharge treatment on the surface when the adhesion to the dye receiving layer formed on the surface is poor.

The dye receiving layer formed on the surface of the base sheet is for receiving the 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 polyacrylic ester, polyethylene terephthalate and poly Examples include 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.

In one embodiment of the thermal transfer image-receiving sheet of the present invention, at least one surface of the above-mentioned base material sheet is coated with one of the above-mentioned resin for dye receiving layer and one of a catalyst-curable release agent and a curing catalyst. Addition as an essential component and addition of other necessary additives, dissolved in a suitable organic solvent as described below, or a dispersion prepared by dispersing in an organic solvent or water, for example, gravure printing method, screen printing method , Coating by a forming means such as a reverse roll coating method using a gravure plate, drying and heating to bleed out the catalyst-curable release agent or curing catalyst contained in the dye receiving layer to the surface of the dye receiving layer. , The surface of the bleed-out catalyst-curing release agent or curing catalyst is coated with a coating liquid containing a curing catalyst or a catalyst-curing release agent, whereby the surface of the dye receiving layer is coated. To form a cured release layer.

In another embodiment of the present invention, as in the prior art, a dye receiving layer is formed on the surface of the substrate sheet, and a coating containing a catalyst-curable release agent is formed on the surface of the dye receiving layer. The coating liquid containing the liquid or the curing catalyst is applied, and then either the coating liquid containing the curing catalyst or the coating liquid containing the release agent is applied to form the release layer.

On the other hand, in the prior art, both the catalyst-curing release agent and the curing catalyst were added to the dye-receiving layer coating liquid, so that the stability of the coating liquid was poor and the dye-receiving The catalyst-curable release agent and the curing catalyst reacted during the formation of the layer, and the bleed-out of the release agent to the surface was insufficient. The present invention sufficiently solves the above-mentioned drawbacks of the prior art.

The dye receiving layer formed as described above may have any thickness, but it is generally 1 to 50 μm thick.
Further, such a dye receiving layer is preferably a continuous coating, but it may be formed as a discontinuous coating by using a resin emulsion or a resin dispersion.

In forming the dye receiving layer, titanium oxide, zinc oxide, kaolin clay, calcium carbonate, fine powder silica, etc. may be used for the purpose of improving the whiteness of the dye receiving layer and further improving the sharpness of the transferred image. Pigments and fillers can be added.

As the catalyst-curing release agent used in the present invention, any of those used in the prior art can be used. Preferred release agents are, for example, epoxy-modified, alkyl-modified, Examples thereof include amino-modified, carboxyl-modified, alcohol-modified, fluorine-modified, alkylaralkylpolyether-modified, epoxy-polyether-modified, polyether-modified, addition-polymerizable silicone, and modified silicone oil such as hydrogen-modified silicone. Among these, a combination of addition-polymerizable silicone and hydrogen-modified silicone is preferable.

Catalysts Used in the Present Invention These reactive silicone oils are preferably used in combination with compounds which react with each other, such as a combination of amino modification and epoxy modification. For example, amino modified It may be used in a mode in which the same substances are reacted with each other through a cross-linking agent such as polyisocyanate such as or alcohol-modified silicone.

As the curing catalyst used in the present invention, platinum catalysts, radical generating catalysts and the like are used, but platinum catalysts are particularly suitable.

The proportion of the release agent used is the resin 1 for forming the dye receiving layer.
2 to 30 parts by weight per 00 parts by weight, and
The amount of the curing catalyst used is 4 to 12 per 100 parts by weight of the release agent.
A ratio of 0 parts by weight is a preferred ratio.

In the present invention, when a catalyst-curable release agent is contained in the coating liquid for the dye-receiving layer, the coating liquid containing the curing catalyst is applied onto the release agent bleeding out on the surface of the dye-receiving layer. To react with each other to form a cured release layer.
As the liquid medium of the coating liquid for dissolving or dispersing the curing catalyst, any organic solvent used in general gravure coating liquid can be used, for example, methyl ethyl ketone, toluene, xylene, ethyl acetate, cellosolves. ,
Preferred examples include methyl isobutyl ketone and mixed solvents thereof. In order to improve the coating suitability when preparing these coating liquids, the dye-receiving layer-forming resin is used as a binder or a film-forming auxiliary in a range that does not impair the releasability of the release layer to be formed. You can do it.

In the present invention, when a curing catalyst is contained in the dye receiving layer coating liquid, the bleed-out curing catalyst is coated on the surface of the dye receiving layer with a coating liquid containing a catalyst-curing release agent. Are reacted to form a cured release layer.
The liquid medium of the coating liquid for dissolving or dispersing the catalyst-curable release agent is the same organic solvent as described above, and the dye-receiving layer-forming resin is used as a binder or a film-forming auxiliary as described above. You can do it.

In another embodiment of the present invention,
After the dye receiving layer is once formed, the curing release layer is formed using the coating liquid containing the releasing agent and the coating liquid containing the curing agent as described above. Each coating liquid used at this time may be the same as in the above-mentioned embodiment.

In the above-mentioned method for forming the release layer, the release layer having excellent releasability can be easily formed by applying a coating solution containing a curing catalyst or a catalyst-curing release agent, drying, heating and aging. To be done. The thickness of the release layer formed is 0.01 to 20 μm.
Is preferred.

Further, the image-receiving sheet of the present invention can be applied to various applications such as a heat-transferable sheet capable of thermal transfer recording, cards, and a transmission type original preparation sheet by appropriately selecting a substrate 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, and by providing such a cushion layer, there is less noise during printing and the image is reduced. Images corresponding to information can be transferred and recorded with good reproducibility.

Examples of the material forming 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 slipping layer can be provided on the back surface of the base material sheet. Examples of the material of the slippery layer include a methacrylate resin such as methyl methacrylate or a corresponding acrylate resin, a vinyl-based resin such as a vinyl chloride-vinyl acetate copolymer, and the like.

Further, it is 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, and for example, the detection mark that can be detected by the photoelectric tube detection device can be provided on the back surface of the base material 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 a sheet in which a dye layer containing a sublimable dye is provided on paper or a polyester film, and is conventionally known. Any thermal transfer sheet can be used as it is in the present invention.

Further, as the means for applying the heat energy during the thermal transfer, any conventionally known applying means can be used.
By controlling the recording time with a recording device such as a thermal printer (for example, video printer VY-100 manufactured by Hitachi, Ltd.), 5 to 100 mJ / m
The intended purpose can be sufficiently achieved by applying thermal energy of about m ² .

Next, the present invention will be described more specifically with reference to Reference Examples, Examples and Comparative Examples. In the text, part or%
Unless otherwise specified, the weight is based on the weight. Also,
Among the following examples, Example A14 and Example B3 are reference examples.

The contents of addition-polymerizable silicones and hydrogen-modified silicones used in the examples below are shown in Tables A1 and A2 below.

[0101]

[Table 1] * The methyl siloxane, phenyl siloxane, and addition-polymerizable siloxane units in the side chain are randomly arranged. * Ratio to all siloxane units

[0102]

[Table 2] * The methyl siloxane, phenyl siloxane, and hydrogen siloxane units in the side chain are randomly arranged. Example A1 Synthetic paper (Yupo-FRG-150, thickness 150 μm, manufactured by Oji Yuka Co., Ltd.) was used as a base sheet, and a coating solution having the following composition was dried on one of the surfaces by a bar coater at a rate of 5.0 g /
Apply at a ratio of m ² and dry with a dryer, then
The dye receiving layer was formed by heating for 30 seconds in an oven at 0 ° C. to obtain a thermal transfer image receiving sheet of the present invention. Coating liquid composition : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 80 parts Polyester resin (Vylon 600, manufactured by Toyobo) 20 parts Release agent No.A 2 parts Release agent No.a 4 parts Epoxy modified silicone (X22-3000T, manufactured by Shin-Etsu Chemical) 6 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 400 parts Example A2 Example A1 The following coating liquid is used as the coating liquid in
A dye receiving layer was formed in the same manner as in Example A1 except for the above to obtain a thermal transfer image receiving sheet of the present invention. Coating liquid composition : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 80 parts Polyester resin (Vylon 600, manufactured by Toyobo) 20 parts Release agent No.B 2 parts Release agent No.a 4 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 400 parts Example A3 The following coating liquid was used as the coating liquid in Example A1.
A dye receiving layer was formed in the same manner as in Example A1 except for the above to obtain a thermal transfer image receiving sheet of the present invention. Coating liquid composition : Vinyl chloride / vinyl acetate copolymer (# 1000GK, manufactured by Denki Kagaku Kogyo) 75 parts Polyester resin (Vylon 200, manufactured by Toyobo) 25 parts Release agent No.C 2 parts Release agent No.b 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 400 parts Example A4 The following coating solution was used as the coating solution in Example A1.
A dye receiving layer was formed in the same manner as in Example A1 except for the above to obtain a thermal transfer image receiving sheet of the present invention. Coating liquid composition : Vinyl chloride / vinyl acetate copolymer (# 1000GK, manufactured by Denki Kagaku Kogyo) 75 parts Polyester resin (Vylon 200, manufactured by Toyobo) 25 parts Release agent No.D 3 parts Release agent No.c 9 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 400 parts Example A5 Synthetic paper as a base sheet (Yupo-FRG-150, thickness 150 μm, Oji Oka Kabushiki Kaisha), and a coating liquid for a dye receiving layer having the following composition is applied to one surface of the coating liquid at a rate of 2.5 g / m ² when dried by a bar coater and dried to form a dye receiving layer. Then, a release layer coating solution having the following composition was applied on the surface thereof at a rate of 2.0 g / m ² when dried and dried by heating to form a release layer to obtain a thermal transfer image-receiving sheet of the present invention. . Composition of coating liquid for dye receiving layer : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 40 parts Polyester resin (Vylon 200, manufactured by Toyobo) 20 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 240 parts Release layer coating liquid composition : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 40 parts Release agent No. 2 parts Release agent No. a 4 parts Platinum curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 160 parts Example A6 The following coating liquids were used as the coating liquids in Example A5, and others were used in Example A5. A dye receiving layer was formed in the same manner as described above to obtain a thermal transfer image receiving sheet of the present invention. Composition of coating liquid for dye receiving layer : Vinyl chloride / vinyl acetate copolymer (# 1000GK, manufactured by Denki Kagaku Kogyo) 25 parts Polyester resin (Vylon 200, manufactured by Toyobo) 25 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 200 parts (coating amount 2.0 g / m ² ) Composition of coating liquid for release layer : Vinyl chloride / vinyl acetate copolymer (# 1000GK, manufactured by Denki Kagaku Kogyo) 50 parts Release agent No.C 2 parts Release type agents No.B 5 parts platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co.) 3 parts Methyl ethyl ketone / toluene (1/1 by weight) 200 parts (coated amount 2.5 g / m ²⁾ example A7 embodiment The following coating liquids were used as the coating liquids in Example A5, and the dye receiving layer was formed in the same manner as in Example A5 except for the above to obtain a thermal transfer image-receiving sheet of the present invention. Composition of coating solution for dye receiving layer : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 80 parts Polyester resin (Vylon 600, manufactured by Toyobo) 20 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 400 parts (coating amount 4.5 g / m ² ) Coating liquid composition for release layer : Release agent No.A 2 parts Release agent No.a 4 parts Platinum curing catalyst (PL-50T, Shin-Etsu Chemical Co., Ltd.) 2 parts methyl ethyl ketone / toluene (weight ratio 1/1) 30 parts (coating amount 5.0 g / m ² ) Example A8 The following coating liquids were used as the coating liquids in Example A5, and others were used. A dye receiving layer was formed in the same manner as in Example A5 to obtain a thermal transfer image receiving sheet of the present invention. Composition of coating liquid for dye receiving layer : Vinyl chloride / vinyl acetate copolymer (# 1000GK, manufactured by Denki Kagaku Kogyo) 50 parts Polyester resin (Vylon 600, manufactured by Toyobo) 50 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 400 parts (coating amount: 4.5 g / m ² ) Coating liquid composition for release layer : Release agent No. B 3 parts Release agent No. a 6 parts Platinum curing catalyst (PL-50T, Shin-Etsu Chemical Co., Ltd.) 3 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 50 parts (Coating amount 0.5 g / m ² ) Comparative Example A1 The following coating liquid was used as the coating liquid in Example A1.
A dye receiving layer was formed in the same manner as in Example A1 except for the above to obtain a thermal transfer image receiving sheet of a comparative example. Coating liquid composition : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 80 parts Polyester resin (Vylon 200, manufactured by Toyobo) 20 parts Amino-modified silicone (KS-343, manufactured by Shin-Etsu Chemical) 5 parts Epoxy-modified silicone (KF-393, manufactured by Shin-Etsu Chemical) 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 8 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 400 parts Comparative Example A2 Each in Example A5 Dye receiving layers were formed in the same manner as in Example A5 except that the following coating liquids were used as coating liquids to obtain thermal transfer image receiving sheets of Comparative Examples. Composition of coating liquid for dye receiving layer : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 40 parts Polyester resin (Vylon 600, manufactured by Toyobo) 20 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 250 parts (coating amount 2.5 g / m ² ) Coating liquid composition for release layer : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 40 parts Amino-modified silicone (KS-343, Shin-Etsu) Chemical) 5 parts Epoxy-modified silicone (KF-393, manufactured by Shin-Etsu Chemical) 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Methyl ethyl ketone / toluene (weight ratio 1/1) 150 parts (coating) the amount 2.0 g / m ²⁾ on the other hand, a dye layer forming coating solution having the following composition was prepared, a polyethylene terephthalate film of 6μm thick subjected to heat treatment to the back, a dry coating weight of 1. to give a thermal transfer sheet used in the coating and drying the present invention by gravure printing so as to be g / m ^2. Coating solution composition : Kayaset Blue 714 (CI Solvent Blue 63, manufactured by Nippon Kayaku) 5.50 parts Polyvinyl butyral resin (ESREC 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 above thermal transfer sheet and the above-mentioned thermal transfer image receiving sheet of the present invention and the comparative example are superposed with their dye layers and dye receiving surfaces facing each other, and a thermal head is placed from the back surface of the thermal transfer sheet. Using head applied voltage 12.0V, applied pulse width 1
Step pattern that decreases sequentially from 6.0 msec./line every 1 msec., 6 line / mm (33.3 mse in the sub-scanning direction)
c. / line), the thermal head recording is performed, and the peelability of the both after forming a cyan image is examined and the following Table A3 is shown.
Got the result.

[0103]

[Table 3] (1) Curability: As a drying condition for preparing an image-receiving sheet, it was left in an oven at 120 ° C. for 3 minutes, then cooled at room temperature, and the sliminess of the surface of the receiving layer was observed by touch with a finger.

◯: Good ×: Poor (2) Releasability: The image-receiving sheet and the thermal transfer sheet were superposed on each other, and after the thermal head recording, the adhesiveness between them was evaluated by peeling off the thermal transfer sheet. . The smaller the adhesiveness, the better the releasability. When heat-sealed, the image-receiving sheet and the thermal transfer sheet cannot be separated from each other, and the base material may be damaged in some cases.

◯: Good Δ: Partial peeling is bad ×: Poor (3) Coating film scratch resistance: Rubbing the surface of the image receiving sheet with gauze,
The degree of scratches before and after that was visually observed.

◯: Good Δ: Slightly scratched ×: Poor (4) Strength of coating film of receiving layer: Folded in two with the receiving layer surface of the image-receiving sheet inside, and observed the crease under a microscope to evaluate the cracking condition. did.

◯: Good Δ: Some cracks are seen ×: Poor Examples The general formulas of the addition-polymerizable silicones and hydrogen-modified silicones used in Examples A9 to A21 are shown below, and their contents are shown in Table A.
4, described in Table A5.

[0108]

[Chemical 4]

[0109]

[Table 4]

[0110]

[Table 5] Example A9 The following ink was applied and formed on 150 μm of Yupo in the same manner as in Example A1 so as to have a dry amount of 5.0 g / m ² .

Polyester resin (Vylon 600) 40 parts Vinyl chloride / vinyl acetate copolymer (Dencarac # 1000A) 40 parts Styrene acrylic modified vinyl chloride / vinyl acetate copolymer (Dencarac # 400) 20 parts Release Agent No. E 5 parts Release agent No. d 5 parts Platinum curing catalyst (PL-50T, Shin-Etsu Chemical Co., Ltd.) 6 parts Reaction inhibitor (PLR-5, Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / toluene solids Amount of 20 wt%. By using a styrene-acryl-modified vinyl chloride / vinyl acetate copolymer, the drying property can be improved. Example A10 Polyester resin (Vylon 600) 40 parts Vinyl chloride / vinyl acetate copolymer (Dencarac # 1000A) 40 parts Styrene acrylic modified vinyl chloride / vinyl acetate copolymer (Dencarac # 400) 20 parts Release Agent No. F 5 parts Release agent No. g 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts Reaction inhibitor (PLR-5, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / toluene solids Amount of 20 wt% Example A11 Polyester resin (Vylon 600) 40 parts Vinyl chloride / vinyl acetate copolymer (Dencarac # 1000A) 40 parts Styrene acrylic modified vinyl chloride / vinyl acetate copolymer (Dencarac # 400) ) 20 parts Release agent No. G 5 parts Release agent No. f 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts Reaction inhibitor (P R-5, manufactured by Shin-Etsu Chemical Co.) 5 parts Methyl ethyl ketone / toluene solids becomes 20 wt% amount in Example A12 a polyester resin (Byron 600) 40 parts Vinyl chloride / vinyl acetate copolymer (Denka rack # 1000A) 60 parts release Agent No. H 6 parts Release agent No.e 4 parts Platinum curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts Reaction inhibitor (PLR-5, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / toluene solids Amount of 20 wt% Example A13 Polyester resin (Vylon 600) 40 parts Vinyl chloride / vinyl acetate copolymer (Dencarac # 1000A) 60 parts Release agent No.I 5 parts Release agent No.e 5 parts Platinum-based Curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts Reaction inhibitor (PLR-5, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / toluene Solid content 20 wt% Example A14 Polyester resin (Vylon 600) 40 parts Vinyl chloride / vinyl acetate copolymer (Dencarac # 1000A) 40 parts Styrene acrylic modified vinyl chloride / vinyl acetate copolymer (Dencarac # 400) 20 parts Release Agent No. J 5 parts Release agent No. g 5 parts Platinum curing catalyst (PL-50T, Shin-Etsu Chemical Co., Ltd.) 6 parts Reaction inhibitor (PLR-5, Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / toluene solids Amount of 20 wt% Example A15 Polyester resin (Vylon 600) 40 parts Vinyl chloride / vinyl acetate copolymer (Dencarac # 1000A) 40 parts Styrene acrylic modified vinyl chloride / vinyl acetate copolymer (Dencarac # 400) ) 20 parts Release agent No.K 5 parts Release agent No.h 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts Reaction inhibitor (P R-5, manufactured by Shin-Etsu Chemical Co.) 5 parts Methyl ethyl ketone / toluene a solid content of 20 wt% amount in Example A16 a polyester resin (Byron 600) 40 parts Vinyl chloride / vinyl acetate copolymer (Denka rack # 1000A) 40 parts styrene-acrylic Modified vinyl chloride / vinyl acetate copolymer (Dencarac # 400) 20 parts Release agent No.L 2.5 parts Release agent No.i 7.5 parts Platinum curing catalyst (PL-50T, Shin-Etsu Chemical) Industrial) 6 parts Reaction inhibitor (PLR-5, Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / toluene Solid content 20 wt% Example A17 Polyester resin (Vylon 600) 40 parts Vinyl chloride / vinyl acetate copolymer ( Dencarac # 1000A) 40 parts Styrene acrylic modified vinyl chloride / vinyl acetate copolymer (Dencarac # 400) 20 parts Release agent No. .J 5 parts Release agent No.h 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 6 parts Reaction inhibitor (PLR-5, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / toluene Solid content 20 wt% Example A18 Coating liquid composition for dye receiving layer (5 g / m ² ) Polyester resin (Vylon 600) 40 parts Vinyl chloride / vinyl acetate copolymer (Dencarac # 1000A) 40 parts Styrene acrylic modified chloride Vinyl / vinyl acetate copolymer (Dencarac # 400) 20 parts MEK / T01 Solid content 20 wt% Coating composition for release layer (0.1 g / m ² ) Polyester resin (Vylon 600) 30 parts Release mold agent No. E 10 parts release agent No. i 10 parts platinum-based curing catalyst (PL-50T) coating Formulation for the amount in example A19 dye-receiving layer comprising 10 parts of ethyl acetate solids 1 wt% (5 g m ²⁾ Polyester resin (Byron 200) 20 parts MEK / T01 80 parts Composition of coating liquid for release layer (0.1 g / m ²⁾ Polyester resin (Byron 600) 30 parts of the release agent No. E 10 parts release Agent No. d 10 parts Platinum-based curing catalyst (PL-50T) 10 parts Ethyl acetate Solid content of 1 wt% Example A20 Dye receiving layer coating liquid composition (5 g / m ² ) Polyester resin aqueous dispersion (Vylonal MD-1200 Toyobo) 50 parts IPA / water (1/1) 50 parts Release layer coating liquid composition (0.1 g / m ² ) Polyester resin (Vylon 600) 30 parts Release agent No. E 10 Part Release agent No.d 10 parts Platinum-based curing catalyst (PL-50T) 10 parts Ethyl acetate Solid content 1 wt% Example A21 Dye receiving layer coating liquid composition (5 g / m ² ) Polyester resin (Vylon 60 ) 40 parts Vinyl chloride / vinyl acetate copolymer (# 1000A) 40 parts Vinyl chloride / vinyl acetate copolymer (# 400) 20 parts MEK / T01 Solid content 20 wt% coating liquid composition for release layer ( 0.1 g / m ² ) Release agent No. E 10 parts Release agent No. i 10 parts Platinum-based curing catalyst (PL-50T) 10 parts Ethyl acetate Solid content 1 wt% Thermal transfer test Under the following printing conditions Then, thermal transfer recording was carried out, and the peelability of the both after forming a cyan image was examined, and the results shown in Table 6 below were obtained. The evaluation film is the same as described above. Thermal head specifications: Model: L-335 (made by TDK) Heating element density: 6 (doz / mm) Heating element average resistance value: 571 (Ω) Printing conditions: Printing speed: 5.5 (msec / line) Applied voltage: 15.7 (V) Applied pulse width: 16-step pattern (releasing property) which is sequentially reduced from 4.4 msec / line every 0.275 msec ◎: Almost no resistance is felt when peeled off, and also with an image receiving sheet There is no problem caused by heat fusion of the thermal transfer sheet,
Good recording was obtained.

◯: There is some resistance when peeled off,
Good recording was obtained without any problems due to heat fusion.

Δ: Peeling is partially defective due to heat fusion.

X: Bad (Scratch resistance) Rubbing the surface of the image receiving sheet 5 times with gauze,
After that, printing was performed under the above printing conditions and the releasability was checked.

◯: The rubbed portion also showed good releasability as did the non-rubbed portion.

Δ: Some dye binder was heat fused to the rubbed portion.

X: The rubbed portion was completely heat-sealed.

Other items are evaluated by the above-mentioned Example A1,
It is similar to the case of A2.

[0119]

[Table 6] According to the present invention as described above, by using a mixture of a specific reactive silicone as a release agent, the reaction rate of the release agent, the coating strength of the release layer and the releasability of the thermal transfer sheet are excellent. A thermal transfer image receiving sheet having a dye receiving layer can be provided. Reference Example B1 Release agent No. E 5 parts Release agent No. d 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 0 or 6 parts Reaction inhibitor (silylated acetylene alcohol (PLR-5 , Manufactured by Shin-Etsu Chemical Co., Ltd.)) 0 or 2 parts Methyl ethyl ketone / toluene (weight ratio 1/1) Solid content of 20% In the above composition, only silicone, silicone and reaction inhibitor, and silicone and reaction inhibition When the relationship between the reaction temperature and the reaction rate (for the conditions described in Example B1) was examined for three kinds of combinations of the agent and the catalyst, the results shown in FIG. 1 were obtained. Example B1 Synthetic paper (Yupo-FRG-150, thickness 150 μm, manufactured by Oji Yuka Co., Ltd.) was used as a base sheet, and a coating solution having the following composition was applied to one surface of the synthetic paper by a bar coater at 5.0 g / dry.
Apply at a ratio of m ² and dry with a dryer, then
The dye receiving layer was formed by heating for 30 seconds in an oven at 0 ° C. to obtain a thermal transfer image receiving sheet of the present invention. Coating liquid composition : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 80 parts Polyester resin (Vylon 600, manufactured by Toyobo) 20 parts Release agent No.E 5 parts Release agent No.d 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts Reaction inhibitor (silylated acetylene alcohol (PLR-5, manufactured by Shin-Etsu Chemical)) 0-10 parts Methyl ethyl ketone / toluene (weight ratio 1/1) ) Solid content of 20% The thermal transfer image-receiving sheet obtained above was left for a period of time shown in the following Table B1 immediately after production, and then a test printer (VY
-P1, manufactured by Hitachi, Ltd.), and allowed to stand at a temperature of 40 ° C. for 3 hours, 20 solid prints were continuously printed at the same temperature, and peeling between the thermal transfer sheet and the image receiving sheet was examined.
A result of 1 was obtained.

[0120]

[Table 7] Example B2 Synthetic paper (Yupo-FRG-150, thickness 150 μm, made by Oji Yuka Co., Ltd.) was used as a base sheet, and a coating liquid for a dye receiving layer having the following composition was dried on a bar coater on one surface of the synthetic paper. A dye receiving layer is formed by coating and drying at a rate of 2.5 g / m ² , and then a release layer coating solution having the following composition is coated on the surface at a rate of 2.0 g / m ² when dried. Then, the release layer was formed by heating and drying to obtain a thermal transfer image-receiving sheet of the present invention. Composition of coating liquid for dye receiving layer : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 40 parts Polyester resin (Vylon 600, manufactured by Toyobo) 20 parts Methyl ethyl ketone / toluene (weight ratio 1/1) Amount of solid content 20% Coating composition for release layer : Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 40 parts Release agent No.E 5 parts Release agent No.d 5 Part Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 10 parts Reaction inhibitor (silylated acetylene alcohol (PLR-5, manufactured by Shin-Etsu Chemical)) 0-10 parts Methyl ethyl ketone / toluene (weight ratio 1/1) Amount of solid content 20% The thermal transfer image-receiving sheet obtained above was evaluated in the same manner as in Example B1, and the results shown in Table B2 below were obtained.

[0121]

[Table 8] Example B3 The following coating liquids were used as the coating liquids in Example B2, and the dye receiving layer was formed in the same manner as in Example B2 except for the above to obtain a thermal transfer image-receiving sheet of the present invention. Coating solution composition for dye receiving layer : Vinyl chloride / vinyl acetate copolymer (# 1000GK, manufactured by Denki Kagaku Kogyo) 25 parts Polyester resin (Vylon 600, manufactured by Toyobo) 25 parts Methyl ethyl ketone / toluene (weight ratio 1/1) Amount of solid content 20% (coating amount 2.0 g / m ² ) Composition of coating liquid for release layer : Vinyl chloride / vinyl acetate copolymer (# 1000GK, manufactured by Denki Kagaku Kogyo) 50 parts Amino-modified silicone ( KS-343, manufactured by Shin-Etsu Chemical) 5 parts Epoxy-modified silicone (KF-393, manufactured by Shin-Etsu Chemical) 5 parts Platinum-based curing catalyst (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Reaction inhibitor (silylated acetylene alcohol ( PLR-5, manufactured by Shin-Etsu chemical)) 0 to 10 parts Methyl ethyl ketone / toluene (weight ratio 1/1) the amount of a solid content of 20% (coated amount 2.5 g / m ²⁾ Netsuten obtained above Results in Table B3 were evaluated image-receiving sheet in the same manner as in Example B1 was obtained.

[0122]

[Table 9] According to the present invention as described above, a coating liquid is obtained by using an ink containing a reactive silicone, a reaction catalyst and a reaction inhibitor as essential components in a liquid medium when forming a dye receiving layer or a release layer. In this state, the reaction of the release agent is sufficiently suppressed, and the reaction rate sharply increases after the dye receiving layer or the release layer is formed, so that the image-receiving sheet can be produced with high productivity, and It is possible to provide a thermal transfer image-receiving sheet having a dye receiving layer which is excellent in the coating strength of the mold layer and the releasability of the thermal transfer sheet. Example C1 Synthetic paper (Yupo-FRG-150, thickness 150 μm, manufactured by Oji Yuka Co., Ltd.) was used as a base sheet, and a coating liquid for a dye receiving layer having the following composition was dried on a bar coater on one surface of the synthetic paper 5.0 g / m ²
To about 130 ℃ after drying with a dryer.
Heat treatment was carried out for 30 seconds in the above-mentioned oven to form a dye receiving layer. Then, a proportion of a 20% solution of a platinum-based catalyst PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) in a mixed solvent of methyl ethyl ketone / toluene 1: 1 becomes 50 wt% with respect to the catalyst-curable silicone added to the receiving layer when dried. Then, the surface of the dye receiving layer was coated and heat-treated in an oven at 130 ° C. for 30 seconds to obtain a thermal transfer image-receiving sheet of the present invention. Composition of coating liquid for dye receiving layer: Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 80 parts Polyester resin (Vylon 600, manufactured by Toyobo) 20 parts Release agent No. E 5 parts Release Agent No. d 5 parts Epoxy-modified silicone (X22-3000T, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / toluene (weight ratio 1/1) Amount of solid content 20% Example C2 On one side, a coating solution for dye receiving layer having the following composition was dried by a bar coater at 2.5.
It was applied at a rate of g / m ² , dried with a drier, and then heat-treated in an oven at about 130 ° C. for 30 seconds to form a dye-receiving layer. Then, a release layer coating liquid having the following composition was applied and dried on the surface in the same manner as above at a rate of 2.5 g / m ² when dried, and platinum-based catalyst PL-50T (Shin-Etsu) was used in the same manner as in Example C1. (Chemical Industry) 20% solution of a mixed solvent of methyl ethyl ketone / toluene 1: 1 was applied in a dry amount of 5 to the catalyst-curable silicone added to the receiving layer.
The dye receptive layer surface is coated at a ratio of 0 wt%, 13
It was heat-treated in an oven at 0 ° C. for 30 seconds to obtain a thermal transfer image-receiving sheet of the present invention. Composition of coating liquid for dye receiving layer: Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 40 parts Polyester resin (Vylon 600, manufactured by Toyobo) 20 parts Methyl ethyl ketone / toluene (weight ratio 1/1) Amount of solid content 20% Coating composition for release layer: Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 40 parts Release agent No.E 5 parts Release agent No.d 5 Parts Epoxy-modified silicone (X-22-3000T, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / toluene (weight ratio 1/1) Solid content 20% Example C3 One side of the same base sheet as Example C1 When a coating solution for dye receiving layer having the following composition was dried by a bar coater at 4.5.
It was applied at a rate of g / m ² , dried with a drier, and then heat-treated in an oven at about 130 ° C. for 30 seconds to form a dye-receiving layer. Then, a release layer coating solution having the following composition was applied and dried on the surface in the same manner as above at a rate of 2.5 g / m ² when dried, and platinum catalyst PL-50T ( A 20% solution of a mixed solvent of methyl ethyl ketone / toluene 1: 1 (produced by Shin-Etsu Chemical Co., Ltd.) is applied to the surface of the dye receiving layer at a ratio of 50 wt% with respect to the catalyst-curable silicone added to the receiving layer when dried. 1
It was heat-treated in an oven at 30 ° C. for 30 seconds to obtain a thermal transfer image-receiving sheet of the present invention. Composition of coating liquid for dye receiving layer: Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 65 parts Polyester resin (Vylon 600, manufactured by Toyobo) 35 parts Methyl ethyl ketone / toluene (weight ratio 1/1) Amount of solid content of 20% Coating liquid composition for release layer: Release agent No. E 5 parts Release agent No. d 5 parts Epoxy modified silicone (X-22-3000T, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Methyl ethyl ketone / Toluene (weight ratio 1/1) Amount to give a solid content of 20% Example C4 One side of the same base sheet as in Example C1 was coated with a coating solution for dye receiving layer having the following composition by a bar coater when dried 4 .5
It was applied at a rate of g / m ² , dried with a drier, and then heat-treated in an oven at about 130 ° C. for 30 seconds to form a dye-receiving layer. Then, a release layer coating solution having the following composition was applied to the surface of the dye receiving layer at a rate of 0.5 g / m ² and heat-treated in an oven at 130 ° C. for 30 seconds to release the release layer (thickness: 0). 0.5 g / m ² ) to obtain a thermal transfer image-receiving sheet of the present invention. Composition of coating liquid for dye receiving layer: Vinyl chloride / vinyl acetate copolymer (# 1000A, manufactured by Denki Kagaku Kogyo) 80 parts Polyester resin (Vylon 600, manufactured by Toyobo) 20 parts Platinum catalyst (PL-50T, Shin-Etsu Chemical) Industrial) 5 parts Methyl ethyl ketone / toluene (weight ratio 1/1) Solid content 20% Release liquid coating composition: Release agent No.E 5 parts Release agent No.d 5 parts Epoxy-modified silicone (X-22-3000T, manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Example C5 Composition of coating liquid for dye receiving layer (5 g / m ² ) 40 parts of polyester resin (Vylon 600) Vinyl chloride / vinyl acetate copolymer (# 1000A) ) 40 parts Styrene acrylic modified vinyl chloride / vinyl acetate copolymer (# 400) 20 parts Release agent No.E 2 parts Release agent No.d 2 parts MEK / T01 (1/1) Solid content 20 wt% become Quantity Coating liquid composition for release layer (0.1 g / m ² ) Polyester resin (Vylon 600) 10 parts Platinum-based curing catalyst (PL-50T) 10 parts Ethyl acetate Solid content 1 wt% Example C6 Dye receiving Layer coating liquid composition (5 g / m ² ) Polyester resin aqueous dispersion (Vylonal MD-1200) 50 parts Release agent No. E emulsion 2 parts Release agent No. d emulsion 2 parts EPA / water (1/1) 50 parts Release layer coating liquid composition (0.1 g / m ² ) Polyester resin (Vylon 600) 10 parts Platinum-based curing catalyst (PL-50T) 10 parts Ethyl acetate Solid content 1 wt% Amount evaluation example When preparing the thermal transfer image-receiving sheet, after leaving each coating liquid used in each example for a certain period of time, test the releasability of each thermal transfer image-receiving sheet when the thermal transfer image-receiving sheet is produced using printer (VY-P1, manufactured by Hitachi, Ltd.) and left at 40 ° C. for 3 hours, 20 solid dark prints were continuously printed at the same temperature, and the releasability between the thermal transfer sheet and the image receiving sheet was examined. The result of C1 was obtained.

[0123]

[Table 10] As is clear from Table C1 above, according to the method of the present invention, the stability of the coating liquid used is good, and it is not necessary to use the coating liquid immediately after preparation, and a large amount of coating liquid is prepared in advance. In addition, it is possible to continuously produce the thermal transfer image-receiving sheet for a long time.

According to the present invention as described above, when a release layer comprising a catalyst-curable release agent and a curing catalyst is formed on the surface of the dye receiving layer, the release agent and the curing catalyst are separately used. It is possible to produce a thermal transfer image-receiving sheet having a dye receiving layer excellent in coating film strength of the release layer and releasability from the thermal transfer sheet with good productivity.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the reaction rate of reactive silicone and the reaction temperature.

Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) B41M 5/38-5/40

Claims (8)

(57) [Claims] 1. A thermal transfer image-receiving sheet comprising a base sheet and a dye-receiving layer formed on at least one surface of the base sheet, wherein the dye-receiving layer comprises a release agent mixture comprising an addition-polymerizable silicone and a hydrogen-modified silicone. A cured product of a composition containing a curing catalyst, and a dye-receptive resin, wherein the molar ratio of the reactive groups of the addition-polymerizable silicone to the hydrogen of the hydrogen-modified silicone is 4/1 to 1/4. At least one of the addition-polymerizable silicone and the hydrogen-modified silicone contains diphenylsiloxane as a constituent component, and the content is 5 to 50 mol% of all siloxane units. A thermal transfer image receiving sheet. 2. A thermal transfer image-receiving sheet having a dye-receiving layer formed on at least one surface of a substrate sheet, wherein the surface of the dye-receiving layer is a release layer comprising an addition-polymerizable silicone and a hydrogen-modified silicone. A composition comprising an agent mixture and a curing catalyst, wherein the molar ratio of the reactive groups of the addition-polymerizable silicone to the hydrogen of the hydrogen-modified silicone is 4/1 to 1/4, and the addition-polymerization is performed. Of addition-polymerizable silicones and hydrogen-modified silicones in which at least one of the polymerizable silicone and hydrogen-modified silicone contains diphenylsiloxane in its constituents, and the content is 5 to 50 mol% of all siloxane units. A thermal transfer image-receiving sheet comprising a release layer formed of a cured product of the composition 3. The thermal transfer image-receiving element according to claim 2, wherein the release layer further contains a binder resin, and at least one component of the binder resin is a resin of the same system as the resin component forming the dye receiving layer. Sheet. 4. The thermal transfer image-receiving sheet according to claim 1, wherein the addition-polymerizable silicone is a silicone containing an unsaturated bond. 5. The thermal transfer image-receiving sheet according to claim 1, wherein the silicone containing an unsaturated bond is a vinyl-modified silicone. 6. The molar ratio of the reactive groups of the addition-polymerizable silicone to the hydrogen of the hydrogen-modified silicone is 4/1 to 1/4 on at least one surface of the base sheet, and the addition-polymerizable silicone and A composition comprising a release agent mixture comprising a hydrogen-modified silicone, a curing resin, and a dye-accepting resin, wherein at least one of the addition-polymerizable silicone and the hydrogen-modified silicone is a constituent component thereof. The base sheet by coating with a composition containing diphenylsiloxane in an amount of 5 to 50 mol% of all siloxane units, and curing the composition thus coated. A method for producing a thermal transfer image-receiving sheet, which comprises forming a dye receiving layer on the top. 7. A dye receptive layer comprising a dye receptive resin is formed on at least one surface of a base sheet, and then a release agent comprising an addition polymerizable silicone and a hydrogen-modified silicone is formed on the surface of the dye receptive layer. A composition comprising an agent mixture and a curing catalyst, wherein the molar ratio of the reactive groups of the addition-polymerizable silicone to the hydrogen of the hydrogen-modified silicone is 4/1 to 1/4, and the addition polymerization is performed. Of addition-polymerizable silicone and hydrogen-modified silicone in which at least one of a polymerizable silicone and a hydrogen-modified silicone contains diphenylsiloxane in its constituents and the content is 5 to 50 mol% of all siloxane units. The dye-receiving composition is coated with the composition described above and the composition thus coated is cured. A method for producing a thermal transfer image-receiving sheet, which comprises forming a release layer on the layer. 8. The method for producing a thermal transfer image-receiving sheet according to claim 7, wherein the composition for forming the release layer further contains a resin binder.