JP2002274064A - Heat-transfer sheet and image printed article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-transfer sheet which can impart excellent imprinting property, writing property and durability to an image formed on an image receiving sheet, and an image printed article equipped with an image which can absorb and fix a water base ink, and is excellent in imprinting property and writing property, and also, has durability. SOLUTION: At least at one section on one surface of a base material sheet, a heat-transferring protective layer wherein a water absorbing layer and a bonding layer are laminated in this order is peelably provided to form this heat-transfer sheet. In this case, the major components of the water-absorbing layer is a mixture of a polyvinyl alcohol, a spherical fine powder silica and a colloidal silica. Then, the protective layer is transferred by the heat-transfer sheet in such a manner that at least one section of an image formed on a base material by the heat transfer method may be covered, to obtain the image printed article.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal transfer sheet and a printed material, and particularly to a printed material having an image on a substrate, which imparts excellent printing and writing properties to an image and at the same time imparts durability. The present invention relates to a heat transfer sheet which can be used and a printed matter having an image excellent in stamping property, writing property and durability.

[0002]

2. Description of the Related Art Conventionally, a binary image such as a gradation image, a character, or a symbol is formed on a base material by using a thermal transfer method. As the thermal transfer method, a heat-sensitive sublimation transfer method and a heat-sensitive fusion transfer method have been widely used. Of these, the thermal sublimation transfer method is a method in which a thermal transfer sheet in which a dye layer in which a sublimable dye used as a coloring material is dissolved or dispersed in a binder resin is carried on a base sheet is superimposed on an image receiving sheet.
In this method, an image is formed by transferring sublimable dye contained in a dye layer on a thermal transfer sheet to an image receiving sheet by applying energy according to image information to a heating device such as a thermal head.

[0003] In the heat-sensitive melt transfer system, a heat transfer sheet having a heat-fusible ink layer containing a coloring agent such as a pigment and a vehicle such as a wax on a base sheet is overlaid on an image-receiving sheet and heated by a thermal head or the like. This is a method of applying an energy corresponding to image information to a device to transfer a softened heat-meltable ink layer component to an image receiving sheet to form an image.

By the way, many cards such as identification cards, driver's licenses, membership cards, etc., and passports, etc., record various types of information which clarify the identity of the owner.
Some include an image of a face photograph along with character information such as an address and a name. As a method of giving a face photograph to various cards, passports, and the like, there is a method of attaching the face photograph to a predetermined portion of the base material using an adhesive, but this method is very complicated in operation, There is a problem that unevenness is generated on the surface, the smoothness is lost, and further, falsification or forgery is easy by replacing a face photograph. For this reason, information is recorded on a base material using the above-described thermal transfer method, in which formation of various images, characters, symbols, and the like is easy.

[0005]

However, images recorded by a thermal sublimation transfer system or a thermal melt transfer system,
In particular, images such as face photographs recorded by the thermal sublimation transfer method are inferior in resistance to friction, chemical resistance to plasticizers and the like, and light resistance. When various durability is required, there is a problem that it cannot be used.

As means for solving such a problem, a thermal transfer sheet having a thermal transferable resin layer is superimposed on an image recorded by a thermal sublimation transfer system or a thermal melt transfer system, and a thermal head or a heating roll is used. Transfer to form a protective layer is known. By providing such a protective layer, the rub resistance, chemical resistance,
Durability such as solvent resistance can be improved to some extent,
Further, light resistance can be improved by adding an ultraviolet absorber or the like to the protective layer. However, the image formed with the protective layer as described above, since the protective layer does not have any water absorption, it can not be used for applications that require stamping such as an aqueous stamp, for example, ID photo applications. Was. Therefore, there is a problem in that when writing characters or pressing a stamp, the types of writing tools and stamp ink that can be used are limited. In addition, when used for ID photos, etc., in order to prevent forgery, higher chemical resistance and solvent resistance are required, and with the conventional protective layer, the resin is sufficiently cured and cross-linked. Even if formed, sufficient durability has not been obtained.

The present invention has been made in view of the above-mentioned circumstances, and provides a thermal transfer sheet capable of imparting excellent printing, writing, and durability to an image formed on an image receiving sheet.
An object of the present invention is to provide a printed matter which is capable of absorbing and fixing a water-based ink, is excellent in stamping and writing properties, and has a durable image.

[0008]

In order to achieve the above object, the thermal transfer sheet of the present invention is provided with a heat transferable protective layer on at least a part of one surface of a substrate sheet so as to be peelable. The water-absorbing layer and the adhesive layer are laminated in this order from the base sheet side, and the water-absorbing layer is mainly composed of a mixture of polyvinyl alcohol, spherical fine powder silica, and colloidal silica. The configuration was adopted.

In a preferred embodiment of the present invention, the spherical fine powder silica is contained in a range of 5 to 500 parts by weight based on 100 parts by weight of polyvinyl alcohol, and the colloidal silica is contained in an amount of 50 to 100 parts by weight of polyvinyl alcohol.
It was configured to be contained in the range of up to 1000 parts by weight.

[0010] In a preferred aspect of the present invention, the heat transferable protective layer includes a primer layer between the water absorbing layer and the adhesive layer, and the primer layer is formed of polyvinylpyrrolidone, a water-soluble polyester resin, an alkyl vinyl ether resin, and maleic acid. It was configured to contain at least one of a copolymer resin, a cellulosic resin, and a water-soluble alkyd resin.

In a preferred aspect of the present invention, the adhesive layer contains at least one of an ultraviolet absorbing resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, an epoxy resin, a polyester resin, and a polycarbonate resin. Configuration.

In a preferred embodiment of the present invention, the transmittance of the heat transferable protective layer is a spectrophotometer UV-3 manufactured by Shimadzu Corporation.
6 in the 400 nm wavelength range measurement with 100PC
% Or more. A preferred embodiment of the present invention is configured such that at least one of a thermosublimable color material layer and a heat-meltable color material layer is provided in a region other than a region on the base sheet where the heat transferable protective layer is formed, in a plane-sequential manner. And

Further, the print of the present invention comprises a substrate, an image formed on at least one surface of the substrate by a thermal transfer method, and a protective layer provided so as to cover at least a part of the image. The protective layer was configured such that the thermal transferable protective layer was formed by transfer using any one of the thermal transfer sheets described above. In a preferred aspect of the present invention, the aqueous ink is imprinted on the protective layer of the print.

In the present invention, the water-absorbing layer containing a mixture of polyvinyl alcohol, spherical finely divided silica, and colloidal silica as a main component is formed so as to be releasable on the base sheet together with the adhesive layer. By transferring this thermal transferable protective layer onto an image, the water-absorbing layer is located on the outermost surface, and the printed matter covered with the protective layer is subjected to printing with an aqueous ink or an aqueous pen. , And has good resistance to externally applied forces, chemicals, light and the like.

[0015]

Embodiments of the present invention will be described below with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the thermal transfer sheet of the present invention. In FIG. 1, the thermal transfer sheet 1 of the present invention includes a heat transferable protective layer 3 on one side of a base sheet 2 so as to be peelable, and a back layer 7 on the other side of the base sheet. The heat transferable protective layer 3 is a laminate in which the water absorbing layer 4 and the adhesive layer 5 are laminated in this order from the base sheet 2 side. The thermal transfer sheet of the present invention may be a thermal transfer sheet 1 ′ having a release layer 8 between the base sheet 2 and the thermal transferable protective layer 3, as shown in FIG.

As the base sheet 2 constituting the thermal transfer sheets 1 and 1 'of the present invention, a base sheet used for a conventional thermal transfer sheet can be used. Preferred base sheet
Examples of glass are thin paper such as glassine paper, condenser paper, and paraffin paper, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ketone, polyether ketone, polyether sulfone and other high heat-resistant polyester, polypropylene, Stretched or unstretched films of plastics such as fluororesin, polycarbonate, cellulose acetate, derivatives of polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polymethylpentene, ionomer, etc. No. The thickness of the base sheet 2 is
Although it can be appropriately selected according to the material so that the strength and heat resistance are appropriate, usually, those having a thickness of about 2 to 100 μm are preferably used.

Thermal transfer protective layer 3 of thermal transfer sheets 1 and 1 '
The functions to be provided by the base sheet 2 during thermal transfer are as follows.
Or, it is surely peeled off (with good foil-cutting property) from the release layer 8 provided thereon, and as a protective layer of a printing screen, it absorbs water-based ink, has water-based printing properties, and has writing properties with a non-oil-based material. That various resistances such as friction resistance and scratch resistance, as well as chemical resistance and solvent resistance can be imparted, that the image is faithfully reproduced with good transparency, and that the image is sharpened over time by ultraviolet rays etc. Not impairing the weather resistance, that is, improving the weather resistance.

The water absorbing layer 4 constituting the heat transferable protective layer 3 is
It is preferable to have not only water absorption performance but also water resistance, solvent resistance, plasticizer resistance and the like. Such a water absorbing layer 4 is mainly composed of a mixture of polyvinyl alcohol, spherical fine silica powder and colloidal silica,
It has a substantially transparent porous structure.

Polyvinyl alcohol functions as a binder for spherical fine powdered silica or colloidal silica, and particularly forms a porous layer by binding each fine particle of colloidal silica. In addition, by curing the binder resin using a known curing agent and a curing method, it is possible to further improve the water resistance and the solvent resistance of the water-absorbing layer, which is preferable. As a curing agent, for example, Sumiresu Pharmaceutical Co., Ltd. Sumiresu resin 5004, Sumiresu resin 613, Daiichi Kogyo Seiyaku Co., Ltd. Elastron W-11, Elastron W-22, Elastron W
−33 or the like can be used. Resins having different degrees of saponification depending on the required level of water resistance can be used. The saponification degree is preferably 70% or more, and if it is in the range, the printability (water absorption) can be sufficiently exhibited.

The spherical fine powder silica is contained for the purpose of imparting aqueous printing properties and writing properties with a non-oil-based material to the water-absorbing layer 4, and has an average particle size of 1 to 50 μm, preferably 4 to 10 μm.
Are preferably used. If the average particle size is less than 1 μm, it is difficult to impart sufficient water absorption and writing properties, and if it exceeds 50 μm, it is difficult to maintain the transparency of the water absorbing layer, which is not preferable.

The content of the fine spherical silica powder is in the range of 5 to 500 parts by weight, preferably 50 to 100 parts by weight, per 100 parts by weight of polyvinyl alcohol. When the content of the spherical fine powder silica is less than 5 parts by weight, it becomes difficult to form a porous structure, and when it exceeds 500 parts by weight, it becomes difficult to maintain the transparency of the water-absorbing layer. Absent.

The colloidal silica is contained for the purpose of imparting the foil absorbability to the water-absorbing layer 4 while maintaining transparency. The content of colloidal silica is polyvinyl alcohol 10
50 to 1000 parts by weight, preferably 100 parts by weight per 0 parts by weight
It is in the range of 300 parts by weight. If the content of colloidal silica is less than 50 parts by weight, it will be difficult to obtain sufficient foil breaking properties, and if it exceeds 1000 parts by weight, the effect of polyvinyl alcohol as a binder resin as a binder will not be obtained. It is not preferable because it is sufficient. The shape of the above colloidal silica is not particularly limited, and may be any shape such as a spherical shape, an acicular shape, and an amorphous shape.However, when spherical particles are used, the particle size is increased in order to increase the porosity of the porous structure. It is desirable to be as uniform as possible. The average particle size of the colloidal silica is 10 to 1000 nm, preferably 100 to 1000 nm.
It is about 500 nm. If the average particle size is less than 10 nm, it is necessary to add a large amount of colloidal silica in order to give desired foil breakability. If the average particle size exceeds 1000 nm, the transparency is insufficient and the peelability is poor, which is not preferable. . Preferred colloidal silicas include, for example, the Snowtex series manufactured by Nissan Chemical Co., Ltd., and the cataloid series manufactured by Catalysis Kasei Kogyo Co., Ltd. further,
By adding additives such as an ultraviolet absorber, an antioxidant, and a fluorescent whitening agent to the water absorbing layer 4, gloss, light resistance, weather resistance, whiteness, and the like of an image or the like covered by the water absorbing layer 4 after being transferred are transferred. Can be improved.

As a method for forming the water-absorbing layer 4 on the base sheet 2, polyvinyl alcohol, spherical finely divided silica and colloidal silica are mixed, and an ink is prepared by adding an additive if necessary. Is coated on the base sheet using a known means such as gravure coating, gravure reverse coating, and roll coating (coating amount: 0.5 to 10 g /
m ² (dry)), followed by drying. The water absorbing layer 4 thus formed has a highly transparent porous structure.

When the release property between the base sheet 2 and the heat transferable protective layer 3 is not appropriate, the release layer 8 adjusts the adhesiveness between the base sheet 2 and the heat transferable protective layer 3 so that the heat transfer property is improved. The protective layer 3 is provided in order to satisfactorily separate the protective layer 3. Such a release layer 8 is made of wax, silicone wax, silicone resin, fluororesin, acrylic resin, water-soluble resin, cellulose derivative resin, urethane resin, acetic acid vinyl resin, acryl vinyl ether resin, maleic anhydride resin. And a coating solution containing at least one copolymer of these resin groups can be formed by coating and drying by a conventionally known coating method, and has a thickness of about 0.1 to 2 μm.

Further, fine irregularities are formed on the surface of the release layer 8, whereby the surface area of the water absorbing layer 4 constituting the heat transferable protective layer 3 can be increased, and the water absorbing performance can be improved. However, when the release layer 8 is provided like the thermal transfer sheet 1 ′, the thermal transferable protective layer 3 is peeled off from the release layer 8 by transfer, and the release layer 8 itself is formed so as to remain on the base sheet 2 side. . That is, it is important that the adhesive strength between the release layer 8 and the base material sheet 2 is higher than the adhesive strength between the release layer 8 and the water absorbing layer 4. It causes abnormal transfer such as transfer of the protective layer 3.

Thermal transfer protective layer 3 of thermal transfer sheets 1 and 1 '
The adhesive layer 5 has a function of facilitating the transfer of the thermal transferable protective layer 3 to the transfer target. As the adhesive forming the adhesive layer 5, at least one of an ultraviolet absorbing resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, an epoxy resin, a polyester resin, and a polycarbonate resin can be used. .

As the above-mentioned ultraviolet absorbing resin, a resin to which a reactive ultraviolet absorbing agent is reactively bonded can be used. Specifically, salicylates, benzophenones, benzotriazoles, substituted acrylonitriles, nickel chelates, which are conventionally known organic ultraviolet absorbers,
Non-reactive ultraviolet absorbers such as hindered amines include, for example, an addition polymerizable double bond such as a vinyl group, an acryloyl group, and a methacryloyl group, or an alcoholic hydroxyl group, an amino group, a carboxyl group, an epoxy group, and an isocyanate group. Can be used. Adhesive layer 5
Can be formed by known means such as gravure coating, gravure reverse coating, and roll coating, and the thickness of the adhesive layer is preferably about 0.5 to 10 μm. Further, the adhesive layer 5 may contain additives such as an antioxidant and a fluorescent whitening agent.

As described above, the overall thickness of the heat transferable protective layer 3, which is a laminate of the water absorbing layer 4 and the adhesive layer 5, is 0.5 to 2 mm.
A range of about 00 μm is preferable. The thermal transferable protective layer 3 is a spectrophotometer UV-3100 manufactured by Shimadzu Corporation.
It is desirable that the transmittance of the PC in the wavelength region of 400 nm is 6% or more, preferably 20% or more. 6 transmittance
%, It is difficult to faithfully reproduce the image on the transfer surface, which is not preferable.

Back layer 7 constituting thermal transfer sheets 1 and 1 '
Is provided for the purpose of preventing heat fusion between a heating device such as a thermal head and the base material sheet 2 and smoothly running. As the resin used for the back layer 7, for example, ethyl cellulose, hydroxy cellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate,
Cellulose resins such as cellulose acetate butyrate, nitrocellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl resins such as polyvinyl pyrrolidone, polymethyl methacrylate,
Acrylic resin such as polyethyl acrylate, polyacrylamide, acrylonitrile styrene copolymer, etc., polyamide resin, polyvinyl toluene resin, coumarone indene resin, polyester resin, polyurethane resin, natural or synthetic such as silicone-modified or fluorine-modified urethane A resin simple substance or a mixture is used. In order to further increase the heat resistance of the back layer 7, use a resin having a hydroxyl group-based reactive group among the above resins, and use a polyisocyanate or the like as a crosslinking agent to form a crosslinked resin layer. Is preferred.

Further, in order to impart slidability with the thermal head, a solid or liquid release agent or lubricant may be added to the back surface layer 7 so as to have heat-resistant lubrication. Examples of the release agent or lubricant include various waxes such as polyethylene wax and paraffin wax, higher aliphatic alcohols, organopolysiloxanes, anionic surfactants,
Use of cationic surfactants, amphoteric surfactants, nonionic surfactants, fluorine surfactants, organic carboxylic acids and derivatives thereof, fluorine resins, silicone resins, fine particles of inorganic compounds such as talc and silica, etc. be able to. The amount of the lubricant contained in the back layer 7 is 5 to 50% by weight, preferably about 10 to 30% by weight. The thickness of such a back layer 7 can be about 0.1 to 10 μm, preferably about 0.5 to 5 μm. When the heat resistance and the slip property of the base sheet 2 are good, the back layer 7 is unnecessary.

In the thermal transfer sheet 1 of the present invention, an easy-adhesion layer may be formed on the substrate sheet 2 for the purpose of improving the adhesiveness between the substrate sheet 2 and the thermal transferable protective layer 3. . The easy-adhesion layer may be any as long as it makes the adhesion between the base sheet 2 and the water-absorbing layer 4 stronger. For example, a polyurethane resin, an acrylic polyol resin, a vinyl chloride-vinyl acetate copolymer, or the like may be used alone or It can be formed by mixing, coating and drying. If necessary, a reactive curing agent such as polyisocyanate may be added, and a titanate or silane coupling agent may be used.

FIG. 3 is a schematic sectional view showing another example of the thermal transfer sheet of the present invention. In FIG. 3, the thermal transfer sheet 11
Is provided with a heat transferable protective layer 13 on one side of the base sheet 12 in a releasable manner, and a back layer 17 on the other side of the base sheet. The heat transferable protective layer 13 is formed of the base sheet 1
2 is a laminate in which a water absorbing layer 14, a primer layer 16, and an adhesive layer 15 are laminated in this order from the second side, except that the primer layer 16 is interposed between the water absorbing layer 14 and the adhesive layer 15; The same as for the protective layer 3. Further, the thermal transfer sheet of the present invention may be a thermal transfer sheet 11 ′ having a release layer 18 between the base sheet 12 and the thermal transferable protective layer 13 as shown in FIG.

The primer layer 16 is formed for the purpose of assisting the water absorbing performance of the water absorbing layer 14 and improving the adhesion between the water absorbing layer 14 and the adhesive layer 15. This primer layer 16
Is a polyvinylpyrrolidone, a water-soluble polyester resin,
It can be formed using at least one of an alkyl vinyl ether resin, a maleic acid copolymer resin, a cellulosic resin, and a water-soluble alkyd resin. The primer layer 16 can be formed by known means such as gravure coating, gravure reverse coating, and roll coating, and the thickness is preferably about 0.1 to 10 μm.

As described above, the water absorbing layer 14 and the primer layer 1
The overall thickness of the heat transferable protective layer 13 which is a laminate of the adhesive layer 6 and the adhesive layer 15 is preferably in the range of about 0.5 to 200 μm. It is also desirable that the thermal transferable protective layer 13 has a transmittance of 6% or more, preferably 20% or more in a 400 nm wavelength region by a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation. The base sheet 12, the water-absorbing layer 14, the adhesive layer 15, the back layer 17, and the release layer 18 constituting the thermal transfer sheets 11, 11 'are the base sheet 2, constituting the above-described thermal transfer sheets 1, 1', Layer 4, adhesive layer 5, back layer 7,
It can be the same as the release layer 8, and the description here is omitted.

FIG. 5 is a schematic sectional view showing another example of the thermal transfer sheet of the present invention. In FIG. 5, the thermal transfer sheet 21
A heat transferable protective layer 23 on one surface of the base sheet 22;
A dye layer 28 (28Y, 28M, 28M) containing a sublimable dye composed of each color of yellow, magenta, cyan, and black.
28C, 28B) are formed face-sequentially, and the base sheet 2
2 is a composite type thermal transfer sheet having a back layer 27 formed on the other surface.

The base sheet 22, the heat transferable protective layer 23 and the back layer 27 constituting the composite thermal transfer sheet 21
The base sheet 2, the heat transferable protective layer 3, and the back layer 7 constituting the above-described thermal transfer sheet 1 can be the same as those described above, and description thereof is omitted here.

Dye layer 2 constituting composite thermal transfer sheet 21
Reference numeral 8 (28Y, 28M, 28C, 28B) denotes a thermosublimable color material layer in which a dye is supported on a binder resin. As the dye to be used, a dye used in a thermal transfer sheet of a conventionally known heat-sensitive sublimation transfer system can be used, and there is no particular limitation. Further, as the binder resin to be used, a binder resin used in a heat transfer sheet of a conventionally known thermal sublimation transfer system can be used, and there is no particular limitation. The dye layer 28 can contain various known additives as necessary in addition to the above-described dye and binder.

The dye layer 28 is formed, for example, by coating or drying an ink prepared by dissolving or dispersing the above dye, binder and other additives in a suitable solvent by a known means such as a gravure coating method. It can be done by doing. In the composite type thermal transfer sheet 21, similarly to the above-described thermal transfer sheet 1, the thermal transferable protective layer 2
For the purpose of improving the adhesiveness between the base material sheet 22 and the dye layer 28 and the base material sheet 22, an easy-adhesion layer may be formed on the base material sheet 22. When the release property between the base sheet 22 and the heat transferable protective layer 23 is not appropriate, a release layer may be formed on the base sheet 22 as in the case of the above-described heat transfer sheet 1 '.

The thermal transfer sheet of the present invention is not limited to the above-mentioned embodiment, but may be a composite thermal transfer sheet comprising a thermal transferable protective layer and a heat-fusible colorant layer, a thermal transferable protective layer, a dye layer and a heat-fusible colorant. It can be arbitrarily set according to the purpose of use, such as a composite thermal transfer sheet with a material layer. In particular, by forming a composite thermal transfer sheet, it is possible to simultaneously perform image formation by the thermal transfer method and transfer of the thermal transferable protective layer to the transfer target.

Next, the printed matter of the present invention will be described.
FIG. 6 is a schematic sectional view showing an example of the print of the present invention.
In FIG. 6, a print 31 has an image receiving sheet 32 and an image 33 recorded on one surface of the image receiving sheet 32 by a heat-sensitive sublimation transfer method or a heat-sensitive fusion transfer method, and is provided so as to cover the image 33. Protective layer 34 provided. The image 33 is composed of a full-color image 33a of three colors of yellow, magenta and cyan, or four colors with black added as necessary, and a binary image 33b of characters and symbols.

In the print 31 shown in FIG. 6 described above, the entire image 33 is covered with the protective layer 34.
Reference numeral 4 has a two-layer structure in which an adhesive layer 35 and a water absorbing layer 36 are stacked from the image receiving sheet 32 side. The protective layer 34 having the two-layer structure is formed by transferring the thermal transferable protective layer 3 so as to cover the image 33 using the above-described thermal transfer sheet 1 of the present invention. Therefore, on the outermost surface of the protective layer 34, the water-absorbing layer 36 mainly composed of a mixture of polyvinyl alcohol, spherical fine silica powder and colloidal silica is located,
In the printed matter 31 of the present invention, the image 33 is given good resistance to external force, chemicals, light, and the like by the protective layer 34, and can be stamped with an aqueous stamp ink or written with an aqueous pen. It has become possible.
Incidentally, the adhesive layer 35 and the water absorbing layer 36 constituting the protective layer 34 are
These correspond to the adhesive layer and the water-absorbing layer that constitute the thermal transferable protective layer of the thermal transfer sheet of the present invention, respectively, and description thereof is omitted here.

The formation of the image 33 on the image receiving sheet 32 can be performed by a known heat-sensitive sublimation transfer method or a heat-sensitive melt transfer method, or a heat transfer protective layer and a dye layer or a heat meltable color material layer as described above. This can be performed using the composite type thermal transfer sheet of the present invention comprising:

The image receiving sheet 32 is made of a plastic sheet such as a polyester resin, a vinyl chloride resin, a vinyl chloride-vinyl acetate copolymer resin, or a polycarbonate, or a card substrate, or a resin layer having a dye receptive property (image receiving layer). A) a heat transfer image-receiving sheet provided on a base sheet described later, a film or sheet made of these resins,
It may be a molded product or the like. Examples of the resin having dye receptivity include polyolefin resins such as polypropylene, halogenated resins such as polyvinyl chloride and polyvinylidene chloride, polyvinyl acetates, vinyl resins such as various polyacrylates, polyethylene terephthalate, and polybutylene terephthalate. Polyester resins, polystyrene resins such as polystyrene or copolymers thereof, polyamide resins, copolymer resins of olefins such as ethylene and propylene with other vinyl monomers, cellulose resins such as ionomers, cellulose diacetate and cellulose triacetate Resins, polycarbonates and the like can be mentioned, and a release agent such as silicone oil for preventing fusion with the thermal transfer sheet of the present invention may be contained in these resin layers.

As a sheet base material used for the image receiving sheet 32, synthetic paper (polyolefin type, polystyrene type);
Fine fiber paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin solution or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, and other natural fiber paper such as cellulose fiber paper; Films and sheets of various plastics such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethyl methacrylate, and polycarbonate can be used, and any composite thereof can also be used. Among them, the synthetic paper preferably has a microvoid layer with low thermal conductivity (high heat insulation) on its surface.

On the dye receiving surface of the image receiving sheet 32,
Color pigments, white pigments, extender pigments, fillers, ultraviolet absorbers, antistatic agents, heat stabilizers, antioxidants, fluorescent brighteners, and the like can also be arbitrarily contained. Further, the image receiving sheet 32 may be provided with a magnetic recording layer, an optical memory, an IC memory, a bar code, or the like on the surface thereof in advance or after recording an image. The printed matter of the present invention is not limited to the above-described example, and has an image formed on any substrate by a thermal transfer method, and at least a part of this image, particularly formed by a heat-sensitive sublimation transfer method. A protective layer is provided so as to cover the image.

[0046]

Next, the present invention will be described in more detail with reference to more specific examples.

Example 1 A back layer ink having the following composition was applied to one surface of a polyethylene terephthalate film (Lumirror, manufactured by Toray Industries, Ltd.) having a thickness of 6 μm by a gravicoat method (coating amount: 1.0 g / m 2). ² (at the time of drying)), dried, and then subjected to a curing treatment to form a back layer. (Composition of the ink for the back layer) Polyvinyl butyral: 15 parts by weight (ESREC BX-1 manufactured by Sekisui Chemical Co., Ltd.) Polyisocyanate: 35 parts by weight (Barnock D450 manufactured by Dainippon Ink and Chemicals, Inc.) Phosphoric acid Ester surfactant: 10 parts by weight (Plysurf A208S manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Talc (Microace P-3 manufactured by Nippon Talc Co., Ltd.): 3 parts by weight

Next, on the surface opposite to the surface on which the back layer was formed,
Gravure coating method by applying a release layer for the ink of the following composition (coating amount 0.7 g / m ² (dry)) and dried to form a release layer, water absorption of the following composition in the releasing layer Layer ink by gravure coating method (coating amount 0.5 g / m
² (at the time of drying) and dried to form a water-absorbing layer. (Composition of ink for release layer)-Silicone-modified acrylic resin ... 16 parts by weight (Celltop 226 manufactured by Daicel Chemical Industries, Ltd.)-Aluminum catalyst ... 3 parts by weight (Celltop CAT- manufactured by Daicel Chemical Industries, Ltd.) A) ・ Methyl ethyl ketone: 8 parts by weight ・ Toluene: 8 parts by weight

(Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle diameter) 4.5 μm)… 3 parts by weight (Sylosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.) ・ Colloidal silica (average particle size 150 nm)… 15 parts by weight (Snowtex O manufactured by Nissan Chemical Industry Co., Ltd.) ・ Water… 30 parts by weight ・ Isopropyl alcohol… 21 parts by weight

Further, an ink for a primer layer having the following composition was applied onto the water-absorbing layer by a gravure coating method (coating amount: 0.4 g / m ² (at the time of drying)) and dried to form a primer layer. An ink for an adhesive layer having the following composition was applied thereon by a gravure coating method (coating amount: 1.5 g / m2).
² ((drying)) and dry to form an adhesive layer,
A thermal transfer sheet provided with a thermal transferable protective layer, which is a laminate of a primer layer and an adhesive layer, was obtained. (Composition of ink for primer layer) ・ Polyvinyl pyrrolidone (PVP) resin ... 50 parts by weight (K-90 manufactured by ISP Co., Ltd.) ・ Methyl ethyl ketone ... 25 parts by weight ・ Isopropyl alcohol ... 25 parts by weight

(Composition of Ink for Adhesive Layer) ・ Polyester resin ... 12 parts by weight (Byron 700 manufactured by Toyobo Co., Ltd.) ・ Acrylic copolymer of ultraviolet absorber ... 3 parts by weight (UVA635L manufactured by BASF Japan Co., Ltd.) ・ Dioxide Silicon powder (average particle size: 1.4 μm)… 2.25 parts by weight (Silicia 310, manufactured by Fuji Silysia Chemical Ltd.)

On the surface of the polyethylene terephthalate film having the back layer formed thereon in the same manner as described above, the respective inks for the dye layer having the following composition were applied by gravure coating to yellow, magenta and cyan. 15cm in length in the order of (the length of the base sheet in the flow direction)
In the coating to prepare a thermal transfer sheet (coating weight 3 g / m ² (dry)) and dried to 3 color thermal sublimation transfer method. (Yellow ink)-Yellow dye: 5.5 parts by weight (Macrolex Yellow 6G manufactured by Bayer)-Polyvinyl butyral ... 4.5 parts by weight (ESREC BX-1 manufactured by Sekisui Chemical Co., Ltd.)-Methyl ethyl ketone / toluene (weight ratio) 1/1) ... 90.0 parts by weight

(Magenta ink)-Magenta dye: 5.5 parts by weight (CI Disperse Red 60)-Polyvinyl butyral ... 4.5 parts by weight (ESREC BX-1 manufactured by Sekisui Chemical Co., Ltd.)-Methyl ethyl ketone / Toluene (weight ratio 1/1) 90.0 parts by weight

(Cyan ink) Cyan dye: 5.5 parts by weight (CI Solvent Blue 63) Polyvinyl butyral: 4.5 parts by weight (ESREC BX-1 manufactured by Sekisui Chemical Co., Ltd.) Methyl ethyl ketone / Toluene (weight ratio 1/1) 90.0 parts by weight

Next, synthetic paper (manufactured by Oji Yuka Synthetic Paper Co., Ltd.)
On one surface of YUPO FRG-150 (thickness: 150 μm), a coating solution for a dye receiving layer having the following composition is applied by a bar coater (coating amount: 4 g / m ² (at the time of drying)) and dried to form a dye receiving layer. And used as a base material. A printer (P-330 manufactured by Olympus Optical Co., Ltd.) in which the dye-coated surface of the thermal transfer sublimation transfer type heat transfer sheet is superimposed on the dye receiving layer of the base material and connected to an electric signal obtained by color separation of a face photograph. Using the thermal head of (1), heat energy was applied from the back layer side of the thermal transfer sheet, and sublimation transfer was performed in the order of cyan, magenta and yellow to form a full-color image. (Composition of the coating solution for the dye receiving layer)-Vinyl chloride-vinyl acetate copolymer ... 20 parts by weight (Electric Vinyl 1000A manufactured by Denki Kagaku Kogyo Co., Ltd.)-Epoxy modified silicone oil ... 1 part by weight (Shin-Etsu Chemical Co., Ltd.) X-22-2900T) ・ Methyl ethyl ketone / toluene (weight ratio 1/1) ... 80 parts by weight

Next, the above-mentioned thermal transfer sheet is overlaid so as to cover the full-color image formed as described above, and the thermal transferable protective layer is transferred using a printer (P-330, manufactured by Olympus Optical Industrial Co., Ltd.) to protect it. A print having an image with layers was prepared.

With respect to the thermal transfer sheet and the printed matter produced as described above, the printing property, the foil cutting property, the transparency and the transfer property were evaluated by the following methods, and the results are shown in Table 1 below. (Sealability) Stamp ink (Gutenberg En
The stamp with the adhesive layer (manufactured by Dorsing Co., Ltd.) is pressed against the image surface with the protective layer of the print, left for 10 minutes, removed, rubbed with the finger, and evaluated whether the ink is fixed by the following criteria. did. Evaluation criteria ◎: The outline of the character remains clearly ○: The outline of the character remains sufficiently △: The character can be read but the outline is considerably unclear ×: Not fixed

(Foil-cutting property) The surface of the print after the transfer of the heat-transferable protective layer and the transfer edge portion of the thermal transfer sheet are visually observed, and whether the foil cut is uniform or no tailing occurs. Was evaluated according to the following criteria. Evaluation criteria ◎: no tailing, no problem ○: tailing less than 0.5 mm, but no practical problem △: tailing 0.5 mm or more and less than 5 mm ×: tailing more than 5 mm

(Transparency) Regarding the thermal transfer sheet,
The transmittance in the wavelength region of 400 nm was measured using a spectrophotometer UV-3100PC manufactured by Shimadzu Corporation, and the measured transmittance was defined as the transmittance of the thermal transferable protective layer. The measurement sample was a 6 μm thick polyethylene terephthalate film (Lumirror manufactured by Toray Industries, Inc.)
The ink for a water-absorbing layer of each of Examples and Comparative Examples was applied thereon by a gravure coating method. Light source uses 50W halogen lamp, scan speed is high, slit width is 20m
m and the sampling bit were 0.2 mm. Further, among the full-color images, O.O.
D. At a value around 2.0, the degree of decrease in density after transfer with respect to that before transfer of the heat transferable protective layer was determined by Macbet.
It was measured by RD-918 manufactured by Company h and evaluated according to the following criteria. Evaluation criteria ：: Decrease rate is less than 10%, there is hardly any decrease in density ×: Density decrease is 10% or more

(Transferability) In the print after transfer of the heat transferable protective layer, whether the protective layer was firmly transferred to the print was evaluated according to the following criteria. Evaluation criteria ：: peeled off at the interface between the release layer and the water-absorbing layer, and only the thermal transferable protective layer was transferred. ×: peeled off at the interface other than the interface between the release layer and the water-absorbing layer. Is not transferred, or part of the heat transferable protective layer is not transferred

Example 2 A thermal transfer sheet was prepared in the same manner as in Example 1, except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) ) ... 3 parts by weight (Sylosphere C-1504, manufactured by Fuji Silysia Chemical Ltd.)-Colloidal silica (average particle size: 150 nm)-15 parts by weight (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.)-Hardening agent ... 25 parts by weight (Sumireth Resin 5004 manufactured by Sumitomo Pharma Co., Ltd.) ・ Water: 30 parts by weight ・ Isopropyl alcohol: 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 3 A heat transfer sheet was prepared in the same manner as in Example 1 except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of ink for water absorbing layer)-Polyvinyl alcohol (PVA) resin ... 3 parts by weight (KP-06 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 71.0-74.0%)-Spherical fine powder silica ( Average particle size 4.5 μm) 3 parts by weight (Sylosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size 150 nm) 15 parts by weight (Snowtex O manufactured by Nissan Chemical Industry Co., Ltd.)・ Water: 40 parts by weight ・ Isopropyl alcohol: 30 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 4 A thermal transfer sheet was prepared in the same manner as in Example 1 except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of ink for water absorbing layer)-Polyvinyl alcohol (PVA) resin ... 3 parts by weight (KH-17 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree: 78.5 to 81.5%)-Spherical fine powder silica ( Average particle size 4.5 μm) 3 parts by weight (Sylosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size 150 nm) 15 parts by weight (Snowtex O manufactured by Nissan Chemical Industry Co., Ltd.)・ Water: 40 parts by weight ・ Isopropyl alcohol: 30 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 5 A thermal transfer sheet was produced in the same manner as in Example 1 except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of ink for water absorbing layer)-Polyvinyl alcohol (PVA) resin ... 3 parts by weight (GL-03 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree 86.5 to 89.0%)-Spherical fine powder silica ( Average particle size 4.5 μm) 3 parts by weight (Sylosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size 150 nm) 15 parts by weight (Snowtex O manufactured by Nissan Chemical Industry Co., Ltd.)・ Water: 40 parts by weight ・ Isopropyl alcohol: 30 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 6 A thermal transfer sheet was prepared in the same manner as in Example 1 except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of ink for water absorbing layer)-Polyvinyl alcohol (PVA) resin ... 3 parts by weight (GH-23, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., degree of saponification 86.5 to 89.0%)-Spherical fine powder silica ( Average particle size 4.5 μm) 3 parts by weight (Sylosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size 150 nm) 15 parts by weight (Snowtex O manufactured by Nissan Chemical Industry Co., Ltd.)・ Water: 40 parts by weight ・ Isopropyl alcohol: 30 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 7 A thermal transfer sheet was prepared in the same manner as in Example 1 except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of ink for water-absorbing layer)-Polyvinyl alcohol (PVA) resin ... 3 parts by weight (NL-05 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree 98.5% or more)-Spherical fine powder silica (average particle size) 4.5 μm) 3 parts by weight (Sylosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.) ・ Colloidal silica (average particle size 150 nm) ... 15 parts by weight (Snowtex O manufactured by Nissan Chemical Industries, Ltd.) ・ Water… 40 parts by weight ・ Isopropyl alcohol… 30 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 8 A thermal transfer sheet was produced in the same manner as in Example 1 except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of ink for water-absorbing layer)-Polyvinyl alcohol (PVA) resin ... 3 parts by weight (NH-26 manufactured by Nippon Synthetic Chemical Industry Co., Ltd., saponification degree 99.4% or more)-Spherical fine powder silica (average particle diameter) 4.5 μm) 3 parts by weight (Sylosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.) ・ Colloidal silica (average particle size 150 nm) ... 15 parts by weight (Snowtex O manufactured by Nissan Chemical Industries, Ltd.) ・ Water… 40 parts by weight ・ Isopropyl alcohol… 30 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 9 The ink for a water-absorbing layer having the following composition was used as the ink for a water-absorbing layer, and the coating amount (at the time of drying) of the ink for a water-absorbing layer was 1.0 g / m ² . A thermal transfer sheet was produced in the same manner as in Example 1. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) ) ... 0.15 parts by weight (Silosphere C-1504, manufactured by Fuji Silysia Chemical Ltd.)-Colloidal silica (average particle size: 150 nm)-7.5 parts by weight (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.)-Water … 30 parts by weight ・ Isopropyl alcohol… 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 10 A primer layer made of a polyester resin was formed using WR-961 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. as an ink for a primer layer.
A thermal transfer sheet was produced in the same manner as in Example 1. Further, a full-color image was formed in the same manner as in Example 1, and the thermal transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Produced. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 11 A water-absorbing layer was formed at an application amount (at the time of drying) of the ink for a water-absorbing layer of 1.0 g / m ^{2, and} was used as an ink for a primer layer by Nippon Gohsei Co., Ltd.
A heat transfer sheet was produced in the same manner as in Example 1, except that a primer layer made of a polyester resin was formed using WR-961. Further, a full-color image was formed in the same manner as in Example 1, and the thermal transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Produced. Example 1 of the thermal transfer sheet and the printed matter produced as described above
In the same manner as in the above, the stamping property, foil cutting property, transparency and transferability were evaluated, and the results are shown in Table 1 below.

Example 12 A thermal transfer sheet was prepared in the same manner as in Example 1, except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) ) ... 0.15 parts by weight (Sylosphere C-1504, manufactured by Fuji Silysia Chemical Ltd.)-Colloidal silica (average particle size: 150 nm)-150 parts by weight (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.)-Water ... 30 Parts by weight ・ Isopropyl alcohol… 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 13 A thermal transfer sheet was prepared in the same manner as in Example 12, except that the amount of the ink for the water-absorbing layer (at the time of drying) was changed to 1.0 g / m ² . Example 1
A full-color image was formed in the same manner as described above, and the thermal transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image, thereby producing a print having an image with the protective layer. With respect to the thermal transfer sheet and the printed matter produced as described above, in the same manner as in Example 1, the printing property, the foil cutting property,
The transparency and transferability were evaluated, and the results are shown in Table 1 below.

Example 14 A thermal transfer sheet was produced in the same manner as in Example 1, except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) 15 parts by weight (Sylosphere C-1504, manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size: 150 nm) 7.5 parts by weight (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.) Water 30 Parts by weight ・ Isopropyl alcohol… 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 15 A thermal transfer sheet was prepared in the same manner as in Example 14, except that the amount of the ink for the water-absorbing layer (at the time of drying) was changed to 1.0 g / m ² . Example 1
A full-color image was formed in the same manner as described above, and the thermal transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image, thereby producing a print having an image with the protective layer. With respect to the thermal transfer sheet and the printed matter produced as described above, in the same manner as in Example 1, the printing property, the foil cutting property,
The transparency and transferability were evaluated, and the results are shown in Table 1 below.

Example 16 A thermal transfer sheet was prepared in the same manner as in Example 1 except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) ) ... 0.15 parts by weight (Silosphere C-1504, manufactured by Fuji Silysia Chemical Ltd.)-Colloidal silica (average particle size: 150 nm)-7.5 parts by weight (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.)-Water … 30 parts by weight ・ Isopropyl alcohol… 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 17 A thermal transfer sheet was prepared in the same manner as in Example 1 except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) 15 parts by weight (Silosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size 150 nm) 150 parts by weight (Snowtex O manufactured by Nissan Chemical Industries, Ltd.) Water 30 parts by weight・ Isopropyl alcohol: 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

Example 18 A thermal transfer sheet was produced in the same manner as in Example 1 except that no primer layer was formed. Further, a full-color image was formed in the same manner as in Example 1, and the thermal transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Produced. About the thermal transfer sheet and printed matter produced as described above, in the same manner as in Example 1,
The sealability, foil breakability, transparency and transferability were evaluated, and the results are shown in Table 1 below.

Example 19 A thermal transfer sheet was prepared in the same manner as in Example 1 except that the amount of the ink for the water-absorbing layer (at the time of drying) was 1.0 g / m ² and no primer layer was formed. did. Further, a full-color image is formed in the same manner as in Example 1, and the formed full-color image is covered.
The thermal transferable protective layer was transferred under the same conditions as in Example 1 to produce a print having an image with the protective layer. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, the foil cutting property, the transparency and the transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 1 below.

[Comparative Example 1] A water-absorbing layer ink having the following composition was used as the water-absorbing layer ink, the applied amount (at the time of drying) of the water-absorbing layer ink was 10 g / m ² , and no primer layer was formed. In the same manner as in Example 1, a thermal transfer sheet was produced. (Composition of ink for water absorbing layer) Polyvinyl alcohol (PVA) resin: 3 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Colloidal silica (average particle diameter: 50 nm): 100 weight (Snowtex OL manufactured by Nissan Chemical Industries, Ltd.)-Isopropyl alcohol: 20 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, foil cutting property, transparency and transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 2 A thermal transfer sheet was prepared in the same manner as in Example 1 except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) ) ... 0.03 parts by weight (Sylosphere C-1504, manufactured by Fuji Silysia Chemical Ltd.)-Colloidal silica (average particle size: 150 nm)-225 parts by weight (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.)-Water ... 30 Parts by weight ・ Isopropyl alcohol… 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, foil cutting property, transparency and transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 3 A thermal transfer sheet was prepared in the same manner as in Comparative Example 2 except that the amount of the ink for the water-absorbing layer (at the time of drying) was changed to 1.0 g / m ² . Further, a full-color image was formed in the same manner as in Example 1, and the thermal transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Produced.
With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, foil cutting property, transparency and transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 4 A thermal transfer sheet was prepared in the same manner as in Example 1 except that a water absorbing layer ink having the following composition was used as the water absorbing layer ink. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) ) ... 0.15 parts by weight (Sylosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.)-Colloidal silica (average particle size 150 nm)-225 parts by weight (Snowtex O manufactured by Nissan Chemical Industries, Ltd.)-Water ... 30 Parts by weight ・ Isopropyl alcohol… 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, foil cutting property, transparency and transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 5 A thermal transfer sheet was prepared in the same manner as in Example 1, except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) 15 parts by weight (Silosphere C-1504 manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size 150 nm) 225 parts by weight (Snowtex O manufactured by Nissan Chemical Industries, Ltd.) Water 30 parts by weight・ Isopropyl alcohol: 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, foil cutting property, transparency and transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 6 A thermal transfer sheet was prepared in the same manner as in Example 1 except that a water absorbing layer ink having the following composition was used as the water absorbing layer ink. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) 21 parts by weight (Sylosphere C-1504, manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size: 150 nm) 1.5 parts by weight (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.) Water 30 Parts by weight ・ Isopropyl alcohol… 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printing property, the foil cutting property, the transparency and the transfer property were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 7 A thermal transfer sheet was produced in the same manner as in Comparative Example 6, except that the coating amount (at the time of drying) of the ink for the water-absorbing layer was changed to 1.0 g / m ² . Further, a full-color image was formed in the same manner as in Example 1, and the thermal transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Produced.
With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, foil cutting property, transparency and transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 8 A thermal transfer sheet was prepared in the same manner as in Example 1, except that the ink for a water absorbing layer having the following composition was used as the ink for a water absorbing layer. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) 15 parts by weight (Sylosphere C-1504, manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size: 150 nm) 7.5 parts by weight (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.) Water 30 Parts by weight ・ Isopropyl alcohol… 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, foil cutting property, transparency and transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

Comparative Example 9 A thermal transfer sheet was prepared in the same manner as in Example 1 except that a water absorbing layer ink having the following composition was used as the water absorbing layer ink. (Composition of water-absorbing layer ink) Polyvinyl alcohol (PVA) resin: 25 parts by weight (Poval C-318 manufactured by Kuraray Co., Ltd., saponification degree: 84 to 86%) Spherical fine powder silica (average particle size: 4.5 μm) 21 parts by weight (Syrosphere C-1504, manufactured by Fuji Silysia Chemical Ltd.) Colloidal silica (average particle size: 150 nm) 150 parts by weight (Snowtex O, manufactured by Nissan Chemical Industries, Ltd.) Water: 30 parts by weight・ Isopropyl alcohol: 21 parts by weight

Further, a full-color image was formed in the same manner as in Example 1, and the heat-transferable protective layer was transferred under the same conditions as in Example 1 so as to cover the formed full-color image. Prints were made. With respect to the thermal transfer sheet and the printed matter produced as described above, the printability, foil cutting property, transparency and transferability were evaluated in the same manner as in Example 1, and the results are shown in Table 2 below.

[0107]

[Table 1]

[0108]

[Table 2]

As shown in Table 1, the thermal transfer sheets of the present invention (Examples 1 to 19) had good foil breaking properties, transparency and transferability, and were protected by using these thermal transfer sheets. It was confirmed that the print having the layer formed had good printability and transparency. On the other hand, as shown in Table 2, in Comparative Examples 1 to 9 in which the content of the fine powdered silica and the colloidal silica was out of the range of the present invention, the foil cutting properties, transfer properties, and printing properties were not at practical levels. Alternatively, the transparency was low, the density was significantly reduced, and the image reproducibility was poor.

[0110]

As described above in detail, according to the present invention, at least a part of one surface of the base sheet is made of a water-absorbing material containing a mixture of polyvinyl alcohol, spherical fine powder silica and colloidal silica as a main component. A thermal transfer protective layer in which a layer and an adhesive layer are laminated in this order is provided in a releasable manner to form a thermal transfer sheet. Since the thermal transfer protective layer is transferred onto the image and the water-absorbing layer is located on the outermost surface, the thermal transfer sheet is covered with the protective layer. The image has excellent printing, writing, and durability, and can be printed with water-based ink or written with a water-based pen. It has good resistance. Further, the printed matter in which an image is formed on the base material by the thermal transfer method, since at least a part of the image is covered with the protective layer, the printing property,
An image having excellent writing characteristics and durability is provided.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing one embodiment of a thermal transfer sheet of the present invention.

FIG. 2 is a schematic sectional view showing another embodiment of the thermal transfer sheet of the present invention.

FIG. 3 is a schematic sectional view showing another embodiment of the thermal transfer sheet of the present invention.

FIG. 4 is a schematic sectional view showing another embodiment of the thermal transfer sheet of the present invention.

FIG. 5 is a schematic sectional view showing another embodiment of the thermal transfer sheet of the present invention.

FIG. 6 is a schematic cross-sectional view illustrating an example of a print of the present invention.

[Explanation of symbols]

 1, 1 ', 11, 11' ... thermal transfer sheet 2, 12 ... base sheet 3, 13, 23 ... thermal transferable protective layer 4, 14, 24 ... protective layer 5, 15, 25 ... adhesive layer 16 ... primer layer 7 , 17, 27 ... Back layer 8, 18 ... Release layer 28 (28Y, 28M, 28C, 28B) ... Dye layer 31 ... Printed matter 32 ... Image receiving sheet 33 ... Image 34 ... Protective layer 35 ... Adhesive layer 36 ... Water absorbing layer

Of the front page Continued (51) Int.Cl. ⁷ identification mark FI theme Court Bu (Reference) B41M 5/40 B41M 5/26 101B B F term (reference) 2C068 AA06 AA22 BB25 BB27 BB33 BD15 BD23 2H111 AA26 AA27 AA52 BA11 BA32 BA53 BA61

Claims (8)

[Claims] 1. A heat transferable protective layer is provided on at least a part of one surface of a substrate sheet so as to be peelable, and the heat transferable protective layer has a water absorbing layer and an adhesive layer laminated in this order from the substrate sheet side. Wherein the water-absorbing layer is mainly composed of a mixture of polyvinyl alcohol, spherical fine silica powder and colloidal silica. 2. The spherical fine powdered silica is contained in an amount of 5 to 500 parts by weight based on 100 parts by weight of polyvinyl alcohol, and the colloidal silica is added in an amount of 50 to 1000 parts by weight based on 100 parts by weight of polyvinyl alcohol. The thermal transfer sheet according to claim 1, wherein: 3. The heat transferable protective layer comprises a primer layer between the water absorbing layer and the adhesive layer, wherein the primer layer comprises polyvinyl pyrrolidone, a water-soluble polyester resin, an alkyl vinyl ether resin, a maleic acid copolymer resin, The thermal transfer sheet according to claim 1, wherein the thermal transfer sheet contains at least one of a cellulosic resin and a water-soluble alkyd resin. 4. The adhesive layer according to claim 1, wherein the adhesive layer contains at least one of an ultraviolet absorbing resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer resin, an epoxy resin, a polyester resin, and a polycarbonate resin. The thermal transfer sheet according to any one of claims 1 to 3. 5. The transmittance of the heat transferable protective layer is determined by
4 by Shimadzu Spectrophotometer UV-3100PC
The thermal transfer sheet according to any one of claims 1 to 4, wherein the ratio is 6% or more in a measurement in a 00 nm wavelength region. 6. A heat-sublimable color material layer and / or a heat-meltable color material layer are provided in a region other than a region where the heat transferable protective layer is formed on the base sheet in a plane-sequential manner. The thermal transfer sheet according to claim 1. 7. A base material, an image formed on at least one surface of the base material by a thermal transfer method, and a protective layer provided so as to cover at least a part of the image. A print, wherein a thermal transferable protective layer is formed by transfer using the thermal transfer sheet according to any one of claims 1 to 6. 8. The printed matter according to claim 7, wherein an aqueous ink is imprinted on the protective layer of the printed matter.