JP2618372B2 - Heat transfer sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat-transferable sheet, and more particularly to a heat-transferable sheet, which can form an arbitrary image with a sublimable dye (heat transfer dye) and paste the formed image on an arbitrary article. Provided is a heat transferable sheet that can be attached.

[0002]

2. Description of the Related Art Conventionally, a thermal transfer (sublimation transfer) method of a fabric using a sublimable dye has been performed for a long time. In this method, a dye pattern layer carrying a sublimable dye is formed on a sheet-like substrate. This is a method in which the dye pattern is transferred to the fabric by heating the fabric over the fabric. Utilizing this technology, coupled with the recent development of image technologies such as precision thermal printers, a variety of precise image forming methods that are not inferior to photographs on plastic films from thermal transfer sheets having a sublimable dye layer on the entire surface have been proposed. Have been. According to this recent method, for example, a camera image, a television image, a graphic image of a personal computer, or the like can be easily copied onto a sheet-like base material such as paper having a polyester layer. Or a level that can sufficiently compete with precision printing technology.

[0003]

The thermal transfer technique as described above has an advantage that an arbitrary image can be easily formed. However, the thermal transfer sheet is limited to a material which can be dyed with a sublimable dye such as polyester. Problem.
On the other hand, the shape of the transferred article is limited to a sheet-like material such as a film or a sheet.
An image cannot be formed on glass, ceramics, and the like. Further, even if plastics such as polyester are used, their image forming surfaces are curved, uneven, or even planar. However, there is a problem that it is difficult to form an image on a three-dimensional molded article other than the sheet-shaped article.

In particular, as the types and fields of use of various cards such as cash cards have expanded in recent years, it is necessary to add images and symbols to these cards to give them various functions and decorations. These cards are flat, but have no flexibility, or have irregularities such as characters and symbols, so that it is difficult to give images to these cards by the above-described thermal transfer method. As a method of solving such a drawback, there is a method of sticking a picture sticker having a desired image to a desired place of an article to be decorated.
In this method, since the sealing material is relatively thick, the sticking portion is discharged, and there is a disadvantage that there is no sense of unity between the seal and the article to be decorated, and that the seal is easily peeled off.

As a method that does not cause such a defect, there is a method using a thermal transfer method using transfer paper.
This method has a drawback that a heating means is always required at the time of transferring an image, and also has a problem that it is difficult to transfer a complicated uneven surface as described above. Therefore, the development of a technology that can easily give a desired image to the surface of an article made of an arbitrary material, having an arbitrary shape and an arbitrary surface shape, and integrating the image and the article to be decorated. Is required.

[0006]

That is, the present invention is characterized in that an image-receiving layer which can be peeled off via a protective layer and which can be dyed with a sublimable dye is provided on one surface of a sheet-like substrate. Is a heat transfer sheet.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail with reference to the accompanying drawings, which schematically show embodiments. FIG.
1 is a diagram schematically illustrating a basic form of a heat transfer sheet of the present invention, and FIGS. 2 to 5 are diagrams illustrating a preferred embodiment of a heat transfer sheet of the present invention. As shown in FIG. 1, the basic configuration of the heat transfer sheet 10 of the present invention is characterized in that an image receiving layer 2 that can be peeled off via a protective layer 5 is provided on one surface of an arbitrary sheet-like substrate 1. And With the heat transfer sheet of the present invention having such a structure, a desired image is formed on the image receiving layer 2 by the heat transfer sheet having a sublimable dye, and then the image receiving layer 2 having the image is protected from the sheet-like substrate 1. By peeling off together with the layer 5 and sticking it to any article by any means, the disadvantages of the prior art as described above are basically solved.

That is, the image receiving layer 2 is limited to a material which can be dyed with a sublimable dye. Depending on the method, glass, metal, wood, or a plastics material which is difficult to dye with a sublimable dye can be freely attached. Further, since the image receiving layer 2 and the protective layer 5 having an image and peeled from the sheet-like base material are very thin and have sufficient flexibility, the surface shape of the article to be decorated is a curved surface or an uneven surface. Can sufficiently follow these surface shapes. Therefore, sticking is not limited by the surface shape of the article to be decorated.

Also, since the image receiving layer 2 and the protective layer 5 having an image are also very thin, unlike conventional seals, they can be easily integrated with the article to be decorated, and there is no swelling of the sticking portion. It does not give a so-called sticking feeling. FIG. 2 shows a preferred example of the heat transfer sheet 10 of the present invention,
Release layers 3 and 3 ′ are provided on the surface of the image receiving layer 2 or between the protective layer 5 and the sheet-like substrate 1 or both. Release layer 3
Is to prevent the heat transfer sheet and the image receiving layer 2 from sticking to each other by transferring a sublimable dye from a heat transfer sheet (not shown) to form an image on the image receiving layer 2. This is not necessary when there is no such release or when such a release layer is provided on the surface of the thermal transfer sheet. Release layer 3 '
Is provided to facilitate peeling of the protective layer 5 after image formation, and is provided when the sheet-like substrate 1 is difficult to peel from the protective layer 5 like paper. If the sheet-like substrate 1 itself has a sufficient releasability from the protective layer 5 as in the case of a polyester film or the like, it is not particularly essential.

3 to 5 are different from the example of FIG. 2 in that an intermediate layer 4 is provided between the image receiving layer 2 and the base material 1 on the sheet. The protective layer 5 prevents deterioration of the image of the image receiving layer 2 when the image receiving layer 2 from which the image has been formed and peeled is adhered with the surface (image forming surface) of the image receiving layer 2 facing the article to be decorated. is there. The protective layer 5 is formed of a material having various physical properties such as abrasion resistance, light resistance, weather resistance, and chemical resistance. By providing such a protective layer 5, it is possible to improve various fastnesses of an image adhered to the article to be decorated.

The intermediate layer 4 is used to transfer a sublimable dye from the thermal transfer sheet to the image receiving layer 2 to form an image.
It is a cushion layer and a heat insulating layer. For example, by providing a layer having a cushioning property as the intermediate layer 4, the adhesiveness between the thermal transfer sheet and the image receiving layer 2 is improved, and the transfer of the sublimable dye at the time of image formation by the thermal head is made uniform, so that an image signal is obtained. A sufficiently compatible image can be formed.

Further, by forming the intermediate layer 4 as a heat insulating layer from a material having heat insulating properties, it is possible to prevent the heat applied from transferring the sublimable dye from the thermal transfer sheet to the image receiving layer 2, thereby preventing the heat radiation. The utilization efficiency is improved, and the formation of a sufficient image is promoted. Of course, these cushion layers or heat insulating layers may be separately provided simultaneously in any order. still,
When the intermediate layer 4 is present on the upper side of the release layer 3 ′ in the drawing, the intermediate layer 4 is also peeled off when the image receiving layer 2 is peeled off, while the intermediate layer 4 is removed on the drawing than the release layer 3 ′. When the intermediate layer 4 exists in the lower layer, the intermediate layer 4 remains on the sheet-like substrate 1 after the image receiving layer 2 is peeled off. Therefore, in the former case, the intermediate layer 4 is desirably substantially transparent when the peeled image receiving layer 2 is adhered with the release layer 3 surface facing the article to be decorated.

FIG. 3 shows an example in which an intermediate layer 4 is provided between a protective layer 5 and an image receiving layer 2. FIG. 4 shows an example in which the intermediate layer 4 includes a sheet-like substrate 1 and a release layer 3 '. The intermediate layer 4 remains on the sheet-like substrate 1 after the image receiving layer 2 is peeled off. 5 is an example in which the protective layer 5 also serves as the intermediate layer 4. In any case, by providing the protective layer 5 adjacent to the release layer 3 ′, an image is formed and the image receiving layer 2 is peeled off.
Is provided so as to be the uppermost layer when it is applied to the article to be decorated after being inverted. The main configuration of the heat transfer sheet of the present invention has been described above, and various embodiments other than the preferable examples described above are obvious to those skilled in the art, and these obvious embodiments are naturally included in the present invention.

Next, a method for decorating an article using the above-mentioned heat transfer sheet will be described. The decoration method of the present invention is mainly characterized by utilizing the above-mentioned heat transfer sheet. The basic mode will be described by a method schematically shown in FIGS. The example shown in FIG. 6 uses the heat transfer sheet shown in FIG. 1. First, a conventionally known heat transfer sheet 20 using a sublimable dye as a recording agent is first used as a heat transfer sheet 1.
0 so that the dye-carrying layer 21 of the thermal transfer sheet faces the image receiving layer 2 of the thermal transfer sheet 10,
Alternatively, by applying thermal energy (arrow) according to an image signal by a thermal head from either side of the heat transfer sheet 10, preferably from the heat transfer sheet 20 side,
A desired image 7 is formed on the image receiving layer 2.

Next, the image receiving layer 2 having the image thus formed is peeled off from the sheet-like substrate 1, or is adhered to the article to be decorated 30 without peeling. When the sheet-like substrate 1 is not peeled in advance, the sheet-like substrate 1 is peeled off after the attachment. In each case, an adhesive is applied to either the surface of the article 30 to be decorated or the peeled image receiving layer 2 to invert the image receiving layer 2 and adhere to the article to be decorated 30 (FIG. 7).

Further, since the image receiving layer 2 is generally formed of a thermoplastic resin which can be dyed with a sublimable dye, it does not require any adhesive and can be used as a plastic molded product, cloth, metal, and other materials. It is also possible to fuse them. Although the decoration method using the heat transfer sheet of the present invention has been described above with reference to a basic example, the decoration method can be similarly performed using the heat transfer sheet of the present invention illustrated in FIG.

Next, the present invention will be described in further detail in terms of the materials and the method of forming the heat transfer sheet of the present invention as described above. Examples of the sheet-like base material include (1) synthetic paper (polyolefin-based, polystyrene-based, etc.), (2) high-quality paper, art paper, coated paper, cas-coated paper, wallpaper, backing paper,
Synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin internal paper, paperboard, etc., cellulose fiber paper, (3) various plastics such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, etc. Film or sheet can be used.

Of these, the synthetic paper (1) is preferable because it has a microvoid layer having a low thermal conductivity, in other words, a high heat insulating property, on its surface. Also, a laminate formed by any combination of the above (1) to (3) can be used. As an example of a typical laminated body, there is a synthetic paper composed of cellulose fiber paper and synthetic paper, or a synthetic paper composed of cellulose fiber paper and a plastic film or sheet. Among them, the laminated body of cellulose fiber paper and synthetic paper, the cellulose fiber paper compensates for the thermal instability (stretch etc.) of synthetic paper, and the high printing thermal sensitivity due to the low thermal conductivity of synthetic paper. Can be demonstrated. Further, in order to balance the front and back of the laminate in this combination, it is preferable to use a three-layer laminate of synthetic paper / cellulose fiber paper / synthetic paper, so that curling due to printing is reduced.

As the synthetic paper used for the laminate as described above, any synthetic paper can be used as long as it can be used as a synthetic paper base material of a sheet to be heat-transferred. Synthetic paper provided with a paper-like layer (for example, commercially available synthetic paper YUPO: Oji Yuka synthetic paper) is desirable. The fine holes in the paper-like layer can be formed, for example, by stretching a synthetic resin in a state containing a fine filler. A heat transfer sheet formed using synthetic paper provided with a paper-like layer containing the fine pores has an effect that, when an image is formed by thermal transfer, the image density is high and the image does not vary.

This has a heat insulating effect due to the fine pores,
It is considered that the heat energy efficiency is good and the cushioning property due to the fine pores is provided on the synthetic paper and contributes to the image receiving layer on which an image is formed. It is also possible to provide the paper-like layer containing the fine pores directly on the surface of a core material such as cellulose fiber paper. A plastic film other than the cellulosic fiber paper in the laminate may be used, and a laminate of the cellulose fiber paper and the plastic film may also be used.

Examples of the method of attaching the synthetic paper and the cellulose fiber paper include attaching using a conventionally known adhesive, attaching using an extrusion laminating method, attaching using thermal bonding, and the like. Examples of the method for attaching the synthetic paper and the plastic film include a laminating method and a calendar method which simultaneously form the plastic film. The sticking means is appropriately selected according to the material of the thing to be stuck to the synthetic paper. Specific examples of the adhesive include an ethylene-vinyl acetate copolymer, an emulsion adhesive such as polyvinyl acetate, a water-soluble adhesive such as a polyester containing a carboxyl group, and the like. And an adhesive of an organic solvent solution type such as polyurethane, acrylic or the like.

The material constituting the image receiving layer is for receiving a sublimable dye transferred from the thermal transfer sheet, for example, a sublimable disperse dye, and for maintaining an image formed by the reception. For example, the synthetic resins (a) to (e) are used alone or in combination of two or more. (A) Those having an ester bond. Polyester resin, polyacrylate resin, polycarbonate resin, polyvinyl acetate resin, styrene acrylate resin, vinyl toluene acrylate resin, etc. (B) Those having a urethane bond. Polyurethane resin and the like. (C) Those having an amide bond. Polyamide resin (nylon). (D) Those having a urea bond. Urea resin and the like. (E) Others having a highly polar bond. Polycaprolactone resin, polystyrene resin, polyvinyl chloride resin, polyacrylonitrile resin, etc.

The image receiving layer is composed of a mixed resin of a saturated polyester and a vinyl chloride-vinyl acetate copolymer. As the saturated polyester, for example, Byron 20
0, Byron 290, Byron 600, etc. (all manufactured by Toyobo), KA-1038C (Arakawa Chemical), TP220,
TP235 (all manufactured by Nippon Gosei) or the like is used. The vinyl chloride-vinyl acetate copolymer has a vinyl chloride component content of 8
Those having 5 to 97% by weight and a degree of polymerization of about 200 to 800 are preferred. The vinyl chloride-vinyl acetate copolymer is not necessarily limited to a copolymer of only a vinyl chloride component and a vinyl acetate component, and includes a vinyl alcohol component, a maleic acid component, and the like within a range not to impair the object of the present invention. It may be.

The image receiving layer may be composed of a polystyrene resin, for example, a styrene monomer, for example, a polystyrene resin composed of a homopolymer or a copolymer of styrene, α-methylstyrene and vinyltoluene;
Alternatively, the styrene-based monomer and another monomer, for example, a styrene-based copolymer resin which is a copolymer of an acrylic or methacrylic monomer such as acrylate, methacrylate, acrylonitrile, and methacrylonitrile, or maleic anhydride. No. Among the above synthetic resins, polyester resins are particularly preferred.

In any of the above embodiments, the whiteness of the image receiving layer is improved to further enhance the sharpness of the transferred image, and at the same time, the surface of the sheet to be heat-transferred is given writability, and retransfer of the transferred image is prevented. For this purpose, a white pigment can be added to the image receiving layer. As the white pigment, titanium oxide, zinc oxide, kaolin clay, calcium carbonate, fine powder silica, and the like are used, and these can be used as a mixture of two or more kinds. Further, in order to further enhance the light fastness of the transferred image, an ultraviolet absorber and / or a light stabilizer can be added to the image receiving layer. The amounts of these ultraviolet absorbers and light stabilizers are preferably 0.05 to 10 parts by weight and 0.5 to 3 parts by weight, respectively, based on 100 parts by weight of the resin constituting the image receiving layer.

The protective layer is peeled off from the sheet-like substrate together with the image-receiving layer having an image. The protective layer becomes the uppermost layer when the image-receiving layer is turned over and adhered to the article to be decorated. Improves wear resistance, light resistance, chemical resistance, etc.
For example, as a material for forming the protective layer, epoxy resin, alkyd resin, phenol-modified alkyd resin,
Active energy rays such as thermosetting resins such as amino alkyd resins, phenol resins, urea resins, melamine resins, silicone resins, thermosetting polyurethane resins or room temperature setting resins, and other ultraviolet setting resins and electron beam setting resins Curable resins and the like are useful. The protective layer made of these resins is formed by dissolving these resins in an appropriate solvent as necessary to prepare a coating liquid or ink, and forming the coating liquid between the release layer and the receiving layer. The thickness of such a protective layer is 0.5 to
The thickness is generally about 20 μm. Since the protective layer thus formed is a layer crosslinked sufficiently three-dimensionally, it does not soften or melt even when the temperature at the time of transfer increases, and therefore, the sheet-like substrate or the release layer Without being integrated with
Since the sheet-like substrate after transfer is easily peeled off, it can also serve as a release layer or an intermediate layer.

In the heat transfer sheet of the present invention, a release layer is formed on the image forming side of the image receiving layer in order to improve the releasability from the thermal transfer sheet and the releasability between the protective layer and the sheet-like substrate. Alternatively, a release agent can be contained in the image receiving layer, or a release layer can be provided between the protective layer and the surface on the sheet-like substrate side. Examples of the release agent include solid waxes such as polyethylene wax, amide wax, and Teflon powder; fluorine-based and phosphoric acid ester-based surfactants; silicone oil; and silicone oil is preferred. As the silicone oil, an oily one can be used, but a curable type is preferred. Examples of the curable silicone oil include a reaction curable type, a photocurable type, and a catalyst curable type, and a reaction curable type silicone oil is particularly preferable.

As the reaction-curable silicone oil,
Preferably, an amino-modified silicone oil and an epoxy-modified silicone oil are cured by reaction. Examples of the amino-modified silicone oil include KF-393 and KF-85.
7, KF-858, X-22-3680, X-22-3
810C (above, manufactured by Shin-Etsu Chemical Co., Ltd.), and KF-1 as an epoxy-modified silicone oil.
00T, KF-101, KF-60-164, KF-1
03 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

The catalyst-curable or photocurable silicone oils include KS-705F and KS-770 (these are the catalyst-curable silicone oils: Shin-Etsu Chemical Co., Ltd.)
), KS-720, KS-774 (above, photocurable silicone oil: manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. The addition amount of these curable silicone oils is preferably 0.5 to 30% by weight of the resin constituting the image receiving layer. or,
The release layer may be provided on a part of the surface of the image receiving layer by dissolving or dispersing the above release agent in an appropriate solvent and applying the resultant, followed by drying. As the release agent constituting the release layer, a reaction curing type of the above-mentioned amino-modified silicone oil and epoxy-modified silicone oil is particularly preferable. The thickness of the release layer is 0.01 to 5 μm, particularly 0.05 to 5 μm.
2 μm is preferred.

When a silicone oil is added when forming the image receiving layer, the silicone oil bleeds to the surface after coating. Therefore, after the bleeding, the silicone oil is cured to form a release layer. I can do it. The image-receiving layer is formed by a known coating or printing method using an image-receiving layer forming composition obtained by dissolving or dispersing a material for forming the image-receiving layer on a sheet-like substrate on which a protective layer is formed. In addition to the above, the method is performed by once forming the image receiving layer on a temporary carrier different from the sheet-like substrate on which the protective layer is formed, and then transferring the image-receiving layer onto the sheet-like substrate on which the protective layer is formed again. You may. A sheet whose surface is releasable is used as the temporary carrier. For example, (1) an undercoat layer on a surface of cellulose fiber paper or synthetic paper followed by a release silicone layer, and (2) a polyolefin resin or polyester resin on the surface of the cellulose fiber paper by extrusion. It is coated or (3) a plastic film such as a polyester film having a release silicone layer on the surface.

After forming the image receiving layer on the temporary carrier in the same manner as on the sheet-like substrate, an adhesive layer is formed if necessary. This adhesive layer is for securing the adhesive force between the protective layer and the image receiving layer when the image receiving layer is transferred onto the protective layer. In this method, another layer, for example, an intermediate layer imparting cushioning property or the like is formed on a temporary carrier, and the intermediate layer and the image receiving layer are once formed on the sheet-like substrate on which the protective layer is formed. May be transferred. When the intermediate layer also functions as the adhesive layer, the adhesive layer need not be formed on the temporary carrier. In any case, since the adhesive layer may be interposed between the protective layer and the uppermost layer on the temporary carrier, the adhesive layer is formed on the protective layer, and Only the image receiving layer,
Alternatively, the image receiving layer and the intermediate layer may be sequentially formed and transferred.

When the method of forming the image receiving layer on the temporary carrier once and then forming the image receiving layer on the protective layer by a transfer method is adopted, the surface of the image receiving layer formed on the protective layer has a state of the surface of the temporary carrier. The smoothness is very good because it is transferred, and the image receiving layer formed directly on the protective layer is inferior in smoothness as compared with that by the transfer method, and I want to obtain a clearer and more precise image In some cases, a transfer method is preferably used. Any adhesive can be used as long as it can bond the image receiving layer and the protective layer, and polyester, polyacrylate, polyurethane, polyvinyl chloride, polyolefin, ethylene-vinyl acetate copolymer, synthetic rubber Or an organic solvent solution or emulsion. The adhesive may be a heat bonding type or a room temperature adhesive type. In the case of the heat bonding type, heat bonding with a hot melt type adhesive such as wax, ethylene-vinyl acetate copolymer resin, polyolefin, petroleum resin, or sandwich lamination with an extruded film such as a polyolefin film may be used.

A double-sided tape may be used as an adhesive layer also serving as an intermediate layer. The double-sided tape is obtained by impregnating and drying an acrylic adhesive or the like in rayon paper. The dried double-sided tape has fine pores and is considered to play a role equivalent to a foamed layer. The intermediate layer may be either cushioning or porous depending on the constituent material, or may also serve as an adhesive layer in some cases. The cushioning layer is J
The resin mainly has a 100% modulus specified in IS-K-6301 of 100 kg / cm ² or less, wherein the 100% modulus is 100 kg / cm 2.
^If it exceeds ² , the rigidity is too high, so that even when an intermediate layer is formed using such a resin, sufficient adhesion between the thermal transfer sheet and the image receiving layer at the time of printing cannot be maintained. The lower limit of the 100% modulus is actually about 0.5 kg / cm ² .

The following are examples of the resin meeting the above conditions. Polyurethane resin, polyester resin, polybutadiene resin, polyacrylate resin, epoxy resin, polyamide resin, rosin-modified phenol resin, terpene phenol resin, ethylene / vinyl acetate copolymer resin, etc. The above-mentioned resins can be used alone or in combination of two or more. However, since the above-mentioned resin has relatively tackiness, when there is a problem during processing, an inorganic additive such as , Silica, alumina, clay, calcium carbonate, or an amide-based material such as stearamide.

The cushioning layer is obtained by kneading the above-mentioned resin together with other additives as necessary with a solvent or a diluent to form a paint or ink, and drying it as a coating by a known coating method or printing method. Can be formed by
Its thickness is 0.5 to 50 μm, more preferably 2 to 20 μm.
It is about μm. If the thickness is less than 0.5 μm, the surface roughness of the provided sheet-like base material cannot be completely absorbed, and therefore there is no effect. If the thickness exceeds 50 μm, not only the effect is not improved but also the image receiving layer becomes thick. They are too protruding, hindering winding and stacking, and are not economical. When such an intermediate layer is formed, the reason why the adhesion between the thermal transfer sheet and the heat transfer target sheet is improved is considered to be that the intermediate layer itself is deformed by pressure during printing due to low rigidity. It is presumed that such a resin usually has a low glass transition point and softening point, and the thermal energy given at the time of printing also contributes to a further decrease in rigidity and a tendency to be deformed than at room temperature. You.

The porous layer is: 1) a layer in which a liquid obtained by foaming a synthetic resin emulsion such as polyurethane or a synthetic rubber latex such as methyl methacrylate butadiene by mechanical stirring is applied to a sheet-like substrate and dried; 2) a layer in which a liquid obtained by mixing a foaming agent with the synthetic resin emulsion or the synthetic rubber latex is applied to a sheet-like substrate and dried,
3) A layer obtained by applying a liquid obtained by mixing a synthetic resin such as vinyl chloride plastisol or polyurethane or a synthetic rubber such as styrene-butadiene with a foaming agent on a sheet-like substrate, and heating the mixture to form a foam. 4) A thermoplastic resin Alternatively, a solution obtained by dissolving a synthetic rubber in an organic solvent and a non-solvent that is less likely to evaporate than the organic solvent, has compatibility with the organic solvent, and has no solubility in a thermoplastic resin or a synthetic rubber ( A microporous layer or the like is used which is formed by applying a liquid mixture containing a mixture containing water as a main component) onto a sheet-like substrate and drying the mixture to form a micro-aggregated film.

In the layers 1) to 3), since the size of bubbles is large, when a solution for forming an image receiving layer is applied on the layer and dried, the surface of the image receiving layer formed by drying is uneven. May occur. Therefore, in order to obtain the surface of the image receiving layer in which the unevenness is small and an image with high uniformity can be transferred, it is preferable to provide the microporous layer 4) as porous. Examples of the thermoplastic resin used in forming the microporous layer include saturated polyester, polyurethane, vinyl chloride-vinyl acetate copolymer, cellulose acetopropionate, and the like.
In addition, examples of the synthetic rubber used in the same manner include styrene-butadiene-based, isoprene-based, and urethane-based rubbers. Further, various organic solvents and non-solvents can be used for forming the microporous layer, and as the organic solvent, a hydrophilic solvent such as methyl ethyl ketone and alcohol is usually used. Is water.

The thickness of the porous layer in the present invention is preferably 3 μm or more, more preferably 5 to 20 μm. When the thickness of the porous layer is less than 3 μm, the cushioning and heat insulating effects are not exhibited. As explained before and after,
As described in the method for forming the image receiving layer, the intermediate layer may also serve as the adhesive layer. The above intermediate layer may be provided on the back surface of the heat transfer sheet or on one surface.

An antistatic agent can be contained in at least one of the image receiving layers or on the surface of the image receiving layer in order to suppress the generation of static electricity during the processing step of the heat transfer sheet or during traveling in the printer. Examples of the antistatic agent include surfactants, for example, cationic surfactants (for example, quaternary ammonium salts, polyamine derivatives, etc.), anionic surfactants (for example, alkyl sulfonates, etc.), amphoteric surfactants Surfactants or nonionic surfactants. The antistatic agent may be applied and formed on the image receiving layer surface by gravure coating, bar coating, or the like,
It may be kneaded into the resin of the image receiving layer and transferred to the surface of the image receiving layer during coating and drying of the image receiving layer. As the antistatic agent to be mixed with the image receiving layer resin, a cationic acrylic polymer can be used. The heat transfer sheet of the present invention may be configured such that recording can be performed on at least one of the one or both surfaces by another method. A typical example is to provide a writable layer using an aqueous pen or a pencil. Writable layer, by not providing the image receiving layer partially, the sheet-like substrate surface may be used as it is, but a resin layer containing an extender is arranged with the image receiving layer or provided on the image receiving layer May be formed.

The structure of the heat transfer sheet of the present invention has been described above. A preferable method for forming a desired image on such a heat transfer sheet is to provide a layer having a sublimable dye on a sheet-like substrate. This is a method using a thermal transfer sheet. Both the thermal transfer sheet itself and the transfer method used in this method are known, and these known thermal transfer sheets and transfer methods are all useful in the present invention.
Further, by such a transfer method, both a monochrome image and a full-color image can be easily formed.
For example, by stacking a conventionally known thermal transfer sheet on the heat transfer sheet of the present invention, any of conventionally known transfer devices,
For example, a device such as a thermal printer (for example, a thermal printer TN-5400 manufactured by Toshiba) is used for 5 to 1
By applying thermal energy of 00 mJ / mm ² , a desired image can be formed in the image receiving layer of the heat transfer sheet of the invention.

The image receiving layer on which the image has been formed as described above can be easily peeled, and can be peeled into a thin film having a desired image. The film having such an image is turned over after peeling, that is, the image forming surface is opposed to the article to be decorated, and the film can be stuck or heat-fused to any article to be decorated. In this case, before peeling the image receiving layer,
An image receiving sheet having an image on the surface of the article to be decorated by peeling off the sheet-like base material by attaching a heat transfer sheet having an image to the article to be decorated with the image surface facing the adhesive, if necessary, and then peeling off the sheet-like substrate. The method of leaving a layer is more preferable. As mentioned above,
In the case where the image is inverted and attached to the article to be decorated, the image to be formed is preferably formed in advance as an image having a mirror relationship. Needless to say, the image receiving layer may be attached to the entire surface of the article to be decorated or to a part thereof.

As described above, in the decoration method using the thermal transfer sheet of the present invention, except for using a specific heat-receiving sheet, the image forming method and the method of sticking to the article to be decorated may be any of conventionally known methods. Moreover, the material to be decorated to be subjected to the above-described decoration method is not particularly limited in its material, shape, and the like. For example, cartons, containers, bags, cassette cases, cassette halves, floppy cases, wrapping paper, and the like; Cash vouchers such as stock certificates, checks, bills, securities, certificates, passbooks, tickets, car horse tickets, stamps, stamps, appreciation tickets;
Cash cards, credit cards, members' cards, greeting cards, postcards, business cards, IC cards, and other cards; other forms, envelopes, tags, shiori, calendars, posters, brochures, passports, POs
P supplies, coasters, displays, nameplates,
Keyboards, cosmetics, accessories (watches, lighters), stationery, building materials, radios, televisions, speakers, calculators, car instrument panels, emblems, keys, clothing, footwear, equipment, OA equipment, etc. It may be something.

[0043]

Next, the present invention will be described more specifically with reference to examples. In the description, parts and% are based on weight unless otherwise specified. Example 1 As base materials, synthetic paper (manufactured by Oji Yuka, YUPO FPG150, thickness 150 μm) and polyester film (thickness 6 μm)
And a release varnish (Hakurinis 45, manufactured by Showa Ink) on one side of the polyester film side, and 2,5-bis (5′-te) as an ultraviolet absorber.
(rt-butylbenzoxazolyl (2)) thiophene added to the varnish resin in an amount of 0.5% was applied with a wire bar and dried to form a release layer / protective layer having a dry weight of 1 g / m ^2. Formed. Further, an ink for forming an image receiving layer having the following composition was used on the release layer / protective layer, and the weight after drying was 7 g.
/ M ² and dried.

Ink for forming image receiving layer : 100 parts polyester resin (manufactured by Toyobo, Byron 200) 5 parts amino-modified silicone (KF-393 manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts epoxy-modified silicone (X-22-343 manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts Solvent (methyl ethyl ketone / toluene / cyclohexanone = 4/2/2) 900 parts After applying and drying the above ink, let it stand for 1 day, then 10
Heating was performed at a temperature of 0 ° C. for 30 minutes to bleed the silicone on the surface to obtain an image receiving layer having a cured silicone layer (release layer) on the surface.

A sublimation transfer film in which a cyan sublimable dye (having a molecular weight of 250 or more) is carried on a binder resin is superposed on the obtained image receiving layer, and an electrical signal of a cyan component obtained by color separation of a face photograph is obtained. The thermal energy was applied by a thermal head connected to the printer to obtain a cyan image. Next, sublimation transfer is performed in the same manner using a sublimation transfer film using a magenta sublimation dye (molecular weight is 250 or more) and a sublimation transfer film using a yellow sublimation dye (molecular weight is 250 or more), and a full-color face photograph is obtained. And a display image composed of other characters and figures.

The image receiving layer side of the film on which the display image is formed is superimposed on a card substrate made of a white opaque hard vinyl chloride resin sheet having a thickness of 100 μm, and pressure-bonded with a hot roller at 200 ° C .; Was peeled off at the interface between the release layer and the protective layer to obtain a card to which an image receiving layer having a display image was transferred. The surface of this card was entirely smooth and there was no bulge in the image portion. Further, in the accelerated test in which the image of this card was kept in an atmosphere of 40 ° C. for three months, no image disturbance or delamination occurred at all. When a JIS light fastness test was performed using a carbon arc lamp, the results were JIS 4th to 5th grades, showing good performance. Good durability was also exhibited with respect to surface scratching and the like.

Example 2 In Example 1, after applying a polyester-based adhesive to the image forming surface of the heat transfer sheet on which the face photographic image was formed,
When the image receiving layer having an image was peeled off and attached to the curved surface of the telephone, the image sufficiently followed the curved surface of the telephone, integrated with the curved surface, and did not give a sticking feeling like a seal, and directly applied the image. It gave the impression of printing.

Example 3 A heat transfer sheet was prepared in the same manner as in Example 2, except that no ultraviolet absorber was used for the release layer and the protective layer.
Next, in the same manner as in Example 2, after applying a polyamide-based adhesive to the image forming surface of the heat transfer sheet on which the face photographic image was formed, the image receiving layer having the image was peeled off, and this was adhered to the outer surface of a glass cup. When worn, it did not give a feeling of sticking, and gave a visual impression as if it were printed directly.

[0049]

According to the heat transfer sheet of the present invention as described above,
Conventionally, it was impossible or difficult to form and apply an image.Three-dimensional molded articles, articles having surfaces such as curved surfaces or complicated irregularities, and furthermore, regardless of the material of these articles, were formed with a sublimable dye. Images can be freely added. Further, since a protective layer is formed on the surface of the image formed by the sublimation dye, various fastnesses after sticking to the article to be decorated can be improved. Further, according to the present invention, unlike the conventional so-called picture stickers, the film having the image according to the present invention is thin, so that even when the film is stuck to the article to be decorated, they are sufficiently integrated and stuck. It does not give a feeling and has excellent aesthetics, function and durability.

[Brief description of the drawings]

FIG. 1 is a diagram schematically showing a cross section of a heat transfer sheet of the present invention.

FIG. 2 is a diagram schematically showing a cross section of a heat transfer sheet of the present invention.

FIG. 3 is a diagram schematically showing a cross section of the heat transfer sheet of the present invention.

FIG. 4 is a diagram schematically showing a cross section of the heat transfer sheet of the present invention.

FIG. 5 is a diagram schematically showing a cross section of the heat transfer sheet of the present invention.

FIG. 6 is a view schematically showing formation of an image by a thermal transfer sheet.

FIG. 7 is a diagram schematically showing a decoration state of an article.

[Explanation of symbols]

 1: Sheet-like substrate 2: Image receiving layer 3, 3 ': Release layer 4: Intermediate layer 5: Protective layer 6: Adhesive 7: Image 10: Heat transfer sheet 20: Thermal transfer sheet 21: Dye carrying layer 30: Coating Decorative goods

Continuation of the front page (56) References JP-A-59-169882 (JP, A) JP-A-60-101090 (JP, A) JP-A-60-230889 (JP, A) JP-A-60-203494 (JP) , A)

Claims (4)

(57) [Claims] 1. A heat-transferable sheet comprising a sheet-like substrate provided on one side with an image-receiving layer which can be peeled off via a protective layer and which can be dyed with a sublimable dye. 2. The heat transfer sheet according to claim 1, wherein a release layer is provided on the surface of the image receiving layer. 3. The heat transfer sheet according to claim 1, wherein at least one of a release layer and an intermediate layer is provided between the image receiving layer and the sheet-like substrate. 4. The heat transfer sheet according to claim 1, wherein the image receiving layer is formed from polyester.