JPH0848081A - Heat transfer sheet - Google Patents

Abstract

(57) Abstract: A desired image is easily applied to the surface of an article having an arbitrary shape and an arbitrary surface shape. SOLUTION: The heat transfer sheet is characterized in that an image receiving layer which is peelable and dyeable with a sublimable dye is provided on one surface of a sheet-shaped substrate through a protective layer.

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 method of thermal transfer (sublimation heat transfer) of a cloth with a sublimable dye has been performed for a long time, and this method comprises forming a dye pattern layer carrying a sublimable dye on a sheet-like substrate. Is overlaid on a cloth and heated to transfer the dye pattern to the cloth. Utilizing this technology, together with the recent development of image technology such as precision thermal printers, a method of forming a precise image on a plastic film from a thermal transfer sheet having a sublimable dye layer on its surface is as good as a photograph. Various proposals have been made. 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 made into a hard copy on a sheet-like base material such as paper having a polyester layer. Has reached a level that can fully compete with the 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 transferred article is limited in shape to a sheet-like material such as a film-like or sheet-like material.
Images cannot be formed on glass, ceramics, etc., and even if plastics such as polyester are used, their image forming surfaces are curved, have uneven shapes, and are flat. However, there is a problem that it is difficult to form an image on a three-dimensional molded product other than the sheet-shaped product.

In particular, with the expansion of the types and fields of use of various cards such as cash cards in recent years, it is necessary to give images and symbols to these cards to give them various functions and decorations. However, it is difficult to apply an image to these cards by the above-mentioned thermal transfer method because they are flat, but have no flexibility, or because they have irregularities such as characters and symbols. 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 protrudes, there is no sense of unity between the seal and the article to be decorated, and there is a drawback that it 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, it is possible to easily provide a desired image on the surface of an article made of an arbitrary material and having an arbitrary shape and an arbitrary surface shape, and to integrate the image with the article to be decorated. Development is required.

[0006]

That is, the present invention is characterized in that an image-receiving layer which is peelable via a protective layer and dyeable with a sublimable dye is provided on one surface of a sheet-like substrate. It 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.
[Fig. 3] is a diagram schematically showing a basic form of the heat-transferable sheet of the present invention, and Figs. 2 to 7 are diagrams showing other preferred embodiments of the heat-transferable sheet of the present invention. As shown in FIG. 1, the basic configuration of the heat-transferable sheet 10 of the present invention is characterized in that a peelable image-receiving layer 2 is provided on one surface of an arbitrary sheet-shaped substrate 1. By forming the thermal transfer sheet of the present invention with such a structure, a desired image is formed on the image receiving layer 2 by the thermal transfer sheet having a sublimable dye,
Then, the image-receiving layer 2 having an image is peeled off from the sheet-shaped substrate 1 and attached to any article by any means, whereby the above-mentioned drawbacks of the prior art 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 having an image and peeled from the sheet-shaped substrate is very thin and has sufficient flexibility, even if the surface shape of the article to be decorated is a curved surface or an uneven surface, those surfaces are It is possible to follow the shape sufficiently. Therefore, sticking is not limited by the surface shape of the article to be decorated.

Similarly, since the image-receiving layer 2 having an image is very thin, it can be easily integrated with an article to be decorated, unlike a conventional sticker, and the sticking portion does not rise, so-called sticking feeling is obtained. Is not given. FIG. 2 shows a preferred example of the heat transferable sheet 10 of the present invention, in which release layers 3, 3 ′ are provided on the surface of the image receiving layer 2 or between the image receiving layer 2 and the sheet-shaped substrate 1. Has been. The release layer 3 is provided to transfer a sublimable dye from a thermal transfer sheet (not shown) to prevent adhesion of the thermal transfer sheet and the image receiving layer 2 due to heat when an image is formed on the image receiving layer 2. It is not necessary when such sticking does not occur or when such a release layer is provided on the surface of the thermal transfer sheet. The release layer 3 ′ facilitates the peeling of the image receiving layer 2 after the formation of an image, and is provided when the sheet-shaped substrate 1 is difficult to peel from the image receiving layer 2 like paper. It is not particularly required when the sheet-shaped substrate 1 itself has a sufficient releasability from the image receiving layer 2 such as a polyester film.

The example shown in FIG. 3 shows another preferable example of the heat transferable sheet 10 of the present invention, in which the intermediate layer 4 and / or the peeling layer 3 are provided between the image receiving layer 2 and the sheet-shaped substrate 1. 'Is provided. The intermediate layer 4 and the release layer 3'may be laminated in any order. The intermediate layer 4 referred to here is a layer for sufficiently forming an image when an image is formed by transferring a sublimable dye from the thermal transfer sheet to the image receiving layer 2, and is, for example, a cushion layer or a heat insulating layer. . For example, by providing a cushioning layer as the intermediate layer 4, the adhesion between the thermal transfer sheet and the image receiving layer 2 is improved, and the transfer of the sublimable dye during image formation by the thermal head is made uniform,
An image sufficiently corresponding to the image signal can be formed.

Further, by forming the intermediate layer 4 from a material having a heat insulating property as a heat insulating layer, it is possible to prevent the heat applied from being transferred when the sublimable dye is transferred from the thermal transfer sheet to the image receiving layer 2. Utilization efficiency is improved and 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 located above the release layer 3 in the drawing, the intermediate layer 4 is also released at the same time when the image receiving layer 2 is released, while the intermediate layer 4 is located below the release layer 3 in the drawing. When present, the intermediate layer 4 remains on the sheet-shaped substrate 1 after peeling off the image receiving layer 2. Therefore, in the former case, it is desirable that the intermediate layer 4 be substantially transparent when the peeled image-receiving layer 2 is attached with the surface of the release layer 3 facing the article to be decorated.

4 to 6 are different from the example of FIG. 3 in that a protective layer 5 is further provided between the image receiving layer 2 and the sheet-shaped substrate 1. The protective layer 5 prevents deterioration of the image on the image receiving layer 2 when the image receiving layer 2 on which an image has been formed and peeled off is attached with the surface (image forming surface) of the image receiving layer 2 facing the article to be decorated. It is a thing. 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.

In the example shown in FIG. 4, such a protective layer 5 is used as the intermediate layer 4.
Between the image-receiving layer 2 and the release layer 3 ', and the intermediate layer 4 in the example of FIG. This is an example that also serves as the protective layer 5. In any case, such a protective layer 5 is provided adjacent to the release layer 3 ', and becomes the uppermost layer when the image-receiving layer 2 on which an image has been formed and peeled is reversed and attached to the article to be decorated. It is desirable to provide such. Further, the example of FIG. 7 is an example in which an adhesive layer 6 is further provided between the image receiving layer 2 and the release layer 3 in the example of FIG. Of course, such an adhesive layer 6 can be provided adjacent to the release layer 3'in other illustrated examples as well.

Such an adhesive layer 6 is useful when it is attached to an article to be decorated without inverting the image-receiving layer 2 on which an image has been formed and peeled, and in such an example, FIGS. The protective layer 5 in 6 is unnecessary. By providing the adhesive layer 6 in advance, the image-receiving layer 2 on which an image has been formed and peeled off can be directly attached to the article to be decorated without using a special adhesive means. Such an adhesive layer 6 may be an adhesive layer having tackiness at room temperature, or a heat-sensitive or photosensitive adhesive layer exhibiting tackiness by heat or light. 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, the decoration method using the transfer sheet will be described. The decoration method of the present invention is mainly characterized in that the heat transfer sheet as described above is used. As a basic mode, a method illustrated in FIGS. The example shown in FIG. 8 uses the heat-transferable sheet shown in FIG. 1. First, a conventionally known heat-transferable sheet 20 containing a sublimation dye as a recording material is first transferred to the heat-transferable sheet 10.
In addition, the dye carrying layer 21 of the thermal transfer sheet is attached to the thermal transfer sheet 1
0 so as to face the image receiving layer 2 and apply thermal energy (arrow) from either side of the thermal transfer sheet 20 or the thermal transfer sheet 10, preferably from the thermal transfer sheet 20 side according to an image signal by a thermal head, 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 from the sheet-like substrate 1 or is stuck to the article 30 to be decorated without peeling. When the sheet-shaped base material 1 is not peeled off in advance, the sheet-shaped base material 1 is peeled off after sticking. In the case of peeling, when the adhesive layer 6 is previously formed between the image receiving layer 2 and the sheet-shaped substrate 1,
The adhesive layer 6 is placed so as to face the article to be decorated 30, and
The decoration method is completed by attaching the image receiving layer 2 to the article 30 to be decorated by means of pressure, heat, light or the like depending on the adhesive layer 6. When the adhesive layer is not formed in advance, the surface of the article to be decorated 30 or the peeled image receiving layer 2 in each case.
An adhesive is applied to one of the surfaces of the image receiving layer 2 and the image receiving layer 2 is left as it is or inverted to be attached to the article to be decorated 30 (FIG. 9).

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 it is for molding plastic moldings, cloths, metals and others. It is also possible to fuse them. Although the decorative method using the heat-transferable sheet of the present invention has been described above as a basic example, the decoration method can be similarly carried out using the heat-transferable sheet of the present invention illustrated in FIG.

Next, the present invention will be described in more detail in terms of the materials and the method of constituting the heat transferable sheet of the present invention as described above. Examples of the sheet-shaped substrate include (1) synthetic paper (polyolefin-based, polystyrene-based, etc.), (2) high-quality paper, art paper, coated paper, cast-coated paper, wallpaper, backing paper, synthetic resin, or emulsion-impregnated paper, Synthetic rubber latex-impregnated paper, synthetic resin internal paper, paperboard, etc. Cellulose fiber paper, (3) Polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, polymethacrylate, polycarbonate, etc. Can be done.

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. Further, it is also possible to use a laminate having any combination of the above (1) to (3). As an example of a typical laminated body, there is a synthetic paper composed of cellulose fiber paper and synthetic paper, or cellulose fiber paper and plastic film or sheet. Among them, the laminated body of cellulose fiber paper and synthetic paper, cellulose fiber paper compensates for the thermal instability (stretch etc.) of synthetic paper,
The high thermal sensitivity of printing due to the low thermal conductivity of synthetic paper can be exhibited. 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 above-mentioned laminated body, any synthetic paper can be used as long as it can be usually used as a synthetic paper base material of a heat transferable sheet, and particularly, it contains fine pores. A synthetic paper provided with a paper-like layer (for example, commercially available synthetic paper YUPO: made by Oji Yuka Synthetic Paper) is preferable. The fine pores in the paper-like layer can be formed, for example, by stretching a synthetic resin in a state of containing a fine filler. The heat-transferable sheet formed by using the synthetic paper provided with the 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 good thermal energy efficiency and good cushioning property due to fine pores are provided on the synthetic paper and contribute 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 may be used in addition to the cellulose fiber paper in the above-mentioned laminate, and further, a laminate of the above cellulose fiber paper and a plastic film may be used.

Examples of the method for adhering the synthetic paper and the cellulosic fiber paper include pasting using a conventionally known adhesive, pasting using an extrusion laminating method, and pasting by heat bonding. Examples of the method for attaching the synthetic paper and the plastic film include a laminating method and a calendering method which simultaneously form the plastic film. The above-mentioned sticking means is appropriately selected according to the material of the sticking member and 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, for example, a sublimable disperse dye, which migrates from the thermal transfer sheet, and for maintaining the 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, polyacrylic ester 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 etc. (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 saturated polyester and 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 (above, manufactured by Nippon Gosei) or the like is used. The vinyl chloride-vinyl acetate copolymer has a vinyl chloride 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 limited to the case where it is a copolymer of only a vinyl chloride component and a vinyl acetate component, and contains a vinyl alcohol component, a maleic acid component, etc. within a range not hindering the object of the present invention. May be

The image-receiving layer may also be composed of a polystyrene resin, for example, a polystyrene resin composed of a styrene monomer such as styrene, α-methylstyrene or vinyltoluene homopolymer or copolymer,
Alternatively, a styrene copolymer resin which is a copolymer of the styrene monomer and another monomer, for example, an acrylic or methacrylic monomer such as an acrylic ester, a methacrylic ester, acrylonitrile, methacrylonitrile, or maleic anhydride is used. Can be mentioned. Among the above synthetic resins, polyester resins are particularly preferred.

In any of the above-mentioned modes, the whiteness of the image receiving layer is improved to further enhance the sharpness of the transferred image, the writing property is imparted to the surface of the heat transferable sheet, and the retransfer of the transferred image is prevented. A white pigment can be added to the image-receiving layer for the purpose. As the white pigment, titanium oxide, zinc oxide, kaolin clay, calcium carbonate, fine powder silica and the like are used, and as described above, two or more kinds thereof can be mixed and used. Further, in order to further enhance the light resistance 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.

In order to improve the releasability between the heat transfer sheet and the image receiving layer and the sheet-shaped substrate, the heat transferable sheet of the present invention is releasable from one side or both sides of the image receiving layer. A layer may be formed, or alternatively, a releasing agent may be contained in the image receiving layer. Solid waxes such as polyethylene wax, amide wax, and Teflon powder as release agents; fluorine-based and phosphoric acid ester-based surfactants;
Although silicone oil and the like can be mentioned, silicone oil is preferable. 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,
Those obtained by reacting and curing an amino-modified silicone oil and an epoxy-modified silicone oil are preferable, and 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 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

As the catalyst-curable or photocurable silicone oil, KS-705F, KS-770 (catalyst-curable silicone oil: 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, especially 0.05 to
2 μm is preferable.

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 using a composition for forming an image-receiving layer obtained by dissolving or dispersing the material for forming the image-receiving layer on a sheet-shaped substrate,
In addition to the known coating or printing method, the image-receiving layer may be once formed on a temporary carrier different from the sheet-shaped substrate and then transferred onto the sheet-shaped substrate again. 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 ensuring the adhesive force between the sheet-shaped substrate and the image-receiving layer when the image-receiving layer is transferred onto the sheet-shaped substrate. In this method, another layer, for example, an intermediate layer for imparting cushioning properties, etc., is formed on a temporary carrier, and the intermediate layer and the image receiving layer are simultaneously transferred onto a sheet-shaped substrate. Good. When the intermediate layer also serves as the adhesive layer, the adhesive layer may not be formed on the temporary carrier. In any case, since the adhesive layer may be interposed between the sheet-shaped base material and the uppermost layer on the temporary carrier, the adhesive layer is formed on the sheet-shaped base material and temporarily The image-receiving layer alone or the image-receiving layer and the intermediate layer may be sequentially formed on the carrier and transferred.

When the method of once forming the image receiving layer on the temporary carrier and then forming it on the sheet-shaped substrate by the transfer method is adopted, the surface of the image receiving layer formed on the sheet-shaped substrate is
Since the surface condition of the temporary carrier is transferred, the smoothness is very excellent, and the image receiving layer formed directly on the sheet-shaped substrate is inferior in smoothness to that obtained by the transfer method. If you want to obtain clearer and more detailed images, it is better to use the transfer method. Any adhesive can be used as long as it can bond the image-receiving layer and the sheet-shaped substrate, and polyester-based, polyacrylic ester-based, polyurethane-based, polyvinyl chloride-based, polyolefin-based, ethylene-vinyl acetate copolymer, synthetic A rubber-based organic solvent solution or emulsion can be used. 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, or petroleum resin, or sandwich lamination using an extrusion 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
This is mainly a resin having a 100% modulus of 100 kg / cm ² or less defined in IS-K-6301, wherein the 100% modulus is 100 kg / cm.
^When it exceeds ² , the rigidity is too high, so that even if the intermediate layer is formed using such a resin, sufficient adhesion between the thermal transfer sheet and the image receiving layer during printing cannot be maintained. Further, the lower limit of 100 modulus is practically about 0.5 kg / cm ² .

The resins which meet the above conditions include the following: polyurethane resin, polyester resin, polybutadiene resin, polyacrylic ester resin, epoxy resin, polyamide resin, rosin-modified phenol resin, terpene phenol resin, Ethylene / vinyl acetate copolymer resin, etc.
The above resins can be used alone or as a mixture of two or more, but since the above resins have a relatively adhesive property, when there is a problem during processing, an inorganic additive such as, for example, , Silica, alumina, clay, calcium carbonate, etc.,
Alternatively, an amide-based substance such as stearic acid amide may be added.

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.
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, it is considered that the adhesion between the thermal transfer sheet and the thermal transfer sheet is improved because the intermediate layer itself has low rigidity and therefore is deformed by pressure during printing. It is presumed that such resins usually have a low glass transition point and a softening point, and that the thermal energy applied at the time of printing lowers the rigidity further than at room temperature and makes it easier to deform. It

The porous layer is composed of 1) a layer obtained by coating a sheet-shaped substrate with a liquid obtained by foaming a synthetic resin emulsion such as polyurethane or a synthetic rubber latex such as methyl methacrylate-butadiene based on mechanical stirring, and drying it. 2) A layer obtained by applying a liquid obtained by mixing the synthetic resin emulsion and the synthetic rubber latex with a foaming agent onto a sheet-shaped substrate and drying the same.
3) Synthetic resin such as vinyl chloride plastisol and polyurethane, or synthetic rubber such as styrene-butadiene series, which is mixed with a foaming agent, is applied onto a sheet-like base material, and is heated to foam the layer 4) Thermoplastic resin Alternatively, a solution of a synthetic rubber dissolved in an organic solvent, a non-solvent which is less likely to evaporate than the organic solvent, has compatibility with the organic solvent, and has no solubility with respect to the thermoplastic resin or the synthetic rubber ( A microporous layer or the like formed by applying a mixed solution of a mixture containing water as a main component) on a sheet-shaped base material and drying it to form a microscopically aggregated film is used.

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, and cellulose acetopropionate.
Examples of the above-mentioned synthetic rubber that can be used in the same manner include styrene-butadiene type, isoprene type, and urethane type. 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, and particularly 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. It was mixed up with the explanation,
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 transferable sheet or on one surface thereof.

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 image-receiving layer resin and transferred to the surface of the image-receiving layer during coating and drying of the image-receiving layer. A cationic acrylic polymer can be used as the antistatic agent mixed with the image-receiving layer resin. The heat-transferable sheet of the present invention may be recorded on at least a part of one surface 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 protective layer is to be peeled off from the sheet-like base material together with the image-receiving layer having an image, becomes the uppermost layer when the image-receiving layer is inverted and attached to the article to be decorated, and has a resistance to the image-receiving layer having an image. Improves wear resistance, light resistance, chemical resistance, etc. For example, as the material for forming the protective layer, epoxy resin, alkyd resin, phenol-modified alkyd resin, aminoalkyd resin, phenol resin, urea resin, melamine resin, silicone resin, thermosetting acrylic resin, thermosetting polyurethane resin, etc. The thermosetting resin or the room temperature curable resin, as well as the active energy ray curable resin such as the ultraviolet curable resin and the electron beam curable resin are useful. The protective layer made of these resins, if necessary, these resins,
A coating solution or an ink is prepared by dissolving it in a suitable solvent and is formed between the release layer and the image receiving layer. The thickness of such a protective layer is generally about 0.5 to 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 Since the sheet-like substrate after transfer is easily peeled off without being integrated with the substrate, it can also serve as a release layer or an intermediate layer.

The above is the constitution of the heat transferable sheet of the present invention. A preferable method for forming a desired image on such a heat transferable sheet is to provide a layer having a sublimable dye on a sheet-shaped 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 all of these known thermal transfer sheets and transfer methods are useful in the present invention.
Also, by such a transfer method, both a mono-color image and a full-color image can be easily formed.
For example, a conventionally known thermal transfer sheet is superposed on the thermal transfer sheet of the present invention, and any conventionally known transfer device,
For example, by a device such as a thermal printer (for example, a thermal printer TN-5400 manufactured by Toshiba), 5-1
By applying thermal energy of 00 mJ / mm ² , a desired image can be formed in the image receiving layer of the heat transferable sheet of the present invention.

The image-receiving layer on which an image as described above is peeled off easily, and it can be peeled off into a thin film having a desired image. When the film having the peeled image has an adhesive layer made of the above-mentioned adhesive in advance on the side opposite to the recording surface, it can be directly attached to various articles to be decorated. As a matter of course, the attachment may be performed on the entire surface of the article to be decorated or a part thereof. If the film does not have an adhesive layer in advance, the peeled image can be heat-sealed as it is according to the physical properties or material of the article to be decorated. It is also possible to apply an appropriate adhesive to the film or the article to be decorated and then apply it. Further, the film having such an image can be peeled and then inverted, that is, the image forming surface can be opposed to the article to be decorated and can be attached to any article to be decorated in the same manner as described above. In this case, before the image-receiving layer is peeled off, the heat-transferable sheet having the image is attached to the article to be decorated with the image side facing, and if necessary, the sheet is adhered with an adhesive, and then the sheet-shaped substrate. A method of peeling the material to leave the image receiving layer having an image on the surface of the article to be decorated is more preferable. In the case where the image is inverted and attached to the article to be decorated as described above, the image to be formed is preferably formed in advance as an image having a mirror surface relationship.

As described above, in the decoration method using the thermal transfer sheet of the present invention, the image forming method and the sticking method to the article to be decorated may be conventionally known methods except that a specific heat transfer sheet is used. The material and shape of the article to be decorated, which is the object of the above-mentioned decoration method, is not particularly limited, and examples thereof include cartons, containers, bags, cassette cases, cassette halves, floppy cases, wrapping paper, and other packages; Share certificates, checks, bills, securities, certificates, passbooks, boarding tickets, wagon tickets, stamps, stamps, appreciation tickets, etc.
Cards such as cash cards, credit cards, members' cards, greeting cards, postcards, business cards, IC cards; other forms, envelopes, tags, Shiori, calendars, posters, pamphlets, passports, PO
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.

[0044]

EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the text, "part" or "%" is 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 laminated varnish (Showa Ink, Hakurinisu 4
In 5), 2,5-bis (5'-ter) which is an ultraviolet absorber
t-Butylbenzoxazolyl (2)) thiophene added to the resin content of the varnish at 0.5% was coated with a wire bar and dried to give a release layer / protective layer having a weight of 1 g / m ^2. Was 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 : Polyester resin (Toyobo, Byron 200) 100 parts Amino-modified silicone (KF-393, Shin-Etsu Chemical Co., Ltd.) 5 parts Epoxy-modified silicone (X-22-343, Shin-Etsu Chemical Co., Ltd.) 5 parts Solvent (methyl ethyl ketone / toluene / cyclohexanone = 4/2/2) 900 parts After coating and drying the above ink, let it stand for 1 day, then 10
It was heated at a temperature of 0 ° C. for 30 minutes to cause silicone to bleed on the surface to obtain an image receiving layer having a cured silicone layer on the surface.

On the resulting image-receiving layer, a sublimation transfer film having a cyan sublimation dye (molecular weight of 250 or more) supported by a binder resin was superposed, and an electric signal of a cyan component obtained by color-separating a face photograph was obtained. Thermal energy was applied with a thermal head connected to 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 was formed was superposed 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 heat roller at 200 ° C., and then the polyester film was pressure-bonded. Was peeled off at the interface of the release layer / protective layer to obtain a card to which the 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. In addition, when the JIS light resistance test with a carbon arc lamp was performed, the result was JIS 4-5 grade,
It showed good performance. It also showed good durability against scratches on the surface.

Example 2 In Example 1, the image-receiving layer having the image was peeled off from the heat transfer sheet on which the photographic image of the face was formed, and the polyester adhesive was applied to the peeled surface of the peeled film. When the image was pasted on the curved surface of No. 3, the image sufficiently followed the curved surface of the telephone and was integrated with the curved surface, without giving the sticking feeling like a sticker, and giving the appearance as if the image was printed directly.

Example 3 In the heat transferable sheet of Example 1, no ultraviolet absorber was used, and a thickness of 5 was previously provided between the peeling layer and the image receiving layer.
An image was formed in the same manner as in Example 1 using the one having a polyamide-based pressure-sensitive adhesive layer having a thickness of μm, and then Example 2 was used.
When the image layer was peeled off in the same manner as in (1) and the peeled image layer was attached to the outer surface of the glass cup, it did not give a feeling of attachment and gave a visual sensation as if printed directly.

[0050]

[Effect] 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. Moreover, according to the present invention, unlike a conventional so-called picture sticker, the film having the image according to the present invention is thin, so that even when the film is attached to an article to be decorated, they are sufficiently integrated and attached. It does not give a feeling of wearing and has excellent aesthetics, function and durability.

[0051]

[Brief description of drawings]

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

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

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

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

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

FIG. 6 is a diagram schematically showing a cross section of the heat transferable sheet of the present invention.

FIG. 7 is a diagram schematically showing a cross section of the heat transfer sheet of the present invention.

FIG. 8 is a diagram schematically showing image formation by a thermal transfer sheet.

FIG. 9 is a diagram schematically showing a decorative state of an article.

[Explanation of symbols]

 1; Sheet-shaped substrate 2; Image-receiving layer 3, 3 '; Release layer 4; Intermediate layer 5; Protective layer 6; Adhesive layer 7; Image 10; Thermal transfer sheet 20; Thermal transfer sheet 21; Dye carrying layer 30; Decorative items

Claims (6)

[Claims] 1. A heat-transferable sheet, comprising an image-receiving layer which is peelable and dyeable with a sublimable dye via a protective layer on one surface of a sheet-shaped substrate. 2. The heat-transferable sheet according to claim 1, wherein a release layer is provided on the surface of the image receiving layer. 3. The heat transferable 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-shaped substrate. 4. The heat transferable sheet according to claim 1, wherein an adhesive layer is provided between the image receiving layer and the sheet-shaped substrate. 5. The heat transferable sheet according to claim 1, which is a release layer between the image receiving layer and the sheet-shaped substrate, and an adhesive layer is provided on the surface of the image receiving layer of the release layer. 6. The heat transferable sheet according to claim 1, wherein the image receiving layer is formed of polyester.