JPH0681280A - Dyed product - Google Patents

Abstract

PURPOSE:To obtain a dyed product capable of preventing a dyed image from being chemically and mechanically damaged or changing its color due to light and further altering. CONSTITUTION:This dyed product is obtained by successively laminating a release layer 12 readily releasable from a heat-resistant base film, a hologram- forming layer 13, a transparent thin film layer 14 having a higher refractive index than that of the hologram-forming layer and a bonding layer 16 composed of an ultraviolet ray absorber and a thermoplastic resin having >=50 deg.C glass transition point on the heat-resistant base film. A transparent hologram is formed on an image dyed with a sublimable dye in the dyed product. Thereby, the image cannot be altered without making the hologram disappear.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a dyed product.

More specifically, it is a plastic material whose surface is dyed with a sublimable dye, does not undergo discoloration by ultraviolet rays, does not suffer from bleeding due to infiltration of a plasticizer, and is susceptible to tampering with dye images. Not about dyeing.

[0003]

2. Description of the Related Art Methods for dyeing plastic materials with so-called sublimable dyes are well known. For example, a dye is made into an ink together with a binder resin and printed on a temporary support, and when this printed matter is overlaid on a plastic material and heated, only the dye in the ink penetrates into the plastic material and is dyed (transfer). Dyeing method). At this time, the ink is not transferred and peeled off together with the temporary support.

Alternatively, an ink containing a dye is printed directly on a plastic material and then heated to allow the dye to penetrate into the plastic and dye it (penetration printing method). The ink layer is left as it is, or it is peeled off and removed,
In both cases, the dye has penetrated inside the plastic and the image remains.

Dyes are believed to be sublimable and are believed to change from the solid state directly to the gaseous state, with such gaseous dyes penetrating into the plastic material. For this reason, dyes are generally called sublimable dyes. However, it is not strictly confirmed that there is no liquid state between the solid state and the gas state. It is also not clear whether the penetration into the plastic material occurs in the gaseous state or in the liquid state. For this reason, the dye is sometimes called a vaporizable dye or a heat-melt transfer dye.

A heating plate, a heating roll, an infrared panel heater or the like is used as a heating means for permeating the dye into the plastic material. In recent years, due to the development of dyes with excellent thermal response and the improvement of thermal heads,
A method of forming an image by allowing a dye on a transfer ribbon to penetrate into a plastic material by heat generated by a thermal head has been developed. Plastic material is plastic film,
It is a PVC card such as an identification card.

However, the dyes are generally disperse dyes or oil-soluble dyes. Such a dye has a small polarity, and therefore it easily changes into a gas by heating and penetrates into the plastic material, but on the other hand, its binding force with the plastic material is also small, and it is violated by a plasticizer or an organic chemical, or mechanically damaged by scratching. Easy to receive. Furthermore, the dye is disperse | distributed by light, especially an ultraviolet-ray, and it discolors or fades.

In order to prevent such a problem, an image receiving layer containing a polyester resin as a main component is provided on the surface of the plastic material to fix the dye, or the dye is improved to improve the fastness.

However, none of the methods can essentially prevent chemical or mechanical damage from the outside, and cannot avoid light rays such as ultraviolet rays.

Therefore, the inventor of the present invention has filed Japanese Patent Application No. 3-28773.
5, a sublimation dye diffusion prevention layer and a surface protection layer are sequentially laminated on the surface of a plastic substrate whose surface is dyed with a sublimation dye, via an adhesive layer containing an ultraviolet absorber, and the dye image chemically and We proposed a dyeing product that can prevent mechanical damage and prevent discoloration and fading due to light.

However, although the invention has achieved the initial object, when the dyed product is an information recording card such as a prepaid card or an identification card and an ID card, the dye image is intentionally tampered with. There was a danger.

[0012]

SUMMARY OF THE INVENTION It is therefore an object of the present invention to provide a dyed product which can prevent chemical and mechanical damage to a dyed image, can prevent fading due to light, and can be tamper-proof. And

[0013]

In order to achieve this object, the invention according to claim 1 has an ultraviolet absorber and a glass transition point of 50 ° C. or higher on the surface of a plastic substrate whose surface is dyed with a sublimable dye. There is provided a dyeing product in which a transparent thin film layer having a refractive index larger than that of the hologram forming layer and a hologram forming layer are laminated at least sequentially through an adhesive layer made of the thermoplastic resin.

According to a second aspect of the present invention, the hologram forming layer contains a two-component reactive urethane resin as a main component, and the polyol component of the resin has a glass transition point of 70 ° C. to 150 ° C.
The dyed product according to claim 1, which is an acrylic polyol resin having an OH value in the range of 50 to 150 and a OH value in the range of 50 to 150.

The invention according to claim 3 provides the dyed product according to claim 1, characterized in that a primer layer is provided between the transparent thin film layer and the adhesive layer.

Further, the invention according to claim 4 is characterized in that the primer layer is a urethane resin.
The dyeings described are provided.

[0017]

As described above, in the dyed product according to the present invention, the transparent hologram is formed on the dye image. Therefore, it is difficult to falsify the image without losing the hologram. Further, it is resistant to various chemical and mechanical damages such as scratch resistance, abrasion resistance and solvent resistance together with plasticizer resistance, and can prevent discoloration due to light such as ultraviolet rays. .

Further, since the transparent thin film layer is an inorganic compound, it is possible to prevent the image dyed with the sublimable dye from diffusing to the outside.

The present invention will be described in detail below. Cards such as an identification card and a cash card are assumed as applications of the dyed product of the present invention. The card is used under severe conditions and requires durability. Therefore, the base material on which the dyed image is formed is preferably made of plastic.

Such a card is generally made of hard polyvinyl chloride having a transparent surface. For example, a transparent hard polyvinyl chloride sheet is laminated on both sides of a white polyvinyl chloride sheet by an adhesive or heat fusion.

An example of using an identification card as a plastic substrate is shown in FIG. (2) is a base material composed of a card body, and a face photograph is partially dyed with a sublimation dye (2a).

The substrate surface is dyed by printing an ink containing a sublimable dye and then heating it, or overlaying a printed matter (transfer foil) printed with an ink containing a sublimable dye and heating it to allow only the dye to penetrate. It is possible by the method (transfer dyeing method). When the substrate is the above card or embossed film, a method of stacking ribbon-shaped transfer foils (transfer ribbons) and heating with a thermal head is convenient.

Kayacet Y as a yellow sublimation dye
ellow AG, Kayakut Yellow TDN (Nippon Kayaku Co., Ltd.)
), PTY52, Dianix Yellow 5R-E, Dianix Yellow F3
GE, Dianix Brilliant Yellow 5G-E (above Mitsubishi Kasei Co., Ltd.), Plast Yellow 8040, DY108 (above Arimoto Chemical Co., Ltd.), Sumikaron Yellow EFG, Sumikaron Yell
owE-4GL (Sumitomo Chemical Co., Ltd.), FORON Brilliant
Yellow S6GLPI (manufactured by Sand) can be exemplified.

Examples of magenta sublimable dyes include K
ayacet Red 026, Kayacet Red 130, Kayacet Red B
(Nippon Kayaku Co., Ltd.), Oil Red DR-99, Oil Red
DK-99 (Arimoto Chemical Co., Ltd.), Diacelliton Pink B
(Made by Mitsubishi Kasei), Srmikaron Red E-FBL (made by Sumitomo Chemical Co., Ltd.), Latyl Red B (made by du pont), Sudan Re
Examples include d 7B (manufactured by BASF), Resolin Red FB, Ceres Red 7B (manufactured by Bayer).

Examples of cyan sublimation dyes include Kayalon Fast Blue FG, Kayacet Blue FR, and Kayace.
t Blue 136, Kayacet Blue 906 (Nippon Kayaku Co., Ltd.)
), Oil Blue 63 (manufactured by Arimoto Chemical Co., Ltd.), HSB9 (manufactured by Mitsubishi Kasei Co., Ltd.), Disperse Blue # 1 (Sumitomo Chemical Co., Ltd.)
MS), MS Blue 50 (Mitsui Toatsu Co., Ltd.), Ceres Blue G
N (Bayer), Duranol Brilliant Blue 2G (ICI
Manufactured by the company) can be exemplified.

When a transfer ribbon is used, it is desirable to use a crosslinked polyvinyl alcohol as a binder in the ink. This is because the heat of the thermal head does not adhere to the plastic substrate. Examples thereof include polyvinyl acetal and polyvinyl butyral. As the base material of the transfer ribbon, a polyester film or a polyester film provided with a polyurethane anchor coat layer can be used.

The transfer ribbon can be dyed by stacking it on a plastic substrate such as a card and heating it while pressing it with a thermal head. The heat generation condition may be 5 to 50V.
Such a dyeing method is described in JP-A-63-22693 or JP-A-3-79384.

In the dyed product according to claim 1 of the present invention, an adhesive layer (16) and a transparent thin film layer (14) are formed on the surface of the card body (2) whose surface prepared in the above step is dyed with a sublimation dye. , And the hologram forming layer (13) are sequentially laminated. Further, the dyed product according to claim 3 or 4, further comprises a primer layer (1) between the transparent thin film layer and the adhesive layer.
5) is provided.

The dyed product as described above is produced by coating the surface of the card body (base material) whose surface is dyed with a sublimation dye with the materials for the respective layers, and repeating coating and curing (drying). However, since it is necessary to form a hologram in the hologram forming layer, the base film (11), the peeling layer (12), the hologram forming layer (13), the transparent thin film layer as shown in FIGS. (14), [primer layer (1
5),] A method for producing a dyed product by producing a transfer foil comprising the adhesive layer (16) and transferring the hologram forming layer or the peeling layer or less is convenient.

The method for producing the dyed product of the present invention with a transfer foil will be described below.

As described above, the transfer foil comprises a base film (11), a release layer (12), a hologram forming layer (13), a transparent thin film layer (14), and a [primer layer (1).
5),] The adhesive layer (16). At least the base film (11) is not transferred during thermal transfer.

The base film (11) is required to have heat resistance so that it is not softened and deformed by the heat pressure during transfer. Such a base film (11) is known and has a thickness of, for example, 3 to 50 μm.
The biaxially stretched polyethylene terephthalate film can be used.

The release layer (12) is provided for easy release from the base film (11) during thermal transfer. Further, a material that functions as a protective film after being transferred is preferable. The function of the protective film is to prevent external chemical and mechanical damage of the image by the dye. A mixture of a thermoplastic resin and an anti-friction agent may be used to satisfy both functions. If a hologram forming layer, which will be described later, contains a friction-resistant agent or the like and has a function as a protective film, it is not necessary to provide a peeling layer.

The thermoplastic resin prevents permeation of the plasticizer and chemicals and reduces scratches caused by scratching. As the thermoplastic resin, polymethylmethacrylate or epoxy resin can be used. Methylmethacrylate and epoxy resin have excellent plasticizer resistance among existing thermoplastic resins and base film (11)
And easy to peel. By using these resins in the release layer (12), it is possible to prevent the migration of the plasticizer contained in the soft vinyl chloride sheet or the plastic eraser when they are brought into contact with the transferred image. Further, it is possible to prevent penetration of chemicals such as acids, alkalis, alcohols, and kerosene, and prevent the influence on the image.

The anti-friction agent is added to improve wear resistance and scratch resistance. For example, Teflon powder, polyethylene powder, animal wax, vegetable wax, mineral wax, natural wax such as petroleum wax, synthetic hydrocarbon wax, fatty alcohol and acid wax, fatty acid ester and glycerite wax, hydrogen. Waxes, synthetic ketone waxes, amine and amide waxes, chlorinated hydrocarbon waxes, synthetic animal wax waxes, synthetic waxes such as alpha-olefin waxes, and higher fatty acid metal salts such as zinc stearate. be able to.

The release layer (12) is composed of the thermoplastic resin 85 to 9 with respect to 100 parts by weight of the total amount of the thermoplastic resin and the anti-friction agent.
5 parts by weight and 5 to 15 parts by weight of anti-friction agent may be used. The coating amount may be 1 to 3 g / m ² .

In addition to the above components, the release layer (12) may be mixed with a release improving agent in order to improve the breakage during transfer. For example, linear saturated polyester resin. However, it should be limited to 0 to 3 parts by weight based on 100 parts by weight of the total amount of the thermoplastic resin and the anti-friction agent.

It should be noted that it is desirable not to add other additives such as an ultraviolet absorber to the peeling layer (12). This is because the addition thereof causes a decrease in chemical resistance or facilitates penetration of the plasticizer, which causes deterioration of the mechanical strength of the release layer.

The method of applying the release layer is as follows. First, the release layer composition is made into a coating material with a suitable solvent, and the coating material is applied and dried by a coating method such as gravure coating, roll coating or bar coating. It may be formed.

The hologram forming layer (13) is a layer for forming a hologram by heating and pressing with a surface relief type hologram stamper. Hologram forming layer (1
The resin used in 3) may be a thermoplastic resin, but extremely good results can be obtained by using a two-component reaction urethane resin. That is, the two-component reactive urethane resin has good embossing moldability and is less likely to cause uneven press,
A bright reproduced image is obtained, in addition, the adhesion to the substrate during embossing is good, the adhesion to the metal reflective layer is good, and the releasability at the time of transferring to the transfer target is very good.

Hologram forming layer (13) described in the present invention
The two-component reactive urethane resin as described above is a polyol composed of a polyol component such as a polyether polyol, a polyester polyol, an acrylic polyol, and a prepolymer having an isocyanate group in view of various physical properties such as solvent resistance, heat resistance, and processability. A curable urethane resin is suitable, but among them, the polyol component has a glass transition point of 70 to 1
By using an acrylic polyol resin having an OH group in the range of 50 to 150 in the range of 50 ° C., the coating suitability is good, and the embossing moldability required for the hologram transfer foil and the releasability from the base film. It is possible to obtain a very good transfer foil. As the isocyanate component, toluene diisocyanate (TDI), xylene diisocyanate (XDI), hexamethylene isocyanate (HMDI) and the like can be used.

Further, as a modifier for improving coating suitability and transferability, a cellulose resin such as nitrocellulose, acetylcellulose, cellulose acetate butyrate, cellulose acetate propionate, ethyl cellulose and methyl cellulose is converted into a two-component reactive urethane resin. On the other hand, by adding together at most 30% by weight, better results can be obtained.

As a method of applying such a hologram forming layer (13), a resin which has been made into a coating material is applied by a method such as roll coating or blade coating and dried to form 0.5 to 0.5.
A film thickness of 5 μm may be formed.

The hologram-forming layer (1
3) has a good adhesion to the base film coated with the release layer, has excellent formability by heating and pressurizing during embossing, and has the surface plated with nickel, gold, chrome, etc. It does not adhere to the stamper for hologram pattern formation,
Further, it shows good adhesiveness to the metal reflective layer, and the film is well cut. Furthermore, reliable transfer is possible without peeling defects of the metal reflective layer during hot stamping, transfer unevenness, burrs, and blistering, and due to the excellent heat resistance of the urethane resin, it is generated by the vapor deposition process and heat during hot stamping. It is possible to prevent deterioration of the external appearance, such as cracking, whitening, and breakage of the hogram pattern due to shrinkage. As the shape of the hologram pattern (3a), a repeating pattern of precise and regular line figures, or a pattern in which a logo indicating the issuer and a trademark are combined is preferable.

The transparent thin film layer (14) is made of a material having a higher refractive index than the resin of the hologram forming layer (13) and a high transmittance in the visible light region. When the transparent thin film layer (14) having a high refractive index is provided, it can be seen as a mere transparent body outside the reproducible angle range of the hologram due to the angle dependence of the replay characteristic of the hologram, and the reproducible angle range of the hologram is obtained. Then, the refractive index of light is maximized, and the effect appears as a reflection hologram. Examples of the material of such a transparent thin film layer (14) include the inorganic substances listed in Table 1.

[0046]

[Table 1]

As a method of forming the transparent thin film layer (14), a vacuum deposition method, a sputtering method, an ion plating method or the like can be used. A suitable film thickness is in the range of 100Å to 10000Å.

The transparent thin film layer (14) also has an effect of preventing the diffusion of an image, which is dyed with a sublimable dye on the surface of plastic such as vinyl chloride, to the outside. That is, without the transparent thin film layer (14), the dye diffuses to the hologram forming layer (13) through the adhesive layer (16) when left for a long time, and is sandwiched by an eraser or a soft vinyl chloride containing a plasticizer. If it is left, it will be diffused and transferred to an eraser or soft vinyl chloride, which will cause discoloration of the image.

A primer layer (1
5) is an adhesion improving layer for adhering the transparent thin film layer (14) and the adhesive layer (16). A urethane resin is suitable as such a resin. Specifically, it comprises a polyol ion component such as a polyurethane ionomer resin, a polyether polyol, a polyester polyol, and an acrylic polyol, and a prepolymer having an isocyanate group.

The method of applying the primer layer (15) is as follows.
First, the release layer composition may be coated with a suitable solvent, and the coating may be applied and dried by a coating method such as gravure coating, roll coating or bar coating.

The adhesive layer (16) adheres to the surface of the plastic material and blocks ultraviolet rays to prevent discoloration of the image due to the dye. For this reason, it is composed of a mixture of an ultraviolet absorber and a thermoplastic resin.

The thermoplastic resin used for the adhesive layer (16) may have a glass transition point (Tg) of 50 ° C. or higher. When a resin having a glass transition temperature of less than 50 ° C. is used, after the transfer, the resin causes migration of the dye and causes image bleeding. Further, those having a glass transition point of 110 ° C. or lower are preferable. Glass transition point is 110
When a resin having a temperature above 0 ° C. is used, a high temperature is required for transfer, a load is applied to the heating medium, and a plastic material such as polyvinyl chloride card may be deformed by heat.

Examples of the thermoplastic resin used for the adhesive layer (16) include polyester such as linear saturated polyester, vinyl chloride resin such as polyvinyl chloride and vinyl chloride-vinyl acetate copolymer resin, polyacrylic acid, 2-Methoxyethyl polyacrylate, polymethyl acrylate, 2-naphthyl polyacrylate, isobornyl polyacrylate, polymethacrylomethyl, polyacrylonitrile, polymethylchloroacrylate, polymethylmethacrylate, polyethylmethacrylate, Poly-tert-butyl methacrylate, poly-isobutyl methacrylate, poly-phenyl methacrylate, methyl methacrylate and alkyl methacrylate (provided that the alkyl group has 2 to 6 carbon atoms)
Acrylic resin such as copolymer resin, polystyrene, polydivinylbenzene, polyvinylbenzene, styrene-
Examples thereof include butadiene copolymer resins and vinyl resins such as styrene and alkyl methacrylate (where the alkyl group has 1 to 6 carbon atoms).

The ultraviolet absorber prevents the fading of the dye due to light. That is, wavelength 250 to 400 nm
Absorbs the ultraviolet rays and re-radiates the energy as heat energy harmless to the dye, and the ultraviolet absorber itself does not deteriorate. For this reason, the maximum absorption wavelength is 250 to 400 nm.
Use a UV absorber.

For example, phenyl salicylate, p-ter
Salicylic acid-based UV absorbers such as t-butylphenyl salicylate and p-octylphenyl salicylate, 2,
4-dihydroxybenzophenone, 2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 , 4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-
Benzophenone-based UV absorbers such as 5-sulfobenzophenone, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2-
(2′-hydroxy-3 ′, 5′-ditert-butylphenyl) -5-chlorobenzotriazole, 2-
Benzotriazole-based UV absorbers such as (2'-hydroxy-3 ', 5'-ditert-amylphenyl) benzotriazole, 2-ethylhexyl-2-cyano-
It is a cyanoacrylate-based ultraviolet absorber such as 3,3′-diphenyl acrylate and ethyl-2-cyano-3,3-diphenyl acrylate.

The adhesive layer (16) has a total solid content of 100.
The thermoplastic resin may be 50 to 90 parts by weight and the ultraviolet absorber may be 10 to 50 parts by weight with respect to parts by weight. Coating amount is 1-3g / m
² is preferred.

The method of applying the adhesive layer is as follows. First, the adhesive layer composition is made into a coating material with an appropriate solvent, and the coating material is applied and dried by a coating method such as gravure coating, roll coating or bar coating. It may be formed.

The transfer foil (1) thus prepared is
After overlaying on a plastic substrate dyed with a sublimation dye and applying heat and pressure, only the base film (11) is peeled off and removed,
By transferring, the dyed product of the present invention can be obtained. The transfer can be performed by heating to a temperature equal to or higher than the softening point of the fats and oils at the time of thermoplastic contained in the adhesive layer (16). Usually 150-25
It is 0 ° C. The time may be about 1 to 10 seconds.

It will be apparent that the dyed product of the present invention can be applied not only to cards but also to any plastic material dyed with a sublimable dye.

[0060]

EXAMPLES The present invention will be described in detail below with reference to examples.

Example 1 Composition of Release Layer Coating Composition Polymethylmethacrylate (Tg: 105 ° C.) 10 parts by weight (Mitsubishi Rayon Co., Ltd. BR-80) Teflon powder 1 〃 toluene / 2-butanone (1/1) ) 40〃

Composition of coating material for hologram forming layer Acrylic polyol resin 25 parts by weight (TG: 75 ° C., OH value: 100) Nitrocellulose resin 5 〃 (nitrogen content: 12%, average degree of polymerization: 45, viscosity: 1/2 ) Xylene diisocyanate 5〃 Toluene / 2-butanone (25/20) 45〃 Isobutyl acetate 20〃

Composition of Adhesive Layer Coating Composition Vinyl Chloride-Vinyl Acetate Copolymer (Tg: 65 ° C.) 10 parts by weight (Surek A manufactured by Sekisui Chemical Co., Ltd.) 2- (2′-hydroxy-5′-methylphenyl) -Benzotriazole 2.5 〃 Toluene / 2-butanone (2/1) 40 〃

On the 12 μm thick polyethylene terephthalate film, a gravure coater was used to coat and dry the above release layer coating material so that the dry weight was 2.0 g / m ² , to form a release layer (12). The hologram forming layer paint is dried on the layer with a gravure coater to a dry weight of 1.2 g.
/ M ² so that the hologram forming layer (1
3) is formed, and after aging at 60 ° C. for 72 hours, the hologram forming layer and the hologram pattern forming surface of the stamper are overlapped with a press machine and embossed 16
A hologram was formed on the hologram formation surface by heating at 0 ° C. and 40 kg / cm under pressure. Next, ZnS was vapor-deposited on the hologram formation surface to a thickness of about 500 Å to form a transparent thin film layer (14). Further, the above adhesive layer coating material was applied and dried by a gravure coater to a dry weight of 1.5 g / m ² , to form an adhesive layer (16), and a transfer foil was manufactured.

Each color of yellow, magenta and cyan was transfer dyed onto a polyvinyl chloride card with a sublimation transfer ribbon using a color thermal printer. The transfer foil was laminated on the dyed surface with a laminator (MS Pouch H-140, manufactured by Meiko Shokai Co., Ltd.) at 150 ° C. for 2 seconds to remove the base film. The sublimation transfer ribbon is a 6 μm thick polyester film coated with three color sublimation inks consisting of a dye and polyvinyl butyral. The yellow dye is Kacet Yellow.
AG (manufactured by Nippon Kayaku Co., Ltd.), magenta dye is Kaya
cet Red (manufactured by Nippon Kayaku Co., Ltd.), and the cyan dye is HSB9 (manufactured by Mitsubishi Kasei Co., Ltd.).

Example 2 Composition of Release Layer Coating Composition Polymethylmethacrylate (Tg: 105 ° C.) 10 parts by weight (BR-80 manufactured by Mitsubishi Rayon Co., Ltd.) Teflon powder 1 〃 toluene / 2-butanone (1/1) ) 40〃

Composition of hologram-forming layer coating composition Acrylic polyol resin 25 parts by weight (TG: 75 ° C., OH value: 130) Nitrocellulose resin 5 〃 (nitrogen content: 12%, average degree of polymerization: 45, viscosity: 1/2 ) Xylene diisocyanate 5〃 Toluene / 2-butanone (25/20) 45〃 Isobutylene acetate 20〃

Composition of Adhesive Layer Coating Composition Vinyl Chloride-Vinyl Acetate Copolymer (Tg; 65 ° C.) 10 parts by weight (Estock A manufactured by Sekisui Chemical Co., Ltd.) 2- (2′-hydroxy-5′-methylphenyl) -Benzotriazole 2.5 〃 Toluene / 2-butanone (2/1) 40 〃

A release layer (12) was formed on a polyethylene terephthalate film having a thickness of 25 μm by using a gravure coater and applying and drying the release layer coating material so that the dry weight was 2.0 g / m ² . The above-mentioned hologram forming layer coating material was dried on the layer with a gravure coater to give a dry weight of 0.9 g.
/ M ² so that the hologram forming layer (1
3) is formed, and after aging at 60 ° C. for 72 hours, the hologram forming layer and the hologram pattern forming surface of the stamper are overlapped with a press machine and embossed 16
A hologram was formed on the hologram formation surface by heating at 0 ° C. and 40 kg / cm under pressure. Next, ZnS was vapor-deposited on the hologram formation surface to a thickness of about 500 Å to form a transparent thin film layer (14). Further, the above adhesive layer coating material was applied and dried with a gravure coater so that the dry weight was 1.5 g / m ² , to form an adhesive layer (16), and a transparent hologram transfer foil was manufactured.

The transfer foil obtained above was laminated under the same conditions as in Example 1 to remove the base film.

Example 3 Composition of release layer coating composition Epoxy resin (softening point 148 ° C.) 10 parts by weight (Yukaka Shell Co., Ltd. Epiate 1009) Polyethylene powder 0.5 〃 Toluene / 2-butanone (1/2 ) 40〃

Composition of coating material for hologram forming layer Acrylic polyol resin 25 parts by weight (TG: 75 ° C., OH value: 100) Nitrocellulose resin 5 〃 (nitrogen content: 12%, average degree of polymerization: 45, viscosity: 1/2 ) Xylene diisocyanate 5〃 Toluene / 2-butanone (25/20) 45〃 Isobutylene acetate 20〃

Composition of Anchor Layer Coating Composition Polyurethane Ionomer Aqueous Dispersion 100 parts by weight (DIC HYDRAN AP40, NV: 20% by weight)

Composition of Adhesive Layer Paint Linear saturated polyester resin (Tg; 65 ° C.) 10 parts by weight (Unitika Ltd. UE-3200) 2-hydroxy-4-methoxybenzophenone 6 〃 toluene / 2-butanone (1 / 1) 40〃

A release layer (12) was formed on a polyethylene terephthalate film having a thickness of 25 μm by using a gravure coater and applying and drying the release layer coating material so that the dry weight was 2.0 g / m ² . The above-mentioned hologram forming layer coating material was dried on the layer with a gravure coater to give a dry weight of 0.9 g.
/ M ² so that the hologram forming layer (1
3) is formed, and after aging at 60 ° C. for 72 hours, the hologram forming layer and the hologram pattern forming surface of the stamper are overlapped with a press machine and embossed 16
A hologram was formed on the hologorum-forming surface by performing heating at 0 ° C. and 40 kg / cm under pressure. Next, ZnS was vapor-deposited on the hologram formation surface to a thickness of about 500 Å to form a transparent thin film layer (14). A dry weight of 1.0 g of the above anchor layer paint was applied on the layer using a gravure coater.
Anchor layer (15) was formed by coating and drying so as to be / m ² . Further, the above adhesive layer coating material was applied and dried by a gravure coater to a dry weight of 1.5 g / m ² , to form an adhesive layer (16), and a transfer foil was manufactured.

The transfer foil obtained above was laminated under the same conditions as in Example 1 to remove the base film.

(Examples 4 and 5) A linear saturated polyester resin (Vylon 30 manufactured by Toyobo Co., Ltd.) was used as a peeling improver for 100 parts by weight of the total amount of the thermoplastic resin and the anti-friction agent.
The transfer foil was manufactured in the same manner as in Examples 2 and 3 except that the release layer containing 2 parts by weight of 0) was used. The card and transfer are the same as in Example 1.

Table 2 shows the scratch resistance, abrasion resistance, solvent resistance, heat resistance, tamper resistance, and light resistance of Examples 1-5.

[0079]

[Table 2]

Each data was tested by the following method.

Adhesiveness: Cellotape peeling test (JIS K
5400-1990 / cross-cut tape method), those that do not change are ◯, those that can be partially taken are Δ, and those that can be taken are all ×.

Scratch resistance ... Scratch the surface with a pencil of H to measure the strength. ○ those that are not scratched, × those that are scratched.

Abrasion resistance: Rubbing the surface of the card 2000 times with a dynamic vibration fastness tester (using metal as a friction material),
Observe the change of the surface (fine print). The one that does not change is ○, and the one that changes is ×.

Plasticizer resistance: A soft polyvinyl chloride sheet is brought into contact with the surface of the card, and a load of 200 g / cm ² is applied to the card at 40 ° C. and 90% R.V. H. 24 hours, 48 hours
Save for 100 hours and 100 hours respectively, and observe the color change, fading, and bleeding of the image. Those that do not change are ○, those that have some discoloration or bleeding are △, those that have discoloration or bleeding are ×.

Solvent resistance: Freon, ethanol, and gasoline are soaked in a cotton swab, the surface of the card is rubbed, and changes are observed. The ones that did not change at all were ○, and the ones that changed even once were ×.

Heat resistance: 50 ° C., 90% R.V. H. Stored under the environment for 48 hours and observe the discoloration of the image. The one that does not change is ○, and the one that has faded is ×.

Tamper-proof property: Those in which the hologram pattern is clearly recognizable, x in which the hologram pattern is not recognizable, and Δ in which the hologram pattern is not clear.

Light resistance ... 4 times of ultraviolet rays with a fade meter
After irradiation for 0 hours, the reduction rate of the reflection density of the image is measured.

[0089]

INDUSTRIAL APPLICABILITY As described above, the dyed product according to the present invention can prevent various chemical and mechanical damages of images dyed with a sublimable dye and fading due to light such as ultraviolet rays, and can be tampered with by forming holograms. It can be prevented.

Therefore, it can be used as an information recording card such as a prepaid card or an identification card.

[0091]

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a dyed product related to the dyed product of the present invention.

FIG. 2 is a cross-sectional view of a transfer foil used for producing a dyed product of the present invention.

FIG. 3 is a cross-sectional view of a transfer foil used for producing a dyed product of the present invention.

[Explanation of symbols]

 1 Transfer Foil 2 Card Body 2a Partial Sublimation Dye Face Photo 3a Hologram Pattern 11 Base Film 12 Release Layer 13 Hologram Forming Layer 14 Transparent Thin Film Layer 15 Primer Layer 16 Adhesive Layer

Claims (4)

[Claims] 1. A refractive index higher than that of a hologram-forming layer on the surface of a plastic substrate whose surface is dyed with a sublimation dye, with an adhesive layer made of an ultraviolet absorber and a thermoplastic resin having a glass transition point of 50 ° C. or higher interposed therebetween. A dyed product obtained by laminating a transparent thin film layer having a large size and a hologram forming layer at least sequentially. 2. A hologram forming layer comprising a two-component reactive urethane resin as a main component, and a polyol component of the resin having a glass transition point in the range of 70 ° C. to 150 ° C. and an OH number in the range of 50 to 150. The dyed product according to claim 1, which is a polyol resin. 3. The dyed product according to claim 1, wherein a primer layer is provided between the transparent thin film layer and the adhesive layer. 4. The dyed product according to claim 1, wherein the primer layer is a urethane resin.