JPH07106620B2 - Dyed - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dyed product.

More specifically, the present invention relates to a plastic material whose surface is dyed with a sublimable dye, which does not undergo discoloration by ultraviolet rays, and is free from fear of bleeding due to penetration of a plasticizer.

(Prior Art) A method of dyeing a plastic material using a so-called sublimation dye is 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 directly printed 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 is removed by peeling, but in any case, the dye has penetrated into 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 responsiveness and improvements in thermal heads, a method has been developed for forming images by allowing dyes on the transfer ribbon to penetrate into the plastic material due to the heat generated by the thermal heads. Was done. The plastic material is a plastic film or a PVC card such as an identification card.

However, the dye is generally a disperse dye or an oil-soluble dye. 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 decomposed by light, especially ultraviolet rays, and 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, neither of the methods can essentially prevent external chemical or mechanical damage, and cannot avoid light rays such as ultraviolet rays.

(Problems to be solved by the invention) Accordingly, the present invention is a plastic material dyed with such a sublimable dye, and there is no discoloration due to contact with light rays such as ultraviolet rays or rubber containing a plasticizer. It is also an object of the present invention to provide a dyeing product capable of accurately maintaining an image for a long period.

(Means for Solving the Problem) In order to achieve this object, the invention according to claim (1)
There is provided a dyed product in which a diffusion preventive layer for a sublimable dye and a surface protective layer are sequentially laminated on a surface of a plastic substrate whose surface is dyed with a sublimable dye via an adhesive layer containing an ultraviolet absorber.

The invention according to claim (2) is characterized in that the surface protective layer comprises a friction-resistant agent and a thermoplastic resin, and the thermoplastic resin is polymethylmethacrylate or an epoxy resin. provide.

The invention according to claim (3) provides the above-mentioned dyeing product, wherein the diffusion preventing layer of the sublimable dye is nitrocellulose.

Furthermore, the invention according to claim (4) provides the transfer foil, wherein the adhesive layer is made of an ultraviolet absorber and a thermoplastic resin having a glass transition point of 50 ° C. or higher.

The plastic base material is preferably a card such as an identification card or a cashing card, and the features of the present invention can be particularly utilized at this time. This is because the usage conditions are severe and durability is required.

Such cards are generally constructed of rigid polyvinyl chloride with 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. (1) is a base material composed of a card body, and a facial photograph is partially dyed with a sublimation dye (1a).

Dyeing of the substrate surface is performed by printing ink containing a sublimable dye and then heating it, or stacking printed matter (transfer foil) on which ink containing a sublimable dye is printed and heating it to allow only the dye to penetrate (transfer Staining method) is possible. 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.

Yellow sublimation dyes include Kayacet Yellow AG, Kay
akut Yellor TDN (Nippon Kayaku Co., Ltd.), PTY52, Di
anix Yellow 5R-E, Dianix Yellow F3G-E, Dianix
Brilliant Yellow 5G-E (above Mitsubishi Kasei), Plast Yellow 8040, DY108 (above Arimoto Kagaku),
Sumikaron Yellow EFG, Sumikaron Yellow E-4GL (Sumitomo Chemical Co., Ltd.), FORON Brilliant Yellow S6GLP
Examples include I (manufactured by Sand).

Examples of magenta sublimation dyes include Kayacet Red 02
6, Kayacet Red 130, Kayacet Red B (all manufactured by Nippon Kayaku Co., Ltd.), Oil Red DR-99, Oil Red DK-99 (all manufactured by Arimoto Chemical Co., Ltd.), Diacel liton Pink B (Mitsubishi Chemical ( Ltd.), Simikaron Red E-FBL (Sumitomo Chemical Co., Ltd.)
Made), Latyl Red B (made by du pont), Sudan Red 7B (BA
SF company made, Resolin Red FB, Ceres Red 7B (above Bayer
Manufactured by the company) can be exemplified.

Further, as a cyan sublimation dye, for example, Kayalon
Fast Blue FG, Kayacet Blue FR, Kayacet Blue 136, K
ayacet 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 Blue 50
(Mitsui Toatsu Co., Ltd.), Ceres Blue GN (manufactured by Bayer), Duranol Brilliant Blue 2G (manufactured by ICI), and the like.

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 No. 63-22693, or the specification of Japanese Patent Application No. 216576 in 1989 and the drawings.

The adhesive layer (2) adheres to the surface of the plastic material and blocks ultraviolet rays to prevent discoloration of the image due to the dye. In order to prevent the penetration of the plasticizer, the adhesive layer (2) is separated from the diffusion prevention layer (3). Moreover, it is provided with a plastic material rather than the diffusion prevention layer (3). For this reason, it is composed of a mixture of an ultraviolet absorber and a thermoplastic resin.

The ultraviolet absorber prevents discoloration of the dye due to light. That is, it absorbs ultraviolet rays having a wavelength of 250 to 400 nm and re-radiates the energy as heat energy which is harmless to the dye, and the ultraviolet absorber itself does not deteriorate. For this reason, an ultraviolet absorber having a maximum absorption wavelength of 250 to 400 nm is used. For example, salicylic acid UV absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy- Benzophenone UV such as 4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone Absorbent, 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-3,3'
-Diphenyl acrylate, ethyl-2-cyano-3,
It is a cyanoacrylate-based UV absorber such as 3'-diphenyl acrylate.

The thermoplastic resin used for the adhesive layer (2) may have a glass transition point (Tg) of 50 ° C. or higher. If a resin having a glass transition temperature of less than 50 ° C. is used, after the transfer, migration of the dye occurs due to this resin, and image bleeding occurs. Further, those having a glass transition point of 110 ° C. or lower are preferable. When a resin having a glass transition point of more than 110 ° C. is used, a high temperature is required for transfer, which not only puts a load on the transfer machine, but also plastic materials such as polyvinyl chloride cards may be deformed by heat.

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

The adhesive layer (2) may contain 50 to 90 parts by weight of the thermoplastic resin and 10 to 50 parts by weight of the ultraviolet absorber with respect to 100 parts by weight of the total solid content. The coating amount is preferably 1 to 3 g / m ² .

The sublimation dye diffusion preventing layer (3) is provided to prevent the diffusion of the image dyed with the sublimation dye on the surface of plastic such as polyvinyl chloride to the outside. In order to prevent the diffusion of sublimable dyes, natural polymers such as cellulose or hydrophilic polymers obtained by modifying them are applied. Adhesion with ordinary thermoplastic resins, heat resistance, water resistance Nitrocellulose is the most suitable in consideration of sex.

If there is no diffusion prevention layer (3), the dye will diffuse through the adhesive layer (2) to the peeling layer (12) when left for a long period of time, and will be sandwiched by an eraser or soft vinyl chloride containing a plasticizer. If it is left, it is diffused and transferred to an eraser or soft vinyl chloride, which causes discoloration of the image.

Further, the diffusion transfer layer (3) does not serve as the adhesive layer (2).
This is because nitrocellulose has heat resistance and does not adhere to the substrate due to heat.

The diffusion prevention layer (3) is a hydrophilic polymer simple substance such as nitrocellulose, and the coating amount thereof may be 0.5 to 1.5 g / m ² .

Further, the surface protective layer (4) needs to function as a protective film. The function of the protective film is to prevent external chemical and mechanical damage of the image by the dye. In order to satisfy both functions, a mixture of anti-friction agent and thermoplastic resin may be used.

The thermoplastic resin prevents permeation of plasticizers and chemicals and reduces scratches due to scratches. Further, it is desirable to have a function of preventing permeation of the plasticizer. This is because the diffusion barrier layer alone may not have sufficient plasticizer blocking properties.

As the thermoplastic resin, polymethylmethacrylate or epoxy resin can be used. Among existing thermoplastic resins, polymethylmethacrylate and epoxy resins have excellent plasticizer resistance. By using these resins for the surface protective layer (4), soft vinyl chloride sheet or plastic eraser can be added on the image. When brought into contact with each other, migration of the plasticizer contained therein can be prevented. Further, it is possible to prevent penetration of chemicals such as acids, alkalis, alcohols, and kerosene, and prevent the influence on the image.

Further, the anti-friction agent is added to improve abrasion 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 surface protective layer (4) is the total amount of the thermoplastic resin and the anti-friction agent.
The thermoplastic resin may be 85 to 95 parts by weight, and the anti-friction agent may be 5 to 15 parts by weight with respect to 100 parts by weight.

When a transfer foil is used, the surface protective layer (4) may be mixed with a peeling improver in order to improve breakage during transfer. For example, linear saturated polyester resin. However, the additive 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 surface protective layer (4). This is because the chemical resistance is lowered or the plasticizer is easily introduced by the addition, which causes deterioration of the mechanical strength of the surface protective layer (4).

The coating amount of the surface protective layer (4) may be 1 to 3 g / m ² .

The adhesive layer (2) and the surface protective layer (4) may be directly formed on the plastic substrate (1), but once they are easily peeled off on another base sheet to form a transfer foil, and the plastic substrate surface The method of transferring to is convenient. In this case, the surface protective layer (4) needs to be easily formed from the base film.

The base film (5) of the transfer foil is required to have heat resistance so that it is not softened and deformed by the heat pressure during transfer. Such a base film (5) is known, and for example, a biaxially stretched polyethylene terephthalate film having a thickness of 3 to 30 μm can be used.

The transfer foil (6) is first formed into a paint by coating the surface protective layer composition with an appropriate solvent, and the paint is applied and dried on the base film (5) by a coating method such as gravure coating, roll coating or bar coating. Then, the diffusion prevention layer composition and the adhesive composition may be applied as a paint. The method for coating and applying the diffusion preventing layer composition and the adhesive composition is the same as the method for coating and applying the surface protective layer composition.

The transfer foil (6) thus obtained comprises a base film (5), a surface protective layer (4) and a diffusion preventing layer (2) as shown in FIG.

This transfer foil (6) is placed on a plastic substrate dyed with a sublimable dye, and after hot pressing, only the base film (5) is peeled off and transferred to obtain a dyed product of the present invention. it can. The transfer can be performed by heating to a temperature equal to or higher than the softening point of the thermoplastic resin contained in the adhesive layer (2). It is usually 150 to 250 ° C. The time may be about 1 to 10 seconds.

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

(Example 1) Composition of coating for surface protective layer Polymethylmethacrylate 10 parts by weight (Tg: 105 ° C) (BR-80 manufactured by Mitsubishi Rayon Co., Ltd.) Teflon powder 1〃 toluene / 2-butanone (1/1) 40 〃 Composition of anti-diffusion layer coating Nitrocellulose 15 parts by weight (Cell line FM200 manufactured by Daicel Chemical Industries, Ltd.) Toluene / 2-butanone (1/2) 85 〃 Composition of adhesive layer coating Vinyl chloride-vinyl acetate copolymer 10 Parts by weight (Tg: 65 ° C) (Sekisui Chemical Co., Ltd., S-REC A) 2-2'-hydroxy-5'-methylphenyl) -benzotriazole 2.5〃 toluene / 2-butanone (2/1) 40〃 thickness On the 12-micrometer polyethylene terephthalate film, the said peeling layer coating material was apply | coated and dried so that dry weight might be 2.5 g / m < ² > using the gravure coater, and the surface protection layer (4) was formed.

The above diffusion preventive layer coating material was applied onto the layer with a gravure coater so as to have a dry weight of 0.8 g / m ² , and dried to form a diffusion preventive layer (3). Further, the above adhesive layer coating material was applied and dried on the layer by a gravure coater so that the dry weight was 1.8 g / m ² , and an adhesive layer (2) was formed to produce a transfer foil.

Each color of yellow, magenta and cyan was transfer dyed on 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 dye and polyvinyl butyral. The yellow dye is Kacet Yellow AG (Nippon Kayaku Co., Ltd.), Magenta Dye is Kayacet Red 026 (manufactured by Nippon Kayaku Co., Ltd.), and cyan dye is HSB9 (manufactured by Mitsubishi Kasei Co., Ltd.).

(Example 2) Composition of dye for release layer Epoxy resin (softening point 148 ° C) 10 parts by weight (Epicoat 1009 manufactured by Yuka Shell Co., Ltd.) Polyethylene powder 0.5 〃 Toluene / 2-butanone (1/2) 40 〃 Diffusion prevention Composition of layer coating Nitrocellulose 15 parts by weight (Cell line FM200 manufactured by Daicel Chemical Industries, Ltd.) Toluene / 2-butanone (1/2) 85 〃 Composition of adhesive layer coating Linear saturated polyester resin 10 parts by weight (Tg: 65 (Unit-3) UE-3200 manufactured by Unitika Ltd. 2-Hydroxy-4-methoxy benzophenone 6 〃 Toluene / 2-butanone (1/1) 40 〃 Each of the above paints was applied on a polyethylene terephthalate film having a thickness of 16 µm. A transfer foil was manufactured by applying in the same manner as in.

The card and transfer are the same as in Example 1.

(Example 3) A transfer foil was produced in the same manner as in Example 2 except that a saturated polyester resin having a Tg of 47 ° C (Vylon 300 manufactured by Toyobo) was used in place of the saturated polyester resin having a Tg of 65 ° C.

The card and transfer are the same as in Example 1.

(Example 4) Except for using a release layer in which 2 parts by weight of a linear saturated polyester resin (TOYOBO BYRON 300) was added as a release improving agent to 100 parts by weight of the total amount of the thermoplastic resin and the anti-friction agent. A transfer foil was manufactured in the same manner as in Example 1.

The card and transfer are the same as in Example 1.

Comparative Example 1 The dyed card itself was used as Comparative Example 1 without using the transfer foil.

(Comparative Example 2) A transfer foil was produced in the same manner as in Example 1 except that 2- (2'-hydroxy-5'-methylphenyl) benzotriazole which was an ultraviolet absorber was omitted.

The card and transfer are the same as in Example 1.

(Comparative Example 3) Composition of release layer paint 4 parts by weight of nitrocellulose (Cell line FM200 manufactured by Daicel Chemical Industries, Ltd.) Polymethylmethacrylate 6 〃 (Tg: 105 ° C) (BR-80 manufactured by Mitsubishi Rayon Co., Ltd.) Teflon powder 1 〃 Toluene / 2-butanone (1/1) 40 〃 Composition of adhesive layer coating Vinyl chloride-vinyl acetate copolymer 10 parts by weight (Tg: 65 ° C) (Sekisui Chemical Co., Ltd. S-REC A) 2- (2'-Hydroxy-5'-methylphenyl) -benzotriazole 2.5 〃 Toluene / 2-butanone (2/1) 40 〃 A 12 μm thick polyethylene terephthalate film was dried using a gravure coater. weight
The release layer was formed by coating and drying so as to have a concentration of 3.0 g / m ² .
A transfer foil was manufactured by coating the adhesive layer coating composition on the layer with a gravure coater so that the dry weight was 1.8 g / m ² and drying to form an adhesive layer. The card and transfer are the same as in Example 1.

Table 1 shows scratch resistance, abrasion resistance, solvent resistance, heat resistance, and light resistance of Examples 1 to 3 and Comparative Examples 1 and 2. Each data was tested by the following method.

Scratch resistance ... Scratch the surface with a pencil tester using a pencil of H, measure the strength, ○ for those without scratches, × for those with scratches.

Abrasion resistance: Rubbing the card surface 2000 times with a Gakushin-type fastness tester (using metal as a friction agent) and observing the surface change. 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, a load of 200 g / cm ² is applied, and the sheet is stored at 40 ° C and 90% RH for 24 hours, 48 hours, and 100 hours, respectively. Observe color changes, fading, and bleeding. ○ those that do not change, × those that have discoloration or bleeding.

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

Heat resistance: Store in an environment of 50 ° C and 90% RH for 48 hours and observe the discoloration of the image. The one that does not change is ○, and the one that has faded is ×.

Light resistance ... After irradiating ultraviolet rays for 40 hours with a fade meter,
Measures the reduction rate of image reflection density.

As is clear from this table, Examples 1 to 4 are excellent plasticizers capable of preventing discoloration of the image due to light and preventing diffusion and migration of the image to the outside such as plastic containing a plasticizer. In addition, it is possible to impart various properties and prevent various chemical and mechanical damages such as scratch resistance, abrasion resistance and solvent resistance. In addition, in Examples 1, 2 and 4,
In addition to this, it is possible to produce a plastic dyeing product which does not cause bleeding due to heat.

(Effects) As described above, according to the present invention, a plastic material dyed with a sublimation dye, which is excellent in plasticity, scratch resistance, abrasion resistance, solvent resistance, etc. A dyed product that does not undergo discoloration due to light is obtained. As a result, a dyed product with a stable image can be obtained for a long period of time.

In addition to this, when a thermoplastic resin having a glass transition point of 50 ° C. or higher is used for the adhesive layer, it is possible to obtain the effect of not causing image change due to heat.

Therefore, it can be used as a plastic card having an image with a sublimation dye, such as an information recording card such as a prepaid card or an identification card.

[Brief description of drawings]

FIG. 1 is a sectional view of a dyed product, and FIG. 2 is a sectional view of a transfer foil. (1) ... Plastic substrate (2) ... Adhesive layer (3) ... Dye diffusion prevention layer (4) ... Surface protection layer (5) ... Base sheet (6) ... Transfer foil (6a) ... Transfer layer (1a) ... facial photo with partial sublimation dye

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 27/30 A 8115-4F 27/38 7421-4F

Claims (4)

[Claims] 1. A dyed product comprising a plastic substrate whose surface is dyed with a sublimable dye, and a diffusion preventive layer for the sublimable dye and a surface protective layer, which are sequentially laminated on the surface of an adhesive layer containing an ultraviolet absorber. . 2. The dyed product according to claim 1, wherein the surface protective layer comprises a friction-resistant agent and a thermoplastic resin, and the thermoplastic resin is polymethylmethacrylate or an epoxy resin. 3. The dyed product according to claim 1, wherein the diffusion preventing layer of the sublimable dye is nitrocellulose. 4. The adhesive layer has an ultraviolet absorber and a glass transition point of 50.
The dyed product according to any one of claims (1) to (3), which is made of a thermoplastic resin having a temperature of not less than ° C.