JPH0655487B2 - Dyed - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dyed product.

More specifically, it 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.

(Field of Industrial Application) The present invention relates to a dyed product.

More specifically, it relates to a dyed material which is a plastic material dyed with a so-called sublimation dye and which can prevent discoloration and bleeding of the dye.

(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 permeate the dye into the plastic to be dyed (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 improvement of thermal heads, a method has been developed to form images by allowing dyes on the transfer ribbon to penetrate into the plastic material by 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 a plastic material to fix a dye, or the dye is improved to improve light 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) Therefore, the present invention is a plastic material dyed with such a sublimable dye, which can prevent chemical and mechanical damage of a dyed image and does not cause discoloration due to light. The purpose is to provide a dyed product.

(Means for Solving the Problem) In order to achieve this object, the invention according to claim (1)
There is provided a dyed product comprising a surface protection layer laminated on a surface of a plastic substrate whose surface is dyed with a sublimation dye, with an adhesive layer containing an ultraviolet absorber interposed therebetween.

The invention according to claim (2) provides the dyed product, wherein the surface protective layer is a mixture of a friction-resistant agent and a thermoplastic resin.

The invention according to claim (3) provides the above-mentioned dyeing product, wherein the adhesive layer is a mixture of a thermoplastic resin having a glass transition point of 50 ° C. or higher and an ultraviolet absorber.

The plastic base material is preferably a card such as an identification card or a cash card, and the characteristics 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 face 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 Yellow TDN (Nippon Kayaku Co., Ltd.), PTY52, Di
anix Yellow 5R-E, Dianix Yellow F3G-E, Dianix Bril
liant Yellow 5G-E (above Mitsubishi Kasei), Plast Y
ellow 8040, DY108 (all manufactured by Arimoto Chemical Co., Ltd.), Sumikar
on Yellow EFG, Sumikaron Yellow E-4GL (Sumitomo Chemical Co., Ltd.), FORON Brilliant Yellow S6GLPI (Sand
Manufactured by the company) can be exemplified.

Examples of magenta sublimation dyes include Kayacet Red 02
6, Kayacet Red 130, Kayacet Red B (manufactured by Nippon Kayaku Co., Ltd.), Oil Red DR-99, Oil Red DK-99 (manufactured by Arimoto Kagaku Co., Ltd.), Diacelliton Pink B (Mitsubishi Kasei Co., Ltd.) )
), Srmikaron Red E-FBL (Sumitomo Chemical Co., Ltd.), Lat
Examples include yl Red B (manufactured by du Pont), Sudan Red 7B (manufactured by BASF), Resolin Red FB, Ceres Red 7B (manufactured by Bayer).

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
(Manufactured by Mitsui Toatsu Co., Ltd.), Ceres Blue GN (manufactured by Bayer),
Examples thereof include Duranol Brilliant Blue 2G (manufactured by ICI).

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 in the specification of Japanese Patent Application No. 216576 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. To prevent the penetration of the plasticizer, the adhesive layer (2) is separated from the surface protective layer (3). Moreover, it is provided on the plastic substrate rather than the surface protective 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 that 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, phenyl salicylate, p-tert
-Butylphenyl salicylate, p-octylphenyl salicylate, and other salicylic acid-based UV absorbers, 2,4
-Dihydroxybenzophenone, 2-hydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-44 ' -Dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-
Benzophenone-based UV absorbers such as 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 thermoplastic resin used for the adhesive layer (2) may have a glass transition point (Tg) of 50 or more. When a resin having a glass transition temperature of less than 50 ° C. is used, dye migration occurs due to this resin, and image bleeding occurs. When a transfer foil described below is used, it preferably has a glass transition point of 110 ° C. or lower. Glass transition point is 1
If a resin having a temperature higher than 10 ° C. is used, a high temperature is required for the transfer, not only a load is applied to the transfer machine, but also a plastic material such as a polyvinyl chloride card 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), poly (isobornyl acrylate), poly (methacrylomethyl), polyacrylonitrile, poly (methyl chloroacrylate), poly (methyl methacrylate), poly (ethyl methacrylate), poly (meth-acrylic 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, Examples thereof include styrene-butadiene copolymer resins and vinyl resins such as styrene and alkyl methacrylate (wherein the alkyl group has 1 to 6 carbon atoms).

The adhesive layer (2) comprises 50 to 90 parts by weight of a thermoplastic resin and 10 to 5 parts of an ultraviolet absorber with respect to 100 parts by weight of the total solid content.
0 parts by weight is sufficient. The coating amount is preferably 1 to 3 g / m ² .

Further, the surface protective layer (3) 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. As such a thermoplastic resin, polymethylmethacrylate, nitrocellulose or a mixture of polymethylmethacrylate and nitrocellulose can be used. Methyl methacrylate and nitrocellulose have excellent plasticizer resistance among existing thermoplastic resins, and by using these resins for the surface protection layer (3), soft vinyl chloride sheet or plastic eraser can be brought into contact with the image. When this is done, migration of the plasticizer contained in these 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, plant wax, mineral wax, natural wax such as petroleum wax, synthetic hydrocarbon wax, aliphatic alcohol and acid wax, resin acid ester and glycerite wax, Hydrogenated wax, synthetic ketone wax, amine and amide wax, chlorinated hydrocarbon wax, synthetic animal wax wax, synthetic wax such as alpha-olefin wax, and metal salt of higher fatty acid such as zinc stearate I can give you.

The surface protective layer (3) may contain 100 parts by weight of the total amount of the thermoplastic resin and the anti-friction agent, the thermoplastic resin 85 to 95 parts by weight, and the anti-friction agent of 5 to 15 parts by weight.

When a transfer foil is used, the surface protective layer (3) may be mixed with a peeling improving agent 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 (3). This is because addition of the plasticizer facilitates penetration of the plasticizer and causes deformation of the image.

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

The adhesive layer (2) and the surface protective layer (3) may be directly formed on the plastic base material (1), but once they are easily peeled off on another base sheet to form a transfer foil, and the plastic base material surface is formed. The method of transferring to is convenient. In this case, the surface protective layer (3) needs to be easily formed from the base film.

The base film (4) of the transfer foil is required to have heat resistance so that it is not softened and deformed by the heat pressure during transfer. The base film (4) 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 (5) is first made 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 (4) by a coating method such as gravure coating, roll coating or bar coating. Then, the adhesive composition may be made into a paint and applied. The method of coating and applying the adhesive composition is the same as the method of coating and applying the surface protective layer composition.

The transfer foil (5) thus obtained comprises a base film (4), a surface protective layer (3) and an adhesive layer (2) as shown in FIG.

This transfer foil (5) is placed on a plastic substrate dyed with a sublimation dye, and after hot pressing, only the base film (4) 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 fats and oils at the time of thermoplastic contained in the adhesive layer (2).
It is usually 150 to 250 ° C. The time may be about 1 to 10 seconds.

It is obvious that the present invention can be applied not only to the card but also to any plastic material dyed with a sublimation dye.

(Example 1) Composition of surface protective layer dye Polymethylmethacrylate 10 parts by weight (Tg = 105 ° C) (Mitsubishi Rayon BR-80) Teflon powder 1 part by weight Toluene / 2-butanone 40 parts by weight (1/1) Composition of Adhesive Layer Coating Composition Vinyl Chloride-Vinyl Acetate Copolymer 10 parts by weight (Tg = 65 ° C.) (Sekisui Chemical's S-Rex A) 2- (2′-hydroxy-5′-methylphenyl) benzotriazole 2.5 Parts by weight Toluene / 2-butanone 40 parts by weight (1/2) On a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm, the surface protective layer coating material was dried to a weight of 2.5 g / m ² using a gravure coater. And dried so that a surface protective layer (12) was formed. The above-mentioned adhesive layer paint was dried on the layer with a gravure coater to give a dry weight of 2 g / m ^2.
And dried to form an adhesive layer (13) 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) at 180 ° 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) and the magenta dye is Kayacet Red 02
6 (manufactured by Nippon Kayaku), and the cyan dye is HSB9 (manufactured by Mitsubishi Kasei).

(Example 2) Composition of coating for surface protective layer 4 parts by weight of nitrocellulose (Cell line FM200 manufactured by Daicel Chemical Industries, Ltd.) 6 parts by weight of polymethyl methacrylate (Tg = 105 ° C) (Paraloid A-11 manufactured by Loose and House) Polyethylene powder 0 0.5 parts by weight Toluene / 2-butanone 40 parts by weight (1/2) Composition of adhesive layer coating Linear saturated polyester resin 10 parts by weight (Tg = 65 ° C.) (Unitika UE-3200) 2-hydroxy-4-methoxy Benzophenone 6 parts by weight Toluene / 2-butanone 40 parts by weight (1/1) The above coating materials were applied on a biaxially stretched polyethylene terephthalate film having a thickness of 12 μm in the same manner as in Example 1 to produce a transfer foil. did.

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

(Example 3) Tg = 47 instead of saturated polyester having Tg = 65 ° C.
A transfer foil was manufactured in the same manner as in Example 2 except that a saturated polyester resin at 0 ° C was used.

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

Example 4 With respect to 100 parts by weight of the total amount of the thermoplastic resin and the anti-friction agent,
A transfer foil was produced in the same manner as in Example 1 except that a surface protective layer containing 2 parts by weight of a linear saturated polyester resin (Vylon 300 manufactured by Toyobo) was used as a release improving agent.

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) Transfer layer coating composition Polymethylmethacrylate 10 parts by weight (Mitsubishi Rayon BR-80) Teflon powder 1 part by weight 2- (2'-hydroxy-5'methylphenyl) benzotriazole 4 parts by weight Toluene / 2- Butanone 40 parts by weight (2/1) A transfer layer coating composition having the above composition was applied onto a biaxially stretched polyester film having a thickness of 12 μm using a gravure coater so as to have a dry weight of 3.0 g / m ² and dried. Was formed to produce a transfer foil.

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

Table 1 shows the 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 using a pencil tester with an H pencil to measure the strength. ○ If it is not scratched,
× with scratches.

Abrasion resistance: Rubbing the card surface 2000 times with a Gakushin-type fastness tester (using metal as a friction material) and observing the change in the surface. 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 temperature is 40 ° C and 9
0% R. H. Stored under the environment for 24 hours and observe the color change of images and fading and bleeding. ○ those that do not change, × those that have discoloration or bleeding.

Solvent resistance: Soak Freon, ethanol, and gasoline into a cotton swab, rub the surface of the card, and observe the change. The ones that did not change at all were ○, and the ones that changed even once were ×.

Heat resistance: 50 ° C, 90% R.S. 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 ×.

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

As is clear from this table, in Examples 1 to 4, while preventing discoloration of the image due to light, various chemical and mechanical properties such as scratch resistance, abrasion resistance, plasticizer resistance, solvent resistance, etc. Damage can be prevented. In addition, in Examples 1, 2 and 4, in addition to this, it is possible to produce a plastic dyed 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 has various chemical properties such as scratch resistance, abrasion resistance, plasticizer resistance, solvent resistance, etc. A dyed product that is free from mechanical damage and that does not undergo discoloration due to light such as ultraviolet rays can be obtained. 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 an effect that image change due to heat does not occur.

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

BRIEF DESCRIPTION OF THE 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) …… Surface protection layer, (4) …… Base sheet (5) …… Transfer foil (1a) …… Partial sublimable dye Face photo by

Claims (3)

[Claims] 1. A dyed product obtained by laminating a surface protective layer on a surface of a plastic substrate whose surface is dyed with a sublimable dye, with an adhesive layer containing an ultraviolet absorber interposed therebetween. 2. The dyed product according to claim 1, wherein the surface protective layer is a mixture of an anti-friction agent and a thermoplastic resin. 3. The dyed product according to claim 1, wherein the adhesive layer is a mixture of a thermoplastic resin having a glass transition point of 50 ° C. or higher and an ultraviolet absorber.