JPH02226292A - Ultraviolet ray sensitive article - Google Patents

Abstract

PURPOSE:To use the ultraviolet ray sensitive article where magnetic recording is possible suitably for a credit card, a season ticket, a telephone card, etc., and to enable coloring and color tone variation by the sunlight by providing a magnetic layer on one surface of the substrate of the article and a photochromic layer locally on the other surface. CONSTITUTION:A film which is about 20 - 300mum thick is coated with magnetic paint by a direct coating method and a card base body is stuck on the reflecting surface of the film by using an adhesive. In another way, a film of nearly the same thickness is coated with a peeling layer and further coated with a protection layer, a magnetic layer, and a heat-sensitive adhesive layer to form a specific magnetic tape for transfer, and after the tape is adhered by being pressed and heated and then cooled, only the film is peeled. Then the photochromic layer is provided at least on part of the reflecting surface of the magnetic layer and this layer uses a photochromic compounded consisting of a spiro pyrane compound, a spiro oxiazine compound, a triaryl methane compound, etc., which changes from colorless to colored with ultraviolet rays.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an ultraviolet sensitive article capable of magnetic recording. More specifically, it is a magnetic recording card that can be used as a variety of credit cards and prepaid cards, and has a color that reversibly changes when exposed to ultraviolet light or sunlight, and has excellent abrasion resistance, durability, and repeatability. This invention relates to ultraviolet-sensitive articles.

[Prior Art] Conventionally, sheet-like articles have been produced that take advantage of changes in color tone or changes in color development and fading in response to ultraviolet rays from chemical lamps, ultra-high pressure mercury lamps, and sunlight, by providing a photochromic layer on a substrate. Various types are widely used.

For example, Japanese Unexamined Patent Publication No. 196673/1983 proposes a method of drawing on paper, film, etc. with a photochromic marker pen.

[Problems to be Solved by the Invention] However, such techniques merely relate to sheet-like articles having photochromic properties, and are insufficient from the viewpoint of recording.

On the other hand, cards such as prepaid cards such as telephone cards have various types of printing or photographs on their surfaces, but many of them lack interest.

The present invention aims to solve the problems of the prior art, and provides an ultraviolet-sensitive article that has photochromic properties and is magnetically recordable.

[Means for Solving the Problems] The present invention achieves the above object and has the following configuration.

"An ultraviolet-sensitive article characterized by providing a magnetic layer on one surface of a substrate and providing a photochromic layer on at least a portion of the other surface." The substrate used as the substrate of the present invention includes: , for example, paper substrates such as wood-free paper, semi-synthetic paper, coated paper, resin-impregnated paper and synthetic paper obtained from thermoplastic resins such as polystyrene, polyethylene, polypropylene and vinyl chloride, as well as polyester, polyphenylene sulfide, polypropylene, polyethylene ,
vinyl chloride, cellophane, acetate, polystyrene,
Examples include various film base materials such as polycarbonate, nylon, acrylic resin, and polyimide, and these can be used even if two or more types of base materials are mixed or laminated. Among these, polyester is particularly preferred in terms of the durability of the photochromic layer, its adhesiveness, its adhesion to the magnetic layer, and the like.

As the material for the magnetic layer and the method for manufacturing the same in the present invention, materials generally used in magnetic cards and methods for forming the same can be used.

In other words, a general magnetic paint can be used as the material for forming the magnetic layer, and the manufacturing method is almost the same as the magnetic paint for magnetic tapes such as audio tapes, video tapes, and computer tapes. is used. For example, it is prepared by mixing magnetic powder with a binder resin, such as a urethane resin, and a dispersant, a lubricant, a solvent, etc., and uniformly dispersing the mixture with a dispersing machine. As the dispersing machine, it is preferable to use a sand grind mill, a ball mill, a roll mill, or the like. Magnetic paints can be used in various printing methods, such as offset printing, gravure printing, and screen printing.

The following three methods are generally used to form the magnetic layer.

1. Direct coating method This method is used for the magnetic base material of prepaid cards such as magnetic commuter passes, telephone cards, and orange cards, and is a method in which magnetic paint is uniformly applied to the substrate using the gravure method, doctor blade method, reverse roll method, etc. It is. It is also suitable to coat this with a protective layer of about 1 to 3 μm using a gravure method, and if necessary, for the purpose of preventing forgery, that is, to hide the color of the magnetic layer.
It is also possible to print a 3 μm color layer between the magnetic layer and the protective layer.

2. Tape pasting method A magnetic layer is formed by direct coating on a film with a thickness of about 20 to 300 μm, an adhesive layer is formed on the opposite side of the film, and after punching into a predetermined shape or slit, it is placed on the card base. This method is to attach it to the

In this method, since there is a film and an adhesive layer between the magnetic layer and the card base, the magnetic surface can be made relatively smooth even if the card base has a rough surface such as cloth or paper. It is possible.

36 Magnetic layer transfer method Apply a release agent to a film with a thickness of about 20 to 300 μm,
A protective layer, a magnetic layer, and a heat-sensitive adhesive layer are laminated and coated thereon, and this is slit to a predetermined width to produce a magnetic tape for transfer. Next, this cheap adhesive layer is brought into close contact with the substrate, bonded by applying pressure and heat, and after cooling, the film is peeled off to form a magnetic layer on the card substrate.

The photochromic layer in the present invention is provided on at least a portion of the surface of the substrate opposite to the magnetic layer, and consists of a polymer containing a photochromic compound as a component thereof. The content of the photochromic compound contained in such a photochromic layer should be determined depending on the concentration required for coloring the intended ultraviolet-sensitive article, but is usually 0.5 wt% to 70 wt%. It is preferably used within the range of

Photochromic compounds preferably used in the present invention change from colorless to colored by light in the ultraviolet region,
It is also a compound that reversibly changes from colored to colorless by visible light or heat; specific examples include spiropyran compounds, spirooxazine compounds, spiropyridoxazine compounds, triarylmethane compounds, fulgide compounds, and stilbene compounds. , dithizone mercury complex compounds, organic photochromic compounds such as viologen compounds, silver halide compounds, titanium-containing salt compounds, A
Examples include inorganic photochromic compounds such as g2O-8i02-based compounds.

Among such photochromic compounds, it has excellent light resistance and durability, and it is easy to achieve color density, etc.
Especially spiropyran compounds, spirooxazine compounds,
Ionically cleavable photochromic compounds such as spiropyridoxazine compounds are particularly useful.

In addition, usable polymers include, but are not limited to, styrene resins, acrylic resins, vinyl resins, polyester resins, urethane resins, epoxy resins, polyamide resins, and cellulose derivatives. It's not a thing. These polymers may be used alone or in combination of two or more.

In the present invention, methods for incorporating the photochromic compound into the polymer matrix include (1) simply dispersing the photochromic compound in the polymer, and (2) incorporating the photochromic compound into the polymer by covalent bonding.

In method (2), the photochromic compound and polymer described above can be used.

In addition, in method (2), since it is possible to increase the amount of photochromic compound added, the color density increases, and
This is particularly suitable in terms of preventing bleed-out of the photochromic compound from the photochromic layer and improving light resistance.

As a method for making this covalent bond, a method using vinyl polymerization is advantageous in terms of the performance of the photochromic polymer and the manufacturing cost.

For vinyl polymerization, a compound obtained by adding a polymerizable unsaturated functional group to the photochromic compound is preferably used. Specific examples of such compounds include 6-m=tro 1-(meth)acryloxyethyl-3,3-dimethylindolinospilobenzopyran, 8'-(meth)acryloxymethyl-6'-nitro 1. 3.3-trimethylindolinospirobenzopyran, 6'-nitro 1-(meth)acrylamidoethyl-3,3-dimethylindolinospilobenzopyran, 1-(meth)acryloxyethyl-3,3-dimethylindo Linospironaphthoxazine, 1-(meth)acrylamidoethyl-3,3-dimethylindolinospironaphthoxazine, 1. 3.
3-1 Limethyl-9'-(meth)acryloxyindolinospironaphthoxazine, 1. 3. 3-trimethyl-5'(meth)acryloxymethylindolinospironaphthoxazine, 1. 3. 3-) Dimethyl9'-
Examples include vinylbenzoyloxyindolinospironaphthoxazine and vinyl viologen.

Moreover, as a copolymerizable component with the photochromic compound having these polymerizable unsaturated functional groups, a monomer having a vinyl group is similarly preferable. Specific examples of such monomers include styrene, styrene derivatives, (meth)acrylic acid alkyl esters, (meth)acrylic acid hydroxyalkyl esters, (meth)acrylic acid, (meth)acrylamides, alkyl-substituted (meth)acrylamides, N
Substituted maleimide, maleic anhydride, (meth)acrylonitrile, methyl vinyl ketone, vinyl acetate, vinylidene chloride, divinylbenzene, ethyl alcohol di(meth)
Examples thereof include acrylates and functional (meth)acrylic acid ester compounds thereof.

In the present invention, the solvent for the polymer and photochromic compound used when applying the photochromic layer is an alcohol-based solvent such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, normal butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, etc. Solvents, glycol ether solvents such as methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, propylene glycol monomethyl ether, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, aliphatic solvents such as normal hexane, normal heptane, normal octane, etc. Hydrocarbon solvents, alicyclic hydrocarbon solvents such as cyclohexane and ethylcyclohexane, petroleum solvents such as mineral spirit, ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aromatic solvents such as benzene, toluene and xylene. Various solvents such as hydrocarbon solvents can be used, and these can be used alone or in combination.

In addition, the solid content concentration in the solution of the polymer and photochromic compound used for coating the photochromic layer varies depending on the coating method and coating conditions.
A range of 5 wt% to 75 wt% is preferably used.

In addition, in the photochromic layer according to the present invention, it is also preferable to add a light stabilizer, a sensitizer, etc. to the polymer solution used for coating the photochromic layer for the purpose of improving light resistance and coloring density.

Furthermore, for the purpose of improving printing characteristics, a method of adding a thixotropic agent, a leveling agent, an antisettling agent, a matting agent, etc. is also preferably used.

Coating of the photochromic layer is carried out by commonly used spraying methods, roller coating methods, flow coating methods, offset printing methods, screen printing methods, etc., but is not limited thereto.

Needless to say, the surface coated with the photochromic layer of the ultraviolet-sensitive article of the present invention may be printed with offset printing to enhance the aesthetic appearance of the marking and the article depending on the purpose of use.
It is also effective to print paints using common dyes and pigments other than photochromic coatings by gravure printing and screen printing.

Furthermore, providing a cover film or a transparent overcoat layer on the core layer for the purpose of protecting the photochromic layer in the present invention is also important for improving the durability of the ultraviolet-sensitive article. In particular, the overcoat layer is effective for reducing the level difference in the photochromic layer, and specific examples of materials that can be used as the overcoat layer include acrylic resin, polyester resin, and urethane resin. Those applied by coating are particularly useful for eliminating level differences. On the other hand, as a material used as the cover film, a material equivalent to the film base material described as the material for the base body can be used. Among these, polyester film has excellent abrasion resistance, durability, and weather resistance, and by heat pressing with this polyester film, it is possible to produce UV-sensitive products with excellent appearance and high quality as products. can be provided.

Further, it is a preferable configuration to further improve durability and aesthetic appearance by further applying a cover film on the overcoat.

Further, each cover film can be matted to provide non-glare properties and reduce reflection to improve quality. These substrates and cover films include
Various additives such as printing property improvers, plasticizers, and weather resistance improvers can be used depending on the intended use, and the sheet thickness of the cover film varies depending on the intended use and is not particularly limited. However, especially as a cover film for applications requiring transparency, weather resistance, etc., the thickness is preferably 10 μm to 70 μm.

The cover film can be laminated using conventional methods such as heat-sealing the film, applying adhesive or pressure-sensitive adhesive as necessary to the adhesive surface of the film, and heat-pressing or roll-pressing. It will be carried out in

The ultraviolet-sensitive article having the structure of the present invention has a magnetic layer and a photochromic layer that is resistant to friction caused by fingernails, paper, cloth, etc., so it can be used as a telephone card with an ultraviolet sensor or an intensity check function. , Orange Card, commuter pass, credit card, etc.

[Example] The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1 n-butyl methacrylate, methyl methacrylate, lauryl methacrylate, 1-benzyl 3,3-dimethyl-9'-methacryloxyspiro[indoline-2,3-
-[3H]-naphtho[2°], b](1,4)oxazine] were polymerized in toluene at a temperature of 7°C using azobisdimethylvaleronitrile as an initiator.
Polymerization was carried out at 0° C. for 10 hours under a nitrogen atmosphere to prepare a photochromic compound copolymer solution.

A magnetic layer was prepared by directly applying a magnetic paint made of γ-iron (γ-FeQ3), a urethane resin, and toluene, ethyl acetate, and methyl ethyl ketone to a 100 μm thick PET film by a gravure method. The photochromic compound copolymer solution described above was screen printed on the surface opposite to the magnetic layer, and then dried at 30° C. for about 15 minutes.

The obtained magnetically recordable ultraviolet-sensitive sheet developed a blue color having a maximum absorption wavelength of 60 Qnm when the photochromic layer side was irradiated with ultraviolet light, and had excellent light resistance.

Example 2 In the UV-sensitive sheet obtained in Example 1, a 20-μm-thick adhesive divided PET cover film was further laminated on the photochromic layer using a roll laminator to produce a magnetically recordable UV-sensitive sheet. .

The sheet has an excellent appearance and good abrasion resistance against rubbing with fingernails and cloth, and when the photochromic layer side is irradiated with ultraviolet light, it develops a blue color with a maximum absorption wavelength of 60 Qnm, and has excellent light resistance. It was also excellent.

Example 3 The copolymerization components described in Example 1 were polymerized in the same manner except for the photochromic monomer, and 1-benzyl-3,3-dimethylspiro[indoline-2,3' -[3H]naphtho[2,1-b] (
1,4) Oxazine] was added to prepare a coating polymer solution.

Using the obtained photochromic compound-added polymer solution, a UV-sensitive article was similarly produced according to the method described in Example 1. Furthermore, a cover film was laminated in the same manner as in Example 2.

The resulting UV-sensitive article has excellent appearance and light resistance,
Furthermore, it had good abrasion resistance against rubbing with fingernails, cloth, etc., and also showed good color development to blue when irradiated with ultraviolet light.

[Effects of the Invention] The ultraviolet-sensitive article of the present invention has a magnetic layer, so magnetic recording is possible, and it is useful as a credit card, commuter pass, telephone card, orange card, etc.; Since it can produce color and change in tone, it can also be used as a variety of fashion products and interesting products.

Furthermore, the article of the present invention has excellent light resistance and good appearance, and by protecting the photochromic layer with Coverf 1 film, it provides durability, especially abrasion resistance, which is an important performance in practical terms. It is something.

Claims (1)

[Claims] An ultraviolet-sensitive article characterized in that a magnetic layer is provided on one surface of a base material, and a photochromic layer is provided on at least a portion of the other surface.