JPS61214152A - Optical card - Google Patents

Abstract

PURPOSE:To execute recording with a high density, and to make it difficult to falsify the information by irradiating an energy beam to the second recording layer consisting of a reflecting metallic thin film layer, which is provided on the surface of the first recording layer consisting of a light transmitting part and a light shielding part. CONSTITUTION:The second recording layer 10 consisting of a reflecting metallic thin film layer is formed on the first recording layer 9 consisting of a light transmitting part 7 and a light shielding part 8. When the thin film layer of a low melting point alloy is used as 10, a reflection factor in a pit being a recording part and a reflection factor in a metallic thin film being an unrecorded part are made small, and an excellent information read-out characteristic is obtained. When a read-out use irradiating beam is irradiated, the irradiating beam is absorbed by the light shielding part and the reflection factor goes to small, and in the light transmitting part 7, said beam is not absorbed and the reflection factor becomes a large value. In the layer 9 and the layer 10, a difference of the reflection factors by the light shielding part 8 and the light transmitting part 7, and a difference of the reflection factors by the pit part and the unrecorded part are read, respectively, and information which has been written in a card can be read-out. In this way, recording can be executed with a high density, and also it makes remarkably falsification of the information difficult.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an optical card, and more particularly, it has a novel optical recording material and is capable of writing high-density information.
AW type (direct read-after-w
rtte) Regarding optical cards.

[Technical Background of the Invention and Problems Therein] Conventionally, magnetic materials have been mainly used as recording materials embedded in cards such as credit cards and bank cards. This magnetic material has the advantage that information can be easily loaded and read, but on the other hand, it has the disadvantage that information can be easily amended and high-density recording is not possible.

By the way, in order to solve the above-mentioned problems, information can be transmitted to the photosensitive material by subjecting the photosensitive material to pattern exposure to form an unexposed light-transmitting area and an exposed light-blocking area. Types of optical recording materials have been proposed in which this information can be written and read depending on the light transmission. When attempting to embed such an optical recording material in a card base material and use it as a recording material for a card, the following problems arise.

(a) A card base material is often subjected to various types of printing on its surface, and for this purpose, it is preferable that the card base material be opaque. However, in order to embed the optical recording material as described above, it is necessary to make at least a portion of the base material transparent, which is a significant disadvantage in the production of cards.

(b) With the above-mentioned recording materials, it is difficult to make the difference in light transmittance between the light transmitting part and the light shielding part sufficiently large, and furthermore, when trying to read out written information due to the difference in light transmittance, has the problem that it is greatly affected by dirt on the surface of the card.

For this reason, information is not read out due to differences in light transmittance.
There are also attempts to read information based on differences in light reflectance. For example, cards have been proposed that have a recording layer made of silver particles dispersed in a gelatin matrix. Information is written to the recording layer by irradiating the recording layer with a laser beam to form recording bits. This recording layer can be manufactured continuously using a coating method, and the use of silver ensures uniform reflectance over a wide wavelength range, making it possible to apply it to recording and reproducing devices that use laser beams of various wavelengths. It has the advantage of

However, when recording on this recording layer using a photographic method, it is difficult to simultaneously improve light reflectivity and resolution. For example, increasing the development time improves light reflectivity, but recording There is a tendency for the exposed area to become thicker, resulting in a decrease in resolution. On the other hand, if the development time is shortened, the resolution improves, but there is a problem in that the light reflectivity becomes insufficient.

On the other hand, tellurium is used as a recording layer for a so-called heat mode recording material in which the recording layer of the recording material is irradiated with an energy beam such as a laser beam in a spot shape to change the state of a part of the recording layer. , a gold film made of bismuth, a film made of polystyrene, nitrocellulose, etc., or a tellurium low oxide film using phase transition. These recording materials are so-called DRAW (formerly r13c
Since it is possible to perform high-density recording and additional writing, it is expected that its use as a recording material for disks or cards will expand.

Among these heat mode recording materials, the most widely used recording materials are those made by depositing a metal thin film such as tellurium or bismuth on a substrate. Information is written by using an energy beam such as a laser beam on the metal thin film. This is done by spot irradiating the area to remove the metal in this area by evaporation or melting movement to form a bit.

In addition, to read information, readout light is irradiated onto the recording layer, and the bit area, which is the recorded area, and the metal thin film, which is the unrecorded area, are exposed.
This is done by reading the difference in reflectance. By the way, when writing information, in addition to forming recording bits corresponding to the information to be read, tracking corresponding to a light guide groove and breformatting to specify the bit to be read are also performed. It was necessary to write to the recording layer.

However, the metals that make up the recording layer, such as tellurium and bismuth, have Ifm properties to a certain extent, so they require careful handling, and forming bits by irradiation with energy beams such as laser beams requires advanced control technology. Moreover, since the bit forming process is complicated, it is not necessarily cheap from a cost standpoint.

Therefore, if a recording material were to emerge in which breformatting, which corresponds to a light guide groove, could be formed in large quantities and at low cost by a simple method other than laser beam irradiation, it would be extremely useful. It is expected that a high value will be obtained.

[Purpose of the invention]

The present invention aims to solve the problems associated with these conventional techniques, and has the following objects.

(a) To provide an optical card having an optical recording material that is capable of high density and is difficult to modify the written information.

(b) To provide an optical card having an optical recording material in which written information can be read out based on a difference in light reflectance rather than a difference in light transmittance.

(c) Part of the information to be written on the recording layer can be written by a method that allows for mass production, such as pattern exposure, without using laser beam irradiation, and therefore the manufacturing process can be simplified and mass production is possible. Also, to provide an optical card having an optical recording material that can reduce costs.

(d) To provide an optical card with excellent reliability and durability without deterioration of writing and reading accuracy even after long-term use.

(All of the Inventions) In order to achieve the above object, the DRAW type optical card of the present invention is an optical card in which an optical recording section is provided on a card base material, in which the optical recording section includes (a) an optical recording section; (b) a hardened surface layer provided on the upper surface of the substrate for the optical recording portion; and (c) a light transmitting portion and a light blocking portion provided on the lower surface of the substrate for the optical recording portion. (d) this first recording layer;
a second recording layer made of a reflective gold thin film layer provided on the surface of the recording layer; the card base material is made of a laminate of an opaque material layer and a transparent material layer; A card in which a second recording layer side and an opaque material layer side of the card base material are bonded via an adhesive layer,
By irradiating the recording layer with an energy beam, the second
Information can be written into the recording layer, and the written information can be read out by irradiating recording and reproducing light from the side on which the surface hardening layer is provided.

[Detailed description of the invention]

Hereinafter, the optical card according to the present invention will be explained using specific examples shown in the drawings.

In the optical card 1 of the present invention, as shown in a conceptual cross-sectional view in FIG.
They are joined and integrated through the .

The optical recording section 3 consists of an optical recording section base 1i45, a surface hardening layer 6 provided on the upper surface of the substrate 5, and a light transmitting section 7 and a light blocking section 8 provided on the lower surface of the substrate 5. The first recording layer 9 becomes
and a second recording layer 10 made of a reflective metal layer provided on the lower surface of the first recording layer 9 are laminated.

On the other hand, the card base material 2 is made of a laminate of an opaque material 1112a and a transparent material layer 2b. In some cases, the magnetic recording layer 11 may be provided in the transparent material 1i12b. Further, the first recording layer 9 and the second recording layer 1110 may be provided on a part of the surface of the optical recording portion base material 5 instead of the entire surface. Furthermore, if necessary, an IC memory, a photograph, an engraved image, characters, a mark, an embossed character called an imprint, etc. may be provided on the front or back side of the optical card.

By doing so, one card can be used in various playback methods, and counterfeiting can be more effectively prevented.

In the optical card 1 in another specific example shown in FIG. 2, there is a gap between the first recording layer 9 and the second recording layer 10 of the optical recording section 3. '-1112 is formed, and the other configuration is the same as that of the optical card shown in FIG. 1 above. This burred layer 12 is made of gold II of the second recording layer 10 due to the influence of temperature.
This is provided to prevent deterioration of the film layer, and is particularly useful when the photosensitive material of the first recording layer is a hygroscopic material.

Each component of the optical card of the present invention will be explained in more detail below.

As the card base material 2, any material that can be used as a base material for a normal card can be used. Specifically, polyvinyl chloride, vinyl chloride/vinyl acetate copolymer, polyvinylidene chloride, acrylic polymers such as polymethyl methacrylate, polystyrene, polyvinyl butyral, acetylcellulose, styrene/butadiene copolymer, polyethylene, Polypropylene, polycarbonate, etc. are used. In some cases, iron, stainless steel,
Metal sheets such as aluminum, tin, copper, and zinc, synthetic paper, and paper are also used. Of these, opaque material layer 2
White hard polyvinyl chloride is preferably used as a, and transparent hard polyvinyl chloride is preferably used as the transparent material layer 2b.

All types of optically transparent materials such as glass, ceramic, paper, plastic film, silk cloth, and nonwoven fabric can be used as the base material 5 for the optical recording section, but there are certain issues in terms of productivity and smoothness. A glass or plastic film is preferred. As the plastic, cellulose derivatives, polyester resins, polycarbonate resins, vinyl resins, polyimide resins, acrylic resins, polyether resins, polysulfone resins, polyamide resins, polymethylpentene resins, cellulose triacetate resins, etc. can be used. In terms of transparency and smoothness, cellulose triacetate, polyethylene terephthalate,
Particularly preferred are polycarbonate resin, polyvinyl chloride resin, polysulfone resin, polymethylpentene resin, and the like. These base materials 5 may be subjected to corona discharge treatment, if necessary.
Pretreatment for improving adhesion such as plasma treatment and brimer treatment may be performed.

(1) The first recording layer 9 is composed of a light transmitting section 7 and a light shielding section 8. The first recording wJ9 is formed by, for example, exposing a photosensitive material in a pattern such that unexposed areas are light-transmissive and exposed areas are light-shielding, and then developed. In some cases, the first recording layer 9 may be formed by exposing a photosensitive material in a pattern such that unexposed areas are light-shielding and exposed areas are light-transmitting, followed by development.

The photosensitive material is made of, for example, (a) a transparent resin as a binder, (b) a photodegradable development inhibitor having a diazo group or an azide group, and (c) a metal complex compound or metal compound that is reduced to become a metal development nucleus. It is configured. In this photosensitive material, transparent wood WA100 is used as a binder.
Based on the weight part, the photodegradable development inhibitor T, II agent having a diazo group or an azide group is present in an amount of 1 to 100 parts by weight, preferably 20 to 50 parts by weight, and is reduced to form metal development nuclei. The metal complex compound or metal compound is 0.1 to 1
00 parts by weight, preferably 1 to 10 parts by weight. The development inhibitor, metal complex compound, or metal compound described above is dissolved or dispersed in the transparent resin as a binder, and is preferably dissolved.

As the transparent resin, either oil-based or hydrophilic transparent resin can be used. New oil-based transparent resins include resins with ester groups such as polyvinyl acetate resin, vinyl acetate/acrylic acid ester copolymer resin, acrylic acid/vinyl acetate copolymer resin, ethylene/vinyl acetate copolymer resin, and cellulose acetate. Examples include modified vinyl acetate resins containing 81m having a hydroxyl group, carboxyl m groups, or sulfonic acid groups.

Furthermore, in terms of optical recording properties, it is also effective to add cellulose derivatives such as dicellulose, which has the property of deforming in a heat mode, to these new oil-based transparent resins to increase sensitivity.

In addition, hydrophilic transparent resins include natural polymer compounds such as gelatin, casein, glue, gum arabic, and shellac, carboxymethyl cellulose, egg albumin,
Polyvinyl alcohol (partially saponified polyvinyl),
Synthetic resins such as polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyethylene oxide, and maleic anhydride copolymers are used, but other resins than the above can also be used as long as they are water-soluble or hydrophilic resins. The hydrophilic transparent resin used as a binder has such hydrophilicity that when a photosensitive material layer is formed using this transparent resin and brought into contact with a physical developer, the physical developer penetrates into the photosensitive material layer and physical development is possible. It is preferable that the

In addition, it is also effective to dissolve a low molecular weight substance such as nitrocellulose, which has a property of being easily deformed in a heat mode in terms of optical recording properties, in ethanol and then add it to the above-mentioned hydrophilic transparent resin.

As the development inhibitor, a compound having a diazo group or an azide group is used. Examples of compounds having a diazo group include zinc chloride double salts or fluoroborate salts having a diazo group;
Alternatively, compounds which are condensation products obtained from these compounds and rose formaldehyde are preferred. More specifically, p-N.

N-diethylaminobenzenediazonium zinc chloride double salt, I)-N-ethyl-N-βhydroxyethylaminobenzenediazonium zinc chloride double salt, 4-morpholino-
2,6-jethoxybenzenediazonium zinc chloride double salt, 4-morpholino-2゜5-dibutoxybenzenediazonium zinc chloride double salt, 4-benzoylamino-2,5
-Jethoxybenzenediazonium zinc chloride double salt, 4-
(4'-methoxybenzoylamino)-2,5-jethoxybenzenediazonium zinc chloride double salt, 4-(p-
Chlorides having a diazo group such as (toluylmercapto)-2,5-dimethoxybenzenediazonium zinc chloride double salt, 4-diazo-4'-methoxydiphenylamine zinc chloride double salt, and 4-diazo-3-methoxy-diphenylamine zinc chloride double salt In place of the zinc double salt or the above-mentioned zinc chloride double salt, the above-mentioned borofluoride salts, sulfates, phosphates, etc. can also be used.

Compounds having an azide group include p-azidoacetophenone, 4,4'-diazidechalcone, 2,6-bis-
(4'-azidobenzal)-acetone, 2,6-bis-
(4'-azidobenzal)-cyclohexanone, 2.6
-bis-(4'-7zidobenzal)-4-methylcyclohexanone, 2,6-bis(4'-azidostyryl)-
Acetone, azidopyrene, etc. can be used. Compounds other than those mentioned above can also be used as long as they have a diazo group or an azide group, and two or more of the above-mentioned compounds having a diazo group or an azide group can also be used in combination.

In addition, when using a compound having a diazo group, it is recommended to use a stabilizer that stabilizes this compound. Organic carboxylic acids and organic sulfonic acids can be used as this stabilizer, and more practically p - It is preferable to use toluenesulfonic acid or the like.

Next, the metal complex compound or metal compound which is reduced and becomes a metal development nucleus will be explained.

First, complex compounds of metals such as palladium, gold, silver, platinum, and copper are used as the metal complex compounds that are reduced and become metal development nuclei, and the ligands that serve as electron donors for these metals are usually Any known material can be used. Specifically, the following metal complex compounds are used.

Bis(ethylenediamine)palladium(If>salt, dichloroethylenediaminepalladium(I) salt, dichloro(
Ethylenediamine) platinum (V) salt, tetrachlorodiamine platinum (IV) salt, dichlorobis(ethylenediamine) platinum (rV) salt, tetraethylammonium copper (I)
salt, bis(ethylenediamine steel (II) salt.

Furthermore, as a ligand for forming a metal complex compound, it is preferable to use a so-called chelating agent that forms a cyclic structure by coordinating at two or more sites because the stability of the metal complex compound formed is high. be. Examples of chelating agents include primary, secondary or tertiary amines, oximes, imines, and ketones; more specifically, dimethylglyoxime, dithion, oxine, acetylacetone, glycine, Compounds such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and uramyl diacetic acid are used.

Examples using the above chelating agent include bis(2,
2'-bipyridine) palladium (If > salt, bis (acetylacetonato) palladium (IF), bis (N, N
-diethylethylenediamine) copper(II) salt, bis(2
, 2'-bipyridine) copper (I) salt, bis 1,10-phenanthroline) copper (n) salt, bis (dimethylglyoximate) copper (I), bis (acetylacetonato) copper (
(2), bis(acetylacetonato)platinum (n), and the like are preferred.

As metal compounds that are reduced to give metal development nuclei, metal compounds such as water-soluble salts such as chlorides and nitrates of metals such as palladium, gold, silver, platinum, and copper are used. Specifically, they are used in electroless plating. Salts such as palladium chloride, silver nitrate, and gold tetrachloride contained in the activator solution are preferred, and among these, palladium salts are particularly preferred.

As mentioned above, (a) transparent resin as a binder, (
b) A photodegradable development inhibitor having a diazo group or an azide group, and (c) a metal complex compound or metal compound which is reduced and becomes a metal development nucleus, together with a solvent selected depending on the transparent resin as a binder. They are mixed to form a coating solution for forming a photosensitive material layer having a viscosity of 10 to 1000 centivoise, which is suitable for coating. This coating liquid for forming a photosensitive material layer is applied onto the base material 5 for the optical recording section in an amount of usually 0.1 to 30 μm.
A photosensitive material layer is formed by applying the photosensitive material to a film thickness of m.

Various solvents can be used to dissolve the transparent 1M fat as a binder, but when using a hydrophilic transparent resin, water, a water-miscible solvent such as lower alcohol, ketone, or ether, or water and water can be used. A mixed solvent with a miscible solvent is used. In addition, when using a new oil-based transparent resin, lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, esters such as ethyl acetate and vinegar@n-butyl, and methyl cellosolve, etc. A highly polar solvent is preferably used.

In addition, when using a hydrophilic transparent resin, it is desirable to perform hardening treatment after forming the photosensitive material layer in order to suppress elution of the binder and the like into the developer during physical development.

For example, the hardening treatment can be carried out by pre-mixing the following compound in a coating solution for forming a photosensitive material in an amount of 0.1 to 50 parts per 100 parts of the transparent resin, or by adding an aqueous solution of the following compound to the coating solution that has already been formed. This can be done by coating on the photosensitive material layer.

A1 compounds such as potash light bread and ammonium light bread; C compounds such as chromium light bread and chromium sulfate VB: aldehydes such as formaldehyde, glyoxal, glutaraldehyde, 2-methylglutaraldehyde, and succinaldehyde, 20-benzoquinone , p-benzoquinone, cyclohexane-1,2-dione, cyclopentane-1,
2-dione, diacetyl, 2,3-bentanedione, 2
Diketones such as 5-hexanedione and 2,5-hexanedione; Epoxides such as triglycidyl isocyanurate; Acid anhydrides such as tetraphthaloyl uride and 4,4'-diphenylmethane disulfonyl chloride; Tannic acid , gallic acid, 2゜4-dichloro-6-hydroxy-s-triazine, and the general formula R2NPOx2, R-N-C-N-R' (where R is an alkyl group having 2 to 6 carbon atoms, R' is ( cH3)3N (cH3)3X- group, X is F or (
J, n is 1 or 2) Phosphorus compound or carbodiimide: styrene/maleic acid copolymer, vinylpyrrolidone/maleic acid copolymer, vinyl methyl ether/maleic acid copolymer, ethyleneimine/maleic acid copolymer resins such as methacrylic II/methacrylonitrile copolymer, polymethacrylamide, methacrylic acid ester copolymer, glutaric acid, succinic acid, malic acid,
Lactic acid, citric acid, aspartic acid, gelcholic acid, tartaric acid, etc.

In this way, the photosensitive material layer provided on the optical recording part base material 5 is pattern-exposed, and then developed to form a light-transmitting part 7, which is an unexposed part, and a light-blocking part 8, which is an exposed part. 1
A recording layer 9 is formed. Pattern exposure can be performed, for example, through a mask such as a photomask.

Alternatively, the light shielding portions 8 can be formed in a pattern by condensing the irradiation light into a beam and directly irradiating the photosensitive material layer.

The image information provided by the light transmitting section 7 and the light shielding section 8 in the first recording 1i9 functions as tracking and preformat when reading the information itself or the information.

In the exposed area of the photosensitive material layer, the photodegradable development inhibitor having a diazo group or an azide group is decomposed depending on the exposed layer to form a latent image.

As the light source used for exposure, any light source that can decompose a compound having a diazo group or an azide group can be used, and an ultra-high pressure mercury lamp is usually preferably used.

A latent image formed by decomposition of a compound having a diazo group or an azide group by pattern exposure as described above is brought into contact with an aqueous reducing agent solution to generate metal development nuclei. Note that in the unexposed area, the development inhibitor having a diazo group or an azide group is not decomposed, so even when it comes into contact with the reducing agent aqueous solution, no metal development nuclei are generated and it remains as a light-transmitting area.

Reducing agents used in this case include stannous chloride, stannous sulfate, sodium borohydride, borazane compounds such as dimethylamine borazane, diethylamine borazane, and trimethylamine borazane, borane, diborane, and methyldiborane. Borane compounds, hydrazine, etc. are used. Among these, acidic stannous chloride solution, stannous sulfate solution (Weiss solution), commercially available sensitizer solution for electroless plating, etc. are particularly preferred, but in general, any strong reducing agent can be used.

Next, when the metal development nuclei thus obtained are brought into contact with a physical developer, the metal contained in the physical developer is reduced and precipitated around the metal development nuclei, and the light shielding portion 8 is formed. It is formed.

As a physical developer, a water-soluble reducible metal salt is used.
An aqueous solution containing □ and a reducing agent is used at a low temperature or heated if necessary.

Examples of reducible metal salts include nickel and cobal 1.
-1 Vtb group metals such as iron and chromium, Ib such as copper
Water-soluble salts of group metals are used alone or in mixtures.

It is also possible to obtain a tin or tin/copper metal layer by performing physical development with #4 salt solution and then displacement plating with stannous chloride or tin sulfate.

Among these, considering safety and preservation, nickel,
Copper and tin are preferred. However, unlike vapor deposition, it is possible that small amounts of foreign metals and elements such as phosphorus and sulfur may be mixed in due to the purity of the raw materials and the plating stabilizer, but this does not particularly affect the properties of the material as an optical recording material. do not have.

Specifically, the following are used as suitable water-soluble reducible metal salts.

Cobaltous chloride, cobaltous iodide, ferrous bromide,
Heavy metal halides such as ferrous chloride, nichrome bromide, ferric iodide, cupric chloride; nickel sulfate, ferrous WI acid, cobaltous sulfate, nichrome sulfate, cupric sulfate, etc. Heavy metal sulfates: nickel nitrate, ferrous nitrate, cobaltous nitrate, ferric nitrate, cupric nitrate, etc. Heavy metal WI & nitrates: ferras acetate, cobalt acetate, chromic acetate, Kubrick formate, etc. metal available filW! salt.

These reducible heavy metal salts are contained in the physical developer, for example, 10
~1009/j! Preferably, it is contained in an amount of .

Examples of reducing agents include hypophosphorous acid, sodium hypophosphite, sodium borohydride, hydrazine, formalin, diethylamine borane, dimethylamine borane,
Trimethylamineborane, borane, diborane, methyldiborane, diborazine, borazane, borazine, t-butylamineborazane, pyridineborane, 2,6-ruticineborane, ethylenediamineborane, hydrazinediborane,
Dimethylbosphineborane, phenylphosphineborane! Dimethylarsine borane, phenylarsine borane, dimethylstibine borane, diethylstibin borane, etc. can be used.

These reducing agents are contained in the physical developer in an amount of, for example, 0.1 to
Preferably, an amount of 50 g/J is used.

In order to prevent the heavy metal ions generated by dissolving the above-mentioned reducible heavy metal salts from precipitating as hydroxides, the physical developer contains, for example, monocarboxylic acid, dicarboxylic acid, malic acid, lactic acid, etc. hydroxycarboxylic acid,
Succinic acid, citric acid, aspartic acid, glycolic acid,
One or more complexing agents consisting of organic carboxylic acids such as tartaric acid, ethylenediaminetetraacetic acid, gluconic acid, sugar acid, and quinic acid can be included. These complex chloride agents may be contained in the physical developer at, for example, 1 to 100 g/41
It is preferable to use an amount of .

In addition, physical developers contain pH adjusters such as acids and bases, buffers, preservatives, brighteners, surfactants, etc., to improve the storage and handling properties of the developer and the quality of the resulting images. etc. are added as necessary according to conventional methods.

Among these additives, it is particularly preferable to use aqueous ammonia or aqueous sodium hydroxide solution in order to raise the pH.

Physical development may also be performed under high speed plating conditions in a high temperature nickel plating bath or copper plating machine at 65°C to 90°C using a sodium hypophosphite reducing agent. It is also possible to selectively remove a portion of the transparent resin in the light transmitting portion by treating the image obtained at this time with an aqueous solution of 5% hydrochloric acid or 5% nitric acid for about 5 minutes, for example.

In addition to the above-mentioned systems consisting of transparent resins, development inhibitors, metal complex compounds, or metal compounds, examples of photosensitive materials include (a) silver halide, dry silver (registered trademark);
silver salt-based materials represented by organic silver salts such as system material, (d) acrylic monomer,
Photopolymerizable photoseeding type 7 otobolymer materials (e), such as polyvinyl cinnamic acid, which form toner images
Electrophotographic photoreceptors such as dS, ZnO, and polyvinylcarbazole or their transfer bodies, electrophotographic materials such as thermoplastic electrophotographic photoreceptors that form frost images, (th)leuco dyes and tetrabromide. Combination systems with carbon, (l) combination systems with Dylux (registered trademark) cobalt complex and leuco dye, (l) combination systems with dioxalic acid and iron salts, (n) spiropyran, molybdenum tungsten compounds, etc. Materials such as pigments or dyes that form images are used.

Among the above-mentioned photosensitive materials, some types have light-shielding properties in exposed areas and light-transmitting properties in unexposed areas, while others have light-transmitting properties in exposed areas and light-blocking properties in unexposed areas. . In any case, any photosensitive material can be used as long as it can perform recording consisting of a light-transmitting area and a light-blocking area by developing as necessary after exposure. However, among the above photosensitive materials, (a) transparent resin as a binder, (b)
When using a photosensitive material composed of a photodegradable development inhibitor having a diazo group or an azide group and (c) a metal complex compound or metal compound that is reduced and becomes a metal development nucleus, the light shielding part 8 uses near infrared rays. It has the advantage that it can be read as a high-density object even when reading at low temperatures, has high resolution, and can be handled in a bright room.

As the light for irradiating such a photosensitive material, ultraviolet rays, visible light, infrared rays, Xa, electron beams, etc. can be used.

Next, a second recording layer 10 made of a reflective metal thin film layer is formed on the first recording layer 9 made of the light transmitting part 7 and the light blocking part 8 formed as described above. Form.

Reflective metal mmm is Cr, Ti, F13, Co
, Ni, Cu, Ag, Au1Gc, All,
Mg, 5b1Te, pb, Pd, cd, 3i, 3n.

It is formed using metals such as 3c, in, Ga, Rh, etc. alone or in combination of two or more.

When information is further written on the second recording layer 10 made of a reflective metal thin film layer by irradiation with an energy beam, low melting point metals such as Te, Zn, and Pb are used.

It is preferable that the reflective metal thin film is composed mainly of metals such as Cd5B1.3n, 3e, In, Qa, Rh, etc., particularly Te-8e, Tc-8c-Pb ST
e-Pb, Te-8n-8, Sn-Cu.

Alloys such as To-Cu and Te-Cu-Pb are preferred.

Further, among these alloys, TO-Cu alloy containing 5 to 40 atomic percent Cu or TO-Cu- alloy containing 5 to 40 atomic percent Cu and 1 to 50 atomic percent Pb to Cu. Pb alloys are particularly preferred when the wavelength of the readout irradiation energy beam is 650 nm or more. When a layer of reflective metal made of these alloys is used as the second recording layer, recording bits with less disturbance at the outer periphery can be obtained, and the wavelength of the readout irradiation energy beam is 650 nm or more, especially 700 nm.
900 nll, a reflective metal thin film can be obtained that has excellent information read characteristics such that the reflectance in bits, which are recorded parts, and the reflectance, that is, relative reflectance, in the metal A9 film, which is unrecorded parts, are small.

Furthermore, 5n- containing 1 to 40 atomic percent Qu
When a Cu alloy is used, a reflective metal thin film with less disturbance in the outer periphery of the recording bit shape and with low toxicity can be obtained.

In order to form such a reflective metal thin film layer on the first recording layer, the above-mentioned metal or alloy is prepared and then processed by sputtering method, vacuum evaporation method, ion blating method, electroplating method, etc. The film may be formed on the first recording layer by a conventionally known method. This reflective gold fiIk thin II
The thickness of the I layer is 200 to 10.0OOA, preferably 10.0OOA.
It is preferable that it is 00-5000A. In some cases, a multilayer film made of the above metals, for example In1g1 and Te
Multilayer films with films are also used as reflective metal thin films. Also, composites of the above metals and organic compounds or atomized compounds such as Te-CH1Te-C8, Tc-styrene, 5n-8o2, Ge5-8n, Sn S-8!
'(7) HHI Aluiha Si 02 /Ti /Si
Multi-WJ films such as 02/Ajl can also be used as reflective metal films.

In addition, there are thin films made by aggregating pigments such as cyanine to give light reflectivity, films in which pigments or metal particles such as silver are dispersed in thermoplastic resins such as nitrocellulose, polystyrene, and polyethylene, or films made from thermoplastic resins such as pigments or metal particles such as silver. Reflective metals include those with agglomerated pigments or metal particles on their surfaces. It can be used as a membrane.

Furthermore, TcFlt oxides, sb oxides, MO oxides, Qe oxides,
Alternatively, compounds such as Te oxide-GOlTe-3n can be used as the reflective metal thin film.

In addition, chalcogen or colored M2O3-cu
, vo O3-3n-cu are used as the reflective metal thin film, and in some cases, a multilayer of a bubble-forming organic MIIl and a metal thin film can also be used as the reflective metal thin film.

Gd Co, Tb C01, which are magneto-optical recording materials
GdFe, DyFc, Gd
TbFe.

Gd Fe Bi , Tb Dy Fe , Mn Cu
Bi or the like is also used as a reflective gold film.

It is also possible to use a combination of various types of reflective metal thin films as described above.

K plate Kokita 1 Surface hardening JII6 increases the hardness of the surface of the optical recording section side of the optical card 1 and protects it, thereby preventing the surface from being scratched when the card is carried or used. Thereby, it is possible to improve the durability of the card and the reliability in writing and reading accuracy.

Materials for this surface hardening layer include silicone, acrylic, melamine, urethane, epoxy hard materials (gold-amide such as IJJ Ya AII □03, S i O2,
A plasma polymerized film or the like is used.

The barrier A7 layer 12 is provided to prevent the photosensitive material constituting the first recording layer 9 from having a physical or scientific adverse effect on the second recording layer 10. In particular, when the photosensitive material of the first recording layer is hygroscopic, it is useful for preventing the second recording layer from deteriorating under high humidity.

Materials for the barrier layer include acrylic, melanin,
Urethane or cellulose resin, polyethylene, polyvinyl chloride, polyvinylidene chloride, A1203, S
! In addition to 02 Tonokin gold a oxide, a plasma polymerized film or the like can be used.

Adhesive Layer A variety of adhesives can be used to form the adhesive layer 4, including thermosetting adhesives such as polyurethane or epoxy, acrylic resin, polyvinyl acetate resin, and polyethylene/vinyl acetate copolymer. l! 411
A heat-sensitive adhesive such as I can be used. Among these, thermosetting adhesives, preferably polyurethane adhesives, are used when chemical resistance is required.

Method of manufacturing an optical card Next, a method of manufacturing an optical card according to the present invention will be explained.

First, as described above, a surface hardening layer, a first recording layer, a second recording layer, and, if necessary, a barrier layer are provided on a substrate for an optical recording section to form an optical recording section.

This base material for the optical recording section also plays a role as a card protective layer when assembled as an optical card.

Next, the card base material and the base material for the optical recording section are bonded together using a thermosetting adhesive or a heat-sensitive adhesive such that the second recording layer side of the optical recording section is in contact with the opaque material layer side of the card base material. An optical card can be manufactured by stacking the two layers together with an agent layer interposed therebetween and then pressing them together using a hot roll heated to about 90 to 150°C.

Depending on the case, an optical card can also be manufactured as follows. That is, on the base material for the optical recording part, the hydrophilic e
A first recording layer and a second recording layer containing lIIl as a binder.
After providing the recording layer, a protective film of acrylic resin or the like is applied by screen printing or the like on the second recording layer, which is a reflective gold film, to make this part water-resistant. At this time, the protective film is not provided on the peripheral edge of the base material for the optical recording section. Next, this optical recording material is immersed in warm water to remove the hydrophilic resin in the areas where the protective film is not provided, and then dried.

On the other hand, if necessary, a card base material such as a white polyvinyl chloride film may be formed with four parts for fitting the first recording layer and the second recording layer of the optical recording part by heat pressing or the like. It is also possible to provide an adhesive layer.

Next, the optical recording material and the card base material are connected to the second layer of the optical recording material.
An optical card can be manufactured by overlapping the recording layer so that it is in contact with the card base material and pressing them together with a hot roll or the like.

1. Next, writing of information to the reflective gold WiNWA as described above and reading of information written to the optical card will be explained.

To write information to the reflective gold 11111g1, the gold i*am is irradiated with an energy beam such as a laser beam with a wavelength of 300 to 11000 m, focused by a lens, etc., and the metal in the irradiated area is evaporated or unevenly distributed. This is done by forming recording bits.

At this time, the intensity of the energy beam is 0.1 to 100 mW.
, the pulse width is preferably 5 n5ec to 500 m5ec1, and the beam diameter is preferably 0.1 to 100 μm.

As the energy beam irradiated onto the reflective metal thin mwa, a laser beam such as a semiconductor laser, an argon laser, a helium-neon laser, an infrared flash, or the like is used.

-6 To read the information written on the optical card according to the present invention, the optical card is protected by using a low energy beam, white light, tungsten light, etc. that does not melt the reflective metal 111g layer through a lens or the like. A first recording layer consisting of an optical recording section and a light shielding section from the layer side, and a second recording layer.
This is performed by condensing and irradiating light onto the recording layer and detecting the intensity of the reflected light in association with the phase change.

As mentioned above, the light-shielding portion in the first recording layer is formed with a color close to black due to the metal precipitated around the metal development nucleus, so the reading irradiation beam is irradiated onto this light-shielding portion. Then, the irradiation beam is absorbed in this part and the reflectance becomes small. On the other hand, in the light transmitting part, the irradiation beam is not absorbed much and reaches the reflective metal S film layer, so the reflectance in this light transmitting part becomes a large value.

Also, gold j! corresponds to the unrecorded area in the reflective metal thin film layer. While the 'falI layer provides high reflectance,
The bit portion corresponding to the recording portion has a low reflectance.

In this way, by reading the difference in reflectance between the social part and the light transmitting part in the first recording layer, and the difference in reflectance between the pit part and the unrecorded part in the second recording layer,
Information written on the optical card according to the present invention can be read.

〔Effect of the invention〕

Since the optical card according to the present invention has an optical recording material including a first recording layer made of a photosensitive material layer and a second recording layer made of a reflective metal S film layer, it has the following effects.

(a) Compared to magnetic recording cards, much higher density recording is possible, and it is extremely difficult to modify the written information.

(b) Information written on an optical recording material can be read out based on differences in light reflectance.

(c) Information can be written in the first recording layer of the optical recording material by a mass-producible method such as pattern exposure without laser beam irradiation.

(d) As a photosensitive material, a transparent resin, a development inhibitor,
When using a metal complex compound or a system consisting of a metal compound, operation can be performed in a bright room.

〔Example〕

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

An undercoating agent (Shin-Etsu Chemical Primer PC-4) was gravure coated onto a 400 μm thick polycarbonate film, and then a silicone surface hardening agent (
Shin-Etsu Chemical (X-12-2150) was gravure coated and cured at 100°C for 1 minute to obtain a surface hardened layer.

A coating solution for forming a photosensitive material layer having the following composition was gravure coated on the back side of the above polycarbonate film.

The coating amount of the photosensitive material layer forming coating liquid was 3 g/g when dry.

Polyvinyl methyl ether maleic anhydride (G
, A, F Corp I! J Gani/ll/y
') AN139) 10% methyl ethyl ketone solution: 20 parts by weight polyvinyl acetate (Made by Block Chemical Co., Ltd. Varnish Neil C-2>
20% Methyl ethyl ketone solution = 20 parts by weight Acrylic resin (Soken Chemical L-40) 25% Methyl cellosolve solution = 12 layers of palladium 0
．． 1% methyl cellosolve solution
:38 Heavy Yamabe (Pd CJ□ : concentrated hydrochloric acid : methyl cellosolp = 1 :10:1000) 4-morpholino-2,5-dibutoxybenzenediazonium borofluoride salt (Daito Chemical IJDH3008F4)
10% methyl cellosolve solution: 10 parts by weight Next, the surface of the photosensitive material thus formed and the vertical 15
A row of dots with a width of 5 μm and a pitch of 15 μm was placed in close contact with the mask surface of a negatively patterned photomask with a pitch of 20 μm between the rows, and an ultra-high pressure mercury lamp (3 kW, distance 1 yi) was used from the photo mask side for 10 min.
Exposure for seconds. The photomask pattern used at this time was obtained by photoetching. Its fabrication consisted of forming a Cr-thin film on a glass plate by sputtering, and then applying a photoresist (AZ1350 manufactured by Silapray).
The coated and dried surface was irradiated with a He-Cd laser focused to a beam diameter of 2 μm on a position-controlled XY stage. As a result, rows of dots with a length of 15 μm and a width of 5 μm arranged at a pitch of 15 μm were formed with an inter-row pitch of 20 μm, and the dots were further treated with a resist developer (manufactured by Silapray) and heated at 130° C. for 25 minutes. Then, etching was performed using a ferric chloride solution to obtain a pattern in which the dot portions were transparent to light.

Next, the photosensitive material layer pattern-exposed as described above was immersed in processing solutions (A) and (B) having the following compositions in this order for 60 seconds and 80 seconds, respectively (processing temperature: 30°C).

(A) Shiba Nickel (manufactured by Okuno Pharmaceutical) Boron-based reducing agent 20. 5g Nickel sulfate: 3. Og Sodium citrate: 1.0g water
: 95° 5g(B)TMP
Chemical nickel-A1 TMP chemical nickel-8 1:1 mixture nickel sulfate
= 9°Og Sodium hypophosphite: 7°Og NH aqueous solution (28%): 6.5g Sodium citrate: 10.0g Water: 67. 5g
Thereafter, it was washed with water and dried to obtain a first recording layer having a light-transmitting area and a black positive pattern corresponding to a light-blocking area.

Te −
Cu-Pb alloy (sputter target composition ratio molar ratio
80:15:5) was sputtered to obtain an optical recording material on which a second recording layer was formed.

At this time, no Te-Cu-Pb thin layer was formed at the peripheral edge of the recording layer.

On the other hand, a card base material was produced as follows. First, a character design pattern was formed on both sides of a white hard polyvinyl chloride (thickness: 200 μm) using a screen printing method, and a magnetic recording layer with a width of 6.0 mm was separately formed on a portion of one side of a transparent hard polyvinyl chloride (thickness: 100 μm). It was set at 5am. The back surface and the printed white polyvinyl chloride were stacked on top of each other and placed between two stainless steel plates and heated and pressed at 140° C. for 30 minutes using a scissors press to obtain a card base material.

The optical recording material and card base material created as described above are bonded to the second recording layer of the optical recording material and the white polyvinyl chloride surface (printing surface) of the card base material. Industrial Alpon ELI-4200, EHtJ4
200 with a mixing ratio of 10:1) and pressed together using a roll or the like. After standing for 24 hours, a punched optical card was obtained using a punching die.

115-U Patterned first pattern obtained in the same manner as in Example 1
Melanin-based resin (Dainippon Ink & Chemicals, Toughcoat 112) was coated on the recording layer using a barcode, and heated at 120°C.
A barrier layer (11 thickness: 3 μm) was formed by heat treatment for 3 minutes. Next, a second recording layer was formed by sputtering a Ta-Cu-Pb alloy (sputter target composition ratio molar ratio 80:15:5) to obtain an optical recording material. At this time, the ``re-cu-pbs'' film was not formed on the peripheral edge of the recording layer.

Thereafter, a card base material was prepared in the same manner as in Example 1, bonded to the above-mentioned optical recording material via an adhesive, cured, and then punched out to obtain an optical card.

[Brief explanation of drawings]

1 and 2 are cross-sectional views of an optical card according to the present invention. 1... Optical card, 2... Optical card base material, 2a...
Opaque material layer, 2b... Transparent material layer, 3... Optical recording section, 4... Adhesive layer, 5... Base material for optical recording section, 6.
...Surface hardening layer, 7...Light transmitting part, 8... Light shielding part,
9... First recording layer, 10... Second recording layer, 11...
-Magnetic recording layer, 12...barrier layer.

Claims (3)

[Claims] 1. In an optical card in which an optical recording part is provided on a card base material, the optical recording part is provided on the top surface of (a) a base material for an optical recording part, and (b) the base material for an optical recording part. (c) a first recording layer consisting of a light transmitting part and a light shielding part provided on the lower surface of the base material for an optical recording part; (d) this first recording layer;
a second recording layer made of a reflective metal thin film layer provided on the surface of the recording layer; the card base material is made of a laminate of an opaque material layer and a transparent material layer; A card in which the second recording layer side and the opaque material layer side of the card base material are bonded via an adhesive layer,
By irradiating the recording layer with an energy beam, the second
A DRAW type optical card, characterized in that information can be written to a recording layer, and the written information is read by irradiating recording and reproducing light from the side on which the surface hardening layer is provided. 2. The optical card according to claim 1, wherein the first recording layer and the second recording layer of the optical recording section are laminated with a barrier layer interposed therebetween. 3. The optical card according to claim 1 or 2, wherein the transparent material layer of the card base material has a magnetic recording section.