KR920009199B1 - Optical recording material and its manufacturing method - Google Patents

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Optical recording material and its manufacturing method

1A and 1B are transmission electron micrographs of the cross section of one optical recording material of the present invention in another enlargement.

2A and 2B are transmission electron micrographs of another optical recording material of the present invention at different magnifications.

3a and 3d are perspective views of one side of each optical card according to the invention and FIGS. 3b and 3c are perspective views of the other side of each optical card according to the invention.

4 is a diagram of the optical, mechanical and electrical components of the information recording apparatus.

5 is a block summarizing the use of the optical card of the present invention.

6A and 6B are a flow chart of an operating system for use of the optical card of the present invention.

7A and 7B are diagrams of optical, mechanical and electrical components of the information reading mechanism for the ROM optical card and the ROM optical card as the sound card of the present invention, respectively.

The present invention mainly relates to novel optical recording materials suitable for laser recording and decoding, methods of making the same, and optical cards having the same.

With the development of digitalization of information as well as the remarkable advances in laser-related technology, several types of optical recording materials have been proposed.

An optical disk is mentioned as a typical digital recording material. Separately, optical card materials made from high capacity fluid digital recording materials such as optical disks have been proposed for easy operation (e.g., US Pat. Nos. 4,278,756; 4,463,089; and 4,692,402). As a recording material capable of densely recording information of higher capacity as compared with an optical disk, an optical tape has been proposed, and an optical floppy disk system which is cheaper than an optical disk system has been proposed. According to these proposed systems, various optical recording materials have been developed. If these optical recording materials are made denser in shape or form for transport, they are, for example, very serious conditions affected by sunlight, open air temperature, high temperatures in the car in summer and high humidity due to body temperature and sweating. It is easy to go out. However, various required properties such as write sensitivity, storage stability, write density, and error bit rate are insufficient. Especially in applications for optical cards, optical tapes and optical floppy disks requiring flexibility, new recording materials that can be produced by a reverse coating step having storage stability and reliability and suitable for mass production at low cost are desirable.

It is an object of the present invention to provide an optical recording material having excellent storage stability at high temperatures under high humidity atmosphere and sufficient resistance to severe use conditions such as bending.

Another object of the present invention is to provide an optical recording material having excellent flexibility that can be processed into various forms such as an optical card, an optical tape, an optical floppy disk, and an optical disk.

Furthermore, it is an object of the present invention to provide a method for producing an engineering recording material at low cost.

Another object of the present invention is to provide an optical card having an optical recording material.

According to the invention, a thin film or film of hydrophobic binder; And metallic particles having a diameter of 0.03 μm to 3 μm dispersed in the film or film with a higher density of metallic particles near at least one surface of the film or film as compared to other portions of the film or film, nucleus and outer coating. Each metallic particle having a higher density of the metallic particles, the film or film has a melting point of 250 ° C. to 1800 ° C. with a reflection coefficient of 10 to 90%, and 5 W · m ⁻¹ · K ⁻¹ to 450 W at 0 ° C. M ^-1 An optical recording material containing the outer coating containing at least one metal having a thermal conductivity of K ^-1 , a method of manufacturing the optical recording material, and an optical card containing the optical recording material.

According to the optical recording material of the present invention, the thin film or film of the hydrophobic binder is uniformly scattered metallic particles having a diameter of 0.003 µm to 3 µm on at least one surface or with another layer of low reflectivity adjacent to the metallic glossy layer. In comparison, there is a high reflectivity metallic gloss layer that exists as a uniform and continuous layer at high density, and there may or may not be an apparent boundary between the metallic layer gloss layer and the layer adjacent to the metallic layer gloss.

For laser recording and reading, the reflectivity of the metallic layer gloss layer of the optical recording material of the present invention is preferably placed in terms of designing the detection system. However, when the reflectivity is too high, the metal layer cannot absorb the laser beam efficiently. Thus, the reflectivity is typically 10 to 90%, preferably 25 to 60%, for practical purposes.

Moreover, in order to design in the laser recording and reading system, it is desirable that the optical difference between the recording section and the surrounding non-recording section is large. Therefore, it is preferable that the metallic luster layer of the optical recording material of the present invention and the metallic luster layer and the layer adjacent to the metallic luster layer of the optical recording material of the present invention have the following relationship.

(Where X is the reflectivity of the metallic gloss layer; Y is the reflectivity of the layer adjacent to the metallic gloss layer).

When the value of X-Y / X + Y is 0.03 or less, the optical contrast between the recording portion and the surrounding non-recording portion is low and mistakes are likely to occur in reading the recording portion. On the one hand, although the X-Y / X + Y value is preferably large for recording information, it is difficult to obtain an optical recording material with a value of X-Y / X + Y of 0.9 or more at the same time as the recordable sensitivity for practical purposes.

Moreover, in order to more easily design a laser recording and reading system, it is preferable that the metallic luster layer and the layer adjacent to the metallic luster layer of the recording material of the present invention have the following relationship;

In view of enhancing the read density, the optical recording material of the present invention is as thin as possible and the thickness of the optical recording material is typically 1 to 20 mu m as long as the difference in reflectivity between the metallic luster layer and the layer adjacent to the metallic luster layer can be obtained. desirable.

In the present invention, the reflectivity is expressed as a percentage ratio of the intensity of the reflected beam at the reflection angle of -75 degrees to the intensity of the incident beam at the incident angle of 75 degrees, and the wavelength of the beam used for measuring the reflectance is 830 nm.

In addition, thin films or films of hydrophobic binders contain light absorbers in the range of wavelengths of semiconductor lasers to increase sensitivity and γ values and increase optical contrast in laser recording. The light absorber may be provided as a layer on the metallic luster layer.

In addition, thin films or membranes of hydrophobic binders may contain silver halides and additives such as silver halide formers and color regulators, flow inhibitors and photosensitizers.

The optical recording material of the present invention may be used by itself or may be provided on a transparent, translucent or opaque, rigid or flexible substrate.

Moreover, in order to protect the optical recording material of this invention, the optical recording material can be laminated by heating a transparent protective layer or by an adhesive agent.

Further, for example, the reinforcement layer can be laminated onto the substrate to reinforce the optical recording material against bending.

Metallic particles of the outer covering of the metallic particles that can be used in the present invention has a core and a shell is from 250 ℃ to the melting point and the 0 ℃ ^{1800 ℃ 5W · m -1 · K} -1 to 450W · m ^-1 · K ^-1 Has thermal conductivity. When the melting point of the metal is 250 ° C. or less, the stability of the metallic luster layer tends to decrease. On the other hand, when the melting point is 1800 DEG C or higher, the sensitivity of the metallic gloss layer in laser writing or writing decreases. In addition, when the thermal conductivity is 5 W · m ⁻¹ · K ⁻¹ or less at 0 ° C., the shape of the pit is disturbed in the laser recording, increasing the bit error rate for practical purposes, and the thermal conductivity at 0 ° C. is 450 W · m ⁻¹ · When greater than K ⁻¹ , the sensitivity of the metallic gloss layer in laser recording is significantly reduced.

Typical metals of the sheath of the metallic particles include silver, gold, copper, tellurium, bismuth, palladium, cobalt, nickel, lead, chromium and titanium. Of these metals, silver is preferred.

The metal of the nucleus of the metallic particles is the metal of the skin, the metal more valuable than the metal of the skin, alloys thereof, sulfides thereof or oxides thereof.

Typical metals that are more valuable than sheaths are silver, palladium, platinum, gold, rosium, ruthenium thallium, mercury and their alloys, sulfides and oxides thereof. Among these metals, silver is preferred.

The production of the optical recording material of the present invention will now be described.

The homogeneous solution or suspension of the composition for the optical recording material of the present invention is an organometallic compound and a solvent which can be formed alone or together with a compound capable of reducing the organometallic compound (herein referred to as “reducing agent”). It may be prepared by dissolving or dispersing the hydrophobic binder of.

Organometallic compounds capable of forming metallic particles that can be used in the present invention include organometallic salts, organometallic complexes and metals of silver, gold, copper, tellurium, bismuth, palladium, platinum, rhodium, cobalt, nickel, lead, chromium or The organometallic chelate compound which is titanium is mentioned. Among these compounds, organic silver compounds are preferred.

Examples of the organic silver compound capable of forming metallic silver by reduction usable in the present invention include low molecular weight silver compounds or hydrophobic binders and high molecular weight silver compounds that are water-soluble or insoluble in organic solvents.

Typical low molecular weight compounds include silver salts of carboxylic acids such as silver acetate, inpyruvate, silver citrate, silver oxalate, silver benzoate and silver-2 ethyl hexaneate; Silver salts of long-chain carboxylic acids such as silver behenate, silver stearate, silver palmitate, silver myristate, silver laurate, silver oleate, silver margarate, silver arachate, silver serotate and silver millinate ; Silver trifluoroacetate, silver pentafluoropropionate, silver heptafluoro-n-butyrate, silver heptafluoroisobutyrate, silver nonafluoropivalate, silver nonafluoro-n-valerate and nona-fluoro Silver salts of perfluorocarboxylic acids such as isovalerate; Silver salts of perfluoro-carboxylic acids with fluorine atoms partially substituted by chlorine atoms; Silver salts of sulfonic acid or sulfinic acid, such as silver phenyldiazosulfonate and silver sulfinate; Fluorine-containing chelating agents such as tenoyltrifluoroacetone, heptafluorobutanoylpivaloylmethane, pivaloyltrifluoroacetone, trifluoroacetylacetone, furoyltrifluoroacetone and hexafluoroacetyl-acetone Silver chelate compounds formed by; Silver thiocarbamate, such as diethyldithiocarbamate; Silver chelate compounds such as silver 5-chlorosalicylidoxime and silver 5-nitrosalicylidoxime; Silver salts of nitrogen-containing compounds such as silver salts of saccharin and silver salts of benzotriazole; Silver salts and silver acetates, silver citrate, silver 2-ethylhexanoate or imidazole, 2-ethyl-imidazole, 1-methylimida complexed with coordination compounds such as silver nitrate, silver cyanate, silver phosphate Silver salts of carboxylic acids such as sol, 2,4-dimethylimidazole, pyridine, 2-methylpyridine, 2,4-dimethylpyridine or silver trifluoro-acetate complexed with phenylmethylsulfide. . In these compounds, silver salts of long chain carboxylic acids and silver salts of perfluorocarboxylic acid are preferred, and silver behenate of trifluoro-acetate is more preferred.

Typical high molecular weight compounds include silver ionic compounds such as silver nitrate and polymers of alkali or alkaline earth metal salts of acrylic acid, methacrylic acid or acrylic acid or methacrylic acid or acrylic acid, methacrylic acid or styrene, C _1-8 alkyl acrylates, C High molecular weight polycars derived from copolymers of alkali or alkaline earth metal salts of acrylic acid or methacrylic acid with copolymerizable monomer compounds such as _1-8 alkyl methacrylate, acrylonitrile, vinyl acetate, vinyl chloride and vinylidene chloride Silver salts of acids; Silver salts of polycarboxylic acids such as silver alginate and silver pectate; And general formula

Β-diketone ligands represented by the formula, wherein R is -O- or -CH _2-

Aromatic polyketones represented by the formula

Aromatic polyhydroxyl compound, aromatic hydroxycarbonyl compound represented by the general formula

Polyvinylamines, 3-vinylaniline polymers, polymers having chelating ligands in the main chain or in the chain comprising an oxime compound, polymerized Schiffbase, polypeptides having chelating groups in the chain, chloromethylated polystyrene and Heterocyclic compounds such as diethanolamine, ethanolamine resins obtained by the reaction of aminophenols, polymers obtained by copolymerization of 5- (hydroxymethyl) -8-quinoline allylether, methylmethacrylate and styrene Examples of the polymer having a high molecular weight, such as a high molecular weight azo compound, include chelate compounds. When silver salts of high molecular weight polycarboxylic acids are used, all or part of the hydrophobic binder can be replaced by them. Also, when silver salts of polycarboxylic acids are used, the metallicity is formed by heating the silver and at the same time the polymer backbone becomes hydrophobic by decarboxylation.

The metal is a metal other than silver, ie, gold, copper, tellurium, bismuth, palladium, platinum, rhodium, cobalt, nickel, lead, chromium or titanium and the organometallic compounds that can be used in the present invention are those in which the metal is replaced by a metal other than silver. The organic silver compounds described above may be compounds. However, organometallic compounds whose metals are more precious than silver, ie gold, palladium, platinum or rhodium, can be used with reducing agents having an equivalent or weaker reducibility to organosilver compounds, and their metals being less precious than silver Organometallic compounds, ie copper, tellurium, bismuth, cobalt, nickel, lead, chromium or titanium, can be used with reducing agents such as ascorbic acid and tin chloride, which have a stronger reducibility to organosilver compounds. Moreover, the latter can be reduced to metal in the form of metal salts of oxalic acid by photoreducibility of ferric oxalate or by autolysis under heating.

Reducing agents that can be used in the present invention may be selected according to the type of organometallic compound used in combination and include monohydroxybenzenes such as p-phenylphenol and p-methoxyphenol; Polyhydroxybenzenes such as hydroquinone, t-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone and catechol; naphthols such as α-naphthol, β-naphthol, 4-aminonaphthol and 4-methoxynaphthol; Hydroxybinafryl such as 1,1'-dihydroxy-2,2'-binafyl and 4,4'-dimethoxy-1,1'-dihydroxy-2,2'-binafyl ; Hydroxylamines such as phenylhydroxyamine and benzylhydroxyl-amine; Pyrazolidones such as 1-phenyl-3-pyrazolidone; phenylenediamines such as p-phenylenediamine and N, N'-dimethyl-p-phenylenediamine; Aminophenols such as N-methyl-p-aminophenol and 2,4-diaminophenol; sulfamidophenols such as p- (p-toluenesulfamido) phenol and 2,6-dibromo-4- (p-toluenesulfamido) phenol; Ascorbic acid; And hindered phenols in which tin chloride and one or two stericly large groups bind to carbon atoms which stericly interfere with carbon atoms or hydroxy groups.

Examples of such hindered phenols are 2,6-di-t-butyl-4-methylphenol, 2,5-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t -Butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), trimethylpentylbis (2-hydroxy-3,5-dimethylphenyl) methane, 2,6-methylenebis ( 2-hydroxy-3-t-butyl-5-methylphenyl) -4-methylphenol, 2,2'-methylenebis [4-methel-6- (1-methylcyclohexyl) phenol], 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane, 2,6-bis (2'-hydroxy-2'-t-butyl-5'-methylbenzyl) -4 -Methyl-phenol and 1,1-bis (2-hydroxy-3-t-butyl-5-methyl-phenyl) pentane, triethylene glycol bis [3- (3-t-butyl-5-cyclohexyl-4 -Hydroxyphenyl) propionate], 1,6-hexanediolbis [3- (3,5-di-t-butyl-hydroxyphenyl) propionate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butyl-anilino) -1,3,5-triazine, pentaerythritol tetrakis [3-3,5-di-t-butyl -4-hydroxyphenyl) propy Nate, 2,2-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, octadecyl-3- (3,5-di-t-butyl- 4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxyphenyl) cinnamid, 3,5-di-t-butyl-4- Hydroxybenzylphosphonate diethyl ester, 1,3,5-triethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl ester) calcium, Tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, N, N'-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propy Onyl] hydrazine, 2,2'-ethylidenebis (4,6-t-butylphenol) and 2,2'-ethylidenebis (4,6-di-methyl-1-cyclohexylphenol); Formula (I)

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each a C _1-8 alkyl group or a halogen atom; each of R ⁷ and R ⁸ is a hydrogen atom, a phenyl group or a C ^1-8 alkyl group.)

Compound represented by the formula and general formula (II)

_Wherein R ⁹ is a cyclohexyl group substituted with a C _4-10 secondary or tertiary alkyl group, a cyclohexyl group, or a C _1-6 alkyl group; R ¹⁰ is a C _1-6 alkyl group; R ¹¹ is C _{1 -10} alkyl group, C _1-10 alkoxy group, C _6-12 aryl group, C _2-10 alkenyl group or C _1-10 alkyl group, C _6-12 cycloalkyl group, C _2-10 alkenyl group, C _A group connected to a _6-12 aryl group or a C _7-12 aralkyl group; R ¹² is a C _1-6 alkyl group or a C _1-6 alkoxy group; R ¹³ is a C _1-6 alkyl group; R ¹⁴ is a hydrogen atom or C _1-6 alkoxy group.)

The compound represented by these is mentioned.

Suitable examples of C _1-8 alkyl groups in formula (I) include methyl, ethyl, sec-butyl, t-butyl, cyclohexyl groups, cyclopentyl groups, iso-amyl, t-amyl and 2-ethylhexyl groups And suitable examples of halogen atoms include chlorine, bromine and iodine atoms.

Typical compounds represented by formula (I) include the following:

Typical examples represented by general formula (II) include the following:

Of these reducing agents, preference is given to phenols and more preferred to hindered phenols.

The amount of reducing agent should be selected according to the organometallic compound used and is 0.01 to 10 moles, preferably 0.1 to 3 moles per mole of the organometallic compound.

The hydrophobic binder that can be used in the present invention is an organic polymer compound insoluble in water or hot water at 60 ° C. and has a glass transition temperature of 10 ° C. to 140 ° C., preferably 40 ° C. to 110 ° C.

Typical organic polymer compounds include polyvinyl formal, polyvinyl futyral, polyvinylacetate, vinyl chloride-vinylacetate copolymer, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, polystyrene, styrene-acrylonitrile copolymer , Styrene-methyl methacrylate copolymer, styrene-butadiene copolymer, polybutadiene, linear polyurethane, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polyisobutylene, polyethyleneadipamide, polyethylene terephthalate And various linear polyesters such as poly-1,4-butylene terephthalate, polymethylmethacrylate and methyl, ethyl, n-butyl, isobutyl, t-butyl, 2-ethylhexyl, isodecyl, n-la Similar resins and binalace of usyl, cyclohexyl acrylate or methacrylate Site, there may be mentioned a resin containing a vinyl chloride, vinylidene chloride, styrene, butadiene, ethylene, vinyl ethers, maleic anhydride or a resin forming monomer and a copolymerizable monomer such as acrylonitrile.

The amount of hydrophobic binder used in the present invention is 10 to 100 parts by weight based on 100 parts by weight of the organometallic compound.

Suitable examples of the solvent include alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol; Ketones such as methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone and acetone; Ethers such as ethyl ether, isopropyl ether, ethyl-n-butyl ether, dioxane; Esters such as ethyl formate, methyl acetate, ethyl acetate; aliphatic hydrocarbons such as n-hexane, n-heptane, cyclohexane; Aromatic hydrocarbons such as toluene and xylene; Halogenated aliphatic hydrocarbons such as chloroform and dichloroethane.

Hydrogen; Halogenated aliphatic hydrocarbons such as chloroform and dichloroethane.

The composition for the optical recording material may contain a silver halide or a silver halide forming compound.

Silver halides or silver halide-forming compounds which can be used in the present invention include silver halides such as silver chloride, silver bromide, silver iodide, silver iodobromide and silver chlorobromide; Hydrogen halides such as hydrogen chloride, hydrogen bromide and hydrogen iodide; Metal chlorides such as lithium chloride, sodium chloride, potassium chloride, calcium chloride, barium chloride, aluminum chloride, iron chloride, zinc chloride, cobalt chloride, lead chloride, mercury chloride, nickel chloride, potassium chloride, manganese chloride, magnesium chloride; Metal bromide or metal iodide corresponding to these metal chlorides; Halogen molecules such as organic complexes of molecular iodine, molecular bromine, bromine iodide and halogen molecules; Organic N-haloamides such as N-bromosuccinimide, N-bromoacetamide, N-bromophthalazone, N-bromophthalimide, N, N-dibromo-benzene-sulfonamide; α-bromodiphenylmethane, α-bromodi (p-nitrophenyl) methane, α-bromodi (p-methoxyphenyl) methane α-bromodi (p-bromophenyl) methane, α-bromodi (p Diaryl halomethanes, such as -methylphenyl) methane; Ammonium halides such as benzyltrimethylammonium iodide, benzyltrimethylammonium bromide and ethyltrimethylammonium bromide; Organic halide compounds of elements of groups IV, V and VI of the periodic table such as triphenylphosphinedibromide, bis (p-anisyl) tellurium dibromide, diphenylgermanium dibromide, triphenyltinbromide and diphenylselenium dibromide; And dihalides of triphenylphosphites such as dibromide of triphenylphosphite and diiodide of triphenylphosphite.

The amount of silver halide or silver halide forming compound that can be used in the present invention is 0.01 to 0.5 mole per mole of organometallic compound.

In order to increase the sensitivity and γ-value of the optical recording material in the information writing or recording and to increase the contrast in reading and retrieving the recorded information, the composition for the optical recording material is in the range of semiconductor laser wavelength, ie 650 nm to 900 nm. It may contain a light absorbing agent.

Examples of such light absorbing agents include cyanine dyes, merocyanine dyes, oxonol dyes, styryl dyes, rhodicyanine dyes, hemicyanine dyes, styrylquinoline dyes, phthalocyanine dyes, naphthalocyanine dyes, xanthene dyes, anthraquinone dyes And triphenylmethane dyes, naphthoquinone dyes, azulenium dyes, squarylium dyes, croconillium dyes and nickel-dithiol complexes. Of these dyes, phthalocyanine dyes, naphthalocyanine dyes, nickel-thiol complexes and azulenium dyes are preferred because these dyes are light absorbers having good weathering properties for light having a wavelength of a semiconductor laser. Typical dyes include aluminum phthalocyanine, copper phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, zinc phthalocyanine, titanium phthalocyanine, aluminum fluoride phthalocyanine, magnesium phthalocyanine, cobalt naphthalocyanine, nickel naphthalocyanine, titanium naphthalocyanine, magnesium Fluoride naphthalocyanine and ethylene-1,2-dithiol nickel complexes.

The amount of the light absorbing agent that can be used in the present invention is 2 to 50 parts by weight based on 100 parts by weight of the organometallic compound.

The composition for an optical recording material may contain various additives in order to improve the properties of the optical recording material. For example, metallic particles, especially metals, can be used to control the desired growth of particle size, color regulators such as phthalazone, antifogants such as water-temperature compounds, and 1,1,1 ', 1'-tetrabromo-o-xylene And photolytic organic halogen compounds such as 1,2,3,4-meso-tetrabromobutane, 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one and N-methyl-2-pyrrolidone Photosensitizers such as can be added as additives. The amount of each additive is 0.01 to 0.5 moles per mole of organometallic compound.

The solution or suspension of the composition for optical recording material is coated on a substrate and dried. The coating may be effected by a coater such as a coater, a curtain coater, a grabur coater, a doctorblet coater or a batik coater.

The substrate may be any film, sheet or plate capable of ensuring the smoothness of the surface of the optical recording material, and may be transparent, translucent or opaque, rigid or flexible.

Examples of such rigid sheets or bleeds include sheets or plates of metal or glass such as aluminum and copper, and examples of flexible films or sheets include polyethylene terephthalate, polyimide, cellulose acetate or polyfluoroacetylene. Plastic films or sheets.

Drying of the coating layer is at a temperature of 15 ° C. to 130 ° C. in air or at a temperature of 15 ° C. to 130 ° C. in an air stream of an inert gas for an optical recording material composition such as air, nitrogen gas, carbon dioxide gas, hydrogen gas, oxygen gas, helium gas, or argon gas. It is carried out at a temperature of 130 ℃.

A thin layer of metal more precious than the metal of the organometallic compound or the metal of the organometallic compound is formed on the surface of the coating layer of the composition for an optical recording material.

Metals more precious than metals of organometallic compounds mean metals that can act as reaction sites or metals that can act as catalyst nuclei for metals of organometallic compounds that can form metallic particles. More specifically, the formation of metallic particles by self-decomposition under heating or by reduction under heating proceeds remarkably at the position where a metal more precious than the metal of the organic compound is present, and as a result, the metallic particles are characterized in that the organometallic compound is less than the metal. It can be formed at a higher density compared to other locations where precious metal is present and where it is not present.

Typical metals that are more precious than metals of organometallic compounds that can be used in the present invention include silver, palladium, platinum, gold, rhodium, rhothenium, thallium, their mercury alloys, their sulfides and their oximes.

When the organometallic compound is an organosilver compound, silver palladium, pratinium, gold, silver oxide and silver sulfide can be used as the precious metal than the metal of the organometallic compound.

Metals that are more precious than metals of organometallic compounds refer to metals that can serve as metal melting catalyst nuclei of organometallic compounds that can form metals or metallic particles that can serve as reaction sites. More specifically, the formation of metallic particles proceeds remarkably at locations where metals that are more precious than metals of organic compounds are present, either by self-decomposition under heating or by reduction under heating, as a result of which the metal particles are more than metals of organometallic compounds. It can be formed at a higher density compared to other locations where precious metal is present and where it is not present.

Typical metals that are more precious than metals of organometallic compounds that can be used in the present invention include silver, palladium, platinum, gold, rhodium, ruthenium, thallium, mercury alloys thereof, sulfides thereof and oxides thereof.

When the organometallic compound is an organosilver compound, silver palladium, platinum, gold, silver oxide and silver sulfide may be used as the precious metal than the metal of the organometallic compound.

As a typical method of forming a thin layer of metal of an organometallic compound or a metal more precious than that of an organometallic compound on the surface layer of the composition for an optical recording material which can be used in the present invention, (1) first, an aqueous tin chloride solution and second For example, palladium may be provided on the surface of the layer by immersing the layer in an aqueous solution of palladium chloride or, firstly, on the surface of the layer by immersing the layer in aqueous solution of first tin chloride and secondly, in an aqueous solution of silver nitrate. Non-electrolytic plating sedimentation method to provide; (2) vacuum evaporating a metal such as platinum, gold, silver or palladium onto the surface of the layer; (3) coating a dispersion of a metal of an organometallic compound or a metal more precious than that of an organometallic compound on the surface of the layer in a solvent containing a suitable binder; (4) blurring the surface of the layer with a strong reducing agent such as ascorbic acid; (5) providing a silver sulfide-forming compound such as sodium sulfide on the surface of the layer; And (6) a method of forming silver on the surface of the layer by, for example, exposing the surface of the layer containing the organic silver compound to a reducing gas such as hydrogen gas for a short time.

The thickness of the thin layer of the metal core is 2 to 1000 kPa, preferably 10 to 200 kPa.

The layer of the composition for an optical recording material having a metal layer of the organometallic compound or a metal layer more precious than the metal of the organometallic compound on the surface at a temperature of 50 ° C. to 200 ° C. for 1 second to 5 minutes, preferably 70 ° C. to 160 ° C. Heating at a temperature of 2 seconds to 100 seconds results in a metallic glossy layer of metallic particles having a diameter of 0.03 μm to 3 μm at a high density on the surface of the layer. Heating conditions should be optimally adjusted to satisfy the required properties of the optical recording material of the present invention.

Furthermore, the substrate is formed by forming a thin layer of a metal that is more precious than the metal of the organometallic compound on the substrate in the same manner as described above, and subsequently coating the solution or suspension of the composition for an optical recording material on the substrate in the same manner as described above. A metallic gloss layer can be formed at the interface between the layer and the layer of the composition. Further, in the same manner as described above, first, a thin layer of a metal that is more precious than metal of an organometallic compound is formed on a substrate, and a solution or suspension of the composition for an optical recording material is coated on a second substrate, and third, on the surface of the coating layer. By forming a thin layer of metal that is more precious than the metal of the organometallic compound, two metallic gloss layers can be formed at the surface of the layer of the composition and at the interface between the substrate and the layer of the composition, respectively.

According to the present invention, the information to be retrieved comprises a layer of a composition for metal recording materials having a thin layer of metal more precious than metal of an organometallic compound on at least one surface through a photomask having information such as a format, 10 ⁻⁷ J A metallic gloss layer of at least one surface of the optical recording material through a port mask having information such as preformatting for 5 to 20 seconds prior to heating or exposure to light having an exposure energy of 10 cm 2 to 10 ⁻² J / cm 2. ^By exposing to light having an exposure energy of ^-1 J / cm 2 to 10 ⁵ J / cm 2 for 100 µsec to 10 seconds after the heating process, it is possible to record in advance to part or all of the optical recording material.

Light sources that can be used for light exposure include ultra-high pressure mercury lamps, halogen lamps, xenon-mercury lamps, tungsten lamps, xenon flash lamps, non-electrode lamps and krypton lamps and lasers. For light exposure after the heating process, xenon flashlight among these light sources is preferable from the viewpoint of obtaining high exposure energy and excellent resolution in a short time, and high productivity light recording in light exposure of at least one surface metallic gloss layer of the optical recording material. Cause.

Furthermore, in order to protect the optical recording material, a transparent protective layer can be laminated on the metallic luster layer of the optical recording material by heating or by an adhesive such as urethane resin and epoxy resin.

Typical transparent protective layers include films or sheets of organic polymer compounds such as polycarbonate, polystyrene, polymethylmethacrylate, polyvinylchloride, polyvinylidenechloride and polyethylene terephthalate.

The substrate may also be laminated as a sheet or film of metal, such as stainless steel, aluminum and copper, glass fiber reinforced sheet or film, carbon fiber sheet or film or ceramic sheet or film, in order to reinforce the optical recording material against bending. .

An optical recording material having a metallic gloss layer on at least one surface can be used without the substrate by removing the substrate with the substrate or after the heating process.

The optical recording material of the present invention may be in the form of a card, disk or tape.

The optical recording material of the present invention has a scanning speed of 10 cm to 3 m per second by various laser beam sources with appropriate forces, typically He-Ne lasers and semiconductor lasers having a radiation force of 5 to 15 mV and a beam diameter of 1 to 10 μm. It can be recorded as

The recording or writing of the information may be effected from the high reflectivity side of the optical recording material or from the low reflectance side of the optical recording material. Also, the pit formed may be a hole in which a portion of the optical recording material is removed, a concave surface formed by a difference in surface tension, or a bubble, in order to change the reflectivity before or at least 10% of the irradiation.

According to the present invention, the optical recording material can be produced by a continuous method at low cost. More specifically, industrial production means such as continuous coating of a solution or suspension of the composition for an optical recording material with a roll coater on a substrate and continuous heating of the coating layer by heat or hot airflow can be used for producing the optical recording material of the present invention. And as a result, the cost of the optical recording material can be reduced.

The optical recording material of the present invention is particularly suitable for an optical card, and the optical card having the optical recording material of the present invention will be described with reference to the drawings.

3A, 3B, 3C, and 3D, the number 1 is the optical recording material of the present invention, the number 2 is a magnetic material, the number 3 is analog information and the number 4 is a Japanese business machine maker association. It is an integrated circuit unit with eight terminals provided a position in accordance with JBMS-38-1988.

When an optical card is used as a financial transaction card such as a bank card, the owner's name, accounting number and personal code number are recorded in advance on the stripe of magnetic recording material. Is analog information and any other information that can reveal the identity of the optical card owner. By presenting the optical card at the reception desk of the bank, the owner can be identified by this analog information. When an optical card is used in a bank, information such as the date of deposit and withdrawal of the bank account, amount of money and balance information are recorded by the laser beam as dots, pits or spots on the stripe of the optical recording material 1.

When the optical card is used as a medical information card such as a health check card, the owner's name, the number of health checks and the owner's code number are recorded in advance on the stripe of magnetic recording material 2 and the owner's name, address and telephone number and health check Analog information, such as the number of times, may also be provided on the same side on the stripes of the magnetic recording material 2.

The method of information recording and information reading in the optical recording material of the present invention will be described with reference to FIG.

The laser beam 21 emitted from the semiconductor laser 15 becomes parallel light by the collimating lens 14 and the parallel light passes through the diffraction grating 13, the polarization beam separator 12, and the objective lens 11 and is concentrated on the optical recording material of the optical card 10. Reflected laser beam 21 passes through polarization beam splitter 12 and is split into two beams. Each beam passes through lenses 19 and 20 and one beam reaches a radio frequency sensor (RF sensor) 18 while the other beam reaches an autofocusing / auto tracking sensor (AF / AT sensor) 17. The RF sensor 18 is a sensor for measuring the change in reflectivity of the optical recording material and a data reading sensor for reading information. The signals of the RF sensor and AF / AT sensor are both controlled by control circuit 45.

For example, when an optical card is used as a purchase card, the encoder 46 converts information such as product number, product name and price provided from the control circuit 45 into a two-digit signal suitable for recording, and according to the signal, the laser beam is bit low in the optical recording material. Is released to form. In reading the information, a two digit signal corresponding to the bit row transmitted from the RF sensor 18 is supplied to the control circuit 45 through the decoder 47. The optical card 10 is moved in the X-axis direction using the feed rollers 42 and the motor 43 and in the Y-axis direction by the movement of the optic 22.

When the optical card has the magnetic recording material 2 shown in FIGS. 3B and 3C, the magnetic recording and reading apparatus 41 is used to read the information in the magnetic recording material 2 of the optical card. Moreover, when the optical card has the IC shown in FIG. 3D, an IC read write 51 is used.

In FIG. 5, which shows a block diagram for using the optical card 10, the card reader 31 is a device for recording information and reading the recorded information. The keyboard 35 enters the product number purchased at the time of purchase on the controller 32. The printer 33 is connected to the regulator 32 in order to output information such as a product number, a product name and a list of product prices.

Figure 6a is a flow chart of this system.

With reference to FIGS. 5 and 6A, the use of a purchase card will be described.

When the optical card is inserted into the card reader, the code number is recovered from the optical recording material. Then, when the personal code number is entered by the keyboard 35, the owner of the card is approved. After the owner's confirmation, information such as product number, product name and price are immediately read from the ROM portion of the optical recording material and shown on the display 34. Then, when the product number to be purchased is entered by the keyboard 35, the total amount of the purchased product name and price and amount are shown on the display 34, and the information is printed on the paper sheet by the printer 33 if necessary. Further, at this time, the purchase degree is recorded in the remaining portion of the optical recording material in the recording portion, the optical card is ejected. Information such as product number to purchase and its quantity may be delivered to the store by the telephone network or a printed list of product numbers to purchase may be delivered to the store by the facsimile.

When the optical card is used as a health examination card, for example, the image input device 36 is additionally used. Moreover, when the optical card is used in various systems using the sound card, the sound generator 37 is additionally used.

Referring to Fig. 5, the use of the IC optical card as the medical information card shown in Fig. 3- (d) is described.

The card reader 31 is a device for recording and reading information of an optical recording material, and for recording, reading and erasing information in an IC by a laser beam. Medical information is entered into the control section 32 via the keyboard 35. There is provided an image input device 36 which is a device sensor in which degradation is combined for inputting image information. A printer 33 for outputting various recorded medical information is connected to the control part 32.

One specific example using this system is shown in the flowchart of Fig. 6- (b) b. 5 and 6b, the use of the medical information card is described. The optical IC card is input into the card reader 31 and the personal code number is input from the keyboard 35 to confirm the owner of the card in the IC. After confirmation, the necessary stored medical information is reproduced and output by the display 34 or printer 33. The doctor, nurse or pharmacist can use the information for diagnosis and as a result of the medical examination, the type and amount of the amount to be prescribed and the medical expenses are input from the keyboard 35 or the image input device 35 and recorded in the IC or the optical recording material. Calculation of medical expenses is carried out within the IC to reduce the workload of the host computer. Finally, the optical IC card is ejected from the card reader 31. A large amount of information can be recorded in the optical recorder, and thus information stored in the IC can be recorded and stored in the optical recorder if necessary or desired. However, the latest data can be stored in the IC. At any time, information recorded in the optical IC card can be output on the paper sheet by the printer 33 if necessary.

It is preferable that the data to be recorded on the optical recording material and that to be recorded on the IC are separated. Image information such as X-ray photographs and X-ray computerized tomographic images are preferably recorded on the optical recording material, while information such as simple diagnostic results and medical expenses can preferably be stored in the IC. Because of the small memory capacity of the IC, it is necessary to erase information other than the minimum necessary information.

In addition, the optical IC card can be used as a personal information and identity card of a company that records all information such as face photographs, family composition, work records, internal savings accounts and business experiences in one card. Moreover, the optical IC card is a bank card for recording information of deposits and withdrawals, and can be used as a membership card for shopping such as a sports club member card, golf club member card, resident club member card and travel agency club member card.

The method of reading the recorded information in the ROM optical card will be described with reference to FIGS. 7- (a) and 7- (b).

Number 61 is a light source and various light sources can be used and typical light sources are lasers or light emitting diodes, where a laser is used. The laser beam emitted from the laser 61 is concentrated on the optical recording material of the optical card 10 through the focusing lens 63. The reflected laser beam is condensed on the line sensor 62 through the objective lens 64, converted into a two-digit electric signal, passed through the decoder 47, and reaches the control circuit 20 to read the information of the optical recording material. The digital information can also be converted into voice data by providing a voice changer and a voice generator having a control circuit.

The movement of the optical card 10 in the X-axis direction is controlled by the X-axis motor servo 67 and the optical card 10 itself is moved by the roller 66. The optical card 10 is moved by the roller 68 by adjusting the optical head 71 by the Y-axis motor servo 69 in the Y-axis direction. X-axis motor servo 67 and Y-axis motor servo 68 are regulated by control circuit 20.

When the ROM optical card is a sound card, the recorded information is read by the deforming device shown in Fig. 7B. The reflected laser beam is collected on the line sensor 62 and demodulated by 8 to 14 modulators 72, passed through decoder 48, de-interleave 73 and decoder 47, and converted from digital to analog by a digital-to-analog converter to output an audio output signal. To obtain. The use of such a sound card is described with reference to FIG. In FIG. 5, number 31 is a card reader writer for reading information recorded in the optical recording material of the sound card of the present invention, number 35 is a keyboard for inputting a signal to the controller 32, and number 37 is an audio output signal converted to voice. Voice generator for When the voice card is inserted into the card reader 31, the voice data is read and converted into an audio output signal which is sent to the voice generator 37. By inputting the required signal from the keyboard 35, the voice data can be adjusted.

The following examples illustrate the invention in more detail.

In the metallic luster layer of the optical recording material, the diameter of the metallic particles and the average interparticle distance between the two metallic particles are obtained as follows:

The optical recording material is buried in an epoxy resin (product of Nissan EM Co., Ltd., trade name “Quettol-812”) and cut into ultra-thin sections by ultra microtome (manufactured by LKB Corporation, trade name “LKB-V”). The ultratin section is placed on a grid attached with a collodione support film and the carbon is vacuum evaporated onto the ultratin section to obtain a microscopic sample. The photograph by transmission electron microscope is taken under the following conditions.

Electron Microscope: H-500 Hitachi Co., Ltd.

Acceleration Voltage: 75㎸

Observation method: transmission electron microscope method

The diameter of the metal particles is measured using a photograph.

The average interparticle distance between two metal particles is calculated from the measurement of the distance of 100 metal particles.

The evaluation of surface uniformity is as follows:

Reflectivity, expressed in%, is measured by a microdensitometer with holes of 1 μm ?? 10 μm. Reflectance is measured at 5μn intervals and 50 points (N). The reflectivity and the mean value of the reflectivity of each point are guided by Di and D, respectively, and the standard deviation σ is expressed by the following equation.

σ ² = Σ (Di-D) ² / N

The uniformity of the metallic luster layer is compared by standard deviation, and the uniformity is better as the standard deviation is smaller.

Example 1

Chromium (III) phenyldiazosulfonate, cobalt (II) phenyldiazosulfonate and copper (I) phenyldiazosulfonate are prepared by reacting phenyldiazosulfonic acid with metal chromium, metal cobalt and copper, respectively.

A suspension having the following ingredients is prepared.

14 g of each of the obtained metal phenyldiazosulfonates

Polyisobutyrene 7g

Methylcyclohexane 62g

16 g of 1-phenyl-3-pyrazolidone

The suspension is ball-milled for about 15 hours to homogenize and passed through a filter with an average pore diameter of 1.5 μm to remove undispersed material. The filter suspension is uniformly coated on 100 μm thick polyethylene terephthalate by a small applicator selected such that the slit forms a 9.5 μm thick coating after drying and dried at 22 ° C. and 50% relative humidity for about 12 hours.

The optical recording material having a metallic luster layer on the surface by vacuum evaporation of silver on the surface of the dry coating to a thickness of 10 kPa at a rate of 1 kPa per second under a vacuum of 10 ^-6 mmHg, followed by heating with a block heater at 135 ° C for 10 seconds. To obtain.

The result of measuring the reflectivity of the optical recording material thus obtained is as follows;

In addition, the vertical cross section of the optical recording material thus obtained is observed by transmission electron microscope. The diameter of the metallic particles in the metallic luster layer is as follows;

Note: Metallic particles having a particle diameter of 5 nm or more are not found in layers other than the metallic luster layer.

Moreover, the average distance between particles between the two metal particles at the surface of the metallic gloss layer is 5 nm to 9 nm, depending on the three types of optical recording materials.

Using a semiconductor laser beam having a radiation wavelength of 830 nm and a radiation output of 20 nm W, positive laser recording is performed and as a result all optical recording materials can be recorded by laser pulses of 50 mu sec.

Example 2

The procedure of Example 1 is repeated except that sulfinic acid is used instead of phenyldiazosulfonic acid and hydroquinone is used instead of 1-phenyl-3-pyrazolidone.

The reflectivity of the optical recording material thus obtained is as follows;

The diameter of the metallic particles in the metallic luster layer is as follows;

The average distance between particles between the two metallic particles at the surface of the metallic luster layer is 6 nm to 8 nm.

Using a semiconductor laser beam having a radiation wavelength of 830 nm and a radiation output of 20 mW, positive laser recording is performed and as a result all three types of optical recording materials can be recorded by a laser pulse of 10 secsec.

Example 3

A suspension having the following ingredients is prepared.

20g silver behenate

Polyvinyl Butyral 18g

Phthalazone 4g

9 g of 2,2'-methylenebis (4-ethyl-6-t-betaylphenol)

Methyl ethyl ketone 240g

Toluene 60g

The suspension is ball milled for about 12 hours to homogenize and passed through a filter with an average pore diameter of 1.5 μm to remove undispersed material. The filter suspension was uniformly coated on a 100 μm thick polyethylene terephthalate film by a small applicator with a slit selected to obtain a 6 μm thick coating after drying under stable light and about 12 hours at a relative humidity of 22 ° C. and 50%. Drying to obtain the intermediate optical recording material (I).

One of the intermediate optical recording materials (I) thus obtained is immersed in an aqueous solution (1) having a component decorated for 10 seconds or less, washed with water and dried in air, and then in an aqueous solution (2) having a component decorated for 10 seconds or less. Washing with water and drying in air yield an intermediate optical recording material (II).

Aqueous solution (1)

Tin Chloride 7g

200ml of distilled water

Concentrated hydrochloric acid 4ml

Aqueous solution (2)

0.1 g of palladium (II) chloride

200ml of distilled water

5 ml concentrated hydrochloric acid

The intermediate optical recording materials (I) and (II) were heated at 130 ° C. for 10 seconds to obtain optical recording materials (I) and (II), respectively. The intermediate optical recording material (I) is blackened, while the optical recording material obtained from the intermediate optical recording material (II) has a silver gloss layer on its coating surface and has a reflectance of 36%.

The diameter of the silver particles in the silver gloss layer is in the range of 15 nm to 35 nm. The average interparticle distance between the two silver particles at the surface of the silver gloss layer is 6 nm.

Using a semiconductor laser beam having a radiation wavelength of 830 nm and a radiation output of a beam diameter of 10 mW of 3 µm, laser recording is performed on the optical recording material by radiation pulses at a scanning speed of 40 cm per second. As a result, a rectangular pit having a diameter perpendicular to the scanning direction of 3 μm and a diameter parallel to the scanning direction of 3.5 μm can be recorded.

Moreover, the optical recording material (II) is stored for one week at 70 ° C. and 80% relative humidity after laser recording. As a result, no change in reflectivity, the shape of the pit and the outside is observed, and it is found that the optical recording material of the present invention has excellent storage stability.

Moreover, one of the intermediate optical recording material (I) and one of the intermediate optical recording material (II) are heated at 130 ° C. for 300 seconds. As a result, the entire surface of the coating of the intermediate optical recording material (I) is blackened, while the coating surface of the optical recording material obtained from the intermediate optical recording material (II) has a silver gloss layer and one surface of the substrate is blackened. The reflectivity is as follows.

Therefore, the value of (X-Y) / (X + Y) of the optical recording material is 0.67.

Using a semiconductor laser beam having a radiation wavelength of 830 nm, a beam diameter of 3 m, and an output of 3 mW, laser recording is performed as an optical recording material by radiation pulses at a scanning speed of 60 cm per second. As a result, a rectangular pit having a vertical diameter in the scanning direction of 3 mu m and a parallel diameter in the scanning direction of 3.5 mu m can be recorded.

Example 4

Spin-coated with a solution having a component decorated to have a coating having a thickness of 0.6 μm after drying on one surface of the same intermediate optical recording material (I) obtained in Example 3, dried at room temperature (22 ° C.) and 24 at 50 ° C. Vacuum drying for a time gives an intermediate optical recording material (II).

10g polyvinyl alcohol

Sodium tetrachloroaurate (III) 100g

Methyl Alcohol 20ml

500ml of distilled water

The intermediate optical recording material (II) is heated at 130 ° C. for 10 seconds to obtain an optical recording material having a silver glossy layer on its surface. The reflectivity is 45%. The same semiconductor laser beam recording as in Example 3 is carried out to form pits of 3 mu m.

Moreover, the optical recording material is stored for one week at 70 ° C. and 80% relative humidity after laser recording. As a result, no change in reflectivity, shape and appearance of the pit is observed and it is found that the optical recording material of the present invention has excellent storage stability.

Moreover, one of the intermediate optical recording materials (II) was heated at 130 ° C. for 300 seconds to obtain an optical recording material having 51% reflectivity on the coating surface and 13% reflectivity on the substrate surface.

Example 5

The same procedure as in Example 4 was repeated except that 100 mg of mercury (II) acetate and 100 mg of hydroquinone were used instead of sodium tetrachloroaurate (III) to obtain an intermediate optical recording material (II).

The intermediate optical recording material (II) is heated at 130 ° C. for 5 seconds to obtain an optical recording material having its surface silver glossy layer. The reflectivity is 21%. It is confirmed that the optical recording material thus obtained can be recorded by the laser beam in the same manner as in Example 3.

Example 6

The same procedure as in Example 3 was repeated except that 0.1 g of potassium tetraiodo platinum (II) was used instead of palladium (II) chloride in the aqueous solution (2) to obtain an intermediate optical recording material (II). .

The intermediate optical recording material (II) thus obtained is heated at 130 ° C. for 5 seconds to obtain an optical recording material having a silver glossy layer on its surface. The reflectivity is 23%. The optical recording material thus obtained can be recorded by the laser beam in the same manner as in Example 3.

Example 7

A suspension having the following ingredients is prepared.

20g silver behenate

Polyvinyl Butyral 18g

Phthalazone 4g

2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methyl-

8 g of phenyl acrylate

Methyl ethyl ketone 185 g

Toluene 55g

Sodium bromide 0.3g

The suspension is ball milled for about 12 hours to homogenize and passed through a filter with an average pore diameter of 1.5 μm to remove undispersed material.

In the same manner as in Example 3, the filter suspension was uniformly coated on a polyethylene terephthalate film so as to form an 11 μm thick coating after drying, and dried under safety light to obtain an intermediate optical recording material (I). Then, in the same manner as in Example 3, palladium nuclei were formed on the surface of the coating to obtain an intermediate optical recording material (II).

The intermediate optical recording material (II) thus obtained is subsequently heated at 150 ° C. for 10 seconds with a block heater to obtain an optical recording material having a silver glossy layer on its surface.

1A and 1B are transmission electron micrographs of the optical recording material thus obtained. 1A and 1B, A is an epoxy resin layer, B is a silver gloss layer and C is a layer of the composition for the optical recording material.

The silver particles in the silver gloss layer have a diameter of 15 nm to 50 nm and a percentage of the diameter of the silver particles larger than 40 nm is at most 3%. The average distance between the two silver particles on the surface of the silver gloss layer is 7 nm.

It is also confirmed that the optical recording material can be recorded by the laser beam in the same manner as in the third embodiment.

Example 8

The same procedure as in Example 7 was repeated except that the suspension additionally had 0.2 g of 1,1,1 ', 1'-tetrabromo-o-xylene to prepare the intermediate optical recording material (II). The coating is dried at 50 ° C. for 10 minutes, then the intermediate optical recording material (I) is stored at 22 ° C. and 50% relative humidity and the whole process is carried out under safety light.

The intermediate optical recording material (II) is heated at 140 ° C. for 10 seconds to obtain an optical recording material. The reflectivity is 47%.

A He-Ne laser beam having a radiation wavelength of 633 nm, a beam diameter of 3 nm, and a radiant output of 3 mW was used at a radiation pulse of 100 mu sec to perform laser recording to form a 3 mu m pit.

The silver particles in the silver gloss layer have a diameter of 10 nm to 38 nm and a percentage of silver particle diameter of 15 nm or more is at most 6%. The average interparticle distance between the two silver particles at the surface of the silver gloss layer is 5 nm.

Example 9

A suspension with the following ingredients is prepared in the dark.

20g silver behenate

15 g of vinyl chloride-vinylacetate copolymers

Phthalazone 6g

10 g of 2,2'-methylenebis (4-t-butyl-6-t-butylphenol)

0.3 g of calcium iodide

0.4 g of cobalt iodide

Methyl ethyl ketone 200 g

Toluene 50g

The same procedure as in Example 3 was repeated using the suspension except that the entire process was carried out under stable light to produce the intermediate optical recording material (II).

The intermediate optical recording material (II) was exposed to 300 W high pressure mercury or the like for 10 seconds through a chromium mask having a 2 µm wide groove at intervals of 10 µm width, and immediately heated the entire intermediate optical recording material at 130 ° C. for 4 seconds. An optical recording material having a silver gloss layer having a non-gloss portion of 2 占 퐉 width in the exposed portion on the surface of is obtained. The non-gloss portion is yellow and transparent and can be used as a tracking guide. The reflectivity of the silver gloss layer is 40%.

Laser recording is performed by a tester for an optical card having a semiconductor laser having a power of 10 mW at a scanning speed of cm per second. As a result, pits are formed and read in the optical recording material.

The optical recording material is stored for one week at 70 ° C. and 80% relative humidity after laser recording. As a result, little change in reflectivity, shape and appearance of the pit is observed and it is found that the optical recording material of the present invention has excellent storage stability.

Example 10

A solution having the following components is prepared.

20 g silver trifluoroacetate

9 g of 2,2-methylenebis (4-ethyl-6-t-butylphenol)

Methyl ethyl ketone 200 g

Toluene 60g

20g polycarbonate

The solution is stirred for about 1 hour to homogenize and passed through a filter with an average pore diameter of 1.5 μm.

After drying, the filtrate was uniformly coated on a 100 μm thick polyethylene terephthalate film by a small applicator with a slit selected to form a 6 μm thick coating, and dried at 22 ° C. and 50% relative humidity to form an intermediate optical recording material (I) is obtained.

The intermediate optical recording material (I) was immersed in the following aqueous solution (1) for 10 seconds, the treated material (I) was washed with water and the washed material (I) was dried and then obtained in the following aqueous solution (2). One of the intermediate optical recording materials (I) obtained in the non-electrode plating process of immersing one material for 10 seconds, washing the treated material (I) with water, and drying the washed material (I) in air. Palladium nuclei are formed on the coated surface to obtain an intermediate optical recording material (II).

Aqueous solution (1)

40 ml of active agent neogantsu 834 (product of Nippon Shering Co., Ltd.)

956 ml of distilled water

Sodium hydroxide 3g

Aqueous solution (2)

Reducing agent Neogantsu WA (product of Nippon Shering Co., Ltd.) 5 ml

5 g of boric acid

950ml of distilled water

The obtained intermediate optical recording material (II) was heated at 150 ° C. for 60 seconds to obtain an optical recording material having a silver glossy layer on its surface. The reflectivity of the optical recording material thus produced is 50.5%.

2A and 2B or transmission electron micrographs of the optical recording material thus obtained. 2A and 2B, D is an epoxy resin layer, E is a silver gloss layer, and F is a layer of a composition for an optical recording material.

On the other hand, when one of the intermediate optical recording materials I is heated at 150 ° C. for 60 seconds, it turns reddish brown and the reflectivity is 8.5%.

The same laser beam recording as Example 3 was performed with the optical recording material to form a pit of about 3 mu m.

Example 11

A solution composed of the following silver components was prepared.

20 g silver trifluoroacetate

9 g of 2,6-di-t-butyl-4-methylphenol

Methyl ethyl ketone 200 g

Toluene 60g

Polyvinyl Butyral 18g

An optical recording material having a silver glossy layer on its surface was produced in the same manner as in Example 10 except that the optical recording material was heated at 140 ° C. for 60 seconds. The reflectivity of the optical recording material is 62%.

The same laser beam recording as Example 10 was carried out with the optical recording material, and as a result, it was confirmed that pits could be formed.

Example 12

The surface of the intermediate optical recording material obtained in Example II was contacted with hydrogen gas to reduce silver trifluoroacetate on the surface of the intermediate optical recording material to form a silver nucleus.

The treated intermediate optical recording material is heated at 150 ° C. for 80 seconds to obtain an optical recording material having a silver glossy layer on its surface. Reflectivity is 50%.

The same laser beam recording as Example 10 was carried out with the optical recording material, and as a result, it was confirmed that pits could be formed.

Example 13

A solution having the following components is prepared.

20 g silver heptafluorobutyrate

Polyvinyl Butyral 18g

2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methyl-

8 g of phenyl acrylate

Isopropyl Alcohol 185g

55 g of cyclohexane

Sodium Iodide 0.3g

0.3 g of cobalt iodide

The solution is stirred for about 2 hours to homogenize and passed through a filter with an average pore diameter of 1.5 μm.

Except for coating the filtrate solution on the substrate under safety light, the same procedure as in Example 10 for producing the intermediate optical recording material was carried out to dry to form an 11 μm thick coating.

The intermediate recording material (II) is heated at 150 ° C. for 40 seconds with a block heater to obtain an optical recording material having a silver glossy layer on the surface. Reflectivity is 75%.

The photomask is placed on the coating surface of the optical recording material and the coating is irradiated for 2 seconds through a photomask having a 300W high-pressure mercury lamp, and then the entire optical recording material is heated at 150 ° C. for 25 seconds to obtain an optical material having a silver-gloss layer on the surface. do. Reflectance on the exposed surface is 9.7% and reflectivity on the unexposed surface is 58%.

The same laser beam recording as in Example 10 was performed with the unexposed surface of the optical recording material, and as a result, it was confirmed that pits could be formed.

Example 14

A solution having the following components is prepared.

20 g silver trifluoroacetirancetonate

Polyvinyl Butyral 18g

2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphen

Nylacrylate 8g

Methyl ethyl ketone 185 g

Toluene 55g

The solution is stirred for about 2 hours to homogenize and passed through a filter having a pore diameter of 1.5 μm. Under safety light, the filtrate was uniformly coated on a polyethylene terephthalate film having a thickness of 100 μm with a small balllaid coater to form a 10 μm thick film, and the film was dried at 50 ° C. for 10 minutes to provide an intermediate optical recording material (I). To obtain. The intermediate optical recording material (I) is stored under safety light at 22 ° C. and 50% relative humidity.

Subsequently, the palladium nucleus is formed by vacuum evaporation of palladium metal on the coating surface of the intermediate optical recording material (I) to obtain the intermediate optical recording material (II).

The intermediate optical recording material (II) is heated at 140 ° C. for 10 seconds with a roll heater to obtain an optical recording material having a silver glossy layer on the surface. The reflectivity is 42%.

Using a He-Ne laser beam having a radiation wavelength of 633 nm, a beam diameter of 3 mu m, and a radiant output of 3 mW, laser recording is performed at a recording pulse of 100 mu sec to form a pit of 3 mu m.

Example 15

A suspension having the following ingredients is prepared.

20g silver behenate

Polyvinyl Butyral 18g

Phthalazone 4.3 g

10 g of 2,2'-methylenebis (4-t-butyl-6-t-butylphenol

Methyl ethyl ketone 20g

Toluene 60g

The suspension is ball milled for about 12 hours to homogenize and passed through a filter with an average hole diameter of 1.5 μm to remove undispersed material. The filtration suspension was dried on a 125 탆 thick polyethylene terephthalate film as a substrate film and then uniformly coated with a small applicator of the selected slit to obtain a 6 탆 thick coating, dried at room temperature (22 ° C.) in air to intermediate optical Obtain the recording material (I).

Separately, the polyethylene terephthalate film as a substrate film was immersed in an aqueous solution (1) having the following components for 120 seconds, washed with water and dried in air, then immersed in an aqueous solution (2) having the following components, washed with water and air To dry. The filtration suspension was coated on a polyethylene terephthalate film treated in the same manner as described above to obtain an optical recording material (II).

Aqueous solution (1)

Tin Chloride 2g

100ml of distilled water

Concentrated hydrochloric acid 2ml

Aqueous solution (2)

0.1 g palladium chloride

200ml of distilled water

5 ml concentrated hydrochloric acid

The intermediate optical recording materials (I) and (II) were heated at 130 ° C. for 200 seconds to obtain optical recording materials (I) and (II), respectively.

The optical recording material (I) was blackened and its reflectivity was 8%, while the optical recording material (I) had silver gloss at the interface between the substrate film and the film, and the reflectivity at the surface of the substrate film and the film surface was 45, respectively. % And 11%.

Using a semiconductor laser beam having a radiation wavelength of 830 mm, a beam diameter of 3 μm, and a radiation output of 6 mW, laser recording is performed with the optical recording material (II) on the radiation pulse at a scanning speed of 80 cm per second. As a result, a rectangular pit having a diameter perpendicular to the scanning direction of 3 mu m and a diameter parallel to the scanning direction at 3.5 mu m can be recorded, and the recording of the pit is confirmed by an increase in reflectivity.

Example 16

One surface of the same intermediate optical recording material (I) as obtained in Example 15 was spin-coated at room temperature (22 ° C.) with a solution having the following components to obtain a 0.2 μm thick film after drying, followed by 24 at 50 ° C. Vacuum dry for hours.

10g polyvinyl alcohol

100 ml of soridi tetrachloroaurate (II)

Methyl Alcohol 20ml

1000ml of distilled water

The same suspension as in Example 15 was uniformly coated on the coating surface as obtained above to obtain a 6 mu m thick film and dried at room temperature (22 DEG C) in air to obtain an intermediate optical recording material.

The obtained material is heated at 130 ° C. for 30 seconds to obtain an optical recording material. It is 46% reflected at the surface of the polyethylene terephthalate film while the reflectance at the surface of the coating is 12%.

The same laser beam recording as in Example 15 was conducted, and as a result, it was confirmed that pits could be formed.

Example 17

A suspension with the following ingredients is prepared in the dark.

20g silver behenate

15 g of vinyl chloride-vinylacetate copolymers

Phthalazone 6 g

10 g of 2,2'-methylenebis (4-t-butyl-6-t-butylphenyl)

Calcium Bromite 0.3g

0.3 g nickel iodide

Methyl ethyl ketone 200 g

Toluene 50g

The intermediate optical recording material (II) was prepared using a suspension in the same manner as in Example 15 under stable light.

The intermediate optical recording material (II) was exposed to 300W high-pressure mercury for 10 seconds through a chromium mask having a 2 µm wide groove at intervals of 10 µm width and immediately heated the entire intermediate optical recording material at 130 ° C. for 200 seconds to expose to the exposed area. An optical recording material having a silver gloss layer having a non-gloss portion of 2 mu m width having a reflectivity of 13% formed is obtained. The reflectivity of the silver gloss layer is 33%.

Laser recording is performed on a tester for an optical card having a semiconductor laser having a power of 10 mW at a scanning speed of 95 cm per second. As a result, the pits can be formed in the optical recording material and read out.

Example 18

One surface of the same intermediate optical recording material (II) as obtained in Example 17 is spin-coated with a solution having the following components to form a 2 탆 thick film after drying.

1 g of methyl methacrylate

Methyl ethyl ketone 100g

Cyanine Dye 0.1g

The coating is dried at 120 ° C. for only 3 seconds to form only a silver gloss layer and the black is cooled at room temperature (22 ° C.) before formation of the particles.

The same laser beam recording as in Example 17 is performed on the surface of the dye coating layer. As a result, the recording of the pit is confirmed in the silver gloss layer by the increase in reflectivity of the pit due to sublimation or decomposition of the dye coating layer.

Example 19

A suspension having the following ingredients is prepared.

20g silver behenate

Polyvinyl Butyral 18g

Phthalazone 4g

As shown in Table 1 of (1) to (13) shown in Table 1

Each reducing agent amount

Methyl Alcohol 20g

Methyl ethyl ketone 200 g

Toluene 60g

0.3 g of calcium bromide

0.3 g of cobalt (II) iodide

Each suspension is uniformed by ball milling for about 12 hours and passed through a filter having an average pore diameter of 1.5 μm to remove undispersed material.

Under dry light, the filtration suspension was uniformly coated on a polyethylene terephthalate film having a thickness of 100 µm by a small applicator to have a 6 µm thick coating after drying, and about 12 hours at a relative humidity of 22 ° C. and 50%. Drying to obtain the intermediate optical recording material (I).

A palladium nucleus is formed on the coating surface of the intermediate optical recording material (I) in the same manner as in Example 3 to obtain the intermediate optical recording material (II).

A mask film having a format was placed on the film of the intermediate optical recording material (II) obtained, and the film was irradiated with 500 W tungsten or the like for 1 second through the mask film, and the entire intermediate optical recording material (II) continuously exposed was 140 ° C. It is heated for 10 seconds at to obtain an optical recording material having a surface of high reflectivity at the unexposed area and a surface of low reflectivity at the exposed area, thus having a preformat.

The uniformity of the surface of the optical recording material is shown in Table 1.

TABLE 1

* Molecular mall of silver behenate

Example 20

The same procedure as in Example 19 was repeated except that each suspension having the following components was used to produce an optical recording material having a preformat.

20g silver behenate

Polyvinyl Butyral 18g

Phthalazone 4g

As shown in Table 2 of (1) to (8) shown in Table 2

Each reducing agent amount

25g methyl alcohol

190 g of methyl ethyl ketone

Toluene 55g

0.3 g of calcium bromide

0.3 g of cobalt (II) iodide

Table 2 shows the uniformity of the surface of the optical recording material.

TABLE 2

* Mole per mole of silver behenate

Example 21

A suspension having the following ingredients is prepared.

Silver Behenate 25g

Polyvinyl Butyral 19g

Phthalazone 5g

As shown in Table 3 of (1) to (8) shown in Table 3,

Each reducing agent amount

Methyl Alcohol 20g

Methyl ethyl ketone 240g

Toluene 60g

0.2 g of calcium bromide

0.2 g of cobalt (II) iodide

The same procedure as in Example 19 was repeated using each suspension 3 to produce an optical recording material having a preformat.

Table 3 shows the uniformity of the surface of the optical recording material.

TABLE 3

* Moles per mole of silver behenate

Example 22

A suspension having the following ingredients is prepared.

20g silver behenate

Polyvinyl Butyral 18g

Phthalazone 4g

As shown in Table 4 of (1) to (15) shown in Table 4

Each reducing agent amount

Methyl ethyl ketone 185 g

Toluene 55g

Sodium bromide 0.3g

0.1 g of 1,1,1 ', 1'-tetrabromo-o-xylene

Each suspension is used in place of an aqueous solution of silver nitrate having 4 g of silver nitrate in place of an aqueous solution containing palladium (II) chloride (2) and a composition of 500 ml of distilled water and 50 ml of 30% by weight aqueous ammonia solution. The same procedure as in Example 19 for producing the intermediate optical recording material (II) was repeated to form a silver nucleus on the surface of the intermediate recording material (I).

The entire intermediate optical recording, which was placed on the film of the intermediate optical recording material (II) that produced the chromium mask having digital information, was irradiated at a distance of about 30 cm for 3 seconds with 500 W tungsten or the like through the mask, and continuously exposed. Ash (II) is heated at 130 ° C. for 30 seconds to obtain an optical recording material having information, that is, ROM.

The bit error rate BER is measured using a reader with a semiconductor laser having a radiation wavelength of 780 mm. The results are shown in Table 4.

TABLE 4

* Molar amount of silver behenate

Example 23

A suspension having the following ingredients is prepared.

20g silver behenate

Polyvinyl Butytal 18g

4 g of 2,2'-methyl enbis (4-ethyl-6-t-butyphenol)

Methyl ethyl ketone 200 g

Toluene 60g

2 mg of (1) to (6) shown in Table 5

Each reducing agent

Sodium bromide 1g

5 g of chloromethane

1 g of methanol

The same procedure as in Example 19 was repeated using each suspension to prepare an optical recording agent having a preformat, except that it was heated at 130 ° C. for 10 seconds instead of at 10 ° C. for 10 seconds.

The same laser beam recording as in Example 3 is carried out to form pits. The C / N ratio of signal reproduction is measured and the bit error ratio (BER) is measured with an error detector with a reproducing power of 0.5 mM. The results are shown in Table 5.

The minimum force required to form the pit by only changing the laser emission power among the recording conditions is shown in Table 5.

Moreover, the accelerated test was carried out for 100 hours at 20,000 lux halogen and the like at 40 ° C. and 90% relative humidity, and the results are shown in Table 5.

The comparative optical recording material was produced by repeating the above-described procedure except that it was removed from the suspension using the light absorbing agent, and the properties of the optical recording material thus obtained are shown in Table 5.

TABLE 5

Example 24

The same procedure as in Example 14 was repeated except that a 100 탆 thick polyfluoroethylene sheet was used as the substrate instead of the polyethylene terephthalate film to obtain an optical recording material.

The optical recording material is taken in a size of 10 mm x 10 mm and peeled off from the substrate with tweezers. The same laser recording as in Example 14 was performed by placing the optical recording material, and the pits were formed by imprinting on a laser recording apparatus.

An optical recording material is inserted between two polyvinylchlorides for titration and then titrated. An optical cart having an optical recording material is produced by stamping the laminated sheet with a stepper for the card.

Example 25

One of the same intermediate recording material (II) as obtained in Example 15 was treated in the same aqueous solution (1) and (2) in the same manner as in Example 15, so that both at the interface between the substrate film and the film and on the surface of the film An intermediate optical recording material (II ') having a palladium nucleus is obtained.

The intermediate optical recording material (II ′) thus prepared is heated at 130 ° C. for 200 seconds to obtain an optical recording material having a silver-gloss layer on both the interface between the substrate film and the film and the surface of the film. The reflectivity at the surface of the substrate and the surface of the film is 44% and 47%, respectively.

A 125 μm thick polyethylene terephthalate film, one surface of which is precoated with a urethane adhesive to a thickness of about 10 μm, is laminated in terms of the adhesive layer on the optical recording material.

The same laser recording as in Example 15 was conducted and it was confirmed that it could be recorded on both sides of the obtained optical recording material.

Example 26

A 10 wt% aqueous solution of sodium polyacrylate having a number average molecular weight of 15,000 was coated on a glass plate and dried in air at 50 ° C. for 12 hours to obtain a 7 μm-thick film. Subsequently, the organic plate having a film of 5% by weight of silver nitrate was immersed in an aqueous solution for 3 minutes to convert the film of sodium polyacrylate into a silver polyacrylate film and dried in air at 50 ° C. for 12 hours. A glass plate with a silver polyacrylate film was immersed in 5 wt% aqueous hydroquinone solution for 3 minutes and dried in air at 40 ° C. for 6 hours.

The palladium metal was vacuum evaporated on the surface of the silver polyacrylate film treated with a thickness of 30 mm 3, and the film thus obtained was heated at 130 ° C. for 100 seconds to form a silver glossy layer on the surface. Reflectivity is 37%.

The same laser beam recording as in Example 3 is made, confirming that a pit can be formed as a result.

Example 27

A solution having the following components is prepared.

Sodium Alginate 20g

Distilled water 800g

60 g of isopropyl alcohol

The solution is stirred for about 1 hour to homogenize and passed through a filter having an average pore diameter of 1.5 μm. The filtrate solution is uniformly coated on a 100 μm thick polyethylene terephthalate film with a small applicator with a slit selected to give a 6 μm thick coating after drying and dried at 22 ° C. and 55% relative humidity for about 12 hours. The film was then immersed in 0.1 N silver nitrate aqueous solution for 3 minutes to convert the film of sodium alginate to a silver alginate film and dried at 50 ° C. for 12 hours in air to obtain an intermediate optical recording material (I).

One of the intermediate optical recording materials (I) was further treated with the same aqueous solutions (1) and (2) in the same manner as in Example 10 to obtain an intermediate optical recording material (II) having palladium nuclei on its surface.

The intermediate optical recording materials (I) and (II) are then heated at 150 ° C. for 100 seconds. As a result, the entire surface of the intermediate optical recording material (I) turned reddish brown and had a reflectivity of 8.5%, while the optical recording material obtained from the intermediate optical recording material (II) had a silver light film layer having a reflectivity of 50.5 on the surface. Have

The same laser beam recording as Example 3 was carried out with the obtained optical recording material, and pits of about 3 mu m were formed.

The same procedure as described above is repeated except that sodium pate is used instead of sodium alginate. As a result, it is confirmed that pits of about 3 mu m are formed by laser beam recording.

Example 28

A chromium photomask having a tracking guide of 3 µm wide grooves at 12 µm wide intervals was placed on the silver glossy layer of the same optical recording material obtained in Example 10, and the silver glossy layer was exposed to 50 J / cm 2 of exposure energy for 10 msec. Having agent

A tracking guide having a low reflectance of 24% is formed by exposure to an element of an organic halide compound or an optical recording material flash, which is a dihalide of triphenylphosphite.

Example 29

The same procedure as in Example 8 was repeated except that the thickness of the coating film of the optical recording composition was changed to 6 µm to prepare the intermediate optical recording material (II), and the coating was dried at 55 캜 for 10 minutes.

The number of items in a dot that has a preformat in a store. A photomask having a catalog of product names and prices, placed on one of the intermediate optical recording materials (II), exposed to a 500W tungsten light for 1 second through a photomask and heated at 130 ° C. for 10 seconds to provide a silver glossy layer on its surface. Records the optical recording material having a.

A 0.4 mm thick polycarbonate sheet is laminated on the silver light layer of the optical recording material with a urethane adhesive and a 0.25 mm thick polyvinyl chloride sheet is laminated with a urethane adhesive. The laminated product thus recorded is taken in the form of a card and the optical card is recorded as a purchase card. The card name store name is printed on the surface of the card.

The procedure described above is repeated, except that a library uses a port mask that has data for the catalog of documents and books in Bitcoe, and as a result the ROM optical card contains the library optical card. The name of the card and library is printed on the surface of the card.

Example 30

A photomask having a preformat was placed on one of the same intermediate optical recording materials II as sown in Example 29, and the optical recording materials II were exposed to 500 W tungsten light for 1 second through the photomask and for 10 seconds at 130 ° C. An optical recording material is obtained that is heated and has a silver glossiness on the surface.

A 0.4 mm thick polycarbonate sheet is laminated on the silver light layer of the optical recording material with a urethane adhesive and a 0.15 mm thick polyvinyl chloride sheet is laminated with a urethane adhesive.

Information such as magnetic recording agent and subject and accounting seal or signature are attached to the polyvinylchloride and a 0.05 mm polyvinyl chloride film is laminated on the magnetic recording material and information as a transparent protective film. The lamination product is written in the form of a card and an optical magnetic card is obtained as a bank card. Print the name of the card and bank on the card.

Example 31

A chip type IC chip having a surface area of 2 mm2 and a thickness of 0.3 mm and having a central processing unit (CPU) and an electrically erasable and programmable read memory (EEPROM) is fabricated. The reverse side of the chip is treated like a slanted surface. The IC chip is fixed to the doped substrate with a urethane adhesive, the board is electrically connected to the IC chip by wire bonding, the IC chip and the remainder of the substrate are sealed with a polyurethane resin, and the reverse side of the IC module is cleaned and softened. The thickness of the IC modium thus obtained is 0.6 mm. Holes having the same size of IC modium are made in a 0.2 mm thick polyvinylchloride sheet and a 0.4 mm thick polycarbonate sheet and the IC module is inserted as a urethane adhesive into the hole between these two sheets. The same optical recording material as obtained in Example 30 was inserted between the sheet without urethane adhesive, 0.1 mm thick polyvinyl chloride sheet was laminated with adhesive on the 0.2 mm thick polyvinyl chloride front surface and thus obtained. Taken in the form of a lamination product card to obtain an optical IC card as a bank card.

Claims (100)

Thin films or membranes of hydrophobic binders; Including metallic particles having a diameter of 0.003-3 μm dispersed in the film or film, wherein the metallic particles have a higher density near at least one side of the film or film as compared to other portions of the flim or film, and the metallic particles are liquid And at least one metal having a shell having a melting point of 250 ° C.-1800 ° C. and a thermal conductivity of 5-450 W · m ⁻¹ · K ⁻¹ at 0 ° C., wherein the metallic particles in the film or film Optical recording material with 10-90% reflectivity of the denser side of the film. The optical recording material according to claim 1, wherein the reflectivity is 25 to 60%. 2. The reflectivity of the surface (a) of the optical recording material having a higher density of metallic particles as compared to other portions of the film or film, and the reflectivity of the portion (b) adjacent to the surface (a) have the following relationship Optical recording material.

(Wherein, X is the reflectivity of the surface (a); Y is the reflectivity of the portion (b).) The optical recording material according to claim 3, wherein the reflectivity of the surface (a) and the reflectance of the portion (b) have the following relationship.

(Wherein, X is the reflectivity of the surface (a); Y is the reflectivity of the portion (b)). The optical recording material of claim 1, wherein the shell is at least one metal selected from the group consisting of silver, gold, copper, tellurium, bismuth, photoradium, cobalt, nickel, lead, chromium, and titanium. The optical recording material according to claim 1, wherein the liquid is at least one metal of the skin or at least one metal that is more precious than the metal of the skin. The optical recording material according to claim 5, wherein the outer shell is silver. The optical recording material according to claim 7, wherein the liquid is silver or a metal more precious than silver. The optical recording material according to claim 8, wherein the more precious metals of silver are palladium, platinum, rhodium, tuthenium, thallium, mercury, alloys thereof, sulfido or oxides thereof. The optical recording material according to claim 8, wherein the liquid is on. 10. The optical recording material according to claim 9, wherein the metal which is more precious than silver is palladium. 10. The optical recording material according to claim 9, wherein the metal which is more precious than silver is gold. The optical recording material according to claim 9, wherein the metal that is more precious than silver is platinum. The optical recording material according to claim 1, wherein the hydrophobic binder is an organic polymer compound insoluble in water or hot water at 60 ° C. The optical recording material according to claim 14, wherein the hydrophobic binder has a glass transition temperature of 10 ° C to 120 ° C. 16. The optical recording material of claim 15, wherein the hydrophobic binder has a glass transition temperature of 40 ° C to 110 ° C. 17. The optical recording material of claim 16, wherein the hydrophobic binder is polyvinylbutyltal. 17. The optical recording material of claim 16, wherein the hydrophobic binder is polymethylmethacrylate. 17. The optical recording material of claim 16, wherein the hydrophobic binder is polycarbonate. The optical recording material according to claim 16, wherein the hydrophobic binder is a vinyl chloride-vinylacetate copolymer. 17. The optical recording material of claim 16, wherein the small hydrophobic binder is polyisobutylene. The optical recording material of claim 1, wherein the thin film or film of the hydrophobic binder contains an onhalide or an onhalide former. 23. The silver halide former according to claim 22, wherein the silver halide former is a hydrogen halide, a metal halide, a halogen molecule, an organic N-haloamide, a diarin halomethane, an ammonium halide, group IV, V and VI of the periodic table. An optical recording material which is an organic halide compound of the element of or a dihalide of triphenyl phosphite. The optical recording material of claim 23 wherein the silver halide former is a metal halide. The optical recording material according to claim 1, wherein the thin film or film of the hydrophobic binder contains a light absorbing agent in a wavelength range of a semiconductor laser. The optical recording material according to claim 1, which contains a thin layer of a light absorbing agent on its surface in the range of a wavelength of a semiconductor laser. 27. The optical recording material according to claim 26, wherein the thickness of the thin layer of the light absorbing agent is 500 kPa to 5 mu m. The optical recording material according to claim 25, wherein the light absorbing agent is a phthalocyanine dye. The optical recording material according to claim 25, wherein the light absorbing agent is an azulenium dye. The optical recording material according to claim 25, wherein the light absorbing agent is a nickel-dithiol complex. The optical recording material according to claim 1, wherein the thin film or film of the hydrophobic binder contains a color control agent. 32. The optical recording material of claim 31 wherein the color control agent is phthalazone. The optical recording material according to claim 1, wherein the thin film or film of the hydrophobic binder contains an antifogging agent. The optical recording material according to claim 33, wherein the antifogging agent is 1,1,1 ', 1'-tetrabromo-o-xylene. The optical recording material according to claim 1, wherein the optical recording material has a thickness of 1 to 20 µm. An optical recording material according to claim 1, provided on a substrate. 37. The optical recording material according to claim 36, wherein the substrate is a metal, glass, or plastic filament, sheet or plate. The optical recording material according to claim 36, wherein a film or sheet of plastic is laminated on the substrate. The optical recording material of claim 1, wherein the transparent film, sheet or plate is laminated onto the surface of the optical recording material. The optical recording material according to claim 1, wherein the information to be read is recorded in advance in the optical recording material. 41. The optical recording material according to claim 40, wherein the information to be read is previously recorded in a part of the optical recording material. 41. The optical recording material according to claim 40, wherein the information to be read is previously recorded in the entire optical recording material. For an optical recording material containing an organometallic compound capable of forming metallic particles having a diameter of 0.003 µm to 3 µm on a substrate, or a compound capable of reducing the organometallic compound together with the organometallic compound, and a hydrophobic binder. Forming a layer of the composition, and providing a thin layer of a metal of the organometallic compound or a metal more precious than the metal of the organometallic compound on the surface of the composition layer for an optical recording material; A first step comprising heating a layer of the composition having the metal layer of the organometallic compound or the thin layer of a metal more precious than the metal of the organometallic compound at a temperature of 50 ° C. to 200 ° C. for 1 second to 10 minutes. Method for producing an optical recording material of claim. Providing on the surface of the substrate a thin layer of metal of an organometallic compound or metal of an organometallic compound that is capable of forming metallic particles having a diameter of 0.003 μm to 3 μm; Forming a layer of a composition for an optical recording material containing a compound capable of reducing the organometallic compound and a hydrophobic binder together with the organometallic compound alone or with the organometallic compound; Heating a layer of the composition having a metal layer of the organometallic compound or a thinner layer of metal more precious than the metal of the organometallic compound on its surface at the temperature of 50 ° C. to 200 ° C. for 1 second to 10 minutes. The method of recording an optical recording material according to claim 1. 45. The method of claim 44, comprising providing a thin layer of metal of the organometallic compound or of a metal that is more precious than the metal of the organometallic compound on the surface of the composition layer for the optical recording material prior to the heating step. 45. The method of claim 43 or 44, wherein the heating step is performed at a temperature of 70 ° C to 150 ° C for 1 second to 100 seconds. 45. The method of claim 43 or 44, wherein the layer of the composition for optical recording materials has a thickness of 1 to 20 mu m. 45. The method of claim 43 or 44, wherein the thickness of the thin metal layer of the metal of the organopolymer compound or of the metal that is more precious than the metal of the organic polymer compound is from 2 to 1000 mm 3. 49. The method of claim 48, wherein the thickness of the metal layer of the organopolymer compound or of a metal that is more precious than the metal of the organopolymer compound is 10 kPa to 200 kPa. 45. The method of claim 43 or 44, comprising forming a thin layer of light absorber in the range of wavelengths of the semiconductor laser of 650 nm to 900 nm. 51. The method of claim 50, wherein the thickness of the thin layer of light absorber is 1-20 GPa. 45. The light according to claim 43 or 44, wherein the photomask having the information to be prerecorded has a light energy having an exposure energy of 10 ^-7 J / cm 2 to 10 ^-2 J / cm ² before the heating step of a portion or the entire optical recording material. Exposing for 5 to 20 seconds. 45. The optical recording material according to claim 43 or 44, wherein a part of the optical recording material or the entire optical recording material is transferred to light having an exposure energy of 10 ^-1 J / cm 2 to 10 ⁵ J / cm 2 after the heating step through a photomask having information to be recorded in advance. Exposing for 100 μs to 10 seconds. 45. The method of claim 43 or 44, comprising laminating a film or sheet of transparent organic polymer compound onto the optical recording material after the heating step. 55. The method of claim 54, wherein the clear organopolymer compound is polycarbonate. 45. The method of claim 43 or 44, comprising laminating a film or sheet of metal, ceramic, organopolymer compound, glass fiber insensitive material or carbon fiber onto the substrate after the heating step. 45. The method of claim 43 or 44, comprising removing the substrate after the heating step or after the exposure step after the heating step. The method of claim 43 or 44, wherein the hydrophobic binder is an organic polymer compound that is insoluble in water or hot water at 60 ° C. 45. 45. The method of claim 43 or 44, wherein the organopolymer compound has a glass transition temperature of 10 ° C to 120 ° C. 60. The method of claim 59, wherein the organopolymer compound has a glass transition temperature of 40 ° C to 110 ° C. 61. The method of claim 60, wherein the organopolymer compound is polyvinylbutyral. 61. The method of claim 60, wherein the organopolymer compound is polymethylmethacrylate. 61. The method of claim 60, wherein the organopolymer compound is polycarbonate. 61. The method of claim 60, wherein the organic polymer compound is a vinyl chloride-vinylacetate copolymer. 61. The method of claim 60, wherein the organopolymer compound is polyisobutylene. 59. The method of claim 58, wherein the amount of hydrophobic binder is 10 to 1000 parts by weight based on 100 parts by weight of the organometallic compound. 45. The method according to claim 43 or 44, wherein the organometallic compound is capable of forming metallic particles by autolysis under heating at a temperature of from 50 ° C to 200 ° C in the presence of a metal of the organometallic compound or a metal that is more precious than the metal of the organometallic compound. How. 68. The method of claim 67, wherein the organometallic compound is a metal salt of oxalic acid, and the metal of the metal salt is silver, gold, copper, tellurium, bismuth, palladium, cobalt, nickel, lead, chromium, or titanium. 43. The method of claim 44, wherein the organometallic compound is capable of forming metallic particles by reduction and the composition contains an organometallic compound capable of reducing the organometallic compound. 45. The method of claim 43 or 44, wherein the organometallic compound is a low molecular weight organo silver compound. 71. The method of claim 70, wherein the silver salt of the carboxylic acid of the low molecular weight organic silver compound, the silver salt of the long chain carboxylic acid, the silver salt of the perfluorocarboxylic acid, the perfluorocarboxylic acid of which the fluorine atom is partially substituted with the chlorine atom, A silver salt, a silver salt of sulfonic acid, a silver chelate compound formed by a fluorine-containing chelate agent, a silver thiocarbaate, a silver chelate compound, a silver salt of a nitrogen-containing compound or a silver salt complexed with a lead compound. The method of claim 71, wherein the organic silver compound is a silver salt of long chain carboxylic acid. 73. The method of claim 72, wherein the silver salt of the long chain carboxylic acid is silver behanate. The method of claim 70, wherein the organic silver compound is soluble in a solvent or hydrophobic binder. 75. The method of claim 74, wherein the organic silver compound is a silver salt of perfluorocarboxylic acid. 76. The method of claim 75, wherein the on-salt of perfluorocarboxylic acid is ontrifluoroacetate. 76. The method of claim 75, wherein the silver salt of perfluorocarboxylic acid is onheptafluorobutyrate. 72. The method of claim 71, wherein the silver chelate compound formed by the fluorine-containing chelating agent is ontrifluurouroacetylacetonate. 45. The method of claim 43 or 44, wherein the organometallic compound is a high molecular weight organic silver compound. 80. The method of claim 79, wherein the high molecular weight compound is a silver salt of high molecular weight polycarboxylic acid, a silver salt of polycarboxylic acid or a high molecular weight silver chelate compound. 81. The process of claim 80, wherein the silver salt of the high molecular weight polycarboxylic acid is derived from a polymer of an alkali or alkaline earth metal salt of acrylic acid, betacholic acid or acrylic acid or methacrylic acid, with or without a silver ion compound and a copolymerizable monomer compound. How to be. 84. The method of claim 81, wherein the high molecular weight polycarboxylic acid is a silver salt onpolyacrylate. 81. The method of claim 80, wherein the silver salt of polycarboxylic acid is silver alginate or silver pectate. 45. The compound according to claim 43 or 44, wherein the compound capable of reducing the organometallic compound is monohydroxybenzene, polyhydroxybenzene, naphthol, hydroxybinafphyl, hydroxylamine, pyrazolidine, panelenediamine, aminophenol , Sulfonaminophenol, methylenebisphenyl, and one or two sterically bulky minor phenols bonded to a carbon atom adjacent to a carbon atom or a hydroxy group bonded carbon atom. 85. The method of claim 84, wherein the compound capable of reducing the organometallic compound is a minor oil phenol. 86. The method of claim 85, wherein the subsidiary phenol is a compound represented by the following general formula (I).

(Wherein R ³ , R ⁴ , R ⁵ and R ⁶ are each a C _1-8 alkyl group or a halogen atom; each of R ⁷ and R ⁸ is a hydrogen atom, a phenyl group or a C _1-8 alkyl group). _Wherein R ⁹ is a cyclohexyl group substituted with a C _4-10 secondary or tertiary alkyl group, a cyclohexyl group, or a C _1-0 alkyl group; R ¹⁰ is a C _1-0 alkyl group and R ¹¹ is C _{1- 10} alkyl group, C _1-10 alkoxy group, C _1-12 aryl group, or group connected to C _7-12 aralkyl group; R ¹² is C _1-0 alkyl group or C _1-5 alkoxy group; R ¹³ is C _{Is a 1-0} alkyl group, R ¹⁴ is a hydrogen atom or a C _1-0 alkoxy group). 45. The method of claim 43 or 44, wherein the composition contains a silver halide or a silver halide forming compound. 89. The method of claim 88, wherein the amount of silver halide or silver halide compound is from 0.01 to 0.5 water per mole of organometallic compound. 43. The method of claim 44, wherein the composition comprises a light absorber in the wavelength range of the semiconductor laser of 650 nm to 900 nm. 91. The method of claim 90, wherein the light absorber is a phthalocyanine dye. 91. The method of claim 90, wherein the light absorber is an azulenium dye. 91. The method of claim 90, wherein the light absorber is a nickel-diol complex. 91. The method of claim 90, wherein the amount of light absorbing agent is from 0.01 to 0.5 moles per mole of organometallic compound. 45. The method of claim 43 or 44, wherein the composition contains a color regulator. 97. The method of claim 95, wherein the color control agent is phthalazone. 97. The method of claim 95, wherein the color regulator is from 0.01 to 5.0 moles per mole of organometallic compound. 45. The method of claim 43 or 44, wherein the composition contains an antifog agent. 99. The method of claim 98, wherein the antifog agent is 1, 1, 1 ', 1-tetrabroo-0-xylene. 99. The method of claim 98, wherein the amount of antifogging agent is from 0.01 to 5.0 moles per mole of organometallic compound.

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