JPH0452236B2 - - Google Patents

Description

[Detailed description of the invention]

(Technical Field) The present invention relates to an optical recording material suitable for heat mode recording with high sensitivity and good productivity. (Prior Art) Conventionally, so-called heat mode recording is known in which a high-density energy beam such as a laser beam is focused on a spot and irradiated onto a recording medium to change the state of a part of the medium for recording. Known heat mode recording media used for this purpose include metal thin films such as tellurium and bismuth, organic thin films such as polystyrene and nitrocellulose, and those that utilize the phase transition of low tellurium oxides. The so-called
It is a DRAW (direct read after write) medium,
Since high-density recording and additional writing are possible, it is expected to be used more widely for disks and cards, and even more stable and sensitive optical recording materials will be required. Among these heat mode recording media, typical metal thin films such as tellurium and bismuth are materials with relatively excellent recording sensitivity, but manufacturing them requires expensive vacuum evaporation equipment, sputtering equipment, etc.
Because it is toxic, it requires careful handling, the manufacturing work environment is poor, it is easily oxidized, and has poor storage stability without special treatment such as when used as a disk, and simple pattern exposure requires no prior information. There are drawbacks such as the inability to insert guide marks etc. In addition, reflective properties can be obtained by special development of high-resolution grade silver salt photographic gelatin sensitive materials, or by dispersing silver particles in gelatin matrix.
A recording medium is known in which actual recording is performed by thermal deformation of a gelatin matrix. These recording media can be manufactured continuously by coating, and by using silver they achieve uniform reflectance over a wide wavelength range, making them highly compatible with recording and reproducing devices that use laser beams of various wavelengths. It has the advantage of However, because these media use expensive silver, it is difficult to produce and supply them stably and inexpensively due to price fluctuations, and because they use high-resolution photographic materials, patterning and development must be done in a darkroom. There are disadvantages such as having to do it indoors. (Objective of the Invention) Therefore, the present invention improves the various drawbacks of these conventional optical recording materials, can be manufactured by continuous coating, is non-toxic, and can be handled in a bright room, making it easier to work in the working environment. The purpose of the present invention is to provide an optical recording material with good performance, improved productivity, and low cost. (Structure of the Invention) The present invention has an optical image recording layer on at least a part of the base material, and the optical image recording layer has a metallic glossy surface and a light-absorbing metal fine particle dispersion layer on the lower part. The object of the invention is an optical recording material characterized by being made of a transparent synthetic resin layer. Hereinafter, the present invention will be explained in detail using the drawings. FIG. 3 is a sectional view showing an example of the optical recording material 1 of the present invention, in which a transparent synthetic resin layer 3 is laminated on the surface of the base material 2, and a part of the surface 3B of the transparent synthetic resin layer is The surface is a metallic luster surface, and the lower part 3C of the surface 3B is a dispersed layer of metal fine particles. In the above, any solid material such as glass, ceramic, paper, plastic film, woven fabric, or nonwoven fabric can be used as the base material 2, but glass and plastic film are preferably used from the viewpoint of productivity and smoothness. As the plastic, cellulose derivatives, polyester resins, polycarbonate resins, vinyl resins, polyimide resins, acrylic resins, polyether resins, polysulfone resins, polyamide resins, etc. can be used, and from the viewpoint of dimensional stability and smoothness. Cellulose triacetate, polyethylene terephthalate, polyimide, etc. are preferred. These base materials 2 may be subjected to pretreatment to improve adhesion, such as corona discharge treatment, plasma treatment, and primer treatment, if necessary. In addition, in the above, the metallic glossy surface 3B is made of nickel,
Group VIb metals such as copalt, iron and chromium, copper etc.
It is selected from group Ib metals, tin, and tin-copper alloys. The metal fine particle dispersion layer below the metallic luster surface 3B basically contains 0.1 to 100 parts, particularly 1 to 10 parts, of metal fine particles per 100 parts of the transparent synthetic resin in a transparent synthetic resin. Layers 3B and 3C are shown as two clearly separated layers, but as will be described later, when manufactured by physical development, at least the surface has a metallic luster and the lower part has a metallic fine particle dispersion. As long as the two layers are layers, the boundary between the two layers may be unclear. Next, a method for manufacturing the above-mentioned optical recording material will be explained. The following processing method is applied to the photosensitive material as shown below. First, as a sensitive material, a photodegradable development inhibitor having a diazo group or an azide group, a metal complex compound or a metal compound that becomes a metal development nucleus when reduced, etc.
A material in which a sensitive layer 3 containing two components in a transparent synthetic resin is provided on a base material 2 is used. The processing method applied to the above-mentioned sensitive material is (a) exposing to light to decompose the development inhibitor and forming a latent image, (b) acting with a reducing agent to form metal development nuclei, and
(c) The step of depositing metal on the latent image area of the sensitive layer by electroless plating (physical development) to form a metal film is performed sequentially. The above-mentioned photosensitive material and processing method will be explained in detail below. Sensitive material The sensitive material used to produce the optical recording material of the present invention has a sensitive material layer as described above on a base material. Each component constituting the sensitive layer contains 0.1 to 100 parts of a metal complex compound or metal compound that will be reduced and become metal development nuclei per 100 parts of the transparent synthetic resin (binder).
part, preferably 1 to 10 parts, a photodegradable development inhibitor having a diazo group or an azide group in an amount of 1 to 100 parts, preferably 20 to 50 parts, and other components dispersed in the transparent synthetic resin. , preferably dissolved. Here, the following components are used. Transparent synthetic resin The transparent synthetic resin can be selected from lipophilic and hydrophilic resins. Examples of lipophilic resins include polyvinyl acetate resin, vinyl acetate/acrylic acid ester copolymer resin, and acrylic acid/acrylic acid ester copolymer resin. Resins with ester groups such as vinyl acetate copolymer resins, ethylene/vinyl acetate copolymer resins, resins with hydroxyl groups such as cellulose acetate, and oil-soluble polyvinyl acetate resins such as modified vinyl acetate resins containing carboxylic acid groups and sulfonic acid groups. Based resins are preferably used for pattern development. Furthermore, in terms of optical recording properties, it is also effective to add cellulose derivatives such as nitrocellulose, which have the property of deforming in heat mode, for increasing sensitivity. Hydrophilic binders include natural polymers such as gelatin, casein, glue, gum arabic, and shellac, carboxymethylcellulose, egg albumin, polyvinyl alcohol (partially saponified polyvinyl acetate), polyacrylic acid, polyacrylamide, polyvinylpyrrolidone, Polyethylene oxide, maleic anhydride copolymer, etc. are used, but other resins than the above can also be used as long as they are water-soluble or hydrophilic resins. The degree of hydrophilicity required for the binder is such that when the sensitive layer 3 is formed and brought into contact with a physical developer, the physical developer permeates into the sensitive layer 3 to enable physical development. In addition, it is also effective to add a low molecular weight substance such as nitrocellulose, which has a property of being easily deformed in a heat mode, dissolved in ethanol in terms of optical recording properties. Development inhibitor A compound having a diazo group or an azide group is used as the development inhibitor, and the compound having a diazo group is a zinc chloride double salt or a borofluoride salt having a diazo group, or a condensation product obtained from these compounds and paraformaldehyde. A compound such as diazo resin is preferably used. More specifically, p-
N,N-diethylaminobenzenediazonium zinc chloride double salt, p-N-ethyl-N-β hydroxyethylaminobenzenediazonium zinc chloride double salt, 4-morpholino-2,5-diethoxybenzenediazonium zinc chloride double salt, 4- Morpholino-2,5-dibutoxybenzenediazonium zinc chloride double salt, 4-benzoylamino-2,5-diethoxybenzenediazonium zinc chloride double salt, 4
-(4'-methoxybenzoylamino)-2,5-diethoxybenzenediazonium zinc chloride double salt, 4
-(p-tolylmercapto)-2,5-dimethoxybenzenediazonium zinc chloride double salt, 4-diazo-4'-methoxydiphenylamine zinc chloride double salt, 4-diazo-3-methoxy-diphenylamine zinc chloride double salt, etc. Alternatively, borofluoride salts, sulfates, phosphates, etc. can also be used instead of the above-mentioned zinc chloride double salts. Examples of compounds having an azide group include p-azidoacetophenone, 4,4'-diazidechalcone, 2,
6-bis-(4′-azidobenzal)-acetone,
2,6-bis-(4'-azidobenzal)-cyclohexanone, 2,6-bis-(4'-azidobenzal)
-4-methylcyclohexanone, 2,6-bis(4'-azidostyryl)-acetone, azidopyrene, etc. can be used. Alternatively, compounds other than those mentioned above may be used as long as they have a diazo group or an azide group, and two or more of the above-mentioned compounds having a diazo group or an azide group may be used in combination. When using a compound having a diazo group, it is recommended to use a stabilizer to stabilize the compound.
Specific examples include organic carboxylic acids and organic sulfonic acids, and more practically, p-toluenesulfonic acid and the like may be used. Metal Complex Compound and Metal Compound Next, the metal complex compound or metal compound which is reduced and becomes a metal development nucleus will be explained. First, complex compounds of noble metals such as palladium, gold, silver, platinum, and copper are used as metal complex compounds that are reduced and become metal development nuclei, and ligands that serve as electron donors to ions of these metals are used. Commonly known compounds can be used as complex compounds, such as the following: bis(ethylenediamine) palladium ()
Salt, dichloroethylenediamine palladium ()
Salt, dichloro(ethylenediamine) platinum ()
salt, tetrachlorodiamine platinum() salt, dichlorobis(ethylenediamine)platinum() salt, tetraethylammonium copper() salt, bis(ethylenediamine copper() salt).Furthermore, there are two ligands that form metal complex compounds. It is preferable to use a so-called chelating agent which coordinates with the above to form a cyclic structure because the stability of the metal complex compound formed is high.As the chelating agent, primary, secondary or tertiary chelating agents are used. Examples include amines, oximes, imines, and ketones, and more specifically, the following: dimethylglyoxime, dithizone, oxine,
Acetylacetone, glycine, ethylenediaminetetraacetic acid, nitrilotriacetic acid, uramyldiacetic acid. Those using the above chelating agent include bis(2,2'-bipyridine) palladium () salt, bis(acetylacetonato) palladium (),
Bis(N,N-diethylethylenediamine)copper() salt, bis(2,2'-bipyridine)copper()
salt, bis(1,10-phenanthroline)copper()
salt, bis(dimethylglyoximate)copper(),
Bis(acetylacetonato)copper(), bis(acetylacetonato)platinum(), etc. are preferred. Metal compounds that are reduced to give metal development nuclei include water-soluble salts such as chlorides and nitrates of noble metals such as palladium, gold, silver, platinum, and copper, such as those contained in the activator solution for electroless plating. Salts such as palladium chloride, silver nitrate, and gold tetrachloride may also be used, and palladium salts are particularly preferably used. When using a metal compound, the above-mentioned metal compound (a commercially available activator liquid for electroless plating can be used as is) is added to a transparent synthetic resin together with a compound having a diazo group or an azide group as a development inhibitor. It is also mixed with a binder solution dissolved in an appropriate solvent selected to obtain a liquid with a viscosity of about 10 to 1000 centipoise suitable for coating, and this is coated on the substrate 1 and dried to give a viscosity of usually 0.1 to 30 μm. Any suitable solvent can be used to dissolve the binder that forms the sensitive layer as a coating film, but when a hydrophilic transparent synthetic resin is used, water is used, or water and lower alcohol, It is best to use a mixed solvent with a water-miscible solvent such as a ketone or ether, or when using a lipophilic solvent, use a lower alcohol such as methyl alcohol, ethyl alcohol, or isopropyl alcohol, acetone, a ketone such as methyl ethyl ketone, or ethyl acetate. , esters such as n-butyl acetate, and highly polar solvents such as methyl cellosolve are preferably used. In addition, when using hydrophilic transparent synthetic resin,
After forming the sensitive layer 3, a hardening process is desirably performed in order to suppress elution of the binder into the developer during physical development. In the hardening process, for example, the following compound is added as a binder to the coating solution for forming the image forming layer 2.
It is carried out by mixing at a ratio of 0.1 to 50 parts per 100 parts, or by coating the aqueous solution on the image forming layer: Al compounds such as potash alum, ammonium alum, etc.: chromium alum, sulfuric acid Cr compounds such as chromium:
Aldehydes such as formaldehyde, glyoxal, glutaraldehyde, 2-methylglutaraldehyde, succinaldehyde; o-benzoquinone, p-benzoquinone, cyclohexane-1,2
-dione, diketones such as cyclopentane-1,2-dione, diacetyl, 2,3-pentanedione, 2,5-hexanedione, 2,5-hexenedione; epoxides such as triglycidyl isocyanurate; tetraphthaloyl Chloride, 4,4'-
Diphenylmethane disulfonyl chloride, 4,
Acid anhydrides such as 4'-diphenylmethanedisulfonyl chloride; tannic acid, gallic acid, 2,4-
Dichloro-6-hydroxy-S-triazine, as well as general formulas R ₂ NPOX ₂ , (R ₂ N) _o POX _3-o ,

【formula】

[Formula] and R-N=C=N-R' (where R is an alkyl group having 2 to 6 carbon atoms, R' is a (CH ₃ ) ₃ N ⁺ (CH ₃ ) ₃ X ^- group, and X is a F
or a phosphorus compound or carbodiimide represented by Cl, n is 1 or 2); styrene/maleic acid copolymer, vinylpyrrolidone/maleic acid copolymer,
Resins such as vinyl methyl ether/maleic acid copolymer, ethyleneimine/maleic acid copolymer, methacrylic acid/methacrylonitrile copolymer, polymethacrylamide, and methacrylic acid ester copolymer. Glutaric acid, succinic acid as dicarboxylic acids, malic acid, lactic acid, citric acid, aspartic acid, glycolic acid, as hydroxycarboxylic acids.
Organic carboxylic acids such as tartaric acid can also be used. Processing Method The photosensitive material 1 having the above-mentioned photosensitive layer 3 is first exposed to light, then subjected to a reduction treatment, and then subjected to a processing method consisting of each step of applying a physical developer. Exposure First, an information recording area is defined on the sensitive layer, and the entire information recording area is uniformly exposed. Alternatively, when recording information in advance or forming guidelines or timing bits for reading information, it is also possible to perform pattern exposure through a transparent original 4 as shown in Fig. 2. . As a result, the compound having a diazo group or an azide group is selectively decomposed in the exposed portion 3A to a degree corresponding to the amount of exposure. As the light source used for exposure, any light source can be used as long as it can decompose the above-described compound having a diazo group or an azide group, and an ultra-high pressure mercury lamp is usually preferably used. Further, the original can be exposed by contact or projection, and can also be exposed by drawing with a converged light beam or laser. Reduction treatment Next, by exposure, a reducing agent aqueous solution is brought into contact with the sensitive layer 3 having a latent image in which a compound having a diazo group or an azide group is decomposed by immersion, so that metal development nuclei are almost uniformly formed in the sensitive layer 3. generate. Examples of reducing agents include stannous chloride, stannous sulfate, sodium borohydride, dimethylamine borazane, diethylamine borazane, trimethylamine borazane, other borazane derivatives, borane,
Borane derivatives such as diborane and methyldiborane, hydrazine, and the like can be used. Particularly preferably, an acidic stannous chloride solution, a stannous sulfate solution (Weiss solution), or a commercially available sensitizer solution for electroless plating is used, but in general, any strong reducing agent can be used. Furthermore, a physical developer is brought into contact with the sensitive layer 3, which has a latent image formed by the decomposition of the metal development nuclei obtained in this way and a compound having a diazo group or an azide group, by immersion, and exposed as shown in FIG. A reflective information recording area 3B is formed in which the metal in the developer is precipitated by reduction, centering on metal development nuclei. The reflectance of the optical recording material obtained by physical development needs to be at least 15% in order to be able to reproduce with a sufficient S/N ratio for the pick-up of the reproduction device, but if it is too high, the recording power will be reduced. It is preferable that it is 80% or less, since this results in a loss and lowers the sensitivity. Therefore, in the laser wavelength range of 400 to 900 nm,
A range of 15% to 80%, more preferably 30 to 55%, is preferably used. Physical Development As the physical developer, an aqueous solution containing a water-soluble reducible metal salt and a reducing agent is used, if necessary, in a heated state. Examples of reducible metal salts include VIP group metals such as nickel, cobalt, iron and chromium, and Ib metals such as copper.
Water-soluble salts of group metals are used alone or in mixtures. In addition, after physical development with a copper salt solution, substitution plating is performed with stannous chloride or tin sulfate to produce tin or tin.
It is also possible to obtain copper-based metal layers. Among these, considering safety and preservation, Nickel,
Copper and tin are preferably used. However, unlike vapor deposition, small amounts of different metals and elements such as phosphorus and sulfur may be mixed in due to the purity of the raw materials, plating stabilizers, etc., but this does not particularly affect the optical recording characteristics. As suitable water-soluble reducible metal salts, for example, the following can be used. Heavy metal halides such as cobaltous chloride, cobaltous iodide, ferrous bromide, ferrous chloride, chromic bromide, chromic iodide, cupric chloride; nickel sulfate, ferrous sulfate , heavy metal sulfates such as cobaltous sulfate, chromic sulfate, cupric sulfate; heavy metal nitrates such as nickel nitrate, ferrous nitrate, cobaltous nitrate, chromic nitrate, cupric nitrate; ferras Organic acid salts of metals such as acetate, cobalt acetate, chromic acetate, and chromic fluorate. These reducible heavy metal salts are contained in the physical developer at a rate of, for example, 10 to 100 g/g. These reducible metal salts are contained in the physical developer at a rate of, for example, 10 to 100 g/g. Examples of reducing agents include hypophosphorous acid, sodium hypophosphite, sodium borohydride, hydrazine, formalin, diethylamine borane, dimethylamine borane, trimethylamine borane, borane, diborane, methyldiborane, diborazane,
Borazene, borazine, t-butylamine borazane, pyridine borane, 2,6-lutidine borane,
Ethylenediamineborane, hydrazinediborane,
Dimethylphosphine borane, phenylphosphine borane, dimethylaldine borane, phenylaldine borane, dimethylstibine borane, diethylstivine borane, etc. can be used. These reducing agents can be added to the physical developer, e.g.
It is used at a rate of 0.1 to 50g/. In order to prevent the heavy metal ions generated by dissolving the above-mentioned reducible heavy metal salts from precipitating as hydroxides, the physical developer contains, for example, monocarboxylic acids; dicarboxylic acids; hydroxyl acids such as malic acid and lactic acid. Carboxylic acid: Contain one or more complexing agents consisting of organic carboxylic acids such as succinic acid, citric acid, aspartic acid, glycolic acid, tartaric acid, ethylenediaminetetraacetic acid, gluconic acid, sugar acid, and quinic acid. I can do it. For example, 1 to 100 g of these complex chloride agents may be added to the physical developer.
used at a rate of Furthermore, the physical developer contains PH regulators such as acids and bases, buffers, preservatives, etc. to improve the storage stability and operability of the developer and the quality of the resulting images.
Brighteners, surfactants, and the like are added as needed in a conventional manner. Among these additives, ammonium salts or ammonia-based additives are used as pH regulators to increase the pH, making it easier to obtain gloss on the surface of the photosensitive material. Particular preference is given to using PH regulators. In addition, metal images with metallic luster can be created on the binder surface by performing physical development in a high-temperature nickel plating bath at 65 to 90°C using sodium hypophosphite as a reducing agent or in high-speed plating with copper plating. Can be formed. Moreover, it is preferable in the present invention because the binder in the non-image area can be selectively removed by treating the obtained image with, for example, a 5% hydrochloric acid or 5% nitric acid aqueous solution for 5 minutes. When using the optical recording material of the present invention, an optical image recording layer is formed directly on the base material 2, or it is formed on a film and then attached to another base material by adhesive or heat fusion. There is a method of adhesion according to the method. The surface of the recording material may be provided with a space, such as in optical disk applications, or may be laminated with a protective material, as in card applications. Examples of protective materials that can be used include glass, polymethyl methacrylate, polycarbonate, and polyvinyl chloride. can be used with an adhesive or heat-sealed, but the structure is such that there are few factors that interfere with the transmission of the recording beam, such as birefringence or interference, or there is no scattering or absorption that would impede the transmission of the recording beam. Alternatively, the protective layer may be formed of any treated material. The optical recording material of the present invention can be used for various purposes by taking an appropriate size and shape, and is also suitable for use in the form of a card due to its high recording density and anti-counterfeiting properties. FIG. 4 is a plan view of a card made from the optical recording material of the present invention, and the card 5 has an optical image recording layer 7 on a part of the card base material 6. FIG. 5 shows an example of a cross-sectional structure of a card, in which an optical image recording layer 7 is laminated on a part of the card base material 6, and the entire surface of the card base material 6 including the optical image recording layer 7 is transparent. A protective layer 8 is laminated thereon. Fourth
In FIG. 5, the optical image recording layer 7 is provided on a part of the card base material 6, but it may be provided on the entire surface, or the optical image recording layer 7 in FIG. It may be provided to the full length. In addition, the card may have a magnetic recording layer 9 and a known photographic or engraved image 10 as shown in FIG. IC even if characters etc. are provided
There is no problem even if it has built-in memory. FIG. 5 shows the card shown in FIG. 4 with pits 11 after recording. The structure and manufacturing method of the card with the structure described above will be explained below. The card base material may be any material that is rigid and suitable for processing such as heat fusion and various types of printing. Good, but usually
Vinyl chloride resin, vinyl chloride-vinyl acetate copolymer resin, vinylidene chloride resin, acrylic resin, styrene resin, vinyl butyral resin, acetyl cellulose resin, styrene-butadiene copolymer resin,
Synthetic resins such as polyethylene resin and fluororesin can be used, and among them, vinyl chloride resin is used because of its ease of processing. In addition, paper, metal foil, etc., and composites of the above materials may also be used. The thickness of the protective layer 8 is 10 to 2000 .mu.m, preferably 200 to 1500 .mu.m. If it is less than 10 .mu.m, the strength as a protective layer is insufficient, and if it exceeds 2000 .mu.m, it becomes difficult for the laser beam to reach the recording layer, which is not preferable. Particularly, a thickness of 1000 to 1500 μm has the effect of avoiding interference with the laser beam due to fingerprints, dust, etc. attached to the surface of the protective layer. Since the main purpose of the protective layer in the present invention is to protect the optical image recording layer, it is sufficient to cover only the surface of the optical image recording layer, but since it is provided on the entire surface of a normal card, it may be provided on the entire surface in the present invention as well. The protective layer can be provided by applying, printing and drying using a known transparent synthetic resin paint, or by gluing or heat-sealing a transparent synthetic resin film or a transparent synthetic resin plate. As the board, the synthetic resin film or sheet described above as the card base material can be used, and the heat fusion conditions are 100-300°C, 40-30°C.
It is 400Kg/ ^cm2 . Note that in order to partially provide an optical image recording layer and a protective layer on a base material, contrary to the above explanation, an optical image recording layer is previously provided on a transparent synthetic resin protective layer, and then a card is attached using an adhesive. Attach to base material, heat-seal,
Alternatively, a method may be used in which a transparent synthetic resin protective layer and an optical image recording layer are further provided on a releasable substrate, and if desired, an adhesive is further applied thereon and the layer is transferred onto a card substrate. (Effects of the Invention) The optical recording material of the present invention has a reflectance suitable for recording and reproducing devices using metal particles having a relatively high melting point such as nickel, cobalt, and iron. Since only the surface layer is made of reflective metal, and the inner layer is made of light-absorbing metal particles in the binder, heat is generated efficiently and the transparent synthetic resin is thermally deformed. In addition to being more sensitive than recording media that use the volatilization of thin metal films, permanent information can be easily recorded on the recording media using conventional photographic methods or beam exposure. It has great advantages. In addition, continuous coating technology similar to the conventional manufacturing method of photographic materials can be applied to the production of this optical recording material. Since the photosensitive wavelength of the inhibitor ranges from the visible region of 5000 Å or less to the ultraviolet region, production can be carried out using illumination through an ultraviolet cut filter or in a bright room using yellow light. , it can be produced in a good working environment without requiring special technology, and the use of metals such as nickel for lipophilic resins is much more effective than using silver salts for hydrophilic resins. The optical recording material of the present invention is industrially superior, as it allows stable production and supply of low-cost, moisture-resistant, and highly stable recording media. (Example) Hereinafter, the present invention will be explained in more detail with reference to Examples. In Examples 1 and 2 below, the palladium chloride solution refers to one having the following composition. Palladium chloride solution Palladium chloride concentrated hydrochloric acid ethanol 1.0g 50g 1 Example 1 Sensitizer liquid polyvinyl acetate resin (Nippon Gosei Kagaku Kogyo Co., Ltd., Cosenyl A50-z5)... 20 parts by weight diazo monomer (Daito Chemical Co., Ltd., DH-300BF ₄ ,
10% MEK solution)... 5.0 parts by weight Palladium chloride solution... 10 parts by weight Polyethylene glycol (MW, = 1500) 5%
MEK solution... 1 part by weight p-toluenesulfonic acid (stabilizer) 5% ethanol solution... 1 part by weight The sensitizer solution with the above composition was applied to a 100 μm thick polyester film (Toray Luminar, #100) with wire bar No. .36 and dried in an oven at 80°C to form a sensitive layer with a coating thickness of 4 μm. An ultra-high pressure mercury lamp (wavelength) was applied to the entire surface of the prepared sensitive layer.
4050 Å, 75 W) for 30 seconds, and then immersed in a physical developer (Okuno Pharmaceutical Co., Ltd., TMP Chemical Nickel) for 200 seconds to obtain an optical information recording medium with a glossy surface. The wavelength of this recording medium is 6330
The total reflectance at Å was 43%. Next He−
Ne laser (wavelength 6330Å) is applied to the recording surface at 3 mW.
The power is focused to a beam diameter of 2 μm and the pulse width is
When irradiated at 0.5 μsec, circular pits with a diameter of 4 μm were recorded. Example 2 Sensitizer liquid Acrylic acid/vinyl acetate copolymer resin (manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd., Coponyl PC-50M(H) 20% ethanol solution...20 parts by weight of diazo monomer (manufactured by Respé Chemical Co., Ltd., No.
11'BF ₄ ) 10% MEK solution... 3.0 parts by weight Palladium chloride solution... 10 parts by weight Polyethylene oxide (manufactured by Steel Chemical Co., Ltd., PEO-
3) 1% methanol solution... 2.0 parts by weight p-toluenesulfonic acid 5% ethanol solution...
... 1.0 parts by weight A photosensitive liquid having the above composition was applied and dried in the same manner as in Example 1 to form a photosensitive layer, followed by contact exposure for 30 seconds through a negative film using an ultra-high pressure mercury lamp. Next, a physical developer at 35°C (manufactured by Okuno Pharmaceutical Co., Ltd., TMP
Developed by immersing it in chemical nickel) for 120 seconds,
An optical information recording medium was obtained which had an information recording area of 80 mm x 15 mm defined by a 2 μ wide line and had a management display that further divided the inside into 20 sections in the longitudinal direction. The total reflectance of the information recording section at a wavelength of 7800 Å was 51%. Next, a beam from a laser diode (wavelength 7900 Å) was applied to the recording surface with a power of 5 mW and a beam diameter of 2 μ.
When the light was focused at m and irradiated with a pulse width of 1 μsec,
A circular pit with a diameter of 7 μm was recorded. Example 3 Nitrocellulose 2 was added to the sensitizer solution of Example 1.
When the same procedure as in Example 1 was carried out except that part by weight was added, and irradiation was performed using the same laser for the same time, the diameter
A circular bit of 10 μm was recorded, confirming high sensitivity. Example 4 Sensitizer liquid Cellulose triacetate... 20 parts by weight diazo monomer (Daito Chemical DH-300BF ₄ , 10%
MEK solution)... 5.0 parts by weight Palladium chloride solution... 10 parts by weight MEK... 10 parts by weight was applied to a 50 μm thick polyester film Example 1
It was coated and dried in the same manner as above to obtain a 2.5 μm thick sensitive layer. A 1WAr laser was used on the prepared sensitive layer.
After drawing a 10μ stripe in a guideline shape with 488nm wavelength light, dimethylaminoborazane 4%
After immersing it in a reducing solution prepared by dissolving it in a 50% water/ethanol solution for 5 seconds, add a copper plating solution (OPC Cutupa No. 1 60ml/manufactured by Okuno Pharmaceutical Co., Ltd., OPC Cutuppur No. 2 25
ml/, OPC Katsupa No. 3 250ml/) at 50℃
It was soaked in water for 15 minutes to obtain a shiny copper plating in 10μ stripes. This total reflectance is approximately 35% (wavelength 6330Å),
When a He-Ne laser was focused on a 2μ spot and irradiated with a pulse of 2μsec at a power of 6mW on the recording surface,
A circular pit with a diameter of 5μ was molded. Example 5 The copper-plated product produced in Example 4 was immersed in a tin substitution plating solution (Okuno Pharmaceutical Co., Ltd., Tape Rate 4MH Make Up A 250ml/, Distilled Water 750ml/, Tape Rate 4MH Component B 80g/) at 55°C for 20 seconds. I got a glaring layer. This total reflectance is
It was 55% at 7800 Å. A beam from a semiconductor laser (wavelength: 7900 Å) is focused on this recording material to a beam diameter of 2 μm with a power of 4 mW on the recording surface, and the pulse width is
When irradiated at 0.5 μsec, circular pits with a diameter of 4 μm were recorded. Example 6 2 g of PdCl ₂ was dissolved in 1000 ml of water together with 20 ml of HCl, and 20 g of the resulting _two PdCl solutions were used to prepare a sensitive material (coating solution for forming an image forming layer) having the following composition. _Two PdCl solutions with the above composition...20g Gelatin (Nitta Gelatin P-2151) 30% aqueous solution...10g Diazoresin (Shinko Giken D-011) 20% aqueous solution...2.5g Glutaric acid...0.12g The above sensitive material Adjust the temperature to 30°C to 40°C, apply it to a polyester film (Toray Lumirror S, 100#) that has been plasma-treated in advance, and dry it.
A coating film of 5μ was obtained. Sensitive film (image forming material) obtained above
The negative film was exposed for 2 minutes using a 2KW ultra-high pressure mercury lamp printer (distance 100cm from the light source). Next, it was immersed in the following reduction bath at 30° C. for 1 minute for reduction treatment. SnCl ₂ ... 1 g HCl ... 40 ml H ₂ O ... 100 c.c. Next, it was treated with a physical developer having the following composition at 90° C. to precipitate the metal and form a glossy image. Nickel chloride...30g Sodium hypophosphite...10g Ammonium oxyacetate...100g Water...900g The total reflectance of this recording medium at a wavelength of 6330 Å is
It was 40%. Next, He−Ne laser (wavelength 6330
Å) on the recording surface with a beam diameter of 2μ at a power of 3mW.
When the light was focused at m and irradiated with a pulse width of 0.5μsec,
A circular pit with a diameter of 4 μm was recorded. Example 7 The sensitive film of Example 6 was exposed to an ultra-high pressure mercury lamp.
Using a 2KW printer (distance 100 cm from the light source), the negative film was exposed for 2 minutes. Next, hydrazine hydrochloride (N ₂ H ₂ · HCl) was added at 1.0 mol/
It was immersed for 1 minute at 40°C in a reducing bath containing a proportion of . The sensitive film was washed with water, dried, and exposed using an ultra-high pressure mercury lamp.
Exposure was performed for 2 minutes using a 2KW printer (distance 100 cm from the light source). Then, it was treated with an electroless plating solution shown below for 8 minutes to obtain an image with metallic luster. Nickel chloride... 50g/ Sodium hypophosphite... 10g/ Sodium citrate... 10g/ The obtained image is a 2μ wide line to limit the information recording area of 80mm x 15mm, and the inside is further expanded in the longitudinal direction.
It had a management display divided into 20 parts, and the total reflectance of the information recording section at a wavelength of 7800 Å was 45%. Next, a beam from a laser diode (wavelength 7900 Å) was applied to the recording surface with a power of 5 mW and a beam diameter of 2 μ.
When the light was focused at m and irradiated with a pulse width of 1 μsec,
Circular pits with a diameter of 5 μm were recorded. Example 8 The sensitizer solution of Example 6 was treated in the same manner as in Example 6 except that 0.5 g of nitrocellulose (Asahi Kasei LS1/4) was added. When irradiated with the same laser for the same time, a circular shape with a diameter of 6 μm was formed. The pit was recorded, confirming the increased sensitivity. Example 9 The following composition: PdCl _{dihydrochloric} acid aqueous solution (Nippon Kanisen Retsudoshauma)... 20g PVA (Japan Synthetic Gozenol NH-14) 0% aqueous solution... 20g Diazoresin (Shinko Giken D-013) 20% aqueous solution... 2.5g Malic acid... ... 0.08 g of the sensitizer was coated on a 50 μm thick polyester film in the same manner as in Example 5, and dried to obtain a 2.5 μm thick sensitizer layer. A 1WAr laser is used for the prepared sensitive layer.
After drawing a 10μ stripe in a guideline shape with 405nm wavelength light, dimethylaminoborazane 4%
After immersing in an aqueous solution (reducing solution) for 5 seconds, copper plating solution (manufactured by Okuno Pharmaceutical Co., Ltd., OPC Katsupa No. 1 60ml/,
OPC Katsupa No.2 25ml/, OPC Katsupa No.
3 250ml/) at 50°C for 15 minutes to obtain a copper gloss in the form of 10μ stripes. This total reflectance is approximately 30% (wavelength: 6330 Å), and when a He-Ne laser is focused on a 2 μ spot and irradiated with a pulse of 2 μsec at a power of 4 mW on the recording surface, a diameter of 5 μ is obtained.
A circular pit was formed. Example 10 The copper-plated product produced in Example 4 was placed in a tin substitution plating solution (manufactured by Okuno Pharmaceutical, Tape Rate 4MH Make Up A 250ml/, distilled water 750ml/Tay Rate 4MH Component B 80g/) at 55°C.
A tin plating layer was obtained by dipping for 20 seconds. The total reflectance was 7800 Å, or 45%. A beam of a semiconductor laser (wavelength 7900Å) is applied to this recording material 4m above the recording surface.
The power of W is focused to a beam diameter of 2 μm and the pulse width is
When irradiated at 0.5 μsec, circular pits with a diameter of 4 μm were recorded.

[Brief explanation of drawings]

Figures 1 to 3 are cross-sectional views showing the manufacturing process of the optical recording material of the present invention, and Figures 4 to 6 show examples in which the optical recording material of the present invention is applied to cards. 4 is a plan view, FIG. 5 is a sectional view, and FIG. 6 is a plan view showing the state after recording. 1...Sensitive material, 2...Base material, 3...Transparent synthetic resin layer (sensitive layer), 3A...Exposed area, 3B...Metallic luster surface, 3C...Metal fine particle dispersion layer, 4...Transmission Original, 5... Card, 6... Card base material, 7... Optical image recording layer, 8... Protective layer, 9... Magnetic recording layer,
10...Image, 11...Pitsuto (light image section)

Claims (1)

[Claims] 1. At least a part of the base material has an optical image recording layer, the surface of the optical image recording layer is a metallic glossy surface, and the lower part is a light-absorbing metal fine particle dispersion layer. An optical recording material characterized by being made of a transparent synthetic resin layer. 2. The optical recording material according to claim 1, wherein the metal constituting the metallic glossy surface is selected from the group consisting of nickel, cobalt, iron, chromium, copper, and tin. 3 Claim 1 in which the base material is a card base material
The optical recording material according to item 1 or 2. 4. The optical recording material according to any one of claims 1 to 3, further comprising a transparent synthetic resin protective layer on the surface.