JPS6147297A - Optical information recording medium - Google Patents

Abstract

PURPOSE:To make it possible to perform highly sensitive recording and regeneration and to enable continuous mass production, by using a flexible support and forming a reflective recording layer by containing reflective fine particles mainly comprising copper in hydrophilic colloid. CONSTITUTION:An optical information recording medium is constituted by providing a reflective recording layer, wherein reflective fine particles mainly comprising copper are contained in hydrophilic colloid, on a flexible support. As a pref. example, the thickness of the recording layer is, for example, 0.01- 0.5mum, the average particle size of copper fine particles is, for example, 0.005- 0.2mum and the support is transparent and one used in a system recorded and regenerated through this support. The particle number density of the copper fine particles is pref. 1X10<15>-1X10<18>/cm<2>. By controlling the particle number density as mentioned above, the absorptivity of recording beam in the recording layer is enhanced and the enhancement of reflectivity and the reduction in reflective irregularity in the vicinity of the interface of the recording layer in the side of the support are attained while sensitivity and a SN ratio can be made high and the recording medium excellent in uniformity and stability is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field of the Invention] The present invention relates to an optical information recording medium for recording and reproducing information using a high-density energy beam such as a laser source. The present invention relates to an optical information recording medium in which fine particles mainly made of copper are contained in a hydrophilic colloid.

[Prior Art J] In a recording medium in which information is recorded and reproduced using a high-density energy beam such as a radar source, immediately after recording, the information Tx <-'t is directly processed. Can be played [DRAW (DirectRead
After Write) A recording medium with J characteristics, a recording medium that can erase all recorded information at will, etc. Recently, it has been attracting attention that it is used as a memory medium for video information such as all document files and image files. are collecting.

Recording layers in such optical information recording media have been available with various compositions, but -
Examples include semimetals such as tellurium, bismuth, and cenone, and their oxides (Yamashita et al., Proceedings of the 28th Applied WJ Science and Related Union Lectures, p. 141 (1981)), selenium-tellurium arsenic ( M., Terace et al.
, P. AppiPhys, 5 Q, p. 6881 (1979)), chalcogen compounds such as tellurium arsenic v
! There is a thin film recording layer made of J. However, with this kind of thin film recording layer, the rate of false digits increases when reproducing recorded information due to deterioration due to oxidation of the compounds contained in the recording layer, and furthermore, some of the compounds used are Many of them also have the drawback of low reliability in terms of safety.

What are their shortcomings? As for what has been resolved, JP-A-57-1
No. 2425, No. 57-24290 and No. 57-399
As disclosed in each publication of No. 89, an optical information recording medium having a metal layer consisting of a metal fine powder having an average particle size of 5 Q nm or less dispersed in a binder is disclosed. 12 However, is this recording medium black body fine powder Song Dynasty? A recording layer that is dispersed?
In the unlikely event that the laser source irradiation process increases the reflectivity of the recording layer, it cannot be used for the ``'C recording'' method, so it is used for the 7-recording method due to the decrease in the reflectivity of the recording layer. Compared to recording media, it has the disadvantage that it is difficult to obtain a tracking signal.

A specific example of a recording medium used in the method of performing two recordings by reducing the reflectivity of the recording layer is disclosed in Japanese Patent Laid-Open No. 56-1
What was disclosed in Publication No. 0491? I can list them. This recording medium consists of a recording layer consisting of fine particles of a metal or 7 oxide dispersed in a binder consisting of 1 trillion oxides.
Particle size of 50A However, this recording medium uses toxic stones and solvents, and uses metallurgical materials. Since the starting material is manufactured by forming fine particles at ℃, not only problems occur in the temperature range during manufacturing, but also the fine particles are unstable and are quickly oxidized, resulting in the recording layer becoming thinner in the thickness direction. There is a defect of non-uniformity, and metal 1 f
, - 9 particles of oxide \i medium "C+')
Since it is a lipophilic polymer, so-called water-based coating is not possible, and the working environment during production is unfavorable from a sanitary standpoint. Furthermore, since this record N has a low reflectance of 30% or less, it is not preferable as a reflective light reading type arithmetic information recording medium.

Another specific example of the recording medium σ used in a method in which recording is performed by reducing the reflectivity of the recording layer is disclosed in Japanese Patent Application Laid-Open No. 55-1999.
No. 108995, No. 56-33995, No. 56-49
296 and No. 56-49297 can be mentioned. This recording medium contains reflective silver particles and a photographic character boundary image and a physical dust image near the surface of a hagnized emulsion layer provided on a support. Analysis Ilf
It goes without saying that gelatin is superior to silver in terms of ablation properties, as compared to silver. It can be said that it is a highly sensitive optical information recording medium. However, on this recording medium? However, since the recording layer has a thickness of 3 to 6 μm, there is a limit to the sensitivity (the silver concentration has a gradient in the thickness direction, and only the area near the surface is highly reflective). Due to the nature of the work, record the work through the support.
4) It is difficult to apply μ to the method of performing reproduction 7.

10,000, the above-mentioned conventional technology? In each of the disclosed publications, there is only a description of a recording medium in which a different surface of the recording layer on the support is reflective. In order to obtain a protective film, it is necessary to provide a protective layer such as silicon oxide or polymethane with a UV-metal or the like, or to encapsulate the entire recording medium. A process such as a face-setting process or an encapsulation process is required.

C (7) Erratic complexity? To avoid this, a method of recording on a transparent support such as polymethyl methacrylate or glass is usually used, and in the case of C, it is known to overlap transparent supports on both sides of the recording medium to provide '''C. .

The present inventors have discovered a suitable recording medium for optical recording and reproduction through such a transparent support. ! -Special application 1987-
It was proposed by the specification of No. 43305. Is the stiffness of the recording medium increased due to the reflectivity near the interface between the transparent support and the recording layer, resulting in a practically usable reflectivity? A thin physical development nucleus layer is provided on a transparent support so as to be formed near the portrait-eye interface. This recording medium is a transparent support that transforms the reflected light into F information? ! - Performs all the reflexes necessary to obtain good signal contrast.

Did the present inventors study the recording medium related to the previously proposed technology mentioned above? As a result, an optical information recording medium with a recording layer of 7M consisting of fine particles mainly composed of copper contained in a colloid containing silver, gold, silver, cobalt, nickel, etc. It is extremely cheap compared to the one used, and lubrication, mercury, f
It has been found that it is preferable from the viewpoint of sufficiently less toxicity (dense σ in the working environment) compared to the one using JEK, and also has high sensitivity and excellent stability.

10,000 records media come in various shapes and sizes depending on the purpose, but in the past, S usually had a certain shape,
Use a support r molded to the size, and write on this support @
Layer 78 (Since the recording medium is used to obtain gold, continuous mass production of the recording medium is possible using the inner cone. Also, when performing the recording layer formation gold coating method, the above-mentioned A phenomenon occurs in which the VC coating liquid swells around the periphery of a molded support, making it impossible to form a coating film with a uniform thickness. Sensitivity unevenness in the periphery is large, making it impossible to perform high-performance recording and playback at N stations.

[Purpose of the invention]

The object of the present invention is to record a recording medium with high absorption rate and reflection rate for the recording and reproducing beam through the support 7,
The object of the present invention is to provide an optical information recording medium that can perform high-sensitivity recording and reproduction and can be mass-produced continuously.

Another object of the present invention is to form a recording layer using a so-called water-based coating. To provide an optical information recording medium that is inexpensive, has low toxicity, is 1/1 ℃ produced during production, has high industrial safety, and does not contaminate the soil environment. There is a particular thing.

[Structure of the invention]

The above object is to provide an optical information recording medium comprising a reflective recording layer on a support, in which the support is flexible, and the reflective recording layer is made of reflective fine particles mainly made of copper. is contained in a hydrophilic colloid and is called "C".

The present invention will be explained in detail below.

In the present invention, reflective fine particles mainly made of copper are provided on a flexible support in a reflective recording layer in which M is contained in a hydrophilic Freud's membrane to constitute an original information recording medium. .

In a preferred embodiment of the present invention, the thickness of the recording layer is, for example, 0.01 to 0.5 μm, and the average particle size of the copper particles is, for example, 0.005 to 0.2 μm. This support is transparent and is used in the recording and playback system. Further, it is preferable that the particle number density of the copper fine particles is about 1015 to 18 pieces. In contrast to controlling the particle number density in this way, the absorption rate of the recording beam that reaches the recording layer is improved by J-, and the reflectivity and reflection unevenness near the recording layer interface on the support side are improved. This results in a recording medium with higher sensitivity and higher than 5NIji, as well as excellent uniformity and stability.

What about the recording layer in the present invention? In the case of T'L injection obtained by precipitating the precipitated nuclei onto a support, hydrophilic colloids are used. Number of copper statue particles contained in the precipitation nucleus layer? By increasing the average particle size during the precipitation treatment while keeping it constant, a recording layer with good uniform dispersibility can be easily produced. In the case of the present invention (2) in which an F recording layer is formed in the precipitation treatment, the precipitation nucleus density in the precipitation nucleus layer, the thickness δ of the precipitation nucleus layer, and the controlling conditions of the precipitation treatment On the other hand, it is possible to obtain a recording layer consisting of dispersed copper fine particles having a suitable particle number density.The particle number density of the copper fine particles is determined by the thickness of the recording layer of the obtained recording medium, the recording layer The amount of copper contained in the gold and the average particle size of the fine copper particles.

For example, C can be easily calculated by measuring VCL using an electron microscope.

The second invention will be described in more detail below with reference to the flesh side, but the non-explosion BA is not limited to this.

FIG. 1 is a sectional view showing an example of the structure of an optical information recording medium precursor (medium before precipitation treatment? optical information recording medium precursor and finish). In the figure, l is the support, 2
3 is the precipitation nucleus layer poured into the precipitation nucleus 7, which is a layer in which the precipitation nuclei r are dispersed in a hydrophilic colloid dispersion medium, and 3 is the precipitation nucleus layer 2 in which the precipitation nuclei are poured.
A copper compound-containing Ml- layer is provided as a counterfeit layer on top.

As above, if the material of the support is made by Sajie, it is transparent F! A: Any material can be used regardless of its opacity; specific examples include polyethylene terephthalate, polyethylene brufeite, cellulose diacetate, cellulose triacetate, polypropylene, polyvinyl chloride polymethyl methacrylate, and polycarbonate. , polyimide resin, polyamide resin, etc.

The thickness of this support is preferably, for example, 1 μm to 2 μm, and in order to perform the continuous coating process favorably, the thickness is further 1 μm to 2 μm.
It is preferable that it is μnZ-300 μm.

Further, although it is not necessarily necessary that the support be subbed treated, it is preferable that the support be subbed treated. In this case, as the subbing treatment agent, for example, a silane coupling agent, a silicate salt, a titanium coupling agent, etc. can be used. Coupling agents are preferred.

Further, the support may be subjected to surface treatment such as corona discharge treatment, plasma discharge treatment, ion bombardment treatment, etc. to improve the fit 11.

Further, if necessary, a base layer such as a N-contact resin may be provided on the support to improve the adhesion of the recording layer to the support.

It can also be used for recording and accurate setting of one's position.

When the flexible support is transparent, the recording medium can be formed so that the recording beam and the reproduction beam can be irradiated from either one side or the other side during recording and reproduction. If the support is opaque, a transparent protection layer is provided on the side of the recording layer opposite to the side on which the support is laminated, and the recording beam and reproduction beam are irradiated from this protective layer side. The recording medium may be formed as follows.

By using a flexible support in this way.

In forming a recording medium, for example, a large-area band-shaped support is wound into a roll to form a roll-shaped support that can be taken out, and one end of the support is wound around a winding shaft to communicate geographical areas. , Continuously perform other processes other than the coating process necessary for forming the recording layer, such as cutting into the desired shape, at appropriate locations along the route of step 7. Therefore, it is possible to carry out continuous large-scale physiology of the recording medium.

In a specific example, as shown in FIG.

One end of the flexible support 8 in the form of a long strip wound around the unwinding shaft core 81 in the form of a roll is placed on a conveying roll 82°83'f.
- For example, a base layer forming mechanism 91 is provided on the winding axis 84 in the conveying direction P in the flexible support 80 passage area for winding. Precipitation nucleus layer formation mechanism 92. Precipitation processing mechanism 93. The cutting mechanism 94 sequentially performs each necessary process to form a recording medium. For example, in the base layer forming mechanism 91, if necessary, an adhesive resin composition is coated on the upper surface of the flexible support 8 by roll coating, and then this composition is dried or cured to form an adhesive layer. Continuously forms the base layer. In the precipitation nucleus layer forming mechanism 9z, details of -'f: will be described later.

For example, a hydrophilic colloid solution made by dispersing precipitation nuclei'e
L is applied by roll coating onto the upper surface of the supporting body 8 or the upper surface of the base layer, and then dried to form precipitation nuclei M4 on the surface EB. In the precipitation processing mechanism 98, the details of step 7 will be described later, or an emulsion in which fine particles of a copper compound are dispersed is coated on the precipitation core layer by roll coating, and dried to form a copper compound-containing layer. The recording medium is passed through a precipitation treatment solution to perform a copper precipitation treatment, and then the body compound-containing layer is peeled off to continuously form a long strip-shaped recording medium.

The cutting mechanism 94 cuts a long strip-shaped recording medium into a desired shape, thereby continuously manufacturing recording media formed into a desired shape. The remaining portion after cutting is wound up on a winding shaft core 84.

By manufacturing the recording medium in this way.

In the coating process, even if a phenomenon occurs in which the coating arm bulges at both side edges of the long strip-shaped flexible support 8, the both side edges are ultimately cut off in the long strip-shaped recording medium. By doing so, it is possible to obtain a recording medium with the desired shape, and therefore a recording medium with a uniform recording layer thickness and no unevenness can be obtained with high efficiency, and therefore information can be recorded and reproduced with high f'1. It is possible to do it in degrees.

In the above process, the long strip-shaped recording medium is wound one turn around the winding shaft to form a low shape, and then the rolled recording medium is unwound and cut into the desired shape. Good too.

The precipitation nucleus material used to form the precipitation nucleus layer is as follows:
Any known precipitation nucleating material can be used.

For example, the sulfides of Jukinzang (4/
Sue is zinc, chromium, potassium, iron, cadmium, cobalt, nickel, lead, and iron.

Sulfides of bismuth, silver, cerium, arsenic, copper, palladium, and rhodium) are preferred, as well as selenides of heavy metals (eg, selenides of lead, zinc, antimony, palladium, and nickel).

Another useful substance σ [Substances include silver and gold.

Examples include precious metals such as platinum, palladium, and ice fields.

These are preferably present as colloidal particles in the hydrophilic colloid at °C. In addition, salts of such metals, preferably simple iron-free and easily reducible salts such as silver nitrate, gold chloride, and silver chloride, can also be used as precipitation nucleating materials.
C.It is useful.

Other useful precipitation nucleating substances include thio compounds 1, such as silver thiooxate, its lead and nickel complex salts, thioacetamide, and the like.

In the present invention, the precipitation nuclei may be formed by forming the various heavy metals, noble metals, their sulfides, selenides, etc. on the support by an appropriate method such as vapor deposition, sputtering, or chemical vapor deposition. can. Such methods such as vapor deposition, sputtering, and chemical vapor deposition can make the layer containing the precipitation nuclei very thin, and therefore have the advantage of effectively utilizing the energy of the recording beam. The film thickness in this case is 5 to 100 OA.

Preferably it is zO~500A. Preferred precipitation nucleating materials are single heavy metal sulfides, such as sulfides such as zinc, cadmium, silver, lead, noceradium, and metals such as silver, gold, palladium, copper, etc.

The particle size of the fine particles forming the precipitation nuclei must be sufficiently small in order to carry out an effective precipitation treatment, and is, for example, 5 to ZOOOA, preferably 10 to 500.

Any method can be used to provide the above-mentioned precipitation nucleus layer on the support. For example, [1] a precipitation core layer may be obtained by dispersing the above-mentioned precipitation core substance in a hydrophilic carp a-F dispersion medium and applying a t-liquid onto a support; Alternatively, a precipitation nucleus layer may be obtained by forming a thin film of a precipitation nucleus material by vapor deposition or sputtering, and then coating it with a hydrophilic colloid dispersion medium, or (3)! 7tOn the contrary, the precipitation nucleation layer may be obtained by applying a hydrophilic colloid dispersion medium onto the support and then forming a thin film of the nucleation material by vapor deposition or sputtering. Among these, preferred is the method C1) or [2] above. Note that a chemical vapor deposition method, a liquid phase formation method, or the like may be used instead of the vapor deposition method or sputtering method.

In addition, the coating methods used at this time include blade coating,
Application methods such as air knife coating, par coating, roll coating, and curtain coating can be used. The thickness of the precipitation nucleus layer thus obtained is, for example, 0.001 to 0.5 μm at 8 degrees, preferably 0.001 to 0.05 μm.

In the precipitation core layer, the weight ratio of hydrophilic colloid to precipitation core is about 10:1 to 1:100.

The density of precipitated nuclei at this time is about 10 to 10.

As the colloid dispersion medium forming the precipitation nucleus layer, a known hydrophilic colloid dispersion medium in which precipitation nuclei can stably exist as colloid particles can be used.
Specific examples of f: include gelatin, alkali-treated gelatin, acid-treated gelatin, gelatin bond conductors, and colloidal albumin.

Casein, cellulose derivatives (calze 1,000 dimethyl cellulose, hydro 1,000 diethyl cellulose W), s-sugar derivatives (sodium alginate, starch derivatives, etc.).

Synthetic hydrophilic polymer (poly-N-vinylpyrrolidone).

(polyacrylic acid copolymer), etc. These can be used in combination in lengths of 2 m or more, if necessary. Among these colloidal dispersion media, preferred are hydrophilic colloids with low thermal conductivity, acrylic acid resins with a copolymer composition containing at least a salt of acrylic acid or a salt of methacrylic acid as a monomer unit, and water-bathable colloids. Cellulose conductors and gelatin are preferred. On the other hand,
Hydrophobic polymeric substances are not preferred because they have weak protective colloidal properties and can prevent the progress of the precipitation process accompanied by the diffusion of copper ions.

The copper compound-containing layer. That is, the copper compound for forming a layer that supplies copper atoms to the precipitation nuclei of the precipitation nucleus layer by a precipitation treatment includes cupric halides such as CuC1, CuBr, and CuI, or mixed crystals thereof.

CuSCN or CuC1, CuBr, CuI2
etc. (7) CI + cupric genide or a mixed crystal thereof,
CuSO4°Cu(NO3)2 or the like can be used. In particular, in order to efficiently supply copper atoms to the precipitation nuclei, it is preferable that the copper compound-containing layer is a dispersed layer of a soluble salt, and in this case, cupric halide is particularly preferably used. .

The copper compound may be contained in the precipitation core layer, or another containing layer may be provided on the precipitation core layer.

Preferably used cupric emulsion is disclosed in the patent application filed in 1973.
It can be prepared by the method described in No. 6-24669 and the cited publication No. 7.

That is, a cupric halide emulsion is obtained by reducing divalent copper ion A with a reducing agent in an acidic aqueous solution containing an R aqueous polymer compound.

When the copper compound-containing layer is formed by coating, it is preferable that the coating solution contains a hydrophilic protective film colloid in a proportion of 0.1 to 20 parts by weight. One example of such hydrophilic protective colloids is gelatin.

Gelatin sieve, arabicum, albumin, Gaidai, seven other natural polymer compounds, polyvinyl alcohol,
+), pylori, cellulose ether, partially hydrolyzed scraps of cellulose acetate, and seven other synthetic polymer compounds. In addition, it is preferable that this hydrophilic protective colloid has high water retentivity from the viewpoint of preventing swelling and elution. As the coating method, roll coating is preferred.

See ← Cao Ye, , , , .

FIG. 2 shows the state of the optical information recording layer after the optical information recording layer 44-r+suno layer has been subjected to the precipitation treatment. −ν of j4 formation
:" is a sectional view showing ". 1 degree Celsius, 1 is the recording layer where copper (due to precipitation treatment) is supplied and exhibits reflectivity, and the layer containing the initial precipitation nuclei has changed, and this is the recording layer 4.
Precipitation also progresses near the interface on the support side, and copper fine particles are present throughout the recording layer 4. 5 is a copper compound dispersed layer in which the amount of copper is reduced as a result of the precipitation treatment.

The precipitation process for forming the recording layer 4 is performed according to the first-order mechanism.

(1) Generation of cuprous ions or their complex ions by the copper compound contained in the copper compound-containing layer and diffusion process of these ion species to the precipitation nuclei (2) Production of cuprous ion species on the precipitation nuclei Growth process of metallic copper The first process (1) is a process in which, when the copper compound in the copper compound-containing layer is a cuprous compound, it is dissolved and diffused in the precipitation treatment solution, and - the sword compound is In the case of a cupric compound, it is dissolved in the precipitation treatment solution, and the cupric ions are converted to cuprous ions by an appropriate reducing agent contained in the precipitation treatment solution.

This is the process of diffusion.

The second process (2) is a process in which a disproportionation reaction of cuprous ions occurs according to the following formula.

2 Cu 4- Cu + Cu” By utilizing such a disproportionation reaction, precipitation treatment can be achieved extremely advantageously compared to the method of producing metallic steel by reducing copper ions. , the standard unipolar potential E based on the standard hydrogen electrode in the reduction reaction of copper ions is as follows.

Cu + e-#Cu E=0.520 (V
) Cu + 2e-# Cu E = 0.33
7 (V) As described above, the value of the standard unipolar potential E of copper is never large, and therefore, in order to reduce copper ions by a reduction reaction, it is necessary to use a reducing agent with considerably large reducing power. However, the use of such reducing agents is accompanied by practical problems.

In order to promote the above-mentioned disproportionation reaction, cuprous ion C
The concentration of u is high, and the cupric ion Cu2+ should be removed from the system, but cupric halogenated compounds have higher solubility in water than, for example, silver halogenide, and therefore are not suitable for application. It is easy to maintain a high concentration of cuprous ions in the precipitation treatment solution. Further, removal of cupric ions can be carried out using a thiolate agent that forms a complex with the cupric ions.

As described above, the precipitation treatment for forming the recording layer is due to the disproportionation reaction of cuprous ions.

Unlike conventional silver-based products, it does not rely on a reduction reaction. That is, the precipitation treatment using a silver halide emulsion is A.
g It is carried out by the diffusion of the complex to the precipitation nucleus and the reduction reaction there (e.g.

T.H.James, The Theory of
the Photographic, Process
(See Chapter 16 (1966) and Japanese Patent Application Laid-Open No. 1983-49296). This means that the standard monopolar potential of silver ions is approximately o, s.
This is because it has a high value of o o (v) and is easily reduced.

From the above, it is necessary to use a precipitation treatment solution containing a compound that promotes the progress of the first and second processes described above in the precipitation treatment for forming the recording layer. , a specific rc is a precipitation treatment containing a compound or compound system that has an appropriate coordination ability for cuprous ions and a larger coordination ability for cupric ions. A liquid is preferably used. Furthermore, when the source of copper ions is a cupric compound, a precipitation treatment solution is used that contains the compound necessary for reduction to cuprous ions, and thus has a suitable reduction method.

As a precipitation treatment solution that can be suitably used for the precipitation treatment, an alkaline aqueous solution containing at least one type selected from the following groups 1, 2, and 3 as a treatment agent is added. can be done.

Group 1: 4-aminophenols and 8-pyrazoli
Group 2 amino acid derivatives, aliphatic carzene imitators, oxycarboxylic acid, ketocarmene, aromatic carmine acid, amines, chlorine derivatives, amine carme/acid and pyridine derivatives Group 3: with the following general formula Ascorbic acid visiting conductor and its chilkali gold gI salt shown in the general formula [wherein, B- represents a hydrogen atom or a hydroxyl group, and n is 1
Represents a positive integer of ~4. However, in the case of 71 x l, 几 represents only a hydroxyl group. ] Also, if necessary, at least two or more types selected from the above three groups may be used in combination.

Specific compounds preferably used among the 4-aminophenols included in the first group include 4-N-methylaminophenol hemisulfate (m-name methol) and 4-N-benzylaminophenol salts. , 4-
N,N-jeteraminophenol hydrochloride, 4-aminophenol sulfate, l-dimethyl-4-aminol hydrochloride, 2,4-diaminophenol, 4-N-
Carbothousandimethylaminophenol, p-thythene phenylglycine, etc. can be mentioned, and specific compounds preferably used among the 3-pyrazolines include ■-
7enyl-8-pyrazolidone 4,4-dimethyl-1-7
enyl-3-pyrazolidone, 4-methyl-phenyl-8
- pyrazolidone and the like.

Specific examples of preferably used compounds included in the second group are shown below.

Malonic acid, citric acid, octosulfuric acid, salinal rR, 5
-sulfosalicylic acid, α-carbo-thousand C〇-anis W
, N, N'-cy(2-hydrothionethyl)ethyle/
Diami7s di(2-7minoethyl)ether, 2-aminomethylpyridine, 2,2-7minoethylpyridine, pyridine-2-carvone rtj/, 5pyridine72,6-
Carboxylic acid uninicotine hydrazide, isonicotinic acid hydrazide, pyridosamine, piperidine-Z, 6-dicarboxylic acid, histamine, 3-methylhistamine, iminodi[2°iminodipropion IR, N-methyliminodiacetic acid.

N-(3,3-dimethylzonal)iminodiacetic acid, phenyliminodiacetic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, hydroxyethyliminodiacetic acid, 2-hydroxycyclohexyliminodiacetic acid, methoxyethyliminodiacetic acid, N -(carnomoylmethyl)iminodiacetic acid, 2-ethoxylic acid
Aminoethylimino diacetic acid, nitrilotriacetic acid, calzexiethyliminodiacetic acid, calzeki-7methylimino dizolobionic acid, N-n-ditylethylenediamine) IJ
vinegar i, N-7 chlorohexylethylenediaminetriacetic acid,
β-alanine, phenylalanine, tyro-7, phosphoserine, methionine, aspartic acid, glutamic acid, ornithine, lysine, arginine, proline, and P-loxoproline, histidine, tryptophan, 1-amino-7
Cloventa/Carvone Cl l-aminocyclohexanecalzene 9, l-aminocyclohexanecarboxylic acid, β
-alanylhistidine, lysine pasoplecn, sodium glutamate, adenosine-5-syrinic acid, adenosine-5-triphosphoric acid, oxicune-5-sulfonic acid, quinoline-2-carboxylic acid, quinoline-8-carboxylic acid, 4
- Human 7-1,5-naphthyridine, 8-hydroxy-1,6-naphthyridine, 8-hydroxy-1,7-cattyridine.

Specific examples of the ascorbic acid derivatives or alkali metal salts thereof represented by the general formula included in the third group include L-ascorbic acid, araboascorbic acid, l-erythroascorbic acid, α-gluco Examples include ascorbic acid and their alkali metal salts, and among these, L-ascorbic acid or its alkali metal salts are particularly preferred.

Preferred solvents used in the precipitation treatment solution include pure water,
Examples include polar solvents such as alcohols (e.g., methyl alcohol, ethyl alcohol, etc.), glycols (e.g., ethylene glycol, diethylene glycol, etc.), and these solvents may be used alone or in combination of two or more as appropriate. Used in combination.

Furthermore, in addition to the processing agent, the above-mentioned precipitation treatment solution may have deposition properties (deposition rate, improvement in storage stability of the precipitation treatment solution, etc.) or appropriate optical properties such as reflectance, absorbance, and spectral properties. ! -Various additives can be added to improve the results. The main additives include, for example, alkaline agents (e.g., alkali metal or ammonia hydroxides, carbonates, phosphates), pH adjustment or buffering agents (e.g., weak acids such as acetic acid, boric acid, (weak bases or salts thereof), preservatives (eg, sulfites, acid sulfites, human mixylamine hydrochloride, formaldehyde bisulfite adducts, alkanolamine bisulfite adducts, etc.).

The concentration of the processing agent in the above-mentioned precipitation processing solution varies depending on the type of processing agent and cannot be specified in part, but it is usually 0.01~
It is about 2.0 mol/l, and the precipitation treatment temperature is usually Lυ ~
It is said to be around 40℃.

Alternatively, instead of using a precipitation treatment solution as described above, some or all of the components of the treatment agent are contained in the copper compound-containing layer, and an alkaline solution that dissolves the copper compound acts in the same manner as the precipitation treatment solution. By doing so, it is also possible to perform the desired precipitation treatment.

Furthermore, copper atoms may be directly supplied to the precipitation nuclei from the solution using a solution for precipitation treatment containing copper ions, without providing a copper compound-containing layer in the optical information recording medium precursor.

In the optical information recording medium of the present invention, for example, copper compound-containing A! shown in FIG. G5 may be peeled off after the precipitation treatment to form a double structure in which the copper compound-containing layer is removed in the process shown in FIG. After this precipitation treatment, the copper compound-containing layer 5 can be removed by, for example, peeling or dissolving. This peeling operation involves raising the temperature during water washing to a temperature at which the hydrophilic colloid dispersion medium of the copper compound-containing layer 5 dissolves or becomes a sol during the water washing step after the precipitation treatment (hereinafter simply referred to as "hot water washing"). ). In this hot water washing, it is preferable to harden the recording layer 4 using a hardening agent, and by doing so, the copper compound-containing layer 5 can be peeled off effectively. As another method, the copper compound-containing layer 5
It can also be suitably peeled off by immersing the film in a concentrated strong electrolyte aqueous solution to cause film contraction and then washing with warm water. The strong electric field material used in this case is
Salts with strong acids and strong bases, such as sodium sulfate, are preferred. -1: Similar effects can be obtained when the above-mentioned strong electrolyte is used by being included in the precipitation treatment solution. The liquid temperature in the above hot water washing is, for example, 20 to 50°C, preferably 40±5°C, when the dispersion medium of the copper compound-containing layer is a hydrophilic colloid and this hydrophilic colloid dispersion medium is gelatin. That's about it.

The thickness of the recording layer in the optical information recording medium of the present invention is 0.
It is preferable that O2N is 2.5 μm′″C, more preferably 0.03 to 0.2 μm.
If the thickness is less than 1 μm, coating unevenness becomes obvious and it becomes difficult to form a uniform and stable recording layer, and if the thickness exceeds 0.5 μIn, the reflectivity of the recording medium becomes low. may make optical reading difficult and reduce signal contrast.

Further, the average particle size of the copper fine particles dispersed in the recording layer is 0.
0.005 to 0.2 μm, more preferably 0.005 to 0.2 μm. Necessary when O2N is 2.1 μm. Average particle size is 0.0
If it is less than 05/Am, the recording energy beam absorption rate and the reproduction energy beam reflection rate will decrease, and recording and reproduction will become almost impossible. On the other hand, the average particle size is 0.
If it exceeds 2 pm, agglomeration of fine copper particles may cause a decrease in critical absorption rate and unevenness in reflectance, resulting in deterioration of recording and reproducing characteristics.

The average particle size here refers to the average value of the longest and shortest widths of copper fine particles. Regarding the particle size distribution of copper fine particles having such an average particle size, it is preferable that the particle sizes are uniform, and usually about 60 inches of the total number of copper fine particles is ±50% of the average particle size.
It should be within %.

In the optical information recording medium of the present invention, information is read using reflected light.
It is necessary to have a reflectance of H, preferably 20 to 70 H (both reflectances for reproduction light). When the reflectance is less than 10%, the SN ratio decreases, making it difficult to read information.

The optical information recording medium of the present invention may be subjected to heat treatment in the presence or absence of oxygen, if necessary, for the purpose of increasing the reflectance or decreasing the film thickness. The preferred heating temperature range in this case is about 250 to 400°C.

FIG. 4 is a cross-sectional view showing an example of the optical information recording medium of the present invention in which pit information is recorded. The irradiated area is melted or blown away (blo
w off ) forms a pit 7 and has a nine configuration. 6 is an arrow indicating irradiation with a high-density energy beam.

In this recording medium, the reduced reflectivity of the pits 7 is utilized to read information using a high-density energy beam that is weaker than the high-density energy beam for writing.
Can be played.

High-density energy beams that can be used to record pit information in the recording medium of the present invention include:
For example, a xenon lamp, a mercury lamp, an arc lamp, a laser beam, etc. can be used, and laser beams are preferred because they allow high-density recording. As the laser light, either continuous wave oscillation or pulse oscillation can be used.

Lasers that can be used include ruby laser (wavelength 6943A) and Alzan ion laser (wavelength 48A).
80A, 5145A), glass laser (wavelength 1.06
μm), helium-neon laser (wavelength 6328A)
, krypton ion laser (wavelength 6471A), Heliwamu force domicum laser (wavelength 4416 people, 325
0A), dye lasers, semiconductor lasers, etc.

The high-density energy beam used for recording on the recording medium of the present invention and the high-density energy beam used for reproducing may be of the same type or different types, and may be irradiated through the support. Alternatively, the radiation may be applied from the surface of the recording layer opposite to the support.

FIG. 6 shows an example of an optical disc constructed using the recording medium of the present invention, and 10 is a rotary disk-shaped optical disc having a through hole 11 in the center for inserting a positioning shaft. The base, 12 is a recording body, and this recording medium 1
2 is arranged in a shape of a groove on one side of the substrate io. In this recording medium 12, 13 is a transparent flexible support, and 14 is a recording layer. The space 15 is filled with an inert gas or the like. In such an optical disc, the base plate 10 is placed in a predetermined position by inserting the central through hole 11 into the positioning shaft on the turntable of the rotation mechanism, and the base plate 1G is rotated around the through hole 11. In this state, the recording layer 14 is irradiated with a recording beam or a reproduction beam from above the support 13 to record or reproduce information. By providing the space 15 between the recording layer 14 and the substrate 10 in this manner, the portion of the recording layer 14 irradiated with the recording beam is extremely easily blown away during recording, making it easy to form bits.

FIG. 7 shows an example of constructing a portable optical card using the recording medium of the present invention, in which 16 is a card-shaped base made of plastic, 17 is arranged on one side of the base 16, and the recording medium is , xBk1m A transparent protective layer is provided above the self-recording medium 17 and covering the entire top surface of the base 16. In this recording medium 17, 19 is a flexible support;
0 to 1! A space 217% is formed between the upper surface of the recording layer 20 and the transparent protective layer 18 to facilitate the formation of bits, and the inside of the space 21 is filled with an inert gas or the like. has been done. In such an optical card, a recording beam or a reproducing beam is irradiated from the upper blade of the transparent protective layer 18 to the recording layer 17 to perform self-recording and reproduction of information. 1 number, name etc. car P
Sentence information is recorded regarding the purpose of use, and it is convenient for portable use. .C can be used.

FIG. 8 shows an example of a case where the recording medium of the present invention is used to construct an optical notebook that can be pasted. 22 is a flexible sheet body, 231 is a flexible sheet body z2 on one side The E recording media stacked through the space 24 are inserted, and 25 is connected to the space 24.
This is the tth spacer forming the . Reference numeral 26 denotes an adhesive layer for pasting, which is laminated on the other surface of the flexible sheet body 22. The recording medium 23 includes a transparent flexible support 27, a recording layer 28, and a peripheral edge of the recording layer 28, which is densely layered on the spacer 25. The space 24 is for facilitating the shaping of the bit, and is filled with an inert gas or the like. In such a light sheet, the recording layer 28 is irradiated with a recording beam or a reproduction beam from above the transparent flexible support 27 to record and reproduce Wi1 information. In addition to being flexible, the sheet body 22 is flexible (supporting), so the entire optical sheet is flexible, and the adhesive layer 26 is provided on the negative side. Planar Mayu can be attached to objects of any shape, regardless of their curved surface.For example, by attaching it to the packaging bag of an article or the outer surface of a can or bottle, it is possible to record and reproduce information related to the article. It becomes possible. For example, in a supermarket, a secondary light sheet that records information such as price, product quality, etc. is attached to the product or its packaging container, and then the original sheet is irradiated with a reproduction beam at the product sales floor. By doing so, necessary information can be obtained quickly and accurately, making it possible to improve the efficiency of sales processing.

〔Effect of the invention〕

As explained in detail above, according to the present invention, since the recording layer is a reflective one in which fine particles mainly made of steel are dispersed in a hydrophilic colloid fractional medium, the high-density energy e-beam of the recording layer Since the absorption coefficient increases, high-performance recording can be performed, and because the reflectance increases, high-performance reading can be performed, and this makes it possible to significantly improve sensitivity and signal-to-noise ratio.

In addition, since the dispersion medium in the recording layer is a hydrophilic colloid, the recording layer can be obtained by aqueous coating, and as a result, unlike conventional methods, organic solvents are not used during manufacturing, resulting in a highly safe working environment. Obtainable.

Since the fine particles are mainly made of copper, manufacturing costs can be reduced, and steel is toxic.
It is highly safe to handle as there is little oxidation.

In addition, since the support is a catchable material, it is possible to wind a long belt-shaped support with a large area into a roll in the recording medium manufacturing process. It is possible to carry out continuous conveyance by pulling out one end of the belt-shaped support to a processing area and then winding it up on a take-up shaft.Therefore, in the processing area, necessary treatments such as coating for forming a recording medium can be carried out. Processing such as processing or cutting into a desired shape can be performed continuously, and as a result, continuous mass production of recording media becomes possible, increasing production efficiency and reducing manufacturing costs. can. In the roll coating process, roll coating allows rapid coating, and even if the coating liquid swells on both sides of the strip-shaped support, the strip-shaped recording medium can be cut into the desired shape. By removing both side edges of a strip-shaped recording medium during the printing process, it is possible to efficiently obtain a recording medium having a recording layer with an even and uniform thickness. Performance can be recorded and played back. In the cutting process, we use a method that allows us to cut out any desired shape, from large areas to small areas, and from large quantities such as optical disks to small items such as optical cards, optical tapes, and optical stickers. The recording medium of the present invention can be used in a wide range of applications.

The recording medium of the present invention, in which the support is flexible,
Not only flat objects but also curved objects can be used to apply this method to, for example, pasting on a curved surface.
- (It can be applied to a recording medium in a high-performance optical cooler, etc., and as a result, the uses of the recording medium can be dramatically increased.

The synergistic effect of the use of a flexible support and the fact that the fine particles in the recording layer are mainly made of copper makes it possible to significantly reduce the manufacturing cost of recording media, which is immeasurable. No big profits can be made.

The spectral characteristics of the recording layer of this type of optical information recording medium depend on the complex refractive index and filling factor that the dispersed metal in the form of fine particles has in the bulk state, and the lull index of the dispersion medium. (J, C, Mnxwe 11 Garnet
,Philos,Trans,R,Soc,
(Lond-203, p. 385 (1904)), the dominant factor being the complex refractive index that the dispersed fine particulate metal has in the bulk state. In the recording medium of the present invention, the above-mentioned fine particulate metal is made of steel, and the real part n and the extinction coefficient in the equation 9 expressing the complex refraction heavy metal of copper are as shown in Table 1. They vary greatly depending on the wavelength, and are also completely different from those for silver shown together.

From this, it is understood that the recording medium of the present invention can be applied to light of wavelengths that could not be applied to conventional bulk metal coated with silver.

Table 1 Specifically, the spectral sensitivity of a recording medium having a recording layer made of silver is about 500 to 600, as shown by curve A in FIG.
The maximum sensitivity is around ntn, whereas the recording medium with a recording layer made of copper has a sensitivity of around 700~ntn, as shown by curve B.
It has maximum sensitivity around 800 nm, and therefore a semiconductor laser with an oscillation wavelength in the infrared region can be used as a high-density energy beam for recording and reading. It becomes possible to realize an optical information recording/reproducing device that is smaller and cheaper than the conventional one.

Copper halide is preferred as the copper compound used as the copper atom source, but since this halide steel does not exhibit photosensitivity, it can be handled in a bright room, which has a great manufacturing advantage.

These effects that characterize the present invention include techniques for producing thin films containing fine particles of metals other than copper, such as crushing of metal lumps;
It cannot be obtained by high-temperature sintering or vapor deposition.

〔Example〕

Examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 A long belt-shaped flexible support made of polymethyl methacrylate having a thickness of 100 μm and a width of 60 crn was wound into a roll, and this was wound around a winding shaft as shown in FIG. The recording medium of the present invention was obtained by sequentially carrying out a base layer forming process, a precipitation nucleus layer forming process, a precipitation process, and a cutting process while being continuously transported to a processing area while being removed. The specific contents of each process are as follows.

Underlayer formation treatment> A MiL polymer composition of ultraviolet curable resin is continuously applied to the upper surface of a strip-shaped support by roll coating, and then the coated layer is cured by irradiating ultraviolet rays using a mercury lamp. 1μ
A welding base layer of m was formed.

Precipitation nucleus layer formation treatment〉 The above substances were stirred at a temperature of 80C and then mixed continuously.
Continue stirring for 15 minutes until the concentration of palladium sulfide (n) is 0.
．． 051! The concentration of hydrophilic colloid is 0.05:!
t%, the average particle size of palladium (II) sulfide fine particles is BO
A palladium sulfide (I[) colloidal solution of A was obtained.

A coating solution prepared by adding a surfactant and a hardening agent to this palladium (n) sulfide colloidal solution was continuously applied to the upper surface of the base layer of the support using a roll and a cloth.

Then, it was dried to form a substantially colorless and transparent precipitation core layer having a thickness of 0.01 μm.

Precipitation treatment Solution A and Solution B having the following compositions were prepared.

The solution At-temperature was kept at 40C, and the temperature was increased to 40C while stirring? ]Y[B was added instantly, and the temperature of the resulting mixed solution was maintained at 40C and stirring was continued for 8 minutes.

Thereafter, a desalting treatment and a water washing treatment were performed, ossein gelatin 247 was added, and an ultrasonic dispersion treatment was performed for t-10 minutes to obtain a Daikyokai cupric emulsion (total #, 5QQm). This emulsion has a pH of 3.5. The weight ratio of copper and gelatin contained is approximately 0.5. The average particle size of fi/%α cuprous oxide particles is 0.0 as measured by transmission electron micrograph.
Probably 5 μm.

This cupric iodobromide emulsion was continuously coated on the precipitation nucleus layer by roll coating, and then dried to a film thickness of 1.2 mm.
A copper compound-containing layer with a thickness of μm is formed, thereby producing an optical information recording medium precursor.Then, the pH is adjusted to 9 with a buffer consisting of a 0.2 M glycine aqueous solution at a temperature of 25°C.
The precursor was immersed in the precipitation treatment solution for 3 minutes to perform the precipitation treatment, and then the temperature was 37.
The copper compound-containing layer (emulsion layer) was peeled off by washing with warm water at ℃ to form a recording medium.

Cutting Process: The strip-shaped recording medium is cut into a circular donut shape to obtain an optical disk recording medium. The remaining portion after cutting was wound onto a winding core.

When the optical disk recording medium obtained by the continuous treatment as described above is observed from the support side, the formation of a copper mirror with metallic luster is observed, and the reflectance for light with a wavelength of 830 nm is 40 cm. Atsuku. The thickness of the recording layer is O.OS μm, and the average particle size of the copper fine particles in the recording layer is 0.00 μm.
The particle number density was 2XlO 4-.

An optical disc having the same structure as shown in FIG. 6 was manufactured using the optical disc recording medium. This optical disc was set on a turntable and rotated until the beam diameter was 1.
Semiconductor laser light with a wavelength of 830 nm focused to 4 μm was scanned at a scanning speed of 10 m/sea, and 1 M
Writing and recording is performed by forming pits in the recording layer by applying a Hz pulse signal (pulse width 500 nsec).9.

The intensity of the laser beam on the recording layer of this optical disc is 10 mW during recording and 2 mW during playback, and the playback SN
When the ratio was measured at 7971 width at 30 KHz, the 8N ratio was 45 dB''c.

[Brief explanation of the drawing]

FIG. 1 is a cross-sectional view of the optical information recording medium precursor before the precipitation treatment, FIG. 2 is a cross-sectional view of the optical information recording medium according to the present invention after the precipitation treatment, and FIG. FIG. 5 is a cross-sectional view of the optical information recording medium according to the present invention after the compound-containing layer has been removed; the fourth factor is a cross-sectional view of the optical information recording medium according to the present invention after irradiation with a high-density energy beam; 7 is an explanatory diagram showing an outline of an example of the manufacturing process of the recording medium of the present invention, the sixth factor is an explanatory cross-sectional view showing an example of a next optical disc constructed using the recording medium of the present invention, and FIG. FIG. 8 is an explanatory sectional view showing an example of an optical card constructed using the recording medium of the present invention, and FIG. 9 is an explanatory sectional view showing an example of a phosphorescent sheet constructed using the recording medium of the present invention. It is a curve diagram showing the spectral sensitivity when the metal is silver and when the metal is copper. l...Support 2...Precipitation core layer 3...Copper compound-containing layer 4...Recording layer (precipitation core layer after precipitation treatment) 5...Copper compound-containing layer 6 after precipitation treatment・High-density energy beam 7 ・Pit 8 ・Flexible support 81 ・
... Unwinding shaft core 84 ... Winding shaft core 82.83
... Conveyance roll 91 ... Base layer forming mechanism 92 ...
・Precipitation nucleus layer forming mechanism 93...Precipitation processing mechanism 94...Cutting mechanism lO・
... Optical disk base 11 ... Through hole 12 ...
-Recording medium 13-...Flexible support weight 4...Recording layer Work 5...Space 16...Substrate
17...Recording medium 18...Transparent protective layer 19...
-Flexible support 20...recording layer 21...space 22...flexible sheet body 23...recording medium 24...space 25...spacer 26...
-Adhesive layer 27...Flexible support 28...Recording layer! ,＋□、Representative Patent Attorney Masahiko Oi 1 ・Figure 1 Figure 2 Figure 3 Figure 4 Decoy

Claims (1)

[Claims] 1) In an optical information recording medium comprising a reflective recording layer provided on a support, the support is flexible, and the reflective recording layer includes reflective fine particles mainly made of copper that are hydrophilic colloids. What is claimed is: 1. An optical information recording medium comprising: