JPS5938092A - Optical information recording medium - Google Patents

Abstract

PURPOSE:To obtain a long-time preservable recording medium with a high reproducibility by arranging a hydroquinone derivative or a phenol derivative into a layer in which fine metal particles are dispersed into an organic high molecular compound in optical information recording medium. CONSTITUTION:A hydroquinone derivative represented by the formula I (where, R<1> is C1-20 alkyl group, acyl group, aryl alkyl group or the like, R<2> hydrogen atom or the same as above and R<3> -SO3Na, halogen atom or the like) or a phenol substance represented by the formula II (where, R<5>, R<6> and R<7> are each hydrogen atom, amino group, alkyl group or the like) is added to a dispersion liquid in which a fine metal particle of Ag, Au, Pt and the like with the particle size of 20-500Angstrom obtained by reducing a solution of silver nitrate, gold chloride acid or the like is dispersed into a gelatin, hydrophilic organic solvent or the like with the content of 20-70wt% and the dispersion solution thus obtained is applied and dried on a support to obtain a recording layer. The recording layer may be subjected to a heat treatment or the like to improve the reflection property of the surface thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a recording medium, and more particularly, to a recording medium (recording medium).
The present invention relates to optical recording media capable of recording) and reflective reading.

Conventionally, information such as audio and video was stored in pits (four parts) or four parts.
As an optical information recording medium used in a method in which changes in the shape and dimensions of a convex part are recorded, optically extracted, converted into an audio or video signal, and reproduced, gold microparticles are thermally conductive. It is known to use as a recording layer a material dispersed in a small organic polymer compound, and it has been proposed, for example, in Japanese Patent No. 56-130214.

In particular, regarding optical information recording media using silver tetragenide emulsions for photosensitivity, JP-A-55-108995 and JP-A-56
-33995, 56-49296 or 56
The recording medium using a photosensitive silver halide emulsion is disclosed in Japanese Patent Application No. 145488/1988.

All of the optical information recording media mentioned above are Te
Unlike optical information recording media that use vacuum-based equipment such as vacuum evaporation equipment and sputtering equipment in the manufacturing process, such as optical information recording media in which the recording layer □ is formed by vapor-depositing SueQ or chalcogenide compounds, it is inexpensive and can be manufactured continuously. It has the advantages of being possible, requires relatively little recording energy, and is non-toxic.

Furthermore, optical information recording media that use silver halide emulsions or copper halide emulsions have the advantage that tracks or certain types of data can be recorded photographically in advance by taking advantage of their photosensitivity. There is.

Further, Japanese Patent Application No. 189060/1983 describes an optical information recording medium using a layer containing physical development nuclei (which becomes a recording layer after being physically developed).

The conventional optical information recording medium mentioned above, which has a layer in which fine metal particles are dispersed in an organic polymer compound, has a surface reflectance sufficient to read the information recorded as pits using reflected light. However, the metal fine particles dispersed in the organic polymer compound are oxidized and deteriorated over time, resulting in a decrease in reflectance, making it impossible to obtain good recording sensitivity and signal contrast (described later). First, there was a drawback that recorded information became difficult to read due to reflection, especially during reproduction.

The purpose of the present invention is to improve the shortcomings of the prior art, to enable long-term storage of 10 years or more, and to record and **! It is an object of the present invention to provide a good optical information storage medium, and the object of the present invention is to provide a layer in which fine gold particles are dispersed in an atomized polymer, and in which a hydroquinone derivative is incorporated into a layer in which gold particles are dispersed in a polymeric compound. Or, it is achieved by an optical information recording medium characterized by containing a phenol derivative.

To manufacture the recording medium according to the present invention, for example, a hydroquinone derivative or a phenol derivative is dispersed in a liquid in which reflective metal fine particles are dispersed in an organic polymer compound, and then this is coated on a support. There is a way.

The support used in the present invention may be any material as long as it has excellent planarity, such as glass, metal, ceramic, resin, polyimide resin, polycarbonate, acrylic such as triacetate I1 cellulose, polyethylene terephthalate, and polymethyl methacrylate. Transparent,
The support may be either translucent or opaque, but when a high-density energy beam is irradiated through the support, the support is preferably substantially transparent to the energy beam. Furthermore, when the recording medium according to the present invention is heat-treated, the support is preferably made of a material that has good dimensional stability at high temperatures.

In the recording medium according to the present invention, the metal used in the layer (hereinafter referred to as the recording layer according to the present invention) in which fine metal particles are dispersed in an organic polymer compound and a hydroquinone derivative or a phenol derivative is contained. Fine particles are Ag % Au 5Nls Pd % Pt, F
These are metal bonding particles such as e, Co, Cu, Hg, and AI, and these metals may be used alone or in combination of two or more.

One method for manufacturing the optical information recording medium according to the present invention is to apply a dispersion of metal fine particles onto a support, dry it, and then
It is heat treated. For example, if the metal is Ag, Au
In the case of Pt and Pt, particle sizes of 10λ to 100O are obtained by solution reduction methods using silver nitrate, chloroauric acid, and chloroplatinic acid, respectively.
Metal fine particles of X can be formed. In order to stabilize the dispersion solution and increase the heat treatment effect described below, the particle size is preferably from 20A to 500A.

As a dispersion medium for metal fine particles according to the present invention, various polymer compounds can be used, in addition to natural polymer compounds such as gelatin and cellulose, or water-soluble polymer compounds such as polyvinyl alcohol, polyacrylic acid, and polyacrylamide. As a solvent, various organic solvents or water, or aqueous solutions of various inorganic compounds (for example, Naα-1, KOH-K
m COs , Na 2 so, , CH, C'0ONa
(aqueous solution) etc. can be used in combination as appropriate.
Handling of dispersion media or solvents, environmental protection, and all 14
111. From the viewpoint of particle dispersion stability, the dispersion medium is preferably water-soluble polymer compounds such as gelatin, gelatin derivatives, cellulose or cellulose derivatives, polyvinyl alcohol or polyvinyl pyridone, and among these, photographic gelatin (including gelatin derivatives) is preferred. is particularly preferred, and the solvent is preferably water or a hydrophilic organic solvent for the same reason as the above-mentioned dispersion medium. Here, the hydrophilic organic solvent refers to water-soluble solvents such as alcohols, ketones, and ethers. For example, alcohols include lower monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, and butyl alcohol, It means the alcohol ether of polyhydric alcohols such as ethylene glycol, triethyl gelicol, glycol, rutyl cellosolve, methyl cellosolve, ethyl carpitol, and butyl carpitol, and the ketones include acetone, methyl ethyl ketone, N-methyl pyrrolidone, The meaning includes so-called ketones and acid amides such as dimethylformamide, dimethylformamide, and hyamide, and examples of ethers include tetrahydrofuran and dioxane.

The metal content in the dispersion liquid of metal fine particles according to the present invention is such that the ratio of metal fine particles is λ) to 70( % by weight) is preferable in terms of efficiency as a recording layer and stability of the dispersion according to the present invention.

The hydroquinone derivative is represented by the following general formula (I).

In General 2〇), R1 is a linear or branched alkyl group having 1 to 20 carbon atoms (-8o, MteM may be substituted, M represents NaSKNLi, NH4), a carbon atom 7 having the number 1 to 14 alkyl node ■ c syvM'ft'co-1 carbon t [child W1. l~
3 represents an arylalkyl group having an alkylene group or an arylalkyl group having a substituent on aromatic atom;
represents a hydrogen atom or the same thing as R1, and R8 is -
SO, M (M is Na sK sLi -INII4
), does not represent a halogen atom or a hydrogen atom.

The substituent that the aromatic ring may have in I (I) is a halogen atom (CI, BrSF)-808M (M is N
a, K, Li.

NH,) or a linear or branched alkyl group having WIl to 4 carbon atoms, a benzyl group, or a phenethyl group.

When used, a mixture of various hydroquinone derivatives represented by the general formula ff may be used.

Exemplary compounds related to general formula (I) are shown below in (Table 1). (The number in front of each substituent represents the substitution position. @A tree symbol in front of a substituent means that the position cannot be specified or it is a mixture of numbers at various positions.

It is a substituted hydroquinone.

On the other hand, the phenol derivative has the following general formula (If).

It is expressed as (m)-1 and (m)-2.

General formula (III) - has an amino group, an amino hydrochloride group, a straight chain or branched alkyl group having 1 to 8 carbon atoms, or a straight chain or branched alkyl group having 1 to 4 carbon atoms R8 represents an alkoxy group R, O-, R'', R1' is an aminoalkyl group having a hydrogen atom, a ms 7 group, a carboxymethylamino group, an amino group, an alkyl group R11 having 1 to 2 carbon atoms ( R')* Represents the same as NC'Hy- or R8, and X is a divalent to tetravalent linking group, examples C and H.

CH.

Among the aromatic rings of the phenol derivative of general formula (II), those bonded from the substituted position, i.e., general formula 0
1), side-1, dll)-2, preferred compounds are those having a linear or branched alkyl group having 1 to 7 carbon atoms as pores, and particularly preferred are R,
This is the case when r is tert -C4Hg.

Furthermore, in the present invention, general formulas (1), (II), [phase]
The compound represented by -1 and (g)-2 is 0.1 to 10% by weight, preferably 0.5-5% by weight, based on the gold me particles.
．． Use 0 weight width.

By containing the heid p-quinone derivative or phenol derivative according to the present invention in a layer in which fine metal particles are dispersed in an organic polymer compound, a decrease in reflectance in the optical information recording medium according to the present invention is prevented. It is possible,
It has become possible to store information for a long period of time (for example, more than 10 years).

A recording layer according to the present invention can be obtained by applying a dispersion solution of the metal fine particles and the hydrogynone derivative or phenol derivative to the support Jt and drying it. As the coating method, any known method such as blade coating, air knife coating, bar coating, and roll coating can be used.

In the recording layer according to the present invention, for example, the metal fine particles can be considered to be substantially uniformly dispersed, but exhibit a distribution that decreases in the depth direction towards conditions suitable for improving the surface reflectivity. You can also make it look like this.

The heat treatment is described in detail in Japanese Patent Application No. 56-130214, and the advantages of heat treatment are increased reflectivity, hardening of the film due to reduction in film thickness, and backing of metal particles (high density stabilization). That is, the reflectance increases from about 10% to 60%, preferably 30% to 60%, and it is also possible to obtain an optical information recording medium suitable for a reflective reading method during recording and reproduction. can.

A radiation method is preferable so that heating can be performed uniformly over the entire surface of the recording layer according to the present invention, but heating methods using a convection open type or a contact type heat source are also included. The heating atmosphere is carried out under normal pressure or reduced pressure, and in the presence of oxygen or absence of oxygen, depending on the characteristics of the metal colloid particles of the recording layer. When the metal is 71g, Au, or pt, the presence of oxygen is preferable. Heating under reduced pressure reduces the film thickness at a greater rate than under normal pressure, and also greatly improves reflectance.

Further, a light-transmitting antireflection layer can also be coated on the recording layer according to the present invention. The antireflection layer that also serves as a protective film is made of, for example, epoxy resin, transparent melamine,
It may contain silicone or polycarbonate.

Further, in order to increase the adhesion between the recording layer and the support according to the present invention, a subbing layer such as a polymer compound may be coated. Further, the support may be subjected to surface treatment such as corona discharge treatment, plasma discharge treatment, ion bombardment, etc. to improve the adhesion. Further, even if a silane coupling agent or a titanium coupling agent is added to the undercoat layer or the recording layer according to the present invention, it is possible to improve the adhesion with M44g or each of the layers without affecting the recording properties. can.

Further, in the optical information recording medium according to the present invention, a layer in which physical development nuclei dispersed in an organic polymer compound is coated on a support (hereinafter referred to as a physical development nucleus layer) is physically developed. can be used as a recording layer. The physical development nuclei are metal fine particles or metal compounds, and more specifically, those selected from the following three groups can be used alone or in combination.

The first group (hereinafter referred to as Group A) uses the aforementioned metal fine particles as physical development nuclei, and uses a layer in which metal fine particles are dispersed by the same method as above as a physical development nucleus layer. be.

The second group (referred to as the third group) uses metal salts as physical development nuclei, and uses simple inorganic and easily reducible salts and organic compounds such as silver nitrate, gold chloride, and gold nitrate. metal rings such as silver thiooxalate and its lead and nickel complex salts, thioacetamide, and the like.

The third group (this will be referred to as group 0) uses heavy metal sulfide or heavy metal selenide as a physical development nucleus. Examples of heavy metal sulfides include sulfides of zinc, lypmium, gallium, iron, cadmira A, fuha A/), nickel, lead, antimony, bismuth, silver, cerium, arsenic, copper, and rhodium. Examples of selenides include lead, zinc, antimony and nickel selenides.

Preferred solar development nuclei are heavy metal sulfides, such as sulfides such as zinc, cadmium, silver, and lead, and metals such as silver, gold, palladium, copper, and the like.

The organic polymer compound used in the recording layer of the present invention is for dispersing metal fine particles, and examples thereof include water-soluble or water-dispersible organic polymer compounds such as gelatin, alkali-treated gelatin, acid-treated gelatin, and Gelatin derivatives, colloidal albumin, casein, cellulose Mi1 (carboxymethylcellulose, human tetraxyethylcellulose, etc.), miderite (sodium alginate, starch derivatives, etc.), synthetic hydrophilic polymer f1: compound (polyvinyl alcohol, (polyN=M elpyrrolidone, polyacrylic acid copolymer, bolamide, etc.). '1 Other polymeric compounds, such as 2-nonyl resin, epoxy resin,
Although melamine resin or the like may also be used, it is preferable to use a water-soluble or water-dispersible organic polymer compound with poor thermal conductivity. This is because when the organic polymer compound used as the dispersion medium has poor thermal conductivity, it is advantageous because the energy cis is small when a high-density energy beam is applied to the recording medium.

These can also be used in combination of two or more types, if necessary.

Examples of the metal-supplying metal compound that supplies metal atoms to the physical development nucleus by physical development include gold halide complexes (referring to chlorauric acid salts, etc., such as sodium chloroauric acid), #
iron salts (e.g. CuCJ, CuSCN), iron salts (
e.g. oxal salts, nitrates), lead salts (e.g. pbQ,
PbCl, PbBr
AgI, AgNOs, AgtSO4, AlhS)
, cobalt salts (e.g. CoC1, CO3O4),
Nickel salts (e.g. Ni(NOs')r, NlCl
! ), HgC1t, B'1C1t,
TeC14, InCl, , InBr3@do can be used, but in the present invention, especially C1'-silver salt, copper-
12. Kel's salt and cobalt salt are preferred, and silver halide is most preferred. In this case, silver halide also has the advantage of being non-polluting. When using a silver halide emulsion as a metal compound for supplying metals, it is desirable to add an antifoggant, a coating aid, and a hardening agent, but since sensitivity to visible light is not required, sensitizing means are not necessarily required. No need to rub.

The metal supply and marine metal compound may be coated and laminated on the physical development nucleus layer and then physically developed, or the metal compound for metal supply may be included in a physical developer and the physical development nucleus layer is physically developed. You may.

The physical development of the physical development nucleus layer is carried out by a known method using a physical developer, and any conventional developer can be used as the physical developer. That is, □
It is an alkaline solution or an acidic solution containing at least a developing agent, and any type of developer known in the art can be used.

The physical development nucleus layer is subjected to physical development 1. Even in the recording layer, the hydroquinone derivative or phenol derivative according to the present invention was effective in preventing the reflectance of the recording layer to a high-density energy beam from decreasing due to storage over time.

IF according to the present invention! Ruby laser (6943A) and argon ion laser are used to record pit information on fl media.
v-(488oX,, 5t4sλ), Karasu laser (1,06μ), He-Ne laser light and laser light for regeneration can be used for the same coffin or different types. For example, the light may be irradiated through a transparent support, but the surface of the recording layer may be irradiated directly without any problem.

The present invention will be specifically explained below with reference to Examples.
This does not limit the embodiments of the present invention.

In the examples below, signal contrast is a parameter that indicates the difference in reflectance between recorded and unrecorded areas, and is defined by the following formula (■). The larger the value, the higher the reflectance of unrecorded areas is. greater than the rate. A value of 0.3 or more is practically preferable.

Signal contrast = (I o - I r) / (
i o + I r), (IV) IO: Reflected light intensity of the recorded area by the reproduction light R: Reflected light intensity of the unrecorded area by the reproduction light Example-1 Physical development nucleus layer dispersion aqueous solution reduces silver nitrate with dextrin 4j The weight ratio of silver to gelatin is 3.
2 arcs, and the particle size of the colloidal particles was approximately 300 A. The coating was applied using a wire bar onto a polymethyl methacrylate plate with a thickness of 1.0 μm, which had been undercoated using a silane coupling agent in an aqueous gelatin dispersion solution. On this physical development nucleus layer, a fine-grain silver iodobromide gelatin emulsion (silver iodobromide 3 mol%, average grain size, O,
OSμrrL) A sample was obtained by coating so that the coated silver amount was 39/d.

This sample was developed for 2 minutes at 40°C with a physical developer having the composition shown below without being exposed to light, and then developed with hot water at a temperature of 1°C.
Only the fine-grain silver iodobromide Zentin emulsion layer was separated and washed with water.

[Developer]

Reflectance at 6328 A through the support is 49.5
%Met.

Furthermore, what is the benefit of the above? Using a rotating mirror, a 1le-Ne laser beam (e32si) with an IB, gmW output and a beam with a diameter of 1.4μ was applied to the sample for 4.9 yisec.
scanning at a scanning speed of 500 nm using an acousto-optic modulator.
When writing and recording was performed by applying a pulse signal of sec to form pits and toss, the lowest energy required for recording (hereinafter referred to as @ value energy) was left in the evening, and the reflectance was similarly 1 and 2. When the recording characteristics were measured, there was hardly any decrease in reflectance, which was 0%, and the recording characteristics were also good, with no influence from hydrothermo.

Comparative Example-1 A recording medium to which Exemplified Compound (I)-5 was not added in Example-1 was prepared in the same manner as in Example-1, and 0
After being left in a hydrotherm at 80% °C for 3 months,
Reflectance and recording characteristics were similarly measured. Before being placed in the hydrotherm, the reflectance at 6328λ of the obtained sample was 47% through the support, but after being placed in the hydrotherm, the reflectance decreased to 38%, and the recording properties also decreased. Degraded 0 Example-2 Exemplified compound (I)-3 instead of Exemplified compound (I)-5
However, there was almost no decrease in reflectance and the results were good. In other words, while the initial reflectance was 51%,
He was 49%.

Example-3 A sample was prepared in the same manner as in Example-1 except that exemplified compound 01)-i was added. The thickness of the recording layer of the obtained sample was 0.13 μm, and the reflectance in 6328 people was 49.0%. When the sample was recorded and reproduced in the same manner as in Example-1, the threshold energy was 2.2.
mW, signal contrast (signal contrast) was left for 3 months, and then the reflectance and recording characteristics were measured. There was almost no decrease in the reflectance, which was 48.0%, and furthermore, the recording characteristics were not affected by hydrothermo. Example 4 An aqueous gelatin dispersion solution of colloidal Ag particles was obtained by reducing silver nitrate with dextrin.
The weight ratio of colloidal particles to gelatin was 33%, and the particle size of the colloidal particles was about 300λ.

Exemplary compound Φ1)-t-3 in the gelatin dispersion aqueous solution
was added in an amount of 0.6% by weight based on the metal fine particles.

The aqueous dispersion solution was applied onto a glass plate with excellent smoothness using a wire bar to a thickness of ω μm, solidified with cold air, and then dried with hot air for a few minutes to form a yellow transparent recording layer with a dry thickness of 3 μm. has been established. This sample was heated using an infrared heating lamp (20
0v, 21C! ) in air at 320±5℃
By heating the medium for 10 minutes, an optical recording medium having a golden luster and a reflectance of 1% at a wavelength of 63,281 was obtained.

The information recording medium was scanned with a He-Ne laser beam with an output of 3 mW on the recording surface focused on a spot with a diameter of 1.0 μm at a scanning speed of 5.0 rrVsec using a rotating mirror, and an acousto-optic change w4 was performed. 100 n5ec due to abandoned child
Recording was performed by applying a pulse signal to form bits. These bits had good contrast in reflection and were easily optically readable. The 1 value energy was below 5 theories and the signal contrast was 0°3.

@ffi #! When the medium was left in a hydrotherm at 60°C and 80% for 3 months, the reflectance and Pl! When the bell characteristics were measured, no change in reflectance was observed and the reflectance was the same as before being left, and the recording characteristics were also good.

Comparative Example-2 A recording medium to which the exemplified compound (1'1l)-1-3 was not added in Example-4 was prepared in the same manner as in Example-4, and was placed in a hydrothermometer at 0°C and 80% for 3 hours. After being left for several months, the reflectance and recording characteristics were measured in the same manner. 6328X of the obtained sample before placing it in the hydrotherm.
The reflectance was 35.5%, but after being placed in a hydrotherm, the reflectance decreased to 25.5% and the recording characteristics also deteriorated.

Agent Kuwa Harawa Mi

Claims (1)

[Claims] An optical information recording medium that records and reproduces information using a high-density energy beam, characterized by containing a hydroquinone derivative or a phenol derivative in a layer in which fine metal particles are dispersed in an organic polymer compound. Optical information recording medium.