JPS5919254A - Recording medium - Google Patents

Abstract

PURPOSE:To obtain a recording medium with high sensitivity which can be consecutively produced, by applying a picture signal to a layer containing an optical hardening agent and a binding agent when necessary in a layer containing a physical phenomenon uncleus, then making the reflecting property of the recording medium to a pattern mode. CONSTITUTION:A supporter 1 is provided, and a photosensitive layer 2 contains a physical phenomenon nucleus and an optical hardening agent. These materials dispersed into a binding agent are usable. A track forming pattern 3 has an extremely small width. An active light beam 4 uses ultraviolet rays, electron beams, etc. and produces a photochemical reaction to the optical hardening agent. Thus the picture exposure is provided on a recording medium. A metallic compound containing layer 5 is removed for the physical phenomenon nucleus by exfoliation, dissolution or peel apart process, etc. The layer 5 can be exfoliated effectively by hardening previously the physical phenomenon nucleus layer 2, i.e., a recording layer with a film hardening agent.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to optical recording media, and more particularly to optical recording media having reflectively readable information tracks.

The recording medium of the present invention records information such as audio and video as changes in the shape and dimensions of pits (four portions or blocks (convex portions)), optically extracts the information, converts it into an audio or video signal, and reproduces it. This is used in the method.

As such a recording medium, for example, JP-A-55-1
Recording media using photosensitive silver halide emulsions are known, as described in Japanese Patent Application Laid-open No. 08995 or Japanese Patent Application Laid-Open No. 56-49296.

This recording medium has the advantage that it can be manufactured continuously and requires relatively little recording energy, unlike recording media made of Te, TeO, or chalcogenide compounds that use a vacuum device in the manufacturing process. There is. Another advantage is that it is possible to photographically record tracks or certain types of data in advance by taking advantage of the photosensitive nature of silver halide emulsions; however, since these use silver halide emulsions, recording It requires a dark room during media production, which has the disadvantage of being unfavorable in terms of work efficiency. Furthermore, since the practical limit of the track width that can be photographically recorded in advance is wide (2μ), it has the disadvantage that tracks cannot be recorded at high density.

Furthermore, since this recording medium is used in a reading method that utilizes the difference in reflectance, the reflectance of non-track areas and pit-formed areas obtained photographically in advance are about the same, so pit information is There is a drawback that non-track portions may be detected incorrectly when reading.

Therefore, the present applicant previously applied for the invention described in Japanese Patent Application No. 56-1570973 for the purpose of eliminating the above-mentioned drawbacks. However, in the invention of the specification, since the tracks are formed by relief, a step of removing the non-track portion of the physical development nucleus layer is required, which makes the manufacturing process complicated.
Moreover, there is a drawback that the physical development nucleus layer swells or peels off from the substrate when the non-track portion is removed, resulting in poor retention.

An object of the present invention is to eliminate the above drawbacks and provide a highly sensitive recording medium that can be manufactured continuously without using a vacuum system.

The object of the present invention is to provide a recording medium in which a layer containing physical development nuclei on a support is made to have 1 reflectivity by physical development, in which a y0 curing agent and, if necessary, a binder is provided in the layer containing physical development nuclei. This was achieved using a recording medium characterized in that an image signal is imparted to a layer containing an agent, and then the reflectiveness of the recording medium is patterned.

To produce the recording medium of the present invention, first, a layer containing physical development nuclei and a photocuring agent is provided on a suitable support such as glass or an acrylic plate, and this recording medium has a track pattern of approximately 1 μm. Wear a mask tightly and avoid exposure to active light such as ultraviolet light (for example, far ultraviolet light, electron beams, X-rays, etc.)
The scanning amount x light of an electron beam or the like may be used] and photocuring is performed in a pattern. Thereafter, physical development may be performed to form a surface having a patterned reflective black metal polish. In this case, it is preferable that the reflective metallic luster surface be non-conductive in order to prevent heat diffusion.

Methods for forming a layer containing physical development nuclei and a photocuring agent on the support include blade coating, air knife coating, bar coating, roll coating, and spinner coating. The thickness of this layer is approximately 0.05μ to 20μ, preferably 0.1μ to 0.3μ.

Physical development nuclei used in the present invention include known physical development nuclei. For example, one group includes heavy metal sulfides (e.g., zinc, chromium, gallium, iron, cadmium, cobalt, nickel, lead, antimony, bismuth, silver, cerium, arsenic, copper and rhodium sulfite), heavy metal selenides (e.g. , lead, zinc, antimony and nickel selenides.

Another group of useful physical development nuclei include noble metals such as silver, gold, platinum, palladium, and mercury, which are preferably present as colloidal particles in the binder. Salts of these metals, preferably simple inorganic and easily reducible salts such as silver nitrate, gold chloride and gold nitrate, are also useful as physical development nuclei.

Another group of useful physical development nuclei includes thio compounds such as silver thioxate and its lead and nickel complex salts, thioacetamide, and the like.

Preferred physical development nuclei are heavy metal sulfides, such as sulfides of zinc, cadmium, silver, lead, and the like.

Metal compounds that supply metal atoms to the physical development nuclei used in the present invention during physical development include gold salts (e.g. storium salts), copper salts (e.g. 0u04, 0uSON), lead salts (
For example, Pbo, Pbc4. PbBr, ),
Iron salts (e.g., oxalate, nitrate), PdM salts (e.g., oxalate, malonate), silver salts (e.g., Aged
.

AgBr, Ag engineering, AgN0. , Ag
, So, , AgS), cobalt salts (e.g. c
oa7%, 0o804), nickel salt (e.g. N1cNos)t, N1olt), Hg"4+
rN-cls, 'rθR4+In01B, engineering n
Although Br3 etc. can be used, silver salts, copper salts, nickel salts, and cobalt salts are preferably used, and silver halides are particularly preferred, and in this case, silver halides also have the advantage of being non-polluting. .

The physical development carried out in the present invention is carried out by a known method using a physical developer, and 1. All conventional developers can be used. 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.

For example, metol, hydroquinone, catechol, p-
A solution containing phenylenediamine, ascorbic acid, and their derivatives, or hydrazine, its hydroxide, or its salt as a developing agent can be used.

Examples of the support of the present invention include cellulose triacetate, polyethylene terephthalate, polymethyl methacrylate, polycarbonate, ceramic, polyimide resin, glass, metal, etc. The support is preferably subjected to subbing treatment. In this case, as the subbing agent, a silicic acid treatment, a silane coupling agent, a titanium coupling agent, etc. can be used.

In the present invention, a silver halide emulsion is used as a metal compound.
In the case of using the film, it is necessary to add an antifoggant, a coating aid, and a hardening agent, but since full sensitivity to visible light is not required, no sensitizing means is required.

In addition, a developing agent, e.g., t
It is also possible to add U-hydroquinone and phenidone and develop the film using only an alkaline bath containing a silver halide solvent to precipitate silver in a silver mirror shape.

Hydrophilic colloids in the binder according to the present invention include, for example, gelatin, alkali-treated gelatin, acid-treated gelatin and gelatin derivatives, colloidal albumin, casein,
Cellulose mis-form <carboxymethylcellulose, hydroxyethylcellulose, etc., sugar derivatives (sodium alginate, starch derivatives, etc.), synthetic hydrophilic polymers (polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide) Can be mentioned.

Other binders include phenol resins, epoxy resins, melanin resins, and the like. These can be used in combination of two or more types as required. Moreover, as these binders, hydrophilic colloids with poor thermal conductivity are preferable. A variety of binders may be used within that range.

Although known high-density energy light can be used to record bit information on the recording medium of the present invention, laser light is preferred. This laser can be used with continuous wave oscillation or pulse oscillation. Specifically, usable lasers include ruby laser (6943A), argon ion laser (4880S, 5145A),
Glass laser (ID6μ) He-Ne laser (
6328A), semiconductor lasers, and the like.

The recording medium of the present invention needs to have a reflectance of 10 to 70%, preferably 20 to 60%, through the substrate because it is necessary to read information using reflected light. If the reflectance is lower than the above, the signal contrast will decrease,
It becomes difficult to read information.

The medium to be subjected to physical development in the method of the present invention can be provided with a protective layer such as acrylic (seedling fat, silicone resin, epoxy resin, etc.) on the support, and if the protective layer is sufficiently thick, n keeps dust and dirt away from the focal plane of the laser beam.

The photocuring agent to be added to the layer having physical development nuclei as the recording medium of the present invention is one that is hardened by the source when subjected to imagewise exposure and has the effect of suppressing metal ions supplied to the physical development nuclei. is preferred. As these substances, diazo compounds, azide compounds, diazide compounds, dichromates, quinone azide compounds, etc. are used. As the diazo compound that hardens the exposed area, there are photodegradable aromatic diazo compounds, and representative examples thereof are as follows.

[1] P-diazomono (or dinoalkylaniline derivative general formula [I] Y'' [wherein R1 and R2 are hydrogen atoms (however, nl.

[R1 is not a hydrogen atom] or represents an alkyl group, and R1 and R' may be cyclized with each other to form a heterocycle. Yl represents any substituent that can be introduced into the benzene ring, and X represents an anion. ] Specific examples include p-diazomethylaniline hydrochloride, p-diazodimethylaniline hydrochloride, p-diazoethylhydroxyethylaniline hydrochloride, p-diazo m-chlorodiethylaniline hydrochloride, p-diazo0-methoxy Examples include diethylaniline sulfate.

[2] 2.5-substituted-4-diacylanilide general formula [n] 2 [wherein R8 represents an alkyl group or an aryl group]
yt and 2 represent an alkyl group or an alkoxy group, and xe represents an anion. ] As a specific example, 4
-Diazo-2,5-jethoxy-N-benzoylanilide and the like.

[3] p-diazodiphenylamine derivative general formula [
III] [In the formula, z2 and Y3 represent an alkyl group or an alkoxy group, and 0 represents an anion. ] Specific examples include p-diazodiphenylamine sulfate.

[4] Sulfur-containing diazo compound general formula [11V] [wherein R4 represents an alkyl group or an aryl group]
y4 represents an alkyl group or an alkoxy group, or an anion. ] As a specific example, 00,H.

0H300H.

etc. can be mentioned.

[5] A mixture of diazo polymer p-diazodiphenylamine with formaldehyde in sulfuric acid, etc.

Although typical examples of photodegradable aromatic diazo compounds have been listed above, the invention is of course not limited to these, and many photodegradable aromatic diazo compounds can be used.

Further, yC-decomposable diazo compounds are described in detail in Chapters 6 and 7 of ``Light-Sensitive Systems - Chemistry and Applications of Photographic Processes'' by J. Kossar, J., Wiley Publishing Co., Ltd. edition.

The diazo compounds preferably used in the present invention include condensation products of para-aminodiphenylamine diazonium salts and aldehydes, or condensation products of para-aminodiphenylamine diazonium salts and formalin, and their 3-ethoxy, -methoxy, 3-methyl, 3,3-di)lthiA/, 2,5-jethoxy, and other substituted derivatives.

Dichromium rI that hardens the n-base! As the salt, ammonium dichromate, potassium dichromate, etc. are used.

As the azide compound and diazide compound whose exposed areas are cured, aromatic azide compounds and aromatic diazide compounds can be used. For example, 4°4'-diazidostilbene, 2,2'-sodium disulfonate, 4,41-
diazidochalcone, 2,6-di(41-diazidobenzal)4-methyl-cyclohexanone, polyvinyl-p
-azidobenshade, 4,4'-diazidostilbene, etc.

The recording medium of the present invention may be subjected to heat treatment in the presence or absence of oxygen, if necessary. The preferred temperature range at this time is about 250°C to 400'C.

Next, the recording medium of the present invention will be described with reference to an embodiment shown in the drawings, but the present invention is not limited to this configuration. 1st
The figure shows the method of exposing the recording medium of the present invention. 1 is a support, 2 is a photosensitive layer containing physical development nuclei and a photocuring agent,
These substances may be dispersed in a binder. 3 is a pattern for forming a track, which is formed to have a very narrow width. 4 indicates active rays such as ultraviolet rays and electron beams, which cause a photochemical reaction in the photocuring agent, and this 7+
The image 1d light is imparted onto the recording medium. .

FIG. 2 shows the physical development f'1 of the metal compound-containing layer 5 after exposure.
21 is a cross-sectional view when applied.

FIG. 3 shows a cross-sectional view of the optical information recording medium of the present invention after the metal compound-containing layer has been removed after physical development.

The operation for removing the metal compound-containing layer 5 after the physical development is performed, for example, by a method such as peeling, dissolving, or beer apart. The above peeling operation is carried out by raising the temperature during water washing to a temperature at which the hydrophilic colloid dispersion medium of the metal compound-containing layer 5 dissolves or becomes a sol during the water washing step after physical development. At this time, the metal compound-containing layer 5 can be effectively peeled off by preferably hardening the physical development nucleus layer 2, that is, the recording layer, by using a hardening agent. As another method, the metal compound-containing layer 5 can be preferably peeled off by immersing it in a concentrated strong electrolyte aqueous solution to cause membrane contraction and then washing it with warm water.

The strong electrolyte used in this case is preferably a salt of a strong acid and a strong base, such as sodium sulfate. Further, the same effect can be obtained even when the above-mentioned strong electrolyte is contained in a physical developer.

For example, when the hydrophilic colloid dispersion medium is gelatin, the liquid temperature during the hot water washing is 20°C to 50°C, preferably around 40'C±5°C.

In this way, physical development progressed in the physical development contact layer 2 in a pattern corresponding to pattern 3, and a highly reflective metal dispersion layer 6 was formed. It seems that in Kosai 1, the supply of metal ions from the metal compound-containing layer 5 was prevented by the photocuring agent.

In this way, when a high-density energy beam (laser beam) is irradiated at position 7 or 8 of a recording medium on which tracks with a reflective surface are formed, the irradiated portion of the metal dispersion layer dissolves or blows off ( (blow-off) n pits can be formed and recorded. Thereafter, the bit information can be read using light weaker than the writing light by utilizing the reflectivity of the metal dispersion layer.

Since the recording medium of the present invention contains a photocuring agent in the layer having physical development nuclei, it is possible to obtain reflectivity in the form of a pattern with a very narrow track width. Since it does not have to be manufactured in bulk, it can be manufactured continuously, is suitable for mass production, and can be provided at a low price. below,
The present invention will be explained with reference to Examples, but the present invention is not limited thereto.

Example 1 An aqueous gelatin dispersion solution of colloidal silver particles, which are physical development nuclei, was obtained by reducing silver nitrate with dextrin, the ratio of silver to gelatin was 32%, and the particle size of the colloidal particles was It was about 300'A. To this aqueous solution, 1 wt % of a co-condensate of p-ruamino diphenylamine diazo compound and formalin was added, and a 1.0 ** thickness was obtained by subbing using a plasma discharge treatment and a Hishilan coupling agent. A physical development nucleus layer having a thickness of 0.2 μm was provided on a polymethyl methacrylate plate by coating using a wire bar.

A mask with a line width of 1 μ obtained by electron beam exposure was closely attached to the sample, and the sample was exposed for about 15 seconds using a contact printer for photomask production manufactured by Dainippon Screen Mfg. Co., Ltd. equipped with a 250 W ultra-high pressure mercury lamp.

Thereafter, a fine-grain silver iodobromide gelatin emulsion (silver iodobromide 3 mol %, average grain size 0.05 μm) as a metal compound was coated on the physical development nucleus layer at a coating ratio of 1 t17/ze. , a sample was obtained.

Without exposing this sample to light, a developer with the following composition was used to
After developing at 0℃ for 2 minutes, with hot water at 35℃,
Only the fine-grain silver iodobromide gelatin emulsion layer was peeled off and washed with water.

[Developer] As a result, when the obtained sample was observed through a polymethyl methacrylate plate as a support, a silver mirror with a patterned reflective image with metallic luster was generated, and the interface with the support was observed. It was confirmed that it was a silver mirror layer. Also,
It was found that tracking was possible based on the difference in reflectance between the exposed and unexposed areas at this time.

Using the sample obtained above, a He-Ne laser C (6
328Ck) was scanned at a scanning speed of 4.9 m/sec using a rotating mirror, and 500 n
・Writing and recording to form bits was performed by applying a pulse signal of sec. As a result, a recording surface with a remarkable difference in reflectance was obtained, good signal contrast was obtained, and optical reading was easily possible.

For example, when recording was performed at a portion corresponding to position 7 in FIG. 3, which exhibits a reflectance of 45%, rM [power was 2 mW and signal contrast was 0.6 mW.

Example 2 A sample of the present invention having patterned metallic luster reflection was obtained in the same manner as in Example 1, except that a colloidal gold solution having the composition shown below was used instead of the physical development nuclei used in Example 1. At this time, the reflectance of the polymethyl methacrylate plate through the support was 44% (6328A) at position 7 in FIG.

Claims (1)

[Claims] In a recording medium in which a layer containing physical development nuclei on a support is physically developed to make it reflective, a photocuring agent is contained in the layer containing physical development nuclei and an image signal is imparted to the recording medium. A recording medium characterized by having patterned reflectivity.