JPS5833243A - Manufacture of optical recording medium - Google Patents

Abstract

PURPOSE:To enlarge exposure range, to facilitate developing conditions, to elevate reflectance of a reflective surface, and to enable easy reading of information in preparing the reflective surface to be used for laser recording and laser reading by exposure, development, and heat treatment of a silver halide emulsion, by executing exposure in the region of solarization. CONSTITUTION:When exposure is carried out in the region of solarization, the concn. gradient of silver grains produced by development and heat treatment is inclined to raise concn. of the silver grains near the surface, and reflectance of the reflective surface is raised by the silver component concd. in presence of oxygen, thus permitting information to be made easily readable, an allowable range of exposure to be enlarged because any exposure may be excecuted in the solarization region, and photographic processing to be made easy, becuae a silver halide emulsion is almost relieved from the limits of blackning degree, developing conditions, etc.

Description

[Detailed description of the invention] The present wA relates to a method for manufacturing an optical recording medium.

More specifically, an improved method of 011117F described in JP-A No. 1155-108195 will be described.

Conventionally, as a laser recording Ik medium, JP-A-55-1081
As described in No. 19S, after the silver halide emulsion layer on the substrate has been subjected to photographic treatments such as exposure, exposure, and fixing, it is exposed to an atmosphere containing acid. - Heating with air until a shiny reflective component is formed on the surface of the DB membrane.
r@ct R@ad Aft@rWrit.) It is disclosed that a recording medium can be obtained. In the official publication, it is stated that silver halide emulsions after photographic processing may be processed using a chemical developer or #i dry development.
1, it is clear that the highest blackening [K] is achieved. However, in order for the silver halide emulsion to have the highest degree of blackening, the exposure range is very narrowly limited in exposure among photographic processes, and furthermore, the current conditions, i.e. Composition of dust liquid, development st
There were drawbacks in the production of the optical recorder I1k1/Is, such as the necessity of strict i control regarding the development time and the like.

On the other hand, if the degree of blackening of the silver halide emulsion is low, the optical reflectance obtained in heating 11, which is made of a reflective material with O chain components near both sides of the surface, will be low, so that laser beams etc. ), remove the shiny reflective material and record a
Even if nts is successful, after recording, scissors @ plot am shooting 1ktl
There was a drawback in its use: ``ljlL え、 情＠ Ｇａｎ み mockery'' was 1 and 'tkh.

As a result of intensive research, the present inventors have discovered a method 1 for producing an optical recording medium that overcomes the drawbacks of recording.

A first object of the present invention is to provide a method for producing an optical recording medium that can expand the exposure range in photographic processing of silver halide emulsions.

A second object of the present invention is to provide an optical recording medium that can facilitate the development conditions of the silver halogenide emulsion in the photographic section 11. To provide a method for producing a medium.

The third object of the present invention is to provide an optical system that has a high reflectance on the reflective surface produced after heat treatment even if the blackening f of the silver chloride hardness is low, so that information can be easily read (WII). It is an object of the present invention to provide a manufacturing method capable of obtaining a recording medium of various types.

The above problems are caused by the use of a silver halide emulsion on a substrate, at least during the exposure and development process, and after that, the reflective component is dusted on the surface by heat treatment, causing wrinkles in the optical recording medium. In the manufacturing method, exposure is carried out in the solarized regions of the emulsion.

The present invention will be explained in detail below.

The optical recording medium used in the present invention consists of at least one silver halide emulsion and a supporting substrate. The substrate is transparent, translucent, or opaque, preferably glass, ceramic, metal, and thermosetting and thermoplastic materials. J (It should be In that is dimensionally stable at high temperatures, such as medium [f fat, especially the condition 1' as a substrate material) #'i, withstands wrinkles up to at least 280℃ without thermal deformation. In particular, it should desirably have heat resistance up to about 380°C. The transparency or light absorption of the substrate means that when the light beam of a reflective reading device impinges on the recorded spot, the light beam passes through the substrate or is absorbed by the substrate with minimal reflection. It is requested that it be one of the following. If the substrate is absorptive, it must have the property of being absorptive at the wavelengths of the recording beam or the reading beam, or both. In this way, it is not always possible to use a substrate for ordinary photographic light-sensitive materials in one size.Furthermore, in order to provide one photographic hole M on the substrate, one fE#i etching is possible, resulting in dimensional stability. It is necessary to have good mechanical strength, not be destroyed by sunlight, and have excellent mechanical strength.
It is also desired that it be relatively inexpensive and generally available in reasonable quantities. Furthermore, when the data record is not transparent and is to be read only by reflection, the base material is a non-reflective, opaque material. - Ninth Error Checking Method and Apparatus for Digital Data in a Recording Media Line, Even a TFR Optical Recording System When the Substrate Is Bright, Disclosed in United States Patent Application Serial No. 845,332 It is read in transparent mode as shown below.

Depending on the thickness of the substrate, the substrate must have sufficient strength to resist destruction when the laser beam is directed at a reflective surface. If the laser beam is then incident through a transparent substrate, the thickness of the transparent substrate must be extremely uniform (even if #'i is a float glass or Preferably one obtained from carefully selected high quality pultruded glass).

The substrate supports the silver halide emulsion coating, and a well-known method can be used for this coating method, and it is preferable that the silver halide emulsion is coated uniformly on the substrate. As a dispersion medium for the silveride emulsion, a water-soluble binder such as gelatin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, hydroxyfurobylmethylcellulose, methylcellulose, polyacrylamide, polyethylene oxade, hydroxyethylcellulose, polyethylene glycol, etc. agent is used.

In addition, halogen Lfs is MugBr, AgI,
Any silver halide can be used, such as kgcl.

Chemical sensitizers, capri inhibitors, stabilizers, external image activators, hardeners, and other photographic additives may be appropriately added to the silver halide emulsion of the present invention.

In the chemical sensitization of silver halide emulsions, Shuhuangsen S is
For example, this can be done by using sodium thiosulfate, thiourea, allylthiourea, etc., and gold sensitization can be done by using, for example, sodium chloroaurate, gold thiocyanate grade potassium, etc. 1. As for gold-sulfur sensitization, chemical sensitization can be carried out using at least 41 types of each of the above-mentioned sensitizers in combination, and in this case, ammonium thiocyanate, etc. t -1f! In addition to K, you can also enhance your learning with A.

Further, the silver halide emulsion used in the present invention can be subjected to a selenium sensitization method in addition to the above-mentioned sulfur sensitization method. For example, selenorea, N,N'-dimethylselenourea, etc.
The method described in Japanese Patent Publication No. 1,574,944, Japanese Patent Publication No. 3591385, Japanese Patent Publication No. 13849/1984, and Japanese Patent Publication No. 1574/1984 can be used.

Further, reduction sensitization can be carried out by applying conventionally known methods, such as aging in a low pAgW atmosphere, using a suitable reducing agent, or using electromagnetic waves such as light and r-rays.

Furthermore, as a stabilizer, Capri-inhibitor*AM, for example, US%
tf xie 2444,607, flij turtle 2,716.0
No. 62, No. 3,512,982, No. 3,342,
596, the specifications of German gjA Patent No. 1,189,380, German Patent No. 205°862, and German Patent No. 211,841,
Particularly preferred compounds are methods using stabilizers and capri-suppressing methods described in Japanese Patent Nos. 11a43-4183, 39-2825, 50-22626, 50-25218, etc. As, ~5,6-
Dorimethylene-7-hydroxy-S-triazolo (1,
5-a) pyrimidine, 5,6-ketramethylene-7-hydroxy-S-)
5-methine-7-hydroxy-8-triazolo(1,5
-a) Pyrimidine, 7-hydroxy-3-triazolo(
1,5-a) Pyrimidines, gallic acid esters (e.g. al-amyl gallate, dodecyl gallate, globil gallate, sodium gallate, etc.), mercaptans (e.g., (if-phenyl-5-mercabutoketrazole,
2-mercaptobenzthiazol nato), benztriazoles (e.g. 5-bromobenztrianol, 4-
methylbenztriazole, etc.), benzimidazole @ (fil, ttf 6-nitrobenz1 midazole, etc.), and the like.

The silver halide emulsion of the present invention contains a cyanine dye, merocyanate;
I can dream of spectral sensitization using a color chart. For example, in the regular area, % Kaimei No. 55-2756, 55
-14743, and in the Orun area, JP-A No. 48-56425, JP-A No. 51-31228, Touko Sho 4.
7-25379, it can be used alone or in combination. Furthermore, the spectral increase at longer wavelengths is 1IFi.
, 8e is WK of 1 view in Japanese Patent Application Laid-open No. 51-126140.
This can be carried out using cyanine color 5t, which has a long methine chain, and one-color addition S can also be carried out arbitrarily by combining color chips.

Once again, iI! As a detergent, aldehyde type and aziridine type (11! Eha PR Report, 19921
, U.S. Patent No. 12,950,197, Pl@2,96
4.404, 2,983,611, 3.2
Each uA specification of No. 71.175, Special Publication No. 4'6-4089
No. 8, % Kaimei No. 50-91315), 1 Sooxazole C example d U.S. Patent No. 331,6
09 specification), epoxy systems (for example: *
1141111! FM No. 3,047,394, West German Patent Ml, No. 885,663, British 1351% House No. 1,03
3,518 and those described in Japanese Patent No. 1148-35495), vinyl sulfone-based Cf1. tbaPBRevo-) 19,920. West 1s Patent No. 1,100,
942, British Patent No. 1,251,091, Patent No. 18
45-54236, 4g-110996, U.S. Pat. No. 353,964, and U.S. Pat. No. 3,490,911);

I# Application No. 48-27949: *National Patent No. 3,64
0.720), carbodiimides (e.g., U.S. Pat. No. 2,938,892,
Special Publication No. 46-38715, Patent Application No. 1509-1983
5), other maleimide-based, acetylene-based, methanesulfonic acid ester-based, triazine-based, and polymer-type hardening agents can be used. In addition, for thickening cutting, US Pat.
LoMotD, Serafon possible! Liii! Qt L Teho IJ t
-le@i (1'll, ttfUSEii%NlI2,9
60,404, Japanese Patent Publication No. 43-4939, and Japanese Patent Application Laid-open No. 48-63715), as Kti latexes, US Patent No. 766,979, and French Patent No. 1,395,544. Specifications, Special Publication No. 1973
-43125, and as a matting agent, those described in English Patent No. 1.221,980 can be used.

Furthermore, any desired agent can be used, such as saponin or sulfosuccinate group activators such as British Patent No. 548.532, Patent No. 1847-896.
Examples of the surfactant or anionic surfactant described in the specifications of No. 30 include Japanese Patent Publication No. 18166/1983, U.S. Patent No. 3,514,293, and French Patent No. 12J.
Specifications of No. 025,688, Patent No. 1843-1024
Those described in Publication No. 7 etc. can be used.

Substrates coated with emulsions having these properties are known as photographic plates, which are commercially available and are used to make photomasks for the manufacture of semiconductor integrated circuits.

The silver halide emulsion on the substrate described above is photographically processed to form black silver (blackened silver), and the subsequent heat treatment produces a silver gradient in the silver component near the surface, resulting in a glossy, reflective optical surface. It becomes a distribution medium. In general, photographic processing first includes a development process and, if necessary, a constant voltage process. That is, the silver halide emulsion on the substrate is exposed to intense radiation from a tungsten lamp, mercury arc lamp, incandescent lamp, or xenon flash lamp, and then developed. In this case, either high-illuminance short-time exposure or low-illuminance long-time focusing may be used. After that, it is fixed as necessary. In this step of the operation, a black zone (blackened silver) is created for conversion into a reflective optical recording medium.

The present inventors have discovered that if the step of forming blackened silver from the above-mentioned silver halide emulsion is carried out in the nuralization area of the lightning T-wrinkle emulsion, then the silver grains produced by heat treatment are It was found that the af gradient causes an increase in fli particles near the surface, and the reflectance of the reflective fRID increases due to the silver component near the surface concentrated in the presence of oxygen. When the value becomes very large, this is a region where the photographic (current *) I) density decreases more than the maximum density.

In other words, the blackened silver produced by development is
If the exposure amount exhibits a transmission density of less than l high transmittance, that is, the maximum transmittance of black IL silver is #1 degree l1oo, then 10
At an exposure amount that exhibits a transmission aft of less than 0, and the maximum appropriate excess I
This is a lightless region larger than the exposure amount when exhibiting IkIiLt. For example, the applicant's silver halide emulsion photographic plate,
Sakura HIGHRE80LUTION PLATg (
The solarization area of product name) has a light intensity of 400
CMll, preferably ilm: 500 CMS or more, more preferably 1,000 CM8 or more. More preferably, the unexploded, loosely formed region is a lightless region in which the transmission am of the darkened silver produced by development is 80 degrees above its maximum transmission a.

In the above-mentioned q# Publication No. 55-108995, as mentioned above, it is stated that a silver halide emulsion is developed to obtain the highest blackness fK. The exposure amount must be less than that which causes solarization, and the optical range is limited. Furthermore, in order to obtain the highest black, it is necessary to strictly open the developing conditions.

Firstly, the exposure in the method for manufacturing an optical recording medium proposed by the present inventors can be carried out within the solarization region of the emulsion, and there are also restrictions on blackening of the silver halide emulsion or development conditions. I don't accept it. Therefore, photographic processing becomes extremely easy.

In the above-mentioned Japanese Patent Application Laid-Open No. 55-108995, as mentioned above, silver halide is developed by heat development using a chemical developer or a dry developer so as to obtain the highest blackness. However, it is expected that the higher the blackness, the higher the reflectance after heating.

However, if there is no light in the solarization region, the strong light will not be completely absorbed by the particle surface.
A submerge *1 comes inside. Since surface development is performed with a normal developer, the fa image formed inside does not participate in blackening, so even though the degree of blackening (transmission dl) i) is low, heat treatment j! ! ! In the concentration gradient of silver particles generated later, silver particles #I# near the surface are biased to increase, and the reflectance of the reflective surface increases to a high value due to the concentrated silver component near the surface due to the presence of elemental #. show. This means providing a good optical recording medium. ') Since the mail recording medium uses the reflectivity of the surface to read the notifications, it is desirable that the reflectance be sufficiently high. ζ Next, the first thing to do in the nuralization area is that even with a small amount of silver halide, it is possible to maintain a high reflectance on the reflective surface, and therefore, it is also possible to save silver and save silver. Connect.

...The photographic processing of the rogenized emulsion to turn it into blackened silver is carried out in a developing chamber, using wet chemical dust. The developing solution contains p-phenylenediamine, p-methylaminophenol, and H1 as reducing agents for silver halide.
Doroquinone, 1-7enyl-3-pyrazolidone, trihydroxybenzene, ferrous oxalate, etc., pHI! Contains general additives such as borax, sodium carbonate, sodium borate, sodium hydroxide, etc., and other common additives such as anti-irritating agents such as sodium carbonate, and capri inhibitors such as potassium bromide. Good too.

Dry heat development can also be used instead of chemical deposition. In 11 development, there are various types of materials that are developed by heating the dusty photosensitive thermographic material, but in all cases very mild heating causes development. . The thermally processed material comprises a dust imaging composition containing silver halide grains. By heating, 1!
IL imagers are activated and sometimes use a moisture chamber derived from an emulsion carrier. In addition, after the current salary, if necessary, AgBr
, acetic acid, N*zBO5, sodium thio[I, chromium alum, etc. may be used regularly.

The photo was taken by Rikai Tsuribe, and the emulsion formed with black (L silver) was heated to a temperature of 280 to 380°C in air or at 200°C during collection.
By heating to a temperature WL of 50 to 380°C, heat treatment is performed until the reflective component is deposited on the surface. It is first converted into an emulsion, a dark cherry-red transparent medium. This conversion begins to occur at temperatures as low as 200°C.

More sieve i! At sharks, such as #1aoo°C, the emulsion begins to become reflective within 1 minute. After further heating, the reflectance becomes clearly noticeable on its top surface and is marked I
The jk#i body exhibits a characteristic golden color. Heating i! 1 is 38
When the temperature exceeds 0° C., the recording medium takes on a silver color. Heating I! For fIL, a range whose reflective surface has a golden color is preferred. The heating power method includes convection open type, contact type heat source, and radiant type heating. In the present invention, radiant type heating is preferable.
This is because it is possible to heat the substrate uniformly at speed A, and to more easily program the substrate by minimizing the thermal impact on the substrate.

The uA of the present invention will be specifically explained below using practical examples, but the practical aspects of the present invention are not limited thereby.

Actual Example-1 5AKURA HIGHRgSOLUTION PLA, a photographic plate manufactured by Konishiroku Photo Industry ■, the applicant of this application.
TE (S T T ) t PH0TO5ENSI
The irradiation was carried out at 100 to 2000 CMS using 'rO Evasion TgRMODEL K S-7B (manufactured by Seiki Kogyo Co., Ltd.). High Re5olutio just above
Soak the plate in Sakura CDl-100 liquid (manufactured by Konishiroku Photo Industry) for 5 minutes at 20±0.5°C.
It was subjected to SR and then washed with water at 19-21°C for 30 seconds.

After that, Sakura CFL-X fixed liquid [manufactured by Konishiroku Photo Industry ■]
Soak for 3 minutes at 19-21℃ to fix, then 19-21℃.
It was washed with water at 21° C. for 5 to 10 minutes and air-dried.

After the above photographic processing, a plate sample t1 with blackened silver formation formula was used. .

As a result, as shown in Fig. 1, one exposure f is 400CM &
Above this, the transmittance jI degree decreases by a maximum of # wrinkles. In other words, the Nuralization area of the 4 dry plates used was 4
It was found that it was 00CMII or higher.

The above plate sample was fixed at 310± using a radiation heat fixing device.
Heated at 10°C for 10 minutes. As a result, it was found that the reflectance of the reflective surface generated by heating exhibits a high value in the region where the exposure dose is 400 cMg or more, that is, in the nularization region of the emulsion, as shown in FIG.

For example, 8akura High Re5oluti
On Plate (8TT), the reflectance when 1250cm8Il light is emitted is 15.7%, and the reflectance is 15.7%.
When exposed (ie, in the solarized region of the emulsion), t; In addition,
Reflectance is 557 type dual wavelength spectral straight needle [Hitachi @m]
It was measured using K, and the bond was set at a wavelength of 63 Q nm.

Actual example-2 &akura) figure Re5solution P
For late (υN) sound 1. qte 250cM8 and 20
00CM8e) irradiation amount, and after heating for 1 to 11 minutes, the reflectance was irradiated at a temperature of 31° to 1θ°C. A measurer measured the reflectance of the surface for two wavelengths of type 557 using a meter needle [manufactured by Hitachi, Ltd.].
The equipment using heating VC, development, constant cooling liquid, etc. were the same as those used in the real ring example - IK. The results obtained are shown in FIG.

As is clear from this result, the depth of light is 20,000MI.
9, that is, when exposure in the solarization region is better, even if the reflectance of the reflective surface is changed by 3Jl, the obtained reflectance is constant at a small level, and it is 1!11g for 1 hour. It turns out that it is not easily affected. That is, it can be seen that when exposed in the solarization region, the development time can be easily controlled with respect to the reflectance of the reflective surface.

[Brief explanation of the drawing]

Figure 1 is a graph showing the relationship between exposure amount and degree of transmission, fJ
, Figure 2 is a graph showing the relationship fIk between exposure amount and relative reflectance, and Figure 3 is a graph showing the relationship between current time and relative reflectance.
It is. Patent applicant: Konishiroku Photo Industry Co., Ltd., agent patent attorney
Nobuaki Sakaguchi (1 person) Figure 1! -tX (CMS)

Claims (1)

[Claims] The silver halide emulsion on the substrate is at least exposed to light,
Edges that produce blackened silver using the current process, and reflective components due to heat treatment! A method for producing an optical recording medium according to the present invention, characterized in that exposure is carried out in the nuralization area of the emulsion.