JPS59201052A - Manufacture of cuprous halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain fine particles of cuprous halide crystals extremely rapidly and easily by reducing cupric ions in a hydrophilic colloidal layer spread on a support in the presence of halogen ions. CONSTITUTION:A film formed by coating with a hydrophilic colloid of a hydrophilic polymer contg. cupric ions, water-soluble halogen ions, and at least one of reducing agent is immersed into an aq. soln. of a reducing agent, halogen ions, and cupric ions to execute reducing reaction in a pH of 0-4. Cuprous halide crystals are prepared by controlling halogen ion concn. to >=120 moles per 100 moles of cupric ions, and concn. of the reducing agent to 100-300moles, and adjusting contact time of each component. The reducing agent usable advantageously are sulfurous and nitrous acids, alkali metal sulfite or nitrite, L-ascorbic acid, aminoborane, dialkylaminoborane, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (1) Background of the Invention Technical Field The present invention relates to a novel method for producing photographic materials using cupric halide.

Prior Art and its Problems Conventionally, ordinary silver halide photography has been widely used as a high-sensitivity photography method. The silver halide photography method has many features such as high sensitivity, high quality, continuous tone gradation, and the ability to perform rapid processing or dry processing.

However, in the case of silver compounds using silver compounds as photosensitive substances and image forming substances, or in the case of silver halide color photography, it is generally necessary to use polyelectrode silver because it is used as an intermediate medium for dye image formation. . In response, recovery and reuse of silver have been proposed, but these have only been implemented in some of the above photographic methods due to equipment and other considerations. For these reasons, silver halide photography is generally
It is expensive, and there are concerns about the depletion of silver resources, and the price of silver is soaring, which is a disadvantage of photographic methods that use silver.

Therefore, there is a need to develop a photographic method that uses less silver or no silver at all.

Many non-silver salt photography methods have been reported, but they generally have lower sensitivity than those using silver, and many non-silver salt photosensitive materials cannot produce images with continuous gradation. I can't get it.

Among these non-silver salt photosensitive materials, halogenated photosensitive materials have relatively high sensitivity and can provide continuous gradations.
Photosensitive materials using copper crystals or photographic methods using cuprous complexes are available at Research Disclosure Shop 151.
66.15251.15252. U.S. Patent No. 3,859
, No. 092, No. 3,860,500, No. 3,86
No. 0,501 and No. 3,880,724.

According to these documents, cupric halide crystals and complexes of -valent copper ions are sensitive to ultraviolet rays, and after a sheet coated with these is irradiated with ultraviolet rays, a physical developer, Alternatively, by developing with a chemical developer, a colored image having continuous gradations can be obtained.

As one method for preparing a coating liquid in which photosensitive cupric halide crystals are dispersed in a binder, the following method is disclosed in Research Fist Disclosure A15], 66.

That is, first, as a method for producing cupric halide crystals, R.N.Keller, H.D.
According to the method described in 46), the cupric halide is reduced by the following reaction using sodium sulfite in an aqueous solution of cupric halide, and the halide is converted into a halogenated product. Create a cuprous crystal.

20uX2 +Na2803+)12Q-+2CuX+
Na2s04+2HX In this method, cupric halide crystals are produced in the absence of a substance having colloidal readability, so the crystals become coarse. For this reason, the halogenated crystals are ground in a Dirumill and then dissolved in an organic solvent such as acetate of a polymer compound such as cellulose acetate butyrate or polyvinyl butyrate.
Copper crystal powder is dispersed and this dispersion is applied onto a support to form a photosensitive film.

However, in this method, since the coarse crystals of cupric halide are pulverized to form fine particles, (1) It takes a long time to perform the pulverization process to form fine particles.

(2) The cupric halide crystals obtained by pulverization have a wide particle size distribution, and the gradation of the image obtained by developing the film is extremely soft and lacks contrast.

(3) There are drawbacks such as poor graininess and low color density of images obtained by developing the film.

On the other hand, Antoni Gulecki and Jan Wo
A report by Jfezak et al.
sji Mat Przyrod” Vol.

7 (No. 4), pages 3-12 (1956).

This report states that ``Ou''+ ions can be reduced using sodium sulfite in an aqueous gelatin solution containing copper sulfate and potassium iodide to form OuI crystals, which can be simultaneously dispersed in the gelatin solution. ”.

However, in the method of this report, (1) Especially when preparing cuprous chloride, cuprous bromide, etc., crystals tend to grow easily and coarse particles are easily formed.

(2) Since the cupric halide crystals prepared by this method have large particles and a wide particle size distribution, the cupric halide crystals prepared by this method are dispersed in an aqueous gelatin solution and coated on a support. The images obtained by developing the photosensitive materials suffer from drawbacks such as low contrast, poor graininess, and low color density.

(3) Furthermore, since cupric halide crystals are produced by reducing Cu2+ ions using sulfite, a large amount of sulfur dioxide gas is generated during the reduction reaction, making it an extremely dangerous method.

The present inventors have conducted extensive research on a method for safely and easily producing fine-particle cupric halide, and have
No. 633, JP-A-57-140317, JP-A-57-
No. 154233 proposes a method for producing a fine-grain cupric halide emulsion.

Of these, the first method is copper, bismuth, silver,
Water-soluble polymers such as gelatin containing colloidal particles of metals such as gold, iron, chromium, zinc, tin, orbabut, or sparingly soluble colloidal metal compounds such as copper sulfide, zinc sulfide, silver sulfide, gold sulfide 2, etc. In the presence of a solution, a water-soluble cupric salt (e.g.
An aqueous solution of cupric nitrate, cupric sulfate), a water-soluble halogen salt (e.g. potassium chloride, potassium bromide) and a reducing agent (
For example, sulfites, nitrites.

(L-ascorbic acid, hydrazine, etc.). Alternatively, there is a method of mixing an aqueous solution of a second halide (cupric chloride, cupric bromide) and an aqueous solution of the above-mentioned reducing agent.

The second method uses an aqueous solution containing cupric nitrate or cupric sulfate and silver nitrate, a water-soluble halogen salt (for example, potassium chloride, potassium bromide, potassium iodide), and an aqueous solution containing the above-mentioned reducing agent. This is a method in which the ingredients are mixed in the presence of a water-soluble polymer such as gelatin.

After mixing these, desalination is performed to remove excess salts.
A light-sensitive material is obtained by washing with water, redissolving, etc., coating the material on a support, and drying it.

According to these methods, the cuprous crystals are fine particles and have a sharp particle size distribution, so the gradation is high, the contrast is high, the granularity of the image is good, and the color density is high.

However, these methods require (1) a long time for desalination treatment to remove excess salts after preparing fine cupric halide crystals;

(2) However, even if this method is used for cuprous chloride, which has a high solubility, the crystal particles tend to be larger compared to cuprous bromide and cuprous crystals. There are drawbacks.

■ Purpose of the Invention The main purpose of the present invention is
No. 3, No. 57-140317, No. 57-154233
We have developed a silver halide cuprous photosensitive material that can obtain fine-grain silver halide cuprous crystals very quickly and easily while maintaining the same photographic performance by improving the method proposed in the above issue. The purpose is to provide a manufacturing method.

The present inventors came up with the idea that in order to achieve the above object, it would be sufficient to form fine-grain cupric halide crystals in a binder, and completed the present invention as described below. Ta.

That is, the present invention is characterized in that cupric ions are reduced in the presence of halogen ions in a hydrophilic colloid layer coated on a support to produce fine cupric halide crystals. Do no・
This is a method for producing a halogenated cupric photosensitive material.

■Specific structure of the invention The specific configuration of the present invention will be explained in detail below.

In the present invention, a hydrophilic roller 4 coated on a support is used.
In the presence of halogen ions in layer 13, C
It reduces u''+ ions.

That is, a coating in which one or more of cupric ions, water-soluble halogen ions, and reducing agents coexist with a hydrophilic colloid made of a hydrophilic polymer is coated with one or more of the reducing agents, halogen ions, and cupric ions. The reduction reaction may be carried out by immersing it in an aqueous solution containing.

In this case, the reduction reaction can be carried out in the range of pH ~ 7, but when p) It is preferable to do this.

A preferred embodiment of the method for producing the photosensitive halogenated thermal control material of the present invention includes a method in which a hydrophilic polymer layer coating containing cupric ions is immersed in an aqueous solution containing halogen ions and a reducing agent; ) A method of immersing a hydrophilic polymer layer coating containing cupric ions and halogen ions in a reducing agent aqueous solution, (0) A method of immersing a hydrophilic polymer layer coating containing a reducing agent in cupric ions and halogen ions. (D) A method in which the hydrophilic polymer layer coating is immersed in a water bath solution containing cupric ions and halogen ions, and then immersed in a reducing agent water bath solution.

In these methods, the halogen ion concentration when preparing the cupric halide crystal is as follows:
The concentration of the reducing agent is 120 mol% or more, and
It is effective to control the concentration of each component or the contact time (immersion time) of each component during cuprous crystal preparation so that the concentration ranges from 00 mol% to 300 mol%.

Next, the most preferred embodiment of the method for producing a photographic material of the present invention will be described in more detail.

(I) A sheet having a layer containing a water-soluble cupric compound, a water-soluble halogen compound, and a hydrophilic polymer compound on a support is immersed in an aqueous reducing agent solution to reduce cupric ions, A method of producing a photosensitive halogenated thermal control material.

More specifically, this embodiment is as follows.

For example, in an aqueous solution prepared by dissolving a water-soluble cupric compound, a water-soluble norogen compound, and a hydrophilic polymer compound, the ratio of halogen ion to cupric ion is 100 to
At 400 mol%, a) the ratio of cupric ions from the cupric compound to the hydrophilic polymer is 0.1 to 1.0 (weight ratio)
, preferably 0.2 to 0.5 (same as above).

This is placed on a support with cupric ions of 10 to 100 μ/
It is coated and dried in a conventional manner at a ratio of 2 blood, preferably 15 to 50 cm/2 blood.

Then, this sheet was treated with a reducing agent (for example, L-ascorbic acid, its derivatives, hydrazine, etc.) at 1.0
1 to 1 in an aqueous solution of ~20%, preferably 2.0 to 10%
Soak for 0 minutes, then wash and dry for 1 to 10 minutes.

(n) A sheet having on a support a layer containing cupric ions and a water-based polymeric compound, such as a water-soluble halogen compound (e.g. potassium chloride).

A method for producing a photosensitive halogenated thermostatic light material by immersing it in an aqueous solution containing potassium bromide, potassium iodide, etc.) and a reducing agent to reduce cupric ions.

This embodiment will be described more specifically as follows.

For example, in an aqueous solution prepared by dissolving a water-soluble cupric compound and a water-residual polymer compound, the ratio (weight ratio) of cupric ions from the cupric compound to the hydrophilic polymer is 0.
．． 1 to 1.0 (weight ratio), preferably 0.2 to 0.5 (
(Same as above).

This is placed on a support with cupric ions of 10 to 1007V.
/dl! 2. Preferably, the coating is applied and dried in a conventional manner so that the rate is 15 to 50 m7/ch2.

Then, this sheet is mixed with a reducing agent of 1.0 to 20%, preferably 2 to 10% and a halogen compound of 1.0 to 20%.
Preferably for 30 seconds to 10 seconds to an aqueous solution containing 3 to 10%
What is necessary is just to soak for 1 to 10 minutes, preferably for 2 to 7 minutes, and then to dry.

qm A sheet having a layer containing a reducing agent and a hydrophilic polymer compound on a support is immersed in a solution containing a water-soluble cupric compound and a water-soluble halogen compound,
A method for producing a photosensitive halogenated diluting material by reducing cupric ions.

More specifically, this embodiment is as follows.

For example, ]0 to 100 yq/ctm2, preferably 1
A reducing agent stoichiometrically necessary to obtain a cupric halide corresponding to metallic copper of 5 to 50 Zdr&2, and a cupric halide obtained by a reduction reaction of cupric ions.
An aqueous solution containing a reducing agent and a hydrophilic polymer is prepared so that the ratio (weight ratio) of copper to monohydrophilic polymer when converted to metallic copper is 0.1 to 1.0. Prepare.

The sheet obtained by coating this on a support and drying it is 0.5
Immersion for 30 seconds to 5 minutes in an aqueous solution containing cupric ions at a concentration of ~10%, preferably 1.0 to 3.0%, and halogen ions at a concentration of 120 to 350 mol% relative to cupric ions. Then 1.0 to 10 minutes, preferably 2.0 to 5 minutes
．． Just wash with water for 0 minutes and dry.

(IVI Supports an aqueous solution of a hydrophilic polymer compound) A sheet obtained by coating and drying on a body is immersed in a reducing agent solution, and then immersed in a solution containing halogen ions and cupric ions to form a hydrophilic polymer coating. Method 2 of producing a photosensitive cupric photosensitive material by reducing cupric ions in the medium
This embodiment will be described in more detail as follows.

For example, a hydrophilic polymer solution with a dry film thickness of 3 to 15 μI
The sheet obtained by coating and drying on a support with a thickness of
, preferably 1.0) cupric ions at a concentration of 3.0%,
and immersed in an aqueous solution containing 120 to 350 mol% of halogen ions relative to cupric ions for 30 seconds to 5 minutes, and then immersed for 1-'O to 10 minutes, preferably 2.0 to 5.0
Just wash with water for a minute and dry.

The average grain size of cupric halide crystals obtained by each of the above methods is usually 0.1 to 3 μm.

In the preparation of the photosensitive halogenated heat regulating material of the present invention, the source of Ou''+ ions may include water-soluble inorganic cupric salts such as cupric nitrate, copper sulfate, chloride, etc. Examples include cupric cupric and cupric bromide, and it is possible to appropriately select and use from these.

The source of halogen ions can be appropriately selected from alkali metal halides such as potassium chloride, sodium chloride, potassium bromide, sodium bromide, potassium iodide, and sodium iodide. However, when cupric halogenide is used as a source of halogen ions, there is no need to add an alkali metal halide as a source of halogen ions, but cuprous chloride, copper chloride, When producing a mixed crystal containing two or more types of halides, such as an embodied cupric crystal, an alkali metal oxide may be added depending on the purpose.

The Ou''+ ion reducing agent used in the production of the photosensitive material of the present invention includes sulfurous acid, an alkali metal salt of sulfite, nitrous acid, and an alkali metal salt of nitrous acid.

L-ascorbic acid, L-ascorbic acid derivatives, alase ascorbic acid, alkali metal salts of L-erythroascorbic acid derivatives, hydrazine, phenylhydrazine, triphenyl phosphite, aminoporan, dialkyl amino i-rane (e.g. dimethyl ·amino·
Pollan) etc. are advantageously used.

In the present invention, the hydrophilic colloids in the hydrophilic colloid layer coated on the support include those useful as protective colloids in the preparation of conventional silver halide emulsions, such as gelatin, gelatin derivatives, gum arabic, albumin,
Any of natural polymeric compounds such as agar, and synthetic polymeric compounds such as polyvinylalcohol, pyrrolitone, cellulose ether, and partially hydrolyzed cellulose acetate may be used. I can do it.

In this case, the hydrophilic polymer compound is used at a concentration within a range that can be coated by a conventional method, but is generally used at a concentration of about 3 to 10%.

Furthermore, those used in cupric photosensitive materials such as porous supports such as paper, glass, aluminum, and copper.

Metal plates such as zinc, and tin, or cellulose acetate, cellulose nitrate, cellulose acetate butyrate/(, J Rix terene terephthalate, polystyrene and baryta paper,
Conventional film supports such as resin-treated paper can be used.

The photosensitive material of the present invention, which is composed of a photosensitive cupric halide crystal prepared in a film of a hydrophilic polymer compound applied to a support by the method described above, is photosensitive in a dry state. Research Disclosure l615166 (1976), A15251 (197
6).

415252 (1976), '415959 (1976)
It is possible to develop the image by applying the exposure and development processing methods described in ).

For example, a photosensitive material is immersed in a known developer using a polar solvent such as water, alcohol (methanol, ethanol, etc.), glycol (e.g. ethylene glycol) for 5 to 60 seconds, and then immersed in a wet state for 260 to Perform imagewise exposure with a light source having a wavelength in the range of 450 mμ, and
By developing with a known developer and performing known fixing, a good image with excellent graininess and high contrast can be obtained.

■Specific Effects of the Invention According to the present invention, the method described in JP-A-57-138633, JP-A-57-140317, and JP-A-57-154283, that is, metal colloid particles or poorly soluble A desalination process in which an aqueous solution of a water-soluble cupric salt, a water-soluble halogen salt and a reducing agent solution are mixed in the presence of a hydrophilic polymer solution containing colloidal particles of a metal compound, and then excess salts are removed. Compared to a sensitive material obtained by washing with water, redissolving, etc., and then coating and drying on a support, the photosensitive halogenated photosensitive material can be directly processed in an extremely short period of time.
It is possible to produce a photosensitive material which can form copper and has photographic properties almost equivalent to the photosensitive cupric chloride photosensitive material obtained by the above method.

(2) Specific Examples, Comparative Examples, and Examples of the Invention The present invention will now be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 The following composition was prepared by printing on lighter paper in the usual manner.
A coated and dried sheet was created.

~ Gelatin 5.0fr/Blood 20uBr28.
85 fr/d*2 Saponin 20η/- Formalin (1-o liquid) 1.5 ml/frG
eLThis sheet was added to solution-1 consisting of the following composition for 20 minutes.
℃ for 2 minutes, and then immersed in pure water for 2 minutes to remove soluble salts and dry. This photosensitive cuprous bromide photosensitive material sheet is designated as sample m1.

(Solution-1) When the content of cuprous bromide crystals in this sample was measured using an X-ray microanalyzer, it was found that the content was 2.21 fr/m'' in terms of metallic copper.
The average particle diameter of the cupric bromide crystal particles was examined by electron micrograph XK and was found to be 5±0.06 μm.

Example 2 A sheet having the following composition was coated and dried on baryta paper according to a conventional method.

This sheet was immersed in Solution 2 having the composition shown below at 25° C. for 2 minutes, then in pure water for 1.0 minutes to remove soluble salts, and dried.

This sheet of photosensitive cuprous chloride photosensitive material is designated as sample fish 2.

(Solution-2) When the cuprous bromide content of this sample was measured using an X-ray microanalyzer, it was found to be 2.1% in terms of metal.
As a result of examining the average grain size of polycrystalline particles from electron micrographs, it was found that the content was 0.7 rr/m2.
It was found to be 4±0.08μ.

Example 3 A sheet having the following composition was coated and dried on baryta paper according to a conventional method.

This sheet was immersed in the reducing agent solution (solution-1) used in Example 1 at 20° C. for 3 minutes, then in pure water for 2 minutes to remove soluble salts, and then dried. This photosensitive cuprous chlorobromide photosensitive material sheet is designated as sample N113.

Regarding this sample, the composition of the cupric dihalide crystal was investigated by elemental analysis, and the result was that O4-: 65 mot%, 13
r-: 35 mot%, and as a result of measuring the cuprous halide content in the film using an X-ray microanalyzer, it was 2059 r/m in terms of metallic copper.
Furthermore, as a result of examining the average grain size of the polycrystalline particles using electron micrographs, it was found that the polycrystalline particles contained 0.63±0.
It was found to be 0.06μ.

Example 4 A gelatin solution of Ou (NO3)2 was coated and dried on 29242 paper according to a conventional method to prepare a sheet having the following composition.

This sheet was immersed in Solution-3 having the following composition at 20° C. for 3 minutes, then in pure water for 1 minute to remove soluble salts, and dried.

This photosensitive cuprous chlorobromide photosensitive material sheet was designated as Sample No. 4.

(Solution-3) The halogen composition of the cupric halide crystal of this sample was investigated by elemental analysis, and the result was cf; 51 mot%.
Br-: 49 mot%, and as a result of measuring the cuprous halide content in the coating using an X-ray microanalyzer, it was 1.9 t in terms of metallic copper.
Furthermore, as a result of examining the average grain size of crystal grains using electron micrographs, it was found that the average grain size of crystal grains was 0.6
It turned out to be 2 Shiho 07μ.

Example 5 A sheet having the following composition was coated and dried on baryta paper according to a conventional method.

This sheet was immersed in Solution-4 having the composition shown below at 20° C. for 2 minutes, then in pure water for 2 minutes to remove soluble salts, and then dried.

This photosensitive cuprous chloride photosensitive material sheet was designated as Sample No. 5.

When this sample was measured for cuprous chloride contained in the gelatin coating using an X-ray microanalyzer, it was found to be 52-10 fr/rr in terms of metallic copper. The average grain size of the crystal grains was examined using electron micrographs and found to be 0.8±0.09μ.

Example 6 A sheet having the composition shown below was prepared by applying an aqueous solution of L-ascorbic acid/gelatin on baryta paper according to a conventional method and drying it.

This sheet was immersed in Solution-5 having the following composition at 25° C. for 3 minutes, then in pure water for 3 minutes to remove soluble salts, and dried.

This photosensitive cuprous chlorobromide photosensitive material sheet was designated as Sample No. 6.

(Solution-5) The halogen composition of the cupric dihalide crystal of this sample was investigated by elemental analysis, and the result was Ct-: 57.4 mo1
%+Br-=41-8 mo1% However, as a result of measuring the content of the Jπ cuprous bromide in the gelatin coating using an X-ray microanalyzer, it was found to be 2.5% in terms of metallic copper.
34tr/rr? Furthermore, as a result of examining the average particle size of crystal grains using electron micrographs, it was found that
It was found to be 0.54 Shiho and 08μ.

Example 7 An aqueous gelatin solution was coated on baryta paper according to a conventional method, and a dried sheet was prepared using the following composition.

Composition This sheet was immersed for 3 minutes at 30°C in solution 6 consisting of the following composition, then immersed in solution 7 for 2 minutes, and further immersed in pure water for 2 minutes to remove soluble salts and dry. .

This photosensitive cuprous chlorobromide photosensitive material sheet is designated as sample m7.

(Solution-6) (Solution-7) Regarding this sample, the halogen composition of the cupric halogenide crystal was investigated by elemental analysis. As a result, 06-865 mo
t%, I-: 128 mot%, and as a result of measuring the cupric chloride iodide content in the gelatin coating using an X-ray microanalyzer, it was 1.51F in terms of metallic copper.
Furthermore, as a result of examining the average grain size of the crystal grains using electron micrographs, it was found that the average grain size of the crystal grains was 0.48 and 07μ.

Comparative example 1 Cuprous chlorobromide crystals were produced using a solution with the following composition.

(Solution-8) That is, while stirring Solution-8 at a liquid temperature of 40°C, Solution-9 was instantly added thereto, and stirring was continued for 20 minutes. Thereafter, desalting and washing with water were performed by the following operations.

As a precipitant, Kao A, To, Utosha Demol N5%
An aqueous solution and a 30% aqueous magnesium sulfate solution were added at a ratio of 1=7 until precipitation occurred. After the precipitate settled by standing still, the supernatant was decanted and 3,000 ml of distilled water was added to redisperse the precipitate.

A 30% aqueous magnesium sulfate solution was added again until a precipitate formed.

After the crystal particles have settled, the supernatant liquid is decanted, an ossein gelatin aqueous solution (containing 45 ml of gelatin) is added, and the mixture is dispersed by stirring at 40°C for 30 minutes.
It was adjusted to 00-.

As a result of examining the polycrystalline grains of this emulsion using electron micrographs, the average grain size was found to be 0.6±0.07 μm. Elemental analysis of this emulsion revealed that the halogen composition of the cupric dihalide crystals As a result of investigating, O6-: 73.7
mo1%, Br-: 26.3 mo. For this cuprous chloride bromide emulsion, the ratio of gelatin to cupric chloride bromide was set to 4:1, and an emulsion solution was prepared so that the gelatin concentration of this emulsion was 59I; Is the coating amount of cuprous oxide 2.0 Yr/tr in terms of metallic copper? It was applied on Nono Writer paper so that

This photosensitive material was used as comparative sample m1. Comparative Example 2 Using two liquids with the following composition, 0uBrl crystals were
L'AM-frZM L*, .

(Solution-IO) , 1 (Solution-1
1) Add solution-11 instantly while stirring solution-1O,
The temperature during the reaction was maintained at 40°C and stirring was continued for 10 minutes. After that, the above Comparative Example-1 was washed with water.

A treatment similar to the desalting treatment was performed.

After washing with water and desalting, an aqueous ossein/gelatin solution (containing 40 tr of gelatin) was added, kept at 40°C, stirred for 30 minutes to disperse, and the total volume was adjusted to i, oo with distilled water.

Adjusted to me.

When the polycrystalline grains of this emulsion were examined using electron micrographs, the average grain size was 0.4±0.06μ, and the halogen composition of the cupric dihalide crystals was examined using elemental analysis. Br-.

91, 6 mot%, knee: 8.2 mot%.

Regarding this copper emulsion, gelatin vs. copper emulsion
The copper ratio is 4:1, and the gelatin concentration of the emulsion is 5:1.
%, and coated on baryta paper so that the coating amount of copper cupric was 2.0 fr/rrl in terms of metallic copper. This photosensitive material was designated as Comparative Sample Pigeon 2.

Examples Experimental Examples 1 to 7 and Comparative Example 1.2 prepared halogenated thermostatic light materials (Samples m1-N17, Comparative Samples
, m2) in a developer having the following composition at 20°C for 30 seconds, and then passed through a light wedge using a light source with ultraviolet rays in the range of 260 to 420 r1m to 10' erf/
CR! After exposure to light of
It was developed for 2.7 minutes at ℃. After that, a fixing and washing treatment was performed.

[Developer]

[Fixer] The results of senmidometry are shown in Table 1.

From the results shown in Table 1, when compared with the conventional production method of cupric halide emulsion according to the previous proposal, according to the present invention, it can be produced by an extremely simple method, and it is almost equivalent to this method. It can be seen that the photographic performance is shown as follows.

Applicant: Konishiroku Photo Industry Co., Ltd. Agent Patent Attorney Yo Ishii -

Claims (1)

[Claims] 1. Halogenation characterized by reducing cupric ions in the presence of halogen ions in a hydrophilic colloid layer coated on a support to produce fine-particle cupric halide crystals No. 1 - Method for producing a thermostatic light material.