JPS59195232A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material having superior developability and maintaining its photographic performance for a long term until it is used after manufacture by forming an emulsion layer contg. silver halide particles whose surface parts are practically made of silver chloride and gelatin having a specified Vogel's reaction value or below. CONSTITUTION:A black-and-white, monochromatic or polychromatic photosensitive silver halide material is obtd. by forming one or more emulsion layers contg. core-shell type silver halide particles whose surface parts contain >=90mol% AgCl and gelatin having <=20 Vogel's reaction value purified by oxidation treatment or other method. It is preferable that the silver halide particles have <=1mum relatively uniform particle size. A harmful compound of Cd, Pb or the like is not required to be added to the emulsion, the resulting photosensitive material has high sensitivity and can be preserved for a long term until it is used after manufacture, and a high contrast image with little fog is formed.

Description

[Detailed Description of the Invention] ■ Background Technical Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically to a silver halide photographic material that has been improved to maintain and exhibit stable photographic performance from the time of manufacture to the time of use. This invention relates to silver halide photographic materials.

Prior art and its problems Silver halide photographic materials are capable of recording information with high sensitivity and high density, and are easy to use. Improving the quality of silver oxide photosensitive materials throughout the transportation process and making handling easier;
Improvements have been made to simplify the development process, making it easier for users to use.In the case of silver halide photographic materials for printing, the development process time has been shortened and the number of processing steps has been reduced. Efforts have been made to simplify the development process by introducing automatic development systems, etc., and productivity improvements are being made to accommodate large-scale development processes in large-scale photofinishing laboratories.For example, in color printing. Development of paper (in this case, the development time is shortened by using resin-treated paper as the support, and the development process is reduced to a two-bath process of color development and bleaching, as described in 7i) On the other hand, automatic processing machines are also becoming space-saving and odor-saving.
The productivity of the entire system in large-scale laboratories has been greatly improved by converting it to a 3-type model.

In response to the increasing demand for silver halide photographic materials, improvements are being made in the productivity of large-scale laboratories. Small-scale laboratories such as Tokomu 11 In-Store Labs, where processing is carried out directly by Tokoro and film/JS stores, have appeared, and the so-called amateur photographers have become less popular.
As there is a growing trend for photo enthusiasts to enjoy developing themselves, there is a need for a developing processing system that is different from the traditional intensive processing in large laboratories.
Koi 1. Accordingly, it has become necessary to improve silver halide photographic materials themselves.

Silver halide color photographic & optical materials for printing, especially color photographic paper (1) High sensitivity is required to produce large quantities of prints in a dog lab.

For this reason, the content is 1. The silver halide used is generally iron chlorobromide or silver chloroiodobromide, which has a high silver bromide content. However, silver halide with a high silver bromide content has lower development activity than silver halide with a high silver chloride content.
In order to develop sufficient photographic performance, it is necessary to activate the processing by increasing the intensity, pH, temperature, etc. of the processing solution, such as a color developing solution, used in the processing.

For this reason, maintaining the composition of the processing solution is considered to be the most important point, and small laboratories and photography enthusiasts (such as those involved in developing processing) often have to perform very complicated operations to maintain the composition of the processing solution. Total destruction is eliminated, and the stability of the development process is 4.

Therefore, one of the universal methods to increase the stability of the development process is to use silver halide photographic materials (which have many silver chloride-containing chains with excellent development characteristics). In this case, in order to maintain good stability of photographic performance such as sensitivity, gradation, and fog (so-called shelf life) when the halogenated photosensitive material is stored in the state before exposure. Up until now, it has been done to stabilize photographic performance by incorporating cadmium, lead, etc. into silver halide, but in recent years there has been a trend toward not using cadmium because it is harmful to the human body. However, if silver halide containing no cadmium and mainly composed of silver chloride is used, it causes a serious problem in that the stability of photographic performance is impaired during the production of silver halide photographic materials.Installation, silver halide grains It is common practice to store a silver halide emulsion in which a silver halide is dispersed in a hydrophilic binder such as gelatin in a refrigerator, or to store a coating solution prepared by adding a coupler dispersion, etc. to this silver halide emulsion. L, but that's it.
As a result of research, it became clear that the storage stability of photographic performance under storage conditions, that is, the storage stability of the emulsion set and the stability of the coating solution, was significantly impaired. bL presence and application Y
It is extremely difficult to maintain good reversibility.

11 Objects of the Invention Objects of the present invention (-) exhibit excellent stability during manufacturing (emulsion set storage, coating ridge stagnation, and fresh storage), and excellent development processing stability; To provide a silver halide photographic light-sensitive material which can maintain stable image quality from the time of manufacture to the time of use.

The above-mentioned object of the present invention is to provide a support with at least one layer of silver halogenide grains whose surface layer portion consists essentially of a chloride value and gelatin having a Vogel reaction value of 20 or less. DETAILED DESCRIPTION OF THE INVENTION The silver halide photographic light-sensitive material of the present invention comprises a silver halide photographic material having an emulsion layer (photosensitive material).
Silver halide grains (hereinafter referred to as silver halide grains) and gelatin with a Vogel reaction value of 20 or less (hereinafter, this gelatin will be referred to as the gelatin of the present invention). ) that contains
Any material having at least one silver halide emulsion layer (hereinafter referred to as the silver halide emulsion layer according to the present invention) is sufficient, and the silver halide photographic light-sensitive material of the present invention may be used as a silver halide emulsion layer of the present invention. The number and order of layers of the halogenated (silver emulsion layer), silver halogenated emulsion layer and non-photosensitive layer, such as the intermediate layer, reef protection layer, filter layer, backing layer, etc. There is no limit to this.Actually, Ming's silver halide photographic light-sensitive materials are single-color/silver halide photographic light-sensitive materials, but they are multi-color silver halide photographic light-sensitive materials. In order to achieve normal color reproduction, a single layer or several layers of each of the 11-11 sensitized yellow caddies, a rogenated emulsion layer, and a Mazenk coupler are applied on the support. A silver halide color photographic light-sensitive material having a green light-sensitive silver halide emulsion layer and a red/1 & light-sensitive silver halide emulsion layer containing an O nitrogen coupler is included. Examples of materials (in particular, one layer, or two or more percent of the layers of these blue, green, and red-sensitive silver halide emulsions are halogenated according to the present invention) Although it is considered to be a silver emulsion layer,
In order to achieve the object of the present invention, it is preferable that all 11 of the blue, green and red-sensitive silver halide emulsions Jq11 are silver halide emulsion layers according to the present invention.

The silver halide grains according to the present invention may be single-shot or polydisperse, normal crystal or twin crystal, and any ratio of +1001 face to (iiiH face) can be used. Also, neutral method, acid method, ammonia method,
It may be manufactured by any method such as a forward mixing method, a back mixing method, a double jet method, or a Chondrald double jet method, and is usually laminated with silver halides having different compositions. -1 may be a so-called core/shell type non-rogenized particle. The shape of the silver according to the present invention may be a hexahedron, an octahedron, a tetradecahedron, a combination of these shapes, an amorphous irregular shape, a spherical shape, etc. The size of 0, which may be 0, is selected as appropriate depending on the specific usage form of the halogenated complex photosensitive material according to the present invention, and is not particularly limited. However, silver halide grains having a relatively uniform particle size of 1 μm or less are preferable, and more preferably, the grain size is 0.1 to 0.8 μm, and even more preferably 03 to 0.6 μm.・It is a silver halide grain.

At least the surface layer portion of the halogenated pocket grains according to the present invention is substantially composed of silver chloride means that almost the entire surface layer portion of the silver halide 1 group according to the present invention is 90% by molar 6 fraction.
This means that it is composed of silver chloride containing more than a mole of silver chloride. The amount of this surface layer portion is preferably 5% by weight or more based on the total amount of silver halide grains according to the present invention. If the particle diameter is less than 5, the interior of the silver halide grains is composed of silver halide with low development activity (this is because the object of the present invention cannot be fully achieved. The silver chloride government-owned J1t on the surface layer is
90 mol of the silver halide photographic light-sensitive material of the present invention is undesirable because it deteriorates the development progress and reduces the stability of the development process. As mentioned above, the surface layer portion 6 of the silver halide grains according to the present invention may be a silver halide containing 90 moles or more of silver chloride. Usually (in addition to chloride, odor fl, tjJ and/or silver iodide are added as components of silver ohalide, and the silver halide in the surface layer becomes silver chloride,
Silver chlorobromide, silver chloroiodobromide, or these silver halides are appropriately added with iridium salts, rhodium salts, etc. for the purpose of improving high-intensity short-time exposure characteristics and increasing contrast. This is what I did. When the surface layer part is silver chloroiodobromide (moss, the content of silver iodide is 1 moleφ in mole percentage)
It is preferable to do the following because the development and processing stability will not be affected by J:Li. Further, the silver halide composition of the silver halide grains other than the surface layer portion of the silver halide grains according to the invention can be selected arbitrarily, and may be the same as or different from the silver halide + ffl composition of the surface layer portion. ,
Silver halide grains according to the present invention may have a composition of +1, such as silver chloride, +4" silver chloride, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide. type)-logenization ψ6
If it is an i particle, the entire shell is covered with a surface layer of 15
In this case as well, it is necessary that almost the entire area of the shell contains silver chloride with a molar concentration of 90 or more, and 4. It is preferable that f' is 1' or more than 5 i1 of the total amount of silver halogenide grains. One embodiment of the silver chloride grains according to the present invention is a chloroiobromide grain containing 90 moles or more of silver chloride, which is prepared by emulsifying and mixing without containing cadmium or lead salt. Silver (preferably the silver iodide content is 1 mol φ or less) and, for example, from silver chloride to silver bromide, and further from silver bromide to silver iodide, which is less soluble. When a core consisting of silver halide grains converted to silver halide is further laminated with silver halide (containing 90 moles or more of silver chloride) as a shell, a Wll conversion core/shell type nologen is formed. Examples include silver oxide particles, but of course they are not limited to these.
It's not something you can do. These modified core/shell type silver halide grains can be prepared, for example, by the method described in Japanese Patent Publication No. 55-42740, etc., or by the method described in Japanese Patent Publication Nos. 51-15423 and 53-75921. No. 56-78831, etc. (by applying the method 5 for preparing silver halide photographic emulsions described therein,
- It can also be prepared by changing silver chloride to one consisting of brocade chloride.

The gelatin according to the present invention has a Vogel reaction value of 20 or less, and the Vogel reaction value is [
Photographic gelatin test jj4”j method baggy method” 5th edition, photographic gelatin test method same number iW Shikikai Chirui 1, +rU
It refers to the Vogel reaction value that can be measured by the method specified in detail in 10/2010, p. 21. Gelatin that can be maintained in a non-flammable state can be obtained by, for example, oxidizing ossein gelatin, hydroceratin (including big skin seratin), etc., to make the Vogel reaction value 20 or less. The oxidation treatment was performed using pre-isolated ossein gelatin and hydrogelatin '7.
F'F, e.g., hypercough and water stress, A°pusin hyper1v111
：It has imitation effect such as 1 installation etc.
This can be easily done by touching + and 7. The compound having the oxidizing effect is 'C(1, acid f
If we consider the stone treatment after treating the decomposition by-product of the ls proboscis, ceratin, or the pollution prevention treatment of the waste fluid, j7.
It is preferable to use hydrogen tetroxide or ozone. Seratins such as ossein gelatin and hydroceratin, which are irritating, should be treated with alkali!% IEk
Processing How many extraction processing methods such as 6271IjV111 (
1. It's okay to wait.

For general properties and manufacturing methods of Serachi, see The Theory of Photographic Process, 4th Edition (
te r- aite james ft.

1' (Jarncs), Macmillan Publishing, 197
7th edition) pp. 51-76, and The Science and Technology Manbu Gelatin (Nie G. Ward + A, G.

Ward Irney Cora (A, Courtf.
I), Academic Press, published in 1977]2
It is described in detail on pages 95-365. In this paper, purification methods such as peroxide ice water, diluted nitrile solution, and ion exchange treatment to remove photographically harmful impurities contained in seratin, as well as a method to highlight gelatin coloring, are described. ing.

However, even with these methods, photographically satisfactory gelatin i1 cannot be obtained. Due to advances in silver halide photographic emulsion technology, in recent years there has been a demand for gelatin to be more inert, and gelatin that meets these demands can provide photographic materials that are stable and have less variation. It is becoming more and more common. However, even if inert gelatin, which is said to be extremely stable in silver halide emulsions, is used, the surface layer remains substantial!・For the silver halide grains of the present invention, which are silver chloride, the above-mentioned emulsion set storage stability and coating solution stagnation property are unmatched at 1S4, and this is far from practical. The above-mentioned book by James and Ward et al. does not suggest the effects of the combination of the silver halide grains of the present invention and the ceratin of the present invention. This effect was completely unexpected even by those skilled in the art. Ceratin for photography generally has a Vogel reaction value of 50 to 50.
70, and even gelatin called an inactive type has a Vogel reaction value in the range of 30 to 40 (this can be clearly distinguished from the gelatin according to the present invention). Obviously, the lower the value, the better, since the preservation deteriorates.In the present invention, by using gelatin with a Forkel reaction value of 20 or less, the effect of the present invention is significantly improved, and it is possible to put it into practical use. It has become a

The molecular edge of the gelatin according to the present invention is 50,000 to 3
．． 000,000, and the amount of free sulfur contained is preferably 20 μg or less per gelatin ry.

In order to obtain gelatin according to the present invention (when using oxidation treatment, this color removal treatment may be performed during or between any treatment steps after seratin is extracted from the raw material, but it may be performed before drying). This is preferred.It is also possible to carry out this process after drying and during dissolution before adding to the silver halide emulsion.

The method for producing gelatin according to the present invention is illustrated below,
There are no limits to this.

Gelatin A (hereinafter referred to as Ge1-A) Inactive type ossein gelatin (hereinafter referred to as Ge1-O) IQ obtained by an alkali treatment method was dissolved in 157 warm water, and 10% hydrogen peroxide solution 25- was stirred. The mixture was added at the same time and reacted at 40°C for 5 hours. Next, add a small amount of 1 strip of sub-partial sodium chloride bath solution and dissolve in excess hydrogen peroxide. Neutralization point (・Take out a part of the hagelatin liquid and perform an iodine reaction (
It was 4'lBg more than this. This gelatin solution was passed to an ion exchange resin, concentrated in a conventional manner, and dried to obtain 840 g of dry gelatin.

Gelatin B (hereinafter referred to as Ge1-B) Hydrogelatin (hereinafter referred to as Ge1-H) by alkali treatment method 1
Dissolve 9 in 15r warm water, add sodium hydroxide solution to adjust the PL (II!': J8), add 25ml of 10% peroxide-based water with stirring, and boil at 40°C for 2 hours. Next, acetic acid was added to the reaction solution to adjust the pH to about 6.5, and the gelatin solution was passed through an ion exchange resin, concentrated in a conventional manner, and dried to give 85% dry gelatin.
Obtained 0g.

Gelatin C (hereinafter referred to as Ge1-C) Big skin gelatin (hereinafter referred to as Ge1-
(called P) lK9 is 51! After dissolving in warm water,
The same method used to obtain Gel-A
Dry gelatin B5oy8 was obtained.

Gelatin D (hereinafter referred to as Get-D) Gel-02
After dissolving 00g in 4F warm water, ozone was generated using Yamato Scientific (medium-broken ozonizer model 0N-11), and the gas was introduced into the gelatin solution through a silicon tube for 2 hours.Then, the gelatin solution was ion-exchanged. resin l
This was followed by concentration and drying to obtain dry gelatin 900).

The Vogel reaction values of the gelatin according to the present invention thus obtained and the gelatin used as a raw material were measured by the baggy method described above. The results are shown in Table 1.

Ceratin according to the present invention can be mixed with other known hydrophilic compounds to form a silver emulsion layer containing the present invention. As a hydrophilic binder, gelatin such as the aforementioned ossein gelatin and tamed gelatin, acylated gelatin, guanidylated gelatin, carleno (mylated gelatin),
Gelatin conductors such as cyanethanolated gelatin and esterified gelatin, colloidal anolbumin, agar,
Gum arabic, Textran, alginic acid, cell one-course dielectrics such as cellulose acetate containing acetyl groups and hydrated to 10-20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol - vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinylamine acetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, obtained by polymerization of protein or saturated acylated protein zf with monomers having vinyl groups; Rai 1. Polymers such as polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate and polyethyleneamine are commonly used. Non-invention (contained in the silver halide emulsion layer) 1.
It is preferable that the amount of gelatin according to the present invention is at least 15M, and more preferably at least 25% by weight, relative to the total amount of the hydrophilic binder including the seratin according to the present invention. The greater the amount of gelatin involved, the more the effects of the fundamental invention can be obtained.

The present invention Q When adding gelatin according to the present invention (45 to Already added at the time of formation, or added to the gelatin for dispersion (or added to the silver halide emulsion W1 and stored as a set? Seratin for use as an additive and additives such as additives (for coupler dispersion, etc.) are added, and a liquid is prepared. Any number of "L" may be used, such as (preferably, the silver halide used in the present invention is 1"/l)
It is advantageous to add 'j, δ water as a dispersing gelatin when dispersing the silver halide grains when 1≧+.
(preferably silver halide holes according to the present invention while maintaining contact with silver halide grains according to the present invention) fl
Adding gelatin as a dispersing gelatin that can remain in J
It is advantageous that the silver halide emulsion according to the present invention contains a hydrophilic binder containing silver halide grains 43 and gelatin according to the present invention. The halogen according to the invention (zg) I am impressed by the characteristics of the 11 layers of breasts, color sensitivity, sensitive limbs, etc. The present invention (this invention is 15 years old)
:/f',, for the invention, halogenation <":1xoo
It is desirable for RJ to use 15 parts by weight or more of the gelatin according to the present invention per part of the silver halide emulsion layer according to the present invention (in this case, 25 parts by weight or more). Wipe the hydrophilic 11 binder containing gelatin according to the present invention. Childish.

An uninvented silver halide photographic material (14 pieces)
It is a mistake to add various additives to the silver halide emulsion layer and other silver halide emulsions. The optical sensitizers used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines,
Steryls, holoporacyanins, hemicyanins,
Contains oxonols and hemioquinols,
These optical JFI sensitizers contain a basic group such as thiazoline or thiazole, or a nucleus of rhodanine, thiohydantoin, oxazolidinedione, barbylic acid, thiobarbital acid, or pyrazolone as a nitrogen-containing nitrogen-containing nucleus. These nuclei are preferably fi-1 substituted with an argyl group, hydroxyalkyl group, sulfoalkyl group, carboxyalkyl group, halogen atom, phenyl group, soano group, or alkoxy group, and are fused with a carbocyclic or pseudocyclic ring. It's okay to say szz 'C. Further, in the silver halide emulsion F4 i3 and other silver halide emulsion layers according to the invention, female fixing agents which are usually used, such as (flZ compound having an azaindene ring, a heterocyclic ring having a mercapto group), etc. It is possible to partially contain compounds, etc.

As a compound having an azaindene ring, (・1,4-hydroxy-6-methyl-e, 3.3a + 7-tetrazaindene is preferable. 2.4"lJ azole ring, "+2+3) lyazole ring, 1, 3, 4-
Thiadiazole ring, 1,2,3-thiadiazole, L
11.2.4-thiadiazole ring, 1,2.5-thiadiazole Jjit, 1,2,3.4-tetrazole ring,
Pyridazine ring, L, 2.3-triazine ring, 1,2.4
-1-Ryazine ring, '+3,5-tri)azine ring, a butterfly in which 2 to 3 rings such as this L are condensed, such as triazolotriazole ring, diazine unbu, triazaindene, tetrazaine DenjJJ, Pentazainten Bu, etc.
Compounds containing a phthalazinone ring, an ink sol, etc. are also more effective, but 1-phenyl-5-mercaftotetrazole is better.

In addition, in the silver halide photographic sensory material of the present invention, C1
7 testimonials used depending on the purpose (7 te (J, example (
J1 dihydroxyalkane is impregnated, and furthermore, the membrane's mobility (Tomoyoshii'': ・J and some (, 1, taU is a combination of flutyl acrylate or alkyl methacrylate and acrylic group). [) L/ < jx Copolymer with methacrylic monomer, styrene-malein j,'\ co-tripolymer, obtained by milk polymerization of styrene anhydride maleic half alkyl ester copolymer 9. Filtration Dispersible imitation particulate commercial molecular substances, etc. are included.Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers,
pH adjuster, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant, brightener, development rate regulator,
It is optional to use matting agents, anti-irradiation dyes, etc.

When the halogenated photographic light-sensitive material of the present invention is used for color use, it is preferable to use a coupler.

The yellow couplers used in the present invention include benzoylacetanilide type, pivaloylacetanilide type, and so-called split-off couplers in which the carbon atom at the single force springing position can be released during coupling (1). Two-dimensional yellow couplers substituted with groups are useful.

Magenta couplers include 5-pyrazolones, pyrazolotriazoles, pyrazolinobenzimidazoles,
Indashilon type or 2-equivalent type Mazenk force dollar having LC split-off group is useful.

Useful cyan couplers include phenolic, naphthol, virazoquinazolone, and 2-equivalent cyan couplers having a split-off group.

Any of these couplers can be selected, and there are no particular restrictions on the method of use or valve ξ5, but
Usually, according to the present invention]・per mole of silver halide,
It is preferable to use the coupler in a proportion of 0.1 to 0.4 mole.

The silver halide photographic light-sensitive material of the present invention has a color for diffusion transfer that releases a diffusible dye in response to the development of silver halide (two donor substances are combined to form a desired color on an image-receiving material during an appropriate development process). It can also be used to obtain a transferred image.As such color image-providing blade materials for diffusion transfer, U.S. Pat. No. 3,227,551 and U.S. Pat.
No. 3,443,939, No. 3, 443.

No. 940, No. 3,658,824, No. 3,698,8
No. 97, No. 3.725,062, No. 3,728,11
No. 3, No. 3,751,406, British Patent No. 840,
No. 781, No. 904, No. 364, No. 1.

No. 038.331, West German Li'r License Publication (OLS)
No. 1, 930.215 @, No. 2,214,381, No. 2,228,361, No. 2,242゜762,
Those described in No. 2,317,134, No. 2,402,900, No. 2゜406.606, No. 2,406,653, JP-A-49-114424, etc. can be used. .

In addition, when forming λ on a color image, in order to prevent fading due to short-wavelength activation of the π-dye image, ultraviolet absorbers such as thiazolidone, benzito-1-nosonopair acrylonitrile, etc. , the use of the benz°phenone system A↑′ snout-section is for A1. l Samurai (Kochinupin P
S, 120, 320, 326, 327, 32
It is advantageous to use 8 (all manufactured by Ciba Geigy) alone or in combination with J.

In addition, it is self-evident) ``Rogonka Ginshashi'' [Kangen Jun-Ishi no Tani 4, ・Isei Heu (・Go, Ren 7 5) 1 ■ Child Jishi'':
AU 4jμ (I, sa-; can be measured. As a hardening agent (J, Chrono, salt, zirconia, aldehyde-based, such as formaldehyde and Mukono 10 Genshi).
・Hard materials such as lotriazine type, polyethylene/compound, ethyleneimine type, vinyl sulfone type, acryloyl type, etc.
You can also use a laxative.

In addition, the uninvented No.
On the support (according to the present invention) - Halogenated fi containing a halogenated emulsion layer ('i emulsion 7, filter single layer, intermediate layer, protective layer, undercoat layer, Kitsunehiki J/5) - 2. Coat the coating of the coating/r of the non-light coating layer such as the ration prevention layer.

Halogenated photographic material of the present invention (J, black and white general use,
For X-ray, for color, for 2 colors, for printing, for infrared,
It can be effectively used for various applications such as micro-
F n'F "ir; 3 + 087 + 817,
6, 7a, iss.

No. 567 and No. 2,983,606, Weyertz et al., U.S. 7. ) 7 Patent No. 3,253,915, Whitemore et al., U.S. Patent No. 1, No. 3,227,550, Pearl et al. i pm no. 3,227゜552;
U.S. Pat. No. 3,415,644 to Biyo and Rand, '
AE 3 + 415 + No. 645 Oyohi same l:p;
As described in No. 314151646+c sd, silver halide photographic materials such as l'f color image transfer methods such as color diffusion transfer method and absorption transfer method can also be applied. In particular, silver halide emulsions, coating solutions, red-sensitive silver halide emulsion layers, green-sensitive silver halide emulsion layers, J5 and positive silver halide emulsion layers in silver halide photographic light-sensitive materials with an exposure of 1ifJ are used. The fact that there is little disruption of the color balance of each dye image is useful as a silver halide photographic light-sensitive material for colors where i>i knee 2&.

As a support on which 1 layer of the silver halide photographic light-sensitive material of the present invention can be applied (any material can be used, a typical support is made of bamboo), Supports (transparent and It may be white and opaque.

(2) Specific Uses of the Invention The silver halide photosensitive material of the present invention thus constructed can be normally used, for example, as a developing treatment, such as imagewise exposure.1. 4S development can be carried out by a known method.

When the silver halide photographic light-sensitive material of the present invention is a silver halide black-and-white photographic light-sensitive material for general black-and-white use, preferred black-and-white developers that can be used in the development process include fi, polyhydroxybenzenes such as hydrochlorinone, As a specific compound of black and white 1-nano phenols, 3-pyrazolidones, ascorbic acid and its derivatives, etc.
Go,/hydroquinone, aminephenol, N-methylaminophenol/L/, 1-phenyl-3-big lJ
Examples include phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, and ascorbic acid.

Rodin 1 silver photosensitive material of the present invention can be used in color developing solutions that are halogenated <tlti color photographic material system. Preferable color development system (G, aromatic first
The main component is raw mulberry.
-phenylenediamine, diethylamine-〇-toluidine, 4-amino-3-methyl-N-ethyl-N-(β-
methanesulfonamidoethyl)aniline, 4-amino-
3-Methyl-N-ethyl-N-1β-hydroquinethyl+7=phosphorus etc. are thickly distributed.

The black-and-white and color development liquids (-1, furthermore, t time-determined) may contain an inhibitor and a development inhibitor. These developer additives are optionally incorporated into the layer film of the photographic light-sensitive material.
You can leave it there. Commonly useful antifoggants include (6-benzotriazoles such as 5-methylbenzotriazole; benzothiazoles; 1-phenyl-5-
Futazan stock thiones such as mercagutotetrazole;
Aromatic and aliphatic mercagutoflZ compounds and the like are included. The developer may also contain a developer accelerator such as a realkylene oxide derivative or a quaternary ammonium salt compound.

Thus, after or before the white development or color development, the silver digenide photosensitive material of the present invention (
This involves the usual processing steps selected from mining, fixing, white fixing/J, water washing, stabilization, hardening, neutralization, reversal, stopping, rinsing, and drying. It is also possible to perform a combined process with color development.

■Specific effects of light Ljij Silver halide photographic cup of the present invention 1. j. Without the use of cadmium, lead, etc. that were conventionally added to helokenized steel emulsions containing silver chloride as a main component, the set storage stability, Uta 58i stagnation and raw storage stability of the silver halide emulsions are improved. 1t, and silver halide hole f whose main component is silver chloride.
f1i (when i is used, the decrease in stimulatory activity can be reduced to less than or equal to C, and the development property is fast) can be used as a silver photographic material.

In this way, the silver halide photosensitive method of the present invention can maintain and exhibit stable photographic performance from the time of manufacture to the time of use, making it ideal for small laboratories and amateur photographers. A good image can be formed even after the development process (・・) From this point of view, silver halide emulsions can be said to have been modified to meet the needs of optical materials. .

vl Specific Embodiments of the Invention The present invention will be described below with reference to specific embodiments.
iy, to clarify, -J! of the present invention! : The mode of travel is not fully limited by this.

Example 1 A bath liquid Al was kept at 65°0, and a bath liquid B and a bath C were mixed at 1O2 by a simultaneous mixing method.
The mixture was poured into portions, mixed, and further aged for 45 minutes.

Next, cool and settle. After removing excess water by washing with water, add pure water to make 6007, and then use vinegar to remove excess water.
The pH was adjusted to 4 and the temperature was raised to 60.0. Next, the bath liquid and the finished h'l E having the following composition were simultaneously mixed by the -r method over a period of 3 minutes, and aged for 20 minutes. 3
+ 38 + 7-thitrazaindene was added and further aged for 75 minutes to obtain an average particle size of 0.4 μ, a core/shell ratio of MS-ratio of 1O/3, and a silver chloride content of the shell of 94
．． A silver halide emulsion containing 5 molar silver halide grains was obtained. Thus obtained silver halide emulsion 1.
The gelatin shown in Table 1 as this dispersed gelatin was 43.3
Add 0.03 f of silver halide and cool.
Five sets of gelatin were separated and stored at 10114" UIFi.

[Bath liquid A]

[Bath solution B] 1 molar concentration of nitric acid 1:2 silver bath solution 500g [Bath solution C] [Bath solution D] 1 molar concentration of nitric acid 12 silver bath solution 150+rLl [solution E
] The silver halogenide emulsion thus stored at a low temperature for 1, 15, 30 and 50 days was redissolved,
A coating solution was prepared by adding the number of couplers in the following formulation, a hardening agent H-■, and Gel-013F as an additional gelatin, and this coating solution was coated on polyethylene laminated paper with a coated silver amount of 0.
．． 411/ηt (the amount of gelatin is 2.09/m). The film was coated in multiple layers and then dried to produce five types of single-color silver halide photographic materials.
5] [Cuffler's solution] 2.4-dichloro-3-methyl-6-(α-2,4-di-tert-(amylphenoxy)butyramide)phenol 2f and 2,5-di-octylhydroquinone 002f were dissolved in ethyl acetate 2πe. The mixture was mixed with a gelatin solution containing 1 metc, sodium dotesylbensene sulfonate, tp, and Gel 0 2f, and protected and dispersed using an ultrasonic method.

[IfjM agent H-1] ti2L:l
UH2 Samples prepared using silver halide emulsions stored at low temperatures for 1, 15, 30, and 50 days were exposed under the following conditions (after exposure in the following processing steps). [Exposure conditions] Using a KS-7 type sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), exposure was performed through a wedge with a density difference of 0.1 O.

[Processing process of development processing]

Temperature Time color development 30±0.5゛0 2 minutes bleach fixing
25±2'01 minute 30 seconds washing 25±5
"0 2 revolutions 80゛0 or less 1 minute 30
Second [Composition of the solution used in the development process] (Color developer) ((Table white fixed sound 7 nights) Thus, the development process was completed. IJ (Fog
l was measured in the following manner. The results are shown in Table 2.

[Includes d river standard]

Sensitivity its+: An exposure meter giving fog (Fogl+a degree of 1.0) was found, the reciprocal of this value was taken, and when the reference sample was taken as 100, four tables were made of the values per eye.

Gradation (γ) Two fogging (Fog) + Intensity 0,25 and fogging (Fog) + D'A L15115 are connected directly, 15! The slope (tanθ) of

Turnip jJ +1'ogl: Not ↑; (Density after development processing of the original part. The density is Sakura Hikari'μ densitometer PDA, -65
(Measurements were made using Konishiroku Photo Industry Co., Ltd.). Here, the reflection density, the transmission density, and the quasi-density (zero point) are measured using the color developer crude drug 4 from the color developer solution. -Amino 3-
Mef/L/-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate salt was removed and the temperature was 41 degrees.

The numbers in Margin Table 2 below indicate the change layer, and in the case of S, the relative value when the S value of the 1st and 1st month is set to 100, and γ and Fog are 1
It represents the difference between the γ value and the Fog value for the sun and moon.

Table 2 shows that the silver halide grains of the present invention (this 1 series) and the present invention (samples 1 to 3 having a halogen extracorporeal emulsion layer containing gelatin are long jtJ). Even when the temperature is increased, the decrease in γ and the increase in Fog are small, and S, γ, and Fog are all stable.

Example 2 Silver halide emulsions identical to those of samples 'i'Fr Nos. 1 and 4 of Example 1 were prepared at θ1, and then this emulsion was
Gel-A and/or Ge1-0 in proportions not shown in Table 3 were added as additional gelatin, and the same coupler solution and hardener as in Sample No. , and the time it takes to apply this coating solution to a polyethylene laminate paper (the time taken to release the coating solution) was 0.5.5.1045 and 20 hours, and the temperature of the coating solution was 40 ± 0.5゛0. pi (I was set as 1), and after coating the halogen ratio silver emulsion layer, gelatin was coated (:
A monochromatic halogen material was prepared by coating in multiple layers so that the amount was 10 g/ba. (Samples 6 to 1 in Table 3)
41 The S and (JF'og values of these samples 6 to 14 are
1jlj>〆 in the same region as column 1, and the result is shown in column 3. K N 6-1" 4 f 50
'Oi trowel 0 days, 2 days and 5 [' between numbers 1 and 'j:
! 211jl "Aged", 9th S, γ and Fo
G□i 瀘 was added to 也11 in the same manner as in Example 1, and A; 棆 and 摆 are shown in Table 3. 1st poem ``O, Frequently''
'! S′l■1 of s +1 and 01 in ioo
When 11" blockade, γ: I3 Yohi FOg I direct is 0th Yang I Yo J Mami 611 f direct, 2nd and 5th"
Sukeai had a baby on 0 days 0-) from fi+i ()) in Meite.

From Table 3 below, in the case of the uninvented halogen-free silver photographic material, the stagnation and shelf life of silver halide emulsions are superior to that of silver halide emulsions by 4t, and iii) The aqueous binder contained in the silver oxide emulsion layer (the specific gravity of the gelatin according to the present invention) The fact that the sex is better than 17Σ is 10l.

Example 3 1 mol. γ1 degree NH4C
lγυ liquid Fpl (6,0 n”A finished 1640m1f
60'O + Kobogar, 0.5 molar AgN
03 Zokuei 1200y+/! was added after 3 minutes and 1fSjy. 600 m of 1 molar N114Br water bath after lO min.
E and 30 πl of a 0.1 mol KI aqueous solution were added and aged for 40 minutes. Next, 600 me of a 0.5 mol AgNOa water bath solution was added to stack silver chloride biological shells to form conversion core/shell type silver halide particles. (X) Change of core due to haze diffraction
It was 6 molti. Also, the composition of the shell
It is a 2 mol strip, and the core/shell ratio is 2/l by weight.
). After that, excess salt was removed by washing thoroughly with water, and after chemical sensitization by adding No. wart and 4-hydroxy-6-methyl-j + 3 + 3 a + 7-titrazaindene, this solution was Gel-A, Ge1-C and i; JG as 3 divided and dispersed gelatin
el-H to 21. 648g was added to. Note that approximately 70% of the gelatin used during emulsification is removed by washing the sediment with water. On the other hand, when laminating shells as a contrasting emulsion, 200+ m of N)I4Br bog solution of 20.5 molar cannonballs! or 4007 force) and 05 molar concentration of AgNO3
An emulsion was prepared using the same strain as above except that Solution M was added. In this case, the composition of the shell (IZ report 4
1 mole ratio, 74 mole ratio. Then, after 1 or 30 days, the thus obtained]-logenated C''Q emulsion was further treated with 4-hydroxy-6-methyl-1,3+3a+7-titrazaindene, mercaptobenzotriazole, styrene-maleic anhydride polymer, as described below. Magenta coupler solution, hardener H-2 below and additional gelatin 'E' A-
Add fJ, l and apply 6 liquids on the undercoated polyester film so that the coating amount is 1゜59/g and the coated gelatin amount is 4.09/bi, and then apply it on this coating/f'i. Coated Gelatin-4, tl, Oy 7771', a gelatin retention layer was coated and dried. (In Table 4, sample 1
5-23) Protected dispersion in Ge 1-0 containing Ge and color stain prevention agent 2,5-Jert-octylhydroquinone dissolved in tricresyl phosphate, dioctyl phthalate and ethyl acetate (C alkanol XC + manufactured by DuPont) What I did.

(4+"Ji Lugo IJ H-2) Samples 15 to 23 thus obtained were exposed and developed in the same manner as in Example 1, and then the emulsion set was stored for 1 day and 30 days. (S, γ and Fog)
Sample 5: Forced senescence S, r and Fog values were measured in the same manner as in Example 1, and the results are shown in Table 4.

In addition, in Table 4, the number of IEs for set preservation and strong 1h (" aging
.

[In this case, the S value is the median value of 61 for the S value on the first day of set storage, and the values other than 11 are relative values, γ and Fog values when the S value on the first day of set storage is set to 100. In other cases, the values are expressed as the difference between the actual measured values.

Below is a margin table 4. In the case of the silver halide photographic materials of the present invention of sample 1 Nos. 15 to 17 from coating 4, the composition of gelatin according to the present invention is triple 11 (compared to sample no. 17, which is the Sample numbers 15 and 16, in which the composition of the gelatin according to the present invention is 75% by weight, are superior in terms of emulsion set storage stability and fresh storage (1%), and the silver halide grains according to the present invention The improvement effect of the combination of ceratin according to the present invention is clearly visible.
Although such an improvement effect is not observed, it is only by combining the silver halide grains according to the present invention and the gelatin according to the present invention that improvements in emulsion set storage stability and raw storage stability are achieved. .

Next, the sample numbers 5.18 and 2 made in the above manner
Each sample of No. 1 was subjected to #i image processing by changing the color development temperature as shown in Table 51 and using the same packaging as in Example 1, and the S and γ values in each treatment were determined as shown in Example 1. Measurements were made in the same manner as in 1, and the results are shown in Table 5 using the case of 30.0'O as a standard.

Public 5 In the table, S's (changeless Hii t) (Go, 30.0-Oiko S
It is expressed as the difference between the relative 1 and γ (variation amount 1 f': t30.Q'0) when 1 shift and minute ioo.

From Table 5, it can be seen that the color development temperature of the photosensitive material of the present invention changes, and the color development temperature changes.
It can be seen that there is little noise change in rIF7<, and that the stability of the development process is improved.

'hT W'F Attachment 7 Copy of Roku Konishi (Mr. Kazuo Wakasugi, Commissioner of the Patent Office of Koka Macashiki Co., Ltd. Patent application dated April 20, 1981, sent by mail 2 Title of the invention Silver halide photographic light-sensitive material 3 Make amendments) Relationship with 11 cases Patent applicant address 1-26-2 Nishi-Shinjuku, Shinjuku-ku, Tokyo 1%
Note (name) (127) Konishiroku Photo Industry Co., Ltd. 4,
Agent 6, engrave the entire statement of contents of the pestle amendment. (No change in content) As shown in the attached sheet.

Claims (1)

[Claims] A halogen halogen characterized by having on a support at least one silver halide emulsion layer containing silver halide grains whose surface layer portion consists essentially of silver chloride and gelatin having a Vogel reaction value of 20 or less. Silver chemical photographic material.