JPS6368837A - Method for developing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of obtaining sufficient sensitivity by a short processing period and enabling to drying for a short period, without remaining a residual color by controlling the amount of an org. substance contd. in an emulsion layer and/or an another hydrophilic colloid layer after processing to <=90wt% that before processing. CONSTITUTION:The org. substance coated as the emulsion layer and the another hydrophilic colloid layer (gelatin, a matting agent, a plasticizer, a synthesized high polymer and another org. substance) is processed by an automatic developing machine in such the way that >=10% of the total org. substances coated before processing flows out during developing-fixing-water washing-drying treatments. Said org. substances may physically flow out or disappear due to the chemical reaction. The emulsion layer and/or the another hydrophilic colloid layer comprises preferably the org. substance which flows out during developing.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a development processing method for silver halide photographic light-sensitive materials, and is particularly suitable for rapid processing, that is, it is highly sensitive with short-time visual processing, and The present invention relates to a technique for improving the drying process, and particularly relates to a developing method for X-ray photosensitive materials.

(Prior Art) In recent years, high-temperature, rapid processing has rapidly become popular in the development process of photographic light-sensitive materials, and the processing time of various light-sensitive materials in automatic processing has been greatly shortened.

In order to achieve high-temperature, rapid processing, we need a developer that can achieve sufficient sensitivity in a short period of time, a photosensitive material that has excellent developability and does not leave any residual color even during short processing times, and dries quickly after washing with water. A sensitive material is required. Many automatic processors have a built-in drying zone, and if the drying properties of the photosensitive material are poor, the automatic processor must have a higher drying capacity. I have no choice but to colander. Furthermore, as a result of the generation of a thermal overheating system, problems such as an increase in the temperature of the room in which the automatic processing machine is installed may occur.

To prevent this from happening, efforts are made to make the drying speed of photosensitive materials as fast as possible. A commonly used method is to add a sufficient amount of hardening agent in advance in the process of thickening the photosensitive material, and to reduce the amount of moisture in the emulsion layer and surface protective layer during the constant development and washing process. This is a method of reducing the water content in the photosensitive material before drying begins. In this method, if a large amount of hardening agent is used, the drying speed lf can be increased accordingly, but by strengthening the hardening agent, development may be delayed and the sensitivity may become low, the covering power may be reduced, and undeveloped halogen Various alignment problems such as delay in fixing speed of silver oxide particles, deterioration of residual color, and increase in residual hypo in the photosensitive material after processing! On the other hand, reducing the water content in the photosensitive material before the drying starts is effective when reducing the amount of water contained in the photosensitive material by reducing the amount of water contained in the photosensitive material by reducing the amount of water contained in the photosensitive material. Hydrophilic low-molecular substances are generally added to prevent dry fog on silver halide grains during the coating process, and removing them will cause fog on the photosensitive material.On the other hand, If gelatin and synthetic polymer substances used as binders for silver halide grains are removed, the amount of binder to silver halide grains will decrease, resulting in so-called high silver.

Reducing the amount of binder has the drawbacks of worsening the graininess in terms of photographic performance and increasing sensitivity due to scratches and bending when handling the photosensitive material before processing. However, due to their arrangement, it is not possible to reduce the amount of binder. Under these circumstances, there has been a need for a technology that achieves sufficient sensitivity in a short processing time, has excellent fixing properties and washability, leaves no residual color, and dries in a short time.

(Objective of the present invention) The object of the present invention is to have a sufficiently fast drying speed, still have covering power, achieve high sensitivity in a short processing time, and have residual color when color sensitized. It is an object of the present invention to provide a method for developing a photographic material that has a small amount of pressure (and does not impair pressure characteristics).

In particular, it is an object of the present invention to provide a method for developing X-ray photographic materials having the above-mentioned performance.

(Means for Achieving the Objects of the Present Invention) To achieve the above object of the present invention, a photographic light-sensitive material t+ having seven halogenated emulsion layers on a support is processed by an automatic processor. In the development process, the emulsions, layers and other hydrophilic colloid layers IC [woven organic materials (e.g. gelatin, matte valleys 11, plasticizers, synthetic polymeric materials, other organic materials)]
This was achieved by developing with an automatic developing machine so that more than 10 inches of the total weight of the coating before processing was washed away during the process of constant development, rinsing, and drying. The organic substance may be washed away by physical elution or by chemical reaction. Specifically, it is preferable to contain organic substances that would flow out during the development process into the emulsion layer and/or other hydrophilic colloids. In the case of caseratin, a substance that is washed away, it is preferable to use a gelatin type that is not involved in the crosslinking reaction of gelatin with a hardening agent.
Examples of this include acetylated gelatin and phthalated gelatin, and those with a small molecular weight are preferred.

- 10,000, as polymeric substances other than gelatin, US Special Specification T
Hydrophilic polymers such as polyacrylamide, polyvinyl alcohol, and polyvinylpyrrolidone as shown in JS3, 27/, /jg can be effectively used, and saccharides such as dextran, sucrose, and pullulan can also be used. It is valid. Among these, polyacrylamide and dextran are preferred, and polyacrylamide is particularly preferred. The average molecular weight of these substances is preferably 20,000 or less, preferably 10,000 or less. Effectively, the flow rate in the treatment is 10% or more and 30% or less of the total weight of the applied organic material other than the halogenated planer particles, and preferably 16% or more and 30% or less is eliminated.

Processing using a hardening film during development and a hardening film during fixing is common in rapid automatic processing of X-ray sensitive materials, but the present invention uses a type of developer that does not apply a hardening film during development. This is also noticeable in automatic imager processing in combination with a type of fixer that does not harden or only slightly hardens during fixing.

The layer containing the organic substance that is washed away in the process of the present invention may be an emulsion layer or a surface protection layer, but if the total amount of the organic substance applied is the same, the layer containing the organic substance in the emulsion layer alone will protect the surface better. It is preferable that the compound be contained in both the layer and the emulsion layer, and it is more preferable that the compound be contained only in the surface protective layer. In a sensitive material having a multilayer emulsion layer structure, if the total amount of the organic substance coated is the same, it is preferable that the emulsion layer closer to the surface protective layer contains more organic substances.

The emulsion layer of the silver halide photographic light-sensitive material of the present invention can contain ordinary copper halide grains (eg, spherical grains). These are bee graphidy (P
, Glafkides) [Shimmy Engineering/Physique/
Photography (Chimie etPhysi)
que Photographique) J (bow/l)
/-Published by Paul Monte1, /ri47
), G.F. Duffi
Written by nJ [Photographic Emulsion Chemistry (Photographic EmulsionC)]
hemistry day (The Focalb L/S TheF
(published by Ocal Press, 1966), V. L. Zelikman et al.
“Making and Coating Photographic Emulsion (Maki)” by an etall
ng and Coating Photography
c Emulsion) J (Four Force A/, Pre, K
Published by The Focal Press, / Rita
It can be prepared using the method described in 2010).

The silver halide may be any of silver bromide, silver iodobromide, iron iodochlorobromide, silver chlorobromide, silver sulfuride, and the like.

...During the process of silver locnide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or 8 salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. are allowed to coexist. Good too. It can also be chemically sensitized if necessary.

As a chemical sensitization method, a gold sensitization method using a so-called gold compound (for example, US Pat. No. 2, G., ot.

No. 3.320.062) or iridium, platinum,
Sensitization method using gold maple such as rhodium or palladium (for example, U.S. Pat. No. 1.1, No. 060, U.S. Pat.
-No. 6, same, 2. j44,263) or ij, sulfur sensitization method using a sulfur compound (for example, U.S. Waken No. 2,22
2.2611), or reduction sensitization using tin salts, polyamines, etc. (for example, U.S. Pat. No. 2,411-7,
gjO, same, 61g, Otori r, same λ, 12/,
2j), or a combination of λ or more of these can be used.

Tabular grains can also be effectively used as silver halide grains applicable to the present invention.

The tabular silver halide grains can be produced by appropriately combining methods known in the art.

The tabular silver halide emulsion is manufactured by Cugnac.
and Chateaul "Evolution of the morphology of silver bromide crystals during physical ripening"
Crystals Dueling Physical Living) J Science/Engineering/Instarie Photography, Volume 33, /162 (/6 copies), pp, /,
2/-/2! , by Duffin [Photographic Emulsion Story]
tographic emulsion chemistry
try) J Focal Press A/+ Press (FocalPres
s) , = knee yoke, /ri A6 year, p, +6~p,
72, A, P, l (, Trivelitor (Tr 1vel l i), W, F, Smith (Smith) 7 Autocratic Journal (
Botographic Journal), Volume 0,
2nd page 5th page (/tag θ year, etc.) is written in Tokkai Showa!
I-/27. λ11 Unexamined Japanese Patent Publication No. 1/13. ri27, Tokukai Sho! Za-/13. It can be easily prepared by referring to the method described above.

In addition, in an atmosphere with a relatively low pBr value of pBr / 3 or less, tabular grains form seed crystals in which more than 0% of tabular grains exist in Tosha, and while maintaining the pBr value of Kochodoko, button and... It is obtained by growing seed crystals while simultaneously adding a bath solution.

During this grain growth process, it is desirable to add a trowel and a Rokun bath solution to prevent the generation of new crystal nuclei.

The size of the tabular silver halide grains can be adjusted by controlling the vortex layer adjustment, the selection of the type and location of the bath agent, the silver salt used during grain growth, the rate of addition of the rokenide, etc.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. Azoles such as benzothiazolium salts, nitroindazoles, nitrobenzibadazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, Aminotriazoles, benzotria 7”-A4.@, = trobenzotriazoles, mercaptotetrazole 98 (%ic/
mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; 7
) tetrazaindenes), pentaazaindenes, etc.;
Compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acid, benzeneulphinic acid, benzenesulfonic acid amide, etc. For example, as described in U.S. Pat. , same 3
,912,! i'hiro 7, special public show jko 2g, A
Those described in No. AO can be used.

The halogenated grains used in the present invention may be spectrally sensitized with a sensitizing dye.

Dyes that can be used include cyanine dyes, melonanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, heba cyanine dyes, steryl dyes and hemioquinol dyes. ! The pigments for [:\j] are pigments belonging to cyanine pigments, melonanine pigments, and complex merocyanine pigments. For these dyes, any of the nuclei commonly used for cyanine dyes can be used as the base-variable ring nucleus. Namely, viroline nucleus, oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, ibatazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; A nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxoquibutol nucleus, naphthoxazole nucleus, benzothiazole nucleus, capthothiazole nucleus, benzoselenium. A zole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable.

These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazoline-yone nucleus, a thiohydantoin nucleus, and a λ-thioxazolidine-2 nucleus having a ketomethylene structure.
．． Hiro-dione nucleus, thiazolidine-2,≠-dione nucleus, rhodanine nucleus, thiobarbyl acid radical, etc.! ~6-membered heteroartic ring nuclei can be applied.

Specifically, Research Disclosure Volume 176R
D-77gμ3 (/7g/February issue) page 23, US Patent 1t2j, Hiroλj issue, direction t.

Those described in Hiromu, 2j, Hiromu, No. 26 can be used.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. For example, aminostilbene compounds substituted with nitrogen-containing heterocyclic groups (eg, U.S. Pat. No. 2.733.320, U.S. Pat. No. 3.1!
, 3j, 7co No. 1, aromatic organic acid formaldehyde condensates (e.g.
, No. 310), cadmium salts, azaindene compounds, and the like. US Patent 3. tis
.

No. 673, 3. Otsu/6. Otsu≠/issue, 3.6/7.2
Ri No. 5, Mukai 3, 63! , the combination Vi described in 7 col@,
Particularly useful.

The sensitizing dye used in the present invention can be mixed with an aqueous solution or water (
It is added to the silver halide emulsion as a solution in a miscible organic bath agent such as methyl, ethanol, propyl alcohol, methyl selon, pyridine, etc.

-l μ - The sensitizing dye used in the present invention is described in US Patent No. 3. III! ,
Melting may be performed using ultrasonic vibration as described in No. A33. In addition, there is a method in which the sensitizing dye of the present invention is dissolved or dispersed and added to an emulsion.
．． lIl'2, 91/No. 3゜316, /! P1,
Same 3. uA! i', PF3, same j, u2r,
13! No. 3.3vco, No. 6OS, British Patent/ ,,
27/, 3λri issue, same/, 031゜02 issue, same/,
The methods described in US Pat. No. 3,631,3116 and US Pat.

The timing of adding the sensitizing dye used in the present invention to the emulsion is as follows:
Generally, the process is carried out before the emulsion is coated on a suitable support, but it may also be subjected to a chemical ripening process or a silver halide grain forming process.

The emulsion layer of the photographic material of the present invention may contain a plasticizer 1 such as a polymer or an emulsion in order to improve pressure characteristics.

For example, British Patent No. 73g and British Patent No. 731. No. A37 contains alkyl phthalates, US Patent No. 731,637 contains alkyl esters, and US Pat. ≠No. 04L contains polyhydric alcohol,
, /2/, No. 060 contains carboxyalkylcellulose, 4e Kaisho 4' Tar-jfO/7 contains paraffin and carboxylate, Tokko Sho! No. 3-3-210 discloses a method using an alkyl acrylate and an organic acid.

The photographic emulsion layer or other hydrophilic colloid 1- of the light-sensitive material prepared using the present invention may be used as a coating aid, antistatic, smoothing property improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (for example, development acceleration, Various surfactants may be included for various purposes such as high contrast, sensitization, etc. Alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycol alkyl amines or electrodes, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenyl succinic acid) Nonionic surfactants such as polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars; alkyl carboxylates, alkyl sulfones!, alkylbenzene sulfonates, alkylnaphthalene sulfonates, Alkyl sulfates, alkyl phosphates, heacyl-mono-alkyl taurines, sulfosuccinates, sulfoalkylpolyoxyethylene alkylphenyl ethers, polyoxy-7ethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as phosphor groups, phosphor groups, sulfuric ester groups, phosphoric ester groups, etc.Niaonic acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acids or phosphoric esters, alkyl carboxylic acids, amine oxides amphoteric surfactants such as; alkylamine salts, aliphatic or aromatic primary ammonium salts, heterocyclic quaternary/-class ammonium salts such as pyridinium and imitazolium, and aliphatic or heterocyclic ring-containing honuphonium or sulfonium salts, etc. Cationic surfactants can be used.

These are Ryohei Oda et al.'s [Surfactants and Their Applications] (Ketsu Shoten, /ri 6, 1999), Hiroshi Horiguchi's ``New Surfactants'' (Sankyo Publishing ■, /ri 7, 1999), and ``Matsuku Cations''. ``Ditargient and Emulsion Fires'' (Mccutcheo Divisions, Mccutcheo)
ns Detergents & Emulsifier
sJ (McCutcheon Divisions,
MCP Publishing Co, / Rizari), JP-A-60-7 7≠/ issue, %1 1986/-/332g issue, same A
/-/1,0! It is stated in No. A, No. B/-3-t62, etc.

As an antistatic agent, in particular, patent application 1973-. 2 Hirori 02
Fluorine-containing surfactants or combinations described in No. 7, No. 6/-32 Hiro A2, JP-A No. 40-74-/g-7μλ, No. 60-za014, No. 60-g0rat
No. 60-40137, No. 4O-7A74t/No.
same! J'-, No. 20r7113, Patent Application 1986-1339
Nonionic surfactants described in No. g, No. 6/-/Ost No. 26, No. 3.2 Hiro 26, etc., or JP-A No. 7-20μj≠Q, Patent Application Showa A/-32
111. ．． The conductive polymer or latex (nonionic, anionic, cationic, amphoteric) described in No. 2 can be preferably used. Inorganic antistatic agents include ammonium, alkali metal, alkaline earth metal halogen salts, nitrates, perchlorates, sulfates, potassium torates, phosphates, thiocyanates, etc. Showa-47-//I
Conductive tin oxide, zinc oxide, or a composite oxide obtained by doping these metal oxides with antimony or the like can be preferably used. Furthermore, various charge transfer complexes, π-conjugated polymers and their doped materials, organometallic compounds, intercalation compounds, and the like can also be used as antistatic agents, such as TCNQ/TTF, polystyrene/polypyrrole, and the like. These are Morita et al., Science and Industry L (3)
), 103~///(/rit), Dosu(Hiroshi),/gu6
~/! ;2 (/riJj).

In addition, the photographic material of the present invention may optionally include an intermediate layer,
It can have a filter layer, an antihalation layer, etc.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated with φS on a flexible support such as a plastic film that is commonly used in photographic materials. Useful flexible supports include cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride,
These include films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate and polycarbonate. The support may be colored using dyes or pigments.

The layer structure of the silver halide photographic light-sensitive material used in the present invention is as described in Japanese Patent Application Publication No. JP-A-JF-/, No. 27-2, No. 27-2, No. 2-27, No. 3-3, No. , special application 1986-≠
It is preferable to have a small number of IfM silver halide emulsion layers on both sides of the support, as described in No. 21jet et al.

In the present invention, there are no particular restrictions on the method of coating the emulsion layer, surface protective layer, etc. on the support, but for example, US Patent No. 761. μ/I issue, 3rd degree sot, 'ya7 issue, same! 2.76/, 7F/, etc. can be preferably used.

The developer used in the present invention can contain known developing agents. As the developing agent, dihydroxybenzenes (for example, -hydroquinone), 3-pyrazolidones (for example, l-phenyl-3-virazolidone), aminophenols (for example, hemethyl-p-aminophenol, etc.) may be used alone or in combination. The developer generally contains other well-known preservatives, alkaline agents,
pI (contains buffering agents, antifoggants, etc., and further contains solubilizing agents, color toning agents, development accelerators (for example, Hiroshi salt,
hydrazine, benzyl alcohol), surfactants, antifoaming agents, water softeners, hardeners (eg, glutaraldehyde), viscosity-imparting agents, and the like.

As the fixer, one having a commonly used composition can be used. As the anchoring bank 1, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used.

The fixing solution may contain a water-bathable aluminum salt as a hardening agent.

The developing method using an automatic processor in the present invention is described in U.S. Patent No. 30λj777, U.S. Patent No. 31163!6, U.S. Pat. It is preferable to use a roller conveyance type automatic developing machine described in et al.

The developing temperature is 3s'C-5o 0C, %3o'
C-as'c is preferable, and the development time is preferably r seconds to aO seconds, particularly t seconds to 2j seconds.

Complete development from the start of development to the end of fixing, water washing, and drying -, 2,
2- The image processing step is preferably 30 seconds to 200 seconds, particularly ≠θ seconds to 10θ seconds.

1-1. Regarding various additives, development method, exposure method, etc. of the photosensitive material of the present invention. There is no limit to fi: (Research Disclosure Magazine / 74% Fitem / 74μ3 (December 1971) and the same / rμ volume item / 1113 / (
You can refer to the numerals of /ri 7ri year g month).

(Example) Next, the present invention will be explained in detail.

Example 1 (1) Potato-shaped grains of silver iodobromide (average grain size 0.21 μm) were formed in the presence of ammonia by the triple jet method (average grain size 0.21 μm), chlorauric acid salt, and sodium thiosulfate. Chemically sensitized with

After chemical sensitization, an antifoggant hydroxy-6-methyl~/+3+3a, y-tetrazaindene is added, and a sensitizing dye (I) having the following structural formula is added to silver halide grains 1.
Orn sensitization was carried out by adding 200 μm per mole.

(I) c 2 Ft 5 ? Furthermore, dodecylbenzenesulfonate as a coating aid and a thickener voribotacium p-vinylbenzenesulfonate v were added to form the basic formulation of the emulsion layer. Silver at this time/
The weight ratio of gelatin was 7.3j. - As a surface retention layer, a 7wt% aqueous gelatin solution containing polymethyl methacrylate fine particles, saponin, polystyrene sulfonate, etc. in addition to gelatin was prepared, and this was used as the basic formulation. This emulsion layer and the surface N retention layer solution have a first
Photographic materials ① to ① were prepared by adding gelatin and a water-soluble polymeric substance in the proportions shown in the table, coating them simultaneously on a polyethylene terephthalate support, and drying them. At this time, different levels of drying speed were prepared by changing the amount of hardener added. Coated silver amount is λ#g/m on one side
It was applied to both sides.

Measurement of amount lost during processing K, which measures whether the amount of organic material applied before processing has been washed away during the constant development, washing, and drying processing, is as follows: It can be measured using various methods. First, the sample was left under conditions of 70% relative humidity until the water content of the sample reached equilibrium with the atmosphere, and then the Mu of the sample was measured. Next, the sample was processed from development to drying using an automatic developing machine, and then 260C1 relative humidity 70%
The sample was left under the following conditions, and the weight was measured when the moisture content reached equilibrium. The weight of the support was measured in advance to ensure that there was no change in weight due to the treatment of only the support. The amount of developed silver was calculated by uniformly or not exposing to light, and from this value and the specific gravity of silver halide, the weight loss due to development, fixing, and [of the silver halide grains themselves] was calculated. From this value, the weight of organic substances washed away during processing was measured.The emulsion also contains inorganic salts, but this has a negligible effect on the weight loss of organic substances. Here, the amount of organic substances washed away was determined by measuring the amount of N, but this value can also be found by measuring the film thickness before and after treatment, and the amount of washed away substances can be determined by analyzing the treated solution. But it can be quantified.

Method for Measuring Drying Speed: For automatic development, a Fuji X-Ray Processor FPM Hiro 000J manufactured by Fuji Photo Film ■ was used.

The developer and fixer had the following compositions.

(Developer) l-phenyl-3-pyrazolidone /, j9hydroquinone 309j-nitrointazole 0. ．． 23g potassium bromide
3.0g anhydrous sodium sulfite
jO! ! potassium hydroxide
30fj/boric acid 70
g Glutaraldehyde 59 Add water to bring the total volume to 73.
Fixer ammonium phthiosulfate soo, og sodium sulfite (anhydrous 1 20.09 boric acid
r, oy disodium ethylenediaminetetraacetate o, ip aluminum sulfate l, 0g sulfuric acid
λ, og glacial acetic acid
, 22.0/;/add water
/ , 01 (pH adjusted to 20 in Hiromu.) The sample was developed using the above-mentioned developer and fixer at FPM Hiro 000 and passed through a fixed-water washing process, and then squeezed and placed in a drying zone. I took out the film just before it was inserted and made the following measurements (at the time of this measurement, FPMIAoo
(The drying air was turned off). While blowing hot air onto the taken-out film using a commercially available dryer, the time required for the film surface temperature to reach 300 C was measured using a surface thermometer. The developing temperature was 3!0C, and the washing water temperature was /g00.

Measurement of Sensitivity and Dmax Processing was carried out using the above-mentioned processing solution and automatic developing machine, with the drying zone also operating normally. The tip of the cone was exposed to white light. The sensitivity value was determined as the logarithm of the reciprocal of the exposure amount required to obtain a degree of blackening of curr y; In addition, even if the maximum exposure Dmax is given,
The value was taken as a value once no increase in production rate occurs. Sensitivity was based on sample /, and cases with higher sensitivity and lower sensitivity were expressed as e.

Using a commercially available nylon scrubber, load 100g/cm2
After rubbing the sample in a dark room, it was processed in the automatic processor described above. A sensory evaluation was performed on the scratches observed after the treatment in stages A-E. For evaluation? As for T, I can't tell that A... has a lot of scratches.

C: Level with no practical problems. The scratches are
I see it clearly.

E: Scratches are very noticeable.

Binding, B, and D were each in an intermediate state.

Evaluation of residual color An unexposed film was processed using the automatic processor and processing solution described above, and the level of residual color was sensory evaluated. As a guideline for evaluation, A... is a state in which you hardly notice that there is a residual color. C...... a state in which you are aware that there is a residual color (but it is not really noticeable in practical terms). E: A state in which residual color clearly remains, and the residual color is a concern in practice, and a state intermediate between B and Dfi.

The results of the above evaluation are shown in Table 7 together with the contents of the samples.

As for the organic substances to be eluted, polyacrylamide and saccharose having an average molecular weight of tOOθ were used, and the drying property without any problem when continuously processed at FPM≠000 was equivalent to -r-kota seconds at the drying speed of this method. There is. The results in Table 7 show that when the amount of organic substances washed out exceeds 10 inches, high sensitivity and high concentration can be obtained when the drying rate is almost the same, and the resistance to Sooty Pulley scratches and residual color are considerably improved. Recognize.

! In addition, looking at the sample results, although it dries in about -10 hours compared to the comparative sample, it has a higher sensitivity and higher Dm than the comparative sample.
ax'! a', and the scratch resistance and residual color have been greatly improved.

When trying to improve the hardener sensitivity and Dmax'lL' using the conventional technology, the drying rate reached a practically problematic level, as in Sample 1, and the scratch resistance deteriorated by 7 ranks. Furthermore, polyacrylamide is more effective than sucrose.

As described above, the effects of the present invention are obvious.

Example 2 Thick plate-like twin grains of silver iodobromide (silver iodide 3゜mol%) were formed in the presence of ammonia and potassium thiocyanate by a double jet method. The average particle size is 0.7 as the average diameter of spheres with the same volume as each particle (sphere equivalent diameter).
It was 1 μm. The particles were chemically sensitized with chloroauric acid salts and sodium thiosulfate. Thereafter, a sensitizing dye (II) having the following structure was added in an amount of 0.00 mm per mole of silver halide grains to effect Orn sensitization.

(n) The silver/gelatin weight ratio of this emulsion was i, os.

Coating aids and thickeners were added in the same manner as in Example 1, and samples having the configurations shown in Table 2 were coated together with a surface protective layer. The drying speed was adjusted by changing the amount of hardening agent added, and the evaluation was performed in the same manner as in Example 1.

The amount of silver coated was [1]iλ, 09/m2, and the polymer paste coated on both sides, which was washed away, was made of polyacrylamide and had an average molecular weight of 7,000 r/1,000.

From Table 2, it is clearly seen that the smaller the molecular weight, the better; the present invention has the same drying speed or higher, sensitivity, and Dm.
It can be seen that the balance between ax, scratch resistance, and residual color has been significantly improved.

Preferred embodiments of the present invention are as described above: 1. A developing processing method according to claim 1, wherein the light-sensitive material is an X-ray light-sensitive material having at least one silver halide emulsion layer on each side of the support.

2. Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, in the emulsion layer and/or the surface protective layer.
The method of 1 above using a photosensitive material containing dextran or sucrose.

3. The method of 1 above, using a photosensitive material containing polyacrylamide having an average molecular weight of -10,000 or more in the emulsion layer and/or the surface protective layer.

The above method G, wherein the average molecular weight of the polyacrylamide is 10,000 or less.

4. The above method 10, wherein the automatic developing machine is a roller conveyance type.

5. The method of 1 above, using a photosensitive material containing polyacrylamide with a molecular weight of 20,000 or less in the surface protective layer.

6. Two or more layers on both sides of the support...Ro3
j- The method according to the above 1, which uses a sensitive material having silver germide emulsion layers, each of which contains polyacrylamide in the emulsion layers located at a distance from the support.

Patent applicant: Fuji Photo Film Co., Ltd. 3t - October 2, 1986 Commissioner of the Japan Patent Office, Mr. Kai 1, Indication of the case: 1924 Patent Application No. 2/3!0.3 2, Name of the invention: Halogen Development processing method for silver chemical photographic materials 3, Relationship with the case of the person making the amendment Patent applicant Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Subject of amendment: Column 5 of “Detailed Description of the Invention” of the specification, Amendment The statement in the "Detailed Description of the Invention" section of the description of contents is amended as follows.

1) 3rd page line [can also be made] “You can do it by letting me do it.” and correct it.

2) Page 22/line [,ys'C-to'CJ [/I'C-10'Cl and correct it.

3) Second! Page l≠th line After "uniform" "Shall we go?" Insert.

4) Line 16 of page λ [The FPMJ that was there] [there was. FPMJ and correct it.

5) Page 3j/line "more than" "below" and correct it.

6) Page 3j // line ``More than 20,000'' "Less than 20,000" and correct it.

7) No. 3 J Sada/3~/Hiroyuki's [Polyacrylic...method. Correct J to "Hiroshi, method 3 above, where the average molecular weight of polyacrylamide is 70,000 or less."

8) 3rd J Sada/! row "Sa automatic developing machine" "j Automatic developing machine" and correct it.

9) Third! page 77th line "r, surface" "60 surfaces" and correct it.

10) Page 35, line 20 16.Support "7. Support" and correct it.

= 3-1, Indication of the incident, 1933/1933 Patent Application No. 2/3103
No. 20 Name of the invention Development processing method for silver halide photographic light-sensitive materials 3, Relationship with the amendment person case Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address 2-26 Nishi-Azabu, Minato-ku, Tokyo 106 No. 30 No. 4, Subject of amendment The description in the "Detailed Description of the Invention" column 5 of the description and the "Detailed Description of the Invention" section of the description of the contents of the amendment is amended as follows.

l) Page 7, line 2 After “preferable.” Attachment - Full text of / Insert.

2) On page 2≠, in the 20th line, before "Amount of silver coated", "The hardener at this time is Compound Example V-21 described in the specification of JP-A-Sho&/-//7!3μ A vinyl sulfone hardener is used, and the amount added is approximately equal to the coated weight of gelatin, which may be involved in crosslinking.

The addition of polymer increased the hardener filtration required to obtain the same drying rate. ” is inserted.

1/- 3) Page 3j, line 1 Before “of the invention” Attachment - Full text of Part 1 Insert.

4) In the third row of page 3, after "Method 1 above", [7. Method 3 above using dextran instead of polyacrylamide t1 Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, dextran in the surface protective layer, Or the above method 1 using a sensitive material in which the content of saccharose is 30 wt % or more, preferably 30 wt % or more of the total binder in the surface pupil retention layer, or the above method j using dextran instead of polyacrylamide. Insert.

[In the present invention, as the binder polymer constituting the image gI that remains even after processing, binders that normally constitute photographic materials can be effectively used. For example, the average molecule t7~
Gelatin (which may be lime-treated or acid-treated) is involved in cross-linking of 100,000, and U.S. Patent No. 3. j
Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, dextodin, etc. disclosed in 2003/Hiroshi, 2r, etc. can be preferably used. Polymers other than gelatin having a molecular weight of 20,000 or more may be added separately from the low molecular weight polymer of the present invention for the purpose of increasing the covering power of silver halide, or may be added separately from the low molecular weight polymer used for the purpose of the present invention. The polymer may have a wide molecular cap distribution and its high molecular weight components may remain, or it may be composed of components from which low molecular weight components have not been completely eluted.

It is preferable that the remaining binder lid has a weight ratio of //J to 3 times the amount of coated silver, particularly preferably 772 to 2 times. Among the binders of photosensitive materials before phenomenon processing,
The gelatin content is preferably tO weight % or more and O weight % or less, more preferably 77 weight % Ii! :% or more and 10% by weight or less.

The amount of remaining binder is i, r~A f per one side.
/ m2, preferably λ~≠f/m2.

The residual binder is generally ensured by curing it with a crosslinking agent of various types.

Various crosslinking agents can be used, but some curing agents are known to be helpful in the art. (RD description) Can be used”
In addition, particularly as a residual binder, gelatin is used as a hardening agent.

Hiro-dichloro-t-hydroxy-/, 3, j-triazine or compounds having an active vinyl group, halo-substituted formamidinium salts, or carbamoylammonium salts can be preferably used.

Examples of compounds having an active vinyl group include JP-A Shoj3-da/λ2/, JP-A Sho! 3-! No. 7217, Tokuko Akihiro/-/, 24/, 2≠ issue, Tokuko Akihiro? -13! A3
No., Machikai Shoj/-V≠16≠ No., Tokukai Shoj2-2IO!
No. 34, U.S. Patent No. 77, U.S. Patent No. 3j3? t4 to Hiroshi, 3tλ11, Tokuko Sho 60-36! 07, Tokukai Sho J Gu 3002.2, Toku Kai Sho 13- & 6260, Toku Ko Sho! λ-4A4'ri No. 5, Special Publication Showa 4A7-173
, U.S. Patent No. 3t, 3j7/I, 30'107
．． Mention may be made of the compounds described in German Patent No. 20 and German Patent No. 172/63.

Examples of compounds having a halo-substituted formamidinium group include JP-A-60-2.2jl≠, JP-A-60-2.2jl≠, JP-A-60-2.2jl≠;
-, 2≠0236 can be mentioned.

Compounds with carbamoylammonium foundations include:
For example, compounds described in Japanese Patent Publication No. 36-/Corz No. 3 and No. 1-J Kootade of Japanese Patent Publication Publication No. 1988 can be mentioned.

Furthermore, as the gelatin hardening agent used in the present invention, a polymer hardening agent can be effectively used.
The polymeric hardener described in -J/7μ2 provides favorable effects. ” Attachment-2 [Example 3 Emulsion grains were formed and coated in the same manner as in Example λ.

However, instead of the polyacrylamide used in Example 1, dextran having an average molecular weight of ≠10,000/10,000 and 7,000 was used as a type of polymer that was washed away.

The results are shown in Table 3. The effect of the present invention is clear from the comparison with Sample A/co~/≠ in Table 2.

Procedural amendment July 12, 1960 1, case indication Showa t/year patent application No. 2/3!03
No. 3, Relationship with the case of the person making the amendment Patent applicant Location 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of the amendment Column 5 of “Detailed description of the invention” in the specification The description in the "Detailed Explanation" section has been amended as follows.

1) After "tetrazaindene" on page 23, line 77 to /lr, "and copolymer latex of ethyl acrylate and methacrylic acid paste j:1 weight ratio (addition amount is 20% by weight based on gelatin)" ” is inserted.

Procedural amendment 1. Display of incident 1986 Patent Application No. 2/3j03
No. 2, Name of the invention, Development processing method for silver halogenide photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent applicant Address: 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment (Detailed explanation column 5, description of the "Detailed explanation of the invention" section of the statement of contents of the amendment as follows)
to correct.

1) From page j, line 73 to page 6/line, change ``On the other hand, other than gelatin is a preferred substance.'' to ``In addition to gelatin, other water-bathable synthetic or natural polymers may be used. "I can," he corrected.

2) Page 6, line B Insert the entire text of the appendix after "preferable."

Attachment ``In addition, the water-soluble polymers used in the present invention include
Examples include synthetic water-bathable polymers and natural water-bathable polymers, both of which can be preferably used in the present invention. Among these, synthetic water-bathable Bo1Jmers include those having, for example, a nonionic group, an anionic group, and a nonionic group and an anionic group in their molecular structure. Examples of nonionic groups include ether groups, ethylene oxide groups, and hydroxy groups; examples of anionic groups include sulfonic acid groups or salts thereof, carboxylic acid groups or salts thereof, and phosphoric acid groups or salts thereof. , etc. are listed.

These synthetic water-soluble polymers include not only homobo IImer but also one or more of them. It may also be a copolymer with a monomer on L. Furthermore, this copolymer may be a copolymer with a partially hydrophobic monomer, as long as it maintains water solubility.

However, the composition of the copolymer is somewhat restricted depending on the location of addition and addition 71Of. That is, especially when adding a large amount to an emulsion layer, it is necessary to limit the composition to a range that does not cause any side effects.

Natural water-soluble polymers include those having, for example, nonionic groups, anionic groups, and both nonionic and anionic groups in their molecular structures.

In the present invention, the water bathing polymer is defined as 0.03 to 1002 water at 200C. It is sufficient to dissolve the water in the bath above n, preferably 0.19 or more.

Furthermore, the higher the solubility of the water-bathable polymer of the present invention in the developer or fixer, the better.
0.019 or more, preferably 0.019 or more. jLi- or more, particularly preferably l or more.

As a synthetic water-bathable polymer, the following general formula [P]
Examples include those containing 10 to 100 moles of the return unit per molecule of the polymer.

General formula [P] In the formula, 几1 and R2 may be the same or different and [each is a hydrogen atom, an alkyl group, preferably an alkyl group having a carbon atom number of 1-hiro (those with substituents may also be used) (e.g. methyl group, ethyl group, propyl group, butyl group, etc.), halogen atom (e.g. chlorine atom) or -CH2C00M
, L is -CON)i-1-N)iCO-1-C
OO-1-oco-1-CO-1-so2-1-NH8
02-1-8O2NH- or -0-, Jll
-r, alkylene group, preferably an alkylene group having a carbon atom number/~10 (including those having substituents; for example, methylene group, ethylene group, propylene group, trimethylene group, butylene group, hexylene group, etc.) , arylene group (including those with substituents, such as phenylene group)
, aralkylene group (substituent casing or +CH2CH2Ote6CH2), m n R (m is an integer of 0-<20, n is an integer of O-≠ as shown in Table 10
M, -NH2, -803M, -0-P-OM.

! 0M - CR9, hydrogen atom or R3. M represents a hydrogen atom or a cationic group, and R9 represents an alkyl group having 1 carbon atoms (for example, a methyl group, an ethyl group, a propyl group,
butyl group, etc.), R3, R4, 几5, R6, R7
and R8 is a hydrogen atom, an alkyl group having up to 20 carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, hexadecyl group, etc.) or an alkenyl group (e.g. vinyl group, aryl group, etc.) , phenyl group (
For example, phenyl group, methoxyphenyl group, chlorophenyl group, etc.), aralkyl group (eg, benzyl group, etc.), X represents an anion, and p and q represent no, Irr, or t, respectively. In particular, it contains acrylic adsorbent or methacrylic adsorbent! Preferred are polymers that

Y represents a hydrogen atom or +L Jf-Q.

q The synthetic water bathing monomer of the present invention can also be copolymerized with ethylenically unsaturated monomers.

Examples of copolymerizable ethylenically unsaturated monomers are styrene, alkylstyrenes, hydroxyalkylstyrenes (
The alkyl group has 7 to 1 carbon atoms. Even one up to t! - vinylbenzenesulfonic acid and its salts, α-methylstyrene, govinylpyridine, N-vinylpyrrolidone, monoethylenic 1[fO esters of aliphatic acids (e.g. vinyl acetate, propionic acid, etc.), vinylbenzenesulfonic acid and its salts, vinyl acids, etc.), ethylenically unsaturated monocarboxylic or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid), acid anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, N,N-diethyl ad-noethyl methacrylate, N,N-diethyl abanoethyl methacrylate), ethylenically unsaturated monocarboxylic or dicarboxylic acid amide (e.g. acrylamide, 2-acryla, etc.) Dokome Senru Prono ξ
sodium sulfonate, N,N-dimethyl-N'-methacryloylpropanediamine acetate betaine), and the like.

Next, specific examples of the synthetic water-bathable foamer of the general formula [P] will be given.

- Otsuichi P-t Number average molecular weight MnO
H♂ 000 it oo.

-J cooti + to.

P-≠ −j C)i2Coo)l C00C)12cH20Ht,oo.

CONH23000 -l　l H3 H P-t　co P-/j Ta O O O one? − P-t CONH2 COOI-1 /, 2, 000 P-/. ! -l　A Ha r　　oo.

P-/7 C) la 10! 100 P-/J' S O3N a (however, nl:n2=jθ mol%: j O mol%,
Number average molecular weight (Mn) = about 10,000) - tY (however, nl: n2 = 7j molch: 2! molch, M n
= about 20.000) -2i /I 000 P-, 2hiro The molecular weight of the synthetic water-bathable polymer of the present invention is 1,000 to 7
00.000 preferably 2,000-to, ooo.

Natural water-soluble polymers are described in detail in the Comprehensive Technical Information Collection of Water-Soluble Polymer Water-Dispersible Resins (Management Development Center Publishing Department), but include lignin, ML pullulan, cellulose, alginic acid, texturan, and texturan. , guar gum, gum arabic, pectin, casein, agar,
Xanthanzam, cyclodextrin, locust bean gum, tragacanth gum, carakeenan, glycogen, udnaran, lignin, ethylene, etc., and derivatives thereof are preferred.

Further, as derivatives of natural water bathing polymers, sulfonated, carboxylated, phosphorylated, sulfoalkylenated, carboxyalkylenated, alkyl phosphorylated ones, salts thereof, polyoxyalkylene (e.g. Preferred are ethylene, glycerin, propylene, etc.) and alkylation (methyl, ethyl, benzylation, etc.).

In the present invention, two or more natural water-soluble polymers may be used in combination.

Also, among the natural water-soluble polymers, glucose polymers and derivatives thereof are preferred; among glucose polymers and derivatives thereof, starch, glycogen, cellulose, lignin, textlan, nigeran, etc. are preferred;
Particularly preferred are dextran and its derivatives.

Dextran is a polymer of α-/,4-linked D-glucose, and is generally obtained by culturing dextran-producing bacteria in the presence of sugars. Therefore, it is possible to react the separated dextran sthalase with a saccharide and obtain it. In addition, these native textlans can be reduced to a desired molecular weight by a partial decomposition polymerization method using acid or alkaline enzymes to obtain those having an intrinsic viscosity in the range of 0.03 to 2.3.

1. Examples of modified dextran include dextran sulfate, carboxyalkyl dextran, and hydroxyalkyl dextran. The molecular weight of the natural water bathable polymer is preferably 1,000 to 100,000, particularly preferably 2,000 to 10,000.

Regarding the production method of dextran and its derivatives, please refer to the special publication. No. 3, U.S. Patent No. 3.
762. Octopus ≠ issue, special public, 1967! -/2J', No. 20, No. 1iLt-/g4tit, No. zt-p.

l≠? No., same≠J-3//? It is stated in No. 2.

The synthetic or natural water bathable polymer used in the present invention is contained in the photographic material in proportion to the total weight of the IO.
Preferably it is contained in an amount of 10% or more and 30% or less.

The amount of the organic substance used in the present invention that flows out during processing is the total weight of the organic substance coated and removed other than silver halide particles.
% or more, jO ratio or less is effective, preferably lj ratio or more,
It is good if less than 30 inches leak out.

Claims (1)

[Claims] At least one photosensitive silver halide emulsion layer is provided on the support.
In a method of developing a silver halide photographic light-sensitive material having a layer using an automatic processor, the amount of organic substance present in the emulsion layer and/or other hydrophilic colloid layer after the development process is 1. A method for developing a silver halide photographic material, characterized in that the amount of silver halide is 90% by weight or less of that of the previous material.