JPS63149641A - Method for developing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance covering power and sensitivity at raised drying speed by specifying an amount of organic material in an emulsion layer and/or another colloidal layer after developing performance. CONSTITUTION:The photosensitive material having one or more silver halide emulsion layers containing flat silver halide grains having an aspect ratio of >=5 is processed with an automatic developing machine, and >=10% of the total weight in the emulsion layer and the other hydrophilic colloidal layers of the photosensitive material is eluted during developing-fixing-rinsing-drying processes, and the material may be eluted by physical or chemical reaction, and as said material to be eluted, acetylated or phthalated gelatin, dextran, and the like can be used. A synthetic water-soluble polymer having repeating units each represented by the formula shown on the right in which each of R1 and R2 is H, alkyl, or the like; L is -CONH- or the like; J is alkylene; Q is -NH2 or the like; Y is H, (L)p-(J)q-Q, or the like; and each of (p) and (q) is 0 or 1.

Description

[Detailed Description of the Invention] (Industrial Application Field) The present invention is as practical as ever! This article relates to a method for developing a silver halide photographic light-sensitive material containing the above tabular grains, and particularly relates to a technique for improving rapid processing suitability, that is, high sensitivity with short development processing and drying in a shorter time. In particular, the present invention relates to a method for developing 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 to achieve sufficient sensitivity in a short time, a photosensitive material that has excellent developability and does not leave any residual color even during short processing times, and dries in a difficult time after washing with water. 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 will be required to have a higher drying capacity. I can't help but burst into tears. Furthermore, as a result of generating a large amount of heat, there are also problems such as an increase in the temperature of the room in which the automatic processor is installed.

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 during the coating process of the photosensitive material to reduce the amount of swelling of the emulsion layer and surface protective layer during the constant development and water washing process. This method reduces the moisture content in the wood before drying begins. In this method, if a large amount of hardening agent is used, the drying speed can be increased accordingly, but by strengthening the hardening agent, development may be delayed and the sensitivity may be lowered. However, these methods have the drawbacks of lowering the covering power, delaying the fixing speed of undeveloped silver halide grains, worsening residual color, and increasing residual hypo in the photosensitive material after processing. On the other hand, the water content in the photosensitive material before drying can be reduced by reducing the amount of hydrophilic substances coated on the photosensitive material, such as gelatin, synthetic polymers, hydrophilic low molecular weight substances, etc. Hydrophilic low-molecular substances are generally added to prevent silver halide grains from drying and fogging during the coating process, and if they are removed, fogging will occur 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 for I/silver halide grains will not decrease, resulting in a so-called high silver content. Become. Decreasing the amount of binder may lead to deterioration of graininess in terms of photographic performance, and especially with high-amount ratio tabular grains, handling of the sensitive material before processing can easily cause increased or decreased sensitivity due to scratches or bends. However, even if an attempt is made to improve drying properties, the amount of binder cannot be reduced due to these disadvantages.

In this situation, sufficient sensitivity can be achieved in a short processing time,
There has been a demand for a technology that has excellent fixability and washability, leaves no residual color, and dries in a short time.

On the other hand, when tabular grains are used, since the grains are oriented parallel to the support, the surface of the coated photosensitive material exhibits a smooth and transparent surface. This characteristic is due to the fact that medical photosensitive materials, especially those with large film sheets such as direct medical films, require indoor ceiling lights or window lighting when doctors interpret the processed film for diagnostic purposes. This causes the inconvenience that it is difficult to diagnose due to reflection.

A technique for using gelatin-incompatible polymers in combination with gelatin for the purpose of preventing surface gloss is disclosed in JP-A-7-20731, and it is also known that gloss can be prevented by using a matting agent or the like. . However, these methods are not sufficient techniques to prevent gloss from the smooth surfaces caused by the use of tabular grains, and are accompanied by an increase in haze after treatment.

In this regard, the present invention can prevent surface gloss after treatment to a sufficient level without increasing haze.

(Objective of the present invention) The object of the present invention is to have a sufficiently fast drying rate, a high covering power, achieve high sensitivity in a short processing time, and take advantage of the characteristics of tabular grains. To provide a method for developing a photographic light-sensitive material that leaves little residual color even when color sensitized by adding a large amount of a sensitizing dye and does not impair pressure characteristics.

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

(Means for achieving the object of the present invention) The above object of the present invention is to provide an aspect ratio of at least one layer on a support! Using an automatic processor for a photographic light-sensitive material having a silver halide emulsion layer containing the above tabular grains. In the development process, organic substances (such as gelatin, matting agents, plasticizers, synthetic polymer substances, and other organic substances) coated on the emulsion layer and other hydrophilic colloid layers undergo a certain development process, washing with water, and drying process. This was achieved by developing the film using an automatic processor so that more than 10% of the total weight of the coated film before processing was washed away during the process. The organic substance may be washed away by physical elution or by chemical reaction. Specifically, it is preferable that the emulsion layer and/or other hydrophilic colloid layers contain organic substances that would flow out during the development process. When the substance to be washed away is gelatin, it is preferably a type of gelatin that is not involved in the crosslinking reaction of gelatin by a hardening agent, such as acetylated gelatin or phthalated gelatin, which preferably has a small molecular weight. On the other hand, as polymeric substances other than gelatin, US Patent No. TIJS, ? ,27/ ,/j1
Hydrophilic polymers such as polyacrylamide, polyvinyl alcohol, and polyvinylpyrrolidone as described in the above publication can be effectively used, and saccharides such as dextran, saccharose, and pullulan are also effective. Among these, polyacrylamide and dextran are preferred, and dextran is a particularly preferred substance. The average molecular weight of these substances is preferably! It is preferably less than 20,000, preferably less than 20,000.

Particularly useful is 10,000 zooo or less and rooo or more.

Effectively, the amount of outflow during the treatment is between toq6 and to% of the total weight of the coated organic substances other than silver halide grains, preferably at least /1% and less than 30%.

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 processing using a combination of a fixer solution that does not harden the film during fixing, or only slightly hardens the film during fixing.

The layer containing the organic substance washed away in the process of the present invention may be an emulsion layer or a surface protective layer, but if the total amount of the organic substance coated is the same, it may not be contained only in the emulsion layer. It is preferable that the compound be contained in the emulsion layer, and it is even more preferable that the compound be contained only in the surface protective layer. In a sensitive material having a multi-Ffjl emulsion layer, if the total coating amount of the organic substance 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 has a certain aspect ratio! The following silver halide grains (e.g. spherical grains)
can be contained. Depending on the purpose, these grains may be used as an upper layer or a lower emulsion layer of an emulsion layer containing tabular grains having an aspect ratio of j or more, or may be used as a single emulsion layer. In the case of 1 milk, the total projected area of the grains in the emulsion layer!
7 suicto ratio for 0 or more! It is preferable that it is above.

In addition, particles with an aspect ratio of j or more have a ratio of zO of the total coated silver amount.
It is preferable that it is at least wt%. these are.

B Gl afk 1des, (P, Gl afk 1des
``Chimie et Physique Photography'' (Chimie et Physique Pho)
tographique) J (Paul Montell Pa
Published by ul Monte 1, 1997), G.F. Dufin (G, F.

Duffin) Photographic Emulsion Chemistry (Photographic Emulsion Chemistry)
lsionChemistry) J (The Focal Press, 1993), Gui L. Zerichman et al. (V, L, Ze
likman etal) [Making and
Coating Photographic Emulsion (Ma
King and Coating Photogra
phic Emulsion) J (Focal Press 'rhe Published by Focal Press, lit.
It can be prepared using the method described in , etc.

The silver halide may be any one such as silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present. Moreover, chemical sensitization can be carried out if necessary.

As a chemical sensitization method, there is a gold sensitization method using a so-called gold compound (for example, US Pat. No. 1, Hiromu, ot.

No. 3.3, No. 0.01) or iridium, platinum,
Sensitization using metals such as rhodium and palladium (for example, U.S. Patent No.
! 263) or a sulfur sensitization method using a sulfur-containing compound (for example, U.S. Pat.
), or reduction sensitization using tin salts, polyamines, etc. (for example, U.S. Pat. No. 2.1717.110, "+!").
/r, 4-r-r, do-ko, j-kol, octopus-j), or a combination of two or more of these can be used.

Next, the tabular silver halide grains applied to the present invention will be explained.

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 Shadow (Chateau)r Morphological evolution of silver bromide crystals during physical ripening (Evolution of the Mol 7 Orgy of Silver Bromide
"Crystals Dueling Physical Lightning)" Science/Industry/Photography, vol. 33, /a2 (/rit2), pp, /J/-
/-2, ``Photography Emulsion Chemistry'' by Duffin.
phic emulsion)chemistry)
J Focal Press
), New York, /ri 4A, p, A6-p, 7
2, A, P, H,) Trivelli, W
, F. Smith Photographic Journal
), Volume 10, Kot! Although it is written on the page (l≠O year) etc., it is JP-A-E! ! -/27. ri21, JP-A-5R-11
3,927, Tokukai Sho! r-//J+ri2Ir.

same! ta 11≠26, ta ta ta ≠ 33 and ta a/-
It can be easily prepared by referring to the method described in 20/23 et al.

In addition, a seed crystal in which tabular grains are present in an amount of μo% or more by weight is formed in an atmosphere with a relatively low pBr value of pBr/, J or less, and silver and halogen solutions are simultaneously added while maintaining the pBr value at the same level. It can be obtained by growing seed crystals.

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

The size of the tabular silver halide grains can be adjusted by controlling temperature adjustment, selection of the type and amount of solvent, silver salt used during grain growth, addition rate of halide, 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. Namely, azoles such as benzothiazolium salts, nitrointazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (in particular l-phenyl-!-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinthione; azaindenes, such as triazaindene. -? Benzene thiosulfate, benzene sulfine! Many compounds known as antifoggants or stabilizers can be added, such as be/zene sulfonic acid amides, etc.

For example, US patent 3°! Hiroshi, ≠7≠ issue, same 3, 21r2
．． ? ≠No. 7, Tokkosho, '; 2-21. tt/) can be used.

The silver halide grains used in the present invention are preferably used after being spectrally sensitized with a sensitizing dye.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, steryl dyes and hemioquinol dyes. A particularly useful dye is cyanine dye.

It is a pigment belonging to merocyanine pigments and complex merocyanine pigments. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., an indolenine nucleus, a benzindolenine nucleus,
Indole nucleus, benzoxadol nucleus, naphthothiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, be/
Zoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. can be applied.

These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -on nucleus, thiohydantoin nucleus, λ-thioxazolidine-2
．． ≠-dione nucleus, thiazolidine-λ, gougeone nucleus, rhodanine nucleus, thiobarbyl acid radical, etc.! ~ can be applied to the member heterosegmental ring nucleus.

Specifically, Research Disclosure Volume 176R
D-/76≠j (/7j/February issue), page 23, US Patent≠, 44.2j, ≠Coj issue, same≠.

≠2! , 1A21. You can use those listed in the No.

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, aminostyline compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat.
! , 7 Co. No. 1), aromatic organic acid formaldehyde condensates (for example, U.S. Pat. No. 3,7173,110)
(described in the above issue), cadmium salts, azaindene compounds, etc. US patent j,t/! +4
No. 13, same 3. t/j, t≠1, same 3,617.2ri j, same! , 631, 72/ is 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 solvent such as methanol, ethanol, flobyl alcohol, methyl cellosolve, pyridine, etc.

The sensitizing dye used in the present invention is described in US Patent No. 3. ≠rz,t
It may be dissolved using the ultrasonic vibration described in No. 3. Other methods for adding the sensitizing dye of the present invention by dissolving or dispersing it into an emulsion include US Patent No. 3. ≠f
2. R/No., same 3゜! rrj, /ri No. 5, same 3. Hiro 6
ri, ri t7, same j, 44, 2j, 131, same 3
．． 3 octopuses, tar.

-British Patent/, 27/, J Kota No., same/, OJ r
+02 issue, same/, 1 co/, /7≠ issue, US patent 3゜1
．． 40, 10/No. 3. The method described in the section for -1 and j da can be used for t.

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

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

For example, British Patent No. 73♂, tir describes a heterocyclic compound, British Patent No. 731, 1.37 describes an alkyl phthalate,
U.S. Patent No. 731,632 describes alkyl esters, U.S. Pat.
, /2/, No. 01,0 contains carboxyalkyl cellulose, published by JP-A-Sho μter! 0/7 issue contains paraffin and carboxylate, special public Shoj! No. 21016 discloses a method using an alkyl acrylate and an organic acid.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, t?liethylene glycol/po+)-j-ropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, d”) Ethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkenylcono-phosphate polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols non-ionic surfactants such as alkyl esters; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphate esters Q, N- Carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphorus, such as acyl-N-alkyl taurine systems, sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc. Anionic surfactants containing acidic groups such as acid ester groups, diamino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphate esters, alkyl betaines,
Ampholytic surfactants such as amine oxides; alkyl amine salts, aliphatic or aromatic cylindrical ammonium salts, heterocyclic ≠ primary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium containing aliphatic or heterocyclic rings. Cationic surfactants such as salts can be used.

These are JP-A-Sho tO-7J74! / issue, special request show tt-/
No. 3391, same J/-140! l, No. 61-32≠
26, etc.

As the antistatic agent, in particular, fluorine-containing surfactants or polymers described in Japanese Patent Application No. 60-2μri No. 017 and No. 41-3211-12, JP-A No. 7A-7A-7A-7A,
-rortit, jO-1Or4At, to-
rotsri issue, 6O-7G7 Hiroshi/issue, same J r -,
20r No. 7443, Patent Application No. 1332/1986, No. 4
/-/60j No. 6, 61-32≠26, etc., or the nonionic surfactants described in JP-A-17-171 Oa! Conductive polymers or latexes (nonionic, anionic, cationic, amphoteric) described in μO, Japanese Patent Application Sho A/-J Cohiro 6λ can be preferably used. Inorganic antistatic agents include ammonium, alkali metal, and alkaline earth metal salts, nitrates, and conductive tin oxides and nitrates described in JP-A-17-12≠2, etc. A composite oxide obtained by doping zinc or an oxide of these metals with antimony or the like can be preferably used.

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.

The layer structure of the silver halide photographic light-sensitive material used in the present invention is as follows:
01'l-/ issue, II-///ri 3μ issue, special request to
-≠2/j≠ etc., it is preferable to have at least one silver halide emulsion layer on both sides of the support.

In the present invention, there are no particular limitations on the method of coating the emulsion layer, surface protective layer, etc. on the support, but for example, U.S. Pat.
The multilayer simultaneous coating method described in No. 2, No. 7j/, No. 7-1, etc. can be preferably used.

The developer used in the present invention can contain known developing agents. As the developing agent, dihydroxybenzenes (e.g. hydroquinone), 3-pyrazolidones (e.g. l-phenyl-3-pyrazolidone), aminephenols (e.g. N-methyl-p-aminophenol, etc.) may be used alone or in combination. can.

The developing solution generally contains other known preservatives, alkaline agents, and
Contains a H buffering agent, an antifogging agent, etc., and further contains a solubilizing agent, a color toning agent, a development accelerator (for example, chlorine salt, hydrazine, benzyl alcohol), a surfactant, an antifoaming agent,
water softeners, hardeners (e.g. glutaraldehyde),
It may also contain a viscosity-imparting agent.

As the fixer, one having a commonly used composition can be used. As the fixing agent, 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-soluble aluminum salt as a hardening agent.

The development processing method using an automatic processor in the present invention is disclosed in US Pat. No. 3,023,772 and US Pat. No. 3J/! It is preferable to use a roller conveyance type automatic developing machine as described in No. 164, No. 3!73 R1≠, No. 3611-7'tjt, British Patent No. 1262241, and the like.

The developing temperature is ir'c-to'c, especially 3o'C.
It is preferable that −≠s Oc, and the development time is preferably r seconds to ≠θ seconds, particularly t seconds to 2j seconds.

The entire development process from the start of development to the end of fixing, water washing, and drying is preferably from 30 seconds to 200 seconds, particularly from 10 seconds to 100 seconds.

There are no particular restrictions on the various additives, development methods, exposure methods, etc. of the photosensitive material of the present invention.
(February) and the same IT Hiroki item /r≠31 (/ri 7 r month) can be referred to.

(Example) Next, one aspect of the present invention will be specifically explained.

Example 1 (1) Preparation of silver iodobromide tabular grains Add 30 f of gelatin and 6 F of potassium bromide to 1 liter of water.
While stirring, a silver nitrate aqueous solution (silver nitrate: F) and a potassium bromide aqueous solution containing an iodizing power of +70, /j were added by double jet method over a period of 1 minute into a container maintained at 0°C. Further, a silver nitrate aqueous solution (ttazy as silver nitrate) and a potassium bromide aqueous solution containing potassium iodide μ and 2'Ji were added by a double jet method. The addition flow rate at this time is that the flow rate at the end of addition is the same as at the start of addition! The flow rate was accelerated to double the amount.

After the addition was completed, soluble salts were removed at Jj'C by a sedimentation method, the temperature was raised to ≠o'C, gelatin 7zy was additionally added, and the pH was adjusted to 6.7. The resulting emulsion consisted of tabular grains with a projected area diameter of 1 μm, an average thickness of 0, 1 μm, and a silver iodide content of 3 mol. This emulsion was chemically sensitized using gold and sulfur sensitization. After chemical sensitization, antifoggant≠-hydroxy-6-
Methyl-l.

! , Ja, 7-chitrazaindene was added, and a sensitizing dye (1) having the following structural formula was added to 1 mole of silver halogenide grains.
00119 was added to perform ortho sensitization. Furthermore, dodecylbenzenesulfonate as a coating aid and polypotassium p-vinylbenzenesulfonate as a thickener were added to form the basic formulation of the emulsion layer. The weight ratio of silver/gelatin at this time was l.

It was Qj. On the other hand, as a surface protective layer, a 7 wt % gelatin aqueous solution containing polymethyl methacrylate fine particles, saponin, polystyrene sulfonate, etc. in addition to gelatin was prepared, and this was used as the basic formulation. Gelatin and a water-soluble polymer substance are added to the emulsion layer and the surface protective layer solution in the proportions shown in Table 1, and the mixture is simultaneously coated onto a polyethylene terephthalate support and dried to produce a photographic material. 0 was created. At this time, different levels of drying speed were prepared by varying the amount of hardener added. The amount of silver coated is 1. It was coated on both sides as P/rIL2.

Measuring the amount lost during processing To measure what percentage (weight ratio) of the organic material that was applied before processing was washed away during the constant development, washing, and drying processes, the following method can be used: It can be measured by First, the sample was allowed to stand under conditions of zOC relative humidity to % until the water content reached equilibrium with the atmosphere, and then the weight of the sample was measured. Next, the sample was put into an automatic developing machine and processed from development to drying, and then again at 2!0C1 relative humidity 10%.
The sample was left under the following conditions, and the weight was measured when the moisture content reached equilibrium. The weight 1 of the support was measured in advance, and it was confirmed that there was no change in weight due to the treatment of only the support. The developed silver IT rate was determined by uniformly or not performing exposure at all, and from this value and the specific gravity of the silver halide, the weight loss due to development and fixing of the silver halide grains themselves was calculated. From these values, the weight of the organic material washed away during the treatment was determined. Although inorganic salts were also contained in the emulsion, their weight was negligible compared to the loss of organic substances. Here, we determined the amount of organic substances O washed away by weight measurement, but this value can also be found by measuring the film thickness before and after treatment, and the lost substances can also be determined by analyzing the processing solution. can.

Method for Measuring Drying Speed The automatic developing machine used was "Fuji X-ray Processor FPM Hiroooo" manufactured by Fuji Photo Film ■.

The developer and fixer had the following compositions.

(Developer) l-phenyl-3-pyrazolidone 1. ! ! Hydroquinone JQp; Troindazole O, Cojf Potassium Bromide
3. Qp anhydrous sodium sulfite
ray potassium hydroxide
309 Boric acid 109
Glutaraldehyde 19 Add water to bring the total volume to /l (pH adjusted to IO, CO) (Fixer) Ammonium thiosulfate COOO, oy Sodium sulfite (anhydrous) 20 Oy/Boric acid r, oy Ethylenediamine 4 Disodium acetate o, ip aluminum sulfate /j, 0 sulfuric acid
λ,oy glacial acetic acid
Add koλ, oy water
/, 01 (pH is adjusted to ≠, 20.) After the sample is developed using the above developer and fixer at FP Muooo and passes through the water washing process, it is squeezed and just before entering the drying zone. The film was taken out and the following measurements were made (at the time of this measurement, ppM4too
(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 JO0C was measured using a surface thermometer. The developing temperature was JJ'C, and the washing water temperature was 1H00.

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. Exposure occurred with 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 fog value +0.2. Further, the maximum density Dmax is a density value at which no increase in density occurs even if a higher exposure amount is applied. Sensitivity is sample l
is the standard, e is the case where the feeling is high, and e is the case where the feeling is low.
It was displayed as .

Evaluation of scratch resistance Using a commercially available nylon scrubber / 00 y 7cm2
After rubbing the sample in a dark room under a load of A-E shows the state of scratches observed after treatment! Sensory evaluation was performed in stages. As a guideline for evaluation, A...I can't really tell that there are any scratches.

C: Level with no practical problems. The scratches are
Hatsuki υ understand.

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 where you can hardly notice that there is any residual color C...... you are aware that there is some residual color, but it is not really noticeable for practical purposes E... . . . There is some residual color left on the markings, and the residual color is a problem in practice, and B and D are in an intermediate state.

The results of the above evaluation are shown in Table 1 together with the contents of the samples.

As organic substances to be eluted, polyacrylamide with an average molecular weight of r000 and dextran with an average molecular weight of 10,000 were used. The problem-free drying property obtained during continuous processing with FPM HirooOO corresponds to a drying rate of UF-22 seconds using this method.

The results in Table 1 show that when the amount of organic substances washed away exceeds 70%, high sensitivity is obtained when the drying rate is approximately the same, and the scratch resistance and residual color are significantly improved. Also,
Looking at the sample results, although it dries in about + time compared to the comparison sample, it has higher sensitivity and higher Dmax than the comparative sample, and its scratch resistance and residual color have been greatly improved. ing.

In the prior art, when trying to reduce the amount of hardener to make the sensitivity and Dmax advantageous, the drying speed was at a practically problematic level, as in Sample 1, and the scratch resistance was also deteriorated by one rank.

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

Example 2 Preparation of pure silver bromide tabular grains Under the preparation conditions of Example 1, all potassium iodide in the halogen solution added by the double jet method was removed. The obtained tabular emulsion has a projected area diameter of Oor μm and an average thickness of O
, ihiro 7 μm. This emulsion was chemically sensitized using gold/sulfur sensitization.

Thereafter, sensitizing dye (1) was added in an amount per mole of silver halide grains to effect ortho-sensitization.

The silver/gelatin weight ratio of this emulsion is /, O! Met.

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 rate was adjusted by adjusting the amount of hardening agent added, and the evaluation was performed in the same manner as in Example 1.

The amount of silver coated is 1. Polyacrylamide with an average molecular weight of 10,000 r, 10,000, and 7,000 r was used as the type of polymer coated on both sides to be washed away.

From Table 2, it is clear that the lower molecular weight 7b is better; the present invention has the same or higher drying speed, sensitivity,
It can be seen that the balance between Dmax, scratch resistance, and residual color is significantly improved.

Preferred embodiments of the present invention are as described above: 1. 2. A processing method according to claim 1, wherein the light-sensitive material is an X-ray light-sensitive material having at least seven silver halide emulsion layers on both sides of the support.

polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone in the emulsion layer and/or the surface protective layer,
The above/mentioned method using a photosensitive material containing dextrin or sucrose.

3. The above method using a photosensitive material containing polyacrylamide and/or dextran with an average molecular weight of less than 10,000 yen in the emulsion layer and/or the surface protective layer.

The above method ≠, wherein the average molecular weight of the polyacrylamide and/or dextran is 10,000 or less.

Hiroshi, the above/mentioned method in which the automatic developing machine is of a roller conveyance type.

! The above/mentioned method uses a photosensitive material containing polyacrylamide and/or dextran having a molecular weight of 20,000 or less in one surface-protecting layer.

t. The above method using a sensitive material having co-layers or more of silver halide emulsion layers on both sides of the support and containing polyacrylamide and/or dextran in the emulsion layers located at positions farther apart from the support. l method.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Date: January 1, 1986! 'FJ”i”18 Fl, Incident Display Showa J/Year Patent Application No. Kota G≠Oj No. 2,
Title of the invention Development processing method for silver halide photographic light-sensitive materials 3 Relationship with the case of the person making the amendment Patent applicant 4 Subject of the amendment Column 5 of "Detailed Description of the Invention" of the specification Details of the contents of the amendment The description in the "Detailed Description of the Invention" section of the book is amended as follows.

1) Hiro page/2nd line ``Add luster'' "Brings shine" and correct it.

2) Page j/Line J~/4L "Add color sensitizing dye" Delete.

3) Page r/line 1 [! The following "Less than 3" and correct it.

4) On page 72/line G, after "I can do it." it says, "As the chemical sensitization method, noble metal sensitization methods such as the gold sensitization method mentioned above, sulfur sensitization methods, etc. can be preferably applied, but please wait. The method described in JP-A-4/-313≠ can be preferably applied." is inserted.

Procedural Amendment July 1960 μ5 Dear Commissioner of the Patent Office 7.・1.Display of the incident Long-awaited Kota r4Los No. 2 in 1939
, Title of the invention Development processing method for silver halide photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent issuer address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Address: 106 Higashi 9, Kyoto, Nishi-Azabu, Iwa-ku 2-26-30 No. 4, subject to amendment
The description in column 5 of "Detailed Description of the Invention" of the specification and the section of "Detailed Description of the Invention" of the contents of the amendment will be amended as follows.

1) After "tetrazaindene" on the 77th line of page 2≠, add "copolymer latex of ethyl acrylate and methacrylic acid paste j:j weight ratio (addition amount is 20% by weight based on gelatin)" insert.

2) Page 36, line 1 Before “of the invention” Attachment-7 Insert.

Attachment/Example 6 As shown in Table 6, Samples 1 and 20 were prepared in exactly the same manner as in Example 1, except that dextran was used instead of polyacrylamide in Example 1.

The results shown in Table 6 were obtained in exactly the same manner as in Example.

Procedural amendment to the Commissioner of the Patent Office, -71
, Indication of the case 1972 Patent Application No.-25'r4'
Oj No. 2, Title of the invention Development processing method for silver halide photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address 106i Jr. 2-chome Zlj, Nishiazabu, Minato-ku, Kyoto No. 30 No. 4, Subject of amendment
Section 5 of the "Detailed Description of the Invention" in the Specification, Contents of Amendment The description in the "Detailed Description of the Invention" section of the description is amended as follows.

1) After "Preferable." on the rth page line, in the attached sheet -/, before the full text "Amount of silver coated,""The hardener in this case is described in the specification of JP-A-4/-//733. A vinyl sulfone hardener of Compound Example V-2♂ described in 1. "The addition of polymer increased the amount of hardener required to obtain the same drying rate."

3) Page 37! After "Method 1 above" in the row, "7. Method 3 above using dextran instead of polyacrylamide? 1. The content of polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, dextran, or sucrose in the surface protective layer is , the above-mentioned method using a photosensitive material having an amount of 30 wt 1 or more, preferably ≠Owt % or more of the total binder of the surface protective layer, and the above-mentioned method j using dextran instead of polyacrylamide.

Separate Tooth-7 "In the present invention, as the binder polymer that remains after processing and constitutes Image II, a binder that normally constitutes a photographic light-sensitive material can be effectively used. For example, a binder with an average molecular weight of 7
Gelatin (which may be lime-treated or acid-treated) involved in cross-linking of ~io million, and U.S. Patent No. 3. j／
Polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, dextran, etc. disclosed in ≠9.2t can be preferably used. Polymers other than gelatin having a molecular weight of iJ0,000 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 of the present invention. The low molecular weight polymer may have a wide molecular weight distribution and its high molecular weight components may remain, or the low molecular weight components may not be completely eluted and may be composed of the next component.

The amount of residual binder is preferably in a weight ratio of //j to 3 times the amount of coated silver, and more preferably 772 to 2 times. Among the binders of the light-sensitive material before development processing, gelatin preferably has a content of 6 t weight % to 0 weight %, more preferably 6 t weight % to 10 weight %.

The amount of remaining binder is i, z~At/ per one side.
m”, preferably 2 to 44 f/@2.

The residual binder is generally ensured by curing it with various crosslinking agents. Various crosslinking agents can be used, but any hardening agent generally known in the industry (as described in RD) can be used. Gelatin is also preferred as a residual binder, but the hardening agent may be bar, ≠-dichloro 4-Hydroxy/.

3,! -) IJ azine or a compound having an active vinyl group, halo-substituted formamidinium salts, or carbamoylammonium salts can be preferably used.

Compounds having an active vinyl group include, for example, Machikai Kaita 3-μlλko 1, JP-A-13-172!7, JP-A-11-/ko-412≠, and Machikosho≠2-13rtJ. issue,
JP-A Sho-j/-1-II/441, JP-A Sho-Yoko 210
! No. 3, U.S. Poetry License No. 3, No. 77, 3j3! F4$
No. 44, Jtaurt No. 10-3! No. 107, Shikaikai J$-3002λ No. 107, Tokukai Sho! rJ-A42≦
No. 0, Tokuko Akira! Ko←luri No. 5, special public Sho 4A7-173
No. z, U.S. Patent No. 363171I, No. 30 No. 0720
Examples include compounds described in No., Nishi[=H.r7λ/j3].

Compounds having a halo-substituted formamidinium group include, for example,
Mention may be made of the compounds described in No. 2140236.

As a compound having a carbamoylammonium group,
For example, Tokuko Showa JG-/2113, Tokuko Showa 11-72
Mention may be made of the compounds described in No. 422.

Furthermore, as the gelatin hardener used in the present invention, a polymer hardener can be effectively used.
The polymer hardener described in -4/7φ2 provides a favorable effect. ” Procedural amendment

Claims (1)

[Claims] In a method of developing a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer containing tabular grains having an aspect ratio of 5 or more on a support using an automatic processor, developing Development processing of a silver halide photographic light-sensitive material, characterized in that the amount of organic substances present in the emulsion layer and/or other hydrophilic colloid layer after completion of processing is 90% by weight or less of that before development processing. Method.