JPS62279329A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an improved wet film strength by incorporating a gelatin contg. >=12wt% high mol.wt. component in the lowest layer among hydrophilic colloid layers contg. >=0.5g/m<2> gelatin, and the gelatin contg. <12wt% high mol.wt. component in an upward layer than the lowest layer of the hydrophilic colloid layer, respectively. CONSTITUTION:In the titled material having at least two layers of the hydrophilic colloid layers mounted on a substrate, the gelatin contg. >=12wt% high mol.wt. component is incorporated in the lowest layer among the hydrophilic colloid layers contg. >=0.5g/m<2> gelatin. At least one layer of the hydrophilic colloid layers lying in upwards than the lowest layer contains the gelatin having <12wt% high mol.wt. component. Thus, the titled material having the improved wet film strength in a liquid developer, etc., and the improved property of the advancement of developing is obtd.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and in particular improves development progress and wet film strength in a processing solution. This invention relates to an improved silver halide photographic material.

(Prior art) Tank development or automatic processor processing is usually used to develop photographic materials, but recently there has been a trend towards faster processing using automatic processors due to demands for faster work. It's getting stronger. The performance required of photographic materials due to rapid processing is good development progress. Good development progress means that the time required to give a certain amount of exposure to a photographic light-sensitive material and produce a certain density is short. An automatic developing machine generally has a developing tank, a stop tank, a fixing tank, a washing tank, a drying zone, etc. within the machine, and the transport speed and processing temperature of the photographic material can be adjusted.

As a means for accelerating the progress of development, it is generally known to increase the swelling of the silver halide emulsion layer of a light-sensitive material. A common means of increasing the swelling of the silver halide emulsion layer is to reduce the amount of gelatin hardener used in this layer.

However, when the amount of gelatin hardener in the silver halide emulsion layer is reduced to increase swelling, the wet film strength in a developer or the like decreases.

If the strength of the wet film decreases, failures may occur, such as the film being torn by the conveyance roller in an automatic processor, resulting in scratches on the photographic image after drying.

It is also conceivable to increase the temperature of the developing solution as a means of accelerating the progress of development, but in this case as well, the swelling of the photographic light-sensitive material becomes large and the above-mentioned failure occurs.

(Problems to be Solved by the Invention) The purpose of the present invention is to improve the wet film strength in a developer,
Another object of the present invention is to provide a silver halide photographic material having excellent development progress properties.

(Means for solving problems) These objects have been achieved by the invention described below.

That is, the present invention provides a silver halide photographic material having at least co-layers of hydrophilic colloid layers on a support, in which the amount of gelatin contained in the layer is 0. ! g/m2 or more, the lowest layer of the hydrophilic colloid layers contains gelatin containing 12% by weight or more of a high molecular weight component, and at least seven hydrophilic colloid layers among the layers above the lowest layer. is a silver halide photographic light-sensitive material characterized by containing gelatin containing less than 12% by weight of high molecular weight components.

Hereinafter, the "lowest layer" hydrophilic colloid layer in the present invention refers to the amount of gelatin contained in the layer of 0. ! It refers to the lowest layer of the hydrophilic colloid layers having a density of g/m2 or more.

A specific configuration of the present invention will be explained in detail.

The silver halide photographic material of the present invention has at least two hydrophilic colloid layers on a support, and the gelatin contained in the lower hydrophilic colloid layer has a high molecular weight component of 12
% by weight or more, preferably 3% by weight or more, preferably 3% by weight or more
The gelatin contained in the upper hydrophilic colloid layer contains less than 12% by weight (including 0% by weight) of high molecular weight components, preferably 2% by weight or more and 10% by weight or less. . In this case, the gelatin may be either lime-treated gelatin or acid-treated gelatin.

The proportion of high molecular weight components of gelatin in the present invention is determined by gel permeation chromatography (hereinafter referred to as "Gel permeation chromatography").
Pc method).

Regarding this method, Takashi Ohno, Hiroyuki Kobayashi, Shinya Mizusawa, “
"Journal of the Photographic Society of Japan", Vol. 2, No. 2, 2013, 237-
It is explained in detail on page 24t7.

The conditions for the GPC method are shown below.

a, Column: GS-Otsu 20 (Asahi Kaseisha split), length r o
o mm, temperature 32 °C1φ7゜mmXj 1 separation liquid 0.0! M Na2HP04-KH2P
O4 aqueous solution, flow rate/ml/min.

C0 detector, ultraviolet absorption spectrophotometer (UV: wavelength 2! dnm) Sample for d0 analysis: Absolute XO, 4tμg gelatin
imeχ The GPC curve obtained by taking the absorbance on the vertical axis is
First, a peak at the exclusion limit appears, then peaks that appear to be the β and α components of gelatin appear, and as the retention time becomes longer, the shape becomes tailed.

The ratio of the high molecular weight component in the present invention is determined by calculating the ratio of the area of the peak of the exclusion limit to the total area. Specifically, retention time 2!
A perpendicular line is drawn from the minimum point of the GPC curve appearing in the quantile to the horizontal axis, and the ratio of the area of the portion to the left of the perpendicular line (high molecular weight component) to the total area is calculated.

The general method for producing gelatin is well known.
For example, Tea, H. James (T.

H. James), The Theory of the Photographic Pouse, < (The Theory
of the Photographic Process
ss) 9th edition, 7977 [Mlcmi 7 (Mlcmi
Published by L an),! ! Page, Scientific Photography Handbook (top)
, 22-7! Page (Maruzen Co., Ltd.), written by Makoto Kikuchi, Photo Chemistry, 7 Layers, 7 Years (Kyoritsu Shuppan), 2 to 3 pages, edited by Akahori 4 and Mizushima 3, Protein Chemistry, 79! Year (Kyoritsu Publishing) Da! It is described on page 3 etc.

For example, lime-processed gelatin is made as follows. First, in order to remove keratin, cow skin and bones are soaked in saturated lime water (lime soaking) in two layers for 3 months, then washed with water, neutralized, and extracted for 3 to 2 hours in hot water of about 6,000 yen (No. 7 Extraction) is carried out, followed by No. 2 extraction at the tt 0 layer, No. 3 extraction at the 2nd layer 00, and finally No. 2 extraction by heating near the boiling point. After extraction,
filtered, concentrated under reduced pressure below General VCRo °C, and concentrated to 1
It is made by cooling and solidifying at around 0°C and drying at around 2!0°C.

For example, the following method can be used to produce gelatin containing a large amount of high molecular weight components according to the present invention.

Manufacturing method ■ In the extraction operation in the above manufacturing method, the gelatin extract from the latter stage of extraction is used to eliminate the gelatin extract from the early stage of extraction.

Manufacturing method ■ In the above manufacturing method, the processing temperature is set to less than 9,080 degrees during the manufacturing steps from extraction to drying.

Manufacturing method ■ Dialyze gelatin gel with cold water (/r'c) [The Journal of Photographic Science,
(The Journal of Photography
phic 5science), volume 23, page 33 (/Wa 7th)].

Production method ■ Fractionation method using isopropyl alcohol [
Discussions of the Faraday Society
raday 5ocity), //volume, 2/? page(/
the law of nature! (see )).

By using the above-mentioned methods alone or in combination, it is possible to obtain the gelatin of the present invention having a high molecular weight component/co-weight of o-cent or more.

As the binder and protective colloid that can be used in the hydrophilic colloid layer of the photosensitive material of the present invention, in addition to the high molecular weight gelatin of the present invention, ordinary gelatin and other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate, dextran, and starch derivatives: Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly(+) N-vinylpyrrolidone,
Multiple synthetic hydrophilic polymeric materials such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

The hydrophilic colloid in the bottom layer of the present invention has a weight of 0.
% or more, especially? Preferably, θ or more is the high molecular weight gelatin according to the present invention, and at least 7 of the hydrophilic colloids in the upper layer have a weight of 60% or more, especially 20
It is preferable that the width or more is gelatin according to the present invention, which has a high molecular weight component of less than 12% by weight.

In the present invention, the hydrophilic colloid layer refers to a layer containing hydrophilic colloid, that is, gelatin, such as a photographic emulsion layer, a protective layer, an intermediate layer, and a back layer.

In the present invention, the lowermost hydrophilic colloid layer and the upper hydrophilic colloid layer may be any of the above layers, and may be either a photosensitive layer or a non-photosensitive layer.

The lowermost hydrophilic colloid layer in the present invention is 0
．． It is preferable that gelatin is contained in an amount of 7 g/m 2 or more and 10 g/m 2 or less.

When there are three or more hydrophilic colloid layers in the photographic light-sensitive material of the present invention, the hydrophilic colloid layer containing gelatin containing less than 12% by weight of a high molecular weight component is provided above the bottom hydrophilic colloid layer. It may or may not be adjacent to the bottom layer. In addition, a layer containing gelatin containing 12% by weight or more of a high molecular weight component, and a layer containing 12% by weight or more of a high molecular weight component.
Each layer containing gelatin containing less than 2 parts by weight
There may be more than one layer. In addition, if there is a layer containing gelatin containing 12% by weight or more of a high molecular weight component other than the bottom layer, that layer may or may not be adjacent to the bottom layer, but it may or may not be adjacent to the bottom layer. It is preferable to

Hardening agents that can be used in the present invention include mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucofenoxybromic acid, formaldehyde, dimethylolurea, trimethylolmelamine, glyoxal, monomethylglyoxal, co-,3-dihydroxy-/ , 4-
Dioxane, λ.

3-dihydroxy-! -methyl/, aldehyde compounds such as 4t-dioxane, succinic aldehyde, 21-dimethoxytetrahydrofuran, glutaraldehyde; divinyl sulfone, methylene bismaleimi)',
j-7sefrou/ , ! -diacryloyl-hexahydro-S-triazine, /,! #-1 Reacryloil-
Hexahydro-3-) riazine, /,! , J--)lipinylsulfonyl-hexahydro-3-triazinebis(
vinylsulfonylmethyl) ether, /, 3-bis(vinylsulfonylmethyl)furopanol roots, bis(α-
Active vinyl compounds such as vinylsulfonylacetamido)ethane: 2. ', t-dichloro-6-hydroxy-/, 3.3-) riazine sodium salt, co-dichloro-methoxy-3-triazine, λ, 9-dichloro-(gousulfoanilino) -a - ) riazine sodium salt, 2, K-”) chloro-t-(
,2-sulfoethylamino)-3-)riazine,N,N
/-Bis(-13-epoxypropyl)methylpropylammonium p-toluenesulfonate, /lt, t-bis(2 ′.

3'-epoxypropyloxy)butane, /, 3゜j-
Triglycidyl isocyanurate, /, 3-diglycidyl-! - Epoxy compounds such as (γ-acetoxyβ-oxinepropyl)in cyanurate: 2.4t, 6
-) diethyleneimino-S-triazine, /, O-hexamethylene-N, N'-bisethyleneurea, bis-β-
Ethyleneimine derivatives such as ethyleneiminoethylthioether; /, 2-di(methanesulfonoxy)ethane7, /, 'l-di(methanesulfonoxy)butane, /,! -Methanesulfonic acid ester compounds such as di(methanesulfoneoxy)pentane; Japanese Patent Publication No. 12713, Ibid. ♂-32399, Tokukai Sho Geter! /ri 9t issue, same! /-! Riotsu 2! No. 6/-
Carbamoylammonium salt-based compounds described in Tao-da/No.: Amidinium salt-based compounds described in JP-A-60-2 Uj/'l♂; and carbodiimide-based compounds: isoxazole-based Compounds; inorganic compounds such as chromium bread and U.S. Patent No. 3.0!7
．． No. 123, No. 3.3, No. 0.29, No. G, /
Examples include polymeric hardeners described in No. 1/, No. 4t07, and the like.

Hardening agent i:f'i varies depending on the type of hardening agent and the drying conditions during the production of photosensitive materials, so it cannot be decided on a case-by-case basis, but 10θg of dry gelatin and 0.7~ ! θ
mmol, especially 0. ! ~/! It can be appropriately adjusted within the millimole range.

The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually prepared by combining a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution with the above-mentioned water-soluble polymer solution containing gelatin. It is made by mixing in the presence of

As the silver halide, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can all be used, and their grain shapes (cubic, dihedral, /Z-hedron, rhombic / co-shaped) can be used. There are no particular limitations on the size distribution (polydisperse or monodisperse).

The photographic emulsion to be used in the present invention may contain a compound of aphids for the purpose of preventing capri during the manufacturing process, storage or photographic processing of the light-sensitive material, or for stabilizing photographic performance. namely, azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, promove/zimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds (e.g. Mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (%/-phenyl-!-mercaptotetrazole], mercaptopyrimidines, mercaptotriazines, etc.); For example, oxadorinthion thioketo compounds; azaindenes [e.g. triazaindenes, tetraazaindenes (especially hydroxy-substituted
/ , 3.3a, 7) Tetraazaindenes), pentaazaindenes, etc.): benzenethiosulfonic acid,
Many compounds known as anti-capri agents or stabilizers can be added, such as benzenesulfinic acid, benzenesulfonic acid amide, etc.

For more detailed examples of these and how to use them, see, for example, U.S. Patent No. 3. Wow! 9°g 7g No. 3.9/ko, Tag No. 2, Tokko Akira! 2-2♂ Those described in Otsu No. 60 can be used.

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

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycols Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Agent: Alkylcarboxylic acid L furkyl sulfonate, alkylbenzene A/7-onate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Anions containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphate esters, etc. Surfactants: Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates, phosphoric esters, alkyl betaines, amine oxides; Alkylamine salts, aliphatic or aromatic 9th class ammonium salts , cationic surfactants such as heterocyclic 9th class ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles;
Japanese Patent Application Publication No. 1012.2, British Patent No. 1,33θ,
3! No. Otsu, Tokukai Sho J3-♂ Gua/No. 2, same J Gu 14t
2nd cog issue, same! 0-//3 here/issue, special request! Tar 23
．． No. 4390, U.S. Patent No. 33! , , No. 20/, same No. 3, No. 304”, British Patent No. 1゜4t/
7. the law of nature/! No., Tokuko Akinoko-263/7, same! 7-2
Otsu No. 779, same! Tar 37! No. 73, Tokukai Sho! ! -/Da993♂ issue, same! Rita and No. 120, same! Goo/y22
Y issue, agreed d'-, 20023! No. 67-/4tt
2g? No. j/-/7jjlg, British Patent Nos. 1 and 4
Fluorine-containing surfactants described in t3, No. 90.2, etc. can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or others. The dyes used include
cyanine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioquinol dyes. Particularly useful dyes are cyanine dyes,
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. Namely, viroline 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 of 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 contain pyrazoline as a core with a ketomethylene structure! -on nucleus, thiohydantoin nucleus, low thiooxazolidine-λ,
4t-dione nucleus, thiazolidine-2,4t-dione nucleus,
It is possible to apply t-member allochthonous nuclei such as rhodanine nuclei and thiobarbic acid nuclei.

The photographic light-sensitive material used in the present invention includes a photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability.
Dispersions of water-insoluble or sparingly soluble synthetic polymers can be included. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer containing a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, US Patent No. 2,4tθ0
．． ! 3λ No. 2. ri, 23. ! -¥9 No. 9, same No. ko,
No. 276.062, No. 3, 4/7, 2♂O, No. j
, No. 712.027, No. 3. ? 0♂, θθ3, British Patent No. 7. the law of nature! Those described in ♂, RI No. 9/, etc. can be used.

There are no particular limitations regarding other constituent elements of the photographic light-sensitive material of the present invention; for example, research disclosure magazine/7
The description in Vol. 22-2, p.

For photographic processing of the light-sensitive material of the present invention, any known method may be used, and known processing solutions may be used. Also, the processing temperature is usually /? The temperature is selected between 0C and 50C, but the temperature may be lower than /♂0C or higher than 50C. Depending on the purpose, either a development process that forms a silver image (black and white photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied. The developer contains dihydroxybenzenes (hydroquinone with side light), 3-pyrazolidones (e.g. /-phenyl-3-pyrazolidone).
, amine phenols (for example, N-methyl-p-amine phenol), and the like can be used alone or in combination.

(Effects of the Invention) According to the present invention, a silver halide photographic material with improved wet film strength in a developer and the like and with improved development progress can be obtained.

(Examples) Hereinafter, specific examples of the present invention will be shown and effects of the present invention will be explained in detail, but the present invention is not limited to these examples.

Example/The Theory of the Photographic Process, written by T. H. James
tographic Processes) 9th edition, 7977
[Published by Macmi 11 an],
! ! Lime-processed gelatin was prepared according to the method described in the literature, et al. In this case, the high molecular weight components were adjusted by the production methods (1) and (2) described in the detailed description of the invention, and gelatins A to D containing high molecular weight components as shown in Table 7 were prepared.

Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous solution of gelatin A shown in Table/ Table/ with vigorous stirring to form a thick plate-shaped silver iodobromide emulsion with an average grain size of 2 μm (AgI = J mole percent). ) was prepared.

Thereafter, it was washed with water by a conventional precipitation method, and chemically sensitized by a gold/sulfur sensitization method using chloroauric acid and sodium thiosulfate. 3&,7-chitrazaindene was added to obtain a photosensitive silver iodobromide emulsion a.

A thick silver iodobromide emulsion with an average grain size of 0.3 μm was prepared in the same manner as emulsion a (but at a lower temperature), and
Chemical sensitization was carried out in the same manner as above, and a stabilizer was added to obtain emulsion a'.

Using these emulsions a and a', the following layers were sequentially placed on a triacetyl cellulose support to prepare a sample.

1st layer (emulsion layer) Emulsion a' Binder, gelatin A K, /g/m2 Coated silver amount: 2. ! g/m2 Application aid Dodecylbenzenesulfonic acid sodium salt 0
, /mg/m2 Poly p-styrene sulfonate phosphorus salt 0, /mg/rn2 first layer (
Emulsion layer) Emulsion a Binder: Gelatin A r, jg/m2 Coating silver amount: j, 9 g/m2 Coating aid, dodecylbenzenesulfonic acid sodium salt 0
, /mg/m2 Poly p-styrene sulfonate phosphorus salt /mg/m2 Hardener: , 2-hydroxyda, ≦-cyclolo s -
Triazine sodium salt 0.0-! mg/m2 Third layer (surface protective layer) Binder: Gelatin A O, 7 g/m2 Coating aid: N-oleoyl-N-methyltauryl sodium salt 0, . 2 mg/m2 Matting agent: Polymethyl methacrylate fine particles (average particle size 3 μm) o, 73 mg/m2 In addition, in emulsion a and emulsion a', gelatin B and gelatin D were used in place of gelatin A to obtain emulsions. Let b-d correspond to emulsion a, and b' to d' correspond to emulsion a'.

Using these emulsions, samples λ to 10 were prepared in the same manner as Sample 1 by combining them as shown in Table 2 below.

In this case, the binder used is also listed.

Table-2 These samples 7 to 10 are xtoCX! It was stored for 7 days after application at the temperature and humidity of CHRH. Each sample was exposed to 900 lux tungsten light through an optical wedge for 7770 seconds, and then developed for 7 minutes, 7 minutes, and 12 minutes at 500C in the following developer solutions, respectively.

The photographic sensitivity of each fixed, washed, and dried sample was measured using the same method at a constant density (optical density of θ, /) higher than the fog density.

Developer Metol 2g Sodium sulfite 100g Hydroquinone
Ogborax tH20/
, J'3g Add water /1 (adjust pH to ?,!) Fixer ammonium thiosulfate, 200.0g sodium sulfite (anhydrous) 2θ, 9g boric acid
♂, Og disodium ethylenediaminetetraacetate 0.1g aluminum sulfate θ, /g sulfuric acid
2.0g glacial acetic acid
Here, add 0g water
/, 01 (pH was adjusted to λ, λ) Furthermore, using these samples, the wet film strength was measured. Wet film strength was measured as follows.

Wet membrane strength sample/~10 in distilled water at 2!0C! After immersion for minutes, a steel ball with a radius of o and rmm is pressed onto the sample membrane surface with a needle attached to the tip, and the load on the needle is continuously changed while moving at a speed of /θmm/sec to destroy the membrane. The load (g) at the time (that is, scratches were generated on the surface of the sample film) was measured.

Furthermore, measurements were made not only in distilled water but also in developer solution. However, the temperature of the developer is 2o0c, and the sample/~
The soaking time for No. 10 was 7 minutes.

The developer used at this time had the above formulation.

These results are shown in Table-3.

As is clear from Table 3, it can be seen that sample Glue B has significantly stronger wet film strength than Samples /~3 and Samples #7~. Moreover, the sensitivity at the early stage of development (4t' development) is equal to or higher than that of Samples/-3 and Samples 7-9. Sample 10 also has a high level of flat film strength compared to samples y to 6, but the sensitivity in y/ and 7' development is not achieved. That is, sample 4t-6 has better development progress.

Emulsions a and a' in Example/Example/A were prepared in the same manner as in Emulsion a and a' (however, a'
(by further lowering the temperature) the average particle size is 0. A plate-like silver iodobromide emulsion with a diameter of 10 μm was prepared, and emulsion a was prepared.

Emulsion a was chemically sensitized in the same manner as a' and a stabilizer was added.
” got.

Using these emulsions a, a', a'', the following layers were placed in order on a triacetyl cellulose support and the sample //
It was created.

1st layer (emulsion layer) Emulsion a // Binder: Gelatin A /, jg/m2 Coating silver amount: 0.7 g 7 m2 Coating aid Nidodecylbenzenesulfonic acid sodium salt 0
, Of mg/m2 Poly-p-styrene sulfonate potassium salt 0.9 mg/m2 Second layer (emulsion layer) Emulsion a'Binder; Gelatin A 2. J'g/m2 Coating silver amount: 7.7 g/m2 Coating aid nidodecylbenzenesulfonic acid sodium salt
0, J'mg/m2 p-styrene sulfonate botanium salt Q, mg/m2 Hardener 2-hydroxy-, 6-dichloro-s-
) Lyazine sodium salt 0°026 mg/m2 3rd layer (emulsion layer) Emulsion a Binder: Gelatin A ♂,! g/m2 coating silver amount: j, 9 g/m2 coating aid, dodecylbenzenesulfonic acid sodium salt 0
, /mg/m2 Poly p-styrene sulfonate potassium salt /mg/m2 Second layer (surface protective layer) Binder Gelatin A O, 7g/m2 Coating aid: N-oleyl-N-methyltauryl sodium salt
0, 2 mg/m2 Matting agent "Polymethyl methacrylate fine particles (average particle size 3 μm) θ, /jmg/m2 In addition, Example /
Emulsions were obtained using gelatins B-D. The emulsions corresponding to emulsion a" are designated as emulsions b//-C". Using these emulsions, combine as shown below to prepare Samples /2 to /! in the same manner as Sample //! It was created.

Table sample //~/! The film was developed in the same manner as in Example/, and the wet film strength was measured. Table these results! It was shown to.

Table-! From sample //~/! Compared to Sample/Da, the sensitivity is almost the same, but the wet film strength is weaker.

Therefore, it can be seen that the photosensitive material of the present invention has excellent wet film strength without impairing the progress of development.

Procedural amendment July 28, 1972 stomach

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least two hydrophilic colloid layers on a support, the lowest layer of the hydrophilic colloid layers in which the amount of gelatin contained in the layer is 0.5 g/m^2 or more contains gelatin containing 12% by weight or more of high molecular weight components, and at least one hydrophilic colloid layer among the layers above the bottom layer contains gelatin containing less than 12% by weight of high molecular weight components. A silver halide photographic material characterized by