JP2796832B2 - Silver halide photographic material that can be processed quickly - Google Patents

Description

The present invention relates to a silver halide photographic material,
More particularly, the present invention relates to a silver halide photographic light-sensitive material which has no processing unevenness and can be processed quickly and has a fast drying property.

[Background of the Invention]

Recently, the processing time of silver halide photographic light-sensitive materials has been increasing in response to the needs of users with the increase in film consumption, and medical light-sensitive materials are no exception.

On the maker's side, the development of the silver halide composition of the photosensitive material itself and the development accelerator are used to improve the developability, and the developer composition and processing conditions are activated to make the processing speedier. Efforts are being made.

However, one of the biggest problems that accompanies the speeding up of processing is that the obtained image has processing unevenness.

In particular, when the processing time is within several tens of seconds, a coloring organic compound such as a spectral sensitizing dye or an irradiation and antihalation dye or a filter dye added to the silver halide photographic light-sensitive material is added to the processing bath. In other words, the time required for decolorization / decomposition or elution from the photosensitive material is insufficient.

As a result, not only a clear image cannot be obtained by leaving uneven color contamination in the processed image, but also a serious negative effect that leads to a misdiagnosis in a medical photographic material is brought.

Another obstacle to rapid processing is the drying properties of the photosensitive material after processing. That is, since the processing time is short, the processing is completed without being sufficiently dried, so that cracks and scratches occur.

Conventionally, various proposals have been made for such obstacles, for example, a technique of making a structure in which pigments and dyes are easily eluted, or gelatin as a means for reducing the water absorption of a photosensitive material with respect to the improvement of drying property of the latter. As a method of increasing the degree of curing of the film or a direct method, there is known a technique of reducing the water absorption by reducing the amount of a binder component, that is, gelatin, in a silver halide emulsion layer or a backing layer.

However, these prior arts still have problems such as little effect on the recent ultra-rapid processing and the fact that the compounds have difficulty in practical use. Further, the method of reducing the weight of gelatin in a silver halide emulsion layer causes, for example, an increase in fog or deterioration of graininess in photographic characteristics, and furthermore, physical resistance such as scratches tends to deteriorate. Also, it is not preferable to reduce the amount of gelatin in the backing layer. For example, it becomes impossible to keep the curling of the film (development curving to the emulsion side or the opposite side) in a well-balanced manner, and as a result, a trouble in automatic conveyance is caused. Results.

As described above, there are many problems on the light-sensitive material side in order to promote rapid processing, and the solution thereof has been strongly desired.

[Object of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic light-sensitive material having a backing layer containing an antihalation dye, capable of forming a clear image free of residual color contamination based on the dye and capable of rapid processing. The object of the present invention is to provide a silver halide photographic light-sensitive material.

A second object of the present invention is to provide a silver halide photographic light-sensitive material which can be rapidly processed and has a backing layer having fast drying properties and sufficient film properties in film drying in a processing step.

 Other objects will be apparent from the following description.

[Configuration of the invention]

As a result of intensive studies, the present inventors have found that in a silver halide photographic material having at least one silver halide emulsion layer on one side of a support and a backing layer on the other side, At least one of the water-soluble polymers represented by the following general formula [I] is contained in at least one of the backing layers in an amount of 5% to 20% of the total weight of the backing layer;
The object of the present invention can be easily achieved by a rapidly processable silver halide photographic material which is processed by a roller transport type automatic developing machine under the conditions represented by the following formula [A] after imagewise exposure. This led to the achievement of the present invention.

Formula [A] l ^0.75 × T = 50 to 130 (0.7 <l <4.0) where l is the processing length (unit:
m), and T represents the time (sec) required to pass through l.

 Hereinafter, the present invention will be described in detail.

The silver halide photographic material has a structure in which a photosensitive silver halide emulsion layer is coated on one or both sides of a support.
Among them, in a photosensitive material having an emulsion layer coated on one surface of a transparent base as a support, an antihalation layer is generally provided below the emulsion layer or on the side opposite to the emulsion layer.

The layer comprises a colored layer that absorbs visible light so that light passing through the photosensitive layer is not reflected.

The backing layer according to the present invention refers to a layer in which the antihalation layer is provided on the side opposite to the silver halide emulsion layer. The dye for forming the colored layer must have appropriate spectral absorption characteristics according to the color sensitivity of the light-sensitive material and also satisfy the following conditions.

(1) It is chemically inert without adversely affecting photographic characteristics.

(2) No decoloration during the development process or elution at the time of processing or washing with water to leave no harmful coloring on the processed photosensitive material. Another requirement is that the film be placed in a safelight in a dark room. When handled below, it is also easy to distinguish between front and back.

As a dye for satisfying such conditions, many studies have been made for a long time, and for example, a water-soluble dye shown below is widely known.

That is, among oxonol dyes, hemioxonol dyes, cyanine or merocyanine dyes, styryl dyes, azo dyes and the like, oxonol and hemioxonol dyes are useful.

Dyes that can be used in the backing layer according to the present invention include, for example, those described in U.S. Pat. No. 2,274,782, British Patent No. 446,583, Japanese Patent Publication No. 39-2269, and Japanese Patent Application Laid-Open No. Sho 57-185038. Preferred, especially JP-A-57-1850
The one described in JP-A No. 38 is preferably used.

Next, the water-soluble polymer used in the backing layer according to the present invention will be described.

In the present invention, the water-soluble polymer is not necessarily required to have high solubility in water, but refers to a polymer having solubility in water.

For example, about 0.05 g or more may be dissolved in 100 g of water at 20 ° C., preferably 0.1 g or more. The water-soluble polymer used is preferably the higher the solubility in a developer or a fixing solution, and the solubility is preferably 0.05 or more, more preferably 100 g of the developer, more preferably
It is preferable to dissolve 0.5 g or more, and particularly preferable to dissolve 1 g or more.

The water-soluble polymer may be natural or synthetic.

Among the water-soluble polymers that can be used in the present invention, examples of the synthetic water-soluble polymer include those having a nonionic group in the molecular structure, those having an anionic group, and those having both a nonionic group and an anionic group. Can be mentioned. Here, examples of the nonionic group include an ether group, an ethylene oxide group, and a hydroxy group. Examples of the anionic group include a sulfonic acid group or a salt thereof, a carboxylic acid group or a salt thereof, and a phosphoric acid group or a salt thereof.

The synthetic water-soluble polymer may be a homopolymer or a copolymer. The copolymer may be a copolymer with a partially hydrophobic monomer, as long as the polymer itself is water-soluble.

Examples of the natural water-soluble polymer include those having a nonionic group, those having an anionic group, and those having both a nonionic group and an anionic group in the molecular structure.

Examples of the water-soluble polymer of the present invention include those containing a repeating unit of the following general formula [I], particularly those containing 10 to 100 mol% in one molecule of the polymer.

These synthetic water-soluble polymers are known compounds, for example, West German Patent Application (OLS) 2,312,708, U.S. Pat.
No. 620,751, No. 3,879,205, JP-B-43-7561, and the like, or a method analogous thereto.

In the formula, R ¹ and R ² may be the same or different and each is a hydrogen atom, an alkyl group, preferably an alkyl group having 1 to 4 carbon atoms (including those having a substituent. For example, a methyl group, an ethyl group, a propyl Group, butyl group, etc., and those having a substituent attached thereto).

L is -CONH-, -NHCO-, -COO-, -OCO-, -CO
—, —SO ₂ —, —NHSO ₂ —, —SO ₂ NH— or —O—.

J represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms (including those having a substituent; for example, a methylene group, an ethylene group, a propylene group, a trimethylene group, a butylene group, a hexylene group, and the like; ), An arylene group (including those having a substituent, such as a phenylene group and the like with a substituent attached thereto), an aralkylene group (including those having a substituent).
For example Or CH ₂ CH ₂ O _m CH _{2 n} , (M represents an integer of 0 to 40, and n represents an integer of 0 to 4).

Q is a hydrogen atom or Or R ³ , wherein M and M ² represent a hydrogen atom or a cation group, and R ⁹ is an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group or the like or R ³ , R ⁴ , R ⁵ ,
R ⁶ , R ⁷ and R ^{8 each} represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a decyl group, a hexadecyl group, etc.) Attached), an alkenyl group (for example, a vinyl group, an aryl group, or the like or a substituent thereof), a phenyl group (for example, a phenyl group, a methoxyphenyl group, a chlorophenyl group, or the like, or a substituent thereof). , An aralkyl group (for example, a benzyl group or the like or a substituent thereof), X represents an anion, and p and q each represent 0 or 1.

Y represents a hydrogen atom or L _p J _{q Q.}

The synthetic water-soluble monomer constituting the unit represented by the general formula [I] can be copolymerized with an ethylenically unsaturated monomer. Examples of the copolymerizable ethylenically unsaturated monomer include styrene, alkylstyrene, hydroxyalkylstyrene (the alkyl group preferably has 1 to 4 carbon atoms, such as methyl, ethyl, and butyl), vinylbenzenesulfonic acid and the like. Salt, α-methylstyrene, 4-
Vinylpyridine, N-vinylpyrrolidone, monoethylenically unsaturated esters of aliphatic acids (eg, vinyl acetate, vinyl propionate, etc.), ethylenically unsaturated monocarboxylic or dicarboxylic acids and salts thereof (eg, acrylic acid, methacrylic acid) ), Maleic anhydride, esters of an ethylenically unsaturated molar carboxylic acid or dicarboxylic acid (eg, n-butyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate).

Next, specific compounds of the synthetic water-soluble polymer having a repeating unit represented by the general formula [I] are exemplified, but the present invention is not limited thereto.

 The numerical value in parentheses is the average molecular weight Mn.

When using the above synthetic water-soluble polymer, its molecular weight is preferably 1,000 to 100,000, more preferably 2,000 to 50,
Use 000 ones.

Among the above, examples of the polymer particularly preferably used in the present invention include, for example, 1-3, 1-7, and 1-12.

Next, examples of the natural water-soluble polymer that can be used in the present invention include those described in detail in a comprehensive technical data collection of a water-soluble polymer water-dispersible resin (publishing department of Business Development Center). In particular, lignin, starch, burlan, cellulose, alginic acid, dextran, dextrin, guar gum, gum arabic, pectin, casein, agar, xanthan zam, cyclodextrin, locust bean gum, tragacanth gum, carrageenan, glycogen, laminaran, lichenin, nigellan, And their derivatives.

Derivatives of natural water-soluble polymers include sulfonated,
Carboxylated, phosphorylated, sulfoalkylated, or carboxyalkylated, alkyl phosphorylated,
And salts thereof, polyoxyalkylenes (eg, ethylene,
Glycerin, propylene, etc.) and alkylation (methyl, ethyl, benzylation, etc.) are preferred.

Two or more natural water-soluble polymers may be used in combination.

Among natural water-soluble polymers, a glycose polymer and a derivative thereof are preferable, and among the glycose polymer and a derivative thereof, starch, glycogen, cellulose, lichenin, dextran, and nigeran are preferable, and dextran and a derivative thereof are particularly preferable. preferable.

Dextran is a polymer of α-1,6-linked D-glycose and is generally obtained by culturing dextran-producing bacteria in the presence of saccharides. Thus, the separated dextran sucrose can be obtained by reacting with saccharides. Further, these native dextrans are reduced to a desired molecular weight by a partial decomposition polymerization method using an acid or an alkaline enzyme, and the intrinsic viscosity is reduced to 0.03.
A range of ~ 2.5 can be obtained.

The dextran-modified product includes dextran sulfate, carboxyalkyl dextran, and hydroxyalkyl dextran.

The molecular weight of these natural water-soluble polymers is preferably from 1,000 to 100,000, and particularly preferably from 2,000 to 50,000.

Methods for producing these dextrans and derivatives thereof are described in JP-B-35-11989, U.S. Patent 3,762,924, JP-B-45-12820, JP-B-45-18418, JP-A-45-40149, and JP-A-45-40149.
No. 6-31192.

In the present invention, a synthetic or natural water-soluble polymer is
In the backing layer, the content is preferably 5% or more of the total weight, more preferably 8% or more and 20% or less. The timing of the addition may be any step before the application of the backing layer.

Next, the silver halide emulsion used in the present invention will be described.

The silver halide grains contained in the silver halide photographic light-sensitive material of the present invention are silver halides containing silver iodide, and may be any of silver iodochloride, silver iodobromide, and silver chloroiodobromide. . In particular, in terms of obtaining high sensitivity,
It is preferably silver iodobromide.

The average silver iodide content in such silver halide grains is 0.5 to 10 mol%, preferably 1 to 8 mol%, and at least 20 mol% or more of high concentration silver iodide is contained inside the grains. There is a localized portion where is localized.

In this case, it is preferable that the inside of the particle is as inner as possible from the outer surface of the particle, particularly 0.01
It is preferable that a localized portion exists at a portion separated by μm or more.

In addition, the localized portion may be present in a layer form inside the particle, or may have a so-called core-shell structure, and the entire core may be a localized portion. In this case, it is preferable that a part or all of the grain core except for a shell part having a thickness of 0.01 μm or more from the outer surface is a localized part having a silver iodide concentration of 20 mol% or more.

The concentration of silver iodide in the localized portion is preferably in the range of 30 to 40 mol%.

The outside of such a localized portion is usually covered with silver iodide-free silver halide. That is, in a preferred embodiment, 0.01 μm or more from the outer surface, particularly
A shell portion having a thickness of 0.01 to 1.5 μm is formed of silver halide containing silver iodide (usually silver bromide).

In the present invention, the inside of the particle (preferably from the outer wall of the particle)
As a method for forming a localized portion of silver iodide having a high concentration of at least 20 mol% or more (inside of grains separated by 0.01 μm or more), a method without using a seed crystal may be used.

When seed crystals are not used, there is no silver halide as a growth nucleus in the reaction liquid phase containing the protective gelatin (hereinafter referred to as mother liquor) before the start of ripening, so that silver ions and at least 20 mol% A growth nucleus is formed by supplying halide ions containing high concentration iodine ions. Then, the particles are further grown from the growing nuclei by continuing the addition and supply. Finally, a shell layer having a thickness of 0.01 μm or more is formed with silver halide containing no silver iodide.

If a seed crystal is used, at least 20 mol% only in the seed crystal
The above-described silver iodide may be formed and thereafter covered with a shell layer. Alternatively, the amount of silver iodide in the seed crystal is set to 0 or within the range of 10 mol% or less, and at least 20 mol% of silver iodide is formed inside the grains in the step of growing the seed crystal, and then the shell is formed. It may be coated with a layer.

In the silver halide photographic material according to the present invention,
At least one of the silver halide grains present in the emulsion layer
Preferably, 50% of the grains have the above-described silver iodide-localized portion.

Another preferred embodiment of the present invention is to use a monodisperse emulsion having a silver iodide-localized portion as described above.

The monodisperse emulsion referred to here is a conventional method, for example, The The
Trivell in Photographic Journal, 79 , 330-338 (1939)
i, at least 95% of the particles by number or weight, when the average particle diameter was measured by the method reported by Smith,
A silver halide emulsion having a mean grain size of ± 40% or less, preferably ± 30% or less.

Such monodisperse emulsion grains are made using a double jet method, as in the case of regular silver halide grains. The conditions at the time of the simultaneous mixing are the same as in the method for producing regular silver halide grains.

Methods for producing such monodispersed emulsions are known, for example, J. Pho
t.Sic., 12,242-251 (1963) JP-A-48-36890, 52
16364, JP-A-55-142329 and JP-A-58-49938.

In order to obtain the above-mentioned monodispersed emulsion, it is preferable to grow a grain by using a seed crystal and supplying silver ions and halide ions using the seed crystal as a growth nucleus.

The wider the grain size distribution of the seed crystal, the wider the grain size distribution of the grain nuclei. Therefore, in order to obtain a monodisperse emulsion, it is preferable to use an emulsion having a narrow grain size distribution at the seed crystal stage.

The silver halide grains as described above used in the silver halide photographic light-sensitive material of the present invention are described, for example, in TH James
Theory of the Photographic Process "4th edition, Macmil
Neutral method, acidic method, ammonia method, forward mixing, reverse mixing, double jet method, controlled-double jet method, conversion method, core described in the literature such as pages 38-104 of Lan Corporation (1977) It can be manufactured by applying a method such as a / shell method.

Known photographic additives can be used in the silver halide photographic emulsion of the present invention.

Known photographic additives include, for example, compounds described in Research Disclosure RD-17643 and RD-18716 shown in the following table.

In the silver halide photographic light-sensitive material according to the present invention, a dye can be used in a layer below the emulsion layer of the present invention, which is in contact with the support, in order to reduce the so-called crossover effect. A dye may be added to the protective layer and / or the emulsion layer of the present invention to improve the properties or reduce fog caused by safety light. As the dye, any known dye for the above purpose can be used.

The support used for the silver halide photographic emulsion of the present invention includes all known ones, for example, a polyester film such as polyethylene terephthalate, a polyamide film, a polycarbonate film, a styrene film and the like.

It should be noted that the photosensitive material according to the present invention contains colloidal silica, which is effective in preventing development unevenness when rapid development processing is performed. The layer containing colloidal silica may be either a silver halide emulsion layer or a protective layer thereof, but is preferably added to the protective layer.

The preferable addition amount is, for example, 2 to 15%, particularly preferably 3.5 to 10%, based on the amount of gelatin used in the silver halide emulsion layer.

A specific example of colloidal silica is EIdu Pon
Ludox AM, LudoxA S, L from t de Nemours & Co, (USA)
udoxL S, LudoxT M, LudoxH S Sugar brand name from Nissan Chemical Co., Ltd. (Tokyo, Japan), such as Snowtex 20, Snowtex C, Snowtex N, Snowtex O, Monsan toCo, (USA) from Syton C-30, Sy
Product name such as ton200, and N from Nalco Chem, Co, (USA)
Alcoag 1030, Nalcoag 1060, and those commercially available under trade names such as 21-64 to Nalcoag ID can be mentioned.

These colloidal silicas have an average particle size of 7 to 120 μm.
m, the main component of which is composed of silicon dioxide, and may include alumina or sodium alginate as minor components.

Further, these colloidal silica stabilizers may contain inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonium hydroxide, and organic salts such as tetramethylammonium ion. Particularly as a colloidal silica stabilizer potassium hydroxide or
Colloidal silica comprising ammonium hydroxide is preferred.

For details on colloidal silica, see Egon Mat
ijevic, Surface and Colloid Science Volume 6, 3
-100 (1973, John Wiley & Sons).

The present invention is applicable to all silver halide photographic light-sensitive materials, but is particularly suitable for high-sensitivity black-and-white or color negative light-sensitive materials.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing by a commonly used known method.

The developer may be a commonly used developer such as hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-
Those containing a single substance such as p-aminophenol or p-phenylenediamine or a combination of two or more thereof are used, and conventional additives can be used. When the light-sensitive material is for color, color development can be performed by a commonly used color development method.

A developer containing an aldehyde hardener can also be used in the silver halide light-sensitive material according to the present invention. For example, maleic dialdehydes such as dialdehydes or glutaraldehyde and sodium bisulfite thereof can be used. Known developers in the field of photographic materials can be used.

Next, the conditions under which the photosensitive material of the present invention is processed will be described.

L, which is the processing length when processing the light-sensitive material of the present invention,
The range is more than 0.7 and less than 4.0 (unit: m). l is 0.7
In the following cases, each processing step may be reduced and the sensitivity may be reduced. Further, when the present invention is applied to a roller-type apparatus for transporting a photosensitive material, the number of rollers to be used is reduced and transportability is deteriorated. Conversely, if l is 4.0 or more,
The transport speed becomes too high, and the film is easily scratched.

The product of l ^0.75 and T is 50 or more and 130 or less. If this value is less than 50, the sensitivity of the light-sensitive material may be reduced, or color remaining may become a problem. More preferably, the product of l ^0.75 and T is 76 or more.

On the other hand, when the product of l ^0.75 and T exceeds 130, the graininess of the photographic image deteriorates and the fog increases even though the sensitivity hardly increases.

According to the above-mentioned processing conditions according to the present invention, good sensitivity can be obtained with high granularity while having high sensitivity, and poor fixing and poor washing.

When processing using an automatic developing machine, it is preferable to use a roller-conveying automatic developing machine, in which case the number of all conveying rollers, the value obtained by dividing the processing length l by the number of rollers is in the range of 0.01 to 0.04. Is preferable. The time of each processing part is preferably in the following range.

Inserting + developing + migratory 25-40% Fixing + migratory 12-25% Washing + migratory 10-25% squeeze + drying 25-45% total 100% The roller used is 12mm-60mm
The length is preferably between 30 cm and 110 cm, and various materials can be used. For example, bakelite-based materials (which may include glass powder, metal powder, and plastic powder) in the areas of development, fixing, washing, and drying are used. And rubber (neoprene, isoprene, silicone rubber, etc.). It is preferable to use water-repellent and elastic silicon rubber or the like, or "Kurarino" (trade name, a product of Kuraray Co., Ltd.), a synthetic leather having high water absorption, for the transition portion and the squeeze portion.

The processing solution such as a developing solution and a fixing solution used in the processing can be appropriately selected depending on the photosensitive material.

1 of FIG. 1 and FIG.
2 is the last roller at the drying outlet, 3a is the developing tank, 36 is the fixing tank, 3c is the washing tank, 4 is the photosensitive material to be processed, 5 is the squeezing section, 6 is the drying section, 7 is the dry air. Shows the outlet.

〔Example〕

Hereinafter, embodiments of the present invention will be described in detail. Note that, needless to say, the present invention is not limited to the embodiments described below.

Example-1 [Preparation of film-1] 2.2 mol% of silver iodide having an average grain size of 0.20 µm by a double jet method while controlling at 60 ° C, pAg = 8.0 and pH = 2.0.
A monodispersed cubic silver iodobromide emulsion containing A part of this emulsion was used as a core and grown as follows. That is, a solution containing the core particles and gelatin at 40 ° C., pAg7.37, pH
At 9.8, an ammoniacal silver nitrate solution and a solution containing potassium iodide and potassium bromide were added by a double jet method to form a first coating layer containing 40 mol% of silver iodide. And even pAg
= 9.86, pH = 9.0, an ammoniacal silver nitrate solution and a potassium bromide solution were added by a double jet method to form a second coating layer of pure silver bromide, and a cubic monodispersed iodine odor having an average particle size of 0.40 μm. A silver halide emulsion (silver iodide content: 2.2 mol%) was prepared. After removing excess salts by the coagulation sedimentation method, 8 × 10 ⁻⁷ mol of chloroaurate, 7 × 10 ⁻⁶ mol of sodium thiosulfate and 7 × 10 ⁻⁴ mol of ammonium thiocyanate were added per 1 mol of silver halide. Optimum gold / sulfur sensitization was performed, and the following sensitizing dye and potassium iodide 1 × 10 ⁻³ mol / mol AgX were added to perform optimal spectral sensitization.

After completion of the spectral sensitization, 4-hydroxy-6-
Methyl 1,3,3a, 7-tetrazaindene was added in an amount of 3 g per mol of silver halide.

Next, the following additives were added to prepare emulsions. The amount of addition was shown per mole of silver halide.

The following compounds were added to the protective layer per 1 g of gelatin.

As a hardening agent, formalin (35% solution) and glyoxal (40% solution) were added under conditions described below so that the melting time was 30 minutes.

Next, the emulsion coating solution and the protective layer solution were mixed to a thickness of 175 μm.
m was applied to one side of a blue-colored polyethylene terephthalate film which had been subjected to an undercoating treatment with a slide hopper coater.

The coated silver amount is 3.2 g / m ² on one side and the gelatin is 2.2 g / m ^{2 on} one side
Also, the protective layer is 1.1 g / m ² as gelatin weight.
1.1 g / m ²
At the same time.

Thus, Film-1 comprising a monodisperse silver iodobromide emulsion was prepared.

[Preparation of Film-2] A tabular silver iodobromide having an average grain diameter of 1.60 μm and an aspect ratio of about 14: 1 by the method described in Emulsion 3 (Example) of JP-A-58-113927. An emulsion containing the grains was prepared.

The grains account for at least 80% of the total projected area of the silver iodobromide grains. However, before desalting, 1000 mg per mol of silver halide of spectral sensitizing dyes A and B were added to the grains in a weight ratio of 200: 1.

When the spectral sensitizing dye was added, the pH was adjusted to 7.60. After 15 minutes, phenylcarbamylated gelatin was added, the pH was lowered with acetic acid, the mixture was aggregated, and the supernatant was removed.

Pure water was added to the thus obtained grains so that the volume per mole of silver halide grains was 500 ml, heated to 52 ° C., and the spectral sensitizing dye was mixed with the spectral sensitizing dye at a weight ratio of 200: 1. A total amount of 100 mg was added per mole of silver halide, and after 10 minutes, ammonium thiocyanate was added by adding 2.8 × 10 ^-3 mole per mole of silver and appropriate amounts of chloroauric acid and hypo. Aging started. Then, after performing chemical ripening for 80 minutes, 4-hydroxy-6-methyl-1,
Chemical ripening was completed by adding an appropriate amount of 3,3a, 7-tetrazaindene.

The obtained emulsion was coated with the same various additives as in the above [Film-1], together with a protective layer.

Thus, Film-2 comprising tabular silver iodobromide grains was prepared.

A coating solution having the following composition was prepared as a backing layer for the obtained films-1 and 2.

<Backing layer> (Backing lower layer solution) Lime-treated gelatin 70 g Acid-treated gelatin 5 g Trimethylolpropane 1.5 g Backing dye A (described later) 1.0 g Backing dye B (described later) 1.0 g per coating solution Next, the water-soluble polymer of the present invention and the comparative water-soluble polymer (a) were added in the amounts shown in Table 1, respectively, and the same hardening agent as described above was used. It was adjusted to the time indicated and added.

The backing layer and the backing upper layer solution were applied on the back of the above-mentioned films-1 and 2 in a total amount of 3.0 g and 1.2 g per square rice, respectively, as a total of gelatin and a water-soluble polymer.
The emulsion layer, the protective layer and the backing layer were coated simultaneously and dried in 2 minutes and 20 seconds to obtain a sample.

The obtained sample was treated under the conditions shown in Table 1 to evaluate the drying property and the loss of the dye in the backing layer. Each evaluation was performed according to the following criteria.

Dryness evaluation criteria 1. Completely dry, sample is warm A 2. Completely dry, sample is cold B 3. Slightly wet (less than 1/3) C 4. Wet (2 / 5 or less) D 5. Wet (more than 2/3) E The measurement of the melting time was performed as follows. That is, the time at which the elution of the film was started after the 1 × 3 cm sample was immersed in a 1.5% NaOH aqueous solution at 60 ° C. was defined as the melting time.

In addition, as a measuring method of the melting time, 1 × 3c
When the m sample is immersed in a 50% aqueous solution of 1.5% NaOH, elution of the membrane is initiated.

 The results obtained are shown in Table 1 below.

As is clear from Table 1, according to the method of the present invention, a silver halide photographic light-sensitive material can be obtained which is excellent in dropping property of a dye and does not deteriorate in drying property and photographic properties even when processed rapidly.

Example 2 A colloidal silica Ludox AM (manufactured by DuPont) was used in the protective layer on the emulsion layer using the same sample as the sample No. 1-7 prepared in Example 1 as a reference sample. Three kinds of samples were prepared by adding as shown in Table 2. The obtained sample was developed under the same conditions as in Examples 1 to 1, and then development unevenness was evaluated. (However, the transmitted light density of the sample after development is
Light exposure was given to 1.3. As can be seen from Table 2, when colloidal silica was used on the emulsion layer side of the sample according to the present invention, development unevenness was reduced.

In addition, the unevenness of the development is visually evaluated by the following five-step method, and if it is Δ or more, it is within a practically allowable range.

[Effects of the Invention] According to the present invention, a silver halide photographic light-sensitive material which can be rapidly processed without causing contamination by a dye in a backing layer is obtained.

Further, a silver halide photographic light-sensitive material having an excellent image with quick drying of the film at the time of rapid processing and without deterioration of the film properties was obtained.

[Brief description of the drawings]

FIG. 1 and FIG. 2 are configuration diagrams of an automatic developing machine used in an embodiment of the present invention.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/76 502 G03C 5/26

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on one side of a support and a backing layer on the other side, wherein at least one of the backing layers is provided. Wherein at least one selected from water-soluble polymers represented by the following general formula [I] is contained in an amount of 5% to 20% of the total weight of the backing layer, and after imagewise exposure, represented by the following formula [A] A silver halide photographic light-sensitive material which can be processed quickly under the conditions of being processed by a roller transport type automatic developing machine. In the formula, R ¹ and R ² may be the same or different and each represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. L is -CONH-, -NHC-, -COO-, -OCO
-, - CO -, - SO 2 -, - NHSO 2 -, - SO 2 NH- or -
Represents O-. J represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, a substituted or unsubstituted arylene group, or a substituted or unsubstituted aralkylene group. Q is a hydrogen atom or Or R ³ , M and M ^{2 each} represent a hydrogen atom or a cation, and R ⁹ represents an alkyl group having 1 to 4 carbon atoms. R ³ ,
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkenyl group, a phenyl group, an aralkyl group, X represents an anion, p and q each represent 0 or 1. Y represents a hydrogen atom or _L p _{J q Q.} Formula [A] l ^0.75 × T = 50-130 (0.7 <l <4.0) where l is the processing length (unit: m) when processing the photosensitive material
And T represents the time (sec) required to pass through l.