JPH0667329A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material having satisfactory dryability at the time of very rapid development, almost free from roller marks and scuff blackening and excellent in processability. CONSTITUTION:This silver halide photographic sensitive material contains a polymer having carboxyl groups in a hydrophilic colloidal layer on the silver halide emulsion side of the base and at least one kind of gelatin used in the hydrophilic colloidal layer contains 2,000ppm or less Ca<2+> based on the amt. of dry gelatin. The polymer having carboxyl groups contains 15mol% or more units of a monomer having a carboxyl group or has 1.5meq/g or higher acid value, where excluding polyacrylic acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and in particular, it has excellent drying property during development processing, improves generation of roller marks when processed by an automatic processor, and fixes during processing. The present invention relates to a technique for remarkably improving the property, and more particularly to a photographic light-sensitive material having ultra-rapid processing suitability.

[0002]

2. Description of the Related Art In recent years, high-temperature rapid processing has rapidly spread in the development process of photographic light-sensitive materials (hereinafter referred to as "light-sensitive materials"), and the processing time for automatic light-processing machines for various light-sensitive materials has been greatly shortened. Came. In order to achieve rapid processing, a developer for achieving sufficient sensitivity in a short time, a photosensitive material that is excellent in development progress and gives a sufficient degree of blackening in a short time, and is dried in a short time after washing with water. Characteristics are required. As a method commonly used to improve the drying property of the light-sensitive material,
Before the start of drying, a sufficient amount of hardener (gelatin crosslinking agent) is added in advance in the process of applying the light-sensitive material to reduce the swelling amount of the emulsion layer or the hydrophilic colloid layer in the process of development-fixing-water washing. There is a method of reducing the water content in the light-sensitive material. In this method, if a large amount of a hardener is used, the drying time can be shortened by that much, but the decrease in the swelling amount leads to a delay in the development, a desensitization or softening, and a reduction in the covering power. Even if the development progress can be improved, the delay of the fixing speed due to the high hardness causes problems such as residual silver, residual hypo, and residual color of the sensitizing dye, which is an obstacle to shortening the processing time.

On the other hand, a method for increasing the developing activity of a processing solution is also known, and it is possible to increase the amounts of the main agent and auxiliary developing agent in the developing solution, increase the pH of the developing solution, and increase the processing temperature. However, all of these methods have drawbacks such as impairing the preservability of the treatment liquid, softening the tone even if the sensitivity is increased, and being easily covered.

For the purpose of improving the viewpoints described above, a technique utilizing tabular grains is disclosed in US Pat. No. 4,43.
9, 520, 4,425, 425 and the like. Also, JP-A-63-305343 and JP-A-1-77
No. 047 discloses a technique for improving the development progress and the sensitivity / fogging ratio by controlling the development start point of a silver halide grain having a (111) plane to the apex and / or lobe of the grain and the vicinity thereof. . Further, JP-A-58-11193
The tabular grains were used for 3 and the swelling of the hydrophilic colloid layer was 20
It has a high covering power by setting it to 0% or less,
Radiographic photographic elements are disclosed that do not require the addition of a dura during processing. These known techniques are excellent techniques for improving the development progress of the light-sensitive material and have high utility value. However, development / fixing /
When the processing time of each step of washing with water is shortened, not only the photographic sensitivity is lowered, but also the fixing property is deteriorated and the residual silver and the residual hypo are deteriorated. In addition, the problem of residual color is brought to the surface in a light-sensitive material that has been spectrally sensitized with a sensitizing dye. These problems other than photographic properties are limited in improvement by modification of silver halide grains, and ultimately result in problems of film quality. That is, the thickness of the hydrophilic colloid layer regulates fixing and residual color, which is an obstacle to speeding up.

Regarding this point, JP-A-64-7333.
3, JP-A-64-86133, JP-A-1-10524
4, JP-A-1-158435, JP-A-1-158436
For example, the amount of gelatin on the side having the hydrophilic colloid layer including the silver halide emulsion layer is adjusted to be in the range of 2.00 to 3.50 g / m ² , and the total processing time is 20 by combining with other technical elements. Means for achieving ultra-rapid processing in the range of seconds to less than 60 seconds are disclosed. Further, in JP-A-2-68537, means for achieving ultra-rapid processing by adjusting the weight ratio (silver / gelatin) of silver and gelatin of the photosensitive silver halide coated in the emulsion layer to 1.5 or more. Is disclosed. Further, in JP-A-63-221341, the silver halide grains in the emulsion layer mainly consist of tabular grains having a grain size of 5 times or more the grain thickness, and the amount of gelatin is from 2.00 to 3.20 g.
/ M ² and a melting time of 8 minutes or longer and 45 minutes or shorter, a means for achieving an ultra-rapid treatment with a total treatment time of 20 seconds or more and less than 60 seconds is disclosed.

However, when these prior arts were examined, when the amount of gelatin was reduced or the silver / gelatin ratio was increased while keeping the amount of coated silver constant, abrasion blackening and roller marks were significantly deteriorated. It turned out that the level became too unacceptable for practical purposes, which made it impossible to complete a product that could be processed extremely quickly.

[0007] Scratch blackening refers to a phenomenon in which, when the film is handled, the films are rubbed with each other, or when the film is rubbed with another substance, a scratch-like blackening is generated after the development processing. The roller mark is a phenomenon in which, when the photosensitive material is processed by an automatic developing machine, pressure is applied to the photosensitive material due to fine irregularities on the surface of the transport roller, resulting in black spot-like density unevenness. When the total processing time is set to 60 seconds or less, especially 40 seconds or less, the appropriate amount of time is allocated to the developing / fixing / washing process, resulting in a gelatin coating amount of 2.5.
If it is not g / m ² or less, the drying property may be hindered when the installation environment of the automatic processor is high humidity. On the other hand, such reduction of the gelatin coating amount is not acceptable in terms of roller marks and blackening of scratches.

As described above, simply by adjusting the coating amount of gelatin, drying property, pressure property, fixing property (or residual color property),
It was not possible to satisfy each performance of.

It is well known to use polymers having --COOH or its salt structure in photographic materials, and with gelatin which is a hydrophilic colloid. For example, Japanese Examined Patent Publication Nos. 57-53587 and 57.
-15375, West German Patent 1,745,061, Japanese Patent Publication Nos. 49-23827, 55-14415, 55.
-15267, JP-A-48-89979, U.S. Pat. Nos. 2,279,410, 3,791,831, and JP-B-47-28937 disclose polymers having a carboxyl group for preventing electrification of photographic light-sensitive materials. Attempts to utilize are disclosed.

However, there is no mention of controlling the swelling ratio of the hydrophilic colloid layer and accelerating the drying speed of the light-sensitive material with this type of anionic polymer antistatic agent. In general, an anionic antistatic agent is used in a large proportion in a specific hydrophilic colloid, and a large amount of a gelatin hardening agent is often used to improve the physical properties of the film. When the invention is used for reducing the drying load by controlling the swelling property after the treatment, the above-mentioned JP-A-5-58 is disclosed.
As described in No. 8-111933, problems such as residual silver and residual hypo occur.

Also, European Patents 75231 and 1670
81, JP-A-53-7231, and JP-A-60-12664.
4, No. 60-156056, JP-A-2-20861.
No. 1, Japanese Patent Publication No. 14574, and US Pat. No. 4,142,894.
JP-A No. 1994-242242 discloses a polymeric matting agent containing a carboxyl group. However, originally, the matting agent exposes particles of about 0.2 to 10 μm to the surface of the photosensitive material, and the unevenness on the surface causes its function to shine.
Such coarse particles do not have a sufficient function of controlling the swelling property after treatment as in the present invention.

Further, in Japanese Patent Application No. 1-27955, by introducing a polyacrylic acid derivative into a photosensitive material containing an antihalation layer containing a polymeric mordant having an ammonium structure and an anionic dye, an anionic dye of It is disclosed that the decolorization property is improved. However, the patent does not describe swelling control after treatment with a -COOH-containing polymer, and the acrylic acid homopolymer according to the embodiment swells after treatment in a treatment substantially containing no hardener. It was revealed by the study of the present inventors that there is no drying property improving effect based on the property controlling effect.

[0013]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material which exhibits excellent drying properties during processing, especially in rapid processing. Secondly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in drying property and has excellent processability even in rapid processing. Thirdly, an object of the present invention is to provide a silver halide photographic light-sensitive material satisfying the above objects, having high sensitivity and having high covering power.

[0014]

The above object of the present invention has been achieved by the following means. In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one carboxyl group-containing polymer (carboxyl group-containing monomer unit) is provided on at least one silver halide emulsion layer coated surface side. Is 15 mol% or more,
Or a hydrophilic colloid layer containing an acid value of 1.5 meq / g or more, excluding polyacrylic acid), and
A silver halide photographic light-sensitive material, characterized in that at least one gelatin used as a hydrophilic colloid layer has a calcium ion (Ca ²⁺ ) content of 2,000 ppm or less based on dry gelatin. The preferred embodiments are shown below. (Aspect I) The amount ratio of the carboxyl group-containing polymer and gelatin on the side coated with the silver halide emulsion layer is 0.01 to 0.
3. The silver halide photographic light-sensitive material as described above, wherein (Aspect II) The silver halide photograph of Aspect I, wherein the swelling ratio of the all hydrophilic colloid layer on the side having the carboxylic acid polymer-containing layer with respect to the support in distilled water is 200% or more. Photosensitive material. (Here, the swelling ratio in distilled water was determined by incubating the photographic material at 40 ° C. and 60% RH (percent relative humidity) for 16 hours, and then swelling it in distilled water at 21 ° C.
The change in thickness when immersed for a minute shall be measured. (Aspect III) The silver halide photographic light-sensitive material according to aspect II above, wherein methacrylic acid is used as the carboxyl group-containing monomer unit of the carboxyl group-containing polymer.

The present invention will be described in detail below. The carboxyl group-containing polymer used in the present invention means a polymer having a carboxyl group-containing monomer unit of 15 mol% or more or an acid value of 1.5 meq / g or more. The carboxyl group-containing polymer used in the present invention, a homopolymer of a carboxyl group-containing unsaturated ethylenic monomer,
Copolymers or natural polymer derivatives are preferred. Examples of the carboxyl group-containing unsaturated ethylenic monomer include the followings. Acrylic acid, methacrylic acid, maleic acid, monoalkyl maleate (eg, monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.), itaconic acid, monoalkyl itaconate (eg, monoethyl itaconate, etc.), fumaric acid , Monoalkyl fumarate, crotonic acid,
Vinyl benzoic acid, maleic acid monoamide, itaconic acid monoamide, etc. Of these, the acid may be a salt of an alkali metal, preferably Na, K or ammonium ion.

Among these monomers, acrylic acid, methacrylic acid, and maleic acid are preferable from the viewpoints of polymer solubility, transparency, lipophilicity, hydrophilicity, affinity with protective colloid, easy polymerizability and the like. Above all, photographic performance (sensitivity /
Methacrylic acid is particularly preferable in terms of residual color and roller mark) drying property. Also, it does not matter if two or more of these monomers are introduced into the polymer.

The monomer copolymerizable with the carboxyl group-containing unsaturated ethylenic monomer is not particularly limited, but for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, vinyl esters, vinyl ketones, Allyl compounds, olefins, vinyl ethers, N-vinyl amides, vinyl heterocyclic compounds, maleic acid esters, itaconic acid esters, fumaric acid esters, crotonic acid esters and the like. More specific examples include the following.

Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, amyl acrylate,
Hexyl acrylate, octyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate,
Dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, diethylene glycol monoacrylate, triethylene glycol monoacrylate, glycerol monoacrylate, trimethylolethane monoacrylate,
Pentaerythritol monoacrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, ω-methoxypolyethylene glycol acrylate (addition mole number n = 9), 1-bromo-2-methoxy Ethyl acrylate, 2-hydroxy-3-chloropropyl acrylate, t-butyl acrylate, isobornyl acrylate, phenyl acrylate, p-chlorophenyl acrylate, methyl methacrylate, ethyl methacrylate, i-propyl methacrylate, t-butyl methacrylate, amyl methacrylate. , N, N, diethylaminopropyl methacrylate, 2-hydroxyethyl methacrylate, diethylene glycol monomethacrylate, triethyl Glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate,

Acrylamide, methacrylamide, N-
Methyl acrylamide, N-ethyl acrylamide, N
-N-propyl acrylamide, N-iso-propyl acrylamide, Nn-butyl acrylamide, N-te
rt-butyl acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, hexyl acrylamide, octyl acrylamide, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, allyloxyethanol, allyl butyl ether, 2-ethylbutyl vinyl ether, Hydroxyethyl vinyl ether, vinyl acetate, vinyl propionate, N-vinyl oxazolidone, vinyl pyridine, N-vinyl imidazole, N-
Vinyl-2-methylimidazole, N-vinyltriazole, N-vinyl-3,5-dimethyltriazole, N-
Vinylpyrrolidone, N-methyl-N-vinylpropionamide, N-vinylpyrrolidone, N-vinyl-2-pyridone, ethylene, propylene, 1-ptene, 1-heptene, 1-octene, dioctyl itaconate, dibutyl itaconate, Dihexyl maleate, dibutyl maleate,

Acrylic acid esters such as styrene, methylstyrene, dimethylstyrene, benzylstyrene, chloromethylstyrene, chlorostyrene, methyl vinylbenzoate, vinylchlorobenzoate, acrylonitrile, methacrylonitrile, vinyl chloride, etc.
Methacrylic acid esters, acrylamides, and styrenes are preferable.

For the synthesis of these carboxyl group-containing polymers, British Patent No. 1,211,039, British Patent No. 961,395, US Pat. No. 3,227,672,
No. 3,290,417, No. 3,262,919
No. 3,245,932, No. 2,681,89
No. 7, No. 3,230,275, John, C., Petropoulos, et al., "Official Digest" (John
C.Petropoulos et al: Official Digest) 33, 719〜
736 (1961), edited by Shunsuke Murahashi et al., “Synthetic Polymer” 1
It is convenient to carry out with reference to the methods described in 246 to 290, 31 to 108 and the like.

Examples of natural polymer derivatives include gelatin derivatives (maleylated gelatin, succinylated gelatin, etc.), protein derivatives such as gelatin and other polymer graft polymers (polyacrylic acid grafted gelatin, etc.), and cellulose. Examples thereof include sugar derivatives such as derivatives (carboxymethyl cellulose, etc.), dextran derivatives, starch derivatives and the like. Of these, gelatin derivatives are particularly preferable.

Specific examples of the carboxyl group-containing polymer used in the present invention will be given below, but the present invention is not limited thereto. (Numbers represent mol%) P-1 Acrylic acid / methacrylic acid copolymer (20/80) P-2 Acrylic acid / methyl acrylate copolymer (40/60) P-3 Acrylic acid / butyl methacrylate copolymer Combined (40/60) P-4 acrylic acid / 2-hydroxyethyl acrylate copolymer (40/60) P-5 acrylic acid / acrylamide copolymer (40/60) P-6 acrylic acid / ethyl acrylate / methyl Acrylate copolymer (40/20/40) P-7 Polymethacrylic acid P-8 Methacrylic acid / methyl acrylate copolymer (40/60) P-9 Methacrylic acid / methyl methacrylate copolymer (60/40) P -10 Methacrylic acid / methyl methacrylate copolymer (40/60) P-11 Methacrylic acid / methyl methacrylate copolymer (20/80) P-12 Methacrylic acid / ethyl methacrylate copolymer Body (40/60) P-13 Methacrylic acid / ethyl acrylate copolymer (40/60) P-14 Methacrylic acid / n-propyl acrylate copolymer (40/60) P-15 Methacrylic acid / n-propyl methacrylate Copolymer (40/60) P-16 methacrylic acid / iso-propyl acrylate copolymer (40/60) P-17 methacrylic acid / iso-propyl methacrylate copolymer (40/60) P-18 methacrylic acid / n-Butyl acrylate copolymer (40/60) P-19 Methacrylic acid / tert-butyl acrylate copolymer (40/60) P-20 Methacrylic acid / tert-butyl methacrylate copolymer (40/60) P- 21 Methacrylic acid / n-hexyl acrylate copolymer (40/60) P-22 Methacrylic acid / cyclohexyl acrylate copolymer (40/60) P-23 Methacrylic acid / cyclohexyl methacrylate Polymer (40/60) P-24 Methacrylic acid / phenyl acrylate copolymer (40/60) P-25 Methacrylic acid / 2-hydroxyethyl acrylate copolymer (40/60) P-26 Methacrylic acid / 2- Hydroxypropyl methacrylate copolymer (40/60) P-27 Methacrylic acid / 3-hydroxypropyl acrylate copolymer (40/60) P-28 Methacrylic acid / 2-methoxyethyl acrylate copolymer (40/60) P -29 Methacrylic acid / 2-butoxyethyl acrylate copolymer (40/60) P-30 Methacrylic acid / 2- (2-methoxyethoxy) ethyl acrylate copolymer (40/60) P-31 Methacrylic acid / acrylamido copolymer Polymer (40/60) P-32 Methacrylic acid / N-iso-propyl acrylamide copolymer (40/60) P-33 Methacrylic acid / N-tert-butyl acrylamide copolymer 40/60) P-34 methacrylic acid / methyl vinyl ether copolymer (40/60) P-35 methacrylic acid / N-vinylpyrrolidone copolymer (40/60) P-36 methacrylic acid / styrene copolymer (40 / 60) P-37 methacrylic acid / acrylonitrol copolymer (40/60) P-38 methacrylic acid / methyl acrylate / methyl methacrylate (40/30/30) P-39 methacrylic acid / methyl acrylate / n-butyl acrylate ( 40/40/20) P-40 Methacrylic acid / methyl methacrylate / tert-butynyl acrylate (40/40/20) P-41 Methacrylic acid / methyl methacrylate / cyclohexyl acrylate copolymer (40/40/20) P- 42 Methacrylic acid / methyl acrylate / 2-hydroxyethyl acrylate copolymer (40/40/20) P-43 Methacrylic acid / methyl acrylate / acrylamide copolymer (40/4 0/20) P-44 methacrylic acid / methyl methacrylate / styrene copolymer (40/40/20) P-45 methacrylic acid / methyl acrylate / 2-hydroxyacrylate / acrylonitrile copolymer (40/40/10 / 10) P-46 methacrylic acid / methyl methacrylate / tert-butyl methacrylate / 2-hydroxyethyl methacrylate (40/30/20/10) P-47 maleic acid / styrene copolymer (50/50) P-48 maleic acid / Isobutylene copolymer (50/50) P-49 Acrylic acid block copolymer on polyvinyl alcohol P-50 Acrylic acid graft copolymer on polyvinyl alcohol P-51 Maleylated gelatin P-52 Succinylated gelatin P- 53 Carboxymethyl cellulose

In a preferred embodiment of the present invention, the molecular weight of the carboxyl group-containing polymer added to the hydrophilic colloid is preferably 5 × 10 ³ or more, particularly preferably 1 × 10 3.
⁴ to 5 × 10 ⁶ (all weight average molecular weights). The amount of the carboxyl group-containing polymer to be added varies depending on the kind of the light-sensitive material, etc., but is 0.01 g.
/ M ^{2 to 2} g / m ² is preferable, more preferably 0.05 g
/ M ^{2 to 1} g / m ² . More preferably 0.1 g / m ²
~ 0.5 g / m ² .

In the case of a silver halide photographic light-sensitive material having two or more hydrophilic colloid layers, the acid polymer having a --COOM group may be contained in all hydrophilic colloid layers or at least one layer. Therefore, it does not have to be included in other layers. Further, the amount of the acid polymer in each layer when the carboxyl group-containing polymer of the present invention is applied to two or more hydrophilic colloid layers can be arbitrarily changed.

--CO which is preferably used in the present invention
The neutralization ratio of the polymer having an OM group can be variously changed depending on the kind and amount of the hydrophobic monomer or the structure of the repeating unit having a -COOM group. Therefore, all -COOM groups have a salt structure by neutralization. May be all-COOM
The group may have a -COOH structure. Basically, the neutralization rate may be set with reference to the range in which the polymer becomes water-soluble when it is made into a mixed aqueous solution with a hydrophilic colloid.

When the carboxyl group-containing polymer of the present invention is used, it is preferably dissolved in water and introduced into the photographic material by adding the aqueous solution. For dissolution, it is more preferable to use a suitable alkali and salt. Also water-miscible organic solvents (eg acetone, methanol,
Ethanol, acetonitrile, dimethyl sulfoxide,
Dimethylacetamide, etc.) may also be used. Gelatin is preferably used as the hydrophilic layer colloid that forms the hydrophilic colloid layer containing the carboxyl group-containing polymer of the present invention. As the gelatin, besides lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and a hydrolyzed product or an enzymatically decomposed product of gelatin may also be used. The content of calcium ion (Ca ²⁺ ) in the gelatin used in the present invention needs to be 2,000 ppm or less, and particularly preferably 1,000 ppm or less, more preferably 500 ppm or less. The calcium ion in gelatin is derived from the raw material, but in order to obtain the gelatin having the calcium ion content of the present invention, the raw material selection, the production condition selection, the ion exchange treatment and the like may be appropriately combined. The ion exchange treatment may be carried out by extracting gelatin from the raw material of beef bones, pork skin, etc. and then performing ion exchange using an ion exchange resin (for example, IRA type available from Rohm and Haas Co.). Quantification of the calcium ion content after the ion exchange treatment may be carried out according to the method described in the sixth edition of the photographic gelatin test method for photographs (abbreviated as Pagui method) established by the Joint Committee for Gelatin Test Method. In the present invention,
The total gelatin in the hydrophilic colloid layer containing the carboxyl group-containing polymer has a calcium ion content of 2,000 pp.
It is preferably m.

Also, hydrophilic colloids other than gelatin can be preferably used. For example, glucose, dextran, natural polymers such as cellulose, vinyl alcohol, polyvinyl alcohol partial acetal, poly-N
-A variety of synthetic hydrophilic polymeric substances such as vinylpyrrolidone, polyacrylic acid, polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used. The ratio of the carboxyl-containing polymer and gelatin used in the photographic material of the present invention (polymer content ratio) is (the coating amount of the carboxyl group-containing polymer) / (the coating amount of the carboxyl group-containing polymer +
Gelatin coating amount), and this value is 0.01 ~
It is preferably 0.3. More preferably 0.05
Is about 0.2.

The swelling rate of distilled water in the present invention is given by (thickness of layer when immersed in distilled water-initial layer thickness) / (initial layer thickness) x 100%. Here, the thickness of the layer when immersed in distilled water means the thickness of the layer when the photographic material is immersed in distilled water at 21 ° C. for 3 minutes. The photographic material used here was 16 ° C at 40 ° C and 60% RH.
Incubated for a period of time. Further, in measuring the thickness of the layer when immersed in distilled water, US Pat.
41872 is defined by the method described in Example 12 (however, the measuring part of the measuring instrument is made of ceramic). In the photographic material of the present invention, the swelling ratio of distilled water is
From the viewpoint of photographic performance and drying performance, 200% or more is preferable. The swelling rate can be set by changing the amount of hardener used.

The photographic light-sensitive material using the carboxyl group-containing polymer of the present invention is suitable for rapid processing. Especially Dry
It is preferable that the to Dry processing is performed within 60 seconds. It is more preferably within 45 seconds, and even more preferably within 38 seconds.

In the light-sensitive material of the present invention, at least one light-sensitive silver halide emulsion layer may be provided on one side of the support, or at least one layer may be provided on both sides of the support. Good. The light-sensitive material of the present invention can have a hydrophilic colloid layer in addition to the light-sensitive silver halide emulsion layer if necessary, and for example, a protective layer is preferably provided.

In the photographic material of the present invention, the coating amount of gelatin, which is preferably used as the hydrophilic binder, is not particularly limited, but is preferably 2.5 g / m ² or more per one side.

Next, emulsion grains preferably used in the present invention will be described. The silver halide grains in the emulsion are preferably tabular grains having an aspect ratio of 3 or more. It is preferably 5 or more. Particularly preferably, it is 7 or more. The tabular silver halide grains can be produced by appropriately combining methods known in the art. Tabular silver halide emulsions are disclosed in JP-A-58-127,921 and JP-A-58.
-113,927, JP-A-58-113,928, and the like can be easily prepared. The aspect ratio of tabular silver halide grains can be adjusted by controlling the temperature, selecting the type and amount of solvent, and the addition rate of silver salt and halide used during grain growth. The tabular grains in the silver halide emulsion of the present invention are 5
It is preferably present in an amount of 0% or more (in projected area), particularly 80% or more. The sphere-equivalent average particle size of the same volume as the particles is preferably 0.4 μm or more. Especially 0.5 ~
It is preferably 2.0 μm. The particle size distribution should be narrow.

As the composition of silver halide, silver iodobromide is preferable because of its high sensitivity. The silver halide grain of the present invention may contain a trace amount of silver chloride to the extent that it does not affect the photographic properties, but it is desirable that it does not contain silver chloride. As the emulsion of the present invention, both monodisperse emulsion and polydisperse emulsion can be preferably used. The silver halide emulsion used in the present invention may be a core / shell type monodisperse emulsion, and these core / shell emulsions are known from JP-A-54-48521. The silver halide grains in the emulsion are preferably tabular grains, but regular grains such as cubes and octahedra, which have a crystalline form, irregular grains such as spheres and potatoes.
Those having an (irregular) crystal form may be used at the same time.

In order to effectively use the effects of the present invention,
In the chemical sensitization during the emulsion preparation process as disclosed in JP-A-2-68539, 0.5 mmol or more of sensitizing dye per mol of silver halide, or silver halide adsorption corresponding to a class of photographic performance stabilizers. It is preferable that a volatile substance is present.
That is, azoles {eg benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.); mercapto compounds {eg mercaptothiazoles , Mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines and the like}; for example, oxa Thioketo compounds such as drinthione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy) Many compounds known as antifoggants or stabilizers such as substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes); it can. Furthermore, purines or nucleic acids, or Japanese Patent Publication No. 6
The polymer compounds described in JP-A No. 1-36213, JP-A-59-90844, etc. are also adsorbable substances that can be used. Of these, azaindenes, purines, and nucleic acids are particularly preferable and can be used in the present invention. The addition amount of these compounds is 300 to 300 per mol of silver halide.
It is 0 mg, preferably 500 to 2500 mg. As the silver halide-adsorptive substance of the present invention, a sensitizing dye can realize preferable effects. As a sensitizing dye, a cyanine dye,
A merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used.

Useful sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052 and 3,619,19.
No. 7, No. 3,713, 828, No. 3, 615, 643
Issue No. 3,615,632 Issue 3,617,293
No. 3,628,964, 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,312,349, No. 3,677,765
Nos. 3,770,449, 3,770,440
Issue No. 3,769,025 Issue No. 3,745,014
Issue 3, Issue 3,713,828, Issue 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807. The amount of sensitizing dye added is 3 per mol of silver halide.
00 mg or more and less than 2000 mg, preferably 500 mg or more 1
Less than 000 mg is good. Specific examples of the sensitizing dye effective in the present invention are shown below.

[0037]

[Chemical 1]

[0038]

[Chemical 2]

Of the above, cyanine dyes are particularly preferable.
The combined use of the sensitizing dye and the above-mentioned stabilizer is a preferred embodiment. The sensitizing dye used in the present invention may be added after chemical sensitization and before coating.

Among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and manufacturing method of the monodisperse hexagonal tabular grains according to the present invention are described in JP-A-63-151618. The chemical sensitization method of the silver halide emulsion used in the present invention includes sulfur sensitization method, selenium sensitization method, reduction sensitization method, gold sensitization method, etc. in the presence of the above-described silver halide adsorbing substance. Known methods can be used, either alone or in combination. Regarding the method for producing the tabular silver halide grains of the present invention and the chemical sensitization method thereof, the description in JP-A-2-68539, page 8, lower right column to page 10, upper right column, Japanese Patent Application No. 3-105035.
The descriptions of No. 3, No. 3-183863, No. 3-213063 and No. 3-235737 can be preferably used. The photographic emulsion used in the present invention prevents fog during the manufacturing process of the light-sensitive material, storage or photographic processing,
Alternatively, for the purpose of stabilizing photographic performance, various compounds can be contained in addition to the silver halide adsorbing substance in the chemical sensitization step of the present invention.

That is, azoles (eg, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, nitroindazoles, benzotriazoles, aminotriazoles, etc.); mercapto compounds {For example, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles,
Mercaptothiadiazoles, mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc .; thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,
3,3a, 7) Tetraazaindenes), pentaazaindenes, etc.); Many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. Can be added.

Particularly, JP-A-60-76743 and 60-
Nitron and its derivatives described in JP-A-87322, mercapto compounds described in JP-A-60-80839, heterocyclic compounds described in JP-A-57-164735, and heterocyclic compound-silver complex salts (for example, 1-phenyl-5-mercaptotetrazole silver) and the like can be preferably used. Even when a sensitizing dye is used as the silver halide adsorbing substance in the chemical sensitization step, a spectral sensitizing dye in another wavelength range may be added, if necessary. For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, a slip property improving agent, an emulsifying dispersion agent, an adhesion preventing agent and a photographic characteristic improving agent (for example, development acceleration, hardening). Various surfactants may be included for various purposes such as agent and sensitization).

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene oxide adducts of silicone),
Nonionic surfactants such as sugar alkyl esters;
Alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyl taurines,
Anionic surfactants such as sulfosuccinates and sulfoalkyl polyoxyethylene alkylphenyl ethers; amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines; aliphatic or aromatic quaternary ammonium salts, pyridinium salts A cationic surfactant such as imidazolium salt can be used.

Of these, saponin, Na salt of dodecylbenzene sulfonic acid, Na salt of di-2-ethylhexyl α-sulfosuccinic acid, Na salt of p-octylphenoxyethoxyethane sulfonic acid, Na salt of dodecyl sulfate, Na salt of triisopropylnaphthalene sulfonic acid. , N-methyl-oleoyl taurine Na salt, anions such as dodecyltrimethylammonium chloride, N-oleoyl-N ',
Cations such as N ′, N′-trimethylammoniodiaminopropane bromide and dodecylpyridinium chloride, betaines such as N-dodecyl-N, N-dimethylcarboxybetaine and N-oleyl-N, N-dimethylsulfobutylbetaine, and polyynes. (Average degree of polymerization n = 10) oxyethylene cetyl ether, poly (n = 25) oxyethylene p-nonylphenol ether, bis (1-poly (n = 15) oxyethylene-oxy-2,4-di-t
Nonionics such as -pentylphenyl) ethane can be used particularly preferably.

As the antistatic agent, perfluorooctanesulfonic acid K salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly (n = 3) oxy Ethylene butanesulfonic acid Na salt, N
-Perfluorooctanesulfonyl-N ', N', N '
-Totamethylammoniodiaminopropane chloride,
N-perfluorodecanoylaminopropyl-N ',
Fluorine-containing surfactants such as N'-dimethyl-N'-carboxybetaine, JP-A-60-80848 and 61-
112144, 62-172343, 62-1
Nonionic surfactants such as those described in No. 73459, alkali metal nitrates, conductive tin oxide, zinc oxide, vanadium pentoxide, or composite oxides obtained by doping these with antimony or the like can be preferably used.

In the present invention, as a matting agent, US Pat. Nos. 2,992,101, 2,701,245 and 41,428 are used.
94, 4396706 homopolymers of polymethylmethacrylate or copolymers of methylmethacrylate and methacrylic acid, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, sulfuric acid, and strontium barium. You can
The particle size is 1.0 to 10 μm, especially 2 to 5 μm
Is preferred. In the surface layer of the photographic light-sensitive material of the present invention, as a slip agent, US Pat.
Silicon compounds described in 047958, etc.
In addition to the colloidal silica described in JP-A-6-23139, paraffin wax, higher fatty acid ester, den powder derivative and the like can be used.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer in the hydrophilic colloid layer of the photographic light-sensitive material of the present invention. As the binder or protective colloid that can be used in the emulsion layer, intermediate layer and surface protective layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used. .

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. Examples of hardening agents include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives ( 2,3-dihydroxydioxane, etc., compounds acting by activating a carboxyl group (carbenium, 2-naphthalene sulfonate, 1,1-bispyrrolidino-1-chloro-, pyridinium, 1-morpholinocarbonyl-3
-(Sulfonatoaminomethyl)-and the like). Active vinyl compound (1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methane,
N, N'-methylenebis- [β- (vinylsulfonyl)
Propionamide])). Active halogen compounds (2,
4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin etc. , And can be used alone or in combination. Among them, vinyl sulfone type hardeners or carboxylic acid activated type hardeners can be preferably used in view of film physical properties such as photographic performance (sensitivity, residual color) and drying property. In the present invention, the amount of the hardener used is not particularly limited, but from the viewpoint of photographic performance and drying performance, it is preferably 4 to 16 mmol per 100 g of gelatin.

The light-sensitive material of the present invention preferably contains a dye dispersed in a microcrystalline state for the purpose of reducing crossover and preventing halation. The microcrystalline dispersion in the present invention is insufficient in solubility of the dye itself, so that it cannot exist in a molecular state in the intended colored layer, and is a solid of a size substantially incapable of diffusion in the layer. Means the existence state as. Regarding the adjusting method, International Application Publication (WO) 88/04794, European Patent (EP) 0276566A1, JP-A-63-19794.
As described in No. 3 and the like, a method of ball milling and stabilizing with a surfactant and gelatin, and a method of dissolving a dye in an alkaline solution and then lowering the pH to cause precipitation are preferably used. However, the present invention is not limited to these adjustment methods. Regarding the method of dispersing such a dye in a microcrystalline state, JP-A-56-12639 and 55-55
-155350, 55-155351, 52-
92716, 63-197943, 63-27.
No. 838, No. 64-40827, European Patent 00
Reference can be made to the descriptions of No. 15601B1, No. 0276566A1, International Application Publication No. 88/04794, and the like. In particular, Japanese Patent Application Nos. 2-118042 and 2-1458.
No. 33, No. 2-293046, No. 2-303170.
The dyes described in JP-A Nos. 3-121749 and 3-189594 can be preferably used.

The support is preferably a polyethylene terephthalate film or a cellulose triacetate film. In order to improve the adhesion to the hydrophilic colloid layer, the support is preferably subjected to corona discharge treatment, glow discharge treatment or ultraviolet irradiation treatment on its surface, or is made of styrene butadiene latex, vinylidene chloride latex, etc. A subbing layer may be provided, and a gelatin layer may be further provided on the subbing layer.

Further, an undercoat layer using an organic solvent containing a polyester swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrophilic colloid layer can be further improved. The emulsion layer of the photographic light-sensitive 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. 738,618 describes heterocyclic compounds.
No.8,637, alkyl phthalate, 738,6
Alkyl ester is described in US Pat.
No. 0,404 is polyhydric alcohol, No. 3,121,0
Carboxyalkyl cellulose is disclosed in JP-A No.
No. 9-5017 discloses a method using a paraffin and a carboxylic acid salt, and Japanese Patent Publication No. 53-28086 discloses a method using an alkyl acrylate and an organic acid.

The other constitution of the emulsion layer of the silver halide photographic light-sensitive material of the present invention is not particularly limited, and various additives can be used if necessary. For example, Rese
archDisclosure 176, 22-28 (1978, 1
The binders, surfactants, other dyes, ultraviolet absorbers, coating aids, thickeners, etc. described in (February) can be used.

No particular limitation is imposed on the method of developing the silver halide photographic light-sensitive material of the present invention, but for example, JP-A No. 2-1.
03037, page 16, upper right column, line 7 to page 19, lower left column, line 15. The method described in JP-A-2-115837, page 3, lower right column, line 5 to page 6, upper right column, line 10 can be preferably used. Especially the present invention
It can be preferably used for ultra-rapid processing in which Dry is 60 seconds or less, particularly 45 seconds or less. When developing the silver halide photographic light-sensitive material of the present invention, an automatic developing machine having a zone for drying with infrared rays can be preferably used from the viewpoint of drying property and drying unevenness. Examples of the method using infrared rays include JP-A-1-206345, JP-A-1-118840, JP-A-54-26734, and JP-A-56-130937.
JP-A-1-260445, JP-A-2-14074
No. 1, JP-A-2-149845, JP-A-2-1577.
54, 51-52255, 53-53
No. 337, Japanese Patent Application No. 1-99193, Japanese Patent Application No. 1-991
No. 92, Japanese Patent Application No. 1-99191, Japanese Patent Application No. 1-9919
No. 0, Japanese Patent Application No. 1-99189, Japanese Patent Application No. 1-24100
4, Japanese Patent Application No. 2-52967, Japanese Patent Application No. 2-51351
No. can be used. The drying temperature is not particularly limited, but is preferably 40 ° C to 80 ° C.

[0054]

Example 1 Preparation of tabular grains 4.5 g potassium bromide and 2 gelatin in 1 liter of water.
0.6 g, 5 of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
% Aqueous solution (2.5 cc) and stirred in a container kept at 60 ° C. while stirring, 33 cc of aqueous solution of silver nitrate (3.43 g of silver nitrate), 33 cc of aqueous solution containing 2.97 g of potassium bromide and 0.363 g of potassium iodide are double jet method. For 37 seconds. Next, an aqueous solution of 0.9 g of potassium bromide was added, and then the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (silver nitrate 4.
90 g) was added over 13 minutes. Here, 15 cc of 25% aqueous ammonia solution was added, and after physically aging for 20 minutes at the same temperature, 14 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the pAg at 8.5. Next, 10 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.26 mol%, an average projected area diameter of 1.10 μm, a thickness of 0.157 μm and a variation coefficient of 18.5% were obtained.

After that, soluble salts were removed by a precipitation method. The temperature was again raised to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol, and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH was adjusted to 5.90 and pAg was adjusted to 8.25 with caustic soda and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added and the mixture was held for 22 minutes as it was for reduction sensitization. Next, 20 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and sensitizing dye

[0056]

[Chemical 3]

400 mg of was added. Further, 0.83 g of calcium chloride was added. Subsequently, 1.3 mg of sodium thiosulfate, 2.7 mg of selenium compound-1, 2.6 mg of chloroauric acid, and 90 mg of potassium thiocyanate were added.
After 0 minutes, it was cooled to 35 ° C. Thus, preparation of tabular grains T ₁ was completed. Selenium compound-1

[0058]

[Chemical 4]

(Preparation of coating sample) Silver halide ₁ of T 1
A coating sample was prepared by adding the following chemicals per mol to prepare a coating liquid. -Gelatin A to D described in Table-1-Trimethylolpropane 9g-Dextran (average molecular weight 39,000) 18.5g-Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8g

[0060]

[Chemical 5]

(Preparation of Coating Solution for Surface Protective Layer) The surface protective layer was prepared and prepared so that each component had the following coating amount. (Contents of the surface protective layer) (Coating amount) -Gelatin A-D described in Table-1. Polymer P-7 described in Table-1. Polymer P-18 described in Table-1. Polyacrylic acid described in Table-1. -Hardening agent 1,2-bis (vinylsulfonylacetamide) ethane Addition amount was adjusted so that the swelling rate shown in Table-1 was obtained. However, when changing to gelatin A to D, the amount of hardener of gelatin A was fixed.・ 4-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 0.015 g / m ²

[0062]

[Chemical 6]

[0063] Polymethyl methacrylate (average particle size 3.6μm) 0.087g / m ² · Proxel (prepared in pH7.4 with NaOH) 0.0005g / m ² It is noted that the polymer P-7, polymer P-18, Polyacrylic acid was added with an alkali to prepare a 7.5 wt% transparent aqueous solution having a pH of 7.0, and the solution was added to the surface protective layer coating solution. The pH of the surface protective layer coating solution was adjusted to 7.0. Preparation of Support (1) Preparation of Dye D-1 for Undercoat Layer The following dyes were ball-milled by the method described in JP-A-63-197943.

[0064]

[Chemical 7]

434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 4
00 ml (2 mm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observing the obtained dye dispersion, the particle size of the crushed dye has a wide range of diameters from 0.05 to 1.15 μm, and the average particle size was 0.37 μm. Further, centrifugation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D-1 was obtained. (2) Preparation of support Corona discharge treatment was performed on a polyethylene terephthalate film having a thickness of 183 μm that was biaxially stretched, and the first undercoat liquid having the following composition was applied so that the coating amount was 5.1 cc / m ^2. It was applied with a wire bar coater and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the following structure.

[0066]

[Chemical 8]

Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79 cc

[0068]

[Chemical 9]

2,4-Dichloro-6-hydroxy-s-triazine sodium salt 4% solution 20.5 cc distilled water 900.5 cc A second undercoat having the following composition on the above-mentioned first undercoat layers. Layers are coated on each side so that the coating amount is as described below, and 150 ° C on both sides by the wire bar coater method.
It was applied and dried.・ Gelatin 160 mg / m ²・ Dye Dispersion D-1 (26 mg / m ² as a solid dye component)

[0070]

[Chemical 10]

Matting agent Polymethylmethacrylate having an average particle diameter of 2.5 μm 2.5 mg / m ^{2 The} following A to D were used as gelatin. (Gelatin type) (Processing method) (Calcium ion content) Gelatin A Alkali-treated gelatin 5,000ppm Gelatin B Gelatin A desalted 2,000ppm Gelatin C Gelatin A desalted 500ppm Gelatin D Gelatin A desalted Treated 50ppm

Preparation of Photographic Material The emulsion layer and the surface protective layer were coated on both sides of the prepared support by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . The swelling ratio was set as shown in Table 1 by adjusting the amount of gelatin added to the emulsion layer and the amount of hardener. Thus, photographic materials 101 to 119 were obtained.

Evaluation of Photographic Performance Each sample of the photographic materials 101 to 119 was exposed to light from both sides for 0.05 seconds using an X-ray orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd., and sensitivity was evaluated. Was done. After the exposure, the following processing was performed. The sensitivity is represented by the reciprocal of the ratio of the exposure amount that gives a density of 1.0 based on the photographic material 1.

Processing I Automatic processor ... SRX-5 manufactured by KONICA Co., Ltd.
01 Developer ... RD- manufactured by Fuji Photo Film Co., Ltd.
3 Fixer ... Fuji, manufactured by Fuji Photo Film Co., Ltd.
iF Processing speed: Dry to Dry 90 seconds Development temperature: 35 ° C Fixing temperature: 32 ° C Drying temperature: 45 ° C Replenishment amount: Developer 22 ml / 10 × 12 inches Fixer 30 ml / 10 × 12 inches

Processing II Automatic developing machine ... SRX50 manufactured by KONICA Co., Ltd.
The drive motor and gear of No. 1 were modified to speed up the transfer speed. Developer ... RD- made by Fuji Photo Film Co., Ltd.
10 Fixer ... Fuji Photo Film Co., Ltd. RF-
10 Processing speed… Dry to Dry 30 seconds Development temperature… 35 ℃ Fixing temperature… 35 ℃ Drying temperature… 55 ℃ Replenishment amount… Developer 22ml / 10 × 12 inches Fixer 30ml / 10 × 12 inches

(Evaluation of roller mark) Photographic material 101
.About.119 were uniformly exposed to a density of 1.0 in a size of 10.times.12 inches, and then processed under the same conditions as the evaluation of photographic performance. However, the carrying roller of the developing tank and the crossover roller from developing to fixing used at this time were intentionally fatigued rollers. The roller surface had irregularities of up to ± 10 μm. Depending on the photographic material, a large number of fine spots due to the unevenness of the roller were generated on the processed photosensitive material. This state was sensory-evaluated in the following four stages. The evaluation results are summarized in Table-1. ◎ ... Almost no spots were observed. ○… It is a level where there are slight spots, but this is not a problem for practical use. Δ: Spots are generated, but not on a normal roller. Acceptable level. × ... Many spots, which are not practical for ordinary rollers.

(Evaluation of Drying Property) Under the same conditions as in Process II for evaluating photographic performance, the dryness of a film when each photographic material having a size of 4 pieces was continuously processed was sensory-evaluated by touch. The film was processed continuously with the short side in the transport direction. The results are summarized in Table-1. ◎ Even after the 30th sheet, the film appears warm and dry. No problem at all. ○ Even on the 30th sheet, the film is completely dry. The temperature when touched was about the same as that of the film left at room temperature. △ At the 30th sheet, the film was slightly cold, but the continuously processed film did not adhere to the film and was practically acceptable. × At the 30th sheet, the film is wet and undried. Film comrades adhere.

Evaluation of Residual Color Property The residual color property of the film was evaluated when the same treatment (Treatment III) as Treatment II was carried out except that the temperature of the washing water was changed to 10 ° C. The evaluation criteria were made by visually comparing the actual films of Treatment I and Treatment III.

(Measurement of swelling rate of distilled water) The swelling rate of each photographic material was measured according to the above-mentioned measuring method. The results are summarized in Table-1.

[0080]

[Table 1]

In Table 1, the photographic materials 101 to 106 having a gelatin coating amount of 2.7 g / m ² cannot satisfy both the drying property and the residual color property even if the type of gelatin is changed. On the other hand, with the photographic material 107 having a gelatin coating amount of 2.4 g / m ² , although the drying property and the residual color property are satisfied, the roller mark is deteriorated. Further, a photographic material 10 using the polymer of the present invention
In Nos. 8 and 112, the drying property is improved but the residual color property is not improved. Here, by using the polymer of the present invention and gelatin having a calcium ion content of 2000 ppm or less, it is possible to satisfy all of the drying property, the roller mark and the residual color property. Further, when polyacrylic acid is used, satisfactory results cannot be obtained in terms of drying property.

Example 2 (Preparation of tabular grains) In 1 liter of water, 4.5 g of potassium bromide, 12.0 g of gelatin and thioether HO (CH ₂ ) ₂
Add _2.5 cc of 5% aqueous solution of S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH and add 55 ℃
While stirring, 37 cc of an aqueous solution of silver nitrate (3.43 g of silver nitrate), 33 cc of an aqueous solution containing 2.97 g of potassium bromide and 0.363 g of potassium iodide were added to the vessel kept at 37 ° C. for 37 seconds by the double jet method. Next, potassium bromide 0.
After adding 9 g of the aqueous solution, the temperature was raised to 70 ° C. and 53 cc of an aqueous silver nitrate solution (4.90 g of silver nitrate) was added over 13 minutes. Here, 8 cc of 25% aqueous ammonia solution was added, and after physically aging for 10 minutes at the same temperature, 7 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added over 35 minutes by the control double jet method while maintaining the pAg at 8.5. Next, 10 cc of 2N potassium thiocyanate solution and AgI fine particles with a diameter of 0.07 μm were used for the total silver amount to 0.0.
5 mol% was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, the total silver iodide content was 0.31 mol%, the average projected area diameter was 0.60 μm,
Monodisperse tabular grains having a thickness of 0.120 μm and a variation coefficient of diameter of 16.5% were obtained.

After that, soluble salts were removed by a precipitation method. The temperature was again raised to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickening agent were added, and pH was adjusted to 5.90 and pAg was adjusted to 7.90 with caustic soda and silver nitrate solution. This emulsion was chemically sensitized while being kept at 56 ° C. with stirring. First, 0.043 mg of thiourea dioxide was added and the mixture was held for 22 minutes as it was for reduction sensitization. Next, 250 mg of the same sensitizing dye as in Example-1 was added. Subsequently, sodium thiosulfate The following selenium sensitizer was added at a molar ratio of 6: 4.

Subsequently, chloroauric acid and potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. In this way, preparation of tabular grains T _A was completed.

(Preparation of Emulsion Layer Coating Solution) The following chemicals were added to 1 mol of silver halide of tabular grains T _{A to} prepare an emulsion layer coating solution. -2,6-bis (hydroxyamino) -4-diethylamino 1,3,5-triazine 72-Gelatin A to D described in Table-2-Dextran (average molecular weight 39,000) 18.5 g-Sodium polystyrene sulfonate (Average molecular weight 600,000) 1.8g

[0086]

[Chemical 11]

[0087]

[Chemical 12]

Snowtex C (manufactured by Nissan Chemical Industries, Ltd.) 9.6 g as solid content Dextran (average molecular weight of 39,000) 5.8 g The pH of the emulsion layer coating solution was 6.0. (Preparation of Surface Protective Layer) The surface protective layer of the emulsion layer was prepared and prepared so that each component had the following coating amount. -Gelatin A to D Listed in Table-2 Polymer P-7 Listed in Table-2 Polymer P-18 Listed in Table-2 Polyacrylic acid Listed in Table-2 Hardener 1,2-bis (vinyl) Sulfonylacetamido) ethane Addition amount was adjusted so that the swelling ratio shown in Table-2 was obtained. However, when changing to gelatin A to F, the amount of the hardener of gelatin A was fixed.・ 4-Hydroxy-6-methyl-1,3,3a, 7-tetraazaindene 0.003 g / m ²・ Polymethyl methacrylate (average particle size 2.5 μm) 0.05 g / m ²・ Proxel 0.0005 g / m ²

[0089]

[Chemical 13]

The polymers P-7, P-18 and polyacrylic acid were each added with an alkali at pH 7.0,
A 7.5% by weight transparent aqueous solution was prepared and added to the surface protective layer coating solution. The pH of the surface protective layer coating solution was 7.0. The prepared emulsion layer coating solution and surface protective layer coating solution were coated on one side by a simultaneous extrusion method on a polyethylene terephthalate film having a thickness of 183 μm which was biaxially stretched and previously coated with an undercoat layer. Coating silver amount is 2.5
It was adjusted to be 5 g / m ² . In the polyethylene terephthalate used, the dye having the same structure as in Example 1 was 0.0
The one containing 4 wt% was used.

(Preparation of Antihalation Layer) An antihalation layer and a surface protection layer of the antihalation layer were coated on the side coated with the emulsion layer and the surface protection layer, and on the side opposite to the support. Each layer was prepared so as to have the following coating amount. (Antihalation layer) ・ Gelatin 1.5 g / m ²・ Phosphoric acid 5.2 g / m ²・ Snowtex C (Nissan Chemical Co., Ltd.) 0.5 g / m ² as solid content ・ Potassium polystyrene sulfonate (average molecular weight) 600,000) 25 g / m ² · Polymer latex (poly (ethyl acrylate / methacrylic acid) = 97/3) 0.53 g / m ²

[0092]

[Chemical 14]

[0093]

[Chemical 15]

(Surface Protective Layer of Antihalation Layer) Gelatin 1.05 g / m ² Polymethylmethacrylate (average particle size 3.5 μm) 65 mg / m ²

[0095]

[Chemical 16]

C ₈ F ₁₇ SO ₃ K 1.7 mg / m ² · potassium polystyrene sulfonate (average molecular weight 600,000) 2 mg / m ² · NaOH 2.5 mg / m ² Antihalation layer and its surface protection layer It was simultaneously coated and dried by the simultaneous extrusion method. Fuji Photo Film Co., Ltd. uses the photographic material thus obtained as an automatic processor.
The same evaluation as in Example 1 was carried out except that FPM-9000 manufactured by Mfg. Co., Ltd. (which was modified so that the transport speed of the film could be increased) was used, and the results are summarized in Table 2.

[0097]

[Table 2]

From the results shown in Table 2, when the polymer of the present invention is used and gelatin having a calcium ion content of 2000 ppm or less is used, all of the drying property, the roller mark and the residual color property are satisfied without deteriorating the photographic performance. I understand that

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one type of carboxyl group-containing polymer (carboxyl group-containing monomer unit is 15 mol% or more, or acid value is 1.5 meq / g or more, provided that at least one silver halide emulsion layer-coated surface is polyacrylic acid. Except that the content of calcium ion (Ca ²⁺ ) of at least one gelatin used as the hydrophilic colloid layer is 2,000 ppm or less based on the dry gelatin. A silver halide photographic light-sensitive material characterized by the above. 2. The amount ratio of the carboxyl group-containing polymer and gelatin on the side coated with the silver halide emulsion layer is 0.01 to.
The silver halide photographic light-sensitive material according to claim 1, wherein the silver photographic light-sensitive material is 0.3. 3. The swelling ratio of the all-hydrophilic colloid layer on the side having the carboxylic acid polymer-containing layer with respect to the support in distilled water is 200% or more, and the swelling ratio is 200% or more. Silver halide photographic light-sensitive material. (Here, the swelling ratio in distilled water was obtained by incubating the photographic material at 40 ° C. and 60% RH (percent relative humidity) for 16 hours, and immersing it in distilled water at 21 ° C. for 3 minutes to measure the change in thickness. And) 4. The silver halide photographic light-sensitive material according to claim 3, wherein methacrylic acid is used as a carboxyl group-containing monomer unit of the carboxyl group-containing polymer.