JPH04158357A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain a material with excellent size stability by dipping a photosensitive material provided with a silver halogenide emulsion layer and a barrier layer having the gelatin quantity of a silver halogenide photographic photosensitive material within the specific g/m<2> range and the water absorbing speed of a supporter with specific g/cm<2>.min in a liquid for specific sec. CONSTITUTION:In a silver halogenide photographic photosensitive material having at least one layer of a silver halogenide photographic photosensitive material on one side of a supporter and a backing layer on the other side, the gelatin quantity on the side having the silver halogenide emulsion layer is set within the range 0.5-2.5 g/m<2>. The total gelatin quantity of the silver halogenide photographic photosensitive material is set within the range 1.0-5.0 g/m<2>. The silver halogenide photographic photosensitive material having a barrier layer so that the water absorbing speed of the supporter is set to 1.5X10<-2> g/(cm<2>.min) or below (for supporter 100mum) is processed for the dipping time 10-70 sec. The silver halogenide photographic photosensitive material with excellent size stability and little fluctuation in size before and after processing such as developing is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material having excellent dimensional stability.

[Background of the invention]

Silver halide photographic materials (hereinafter referred to as "photosensitive materials") have the property of shrinking when humidity is low and elongating when humidity is high.

Furthermore, apart from this, photosensitive materials have the characteristic that their dimensions change before and after development processing. This is a phenomenon in which the photosensitive material and the image size on the photosensitive material at the time of exposure and the photosensitive material and the image size on the photosensitive material after development are different, and the temperature conditions at the time of exposure and the drying temperature and humidity during the development process are different. It is caused by the influence of conditions.

This dimensional change in the photosensitive material becomes an extremely serious drawback in photosensitive materials for printing, which require reproduction of halftone dot images or precise line drawings for multicolor printing, for example.

Specifically, film master plates for color printing consist of four master plates, including cyan, magenta, and yellow 311 [plates or blackout plates], so dimensional stability is required. . Therefore, if the dimensional accuracy of these four color originals does not strictly match, color shift may occur. Also, dimensional accuracy is extremely required for maps and the like.

As a method for obtaining a photosensitive material with excellent dimensional stability and little change in dimensional accuracy, a technique for regulating the thickness ratio between the hydrophilic colloid layer and the support is disclosed in US Pat. No. 3,201.
No. 250, and Japanese Patent Publication No. 39-4272 and No. 3 disclose the technology of incorporating polymer latex into the hydrophilic colloid layer.
No. 9-17702, Conductivity No. 43-13482.

No. 435-5331, U.S. Patent No. 237600, No. 2
No. 763625, No. 2772166, No. 285238
No. 6, No. 2853457, No. 3397988, No. 3
It is described in No. 411911 and No. 3411912.

However, the inclusion of these polymer latexes in the hydrophilic colloid layer has an adverse effect on the film strength in the developing solution, the abrasion resistance, and the adhesion of these layers to the support.

U.S. Patent No. 3,459,790, U.S. Patent No. 3,488,708, U.S. Patent No. 3
No. 554987, No. 3700456, No. 393913
No. 0, British Patent No. 1491701, etc. disclose techniques to improve the above problems by using polymers that react with conventional gelatin hardeners, but they do not meet the above-mentioned strict requirements for dimensional stability. I can't be satisfied.

The above-mentioned measures for the hydrophilic colloid layer alone are insufficient; the support also stretches due to the water during the treatment process, but does not return to its original shape after a long period of time after drying.

In order to improve the properties of such a support, for example, Japanese Patent Laid-Open No. 64-538 discloses a technique of coating a polyester support with a polymer layer containing vinylidene chloride.

In addition, Japanese Patent Application Laid-open No. 60-250041 describes a support with excellent blocking resistance, gas barrier properties, and printability.
A technique has been disclosed in which a vinylidene chloride copolymer is applied to a film and heat treated.

However, at present, even with these techniques, it cannot be said that the dimensional stability has been sufficiently improved.

[Purpose of the invention]

In view of the above-mentioned problems, an object of the present invention is to provide a silver halide photographic light-sensitive material, which exhibits particularly excellent dimensional stability with little dimensional change before and after processing.

[Structure of the invention]

The above object of the invention is to provide at least one on one side of the support.
A silver halide photographic material having a layer of silver halide photographic material and a packing layer on the other side,
The amount of gelatin on the side having the silver halide emulsion layer is 0.
5 to 2-5 g/rm", and the total amount of gelatin in the silver halide photographic light-sensitive material is 1.0 to 5.0 g/rm".
(2) The water absorption rate of the support is 1.5XlO
-6g/(cm!・min) or less (support thickness 100μ
This is achieved by an image forming method characterized by processing a silver halide photographic material provided with a barrier layer so as to obtain (m) by immersing it in a liquid for 10 to 70 seconds.

A more preferred embodiment is that the silver halide emulsion layer contains 0.3 g/*' or more of polymer latex.

The present invention will be explained in detail below.

The amount of water absorbed in the present invention refers to the amount of water absorbed per minute, and is specifically measured by the following method.

Humidify a 100 cm" support in an environment of 20% RH for at least 3 days, then weigh it. Next, soak it in water at 23°C for 1 minute, remove the water adhering to the surface, immediately measure the weight, and remove the water. The amount of change in water absorption per 1 cm is determined from the difference in weight before and after immersion in water, and this is taken as the water absorption rate.

The water absorption rate is preferably 1.3XlO-6g/(cm"・■in) or less, and 1.0X10-@g/(am"・mi
n) The following are particularly preferred.

Generally, the physical properties of photosensitive materials are greatly affected by drying conditions. In particular, the drying conditions at the reduction rate stage (drying rate between about 30 and 10%) have a large influence, and rapid drying has a negative effect on the physical properties.

Therefore, drying at too high a temperature and low humidity is not preferable.

In the present invention, the method for adjusting the water absorption rate of the support is not particularly limited, but for example, there is a method of using polyester as the support and further coating polyvinylidene chloride as a water barrier layer on the polyester support.

When applying vinylidene chloride to a support film such as polyester, the following two methods are known.

A method of applying vinylidene chloride latex after the oriented crystallization of polyester is completed.

A method of applying vinylidene chloride latex before the completion of oriented crystallization of polyester.

In this case, heat treatment called heat setting is performed.

In the present invention, any of the above methods may be used.

Here, the vinylidene chloride copolymer refers to a copolymer containing vinylidene chloride, a copolymer consisting of vinylidene chloride/acrylic acid ester/vinyl monomer having alcohol in the side chain described in JP-A-51-135526. Copolymer of vinylidene chloride/alkyl acrylate/acrylic acid as described in U.S. Pat. No. 2,852.378, copolymer of vinylidene chloride/acrylonitrile/itaconic acid as described in U.S. Pat. No. 2,698.235, U.S. Pat. 3,78
Examples include a copolymer of vinylidene chloride/alkyl acrylate/itaconic acid described in No. 8.856.

Specific examples of compounds include the following.

All numbers in parentheses represent weight ratios.

Copolymer of vinylidene chloride: methyl acrylate: hydroxyethyl acrylate (83:12:2) Copolymer of vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (82:10:8) Vinylidene chloride: hydroxydiethyl methacrylate (
Copolymer of vinylidene chloride:butyl acrylate:acrylic acid (92:8)
4:4:2) copolymer of vinyldene chloride:butyl acrylate:itaconic acid (7
5:20:5) copolymer of vinylidene chloride:methyl acrylate:itaconic acid (9
Copolymer of vinylidene chloride: methyl acrylate dimethacrylic acid (93:4:3) vinylidene chloride: itaconic acid monoethyl ester (96
:4) copolymer of vinylidene chloride:acrylonitrile:acrylic acid (96
Copolymer of vinylidene chloride: methyl acrylate: acrylic acid (90:5:5) Copolymer of vinylidene chloride: ethyl acrylate: acrylic acid (90:5:5)
2:5:2) copolymer vinylidene chloride:methyl acrylate-co-3-chloro-2
- Copolymer of hydroxypropyl acrylate (84:9) Vinylidene chloride: Methyl acrylate: N- Copolymer of ethanol acrylamide (85:10:5) Vinylidene chloride: Methyl acrylate: Acrylic acid (9)
Copolymer of vinylidene chloride: methyl acrylate: itaconic acid (9:l:l)
7: l: copolymer of 2) copolymer of vinylidene chloride: acrylonitrile: acrylic acid (99:0.5:0.5) copolymer of vinylidene chloride: ethyl acrylate: acrylic @ (98: l:1) Polymer vinylidene chloride: Methyl acrylate nya-acrylic acid (
65:34:1) copolymer vinylidene chloride: methyl acrylate: itaconic acid (7
Copolymer vinylidene chloride:acrylonitrile:acrylic acid (70:29:1)
:29:l) copolymer of vinylidene chloride:ethyl acrylate:acrylic acid (6
8:31:1) copolymer and polyester film, for example, JP-A-52-54
It can be manufactured using a known biaxial stretching method as described in No. 428.

Various treatments can be applied to create a strong bond between the polyester and polyvinylidene chloride polymer latex layers.

For example, surface treatment with chemicals, mechanical treatment, corona discharge treatment,
Flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment,
Surface activation treatments such as active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, etc., acid components, hydroxyl group components, epoxy group components, N-alkanol group components, diolefin monomer components, polymer latex components, etc. These methods include coating an undercoat layer containing one or more components selected from among these. In addition, known means for preventing electrification may be used independently. For example, there is a method in which a fluorine-based surfactant, various conductive polymers, inorganic oxides, organic antistatic agents, etc. are contained in the undercoat layer.

These treatments may be performed on only one side of the support or on both sides, and of course, the treatment applied to one side of the support may be applied to the other side. It does not matter if the process is different from the process performed. Furthermore, two or more different types of processing may be used together.

The photographic light-sensitive material of the present invention has photographic constituent layers including at least one light-sensitive silver halide emulsion layer.

The photographic constituent layer is a hydrophilic colloid layer, and the hydrophilic colloid used in the core layer is preferably gelatin.

The gelatin used in the present invention may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964). Hydrophilic colloids other than gelatin that can be used in the present invention include, for example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate, etc. Sugar derivatives such as cellulose derivatives, sodium alginate, starch derivatives; single or There are a wide variety of synthetic hydrophilic polymeric materials such as copolymers.

The amount of hydrophilic colloid in the constituent layers of the photographic light-sensitive material of the present invention is from 1.0 to
The total amount of gelatin in the silver halide photographic light-sensitive material is preferably 2 to 3 g/m.

The constituent layers constituting the photographic material of the present invention preferably contain a polymer latex in order to more effectively achieve the object of the present invention.

Examples of the polymer latex included in the photographic material of the present invention include US Pat. No. 2,772,166;
No. 3,325.286, No. 3,411.911, No. 3,311.912, No. 3,525,620, Research Disclosure (Research D
1sclosure) Magazine No. 19519551 (19
There are hydrates of vinyl polymers such as acrylic esters, methacrylic esters, and styrene, as described in Jul. 1980).

Polymer latexes preferably used in the present invention include homopolymers of meth-alkyl acrylate such as methyl methacrylate and ethyl methacrylate, styrene homopolymers, meth-alkyl acrylate, styrene and acrylic acid, N-methylol acrylamide, glycidol methacrylate, etc. copolymers of alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate, or copolymers of alkyl acrylates with acrylic acid, N-methylolacrylamide, etc. (preferably, the copolymerization component such as acrylic acid is (up to 30% by weight), homopolymers of butadiene or butadiene and styrene, butoxymethylacrylamide,
Copolymer with one or more of acrylic acid, vinylidene chloride
Examples include methyl acrylate-acrylic acid terpolymer.

Next, specific examples of polymer latex preferably used in the present invention will be given, but the present invention is limited to these [Specific latex examples] L-1 Q ■ Suga Cx/y/z = 40/20/40) (x/ y/
z -39,4/ 59/ 1.6) CH.

― R CH.

CH.

insect IJI;tl, OHCM.

(x/y/z=93/3/4) ■ CH3 (x/y/z=93/3/4) Shi-〇 R L-17 C.I.

(x/y/z -93/3/4) CM.

Cθ CI/y/z -85/13/2) (w/x/y/z -45/43/8/4) The preferred range of the average particle size of the polymer latex used in the present invention is 0.
005-1 perr, especially 0.02-0.1 pm.

The polymer latex used in the present invention may be contained on only one side of the support, or may be contained on both sides. When the polymer latex is contained on both sides of the support, the type and/or amount of polymer latex contained on each side may be the same or different.

The polymer latex is preferably added to at least the emulsion layer of the light-sensitive material. It may also be contained in the uppermost non-photosensitive colloid layer, which is usually called a protective layer. If an intermediate layer exists between the thermal layer and the uppermost layer, such as a subbing layer or a photosensitive silver halide emulsion layer, the intermediate layer may be used. Furthermore, the polymer latex may be contained in any single layer in a multilayer structure.

In the present invention, the content of polymer latex is 0.3 to 10.0/m'' as included in the photosensitive emulsion layer,
More preferably, it is 0.5 g/+a'' to 5.0 g/m''.

When a packing layer is provided, the amount of polymer latex in that layer is preferably 0.1 to 10.0 g/2, more preferably 0.2 to 5.0 g/+o''. The amount of the polymer latex is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 4.0 parts by weight, per 1 part by weight of the hydrophilic colloid.

Further, the photosensitive materials of the present invention include Japanese Patent Publications No. 59-17825, No. 59-17818, No. 59-17819, No. 5
No. 9-17820, No. 59-17821, No. 59-1
Tetrazolium compounds disclosed in No. 7826 and No. 59-17822, and JP-A-53-16623,
No. 53-20927, No. 53-84714, No. 57
A hydrazine compound disclosed in Japanese Patent No. 58137 and the like can be contained as a contrast enhancing agent.

Further, as a specific example of the tetrazolium compound used in the present invention, the general formula T described in JP-A-62-11253 is
-1. The compound represented by T-2 and T-3 is [T-1) (T-2) [T-3) in the formula R,,R,R,,R,,R,,,R,,, R...
and R1° each represent an alkyl group (e.g. methyl group, ethyl group, propyl group, dodecyl group, etc.), an allyl group, a 7-enyl group (e.g. phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl group, aminophenyl group) , mercaptophenyl group, methoxyphenyl group, etc.), naphthyl groups (e.g., σ-naphthyl group, β-naphthyl group, hydroxynaphthyl group, carboxynaphthyl group, aminonaphthyl group, etc.), and heterocyclic groups (e.g., thiazolyl group, benzothiazolyl group) , oxacylyl group, pyrimidinyl group, pyridyl group, etc.), and any of these may be a group that forms a metal chelate or a complex.

R1~R,. and R1, respectively, are allyl group, phenyl group, naphthyl group, heterocyclic group, alkyl group (e.g. methyl group, ethyl group, propyl group, butyl group, mercaptomethyl group, mercaptoethyl group, etc.), hydroxyl group, alkylphenyl group, Selected from alkoxyphenyl group, carboxyl group or salt thereof, carboxyalkyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group), amino group (e.g. amino group, ethylamino group, anilino group, etc.), mercapto group, nitro group, and hydrogen atom represents a group, D
represents a divalent aromatic group, E represents a group selected from an alkylene group, an arylene group, and an aralalkylene group;
represents an anion, and n represents 1 or 2. However, when the compound forms an inner salt, n is 1.

Next, specific examples of the cation moiety of the tetrazolium compound used in the present invention will be shown, but the cation moiety of the compound that can be used in the present invention is not necessarily limited to these.

(T-1) 2-(benzothiazol-2-yl)-
3-phenyl-5-dodecyl-2H-tetrazolium (T-2) 2.3-diphenyl-5-(4-t-
octyloxyphenyl)-2H-tetrazolium (T
-3) 2,3.5-triphenyl-2H-tetrazolium (T-4) 2.3.5-tri(p-carboxyethylphenyl)-2H-tetrazolium (T -5') 2-(benzothiazole- 2-yl)-3-phenyl-5-(o-chlorphenyl)-
2H-tetrazolium (T-6) 2.3-diphenyl-2H-tetrazolium (T-7) 2.3-diphenyl-5-methyl-2
H-tetrazolium (T-8) 3-(p-hydroxyphenyl)-
5-Methyl-2=phenyl-2H-tetrazolium (
T-9) 2.3-diphenyl-5-ethyl-2H
-Tetrazolium (T-10) 2,3-diphenyl-5-n-hexyl-2H-tetrazolium (T-11) 5-cyano-2,3-diphenyl-2H-tetrazolium (T-12) 2-(benzothiazole -2-yl)-5-phenyl-3-(4-tolyl)-2H-tetrazolium(T-13) 2-(benzothiazol-2-yl)-5-(4-chlorophenyl)-3-(4 -nitrophenyl)-2H-tetrazolium (T-14) 5-ethoxycarbonyl-2,3-
Di(3-nitrophenyl)-2H-tetrazolium (
T-15) 5-acetyl-2,3-di(p-ethoxyphenyl)-2H-tetrazolium (T-16) 2,5-diphenyl-3-(p-tolyl)-2H-tetrazolium (T-17) 2.5-diphenyl-3-(p-iodophenyl)2H-tetrazolium (T-18) 2.3-diphenyl-5-(p-diphenyl)-2H-tetrazolium (T-19) 5-(p-bromo phenyl)-2
-Phenyl-3-(2,4,6-)lychlorophenyl)-2H-tetrazolium (T-20) 3-(p-hydroxyphenyl)-5-(p-nitrophenyl)-2-phenyl-
2H-tetrazolium (T-21) 5-(3,4-dimethoxyphenyl)-3-(2-ethoxyphenyl)-2-(4-methoxy1 phenyl)-2H-tetrazolium (T-22) 5-(4 -cyanophenyl)-2
, 3-diphenyl-2H-tetrazolium (T-23) 3-(p-acetamidophenyl)-2゜5-diphenyl-2H-tetrazolium (T
-24) 5-acetyl-2,3-diphenyl-
2H-Tetrazolium (T-25) 5-(Flu-2yl)-2,3-diphenyl-2H-tetrazolium (T-26) 5-(Flu-2yl)-2,3-diphenyl-2H-tetrazolium (T- 27) 2.3-diphenyl-5-(pyrid-4yl)-2H-tetrazolium (T-28) 2.3-diphenyl-5-(quinol-2yl)-2H-tetrazolium (T-29) 2. 3-diphenyl-5-(benzoxazol-2yl)-2H-tetrazolium (T-
30) 2.3-diphenyl-5-nitro-2H-
Tetrazolium (T-31) 2.2', 3.3'-tetraphenyl-5°5'-1,4-butylene-di(2H-tetrazolium) (T-32) 2.2', 3.3' −
Tetraphenyl-5゜5'-p-phenylene-di(2H-tetrazolium) (T-33) 2-(4,
5-dimethylthiazol-2yl)-3,5-; phenyl-2H-tetrazolium (T-34) 3.5-
Diphenyl-2-(triazin-2yl-2H-tetrazolium) (T-35) 2-(benzothiazol-2yl)
-3-(4-methoxyphenyl)-5-7ene-28-tetrazolium (T-36) 2.3-dimethoxyphenyl-5-
7 enyl 2H-tetrazolium (T-37) 2,3.5-tris(methoxyphenyl)-2H-tetrazolium (T-38) 2.3-dimethylphenyl-5-phenyl-2H-tetrazolium (T-39) 2 .3-hydroxyethyl-5-phenyl-2H-tetrazolium (T-40) 2.3-hydroxymethyl-5-7enyl-2H-tetrazolium (T-41) 2.3-cyanohydroxyphenyl-5-7enyl-2H -Tetrazolium (T-42) 2.3-di(p-chlorophenyl)-
5-7 enyl-2H-tetrazolium (T-43) 2.3-di(hydroxyethoxyphenyl)-5-7 enyl-2H-tetrazolium (T-
44) 2.3-di(2-pyridyl)-5-7ene-2H-tetrazolium (T-45) 2.3.5-tris(2-pyridyl)
-2H-tetrazolium (T-46) 2.3.5-tris(4-pyridyl>
-2H-Tetrazolium When a tetrazolium compound is used as a non-diffusible compound, a non-diffusible compound obtained by appropriately selecting a cation moiety and an anion moiety is used.

Examples of the anion moiety of the tetrazolium compound used in the present invention include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as sulfuric acid, nitric acid, and perchloric acid, sulfonic acid,
Acid groups of organic acids such as carboxylic acids, lower alkylbenzenesulfonic acid anions such as p-) luenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-)'y' silbenzenesulfonic acid anions, lauryl sulfate anions, etc. Higher alkyl sulfate ester anions, dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxy sulfate anions, higher fatty acid anions such as stearate anions, polyacrylic Examples include polymers such as acid anions with acid groups attached.

By appropriately selecting the anion moiety and the cation moiety, the non-diffusible tetrazolium compound according to the present invention can be synthesized. The compounds according to the present invention synthesized in this way include, for example, 2゜3.5-triphenyl-2H-tetrazolium-dioctylsuccinate sulfonate, and these are as detailed in Examples below. After each soluble salt is dispersed in gelatin, the two are mixed and dispersed in a gelatin matrix;
Crystals of the oxidizing agent may be synthesized in pure form, dissolved in a suitable solvent (eg dimethyl sulfoxide), and then dispersed into a gelatin matrix.

If it is difficult to achieve uniform dispersion, emulsification and dispersion using an appropriate homogenizer such as ultrasonic waves or a Manton-Gorlin homogenizer may give good results. In addition, finely dispersed in high boiling point solvents such as dioctyl phthalate,
It is also possible to protect it and disperse it in a hydrophilic colloid layer.

Next, hydrazine derivatives (e.g. U.S. Pat. No. 4,166.7)
No. 42, No. 4,168,977, No. 4,221,85
No. 7, No. 4,224゜401, No. 4,243.739
No. 4,272.606 and No. 4,311゜781, a negative-working silver halide photographic light-sensitive material to which a specific acylhydrazine compound was added was heated to pH 11.
, 0 to 12.3, and a method for obtaining high contrast negative images by processing with a solution containing 0.15 mol/a or more of a sulfite preservative (hereinafter referred to as a hydrazine high contrast developing system) will be described.

Examples of hydrazine derivatives used in this method include the aryl hydrazides described in JP-A Nos. 63-29751 and 63-223744, as well as compounds represented by the following general formula (H). It will be done.

General formula (H) In the formula, R11 is an alkyl group (e.g., octyl, t-octyl, decyl, dodecyl, tetradecyl, etc.), an aryl group (e.g., evaphenyl, p-propyl, phenyl, naphthyl, etc.), or a heterocyclic group. (For example, groups such as pyridyl, tetrazoline, oxasilyl, penzolooxasilyl, benzothiazolyl, benzimidazolyl, etc.).

Preferred alkyl groups for R11 have 6 to 2 carbon atoms.
It is a group of 0.

Preferred aryl groups for R11 include X being a substituted or unsubstituted alkyl group (e.g., methyl, ethyl, methoxy, i-propyl, etc.), acylamino (e.g., octanamide, tetradecanamide, etc.), ureido (e.g., hexyl). ureido, δ-(2,4-di-t-acylphenoxy)butylureido, etc.), hydrazinocarbonylamino (e.g. 2,2-dibutylhydrazinocarbonylamino, 2-phenyl-2-methylhydrazinocarbonylamino) etc.), sulfonamides (e.g. groups such as hexadecanesulfonamide, 4-butoxybenzenesulfonamide, morpholinosulfonamide etc.), aminosulfonamides (e.g. groups such as N,N-dibutylsulf7moylamino, N,N-dimethylsulf7amoylamino, etc.) group), oxycarbonylamino (e.g. octyloxycarbonylamino, benzyloxycarbonylamino, etc.), -S-carbonylamino (e.g. CaH+yS
CONH, CaHaSCONH-, etc. groups) R1 and R2
are hydrogen atoms, alkyl (e.g., groups such as methyl, ethyl, propyl, butyl, cyclohexyl, etc.), aryl (e.g., groups such as phenyl, naphthyl, etc.), and heterocycles (e.g., groups such as pyridyl, thienyl, piperidino, morpholino, etc.). It represents 6 groups, and R1 and R2 have a nitrogen atom and a ring (
For example, rings such as piperidino, piperazino, morpholino, etc.) are p.

M.

R1 and R6 are each a hydrogen atom or a substitutable group (
For example, groups such as alkyl, aryl, heterocycle, etc.) and rings (for example, cyclohexane, thiazole, oxazole,
A ring such as benzothiazole) may be formed.

R1 is a hydrogen atom, aryl (e.g., phenyl, naphthyl, etc.), heterocycle (e.g., piperidino, monophorino, tetrahydropyranyl, pyridyl, thienyl, etc.) 6
represents a group.

zI is a substitutable group (e.g. alkyl, aryl, heterocycle, hydroxy, alkoxy, amino, acylamino,
ureido, hydrazinocarbonylamino, sulfonamide, aminosulfonamide, oxycarbonylamino,
-8-carbonylamino, halogen, etc.).

A1 and A are both hydrogen atoms, or one is a hydrogen atom and the other is acyl (e.g., groups such as acetyl, trifluoroacetyl, etc.), sulfonyl (e.g., groups such as methasulfonyl, toluenesulfonyl, etc.), oxalyl (e.g., ethoxalyl, etc.) represents six groups of (group), but it is most preferable that A1 and A2 are both hydrogen atoms. R1□ is a hydrogen atom, alkyl as a blocking group (e.g., methyl, ethyl, benzyl, methoxymethyl, trifluoromethyl, phenoxymethyl, hydroxymethyl, methylthiomethyl, phenylthiomethyl, etc.), aryl (e.g., phenyl, (groups such as chlorphenyl), heterocycles (e.g. pyridyl, thienyl, (7) groups such as 7!J/L), R+ R1 and R2 are hydrogen atoms, alkyl (e.g. groups such as methyl, ethyl, benzyl), alkenyl ( For example, allyl
groups such as butenyl), alkynyl (e.g. propargyl,
butynyl, etc.), aryl (e.g., phenyl, naphthyl, etc.), heterocycles (e.g., 2,2,6,6-titramethylpiperidinyl, N-ethyl-N'-ethylpyrazolidinyl, pyridinyl, etc.) R6 and R
7 may form a ring (eg, piperidino, morpholino, etc. ring) together with the nitrogen atom.

R4 is a hydrogen atom, alkyl (e.g., methyl, ethyl, hydroxyethyl, etc.), alkenyl (e.g., allyl,
groups such as butenyl), alkynyl (e.g. propargyl,
butynyl, etc.), aryl (e.g., phenyl, naphthyl, etc.), and heterocycle (e.g., 2,2,6.6-titramethylpiperidinyl, N-methylpiperidinyl, pyridyl, etc.). represents.

Specific compound examples are listed below.

Specific compound examples (H-1) CH.

(H-3) (H-4) (H-5) (H-6) L (H-7) C.I.

ShiH3 (H-8) (H-9) rHl (H-10) (H-11) (H-12) (H-13) (H-14) (H-15) (H-16) (H-17) (H-18) (H-19) Shill5 (H-20) (H-21) 1’Jl.

(H-23) CHl (H-24) (H-26) (H-27) rHl (H-28) (H-30) (H-32) (H-33) (H-34) (H- 35) (H-36) (H-37) (H-38) (H-39) (H-40) (H-43) (H-45) (H-46) (H-47) (H- 48) (H-50) (H-51) (H-52) (H-53) ・C,,H,,SO,NH (H-54) (H-55) (H-56) (H- 57) (H-58) (H-59) (H-60) (H-61) (H-62) (H-63) (H-64) (H-65) (H-68) (H- 69) (H-70) 1-cisFh In the present invention, the hydrazine derivative is preferably contained in an amount of IX 10-' mol to 5 A preferred addition amount is in the range of 2 x 10-'' moles.

In the present invention, when a hydrazine derivative is contained in a photographic light-sensitive material, it is used as an aqueous solution if it is water-soluble, or as an alcohol (for example, methanol or ethanol) if it is water-insoluble.
It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as esters (ethyl acetate) or ketones (for example, acetone).

The average grain size of the photosensitive silver halide grains used in the present invention is defined as the diameter in the case of spherical grains, or the projected image converted into a circular image of the same area in the case of grains with a shape other than spherical. The average particle diameter is 0.05 μm to 0.3 μm.

Method for producing silver halide emulsion used in the present invention, sensitization method,
As for binder additives, etc., techniques known in the photographic industry can be used. For example, research on additives
Disclosure Volume 176, No. 17643 (1
December 978) and Volume 187, No.

18716 (November 1979).

Silver halide emulsions used in the present invention (hereinafter referred to as silver halide emulsions) include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, etc. Any conventional silver halide emulsion can be used, but preferably silver chlorobromide containing 60 mol% or more of silver chloride or positive-working silver halide emulsion is used as a negative-working silver halide emulsion. These are silver chlorobromide, silver bromide, and silver iodobromide containing 10 mol% or more of silver bromide as a silver emulsion.

Silver halide grains used in silver halide emulsions contain cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt ( Metal ions can be added using at least one selected from iron salts (complex salts containing) and iron salts (complex salts containing iron salts) to contain these metal elements inside the particles and/or on the particle surfaces. In particular, water-soluble rhodium Preferably, it contains salt. Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

When adding a water-soluble rhodium salt, preferably l x 1
0-'-IX 10-'% Le/AgX1 Mo4ka is better.

As the optical brightener, stilbene-based, triazine-based, pyrazoline-based, coumarin-based, and acetylene-based optical brighteners can be preferably used.

These compounds may be water-soluble, or insoluble ones may be used in the form of a dispersion.

As a matting agent, British Patent No. 1.055.713, US Patent No. 1.939.213, US Patent No. 2,221.8
No. 73, No. 2,268, No. 662, No. 2,332.0
No. 37, No. 2,376.005, No. 2,391.18
No. 1, No. 2,701.245, No. 2,992.101
No. 3゜079.257, No. 3,262.782, No. 3,516.832, No. 3゜539.344,
Organic matting agents described in Japanese Patent No. 3,591.379, Japanese Patent No. 3,754,924, Japanese Patent No. 3.767.448, West German Patent No. 2,592.321, British Patent No. 760.
No. 775, ibid.

No. 260.772, U.S. Patent No. 1,201.905,
2,192.241, 3,053,662, 3,062,649, 3,257.206, 3
, 322.555, 3,353.958, 3,
370°951, 3,411,907, 3,4
37.484, 3,523°022, 3,61
5.554, 3,635,714, 3,769
No. 020, No. 4,021,245, No. 4,029.
Inorganic matting agents such as those described in No. 504 can be preferably used.

The present invention can be applied to various photosensitive materials such as for printing, for X-ray, for general negatives, for general reversals, for general positives, for direct positives, etc., but extremely high quality is required. Particularly remarkable effects can be obtained when applied to photosensitive materials for printing.

Various types of development processing such as black and white, color, and reversal processing using known methods can be used to develop the photosensitive material according to the method of the present invention. It is valid.

In the present invention, dyes used for filter dyes, antihalation, and various other purposes include triallyl dyes, oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful. Furthermore, dyes of the general formulas CVI-a) to (Vl-d) described in Japanese Patent Application No. 153156/1982 can be used in the present invention.

The silver halide photographic light-sensitive material of the present invention can be processed using any ordinary printing developer, but when using a tetrazolium compound or hydrazine compound, the pH
Particularly favorable results can be obtained by processing with a PQ or MQ developer containing a sulfite of 10.0 to 12.9 T O,5-F-rule/0 or more. When a polyalkylene oxide compound is used, preferable results can also be obtained by using a so-called lithium type developer in addition to the above-mentioned PQ and MQ type developers. However, the present invention is not limited to such combinations.

In the present invention, the fixer preferably contains an AQ compound in order to improve the hardness of the photosensitive material, and when the content is 0°1 to 3 g#l in terms of AI2 in the solution used. More preferred.

The preferred concentration of sulfite contained in the fixer is 0.03 to 0.
The amount is 4 mol/Q, more preferably 0.04 to 0.3 mol/a.

The preferred pH of the fixer is 3.9 to 6.5;
The fixer gives favorable photographic performance, and the effect of the packaging material of the present invention becomes significant. The most preferred solution has a pH of 4.
．． It is 2 to 5.3.

In the present invention, the immersion time in a liquid of 10' to 70' refers to development,
This is the time for the fixing, washing, and soaking of the seeds in the solution, and does not include wading.

〔Example〕

EXAMPLES The present invention will be specifically explained below with reference to Examples.

It should be noted that, as a matter of course, the present invention is not limited to the embodiments described below.

Example-1 A sample was prepared as follows.

(Preparation of support) Vinylidene chloride/ethyl acrylate/itaconic acid/
An aqueous dispersion of a copolymer of acrylic acid-86,6/11.1/2.010.3% by weight was coated and dried to a thickness of 1.2 μm, and a polyvinylidene chloride layer was laminated. A film support was prepared, and the water absorption rate was measured using the method described below.

Humidify a 10 cm2 x 100 cm sample to 20 RH% for at least 3 days, weigh it, then soak it in 23°C water for 1 minute, remove the water adhering to the surface, weigh it immediately, and measure the weight before and after soaking in water. The water absorption amount is measured from the difference in weight, and the water absorption amount per 1 crn” of the sample is calculated as the water absorption rate g/(cm2・cm2・
min). The results are shown in Table 1.

Table 1 Sample No., Barrier layer Water absorption rate Xl0-6g
/(cm2・min) Without a-1 2.0 With a-2 1.6 a-31,3 a-41,0 (Preparation of photosensitive material) Western silver halide photosensitive material as a bright room photosensitive material The materials were prepared as follows.

A silver nitrate aqueous solution, sodium chloride, and a potassium bromide aqueous solution were simultaneously mixed into an aqueous gelatin solution while stirring to prepare silver halide particles, and desalted by a conventional method. After chemically sensitizing this emulsion in a conventional manner, 1.3 g of the following tetrazolium compound was added per mole of silver to form the support a-1.
, a-2, a-3, and a-4 together with a commonly used protective film. The amount of gelatin at this time was as shown in Table 2, and the amount of coated silver was 3.0 g/m2. In addition, a layer containing a known dye is applied as a packing layer on the opposite side of the support.
I.

The dimensional stability of the obtained sample of the tetrazolium compound was evaluated by the following method.
child .

(Evaluation of dimensional stability) The obtained sample was cut into a size of 30 cm x 60 cm and was printed using a light room printer P-627FM (manufactured by Dainippon Screen Equipment).
Two thin lines were imagewise exposed at a spacing of 56 cm using a microprocessor, and the resulting image was developed and used as a manuscript.

This manuscript, an unexposed sample (same size as the manuscript), a printer, and an automatic processor were conditioned for 2 hours at 23°C and 520% RH, then stacked on top of the original manuscript and observed using a graduated magnifying glass to see how much the spacing between the thin lines had shifted. It was measured with

Measurements were performed with n=6 and the average was taken. The results are shown in Table 3. The development processing conditions and composition are as follows.

Developer recipe (composition A) Pure water (ion-exchanged water) 150 m4 Ethylenediaminetetraacetic acid disodium salt g Diethylene glycol 50 g Potassium sulfite (55% v/v aqueous solution) 100 mQ Potassium carbonate 50 g Hydroquinone
15g 5-methylbenzotriazole 200mg 1-phenyl-5-mercaptotetrazole 30+ng Potassium hydroxide Amount to bring the pH of the working solution to 1O06 Potassium bromide 4.5g (composition) Pure water (ion-exchanged water) 3m12 Diethylene glycol 50g Ethylenediaminetetraacetic acid 2 Sodium salt 5mg Acetic acid (90% aqueous solution) 0.3mQ2
-Mercapto-benzimidazole-5-sodium sulfonate 50+g1-Phenyl-3-pyrazolidone 500+When using the ag developer, the above compositions were dissolved in the order of the composition A1 in 500 mff of water and used after finishing to lβ.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 30
mff Sodium sulfite 9.5g Sodium acetate trihydrate 15.9g Boric acid
6.7g sodium citrate・
Dihydrate 2g acetic acid (90% w/w aqueous solution)
8.1mQ (composition) Pure water (ion exchange water) 17mQ Sulfuric acid (50% w/w aqueous solution) 5-8g
Aluminum sulfate (A (aqueous solution with 220x equivalent content of 8.1% w/w) 2
6.5 g When using a fixer, the above composition A1 was dissolved in 500 mff of water in the order of composition, and finished to 1a. The pH of this fixer was about 4.6.

(Rapid development processing conditions) (Process) (Temperature) (Time) (Immersion time in solution) Water
Washing 18°0 18 seconds 18 seconds Drying 45°C 14 seconds Total 66 seconds Each process time includes the so-called wading conveyance time to the next step, and the immersion time in the liquid does not include the wading conveyance time.

Further, samples No. 4 and No. 9 were treated by changing the immersion time in the liquid as shown below.

Processing Time of immersion in solution (seconds) A 10 B 30 C50 D 66 E 80 F 120 The time ratios for development, fixing, and washing were all 13:11:9.

Table 3 Generally, the accuracy error of photographic materials for color printing is ±20
It is required that the change be within about μl, and a dimensional change of +21 μm or more shown in Table 3 is not preferable.

Therefore, in the case of the present invention, the dimensional change is in the range of 13 to 20 μm, and extremely effective performance is obtained.

Example 2 A hydrazine compound (HD) was used as a contrast enhancer instead of the tetrazolium compound T used in Example 1, and 80 mg/g of the following compound (a) was added to the silver halide emulsion layer.
m” was added.

As a result, the same results as in Example 1 could be obtained.

Incidentally, a developer having the composition C shown below was used, and the developing conditions were shown below.

Compound (HD) I'1. L; tl.

Compound (a) H Developer composition (C) Ethylenediaminetetraacetic acid sodium salt g Sodium sulfite 60 g Trisodium phosphate (12 hydrate) 75 g Hydroquinone
22.5g sodium hydroxide
8g sodium bromide
3g5-methylbenzotriazole 0.
25g 1-phenyl-5-mercaptotetrazole 0.
08g metol 0.25g phenitylbicolinium bromide 2.5g Add water 11pH 10.5 (Development processing conditions) Total 40 seconds Example 3 Example 1 table except that the emulsion layer contains polymer latex as shown in Table 5. A l=sample was prepared in the same manner as Sample No. 2 and 14.

The dimensional changes before and after the treatment were measured in the same manner as in Example 1 and are shown in Table 4.

Table 4 As a result of the present invention, extremely stable finished dimensional performance was obtained, with dimensional changes before and after treatment being within 10 g.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic material having excellent dimensional stability with little dimensional variation before and after processing such as development.

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one layer of a silver halide photographic light-sensitive material on one side of a support and a packing layer on the other side, the side having the silver halide emulsion layer Gelatin amount is 0.5-2.5g/
m^2, and the total amount of gelatin in the silver halide photographic light-sensitive material is in the range of 1.0 to 5.0 g/m^2, and the water absorption rate of the support is 1.5 x 10^. -＾6g/
(cm^2・min) or less (when the support thickness is 100 μm). Image formation is characterized by processing a silver halide photographic material provided with a barrier layer in a liquid for a time of 10 to 70 seconds. Method. (2) The silver halide emulsion layer according to claim 1 is 0.3 g/
An image forming method comprising a polymer latex having m^2 or more.