JP2673474C - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION       [0001]     [Industrial applications]   The present invention relates to a silver halide photographic light-sensitive material, and in particular, has excellent drying property during processing and
Improves the appearance of roller marks when processing with a dynamic developing machine, and significantly improves sensitivity
Technology, especially for photographic materials with ultra-rapid processing aptitude.
Related.       [0002]     [Prior art]   In recent years, the rapid development of high-speed rapid processing in the development process of photographic light-sensitive materials (hereinafter
With the widespread use, the processing time has been greatly reduced in the automatic developing machine processing of various photosensitive materials.
Have been. In order for rapid processing to be achieved, it is necessary to achieve sufficient sensitivity in a short time.
Sensitive material that gives a sufficient degree of blackening in a short time with excellent developer and development progress, and washing with water The property of drying in a short time afterwards is required. In general, to improve the drying properties of photosensitive materials
A common method is to use a sufficient amount of a hardener (gelatin
Cross-linking agent) to form emulsion layers and hydrophilic colloid layers in the development-fixing-washing process.
There is a method to reduce the water content in the photosensitive material before the start of drying by reducing the amount of swelling
. This method can shorten the drying time by using a large amount of hardener,
As the amount of moisture decreases, the development is delayed, resulting in lower sensitivity and softening,
Power will be reduced. Also, even if the development progress can be improved
Delay in fixing speed due to high hardening film causes problems such as residual silver, residual hypo and residual color of sensitizing dye.
And caused an obstacle to shorten the processing time.       [0003]   On the other hand, a method for increasing the developing activity of a processing solution is also known, and a main agent and an auxiliary agent in the developing solution are known.
Increasing the amount of developing agent, increasing the pH of the developer, increasing the processing temperature,
it can. However, all of these methods impair the preservation of the processing solution,
Even if it was raised, there was a drawback that it was soft and easy to suffer.       [0004]   For the purpose of improving the viewpoints described above, a technology utilizing tabular grains has been developed in the United States.
Patents 4,439,520, 4,425,425, etc. Also
JP-A-63-305343 and JP-A-1-77047 disclose a (111) face.
Control the development start point of silver halide particles at and near the top and / or ridge of the grains.
Thus, a technique for improving the development progress and the sensitivity / fogging ratio has been disclosed. Sa
Further, JP-A-58-111933 discloses that swelling of a hydrophilic colloid layer is performed using tabular particles.
200% or less, high covering power, and additional hardening during processing
Radiographic photographic elements are disclosed that do not need to be cleaned. These known
Technology is an excellent technology for improving the development progress of photosensitive materials, and its value
Is high. However, the processing time for each of the development, fixing, and washing steps has been reduced.
In addition to the decrease in photographic sensitivity, residual silver and residual hypo
Come. In addition, there is also the problem of residual color in sensitized materials that have been spectrally sensitized with sensitizing dyes.
Surface. These non-photographic problems are due to the improvement by modifying silver halide grains.
Are limited and ultimately result in film quality issues. Ie hydrophilic colloid The thickness of the printed layer limits fixing and residual color, which is an obstacle to speeding up.
.       [0005]   Regarding this point, JP-A-64-73333, JP-A-64-86133,
JP-A-1-105244, JP-A-1-158435, JP-A-1-158436, etc.
Means that the amount of gelatin on the side having the hydrophilic colloid layer including the silver halide emulsion layer is 2.0
0 to 3.50 g / m^TwoPrepared in the range of and combined with other technical elements to complete processing
Means for achieving ultra-rapid processing with a time between 20 seconds and less than 60 seconds is disclosed. Ma
JP-A-2-68537 discloses that silver and zeolite of photosensitive silver halide coated on an emulsion layer are used.
Ultra-rapid processing is achieved by adjusting the weight ratio of silver (silver / gelatin) to 1.5 or more
Means are disclosed. Further, JP-A-63-221341 discloses an emulsion layer.
The silver halide grains contained therein are mainly tabular grains having a grain size of 5 times or more the grain thickness.
And the amount of gelatin is 2.00 to 3.20 g / m^Two8 minutes melting time
The super-rapid processing in which the total processing time is 20 seconds or more and less than 60 seconds by setting the time to
Means of achieving are disclosed.       [0006]   However, when examining these prior arts, it was found that the amount of gelatin was
Increasing the gelatin ratio while keeping the amount of coated silver constant will result in blackening of the scratches and roller marks.
Work has become severely deteriorated until it becomes practically unacceptable.
That makes it impossible to complete as a product that can be processed very quickly
There was found.       [0007]   Abrasion blackening means that when handling the film,
Alternatively, if the film is rubbed with another substance, abrasion-like blackening may occur after development.
It refers to a cheating phenomenon. Roller marks are used to transfer photosensitive materials when they are processed by an automatic processor.
Pressure is applied to the photosensitive material due to fine irregularities on the surface of the feed roller, resulting in black spot density
A phenomenon that causes unevenness. Total processing time was set to 60 seconds or less, especially 40 seconds or less
If the appropriate time distribution for the development, fixing, and washing steps is performed, the amount of gelatin
Is 2.5 g / m^TwoOtherwise, if the installation environment of the automatic processor is high humidity In some cases, drying properties were affected. On the other hand, such a reduction in the amount of gelatin applied is
, Roller marks and scratches are not acceptable.       [0008]   Thus, by simply adjusting the amount of gelatin applied, drying, pressure, fixing (
Or residual color) could not be satisfied.       [0009]   In a photographic material, a polymer having -COOH or a salt structure thereof is used.
Is well known to be used with gelatin, a hydrophilic colloid.
I have.   For example, Japanese Patent Publication Nos. 57-53587 and 57-15375, West German Patent 1,7
45,061, JP-B-49-23827, JP-B-55-14415, JP-B-55-
15267, JP-A-48-89979, U.S. Pat.
No. 3,791,831 and JP-B-47-28937 have a carboxyl group.
Attempts have been made to utilize polymers for preventing static electricity in photographic materials.       [0010] However, this type of anionic polymer antistatic agent causes the hydrophilic colloid layer
There is no mention of controlling the swelling rate of the photosensitive material and increasing the drying speed of the photosensitive material. Ma
Generally, anionic antistatic agents are present in large amounts in certain hydrophilic colloids.
And a large amount of gelatin hardener is often used to improve film physical properties.
In addition, if the swelling property after the treatment is controlled as in the present invention, it is used to reduce the drying load.
In this case, as described in JP-A-58-111933, residual silver and residual
A problem such as a hypo occurs.       [0011]   Further, European Patent Nos. 75231 and 167081, JP-A-53-7231,
60-126644, 60-15656, JP-A-2-20861,
Japanese Patent Publication No. 1-14574 and US Pat. No. 4,142,894 include carboxyl groups.
Polymer matting agents are disclosed. However, the matting agent is originally 0.2
The particles of about 10 μm are exposed on the surface of the photosensitive material, and the irregularities on the surface
Such a coarse particle has a function after the treatment, as in the present invention. The ability to control swelling is not sufficient.       [0012]   Further, Japanese Patent Application No. 27895/1990 discloses a polymer mordant having an ammonium structure.
Photosensitive material containing an antihalation layer containing
The introduction of a luic acid derivative can improve the decolorization of anionic dyes.
It has been disclosed.   However, in this patent, control of swelling after treatment with a polymer containing -COOH is disclosed.
Is not described, and the acrylic acid homopolymer described in the embodiment is substantially hardened.
There is no drying property improvement effect based on the swelling control effect after treatment in the treatment without agent
This has been clarified by the study of the present inventors.       [0013]     [Problems to be solved by the invention]   An object of the present invention is to firstly exhibit a superior drying property during processing, particularly in rapid processing.
An object of the present invention is to provide a silver halide photographic material.   The object of the present invention is, secondly, excellent drying properties, and the occurrence of blackening of roller marks and scratches.
To provide a silver halide photographic light-sensitive material at a sufficiently practical level
.   Thirdly, the object of the present invention is to satisfy the above-mentioned object and to provide a high sensitivity and high coverability.
Silver halide photographic light-sensitive material with excellent power and rapid processing suitability
Is to do.       [0014]     [Means for Solving the Problems]   The object of the present invention has been achieved by the following means.   That is,[I]Halogen having at least one silver halide emulsion layer on a support
In silver halide photographic materials, at least one of the silver halide emulsion layers
At least one kind of carboxyl group-containing polymer (carboxyl group-containing monomer unit
15 mol% or more, or acid value of 1.5 meq / g or more, except for polyacrylic acid
C) containing a hydrophilic colloid layer,The carboxyl group-containing polymer and Zera
The ratio of the coating amount per side of the tin (polymer content ratio) is expressed by the following equation, and the value of the equation Is 0.03-0.3, Halogenation in at least one silver halide emulsion
Silver is tabular grains having an aspect ratio of 3.0 or more;The polymer relative to the support
At least one hydrophilic colloid layer on the content side is coated with a vinyl sulfone-type hardener.
ContainsAnd all hydrophilic colloid layers on the side of the polymer-containing layer with respect to the support
Having a swelling ratio of not more than 250% in distilled water
Silver photographic photosensitive material. (Here, the swelling ratio in distilled water is as follows.
(Percent relative humidity) for 16 hours in distilled water at 21 ° C.
The change in thickness when immersed for 3 minutes is assumed to be measured. )       [0015]       [0016]     (Equation 2)       [0017]   Particularly preferred embodiments of the present invention are the following [II] to [IX]. [II] Inclusion of vinyl sulfone type hardener The amount is 4-16 for 100 g of gelatin.
characterized in that it is mmol[I]Silver halide photographic material.(III) Characterized by containing dextran and / or acrylamide
the above(II)Silver halide photographic material.(IV)   The above, characterized by containing a dye dispersed in a microcrystalline state(II)of
Silver halide photographic material.[V]   In the development process, from the start of processing to the end of processing (Dry to Dry processing
The above-mentioned (interval) is within 60 seconds.(II), (III) and (IV)No ha
Silver halide photographic material.[VI]   Using a developing solution and a fixing solution substantially free of a hardener, a developing process for 8 seconds
When developing in 7 seconds for the immersion step and 7 seconds for the rinsing step, the swelling ratio of distilled water is
Wherein the ratio of the swelling ratio at the time of completion of the step is 1.0 or less,
Silver gemide photographic material. (VII)   Using a developing solution and a fixing solution substantially free of a hardener, a developing process for 8 seconds,
When the developing process is performed in a fixing process of 7 seconds and a washing process of 7 seconds, the swelling ratio at the completion of the developing process is reduced.
On the other hand, the ratio of the swelling ratio at the completion of the washing step is not more than 1.0.
I] The silver halide photographic light-sensitive material.(VIII)   When the carboxyl group-containing polymer is polymethacrylic acid or methacrylic acid
The above [I] to being characterized by being a polymer(VII)Silver halide photographic materials
Fees.[IX] Above [II] Method for developing silver halide photographic materials
Silver halide characterized by processing in an automatic processor having a zone for drying
Development method of photographic photosensitive material.       [0018]   Hereinafter, the present invention will be described in detail.   The carboxyl group-containing polymer used in the present invention is a carboxyl group-containing monomer.
-Means 15 mol% or more or an acid value of 1.5 meq / g or more.
You.   The carboxyl group-containing polymer used in the present invention includes a carboxyl group-containing polymer.
Homopolymers, copolymers or natural polymer derivatives of saturated ethylenic monomers are preferred.
Good.   Examples of carboxyl group-containing unsaturated ethylenic monomers include, for example,
Things.   Acrylic acid, methacrylic acid, maleic acid, monoalkyl maleate (for example,
, Monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.
), Itaconic acid, monoalkyl itaconate (eg, monoethyl itaconate,
Fumaric acid, monoalkyl fumarate, crotonic acid, vinylbenzoic acid, male
Monoacids of formic acid, monoamides of itaconic acid and the like.   Among these, the acid is an alkali metal, preferably Na, K or ammonium ion.
Even if it is salt, it can be used.       [0019]   Among these monomers, polymer solubility, transparency, lipophilicity, hydrophilicity, protection Acrylic acid, methacrylic acid, maleic acid, etc.
Inic acid is preferred. Above all, photographic performance (sensitivity, residual color, roller mark) drying
Methacrylic acid is particularly preferred in this respect. In addition, two of these monomers
The above may be introduced into the polymer.       [0020]   As a monomer copolymerizable with a carboxyl-containing unsaturated ethylenic monomer
Is not particularly limited, for example, acrylates, methacrylates
, Acrylamides, methacrylamides, vinyl esters, vinyl ketones
, Allyl compounds, olefins, vinyl ethers, N-vinylamides, vinyl
Heterocyclic compounds, maleic esters, itaconic esters, fumaric acid ester
There are ters and crotonic esters. More specifically, for example,
There are the following.       [0021]   Methyl acrylate, ethyl acrylate, n-propyl acrylate, iso
Propyl acrylate, n-butyl acrylate, isobutyl acrylate, se
c-butyl acrylate, amyl acrylate, hexyl acrylate, octyl
Acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate,
Dimethylaminoethyl acrylate, 2-hydroxyethyl acrylate, 3-
Hydroxypropyl acrylate, diethylene glycol monoacrylate,
Ethylene glycol monoacrylate, glycerol monoacrylate, tri
Methylolethane 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-methoxyethyl acrylate
Rate, 2-hydroxy-3-chloropropyl acrylate, t-butyl acrylate
, Isopropyl acrylate, phenyl acrylate, p-chlorophenyi
Ruacrylate, methyl methacrylate, ethyl methacrylate, i-propyl
Methacrylate, t-butyl methacrylate, amyl methacrylate, N, N,
Diethylaminopropyl methacrylate, 2-hydroxyethyl methacrylate , Diethylene glycol monomethacrylate, triethylene glycol monometh
Acrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate
rate,       [0022] Acrylamide, methacrylamide, N-methylacrylamide, N-ethyla
Crylamido, N-n-propylacrylamide, N-iso-propylacryl
Amide, Nn-butylacrylamide, N-tert-butylacrylamide, N
, N-dimethylacrylamide, N, N-diethylacrylamide, hexylurea
Acrylamide, octylacrylamide, methyl vinyl ether, ethyl vinyl
Ether, propyl vinyl ether, butyl vinyl ether, allyloxy eta
Knol, allyl butyl ether, 2-ethyl butyl vinyl ether, hydroxy
Ethyl vinyl ether, vinyl acetate, vinyl propionate, N-vinyl
Oxazolidone, vinylpyridine, N-vinylimidazole, N-vinyl-2-
Methyl imidazole, N-vinyl triazole, N-vinyl-3,5-dimethyl
Triazole, N-vinylpyrrolidone, N-methyl-N-vinylpropionamide
, N-vinylpyrrolidone, N-vinyl-2-pyridone, ethylene, propylene,
1-butene, 1-heptene, 1-octene, dioctyl itaconate, itaconic acid
Dibutyl, dihexyl maleate, dibutyl maleate,       [0023] Styrene, methyl styrene, dimethyl styrene, benzyl styrene, chloromethy
Styrene, chlorostyrene, vinyl methyl benzoate, vinyl chlorobenzoate
, Acrylonitrile, methacrylonitrile, vinyl chloride, etc.   Among them, acrylic esters, methacrylic esters, acrylic
Amides and styrenes are preferred.       [0024]   The synthesis of these carboxyl group-containing polymers involves the use of British Patent 1,211,0.
39, UK Patent No. 961,395, US Patent No. 3,227,672,
No. 3,290,417, No. 3,262,919, No. 3,245,932
No. 2,681,897, No. 3,230,275, John C. Pete "Official, Digest," by Lopulos et al. (John C. Petropoulos etal: Of
ficial Digest) 33, 719-736 (1961), edited by Shunsuke Murahashi et al.
246-290, 31-108, etc.
It is convenient.       [0025]   Examples of natural polymer derivatives include, for example, gelatin derivatives (maleylated gelatin).
, Succinylated gelatin, etc.), and graft polymers of gelatin and other
Protein derivatives such as acrylic acid-grafted gelatin), cellulose derivatives
(Such as carboxymethylcellulose), dextran derivatives and starch derivatives
Sugar derivatives and the like can be mentioned.   Among these, gelatin derivatives are particularly preferred.       [0026]   Here are specific examples of the carboxyl group-containing polymer used in the present invention,
It is not limited to these. (The 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 (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 (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 copolymer (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         Coalescing (40/60) P-31 Methacrylic acid / acrylamide copolymer (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 / acrylonitrile 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-bunyl 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                                                             (40/40/20) P-44 Methacrylic acid / methyl methacrylate / styrene copolymer (40/40/20) P-45 methacrylic acid / methyl acrylate / 2-hydroxy acrylate / ac         Lilonitrile 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 maleated gelatin P-52 succinylated gelatin P-53 carboxymethylcellulose       [0027]   In a preferred embodiment of the present invention, a carboxyl group-containing compound added to a hydrophilic colloid is used.
The molecular weight of the polymer is preferably 5 × 10^ThreeAbove, particularly preferably 1 × 10^FourAbsent
5 × 10⁶(Both are weight average molecular weights).   The amount of the carboxyl group-containing polymer to be added depends on the type of the photosensitive material, etc.
0.01 g / m^Two~ 2g / m^TwoIs preferable, and more preferably 0.05
g / m^Two~ 1g / m^TwoIt is. More preferably 0.1 g / m^Two~ 0.5g / m^TwoIs
.       [0028]   In the case of a silver halide photographic material having two or more hydrophilic colloid layers, -C The acid polymer having OOM groups may be contained in all the hydrophilic colloid layers,
If it is contained in at least one layer, it may not be contained in other layers. In addition, two or more hydrophilic cores
The acid polymer of each layer when the carboxyl group-containing polymer of the present invention is coated on the loyd layer
The amount can be varied at will.       [0029]   The neutralization ratio of the polymer having a -COOM group preferably used in the present invention is
, Type and amount of hydrophobic monomer, or structure of a repeating unit having a -COOM group
, All -COOM groups have a salt structure by neutralization.
Or all of the -COOM groups may have a -COOH structure. Basically
The range in which the polymer becomes water-soluble when used as an aqueous solution mixed with a hydrophilic colloid is a standard.
What is necessary is just to set the neutralization rate as follows.       [0030]   When the carboxyl group-containing polymer of the present invention is used, it is dissolved in water and
Is preferably introduced into the photographic material by the addition of When dissolving,
More preferably, alkalis and salts are used. Water-miscible organic solvents (eg,
, Acetone, methanol, ethanol, acetonitrile, dimethyl sulfoxide
, Dimethylacetamide, etc.).   Form hydrophilic colloid layer containing carboxyl group-containing polymer of the present invention
Gelatin is preferably used as the hydrophilic layer colloid.   Examples of gelatin include lime-treated gelatin, acid-treated gelatin and enzyme-treated gelatin.
It is also possible to use hydrolysates or enzymatic degradation products of gelatin.
Wear.       [0031]   Further, hydrophilic colloids other than gelatin can also be preferably used.   For example, natural polymers such as glucose, dextran and cellulose, vinyl alcohol
Alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone
, Polyacrylic acid, polyacrylamide, polyvinylimidazole, polyvinyl
Using various kinds of synthetic hydrophilic high molecular substances such as single or copolymer such as pyrazole
Can be   Among these, together with gelatin, dextran and polya having an average molecular weight of 50,000 or less are used.
Use of acrylamide in combination is particularly preferred in terms of sensitivity and covering power.
New The methods described in JP-A-63-68837 and JP-A-63-149641 are disclosed in the present invention.
It is effective even if it is clear.       [0032]   After mixing the carboxyl group-containing polymer of the present invention and a hydrophilic binder, coating is performed.
In such a case, the pH of the coating liquid is 6.0 to 9 in the coating liquid for forming the non-photosensitive layer.
0 is preferred. More preferably, 6.5 to 8.0, even more preferably 7.0 to 7
. 5 In a coating solution for forming a silver halide emulsion layer, 5.0 to 8.0 is preferable.
New More preferably, 5.5 to 7.0, still more preferably 5.8 to 6.5.
You.       [0033]   Carboxyl group-containing polymer used in the photographic material of the present invention and a hydrophilic resin
The ratio of the loyd (polymer content ratio) should be 0.03 to 0.3 in the above equation.
Is preferred. More preferably, it is 0.05 to 0.2. More preferably, 0
. 10 to 0.15.       [0034]   The swelling ratio at the completion of the developing step, the swelling ratio at the completion of the washing step, and the swelling of distilled water in the present invention.
The moisture percentage is represented by the following equation.       [0035]     (Equation 3)       [0036]   Here, the thickness of the layer at the completion of the development step is determined by immersing the photographic material in a developer at 35 ° C. for 8 seconds.
It means the thickness of the layer when immersed. The layer thickness at the completion of the washing process
Developing step 35 ° C, 8 seconds, fixing step 35 ° C, 8 seconds, washing step 20 ° C, 7 seconds
The thickness of the last layer in the washing step when processing continuously in the order of development → fixing → washing under the conditions
means. The thickness of the layer when immersed in distilled water means that the photographic material is immersed in distilled water at 21 ° C. for 3 minutes.
It means the thickness of the layer when immersed. The photographic material used here is 40 ° C.
, 60% RH for 16 hours.       [0037]   When measuring the thickness of the layer under each condition when determining the swelling ratio of each step in the present invention
Is measured by the method described in Example 12 of U.S. Pat.
The fixed part is made of ceramic).       [0038]   In the present invention, a developer and a fixer substantially containing no hardener are referred to as hardeners in the art.
Means a developer and a fixer substantially free of a compound called an agent.
Specifically, RD-10 manufactured by Fuji Photo Film Co., Ltd. was used as a developer.
An example is RF-10 manufactured by Fuji Photo Film Co., Ltd.       [0039]   According to the present invention, the swelling ratio at the time of completion of the washing step relative to the swelling ratio at the time of completion of the development
The ratio can be less than 1.0. In particular, dissolve carboxyl group-containing polymers in water.
Thus, by adding the hydrophilic colloid layer, the ratio can be reduced to 1.0 or less.
preferable. This means that photographic materials with excellent drying properties do not interfere with the development process.
It means there is.   According to the present invention, the ratio of the swelling ratio at the completion of the washing step to the swelling ratio of distilled water is 1
. It can be 0 or less.   This is a photographic material with excellent drying properties without interrupting the development process.
Means that.   In the photographic material of the present invention, the swelling ratio in distilled water depends on the photographic performance and drying performance.
It is necessary to be less than 250% to satisfy both performances. The swelling ratio is It can be set by changing the amount of the hardener used.       [0040]   The photographic light-sensitive material of the present invention is suitable for rapid processing. Especially during Dry to Dry processing
Preferably, it is within 60 seconds. More preferably within 45 seconds, even more preferably
Is within 38 seconds.       [0041]   In the light-sensitive material of the present invention, the light-sensitive silver halide emulsion layer is provided on one side of the support.
And at least one layer on each side of the support.
Layers may be provided.   If necessary, the light-sensitive material of the present invention may be hydrophilic in addition to the light-sensitive silver halide emulsion layer.
It can have a colloid layer, for example, preferably provided with a protective layer.       [0042]   Zera preferably used as a hydrophilic binder in the photographic material of the present invention.
The amount of chin applied is not particularly limited, but is 1.5 g / m^Two~ 4.5g
/ M^TwoIs preferred. In addition, 1.8 g / m^Two~ 3.6 g / m^TwoIs particularly preferred.       [0043]   Next, emulsion grains preferably used in the present invention will be described.   The silver halide grains in the emulsion must be tabular grains having an aspect ratio of 3 or more.
. Preferably it is 5 or more. Particularly preferably, it is 7 or more.   As a method for producing tabular silver halide grains, methods known in the art may be appropriately combined.
Can be achieved.   Tabular silver halide emulsions are described in JP-A-58-127,921 and JP-A-58-11.
3,927, JP-A-58-113,928, etc.
Can be prepared.   The aspect ratio of tabular silver halide grains can be controlled by adjusting the temperature and selecting the type and amount of solvent.
, Control the addition rate of silver salt and halide used during grain growth
Can be adjusted.   In the silver halide emulsion of the present invention, tabular grains account for at least 50% (in terms of projected area).
Is preferably 80% or more.   The average equivalent spherical particle size of the same volume as the particles is preferably 0.4 μm or more.
No. In particular, it is preferably from 0.5 to 2.0 μm. Narrower particle size distribution
Good.       [0044]   Silver iodobromide is preferred as the silver halide composition because of its high sensitivity.   The silver halide grains of the present invention contain a trace amount of silver chloride that does not affect photographic properties.
It may be contained, but desirably not contained.   As the emulsion of the present invention, both a monodisperse emulsion and a polydisperse emulsion are preferably used.
Can be   The silver halide emulsion used in the present invention is a core-shell type monodisperse emulsion.
These core-shell emulsions are known from JP-A-54-48521.
is there.   As the shape of the silver halide grains in the emulsion, tabular grains are preferred, but cubic,
Octahedral, regular, crystalline, spherical, potato-like
Any irregular crystal form can be used at the same time.
Absent.       [0045]   In order to make effective use of the effects of the present invention, it is necessary to use an emulsion tone as disclosed in JP-A-2-68539.
During chemical sensitization during the production process, the amount of
Contains silver halide-adsorbing substances equivalent to dyes or photographic performance stabilizers
Preferably.   That is, azoles such as benzothiazolium salts, benzimidazonium salts,
Imidazoles, benzimidazoles, nitroindazoles, triazoles
, Benzotriazoles, tetrazoles, triazines, etc.｝; mercapto
Compounds such as mercaptothiazoles, mercaptobenzothiazoles,
Lucatoimidazoles, mercaptobenzimidazoles, mercaptobenzo
Oxazoles, mercaptothiadiazoles, mercaptooxadiazoles
, Mercaptotetrazole, mercaptotriazoles, mercaptopyrimidi
, Mercaptotriazines, etc .; thiols such as oxadrinethione Keto compounds; azaindenes {eg triazaindenes, tetraazaindene
(Especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes),
Known as antifoggants or stabilizers
Many compounds can be mentioned as silver halide adsorbing substances.   Further, purines or nucleic acids, or JP-B-61-36213,
No. 59-90844, and the like.
is there.   Among them, azaindenes, purines, and nucleic acids are particularly preferred in the present invention and used.
be able to. The addition amount of these compounds is 300 to 3 per mole of silver halide.
000 mg, preferably 500 to 2500 mg.   As the silver halide-adsorbing substance of the present invention, the sensitizing dye realizes a preferable effect.
sell.   As sensitizing dyes, cyanine dyes, merocyanine dyes, complex cyanines
Dye, complex merocyanine dye, holo-holer cyanine dye, styryl
Use dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc.
be able to.       [0046]   Useful sensitizing dyes for use in the present invention include, for example, U.S. Pat. No. 3,522,052,
3,619,197, 3,713,828, 3,615,643,
3,615,632, 3,617,293, 3,628,964,
3,703,377, 3,666,480, 3,667,960,
3,679,428, 3,672,897, 3,769,026,
3,556,800, 3,615,613, 3,615,638,
3,615,635, 3,705,809, 3,632,349
3,677,765, 3,770,449, 3,770,440,
No. 3,769,025, No. 3,745,014, No. 3,713,828,
3,567,458, 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525, Belgian Patent No. 691,
807, etc. The amount of the sensitizing dye added is per mole of silver halide. The dose is 300 mg or more and less than 2000 mg, preferably 500 mg or more and less than 1000 mg.   Specific examples of the sensitizing dye effective in the present invention are shown below.       [0047]     Embedded image      [0048]     Embedded image       [0049]   Of these, cyanine dyes are particularly preferred.   It is a preferred embodiment to use a sensitizing dye in combination with the above-mentioned stabilizer.   The sensitizing dye used in the present invention may be added after chemical sensitization and before coating.       [0050]   Monodisperse hexagonal tabular grains are particularly useful among tabular silver halide grains.
is there.   Details of the structure and production method of the monodisperse hexagonal tabular grains referred to in the invention are described in JP-A-63-1.
According to the description of 51618.   The method of chemical sensitization of the silver halide emulsion used in the present invention includes the halogenation described above.
Sulfur sensitization, selenium sensitization, reduction sensitization, gold sensitization in the presence of silver halide adsorbent
Known methods such as can be used, and used alone or in combination.
Regarding the production method of the tabular silver halide grains of the present invention and the chemical sensitization method thereof, see
JP-A-2-68539, page 8, lower right column to page 10, upper right column, Japanese Patent Application No. 3-1.
05035, 3-183863, 3-213063 and 3-235
737 can be preferably used.   The photographic emulsion used in the present invention includes a photographic material during the manufacturing process, during storage or during photographic processing.
The purpose of the present invention is to prevent fogging during processing or to stabilize photographic performance.
Including various compounds in addition to the silver halide-adsorbing substance in the chemical sensitization process
Can be.       [0051]   Azoles, such as benzothiazolium salts, nitroimidazoles,
Nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimid
Dazoles, nitroindazoles, benzotriazoles, aminotriazole
Mercapto compounds {eg, mercaptothiazoles, mercapto
Benzothiazoles, mercaptobenzimidazoles, mercaptothiadiazo
, Mercaptotetrazole, mercaptopyrimidines, mercaptotri
Azines and the like｝; thioketo compounds such as oxadrinethione;
Denes {eg, triazaindenes, tetraazaindenes (especially 4-hydroxy Substituted (1,3,3a, 7) tetraazaindenes and pentaazaindenes
); Benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonate
Add many compounds known as antifoggants or stabilizers such as
be able to.       [0052]   In particular, the nitrones described in JP-A-60-76743 and JP-A-60-87322.
And derivatives thereof, mercapto compounds described in JP-A-60-80839,
A heterocyclic compound described in JP-A-57-164735, and a heterocyclic compound;
Silver complex salts (eg, 1-phenyl-5-mercaptotetrazole silver) and the like are preferred.
Can be used. Sensitizing dye as silver halide adsorbing substance in chemical sensitization process
Even when is used, a spectral sensitizing dye in another wavelength region may be added as necessary.   In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention,
Is a coating aid, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention and photographic property improvement (
For various purposes such as acceleration of development, hardener, sensitization, etc., various surfactants are contained.
Is also good.       [0053]   For example, saponins (steroids), alkylene oxide derivatives (for example, poly
Ethylene glycol, polyethylene glycol / polypropylene glycol condensation
Substances, polyethylene glycol alkyl ethers or polyethylene glycol
Alkylaryl ethers, polyethylene oxide adducts of silicone),
Nonionic surfactants such as alkyl esters of sugars;   Alkyl sulfonate, alkyl benzene sulfonate, alkyl naphtha
Lensulfonate, alkyl sulfates,   N-acyl-N-alkyltaurines, sulfosuccinates, sulfoas
Anionic surfactants such as alkylpolyoxyethylene alkyl phenyl ethers
Sexual agent;   Amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines;   Aliphatic or aromatic quaternary ammonium salts, pyridinium salts, imidazo
Cationic surfactants such as lithium salts can be used.       [0054]   Among them, saponin, sodium salt of dodecylbenzenesulfonic acid, di-2-ethylhexene
Sil α-sulfosuccinic acid Na salt, p-octylphenoxyethoxy ethane sulfo
Sodium salt, sodium dodecyl sulfate, sodium triisopropylnaphthalenesulfonate
Salts, anions such as N-methyl-oleoyltaurine Na salt, dodecyltrimethy
Ammonium chloride, N-oleoyl-N ', N', N'-trimethyla
Such as ammonium diaminopropane bromide and dodecyl pyridium chloride
Thione, N-dodecyl-N, N-dimethylcarboxybetaine, N-oleyl-
Betaine such as N, N-dimethylsulfobutylbetaine, poly (average degree of polymerization n =
10) Oxyethylene cetyl ether, poly (n = 25) oxyethylene p-no
Nylphenol ether, bis (1-poly (n = 15) oxyethylene-oxy
Nonionics such as -2,4-di-t-pentylphenyl) ethane are particularly preferably used.
Can be.       [0055]   As antistatic agents, perfluorooctanesulfonic acid K salt, N-propyl-N
-Perfluorooctanesulfonylglycine Na salt, N-propyl-N-perf
Fluorooctanesulfonylaminoethyloxy poly (n = 3) oxyethylene
Tansulfonic acid Na salt, N-perfluorooctanesulfonyl-N ', N', N
'-Totamethylammoniodiaminopropane chloride, N-perfluorodeca
Noylaminopropyl-N ', N'-dimethyl-N'-carboxybetaine
Fluorinated surfactants, JP-A-60-80848, JP-A-61-112144,
Nonionic interfaces described in JP-A-62-172343 and JP-A-62-173449.
Activator, alkali metal nitrate, conductive tin oxide, zinc oxide, vanadium pentoxide
Alternatively, composite oxides doped with antimony or the like can be preferably used.
You.       [0056]   In the present invention, as a matting agent, U.S. Pat.
No. 5, No. 4,142,894 and No. 4,396,706.
Homopolymer of acrylate or copolymer of methyl methacrylate and methacrylic acid -, Organic compounds such as starch, silica, titanium dioxide, sulfuric acid, strontium
Fine particles of an inorganic compound such as barium can be used.   The particle size is preferably 1.0 to 10 μm, particularly preferably 2 to 5 μm.
.   In the surface layer of the photographic light-sensitive material of the present invention, U.S. Pat.
And the silicone compounds described in JP-B-4447958, JP-B-56-23139.
In addition to the colloidal silica described in Japanese Patent Publication No.
Ter, a starch powder derivative, or the like can be used.       [0057]   The hydrophilic colloid layer of the photographic light-sensitive material of the present invention contains trimethylolpropane,
Polio such as butanediol, butanediol, ethylene glycol and glycerin
Tools can be used as plasticizers.   The photosensitive material of the present invention can be used for the emulsion layer, the intermediate layer and the surface protective layer.
It is advantageous to use gelatin as a mixture or protective colloid.
Other hydrophilic colloids can also be used.       [0058]   Inorganic or organic hardeners for photographic emulsions and non-photosensitive hydrophilic colloids of the invention
May be contained.   Examples of the hardening agent include chromium salts (chrome alum, chromium acetate, etc.),
Aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.),
N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.)
), Dioxane derivatives (such as 2,3-dihydroxydioxane), carboxy
Compounds that act by activating the benzyl group (carbenium, 2-naphthalene
Sulfonate, 1,1-bispyrrolidino-1-chloro-, pyridinium, 1-mo
Ruphorinocarbonyl-3- (sulfonatoaminomethyl)-and the like).   Active vinyl compound (1,3,5-triacryloyl-hexahydro-s-tri
Azine, bis (vinylsulfonyl) methane, N, N'-methylenebis- [β- (
Vinylsulfonyl) propionamide], etc.). Active halogen compounds (2,4-
Dichloro-6-hydroxy-s-triazine, etc.), mucohalic acids (mukoku) Loric acid, mucofenoxycyclolic acid), isoxazoles, dialdehydes
Starch, 2-chloro-6-hydroxytriazinated gelatin or the like, alone or
It can be used in combination.   Among them, vinyl sulfone type hardener or carboxylic acid activated type hardener is used for photographic performance (
It can be preferably used in terms of film properties such as sensitivity and residual color) drying property.   In the present invention, the use amount of the hardener is not particularly limited, but photographic performance and drying
From the viewpoint of performance, the amount is preferably 4 to 16 mmol per 100 g of gelatin.       [0059]   The photosensitive material of the present invention reduces crossover and prevents halation
It is preferable that the dye is dispersed and contained in a microcrystalline state for the purpose of carrying out the process.   The microcrystalline dispersion in the present invention is insufficient in the solubility of the dye itself,
Can not be present in the molecular state in the colored layer, and diffusion in the layer is practically impossible
Means a state of existence as a solid of any size.   For the adjustment method, refer to International Patent Publication (WO) 88/04794, European Patent
(EP) 0276566A1, JP-A-63-197943, etc.
, Ball milling, stabilizing with surfactant and gelatin, dye
After dissolution in a potash solution, a method of lowering the pH and precipitating is preferably used. I
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 discloses
Nos. 55-155350, 55-155351, 52-92716,
63-197943, 63-27838, 64-40827, Europe
No. 0015601B1, No. 0276566A1, International Application Publication No. 88 /
No. 04794, etc. can be referred to.   In particular, Japanese Patent Application Nos. 2-118042, 2-145833, and 2-293046.
No. 2-303170, No. 3-121749 and No. 3-189594
Dyes described in the detailed description can be preferably used.       [0060]   Polyethylene terephthalate film or cellulose triacetate as support
Films are preferred.   The surface of the support is rolled to improve the adhesion to the hydrophilic colloid layer.
Preference is given to the method of glow discharge treatment or ultraviolet irradiation treatment.
Or styrene butadiene latex, vinylidene chloride latex, etc.
May be provided, or a gelatin layer may be further provided thereon.
.       [0061]   In addition, an undercoat layer using an organic solvent containing a polyester swelling agent and gelatin is provided.
Is also good. These undercoat layers can be further densified with the hydrophilic colloid layer by applying surface treatment.
It is also possible to improve the wearing strength.   The emulsion layer of the photographic light-sensitive material of the present invention contains a polymer or an emulsion in order to improve pressure characteristics.
And the like.   For example, British Patent No. 738,618 discloses a heterocyclic compound as described in 738,637.
No. 738, 639, alkyl ester, rice
Japanese Patent No. 2,960,404 discloses a polyhydric alcohol, and US Pat. No. 3,121,060.
Is carboxyalkylcellulose, and JP-A-49-5017 discloses paraffin.
And carboxylate, and alkyl acrylate and organic
A method using an acid and the like are disclosed.       [0062]   The other constitution of the emulsion layer of the silver halide photographic light-sensitive material of the present invention is not particularly limited.
There is no limitation, and various additives can be used as needed. For example, Research
 Vine described in Disclosure 176: 22-28 (December 1978)
, Surfactants, other dyes, UV absorbers, coating aids, thickeners, etc.
Can be       [0063]   There is no particular limitation on the method for developing the silver halide photographic light-sensitive material of the present invention.
For example, JP-A-2-103737, page 16, upper right column, line 7 to page 19, lower left
Column 15 line. And Japanese Unexamined Patent Publication (KOKAI) No. 2-15837, page 3, lower right column, line 5 to line 6
The method described in the upper right column, line 10 of the page can be preferably used. In particular, the present invention
 It can be preferably used for ultra-rapid processing with a dry time of 60 seconds or less, especially 45 seconds or less.
Come You.   When developing the silver halide photographic light-sensitive material of the present invention, a zone dried with infrared rays is used.
An automatic developing machine having a pattern can be preferably used in terms of drying properties and drying unevenness.
You. Examples of the method using infrared rays include JP-A-1-206345 and JP-A-1-118.
No. 840, Japanese Utility Model Application Laid-Open No. 54-26734, Japanese Utility Model Application Laid-Open No. 56-130937,
-260445, JP-A-2-140741, JP-A-2-149845,
No. 2-157754, No. 51-52255, No. 53-53337
No., Japanese Patent Application No. 1-99193, Japanese Patent Application No. 1-99192, Japanese Patent Application No. 1-99191.
No., Japanese Patent Application No. 1-99190, Japanese Patent Application No. 1-99189, Japanese Patent Application No. 1-24100
4, Japanese Patent Application No. 2-52967 and Japanese Patent Application No. 2-51351 can be used.   The drying temperature is not particularly limited, but is preferably from 40 ° C to 80 ° C.       [0064]     【Example】 Example 1 Preparation of tabular grains   4.5 g of potassium bromide, 20.6 g of gelatin, thioether in 1 liter of water
HO (CH_Two)_TwoS (CH_Two)_TwoS (CH_Two)_Two2.5 cc of a 5% aqueous solution of OH was added and kept at 60 ° C
While stirring, 37 cc of an aqueous silver nitrate solution (3.43 g of silver nitrate) and 2.9 potassium bromide.
33 cc of an aqueous solution containing 7 g and 0.363 g of potassium iodide by a double jet method
It was added in 37 seconds. Next, an aqueous solution of 0.9 g of potassium bromide was added, and then 70 ° C.
, And 53 cc of an aqueous silver nitrate solution (4.90 g of silver nitrate) was added over 13 minutes.
. Here, 15 cc of a 25% aqueous ammonia solution was added, and the product was kept at the same temperature for 20 minutes.
After ripening, 14 cc of a 100% acetic acid solution was added. Subsequently, silver nitrate 133.
Control while maintaining 3 g aqueous solution and potassium bromide aqueous solution at pAg 8.5
It was added over 35 minutes by the double jet method. Next, 2N potassium thiocyanate solution
10 cc of the liquid was added. After physical ripening at the same temperature for 5 minutes, raise the temperature to 35 ° C.
Lowered. Thus, the total silver iodide content was 0.26 mol%, the average projected area diameter was 1.1.
Monodisperse tabular grains having a thickness of 0.1 μm, a thickness of 0.157 μm, and a variation coefficient of diameter of 18.5%.
Obtained.       [0065]   Thereafter, soluble salts were removed by a sedimentation method. Raise the temperature to 40 ° C again and gelatin
30 g, 2.35 g of phenoxyethanol and polystyrene sulfonate as a thickener.
0.8 g of sodium phonate was added, and pH 5.90 was added with sodium hydroxide and silver nitrate solution.
The pAg was adjusted to 8.25.   This emulsion was chemically sensitized while being kept at 56 ° C. while stirring.   First, thiourea dioxide (0.043 mg) was added and held for 22 minutes to reduce and sensitize.
Was given. Next, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazai
And 20 mg of sensitizing dye       [0066]     Embedded image       [0067] Was added. Further, 0.83 g of calcium chloride was added. Continue
1.3 mg of sodium thiosulfate, 2.7 mg of selenium compound-1 and 2.6 mg of chloroauric acid
And 90 mg of potassium thiocyanate were added, and after 40 minutes, the mixture was cooled to 35 ° C.   Thus, the tabular grains T₁Was completed. Selenium compound-1       [0068]     Embedded image       [0069] Tabular grains T except that the temperature and pAg were appropriately changed₁In the same manner as_Two~ T_FiveMake
Made. (Preparation of coating sample)   T₁A coating sample was prepared by adding the following chemicals per mole of silver halide
Was prepared.   ・ Gelatin Described in Table-1   ・ 9 g of trimethylolpropane   -Dextran (average molecular weight 39,000) 18.5g   ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g       [0070]     Embedded image       [0071] (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 surface protective layer) (Coating amount)   ・ Gelatin Described in Table-1   ・ Polymer 7 Described in Table-1   ・ Polymer 10 Described in Table-1   ・ Polymer 19 Described in Table-1   ・ Polyacrylic acid described in Table-1   ・ Hardener 1,2-bis (vinylsulfonylacetamido) ethane Table-2                 Adjust the amount of addition to achieve the stated swelling rate   ・ 4-hydroxy-6-methyl-1,3,3a, 7-       Tetraazaindene 0.015g / m^Two       [0072]     Embedded image      [0073]   ・ Polymethyl methacrylate (average particle size: 3.6 μm) 0.087 g / m^Two   ・ Proxel (prepared to pH 7.4 with NaOH) 0.0005 g / m^Two   In addition, polymer 7, polymer 10, polymer 19, and polyacrylic acid are respectively
Add an alkali to prepare a 7.5% by weight clear aqueous solution of pH 7.0 to protect the surface
Layer was added to the coating solution. The pH of the surface protective layer coating solution was adjusted to 7.0. Preparation of the 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.
.       [0074]     Embedded image      [0075]   434 ml of water and 6.7% of Triton X-200 surfactant (TX-200)
791 ml of the aqueous solution was placed in a 2 liter ball mill. 20 g of dye in this solution
Was added. Add 400ml (2mm diameter) beads of zirconium oxide (ZrO) and add
The contents were ground for 4 days. Thereafter, 160 g of 12.5% gelatin was added. Defoaming
After that, the ZrO beads were removed by filtration. Observed dye dispersion obtained
However, the particle size of the pulverized dye is as large as 0.05 to 1.15 μm in diameter.
The average particle size was 0.37 μm.   Furthermore, dye particles having a size of 0.9 μm or more are obtained by centrifugation.
Removed.   Thus, a dye dispersion D-1 was obtained. (2) Preparation of support   On a biaxially stretched 183 μm thick polyethylene terephthalate film
After performing a Rona discharge treatment, a first undercoating liquid having the following composition was applied at a coating amount of 5.1 cc /
m^TwoApply with a wire bar coater and dry at 175 ° C for 1 minute
Was.   Next, a first undercoat layer was similarly provided on the opposite surface. Polyethylene teref used A tarate containing a dye having the following structure in an amount of 0.04% by weight was used.       [0076]     Embedded image      [0077]   Butadiene-styrene copolymer latex solution   (Solid content 40% butadiene / styrene weight ratio = 31/69) 79cc       [0078]     Embedded image       [0079]   2,4-dichloro-6-hydroxy-s-triazine sodium     4% salt solution 20.5cc   Distilled water 900.5cc   The second undercoat layer having the following composition was coated on the first undercoat layer on both sides with the following coating amount.
1 each side by the wire bar coater method so that the amount described in
It was applied and dried at 50 ° C.   ・ Gelatin 160mg / m^Two   Dye dispersion D-1 (26 mg / m2 as a dye solid component)^Two)       [0080]     Embedded image       [0081]   ・ Mat agent Polymethyl methacrylate with an average particle size of 2.5 μm 2.5 mg / m^Two       [0082] Adjustment of photographic materials   On the prepared support, the emulsion layer and the surface protective layer were coated on both sides by the simultaneous extrusion method.
Clothed. The amount of silver applied per side is 1.75 g / m^TwoAnd The swelling ratio is added to the emulsion layer.
And the amount was set as shown in Table 1. Thus, the photographic material 10
1-124 were obtained.       [0083] Evaluation of photographic performance   Each sample of the photographic materials 101 to 124 was subjected to X-rayol manufactured by Fuji Photo Film Co., Ltd.
Exposure of 0.05 seconds from both sides using Soscreen HR-4 to evaluate sensitivity
Was done. After the exposure, the following processing was performed. Sensitivity is based on Photographic Material 1
It was expressed as the reciprocal of the ratio of the exposure amount giving a density of 1.0.       [0084] Processing I   Automatic developing machine: SRX-501 manufactured by KONICA CORPORATION   Developer: RD-3 manufactured by Fuji Photo Film Co., Ltd.   Fixer: Fuji Photo Film Co., Ltd. FujiF   Processing speed ... Dry to Dry 90 seconds   Development temperature… 35 ° C   Fixing temperature… 32 ° C   Drying temperature… 45 ° C   Replenishment amount: Developer 22ml / 10 x 12 inches                   Fixer 30ml / 10 × 12inch       [0085] Processing II   Automatic developing machine… KONICA Corporation SRX501 drive motor and gear                   The transport speed has been increased by remodeling part A.   Developer: RD-10 manufactured by Fuji Photo Film Co., Ltd.   Fixing solution: RF-10 manufactured by Fuji Photo Film Co., Ltd.   Processing speed ... Dry to Dry 30 seconds   Development temperature… 35 ° C   Fixing temperature… 35 ° C   Drying temperature… 55 ° C   Replenishment amount: Developer 22ml / 10 x 12 inches                   Fixer 30ml / 10 × 12inch       [0086] (Roller mark evaluation)   Photographic materials 101 to 124 at a density of 1.0 at a size of 10 × 12 inches
And then processed under the same conditions as in the evaluation of photographic performance. However, use at this time
The transport roller in the developing tank and the crossover roller from development to fixing are intentionally
A tired roller was used. The surface of the roller has irregularities of ± 10 μm
Were present. Fine spots due to the unevenness of the roller may appear on the processed photographic material.
Many occurred. The state was sensory evaluated in the following four stages. Evaluation result
Are summarized in Table 1.   ◎: Almost no spots were observed.   …: A level where slight spots are generated, but not practically bothersome.   Δ: Spots are generated but not normally generated with the roller. Acceptable level.   X: Spots are frequent, and even a normal roller is not practical.       [0087] (Evaluation of dryness)   Under the same conditions as in Process II when the photographic performance was evaluated, each photographic material of 4 cut sizes was used.
The dryness of the film after continuous treatment was sensory-evaluated by touch.   The film was continuously processed with the short side in the transport direction. Table 1 shows the results.
Summarized in   ◎ Even on the 30th sheet, the film comes out warm and dry. No problem at all.   ○ Even on the 30th sheet, the film is completely dry. Temperature when touched is room temperature       It was comparable to the film left below.   △ At the 30th sheet, the film is slightly cold, but the continuously processed film will adhere       Practically acceptable level with no swell.   × At the 30th sheet, the film was wet and undried. Film bonding       .       [0088] Evaluation of residual color   When Process II was performed, the residual color of the film was evaluated. Evaluation criteria are Process I and
The invented films of Treatment II were compared visually.       [0089] (Measurement of swelling rate)   For each photographic material, RD-10 manufactured by Fuji Photo Film Co., Ltd. was used as a developer.
Using a fixing solution of RF-10 manufactured by Fuji Photo Film Co., Ltd.
The swelling ratio of each step was measured according to the following.   The results are summarized in Tables 1 and 2.       [0090]     [Table 1]       [0091]     [Table 2]      [0092]   In Tables 1 and 2, the amount of gelatin applied was 2.7 g / m2.^TwoPhotographic materials 101-103
In this case, both the drying property and the residual color property cannot be satisfied.   On the other hand, the gelatin coating amount is 2.4 g / m^TwoIn the photographic material 104, the drying property and the residual color property are full.
Roller marks will be worse, though added.   Here, when the polymer of the present invention is used, any of drying property and roller mark residual color property can be obtained.
I can be satisfied with that. In addition, tabular grains having an aspect ratio of 3.0 or more It can be seen that when is used, the sensitivity is significantly increased.   Further, when polyacrylic acid is used, satisfactory results cannot be obtained in terms of dryness.
The sensitivity when using an average particle having an aspect ratio of 3.0 or more is inferior to that of the present invention.
The result is.       [0093] Example 2   Gelatin, polymer 7, polymer 10, polymer 5, polyacrylic acid hardener (
The amount of 1,2-bis (vinylsulfonylacetamide) ethane) is shown in Table 3.
The evaluation was carried out in the same manner as in Example 1 except for changing to.   The results are summarized in Tables 3 and 4.       [0094]     [Table 3]       [0095]     [Table 4]      [0096]   As shown in Tables 3 and 4, when the polymer of the present invention was used, the swelling ratio of distilled water was 250%.
Excellent sensitivity in the following areas, regardless of dryness, roller mark, and residual color
Satisfactory photographic materials can be obtained.       [0097] Example 3 (Preparation of tabular grains)   4.5 g of potassium bromide, 12.0 g of gelatin, thioether in 1 liter of water
HO (CH_Two)_TwoS (CH_Two)_TwoS (CH_Two)_Two2.5 cc of a 5% aqueous solution of OH was added and kept at 55 ° C While stirring, 37 cc of an aqueous silver nitrate solution (3.43 g of silver nitrate) and 2.9 potassium bromide.
33 cc of an aqueous solution containing 7 g and 0.363 g of potassium iodide by a double jet method
It was added in 37 seconds. Next, an aqueous solution of 0.9 g of potassium bromide was added, and then 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 the temperature was maintained for 10 minutes at the same temperature.
After aging, 7 cc of a 100% acetic acid solution was added. Subsequently, 133.3g of silver nitrate
While maintaining the aqueous solution of potassium bromide and the aqueous solution of potassium bromide at pAg 8.5.
It was added over 35 minutes by the Rujet method. Next, 2N potassium thiocyanate solution 1
0cc and 0.07μm diameter AgI fine particles are added at 0.05mol% to the total silver.
did. After physical ripening at the same temperature for 5 minutes, the temperature was lowered to 35 ° C. Like this
Total silver iodide content 0.31 mol%, average projected area diameter 0.60 μm, thickness 0
. Monodisperse tabular grains having a diameter of 120 μm and a coefficient of variation of 16.5% were obtained.       [0098]   Thereafter, soluble salts were removed by a sedimentation method. Raise the temperature to 40 ° C again and gelatin
30 g, 2.35 g of phenoxyethanol and polystyrene sulfonate as a thickener.
0.8 g of sodium phonate was added, and pH 5.90 was added with sodium hydroxide and silver nitrate solution.
The pAg was adjusted to 7.90.   This emulsion was chemically sensitized while being kept at 56 ° C. while stirring.   First, thiourea dioxide (0.043 mg) was added and held for 22 minutes to reduce and sensitize.
Was given. Next, 250 mg of the same sensitizing dye as in Example 1 was added. Continue
Sodium osulphate The following selenium sensitizer was added in a molar ratio of 6: 4.       [0099]   Subsequently, chloroauric acid and potassium thiocyanate were added, and after 40 minutes, cooled to 35 ° C.
Was. Thus, the tabular grains T_AWas completed.   Tabular grains T except that the temperature and pAg were appropriately changed_AT in the same way as_B-T_EMake
Made.       [0100] (Preparation of emulsion layer coating solution)   Tabular grain T_AEmulsion layer coating by adding the following chemicals per mole of silver halide Liquid.   ・ 2,6-bis (hydroxyamino) -4-diethylamino       1,3,5-triazine 72   ・ Gelatin Described in Table-5   ・ Polymer 7 listed in Table-5   ・ Polymer 10 described in Table-5   ・ Polymer 47 Listed in Table-5   ・ Polyacrylic acid described in Table-5   -Dextran (average molecular weight 39,000) 18.5g   ・ Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g       [0101]     Embedded image       [0102]     Embedded image       [0103]   Snowtex C (manufactured by Nissan Chemical Co., Ltd.) 9.6 g as solid content   Dextran (average molecular weight 39,000) 5.8 g   In addition, polymer 7, polymer 10, polymer 47, and polyacrylic acid are respectively
A clear aqueous solution of 7.5% by weight was prepared at pH 7.0 by adding alkali, and the emulsion layer was prepared.
It was added to the coating solution. 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 such that each component had the following coating amount.   ・ Gelatin Described in Table-5   ・ Polymer 7 listed in Table-5   ・ Polymer 10 described in Table-5   ・ Polymer 47 Listed in Table-5   ・ Polyacrylic acid described in Table-5   ・ 4-hydroxy-6-methyl-1,3,3a, 7-       Tetraazaindene 0.003g / m^Two   ・ Polymethyl methacrylate (average particle size 2.5 μm) 0.05 g / m^Two   ・ Proxel 0.0005 g / m^Two       [0104]     Embedded image       [0105]   In addition, polymer 7, polymer 10, polymer 47, and polyacrylic acid are respectively
A clear aqueous solution of 7.5% by weight was prepared at pH 7.0 by adding an alkali, and the surface was preserved.
It was added to the protective layer coating solution. The pH of the surface protective layer coating solution was 7.0.   Biaxially stretched, 183 μm thick polyethylene pre-coated with an undercoat layer
Put the prepared emulsion layer coating solution and surface protective layer coating solution on the lentephthalate film.
Coating was performed on one side by a simultaneous extrusion method. The coated silver amount is 2.55 g / m^TwoSo that
It was adjusted. The used polyethylene terephthalate had the same structure as in Example-1.
A material containing 0.04% by weight of a material was used.       [0106] (Adjustment of antihalation layer)   Haration on the side on which the emulsion layer and the surface protective layer are coated and on the side opposite to the support
An anti-halation layer and a surface protection layer as an anti-halation layer were applied.   Each layer was prepared so as to have the following coating amount. (Anti-halation layer)   ・ Gelatin 1.5g / m^Two   ・ Phosphoric acid 5.2g / m^Two   -Snowtex C (Nissan Chemical Co., Ltd.) 0.5 g / m2 as solid content^Two   -Potassium polystyrene sulfonate (average molecular weight 600,000) 25 g / m^Two   ・ Polymer latex     (Poly (ethyl acrylate / methacrylic acid) = 97/3) 0.53 g / m^Two       [0107]     Embedded image       [0108]     Embedded image       [0109] (Surface protection layer for antihalation layer)   ・ Gelatin 1.05g / m^Two   ・ Polymethyl methacrylate (average particle size 3.5μm) 65mg / m^Two       [0110]     Embedded image       [0111]   ・ C₈F₁₇SO_ThreeK 1.7mg / m^Two   -Potassium polystyrene sulfonate (average molecular weight 600,000) 2mg / m^Two   ・ NaOH 2.5mg / m^Two   The antihalation layer and its surface protective layer are applied simultaneously by the simultaneous extrusion method
Dried.   The photographic material thus obtained was used as an automatic processing machine by Fuji Photo Film Co., Ltd.
FPM-9000 manufactured by the company
The same evaluation as in Example 1 was performed, except that the results were used in Table 5.
And 6.       [0112]     [Table 5]       [0113]     [Table 6]      [0114]   From the results of Tables 5 and 6, the use of the polymer of the present invention deteriorates photographic performance.
It can be seen that all of the drying property, the roller mark, and the residual color property are satisfied without any problem.       [0115] Example 4   Gelatin, polymer 7, polymer 10, polymer 51, polyacrylic acid hardener
The amount of (1,2-bis (vinylsulfonylacetamido) ethane) was determined according to Table 7. Evaluation was performed in the same manner as in Example 3 except that the amount was changed.   The results are summarized in Tables 7 and 8.       [0116]     [Table 7]       [0117]     [Table 8]      [0118]   Table 7 and Table 8 show that when the polymer of the present invention is used, the swelling ratio of distilled water is 250% or less.
In the lower area, excellent sensitivity, dryness, roller mark, residual color
Satisfactory photographic materials can be obtained.       [0119] Example 5   KON was used as an automatic developing machine for the photographic materials 101 to 124 used in Example 1.
The SRX-1001 manufactured by ICA Co., Ltd. was modified to increase the transport speed,
The same as in Example 1 except that two additional
Were evaluated.   Further, it was evaluated whether or not there was drying unevenness after developing the photographic material. (Evaluation of drying unevenness)   Each photographic material processed for evaluation of dryness was visually evaluated.   乾燥 No drying unevenness was observed in any of the 30 sheets.   × One or more of the 30 sheets showed drying unevenness.   The results are shown in Table-9.       [0120]     [Table 9]       [0121]   Table 9 shows that when the carboxyl group-containing polymer of the present invention is used, it is dried by infrared rays.
No uneven drying and excellent surface quality when processed by an automatic processor with
I understand.

Claims (1)

Claims: 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein at least one type of carboxyl is provided on at least one silver halide emulsion layer-coated side. group-containing polymer (carboxyl group-containing monomer units is 15 mol% or more, or an acid value of 1.5 meq / g or more, provided that polyacrylic acid is excluded) has a hydrophilic colloid layer containing, containing the carboxyl group Polymer and ze
The ratio of the coating amount per one side of the latin (polymer content ratio) is expressed by the following equation.
Silver halide in at least one type of silver halide emulsion is tabular grains having an aspect ratio of 3.0 or more , and the polymer
-At least one hydrophilic colloid layer on the side with the containing layer is a vinyl sulfone hardener
And a swelling ratio of all the hydrophilic colloid layers on the side of the polymer-containing layer with respect to the support in distilled water of not more than 250%. (Here, the swelling ratio in distilled water is as follows.
(Percent relative humidity) for 16 hours, and the change in thickness when immersed in distilled water at 21 ° C. for 3 minutes is measured. ) (Equation 1) 2. The silver halide photographic material according to claim 1 , wherein the content of the vinyl sulfone type hardener is 4 to 16 mmol per 100 g of gelatin. 3. The silver halide photographic material according to claim 2 , which contains dextran and / or acrylamide. 4. The silver halide photographic light-sensitive material according to claim 2 , comprising a dye dispersed in a microcrystalline state. 5. A development process, a silver halide photographic material as claimed in claim 2, 3 or 4 until the process ends the processing start (Dry-to Dry processing time) is equal to or is within 60 seconds . 6. When the developing treatment is carried out in a developing step of 8 seconds, a fixing step of 7 seconds and a washing step of 7 seconds using a developing solution and a fixing solution substantially free of a hardener, the swelling ratio of distilled water is claim 1, the ratio of the swelling rate during the washing process completion for is equal to or less than 1.0
The silver halide photographic light-sensitive material as described above. 7. Swelling at the completion of the developing step when the developing step is carried out in a developing step of 8 seconds, a fixing step of 7 seconds, and a washing step of 7 seconds using a developing solution and a fixing solution substantially free of a hardener. the silver halide photographic material of claim 1, wherein the ratio of the swelling rate during the washing process is complete, characterized in that less than 1.0 relative to the rate. 8. The silver halide photographic material according to claim 1 , wherein the carboxyl group-containing polymer is polymethacrylic acid or a methacrylic acid copolymer. 9. A method for developing a silver halide photographic material according to claim 2, wherein the method is carried out by an automatic developing machine having a zone for drying with infrared rays.