JPH05119417A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material excellent in drying property in the case of ultra high speed processing by dissolving a polymer expressed by specified formula in water and imparting a hydrophilic colloid layer incorporated with this aq. soln. CONSTITUTION:This photographic sensitive material has a hydrophilic colloid layer on at least one side where a silver halide emulsion layer is formed by coating. This hydrophilic colloid layer is incorporated with a polymer expressed by formula I by dissolving the polymer in water and adding the aq. soln. In the formula I, A is at least one monomer expressed by formula II, B is an ethylene-type unsatd. monomer except for A which is copolymerizable with A, x is 10-100mol%, and y is 0-90mol% In the formula II, X, Y and Z are hydrogen atoms, substd. or unsubstd. alkyl groups (1-8 carbons), -COOM, -COOR1, -CONR2R3, or substd. or unsubstd. phenyl groups, however, at least one of X, Y and Z is a substd. or unsubstd. alkyl group (1-8 carbons), -COOR1, -CONR2 R3, or substd. or unsubstd. phenyl group.

Description

Detailed Description of the Invention

[0001]

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

[0002]

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

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

For the purpose of improving the above-mentioned viewpoint, a technique utilizing tabular grains is disclosed in US Pat. No. 4,43.
9, 520, 4,425, 425 and the like. Moreover, JP-A-63-305343 and JP-A-1-
No. 77047 discloses a technique for improving the development progress and the sensitivity / fogging ratio by controlling the development start point of a silver halide grain having a (111) plane to the apex and / or lobe of the grain and the vicinity thereof. There is. Further, JP-A-58-1119
No. 33 discloses a photographic element for radiography which has a high covering power by controlling the swelling of the hydrophilic colloid layer using tabular grains to 200% or less and does not require the addition of a dura during processing. ing. These known techniques are excellent techniques for improving the development progress of the light-sensitive material and have high utility value. However, development
When the processing time of each process of fixing and washing is shortened, not only the photographic sensitivity is lowered, but also the residual silver and the residual hypo are deteriorated due to the deterioration of the fixing property. In addition, the problem of residual color comes to the surface in a light-sensitive material that has been spectrally sensitized with a sensitizing dye. These problems other than photographic properties are limited in improvement by modification of silver halide grains, and ultimately result in problems of film quality. In other words, the thickness of the hydrophilic colloid layer regulates fixing and residual color, which is an obstacle to speeding up.

Regarding this point, JP-A-64-7333.
3, JP-A-64-86133, JP-A-1-1052.
44, JP-A-1-158435, and JP-A-1-158.
No. 436, the amount of gelatin on the side having a hydrophilic colloid layer including a silver halide emulsion layer is 2.00 to 3.50 g.
Disclosed is a means for achieving an ultra-rapid treatment with a total treatment time of 20 seconds or more and less than 60 seconds by adjusting the amount in the range of / m ² and combining it with other technical elements. In addition, JP-A-2-685
No. 37 discloses means for achieving ultra-rapid processing by adjusting the weight ratio (silver / gelatin) of photosensitive silver halide coated in an emulsion layer to 1.5 or more. .. Further, in JP-A-63-221341, the silver halide grains in the emulsion layer are mainly composed of tabular grains having a grain size of 5 times or more the grain thickness, and the amount of gelatin is 2.00 to 2.00.
3.20g / m ² and a melting time of 8 minutes or more 4
A means for achieving an ultra-rapid treatment with a total treatment time of 20 seconds or more and less than 60 seconds by setting the treatment time to 5 minutes or less is disclosed.

However, when these prior arts were examined, when the amount of gelatin was reduced or the silver / gelatin ratio was increased while keeping the amount of coated silver constant, abrasion blackening and roller marks were markedly deteriorated. It was found that the product would not be practically acceptable, which would make it impossible to complete a product that could be processed extremely quickly.

[0007] Scratch blackening is a phenomenon in which, when the film is handled, when the films are rubbed with each other, or when the film is rubbed with another substance, a scratch-like blackening occurs after the development processing. The roller mark is a phenomenon in which, when the photosensitive material is processed by an automatic developing machine, pressure is applied to the photosensitive material due to fine irregularities on the surface of the transport roller, resulting in black-spotted uneven density. When the total processing time is set to 60 seconds or less, especially 40 seconds or less, the appropriate amount of time is allocated to the developing, fixing, and washing steps, resulting in a gelatin coating amount of 2.5.
If it is not less than g / m ² , the dryness may be impaired when the environment in which the automatic processor is installed is high humidity. On the other hand, such reduction of the gelatin coating amount is not acceptable in terms of roller marks and blackening of scratches. In this way, it was not possible to satisfy the respective properties of drying property, pressure property and fixability (or residual color property) only by adjusting the gelatin coating amount.

It is well known in photographic materials to use polymers having the structure --COOH or salts thereof and with gelatin which is a hydrophilic colloid. For example, Japanese Examined Patent Publication Nos. 57-53587 and 57-15.
375, West German Patent 1,745,061, JPB49
-23827, 55-14415, 55-15
267, JP-A-48-89979, and US Pat.
No. 79,410, No. 3,791,831, Japanese Patent Publication No. 47
No. 28937 discloses an attempt to utilize a polymer having a carboxyl group for preventing static charge of a photographic light-sensitive material. However, there is no mention of controlling the swelling ratio of the hydrophilic colloid layer and accelerating the drying speed of the light-sensitive material with this type of anionic polymer antistatic agent. Further, generally, an anionic antistatic agent is used in a large proportion in a specific hydrophilic colloid, and a large amount of a gelatin hardening agent is often used in order to improve the physical properties of the film. If it is used to reduce the drying load by controlling the swelling property, the problems such as residual silver and residual hypo will occur as described in JP-A-58-111933.

Further, European Patent Nos. 75231 and 1670
81, JP-A-53-7231, and JP-A-60-12664.
4, JP-A-60-156056, JP-A-2-20861.
Japanese Patent Publication No. 14574 / US Pat. No. 4,142,894.
JP-A No. 1994-242 discloses a polymer matting agent containing a carboxyl group. However, the matting agent originally exposes particles of about 0.2 to 10 μm on the surface of the photosensitive material, and exerts its function by the unevenness on the surface. The function of controlling the swelling property after treatment is not sufficient.

Further, in Japanese Patent Application No. 1-27895, a polyacrylic acid derivative is introduced into a light-sensitive material containing an antihalation layer containing a polymeric mordant having an ammonium structure and an anionic dye to decolorize the anionic dye. It is disclosed that the sex is improved. However, the patent does not describe the control of swellability after treatment with a -COOH-containing polymer, and the acrylic acid homopolymer according to the embodiment has a swellability after treatment in a treatment substantially containing no hardening agent. The inventors of the present invention have revealed that there is no drying effect improving effect based on the control effect.

[0011]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a silver halide photographic light-sensitive material exhibiting excellent drying properties during processing, especially in rapid processing. Secondly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in drying property and has a roller mark and scratch blackening at a sufficiently practical level. A third object of the present invention is to provide a silver halide photographic light-sensitive material satisfying the above-mentioned objects, having high sensitivity, high covering power, and excellent suitability for rapid processing.

[0012]

The above objects of the present invention have been achieved by the following means. (1) In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, at least one silver halide emulsion layer coated surface side has a weight represented by the following general formula [I]. A silver halide photographic light-sensitive material comprising a hydrophilic colloid layer obtained by dissolving the coalescence in water and adding the aqueous solution. The general formula [I]-(A) _x- (B) _y -A is at least one polymerized monomer represented by the general formula [I], and B is an ethylenic unsaturated other than A copolymerizable with A. Monomer. x is 10 to 100 mol% y is 0 to 90 mol% General formula [II]

[0013]

[Chemical 2]

X, Y, Z: hydrogen atom, substituted or unsubstituted alkyl group (C ₁ -C ₈ ), --COOM, --CO
OR ₁ , -CONR ₂ R ₃ or a substituted or unsubstituted phenyl group, provided that at least one of X, Y and Z is a substituted or unsubstituted alkyl group (C _{1 to} C ₈ ), -COOR, -CONR
₂ R ₃ , either a substituted or unsubstituted phenyl group. R ₁ ; substituted or unsubstituted alkyl group (C _{1 to} C ₁₈ ), aryl group (C _{6 to} C ₁₈ ) or aralkyl group (C _{7 to} C ₁₂ ) R ₂ ; hydrogen atom, substituted or unsubstituted alkyl group (C _{1 to} C
_4), phenyl or aralkyl group _{(C 7 ~C 10) R 3} ; a hydrogen atom, R ₂ or - (R ₄ -CONH) _N -R
_4- COR ₅ R ₄ ; C ₁ -C ₁₂ aliphatic or aromatic divalent group R ₅ ; OM or -NR ₂ R ₃ M; hydrogen atom or cation N; integer from 0 to 6

The present invention will be described in detail below. It is well known to use a polymer having -COOH or a salt structure thereof in a photographic material, but a polymer represented by the general formula [I] is used in the present invention on the silver halide emulsion layer and the coated surface side. It was an unexpected and surprising fact that a photographic light-sensitive material excellent in drying property in rapid processing was obtained by dissolving it in and using it. The polymer represented by formula (I) will be described in detail below. Specific examples of the monomer represented by the general formula [II] used in the general formula [I] include the followings. Methacrylic acid, crotonic acid, cinnamic acid, citraconic acid, α, β-dimethylmaleic acid, α-ethylacrylic acid, of which the acid is an alkali metal, preferably N
The salt of a, K or ammonium ion may be used.

Any monomer other than A may be used as the monomer that gives B. For example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, vinyl esters, vinyl ketones, allyl compounds, Olefins, vinyl ethers, N-vinyl amides, vinyl heteronode compounds, maleic acid esters,
Itaconic acid esters, fumaric acid esters, crotonic acid esters and the like are included. More specifically,
For example:

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

Acrylamide, methacrylamide, N-
Methyl acrylamide, N-ethyl acrylamide, N
-N-propylacrylamide, N-iso-propylacrylamide, Nn-butylacrylamide, N-te
rt-butyl acrylamide, N, N-dimethyl acrylamide, N, N-diethyl acrylamide, hexyl acrylamide, octyl acrylamide, allyloxyethanol, allyl butyl ether, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethyl butyl vinyl ether, Hydroxyethyl vinyl ether, vinyl acetate, vinyl propionate, N-vinyl oxazolidone, vinyl pyridine, N-vinyl imidazole, N-
Vinyl-2-methylimidazole, N-vinyltriazole, N-vinyl-3,5-dimethyltriazole, N-
Vinylpyrrolidone, N-methyl-N-vinylpropionamide, N-vinylpyrrolidone, N-vinyl-2-pyridone, ethylene, propylene, 1-ptene, 1-heptene, 1-octene, dioctyl itaconate, dibutyl itaconate, Dihexyl maleate, dibutyl maleate, styrene, methylstyrene, dimethylstyrene, benzylstyrene, chloromethylstyrene, chlorostyrene, methyl vinylbenzoate, vinyl chlorobenzoate, acrylonitrile, methacrylonitrile, vinyl chloride, etc.

Among these monomers, the solubility of the polymer,
Methacrylic acid is preferred in the general formula [II] from the viewpoints of transparency, lipophilicity, hydrophilicity, affinity with protective colloid, easy polymerization and the like. Further, as the monomer forming B, methacrylic acid esters, acrylic acid esters,
Styrenes are preferred.

Regarding the composition ratio of the polymer of the present invention represented by the general formula [I], a sufficient effect can be obtained even if a homopolymer of the monomer of the general formula [II] in which x is 100 is obtained. The larger the ratio of the monomer component of [II], the more excellent the effect. Therefore, x is preferably 10 to 100 mol%, preferably 20 to 80 mol%, and particularly 30 to 60 mol%. Further, y is 0 to 90 mol%, preferably 2
0-80 mol% and especially 40-70 mol% are suitable.

For the synthesis of the copolymer having the repeating unit represented by the general formula [I], British Patent Nos. 1 and 2 are used.
11,039, Japanese Patent Publication No. 46-29195, British Patent No. 961,395, and US Patent No. 3,227,672.
No. 3,262,919, No. 3,245,93
No. 2, No. 3,230,275, "Official Digest" by John C. Petropoulos and others (John
C.Petropoulos et al: Official Digest) 33, 719-
736 (1961), Shunsuke Murahashi et al., “Synthetic Polymer” 1,
It is convenient to carry out by referring to the methods described in 246 to 290, 3, 1 to 108 and the like.

The compounds represented by formula (I) of the present invention are shown below, but the present invention is not limited thereto. (The parentheses represent the molar ratio of the monomer components.) P-1 Polymethacrylic acid P-2 Methacrylic acid / methyl acrylate copolymer (40/60) P-3 Methacrylic acid / methyl methacrylate copolymer (60/40) P-4 Methacrylic acid / methyl methacrylate copolymer (40/60) P-5 Methacrylic acid / methyl methacrylate copolymer (20/80) P-6 Methacrylic acid / ethyl acrylate copolymer (40/60) P- 7 Methacrylic acid / ethyl methacrylate copolymer (40/60) P-8 Methacrylic acid / n-propyl acrylate copolymer (40/60) P-9 Methacrylic acid / n-propyl methacrylate copolymer (40/60) P-10 Methacrylic acid / iso-propyl acrylate copolymer (40/60) P-11 Methacrylic acid / iso-propyl methacrylate copolymer (40/60) P-1 2 Methacrylic acid / n-butyl acrylate copolymer (40/60) P-13 Methacrylic acid / tert-butyl acrylate copolymer (40/60) P-14 Methacrylic acid / tert-butyl methacrylate copolymer (40 / 60) P-15 methacrylic acid / n-hexyl acrylate copolymer (40/60) P-16 methacrylic acid / cyclohexyl acrylate copolymer (40/60) P-17 methacrylic acid / cyclohexyl methacrylate copolymer (40 / 60) P-18 methacrylic acid / phenyl acrylate copolymer (40/60) P-19 methacrylic acid / 2-hydroxyethyl acrylate copolymer (40/60) P-20 methacrylic acid / 2-hydroxypropyl methacrylate copolymer Combined (40/60) P-21 Methacrylic acid / 3-hydroxypropyl acrylate copolymer (40/60) P-22 Methacrylic acid / 2-methoxyethyl Acrylate copolymer (40/60) P-23 methacrylate / 2-butoxyethyl acrylate copolymer (40/60) P-24 methacrylate / 2- (2-methoxyethoxy)
Ethyl acrylate copolymer (40/60) P-25 methacrylic acid / acrylamido copolymer (40 /
60) P-26 methacrylic acid / N-iso-propyl acrylamide copolymer (40/60) P-27 methacrylic acid / N-tert-butyl acrylamide copolymer (40/60) P-28 methacryl Acid / Methyl vinyl ether copolymer (40/60) P-29 Methacrylic acid / N-vinylpyrrolidone copolymer (40/60) P-30 Methacrylic acid / styrene copolymer (40/60) P-31 Methacrylic acid / Acrylonitrol copolymer (40
/ 60) P-32 methacrylic acid / methyl acrylate / methyl methacrylate (40/30/30) P-33 methacrylic acid / methyl acrylate / n-butyl acrylate (40/40/20) P-34 methacrylic acid / methyl methacrylate / Tert-
Butyl acrylate (40/40/20) P-35 methacrylic acid / methyl methacrylate / cyclohexyl acrylate copolymer (40/40/20) P-36 methacrylic acid / methyl acrylate / 2-hydroxyethyl acrylate copolymer (40 / 40/20) P-37 methacrylic acid / methyl acrylate / acrylamide copolymer (40/40/20) P-38 methacrylic acid / methyl methacrylate / styrene copolymer (40/40/20) P-39 methacrylic acid / Methyl acrylate / 2-hydroxy acrylate / acrylonitrile copolymer (40/40/1
0/10) P-40 Methacrylic acid / methyl methacrylate / tert-
Butyl methacrylate / 2-hydroxyethyl methacrylate (40/30/20/10)

In a preferred embodiment of the present invention, the molecular weight of the acid polymer added to the hydrophilic colloid is preferably 5 ×.
10 ³ or more, particularly preferably 1 × 10 ⁴ to 5 × 10
⁶ (all are weight average molecular weights). The amount of acid polymer added varies depending on the type of photosensitive material,
Preferably ^{0.01g / m 2 ~2g / m 2} , more preferably from ^{0.05g / m 2 ~1g / m 2} . More preferably from ^{0.1g / m 2 ~0.5g / m 2} .

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

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

When the polymer represented by the general formula [I] of the present invention is used, it is necessary to dissolve it in water and introduce it into the photographic material by adding the aqueous solution. Upon dissolution, it is preferable to use a suitable alkali and salt. Also water-miscible organic solvents (eg acetone, methanol,
Ethanol, acetonitrile, dimethyl sulfoxide,
Dimethylacetamide, etc.) may also be used.

Gelatin is preferably used as the hydrophilic layer colloid forming the hydrophilic layer colloid layer containing the polymer represented by the general formula [I] of the present invention. As gelatin, lime-processed gelatin, acid-processed gelatin or enzyme-processed gelatin may be used, and a hydrolyzed product or an oxygen-decomposed product of gelatin may also be used. Also, hydrophilic colloids other than gelatin can be preferably used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sodium alginate, dextran, starch derivatives and the like. Sugar derivative: Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Molecular substances can be used. Among these, it is preferable to use together with gelatin dextran or polyacrylamide having an average molecular weight of 50,000 or less. JP-A-6
The methods described in 3-68837 and 63-149641 are also effective in the present invention.

When the polymer represented by the general formula [I] of the present invention and the hydrophilic binder are mixed and then coated, the pH of the coating liquid is 6. 0
~ 9.0 is preferable. More preferably 6.5-8.0,
More preferably, it is 7.0 to 7.5. The coating solution for forming the silver halide emulsion layer is preferably 5.0 to 8.0. It is more preferably 5.5 to 7.0, and even more preferably 5.8 to 6.5.

The ratio of the polymer represented by the general formula [I] and the hydrophilic colloid (polymer content ratio) used in the photographic material of the present invention is not particularly limited, but the value of the following formula is 0.0.
It is preferably 3 to 0.3. More preferably 0.
It is 05-0.2. More preferably 0.10 to 0.
It is 15.

[0031]

[Equation 2]

The swelling rate at the completion of the developing step, the swelling rate at the completion of the water washing step, and the swelling rate of distilled water in the present invention are respectively represented by the following equations.

[0033]

[Equation 3]

The layer thickness at the completion of the development step means the layer thickness when the photographic material is immersed in a developing solution at 35 ° C. for 25 seconds. What is the thickness of the layer at the time of completion of the water washing step?
Water-washing step means the thickness of the last layer in the water-washing step when the treatment is continuously performed in the order of development → fixing → water-washing under the condition of 20 ° C. for 20 seconds. The thickness of the layer when immersed in distilled water is 21 ° C for the photographic material.
Means the thickness of the layer when immersed in distilled water for 3 minutes.
The photographic material used here was subjected to an incubation treatment for 16 hours at a relative humidity of 40 ° C. and 60% RH.

When determining the swelling ratio of each step in the present invention, the layer thickness under each condition is measured by the method described in US Pat. No. 3,841,872, Example 12 (however, The measuring part of the measuring instrument is made of ceramic)
Is defined.

The light-sensitive material of the present invention can exert its effect particularly when processed with a developer and a fixer containing no hardener. The term "developing solution and fixing solution substantially free of a hardening agent" as used in the present invention means a developing solution and fixing solution which do not substantially contain a compound called a hardening agent in the art. Specifically, the developer is Fuji Photo Film Co., Ltd.
As RD-10 manufactured by Fuji Photo Film Co., Ltd., RF-10 can be used as a fixing solution.

According to the present invention, the ratio of the swelling rate at the completion of the washing step to the swelling rate at the completion of the developing step can be set to 1.0 or less. This does not interfere with the development process,
This means that it is a photographic material having excellent dryness. 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 can be 1.0 or less. This means that the photographic material is excellent in dryness without hindering the development process.

The photographic light-sensitive material using the polymer represented by the general formula [I] of the present invention is suitable for rapid processing. In particular
It is preferable that the dry-to-dry processing is performed within 60 seconds. It is more preferably within 45 seconds, and even more preferably within 38 seconds.

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

In the photographic material of the present invention, the coating amount of gelatin, which is preferably used as a hydrophilic binder, is not particularly limited, but is 1.5 g / m ^{2 to} 4.5 per side.
g / m ² is preferred. Also 1.8g / m ² ~3.6g / m ² is particularly preferred. The swelling ratio of the light-sensitive material of the present invention with distilled water can be freely set by changing the amount of the hardener used. The swelling ratio with distilled water is not particularly limited, but it is 200% when considering the problem of residual silver and residual hypo due to rapid processing, or the problem of residual color of a photosensitive material spectrally sensitized by a sensitizing dye. The above is particularly preferable.

Next, the emulsion grains preferably used in the present invention will be described. The sphere-equivalent average particle size of the same volume as the particles is preferably 0.4 μm or more. It is particularly preferably 0.5 to 2.0 μm. The particle size distribution should be narrow. The silver halide grains in the emulsion may have a regular crystal form such as a cube or octahedron, or an irregular (irregular) crystal form such as a sphere, a plate or a potato. And may consist of a mixture of particles of various crystal forms. The silver halide composition is preferably silver iodobromide because of its high sensitivity.

The silver halide grains of the present invention may contain a small amount of silver chloride to the extent that it does not affect the photographic properties, but it is desirable that the silver halide grains not contain silver chloride. As the emulsion of the present invention, both monodisperse emulsion and polydisperse emulsion can be preferably used. The silver halide emulsion used in the present invention may be a core-shell type monodisperse emulsion,
These core / shell emulsions are known from JP-A-54-48521.

Further, tabular grains having a grain size of 5 times or more the grain thickness are preferably used in the present invention (specifically,
Research Disclosure Volume 225 Item 22
534P. 20-P. 58, January issue, 1983, and JP-A-58-127921 and 58-113926). The tabular silver halide grains can be produced by appropriately combining the methods known in the art.

In order to effectively use the effects of the present invention,
In the chemical sensitization during the emulsion preparation process as disclosed in JP-A-2-68539, 0.5 mmol or more of a sensitizing dye per mol of silver halide or silver halide adsorption corresponding to a class of photographic performance stabilizers. It is preferable that a volatile substance is present.

That is, azoles {eg benzothiazolium salts, benzimidazolium salts, imidazoles, benzimidazoles, nitroindazoles, triazoles, benzotriazoles, tetrazoles, triazines, etc.); mercapto compounds {eg Mercaptothiazoles, mercaptobenzothiazoles, mercaptoimidazoles, mercaptobenzimidazoles, mercaptobenzoxazoles, mercaptothiadiazoles, mercaptooxadiazoles, mercaptotetrazoles, mercaptotriazoles, mercaptopyrimidines, mercaptotriazines, etc.} ;
Thioketo compounds such as oxadrinethione; azaindenes {eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a,
7) Tetraazaindenes), pentaazaindenes, etc.); and many compounds known as antifoggants or stabilizers can be mentioned as the silver halide adsorbing material.

Further, purines or nucleic acids, or Japanese Examined Patent Publication No. 61-36213, JP-A-59-90844.
Nos., Etc. are also adsorbable substances that can be used. Especially azaindenes and purines,
Nucleic acids are preferred and can be used in the present invention. The addition amount of these compounds is 300 per mol of silver halide.
-3000 mg, preferably 500-2500 mg. As the silver halide-adsorptive substance of the present invention, a sensitizing dye can realize preferable effects. As the sensitizing dye, cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holoholer cyanine dye, styryl dye, hemicyanine dye, oxonol dye, hemioxonol dye and the like can be used.

Useful sensitizing dyes used in the present invention are, for example, US Pat. Nos. 3,522,052 and 3,619,19.
No. 7, No. 3,713, 828, No. 3, 615, 643
Issue No. 3,615,632 Issue 3,617,293
Nos. 3,628,964, 3,703,377
Issue No. 3,666,480 Issue 3,667,960
Nos. 3,679,428 and 3,672,897
Issue No. 3,769,026 Issue No. 3,556,800
Issue No. 3,615,613 Issue No. 3,615,638
Nos. 3,615,635 and 3,705,809
No. 3,632,349, No. 3,677,765
No. 3,370,449, No. 3,770,440
No. 3, ibid. 3,769,025, ibid. 3,745,014
Issue 3, Issue 3,713,828, Issue 3,567,458
Nos. 3,625,698, 2,526,632
No. 2,503,776, JP-A-48-76525.
And Belgian Patent No. 691,807. The amount of sensitizing dye added is 3 per mol of silver halide.
00 mg or more and less than 2000 mg, preferably 500 mg or more 1
Less than 000mg is good. Specific examples of the sensitizing dye effective in the present invention are shown below.

[0048]

[Chemical 3]

[0049]

[Chemical 4]

Of the above, cyanine dyes are particularly preferable.
A combined use of the sensitizing dye and the above-mentioned stabilizer is a preferred embodiment. The sensitizing dye used in the present invention may be added after chemical sensitization and before coating. The tabular emulsion of the present invention has a projected area diameter of 0.3 to 2.0 µm, particularly 0.5 to 1.2 µm.
Is preferred. The distance between parallel planes (particle thickness) is 0.05 μm to 0.3 μm, and particularly 0.1 to
It is preferably 0.25 μm, and the aspect ratio is preferably 3 or more and less than 20, particularly preferably 4 or more and less than 8. In the tabular silver halide emulsion of the present invention, silver halide grains having an aspect ratio of 2 or more account for 50% of all grains.
(Projected area) or more, particularly 70% or more, and the average aspect ratio of the tabular grains is preferably 3 or more, particularly 4 to 8.

Among the tabular silver halide grains, monodisperse hexagonal tabular grains are particularly useful grains. The details of the structure and manufacturing method of the monodisperse hexagonal tabular grain according to the present invention are described in JP-A-63-151618. The chemical sensitization method of the silver halide emulsion used in the present invention may be a sulfur sensitization method, a selenium sensitization method, a reduction sensitization method, a gold sensitization method, etc. in the presence of the above-described silver halide adsorbing substance. Known methods can be used, either alone or in combination.

The photographic emulsion used in the present invention may be used in the chemical sensitization step of the present invention for the purpose of preventing fog during the production process of a light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Various compounds can be contained in addition to the silver halide-adsorptive substance.

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

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

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

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

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

In the present invention, as a matting agent, US Pat. Nos. 2,992,101, 2,701,245 and 41,428 are used.
94, 4396706 homopolymers of polymethylmethacrylate or copolymers of methylmethacrylate and methacrylic acid, organic compounds such as starch, and fine particles of inorganic compounds such as silica, titanium dioxide, sulfuric acid, and strontium barium. You can
The particle size is 1.0 to 10 μm, especially 2 to 5 μm
Is preferred. In the surface layer of the photographic light-sensitive material of the present invention, as a slip agent, US Pat.
No. 047958 and other silicone compounds, Japanese Examined Patent Publication No. 5
In addition to the colloidal silica described in JP-A-6-23139, paraffin wax, higher fatty acid ester, den powder derivative and the like can be used.

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

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain the above-mentioned inorganic or organic hardener.

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

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

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

[0064]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to the examples. Example 1 (Preparation of octahedral particles A) Potassium bromide (0.1%) was added to 1 liter of water.
35 g of gelatin and 20.6 g of gelatin were added to a solution kept at 50 ° C. while stirring, with an aqueous solution of silver nitrate 40 cc (0.28 g as silver nitrate) and an aqueous solution of potassium bromide 40 cc (potassium bromide 0.
21 g) were added simultaneously by the double jet method in 10 minutes. Subsequently, 200 cc of an aqueous silver nitrate solution (1.42 g as silver nitrate) and 200 cc of an aqueous potassium bromide solution (1.06 g as potassium bromide) were simultaneously added over 8 minutes. After that, 27 cc of potassium bromide aqueous solution (2.7 g of potassium bromide) was added. Then, an aqueous silver nitrate solution and an aqueous mixed solution of potassium iodide and potassium bromide were added again by the control double jet method. The added silver nitrate aqueous solution was 1 liter (silver nitrate 14
At 0 g), the flow rate was 2 cc / min at the start of the addition, and the addition was accelerated directly to complete the addition in 70 minutes. While controlling the control potential to be pAg = 8.58, a mixed aqueous solution of potassium iodide and potassium bromide was simultaneously added. The amount of potassium iodide consumed here was 0.6 mol% with respect to the total silver amount. Subsequently, 0.1 mol% of 1% KI aqueous solution was added to the total silver amount over 1 minute.

After that, the temperature was lowered to 35 ° C. to remove soluble salts by the precipitation method. The temperature was again raised to 40 ° C., 30 g of gelatin, 2.35 g of phenoxyethanol and 0.8 g of sodium polystyrene sulfonate as a thickener were added, and pH 6.0 was adjusted with caustic soda. Thus, monodispersed silver iodobromide octahedral grains A having a diameter of 0.63 μm and a silver iodide content of 0.7 mol% were prepared. Chloraurate, sodium thiosulfate, and ammonium thiocyanate were added to A for optimal gold-sulfur sensitization, and then the sensitizing dyes A and B described below were added in the amounts shown below, and 4-hydroxy- 6-
Methyl-1,3,3a, 7-tetrazaindene 2 × 10
Stabilized at ^-2 mol. Sensitizing dye A 590mg / Ag mol

[0066]

[Chemical 5]

Sensitizing dye B 15 mg / Ag mol

[0068]

[Chemical 6]

(Preparation of Emulsion Layer Coating Solution) The following chemicals were added to the above chemically sensitized emulsions A-1, A-2, A-3, and A-4 per mol of silver halide for coating. It was a liquid.・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 mg ・ trimethylolpropane 9 g ・ dextran (average molecular weight 39,000) 18.5 g ・ potassium polystyrene sulfonate (average molecular weight) 600,000) 1.8 g-Gelatin Listed in Table-1 Polymer 1 Listed in Table-1 Polymer 6 Listed in Table-1 Polyacrylic acid Listed in Table-1 Hardener 1,2-bis (vinylsulfonyl) Acetamido) ethane Addition amount is adjusted so as to achieve the swelling rate shown in Table 1-Polymer 1, polymer 5 and polyacrylic acid are each added with an alkali to prepare a 7.5% by weight transparent aqueous solution at pH 7.0. It was prepared and added to the emulsion layer coating solution. The pH of the emulsion layer coating solution was 6.0.

(Preparation of Surface Protective Layer Coating Solution) 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 1.0 g / m ²

[0071]

[Chemical 7]

Polymethylmethacrylate (average particle size 3.7 μm) 0.087 Proxel (adjusted to pH 7.4 with NaOH) 0.0005 (Preparation of photographic material) Thickness 183 μ used as a support
As the polyethylene terephthalate of m, an undercoat layer containing 0.04 wt% of a dye having the following structure was previously applied.

[0073]

[Chemical 8]

An emulsion layer and a surface protective layer were coated on both sides of the transparent support by the simultaneous extrusion method. The coated silver amount on one side was 1.7 g / m ² . Thus, Table-1
I got the photographic material. (Evaluation of photographic performance) The photographic materials 101 to 116 are sharp cut filters SC5 manufactured by Fuji Photo Film Co., Ltd.
2 was used to provide a 0.1 second blue exposure from both sides. After exposure, automatic development processing was performed under the following conditions. The sensitivity is represented by the reciprocal of the ratio of the exposure amount that gives a density of 1.0, based on the photographic material 101. <Development processing conditions> Developer: Fuji Photo Film Co., Ltd. RD-10 Fixer: Fuji Photo Film Co., Ltd. RF-10 As an automatic processor, FP manufactured by Fuji Photo Film Co., Ltd.
Modify the M9000 to speed up the film transport speed,
The processing time for Dry to Dry was set to 30 seconds. Rinsing water was flowed at a rate of 3 liters per minute only while the film was passing through, and was stopped for the rest of the time. The developer and fixer replenishment and processing temperatures are And

(Evaluation of Roller Mark) Photographic Material 101
.About.116 were uniformly exposed in a size of 10.times.12 inches to a density of 1.0, and then processed under the same conditions as the evaluation of photographic performance. However, the carrying roller of the developing tank and the crossover roller from developing to fixing used at this time were intentionally fatigued rollers. The roller surface had irregularities of up to ± 10 μm. Depending on the photographic material, a large number of fine spots due to the unevenness of the roller were generated on the processed photosensitive material. This state was sensory-evaluated in the following four stages. The evaluation results are summarized in Table-1.

∘ ... Almost no spots are observed. ○… It is a level where there are slight spots, but this is not a problem for practical use. Δ: Spots are generated, but not on a normal roller. Acceptable level. × ... Many spots, which are not practical for ordinary rollers.

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

(Evaluation of Fixing Property) Each photographic material was subjected to an automatic developing process under the above-mentioned conditions while being unexposed, and then it was swallowed under a fluorescent lamp and observed to evaluate whether or not fixing was completed for the time being. The photographic material in which the cloudy portion was slightly absent was determined to have poor fixability. Needless to say, even if there is no problem in this evaluation, there may be a problem in image storability due to residual silver or residual hypo.

(Measurement of Swelling Ratio) With respect to each photographic material, the above-mentioned measurement was carried out by using RD-10 manufactured by Fuji Photo Film Co., Ltd. as a developing solution and RF-10 manufactured by Fuji Photo Film Co., Ltd. as a fixing solution. The swelling ratio of each step was measured according to the method. The results are summarized in Table-1 and Table-2.

[0080]

[Table 1]

[0081]

[Table 2]

Among the results shown in Table 2, photographic materials 101 to 103
When the amount of coated gelatin is 2.7 g / m ² , it is impossible to satisfy both the drying property and the fixing property. On the other hand, photographic material 10
In No. 4, when the amount of coated gelatin was 2.4 g / m ² , the drying property and the fixing property were satisfied, but the roller mark was significantly deteriorated. Here, when the polymer P-1 or P-6 of the present invention was used, all of the drying property, the roller mark, and the fixing property could be satisfied. Further, the photographic materials 113 to 116 using polyacrylic acid did not have the effect of improving the drying property.

Example 2 Preparation of tabular grains 4.5 g potassium bromide and 2 gelatin in 1 liter of water.
0.6 g, 5 of thioether HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH
% Aqueous solution (2.5 cc) and stirred in a container kept at 60 ° C. while stirring 37 cc aqueous silver nitrate solution (3.43 g silver nitrate), 33 cc aqueous solution containing 2.97 g potassium bromide and 0.363 g potassium iodide by the double jet method. For 37 seconds. Next, an aqueous solution containing 0.9 g of potassium bromide was added, and the temperature was raised to 70 ° C. to 53 cc of an aqueous silver nitrate solution (silver nitrate 4.
90 g) was added over 13 minutes. Here, 15 cc of 25% aqueous ammonia solution was added, and after physically aging for 20 minutes at that temperature, 14 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added by the control double jet method over 35 minutes while keeping the pAg at 8.5. Next, 10 cc of 2N potassium thiocyanate solution was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.26 mol%, an average projected area diameter of 1.10 µm, a thickness of 0.165 µm and a diameter variation coefficient of 18.5% were obtained.

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

[0085]

[Chemical 9]

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

[0087]

[Chemical 10]

(Preparation of Coating Sample) A coating sample was prepared by adding the following chemicals to 1 mol of T-1 silver halide to prepare a coating solution. -Gelatin As described in Table-2-Trimethylolpropane 9g-Dextran (average molecular weight 39,000) 18.5g-Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8g

[0089]

[Chemical 11]

(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-2 Polymer 1 Described in Table-2 Polymer 6 Described in Table-2 Polyacrylic acid Described in Table-2 Hardener 1.2-Bis (vinylsulfonyl) Acetamido) ethane Addition amount is adjusted so that the swelling rate shown in Table 2 may be obtained 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.015 g / m ²

[0091]

[Chemical 12]

[0092] Polymethyl methacrylate (average particle size 3.7μm) 0.087g / m ² Proxel (prepared in pH7.4 with NaOH) 0.0005g / m ² It is noted that polymer 1, polymer 5, polyacrylic acid, each alkali In addition, a transparent aqueous solution having a pH of 7.5% by weight was prepared and added to the surface protective layer coating solution. The pH of the surface protective layer coating solution was adjusted to 7.0. Preparation of Support (1) Preparation of Dye D-1 for Undercoat Layer The following dyes were ball milled by the method described in JP-A-63-197943.

[0093]

[Chemical 13]

2 parts of 434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were added.
Put in a liter ball mill. 20 g of dye were added to this solution. Zirconium oxide (ZrO) beads 40
0 ml (2 mm diameter) was added and the contents were crushed for 4 days. After this, 160 g of 12.5% gelatin was added. After defoaming, the ZrO beads were removed by filtration. Observation of the obtained dye dispersion revealed that the crushed dye had a wide range of particle diameters from 0.05 to 1.15 μm, and the average particle diameter was 0.37 μm. Further, a centrifugation operation was performed to remove dye particles having a size of 0.9 μm or more. Thus, Dye Dispersion D-1 was obtained. (2) Preparation of support Corona discharge treatment was performed on a biaxially stretched polyethylene terephthalate film having a thickness of 183 μm, and a first undercoating liquid having the following composition was applied to a coating amount of 5.1 cc / m ^2. It was applied with a wire bar coater and dried at 175 ° C. for 1 minute. Next, a first undercoat layer was similarly provided on the opposite surface. The polyethylene terephthalate used was one containing 0.04 wt% of the dye having the same structure as in Example-1. Butadiene-styrene copolymer latex solution (solid content 40% butadiene / styrene weight ratio = 31/69) 79cc

[0095]

[Chemical 14]

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

[0097]

[Chemical 15]

Matting agent Polymethylmethacrylate having an average particle size of 2.5 μm 2.5 mg / m ²

Preparation of photographic material On the prepared support, the above emulsion layer and surface protective layer were coated on both sides by the simultaneous extrusion method. The coated silver amount per one side was 1.75 g / m ² . The swelling ratio was adjusted as shown in Table 2 by adjusting the gelatin added to the emulsion layer and the amount of hardener. Thus, photographic materials 201 to 216 were obtained.

Evaluation of photographic performance X-ray orthoscreen HR- manufactured by Fuji Photo Film Co., Ltd. was used for each sample of photographic materials 101 and 201-216.
No. 4 was used to expose each side for 0.05 seconds to evaluate the sensitivity. After the exposure, the following processing was performed.
The sensitivity was expressed as the reciprocal of the ratio of the exposure amount giving a density of 1.0 with respect to the photographic material 1.

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

Processing II Automatic developing machine ... SRX50 manufactured by KONICA Co., Ltd.
The drive motor and gear of No. 1 were modified to speed up the transfer speed.

Developer ... Fuji Photo Film Co., Ltd.
RD-10 fixer manufactured by Fuji Photo Film Co., Ltd. RF-
10 Processing speed… Dry to Dry 30 seconds Development temperature… 35 ℃ Fixing temperature… 35 ℃ Drying temperature… 55 ℃ Replenishment amount… Developer 22ml / 10 × 12 inches Fixer 30ml / 10 × 12 inches

Evaluation of Dryness When the treatment II was performed, the dryness of the film was evaluated. The evaluation criteria were the same as in Example 1.

Evaluation of Roller Mark Each photographic material was evaluated in the same manner as in Example-1.

Evaluation of Color Remaining Property When Process II was carried out, the color remaining property of the film was evaluated. The evaluation criteria were made by visually comparing the actual films of Treatment I and Treatment II.

(Measurement of swelling ratio) The photographic materials were evaluated in the same manner as in Example-1. The above results are summarized in Table 3 and Table 4.

[0108]

[Table 3]

[0109]

[Table 4]

From the results shown in Table 4, it can be seen that the polymer of the present invention satisfies all of the dry roller mark and the residual color property without deteriorating the photographic performance.

Example 3 (Preparation of tabular grains) 4.5 g of potassium bromide, 12.0 g of gelatin and thioether HO (CH ₂ ) _{2 in} 1 liter of water.
Add _2.5 cc of 5% aqueous solution of S (CH ₂ ) ₂ S (CH ₂ ) ₂ OH and add 55 ℃
While stirring, 37 cc of an aqueous silver nitrate solution (3.43 g of silver nitrate), 33 cc of an aqueous solution containing 2.97 g of potassium bromide and 0.363 g of potassium iodide were added to the container kept at 37 ° C. for 37 seconds. Next, potassium bromide 0.
After adding 9 g of the aqueous solution, the temperature was raised to 70 ° C., and 53 cc of an aqueous silver nitrate solution (4.90 g of silver nitrate) was added over 13 minutes. Here, 8 cc of 25% aqueous ammonia solution was added, and after physically aging for 20 minutes at the same temperature, 7 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution of 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added by the control double jet method over 35 minutes while keeping the pAg at 8.5. Next, 10 cc of a 2N potassium thiocyanate solution and AgI fine particles having a diameter of 0.07 μm were used for the total amount of silver of 0.0
5 mol was added. After physically aging for 5 minutes at the same temperature, the temperature was lowered to 35 ° C. Thus, monodisperse tabular grains having a total silver iodide content of 0.31 mol%, an average projected area diameter of 0.61 μm, a thickness of 0.120 μm and a diameter variation coefficient of 16.5% were obtained.

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

Subsequently, chloroauric acid and potassium thiocyanate were added, and 40 minutes later, the mixture was cooled to 35 ° C. In this way, preparation of tabular grains T-2 was completed. (Preparation of emulsion coating solution) The following chemicals were added to 1 mol of silver halide of tabular grains T-2 to prepare an emulsion layer coating solution.・ 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 72 ・ Gelatin described in Table-3 ・ Polymer 1 described in Table-3 ・ Polymer 6 described in Table-3 ・ Polyacrylic acid Described in Table-3: Dextran (average molecular weight 39,000) 18.5 g-Sodium polystyrene sulfonate (average molecular weight 600,000) 1.8 g

[0114]

[Chemical 16]

[0115]

[Chemical 17]

Snowtex C (manufactured by Nissan Kagaku Co., Ltd.) 9.6 g as solid content Dextran (average molecular weight 39,000) 5.8 g Polymer 1, polymer 6 and polyacrylic acid are each added with an alkali. A 7.5% by weight transparent aqueous solution having a pH of 7.0 was prepared and added to the emulsion layer 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 so that each component had the following coating amount. -Gelatin Listed in Table-3 Polymer 1 Listed in Table-3 Polymer 5 Listed in Table-3 Polyacrylic acid Listed in Table-3 4-Hydroxy-6-methyl-1,3,3a, 7-tetra azaindenes 0.003 g / m ² · polymethylmethacrylate (average particle size 2.5μm) 0.05g / m ² · Proxel 0.0005 g / m ²

[0117]

[Chemical 18]

It should be noted that Polymer 1, Polymer 5 and polyacrylic acid were each added with an alkali to give a pH of 7.5 at 7.5.
A transparent aqueous solution of wt% was prepared and added to the surface protective layer coating solution. The coating solution for the surface protective layer had a pH of 7.0. Thickness 18 after being biaxially stretched and pre-coated
The prepared emulsion layer coating solution and surface protective layer coating solution were coated on one side on a 3 μm polyethylene terephthalate film by the simultaneous extrusion method. Coating silver amount is 2.55g / m ²
It was adjusted so that The used polythienylene terephthalate contains 0.04 wt% of the dye having the same structure as in Example-1.
What was contained was used.

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

[0120]

[Chemical 19]

[0121]

[Chemical 20]

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

[0123]

[Chemical 21]

C ₈ F ₁₇ SO ₃ K 1.7 mg / m ² · potassium polystyrene sulfonate (average molecular weight 600,000) 2 mg / m ² · NaOH 2.5 mg / m ² antihalation layer and its surface protective layer The simultaneous extrusion method was applied and dried simultaneously. The photographic material thus obtained was evaluated in the same manner as in Example-2, and the results are shown in the table.
It is summarized in 3, 5 and Table-6.

[0125]

[Table 5]

[0126]

[Table 6]

From the results shown in Tables 5 and 6, it is understood that the use of the polymer of the present invention satisfies all of the drying property, the roller mark and the residual color property without deteriorating the photographic performance.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one silver halide emulsion layer coated surface side is provided with a hydrophilic colloid layer in which a polymer represented by the following general formula [I] is dissolved in water and added by adding the aqueous solution. Silver halide photographic light-sensitive material. The general formula [I]-(A) _x- (B) _y -A is at least one polymerized monomer represented by the general formula [I], and B is an ethylenic unsaturated other than A copolymerizable with A. Monomer. x is 10 to 100 mol% y is 0 to 90 mol% General formula [II] X, Y, Z; a hydrogen atom, a substituted or unsubstituted alkyl group (C _{1 to} C ₈ ), —COOM, —COOR ₁ , and —C, respectively.
ONR ₂ R ₃ or a substituted or unsubstituted phenyl group, provided that
At least one of X, Y, and Z is a substituted or unsubstituted alkyl group (C _{1 to} C ₈ ), —COOR, —CONR ₂ R ₃ , or a substituted or unsubstituted phenyl group. R ₁ ; substituted or unsubstituted alkyl group (C _{1 to} C ₁₈ ), aryl group (C _{6 to} C ₁₈ ) or aralkyl group (C _{7 to} C ₁₂ ) R ₂ ; hydrogen atom, substituted or unsubstituted alkyl group (C _{1 to} C
_4), phenyl or aralkyl group _{(C 7 ~C 10) R 3} ; a hydrogen atom, R ₂ or - (R ₄ -CONH) _N -R
_4- COR ₅ R ₄ ; C ₁ -C ₁₂ aliphatic or aromatic divalent group R ₅ ; OM or -NR ₂ R ₃ M; hydrogen atom or cation N; integer from 0 to 6 2. A developing step for 8 seconds, a fixing step for 7 seconds, and a water washing step for 7 using a developing solution and a fixing solution which do not substantially contain a hardening agent.
The silver halide photograph according to claim 1, wherein the ratio of the swelling ratio at the completion of the washing step to the swelling ratio at the completion of the developing step is 1.0 or less when the development processing is carried out in seconds. Photosensitive material. 3. A developing step for 8 seconds, a fixing step for 7 seconds, and a water washing step for 7 using a developing solution and a fixing solution which do not substantially contain a hardening agent.
2. The silver halide photographic light-sensitive material according to claim 1, wherein the ratio of the swelling ratio at the completion of the water washing step to the swelling ratio of distilled water when the development processing is carried out in seconds is 1.0 or less. . (Here, the swelling ratio of distilled water is 60 ° C for photographic materials at 60 ° C.
Incubation treatment in 16% RH (percent relative humidity) for 16 hours, and change in thickness when immersed in distilled water at 21 ° C for 3 minutes shall be measured. 4. The ratio of the coating amount of one side of the polymer represented by the general formula [I] and gelatin (polymer content ratio) is represented by the following formula, and the value of the formula is 0.03 to 0. 3. The silver halide photographic light-sensitive material according to claim 2 or 3, characterized in that [Equation 1] 5. The silver halide photographic light-sensitive material according to claim 4, wherein in the developing step, the time from the start of processing to the end of processing (Dry to Dry processing time) is within 60 seconds.