JP2794251B2 - Silver halide photographic material - Google Patents

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 during processing and remarkably improves the occurrence of roller marks when processed by an automatic processor. The present invention relates to a photographic light-sensitive material having an ultra-rapid drying processability.

[0002]

2. Description of the Related Art In recent years, high-speed rapid processing has rapidly become widespread in the development process of photographic light-sensitive materials (hereinafter referred to as "sensitive materials"). It has been shortened. In order for rapid processing to be achieved,
A developer for achieving a sufficient sensitivity in a short time, a photosensitive material which is excellent in development progress and gives a sufficient degree of blackening in a short time, and a property of drying in a short time after washing with water are required. As a commonly used method for improving the drying property of a light-sensitive material, a sufficient amount of a hardening agent (gelatin cross-linking agent) is added in advance in the coating step of the light-sensitive material, and then development-fixation- There is a method of reducing the water content in the light-sensitive material before the start of drying by reducing the amount of swelling of the emulsion layer or the hydrophilic colloid layer in the washing step. In this method, if a large amount of hardener is used, the drying time can be shortened accordingly, but the swelling amount becomes small, so that the development is delayed, the sensitivity becomes low, the tone becomes soft, and the covering power decreases. The inconvenience of doing so occurs. Even if the development progress is improved, a delay in the fixing speed due to the high hard film causes problems such as residual silver, residual hypo, and residual color of the sensitizing dye, which is an obstacle to shortening the processing time.

On the other hand, a method for increasing the developing activity of a processing solution is also known, and it is possible to increase the amount of a main agent and an 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 the disadvantage that the preservability of the processing solution is impaired, and even if the sensitivity is increased, the processing solution is softened or easily damaged.

For the purpose of improving the above-mentioned viewpoints, a technique using tabular silver halide grains is disclosed in US Pat. Nos. 4,439,520 and 4,425,42.
No. 5, etc. Also, JP-A-63-3053
No. 43 and JP-A-1-77047, the development starting point of a silver halide grain having a (111) plane is defined as the vertex of the grain and / or
Alternatively, there is disclosed a technology for improving development progress and sensitivity / fogging ratio by controlling the ridge and its vicinity. Further, Japanese Patent Application Laid-Open No. 58-111933 discloses that the swelling of a hydrophilic colloid layer using tabular particles is set to 200% or less, thereby providing high covering power and eliminating the need to add a hardening layer during processing. Photographic elements for radiography are disclosed. These known techniques are excellent techniques for improving the development progress of the light-sensitive material, and have high utility value. However, if the processing time in each of the development-fixing-washing steps is shortened, photographic sensitivity is reduced, and residual silver and residual hypo are deteriorated due to deterioration of fixability. Further, in the case of a sensitized material which has been subjected to spectral sensitization with a sensitizing dye, the problem of residual color also appears. These problems other than photographic properties have limitations in the improvement by modifying silver halide grains, and ultimately result in problems of film quality. That is, the thickness of the hydrophilic colloid layer determines the fixing, which is an obstacle to speeding up.

In this regard, Japanese Patent Application Laid-Open No. Sho 64-7333 discloses
No. 3, JP-A-64-86133, JP-A-1-1052
No. 44, JP-A-1-158435, JP-A-1-158
No. 436 or the like, the amount of gelatin on the side having a hydrophilic colloid layer including a silver halide emulsion layer is from 2.00 to 3.50 g.
/ M ² , and a means for achieving ultra-rapid processing with a total processing time of 20 seconds or more and less than 60 seconds by combining with other technical elements is disclosed. Also, Japanese Patent Application Laid-Open No. 2-6885
No. 37 discloses means for achieving ultra-rapid processing by adjusting the weight ratio of silver to gelatin (silver / gelatin) of the photosensitive silver halide applied to the emulsion layer to 1.5 or more. . Further, JP-A-63-221341 discloses that silver halide grains in an emulsion layer mainly consist of tabular grains having a grain size of 5 times or more the grain thickness, and a gelatin amount of 2.00 to 3.20 g / g. It discloses a means for achieving ultra-rapid processing with a total processing time of 20 seconds or more and less than 60 seconds by setting the melting time to 8 minutes or more and 45 minutes or less with m ² .

However, when examining these prior arts, when the amount of gelatin is reduced or the ratio of silver / gelatin is increased while keeping the amount of coated silver constant, roller marks and abrasion blackening significantly deteriorate. As a result, it was found that the level finally became unacceptable for practical use, and as a result, it was impossible to complete the product as a product capable of ultra-rapid processing.

[0007] 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 minute irregularities on the surface of a transport roller, resulting in black spot-like density unevenness. The term "abrasion blackening" refers to a phenomenon in which, when a film is handled, the film is rubbed together, or when the film is rubbed with another substance, abrasion-like blackening occurs after development processing. When the total processing time is set to 60 seconds or less, particularly 40 seconds or less, an appropriate time distribution of the developing / fixing / washing steps is performed. As a result, if the gelatin coating amount is not 2.5 g / m ² or less, the automatic developing machine When the installation environment was at a high humidity or the like, there was a case where the drying property was hindered. On the other hand, such a reduction in the amount of gelatin applied is not acceptable in terms of roller marks and abrasion blackening.

[0008] As described above, it is not possible to satisfy the respective properties of the drying property, the pressure property, and the fixing property (or residual color property) only by adjusting the gelatin coating amount.

It is well known that a photographic material uses polyurethane and is used together with gelatin which is a hydrophilic colloid. For example, Japanese Patent Publication No. 50-3
No. 6365, JP-A-56-067841, JP-A-61-1.
No. 45556, No. 62-56651, British Patent 134
Nos. 5741 and 2063500, European Patent 0852
No. 48, West German Patent Nos. 1472746 and 3445790
No. 3,607,289 discloses an attempt to use ionic polyurethane for improving the brittleness and sensitivity of a gelatin film. However, most of the anionic polyurethanes disclosed in such patents have sulfonic acid or a salt thereof or phosphoric acid or a salt thereof introduced at a terminal, and are compounds insoluble in water or alkali. Therefore, the effect of controlling the swellability after the treatment as in the present invention is not sufficient, and therefore there is no effect of improving the drying property during the treatment.

On the other hand, British Patent 867,539 discloses an antihalation layer using a water-soluble polyurethane having an anionic group. However, there is no mention in the patent of shortening the drying time of the photosensitive material. Furthermore, generally speaking, a large amount of a water-soluble anionic polymer antistatic agent is used in a hydrophilic colloid layer, and a large amount of a gelatin hardener is used to improve the physical properties of the film. Required. If an attempt is made to reduce the drying load due to the swelling property after the treatment as in the present invention, problems such as residual silver and residual hypo are caused as described in JP-A-58-111933. In fact, all of the examples of the British patent apply ionic polyurethane directly to the support and are not used with hydrophilic protective colloids such as gelatin.

Further, in photographic materials, it is well known that a polymer having a carboxyl group or its salt structure other than polyurethane is used and that it is used together with gelatin which is a hydrophilic colloid. For example, JP-B-57-53587 and JP-B-57-15375, West German Patent 1,745,061, JP-B-49-23827, JP-B-55-14415, JP-A-55-15267, and JP-A-Showa 4
8-89979, U.S. Pat. Nos. 2,279,410 and 3,791,831 and JP-B-47-28937 disclose attempts to use a polymer having a carboxyl group for preventing static electricity of a photographic light-sensitive material. I have. However,
There is no mention of controlling the swelling ratio of the hydrophilic colloid layer and shortening the drying time of the photosensitive material by using this kind of anionic polymer antistatic agent. As described above, anionic antistatic agents are generally used in a large amount in a specific hydrophilic colloid, and a large amount of a gelatin hardener is often used in order to improve film physical properties. If an attempt is made to reduce the drying load by controlling the swellability after the treatment as in the present invention, problems such as residual silver and residual hypo are caused as described in JP-A-58-111933.

Also, European Patent Nos. 75231 and 1670
No. 81, JP-A-53-7231, JP-A-60-12664
4, JP-A-60-156056, JP-A-2-20861
No., JP-B-1-14574, U.S. Pat. No. 4,142,894
Discloses a polymeric 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. Such coarse particles include, as in the present invention, The function of controlling the swelling after the treatment is not sufficient.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material exhibiting excellent drying properties during processing, particularly in rapid processing. A second object of the present invention is to provide a silver halide photographic light-sensitive material which has excellent drying properties and has a sufficient level of practical use for roller marks and abrasion blackening. A third object of the present invention is to provide a silver halide photographic light-sensitive material which satisfies the above objects, has high sensitivity, high covering power, and is excellent in rapid processing suitability.

[0014]

The above object of the present invention has been attained by the following method. At least one on the support
A silver halide photographic light-sensitive material having a silver halide photographic light-sensitive layer, wherein at least one hydrophilic colloid layer contains at least one kind of polyurethane or a salt thereof soluble in water or alkaline water having a carboxyl group , Or
First, the swelling ratio of the photosensitive material with distilled water (here,
The swelling ratio due to water means that a photosensitive material is heated at 40 ° C and 60% RH (=
(Percent relative humidity) for 16 hours
And the thickness when immersed in distilled water at 21 ° C. for 3 minutes.
This represents the rate of change only. Complete the washing process during the development process
The silver halide photographic material ratio of swelling ratio Ryoji is characterized der Rukoto 1.0.

A preferred embodiment of the present invention is the following [I]
To [III]. [I] a polyurethane or a salt thereof is dissolved in an aqueous medium,
The above silver halide photographic material, wherein the hydrophilic colloid layer contained by the addition of the solution is contained on the side where the silver halide emulsion layer is coated. [II] In the composition of the hydrophilic colloid having the silver halide photographic photosensitive layer on the support, the weight of the polymer having the acid residue is divided by the sum of the weight of gelatin and the polymer having the acid residue. The silver halide photographic light-sensitive material as described above, wherein the determined value is from 0.01 to 0.3. [III] The silver halide photographic material as described above, wherein a period from the start of processing to the end of processing (Dry to Dry processing time) is 60 seconds or less in the development processing step.

Hereinafter, the present invention will be described in detail. As described above, it is well known to use a polyurethane or a polymer having a carboxyl group or a salt structure thereof in a photographic material, but it has a carboxyl group in the structure on the side where the silver halide emulsion layer is coated. The photosensitive material contains polyurethane or a salt thereof , and the swelling ratio of the photosensitive material with distilled water (here
The swelling ratio with distilled water means that a photosensitive material is heated at 40 ° C. and 60%
Incubate at RH (= percent relative humidity) for 16 hours
And then immersed in distilled water at 21 ° C for 3 minutes.
It shows the rate of change of thickness when it is pressed. ) Against water during development processing
By the child to the ratio of the swelling rate during the washing process is complete 1.0 or less, excellent be photographic material can be obtained drying the rapid processing was surprising effect of unexpected.

Hereinafter, the water-soluble polyadduct of the present invention will be described. The polyurethane of the present invention is basically synthesized using diol and diisocyanate as reactive components, and is characterized in that at least one of the diol components has a carboxyl group in the structure. When the component containing a carboxyl group is present in a neutralized form, a form such as an alkali metal salt (for example, Na or K salt) or an ammonium salt (for example, a salt of trimethylamine) is preferable, and an alkali metal salt is particularly preferable. Examples of the diol having a carboxyl group include 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxymethyl) butanoic acid,
Examples thereof include 2,5,6-trimethoxy-3,4-dihydroxyhexanoic acid and 2,3-dihydroxy-4,5-dimethoxypentanoic acid, but are not particularly limited thereto.

Examples of the diol having no carboxyl group include alkyl diols and polyether polyols. More specifically, for example, the following may be mentioned, but the present invention is not limited thereto. Ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 2,2-dimethyl -1,
3-propanediol, 1,2-pentanediol,
1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 3,3-dimethyl-
1,2-butanediol, 2-ethyl-2-methyl-
1,3-propanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol, 2-methyl-2,4
-Pentanediol, 2,2-diethyl-1,3-propanediol, 2,4-dimethyl-2,4-pentanediol, 1,7-heptanediol, 2-methyl-2-
Propyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1,3-
Hexanediol, 1,2-octanediol, 1,8
-Octanediol, 2,2,4-trimethyl-1,3
-Pentanediol,

Diethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol, hexaethylene glycol, heptaethylene glycol, dipropylene glycol, tripropylene glycol and the like.

Preferred diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, tolidine diisocyanate, hexamethylene diisocyanate, and isophorone. Diisocyanate, p-phenylene diisocyanate, transcyclohexane 1,4-diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated hexamethylene diisocyanate, lysine diisocyanate, tetramethyl xylene Examples include, but are not limited to, isocyanate and trimethylhexamethylene diisocyanate.

Various combinations of the above diols and diisocyanates can be selected from the viewpoints of the solubility of the polyadduct, the hydrophilicity / hydrophobicity, the compatibility with the hydrophilic colloid, and the ease of production of the polyadduct.

The composition ratio of the polyadduct of the present invention can vary depending on the diol other than the diol having a carboxyl group, the hydrophilicity / hydrophobicity of the diisocyanate, and the like. Is preferably from 5 to 50 for all components
Mol%, particularly preferably 10 to 50 mol%.

The method for synthesizing these acid-containing polyurethanes is as follows:
"Polyurethane Handbook" by Gunter Otel
(Gunter Oertel: Polyurethane Handbook) p. 21
(1985), edited by Shunsuke Murahashi et al., “Synthetic Polymers” V p. 3
It is convenient to carry out with reference to the methods described in 09-359 and the like. It goes without saying that the polyaddition initiator, concentration, polyaddition temperature, reaction time and the like can be widely and easily changed according to the purpose.

Preferred examples of the water-soluble polyadduct of the present invention are shown below by way of non-dissociated carboxylic acids, but the present invention is not limited thereto. Represent). P-1 2,2-bis (hydroxymethyl) propionic acid, / 4,4'-diphenylmethane diisocyanate (50/50) polyadduct P-2 2,2-bis (hydroxymethyl) propionic acid, / tri Diisocyanate (50/50) polyadduct P-3 2,2-bis (hydroxymethyl) propionic acid / hexamethylene diisocyanate (50/50)
Polyadduct P-4 2,2-bis (hydroxymethyl) propionic acid, / 1,5-naphthylene diisocyanate (50/5
0) Polyadduct P-5 2,2-bis (hydroxymethyl) propionic acid, / isophorone diisocyanate (50/50) polyadduct P-6 2,2-bis (hydroxymethyl) propionic acid, / m -Tetramethylxylylene diisocyanate (50/50) polyadduct P-7 2,2-bis (hydroxymethyl) propionic acid, / 4,4'-diphenylmethane diisocyanate /
Hexamethylene diisocyanate / tetraethylene glycol (32.5 / 40/10 / 17.5) polyadduct P-8 2,2-bis (hydroxymethyl) propionic acid, / 4,4'-diphenylmethane diisocyanate /
Hexamethylene diisocyanate (50/45/5) polyadduct P-9 2,2-bis (hydroxymethyl) propionic acid, / 4,4'-diphenylmethane diisocyanate /
Hexamethylene diisocyanate / 1,4-butanediol (42.5 / 35/15 / 7.5) polyadduct P-10 2,2-bis (hydroxymethyl) propionic acid, / 4,4'-diphenylmethane Diisocyanate /
Hexamethylene diisocyanate / triethylene glycol (35/40/10/15) polyadduct P-11 2,2-bis (hydroxymethyl) butanoic acid,
/ 4,4'-diphenylmethane diisocyanate (50
/ 50) polyadduct P-12 2,2-bis (hydroxymethyl) butanoic acid,
/ Tolylene diisocyanate (50/50) polyadduct P-13 2,2-bis (hydroxymethyl) butanoic acid,
/ Hexamethylene diisocyanate (50/50) polyadduct P-14 2,2-bis (hydroxymethyl) butanoic acid,
/ 1,5-Naphthylene diisocyanate (50/50)
Polyadduct P-15 2,2-bis (hydroxymethyl) butanoic acid,
/ Isophorone diisocyanate (50/50) polyadduct P-16 2,2-bis (hydroxymethyl) butanoic acid,
/ M-tetramethylxylylene diisocyanate (50
/ 50) polyadduct P-17 2,2-bis (hydroxymethyl) butanoic acid,
/ 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / tetraethylene glycol (32.5 / 40/10 / 17.5) polyadduct P-18 2,2-bis (hydroxymethyl) butanoic acid ,
/ 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate (50/45/5) polyadduct P-19 2,2-bis (hydroxymethyl) butanoic acid,
/ 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / 1,4-butanediol (42.5 / 35/15 / 7.5) polyadduct P-20 2,2-bis (hydroxymethyl ) Butanoic acid,
/ 4,4'-diphenylmethane diisocyanate / hexamethylene diisocyanate / triethylene glycol (35/40/10/15) polyadduct

An example of synthesizing the polyurethane of the present invention is shown below.
2,2-bis (hydroxymethyl) propionic acid
39 g, 4,4'-diphenylmethane diisocyanate 19.25 g, hexamethylene diisocyanate 5.5
4 g and 1.35 g of 1,4-butanediol were dissolved in 60 g of dimethylacetamide with stirring at room temperature, and 0.08 g of di-n-butyltin dilaurate was added. 90 ° C
, And diluted with 60 g of dimethylformamide and 120 g of methanol. Add methanol 150
After adding 12.5 g of acetic acid diluted with ml, the mixture was cooled to room temperature and precipitated by pouring into 2 liters of water to obtain the desired polyurethane in a yield of 37 g. (99% yield)

In a preferred embodiment of the present invention, the molecular weight of the acid-containing polyurethane added to the hydrophilic colloid is preferably at least 5 × 10 ³ , particularly preferably 1 × 10 ⁴ to 5 × 10 ⁶ (all of which have a weight-average molecular weight). ). The amount of acid added polymer, different but the type of the photosensitive ^{material, 0.01g / m 2 ~2g / m} 2 is preferred. More preferably, it is 0.05 g / m ² to ¹ g / m ² .
More preferably from ^{0.05g / 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 may be contained in all the hydrophilic colloid layers. It need not be added to the layer. When two or more hydrophilic colloid layers are coated with the acid-containing polyurethane of the present invention, the amount of the acid-containing polyurethane in each layer can be arbitrarily changed.

The neutralization ratio of the acid-containing polyurethane preferably used in the present invention can vary depending on the type and amount of the hydrophobic monomer or the structure of the repeating unit having a carboxyl group. Depending on the sum, a salt structure may be formed, or some of the acid residues may remain in the acid structure. Basically, the neutralization ratio is set based on the range in which the acid-containing polyurethane becomes soluble when mixed with a hydrophilic colloid, or an alkali or the like is added during the dissolution. It may be solubilized.

When the water-soluble polyurethane of the present invention is used, it must be dissolved in water and introduced into the photographic material by adding the aqueous solution. Upon dissolution, it is preferable to use an appropriate alkali. Any kind of alkali can be used as long as it can form a salt with an acid-containing polyurethane. As an example, potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonia and the like can be mentioned. These alkalis may be used alone or in an appropriate combination as a mixture. Further, a water-miscible organic solvent (for example, acetone, methanol, ethanol, acetonitrile, dimethylsulfoxide, dimethylacetamide, etc.) may be used as an auxiliary solvent.

As the hydrophilic colloid forming the hydrophilic colloid layer containing the water-soluble copolymer of the present invention, gelatin is preferably used. As gelatin, lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin is used. A hydrolyzate or enzymatic hydrolyzate of gelatin can also be used. In addition, hydrophilic colloids other than gelatin can be preferably used by mixing with gelatin.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates, sodium alginate, dextran and starch derivatives. Saccharide derivatives; various kinds of synthetic hydrophilicity such as single or copolymer of 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 dextran or polyacrylamide having an average molecular weight of 50,000 or less together with gelatin. JP 6
The methods described in 3-68837 and 63-149641 are also effective in the present invention.

When the water-soluble copolymer of the present invention and the hydrophilic binder are mixed and then coated, the pH of the coating liquid is 6.0 to 9 for the coating liquid for forming the non-photosensitive layer. .0 is preferred. More preferably, it is 6.5 to 8.0, and still more preferably 7.0 to 7.5. The coating liquid for forming the silver halide emulsion layer preferably has a pH of 5.0 to 8.0. More preferably, 5.5 to 7.0, even more preferably, 5.8 to
6.5.

The ratio of the water-soluble copolymer to 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 must be 0.01 to 0.3. Is preferred. Polymer ratio = (coating amount of water-soluble polyurethane containing carboxyl group component) / (coating amount of water-soluble polyurethane containing carboxyl group component + coating amount of gelatin) at the completion of the development step referred to in the present invention , The swelling ratio at the completion of the washing step, and the swelling ratio of distilled water are represented by the following equations, respectively.

[0034]

(Equation 1)

Here, the thickness at the completion of the developing step means the thickness when the photographic material is immersed in a developing solution at 35 ° C. for 25 seconds. The thickness of the layer at the completion of the washing step means that the photographic material is continuously processed in the order of development → fixing → water washing under the conditions of a developing step of 35 ° C. for 25 seconds, a fixing step of 35 ° C. for 20 seconds, and a washing step of 20 ° C. for 20 seconds. Means the thickness of the layer at the end of the washing step. The layer thickness when immersed in distilled water means the layer thickness when the photographic material is immersed in distilled water at 21 ° C. for 3 minutes. The photographic material used here was incubated at 40 ° C. and a relative humidity of 60% RH for 16 hours.

In measuring the thickness of the layer under each condition when obtaining the swelling ratio in each step in the present invention, US Pat.
41872 is defined by the method described in Example 12 (however, the measuring portion of the measuring device is made of ceramic).

The term "a developer and a fixer substantially free of a hardener" as used in the present invention means a developer and a fixer substantially free of a compound referred to in the art as a hardener. Specifically, RD-10 manufactured by Fuji Photo Film Co., Ltd. is used as a developing solution, RF-10 manufactured by Fuji Photo Film Co., Ltd. is used as a fixing solution, and RF-produced by Fuji Photo Film Co., Ltd. is used as a fixing solution. 10 can be mentioned.

According to the present invention, the ratio of the swelling ratio at the completion of the washing step to the swelling ratio at the completion of the developing step can be 1.0 or less. This means that the photographic material has excellent drying properties without hindering the developing process. 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 made 1.0 or less. This means that the photographic material has excellent drying properties without hindering the development process.

The photographic material using the water-soluble copolymer of the present invention is suitable for rapid processing. In particular, the dry-to-dry processing time is preferably within 60 seconds. More preferably, it is within 45 seconds, and further preferably, it is 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 light-sensitive silver halide emulsion layer may be provided on both sides of the support. May be. The light-sensitive material of the present invention may have a hydrophilic colloid layer in addition to the light-sensitive silver halide emulsion layer, if necessary. For example, a protective layer is preferably provided.

The amount of gelatin preferably used as a hydrophilic binder in the photographic material of the present invention is not particularly limited, but is preferably 1.5 g / m ² to 1.5 g / m ² per side.
4.5 g / m ² is preferred. In addition, 1.8 g / m ^{2 to} 3.6
g / 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 is 200% or more in consideration of the problem of residual silver and residual hypo due to rapid processing or the problem of residual color of a sensitized material spectrally sensitized with a sensitizing dye. Is particularly preferred.

Next, the emulsion grains preferably used in the present invention will be described. The average equivalent sphere particle size of the same volume as the particles is preferably 0.4 μm or more. In particular, it is preferably from 0.5 to 2.0 μm. The narrower the particle size distribution, the better. The silver halide grains in the emulsion may have a regular crystal form such as cubic or octahedral, or an irregular crystal form such as spherical, plate-like or potato-like. Or a mixture of particles of various crystal forms. Silver iodobromide is preferred as the silver halide composition because of its high sensitivity.

The silver halide grains of the present invention may contain a trace amount of silver chloride which does not affect photographic properties, but desirably does not. As the emulsion of the present invention, both a monodisperse emulsion and a 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.

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

There are no particular restrictions on the various additives used in the light-sensitive material of the present invention.
Japanese Patent Application Laid-Open No. 39-3939 can use those described in the following relevant places. Item The relevant place 1 Silver halide emulsion and its production From line 6 on the lower right column on page 8 of JP-A-2-68539 to line 12 on the upper right column on page 10 of the same. 2 Chemical sensitization method: From page 10, upper right column, line 13 to lower left column, line 16 of the same. 3 Antifoggants / stabilizers: From page 17, lower left column, line 17 to page 11, upper left column, line 7 and from page 3, lower left column, line 2 to page 4, lower left column. 4 Spectral sensitizing dyes, page 4, lower right column, line 4 to page 8, lower right column. 5 Surfactant / Antistatic agent: from page 11, upper left column, line 14 to page 12, upper left column, line 9; 6. Matting agent, slip agent, plasticizer Same as page 12, top left column, line 10 to top right column, line 10. From page 10, line 10 in the lower left column to line 1 in the lower right column. 7 Hydrophilic colloid Same as page 12, line 11 from the upper right column to line 16 from the lower left column. 8 Hardener From page 12, lower left column, line 17 to page 13, upper right column, line 6; 9 Support: From page 7, line 7 to line 20 in the upper right column. 10 Dyes and mordants Same as above, page 13, lower left column, line 1 to page 14, lower left column, line 9. 11 Developing method JP-A-2-103737, page 16, upper right column, line 7 to page 19, lower left column, line 15; From page 3, lower right column, line 5 to page 6, upper right column, line 10 of JP-A-2-15837.

[0046]

The present invention will be further described below with reference to examples. Example 1 (Preparation of tabular grains) 4.5 g of potassium bromide, 20.6 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 60 ℃
While stirring, 37 cc of an aqueous solution of silver nitrate (3.43 g of silver nitrate), 33 cc of an aqueous solution containing 2.97 g of potassium bromide and 0.363 g of potassium iodide were added to the container kept for 37 seconds by the double jet method. Next, add potassium bromide 0.
After adding 9 g of the aqueous solution, the temperature was raised to 70 ° C., and 53 cc of 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 mixture was physically ripened at the same temperature for 20 minutes, and then 14 cc of a 100% acetic acid solution was added. Subsequently, 133.3g of silver nitrate
And an aqueous solution of potassium bromide were added over 35 minutes by a controlled double jet method while maintaining the pAg at 8.5. Next, 10 cc of a 2N potassium thiocyanate solution was added. After physical aging at the same temperature for 5 minutes, 3
The temperature was lowered to 5 ° C. Thus, the total silver iodide content is 0.1.
26 mol%, average projected area diameter 1.10 μm, thickness 0.
Monodispersed tabular grains having a diameter of 165 μm and a coefficient of variation of 18.5% were obtained.

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

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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 40 minutes, it was cooled to 35 ° C. Thus, the tabular grains T-
Preparation 1 was completed. Selenium compound-1

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

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(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 described in Table-1 ・ Polymer 2 described in Table-1 ・ Polymer 18 described in Table-1 ・ Polyacrylic acid described in Table-1 Hardener 1,2- Bis (vinylsulfonylacetamido) ethane Addition amount is adjusted so as to obtain the swelling ratio shown in Table 1. 4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 0.015 g / m ²

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[0055] Polymethyl methacrylate (average particle size 3.7 .mu.m) 0.087 g / m ² · Proxel (prepared in pH7.4 with NaOH) 0.0005 g / m ² In addition, the polymer 2, polymer 18, polyacrylic acid Each was adjusted to pH 7.0 by adding an alkali. 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.

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434 ml of water and 791 ml of a 6.7% aqueous solution of Triton X-200 surfactant (TX-200) were placed in a 2 liter ball mill. 20 g of the dye were added to this solution. Zirconium oxide (ZrO) beads 400
ml (2 mm diameter) was added and the contents were ground for 4 days. Thereafter, 160 g of 12.5% gelatin was added. After defoaming, the zirconium oxide beads were removed by filtration. Observation of the obtained dye dispersion showed that the particle size of the pulverized dye had a wide distribution ranging from 0.05 to 1.15 μm in diameter, and the average particle size was 0.37 μm. Furthermore, dye particles having a size of 0.9 μm or more were removed by centrifugation. Thus, a dye dispersion D-1 was obtained.

(2) Preparation of Support A corona discharge treatment was applied to a biaxially stretched 183 μm-thick polyethylene terephthalate film, and a first coating solution having the following composition was applied in an amount of 5.1 cc / m ² . It was applied by 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 contained a dye having the following structure at 0.04% by weight.

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

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A 2% aqueous solution of 2,4-dichloro-6-hydroxy-s-triazine sodium salt 20.5 cc distilled water 900.5 cc A second undercoat having the following composition on the first undercoat layer on both sides. The layer was applied and dried at 150 ° C. by a wire bar coater method on one side and on both sides so that the application amount was as described below.・ Gelatin 160 mg / m ²・ Dye dispersion D-1 (26 mg / m ² as a solid dye)

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Matting agent 2.5 mg / m ² of polymethyl methacrylate having an average particle size of 5 μm

Preparation of photographic material The emulsion layer and the surface protective layer were coated on both sides of the prepared support by a simultaneous extrusion method. The amount of silver applied per side was 1.75 g / m ² . The coating gelatin amount, the acid-containing polyurethane coating amount, and the swelling ratio determined by the freeze-drying method using a liquid nitrogen method were adjusted according to the amount of gelatin and the hardener added to the emulsion layer and set as shown in Table 1. Thus photographic material 1
01-116 were obtained. Further, as a comparative material, a material containing A in the surface protective layer was set as shown in Table 1, and photographic material 1 was prepared.
17-120 were obtained. (A was insoluble in water, so it was dissolved in dimethylformamide, and then added after being dispersed in water.)

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Evaluation of Photographic Materials Each sample of the photographic materials 101 to 120 was exposed for 0.05 seconds from both sides using an X-ray orthoscreen HR-4 manufactured by Fuji Photo Film Co., Ltd. to evaluate the sensitivity. Was done. After the exposure, the following processing was performed. Sensitivity is photographic material 10
It was shown as the reciprocal of the ratio of the exposure amount giving a density of 1.0 based on 1.

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

Processing II Automatic developing machine: SRX50 manufactured by KONICA CORPORATION
The transport speed has been increased by modifying the drive motor and gear section of No. 1. Developer: RD- manufactured by Fuji Photo Film Co., Ltd.
10 Fixer: Fuji Photo Film Co., Ltd. RF-
10 Processing speed: Dry to Dry 30 seconds Developing temperature: 35 ° C. Fixing temperature: 35 ° C. Drying temperature: 55 ° C. Replenishment amount: Developing solution 22 ml / 10 × 12 inches Fixing solution 30 ml / 10 × 12 inches

(Evaluation of Roller Mark) Photographic Material 101
１２０120 were uniformly exposed to a size of 10 × 12 inches so as to have a density of 1.0, and then processed under the same conditions as in the evaluation of photographic performance. However, the roller used for transporting the developing layer and the crossover roller from development to fixing used here were intentionally fatigued. ± on the roller surface
Unevenness extending to 10 μm was present. The processed photographic material had many fine spots due to the unevenness of the roller depending on the photographic material. The state was sensory evaluated in the following four stages. Table 2 summarizes the evaluation results.

A: Almost no spots are 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. ×: Many spots occur, and even a normal roller is not practical.

(Evaluation of Drying Property) In the developing treatment II, when each photographic material having a size of 4 pieces was continuously processed, the dryness of the film was organoleptically evaluated by touch. The film was continuously processed with the short side in the transport direction. Table 2 summarizes the results. ◎ 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. The temperature when touched was similar to that of a film left at room temperature. △ At the 30th sheet, the film was somewhat cold, but the continuously processed film did not adhere and was at a practically acceptable level. × At the 30th sheet, the film was wet and undried. Films adhere to each other.

Evaluation of Residual Color When the treatment II was performed, the residual color of the film was evaluated. The evaluation criteria were determined by visually comparing the intact films of Process I and Process II.

(Measurement of Swelling Ratio) For each photographic material, the above-mentioned measurement was carried out 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 Tables 1 and 2.

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[Table 1]

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[Table 2]

From the results in Table 2, it can be seen 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.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/79 501 G03C 1/04

Claims (4)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide photographic layer on a support, wherein at least one hydrophilic colloid layer has a carboxyl group-containing water-soluble or alkali-water-soluble polyurethane. Or at least one salt thereof , and the photosensitive material
Is the swelling ratio with distilled water (where the swelling ratio with distilled water is
Means that the photosensitive material is 40 ° C. and 60% RH (= percent relative)
Humidity) for 16 hours, followed by 2 more hours.
Table shows the rate of change in thickness when immersed in distilled water at 1 ° C for 3 minutes.
You. ) For the swelling ratio at the completion of the water washing step during development
Silver halide photography having a ratio of 1.0 or less
True photosensitive material. 2. The method according to claim 1, wherein the polyurethane or a salt thereof is dissolved in an aqueous solvent, and the hydrophilic colloid layer contained by adding the solution is contained on the side on which the silver halide emulsion layer is provided. The silver halide photographic light-sensitive material as described above. 3. A silver halide photographic light-sensitive layer on a support.
In the composition of the hydrophilic colloid on the side of
The weight of the polymer to be mixed is determined by the amount of gelatin and
When the value divided by the sum of the weights of the rimmers is 0.01 to 0.3,
3. The silver halide photographic feeling according to claim 1 or 2.
Light material. 4. A process from the start of processing in the developing process.
Until processing ends (DrytoDry processing time) is within 60 seconds
The method according to any one of claims 1 to 3, wherein
Silver halide photographic light-sensitive material.