EP0564304A1

EP0564304A1 - Process for producing light-sensitive silver halide photographic material

Info

Publication number: EP0564304A1
Application number: EP93302626A
Authority: EP
Inventors: Takeo Konica Corporation Arai; Kenichi Konica Corporation Tanaka; Akio Konica Corporation Fujita
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1992-04-02
Filing date: 1993-04-02
Publication date: 1993-10-06
Also published as: JPH05281655A

Abstract

A process for producing a light-sensitive silver halide photographic material. The process comprises steps of (1) coating one or more layers including at least one silver halide emulsion layer on a support, (2) drying the one or more layers, and (3) winding up the support with the dried coating layers. In the above process, the total amount of gelatin provided on the emulsion coated side of the support is not more than 2.9 g per square meter, and the surface of the coating layers is contacted to air having an absolute humidity not higher than 0.5 % or a relative humidity not higher than 5 % for a time not shorter than 5 seconds at a time after completion of drying step and before start of winding up. Light-sensitive materials produced by the process has a high dimension stability during photographic processing.

Description

FIELD OF THE INVENTION

The present invention relates to a process for producing a light-sensitive silver halide photographic material. More particularly it relates to a process for producing a light-sensitive silver halide photographic material having a superior dimensional stability during its processing.

BACKGROUND OF THE INVENTION

Gelatin is commonly much used as a binder in light-sensitive silver halide photographic materials.
Gelatin is highly swellable and capable of gelling, and can be readily cross-linked using various hardening agents. Thus, gelatin is a binder having very good properties for carrying out uniform coating over a wide area when a coating solution of materials that are easily affected by high temperatures, as light-sensitive silver halides are, is coated while controlling its physical properties.
In the course of development of light-sensitive silver halide photographic materials, silver halide grains change into very hard metallic silver in the state that gelatin layers have much absorbed water to swell. Hence, there can be presented a phenomenon that emulsion layers do not revert to their original forms even after dried, to have different dimensions before and after processing even though the light-sensitive materials are the same.
To prevent this phenomenon, techniques are well known in which a polymer latex is incorporated in silver halide emulsion layers and backing layers to improve physical properties of light-sensitive materials.
Such techniques are disclosed, for example, in Research Disclosure No. 19951, Japanese Patent Examined Publications No. 4272/1964, No. 17702/1964 and No. 13482/1968 and U.S. Patent No. 2,376,005, No. 2,763,625, No. 2,772,166, No. 2,852,386, No. 2,853,457 and No. 3,397,988. Japanese Patent Publications Open to Public Inspection [hereinafter referred to as Japanese Patent O.P.I. Publication(s)] No. 38741/1984, No. 296348/1986, No. 284756/1986, No. 285446/1986 and so forth also disclose methods in which minute oil droplets of paraffin or vinyl polymer are incorporated. None of them, however, are yet satisfactory, and it has been sought to make further improvements. In particular, it has been sought to provide a means to more prevent the phenomenon that the dimensions before and after processing greatly change depending on environmental humidity.
As a means therefor, Japanese Patent O.P.I. Publication No. 123044/1992 discloses a method in which a polymer latex is incorporated in silver halide emulsion layers. This method makes it possible to achieve a dimensional stability before and after processing at the level of no practical problem in an environment of a humidity ranging from 20% to 60%, which, however, is still at unsatisfactory level under conditions of a lower humidity, e.g., a humidity ranging from 5% to 10%RH.
U.S. Patent No. 4,645,731 discloses a light-sensitive silver halide photographic material having a subbing layer comprised of a highly crystalline vinylidene chloride, which, however, still can not perfectly improve the dimensional stability in an environment of an ultra-low humidity.
Japanese Patent O.P.I. Publication No. 230035/1989 also discloses a means by which the difference in dimensions before and after processing at a low humidity is lessened, employing special coating-drying conditions. This means, however, tends to enlarge the difference in the direction in which the difference in dimensions before and after processing at a high humidity is further reduced.

SUMMARY OF THE INVENTION

To solve the problems discussed above, an object of the present invention is to provide a process for producing a light-sensitive silver halide photographic material having a superior dimensional stability, in particular, causing less dimensional elongation after processing at a low humidity, and promising smaller variations or difference in dimensions before and after processing even when changes occur in environmental humidity.
The above object of the present invention can be achieved by a process for producing a light-sensitive silver halide photographic material. The process comprises the steps of (1) coating one or more layers including at least one silver halide emulsion layer on a support, (2) drying the one or more layers, and (3) winding up the support with the dried coating layers. In the above process, the total amount of gelatin provided on the emulsion coated side of the support is not more than 2.9 g per square meter, and the surface of the coating layers is contacted to air having an absolute humidity not higher than 0.5% or a relative humidity not lower than 5% for a time not shorter than 5 seconds at a time after completion of drying and before start of winding-up. In the above, the completion of drying is defined as a time of point at which the average surface temperature of coating layer has become lower by 1°C than the temperature of air for drying.
In preferred embodiments of the invention, the gelatin on the side having the silver halide emulsion layer is in an amount of from 0.5 g/m² to 2.7 g/m², and at least one hydrophilic colloid layer on the side having at least one light-sensitive silver halide emulsion layer, opposite to the support, contains a latex stabilized with gelatin.

DETAILED DESCRIPTION OF THE INVENTION

As the timing at which a coating solution is brought into contact with dry air having the absolute humidity of not lower than 0.5%, preferably 0.01% to 0.5% and/or relative humidity of not lower than 5%, preferably 0.1% to 5%, referred to in the present invention, the coating solution may particularly preferably be brought into contact with the dry air having the stated condition, for a period of at least 5 seconds within 5 minutes from the time of completion of drying the coating layer. The completion of drying is defined by the point at which the average surface temperature of the coating solution has become lower by 1°C than the temperature of the dry air. In a more preferred embodiment of the present invention, the light-sensitive material according to the present invention is, after brought into contact with the dry air having the condition of the present invention and before completely wound up, handled substantially under conditions of a relative humidity of not lower than 50%.
The condition the dry air to be contacted to the coating layer after the completion of drying thereof has in the present invention may particularly preferably be an absolute humidity of not lower than 0.5% and a relative humidity of not lower than 3%.
In the embodiments of the present invention, during completion of drying and start of winding-up, the light-sensitive material may be brought into contact with at least the dry air satisfying the condition of the present invention, and a period may be present for which the light-sensitive material is brought into contact with air having a condition other than the condition of the present invention. For example, in order to obtain good matte properties, the conditions as disclosed in Japanese Patent O.P.I. Publications No. 127049/1991 and No. 288843/1991 may be used in combination.
The gelatin on the emulsion layer side of the light-sensitive material according to the present invention must be in an amount not more than 2.9 g/m², and preferably 0.5 g/m² to 2.9 g/m². It may particularly preferably be in an amount of from 0.5 g/m² to 2.7 g/m².
In the present invention, more preferable results can be obtained when a polymer latex prepared by emulsion polymerization in the presence of gelatin is used.
Usual latexes are in the form of aqueous dispersions making use of surface active agents. The latex polymerized in the presence of gelatin that can be preferably used in the present invention is one in which at least part of the polymerization reaction for the polymer is carried out in a solvent containing the gelatin. The polymer and gelatin that constitutes the latex may have any bond. In such an instance, the polymer and the gelatin may be directly bonded, or may be bonded through a cross-linking agent. Hence, the monomer constituting the latex should preferably contain a monomer having a reactive group such as a carboxyl group, an amino group, an amido group, an epoxy group, a hydroxyl group, an aldehydo group, an oxazoline group, an ether group, an ester group, a methylol group, a cyano group, an acetyl group and an unsaturated carbon bond. In the case when the cross-linking agent is used, those used as usual crosslinking agents for gelatin can be used. For example, it is possible to use cross-linking agents of an aldehyde type, a glycol type, a triazine type, an epoxy type, a vinylsulfone type, an oxazoline type, a methacrylic type and an acrylic type.
There is a preferable range for the amount of the gelatin and latex to be added. The weight ratio of the gelatin to the polymer (Gel/Poly) is preferably from 1/100 to 2/1, and particularly preferably from 1/50 to 1/2.
The present invention can be effective when the amount of the polymer component added in the latex is 20% to 200% based on the amount of the gelatin in a layer to which the latex has been added.
The polymer may be added in an amount of from 0.05 to 5 g/m², and particularly preferably from 0.1 to 2.5 g/m².
The gelatin used for stabilizing the latex of the present invention may include gelatin, gelatin derivatives and graft polymers of gelatin with other macromolecule, and other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives homo- or copolymer synthetic hydrophobic macromolecules can also be used in combination.
Lime-treated gelatin, as well as acid treated gelatin including the acid treated gelatin as disclosed in Bull. Soc. Sic. Phot. Japan, No. 16, page 30 (1966), may also be used as the gelatin. It is also possible to use hydrolysates or enzymolysates of gelatin. As the gelatin derivatives, products obtained by reacting gelatin with various compounds as exemplified by acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleimide compounds, polyalkyleneoxides and epoxy compounds can be used. Examples thereof are disclosed in U.S. Patents No. 2,614,928, No. 3,132,945, No. 3,186,846 and No. 3,312,553, British Patents No. 861,414, No. 1,033,189 and No. 1,005,784, and Japanese Patent Examined Publication No. 26845/1967.
The proteins may include albumin and casein, the cellulose derivatives, hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate, and the sugar derivatives, sodium alginate and starch derivatives, which may be used in combination with the gelatin.
As the graft polymers of gelatin with other macromolecule, it is possible to use polymers obtained by grafting on the gelatin, acrylic acid, methacrylic acid, a derivative such as an ester or amide of any of these or a homo- or copolymer of vinyl monomers such as acrylonitrile or styrene. In particular, polymers having a compatibility with the gelatin to a certain extent as exemplified by graft polymers with acrylic acid, acrylamide, methacrylamide or a hydroxyalkyl methacrylate are preferred. Examples of these are disclosed in U.S. Patents No. 2,763,625, No. 2,831,767 and No. 2,956,884.
The polymer component of the latex that may be incorporated in the light-sensitive photographic material of the present invention may include hydrates of vinyl polymers such as acrylates, methacrylates or styrene, as disclosed, for example, in U.S. Patents No. 2,772,166, No. 3,325,286, No. 3,411,911, No. 3,312,912 and No. 3,525,620 and Research Disclosure No. 19519551 (September, 1980). Stated specifically, any compounds having a double bond, such as acrylic acid, methacrylic acid or a salt thereof, maleic acid or a salt thereof, fumaric acid or a salt thereof, alkyl acrylic acid esters such as methyl acrylate and ethyl acrylate, alkyl methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, styrene, styrene sulfonic acid or a salt thereof, N-substituted or unsubstituted acrylamide, vinyl alcohols, hydroxyalkyl methacrylates and butadiene can be selected as copolymer components.
Preferable examples of the monomer of the latex stabilized with gelatin are shown below. The latex of the present invention may be comprised of any combination (kinds, compositional ratio) of these monomers.

(L - 1)
(L - 2)
(L - 3)
(L - 4)
(L - 5)
(L - 6)
(L - 7)
(L - 8)
(L - 9)
(L - 10)
(L - 11)
(L - 12)
(L - 13)

(̵CH₂-CH₂)̵
(L - 14)

(̵CH₂-CH=CH-CH₂)̵
(L - 15)
(L - 16)
(L - 17)
(L - 18)
(L - 19)
(L - 20)
(L - 21)
(L - 22)
(L - 23)
(L - 24)
(L - 25)
(L - 26)

There are no particular limitations on usual additives, known hardening agents and methods for producing silver halide grains, sensitization methods and so forth used in the present invention. For example, reference can be made on Japanese Patent O.P.I. Publications No. 230035/1989 and No. 127049/1991.
In the present invention, for the purpose of antistatic, which is other properties required for the light-sensitive material, the support may have at least one antistatic layer on its backing side and/or emulsion layer side.
In such an instance, the surface specific resistivity on the side provided with the antistatic layer may preferably be not higher than 1.0 x 10¹² Ω, and particularly preferably not higher than 8 x 10¹¹ Ω, in an environment of 25°C and 50%RH.
The antistatic layer may preferably be an antistatic layer containing a water-soluble conductive polymer, hydrophobic polymer particles and a reaction product of a hardening agent, or a antistatic layer containing a metal oxide.
The water-soluble conductive polymer may include polymers having at least one conductive group selected from a sulfonic group, a sulfate group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group and a polyethylene oxide group. Of these groups, a sulfonic acid group, a sulfonate group and a quaternary ammonium group are preferred. The conductive group must be in an amount of not less than 5% by weight per mole of the water-soluble conductive polymer.
In the water-soluble conductive polymer, a carboxyl group, a hydroxyl group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinylsulfone group or the like is contained. Of these, a carboxyl group, a hydroxyl group, an amino group, an epoxy group, an aziridine group or an aldehyde group may preferably be contained. Any of these groups must be contained in an amount not less than 5% by weight per mole of the polymer. The water-soluble conductive polymer may have a number average molecular weight of from 3,000 to 100,000, and preferably from 3,500 to 50,000.
As the metal oxide, tin oxide, indium oxide, vanadium oxide, antimony oxide, zinc oxide, or any of these metal oxides doped with metallic phosphorus, metallic silver or metallic indium may preferably be used. These metal oxides may preferably have an average particle diameter of from 1 µ to 0.01 µ.
A subbing layer may be used in the present invention, which may include subbing layers using an organic solvent containing polyhydroxybenzenes, as disclosed in Japanese Patent O.P.I. Publication No. 3972/1974, aqueous latex type subbin layers as disclosed in Japanese Patent O.P.I. Publications No. 11118/1974, No. 104913/1977, No. 19941/1984, No. 19940/1984, No. 18945/1984, No. 112326/1976, No. 117617/1976, No. 58469/1976, No. 114120/1976, No. 121323/1976, No. 123139/1976, No. 114121/1976, No. 139320/1977, No. 65422/1977, No. 109923/1977, No. 119919/1977, No. 65949/1979, No. 128332/1982, No. 19941/1984, etc. It may also include vinylidene chloride subbing layers as disclosed in U.S. Patent No. 2,698,235, No. 2,779,684, No. 425,421, No. 4,645,731, etc.
The subbing layer may usually be subjected to chemical or physical treatment on its surface. The treatment may include surface activating treatment such as treatment with chemicals, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high-frequency treatment, glow discharge treatment, active-plasma treatment, laser beam treatment, mixed acid treatment and ozone oxidation treatment.
The subbing layer is distinguished from the coating layers according to the present invention, and there are no limitations on the time at which and conditions under which the subbing layer is provided by coating.
In the present invention, besides usual water-soluble dyes, a solid-dispersed dye may be contained in any hydrophilic colloid layer. The layer to which it is added may be the outermost layer on the emulsion layer side, and, for the purpose of anti-halation, may also be a layer lower than emulsion layers and/or a layer on the backing side. It may also be added in an appropriate amount in an emulsion layer formed for the controlling of irradiation. Of course, plural kinds of solid-dispersed dyes may be added to plural layers.
The solid-dispersed dye may preferably be added in an amount of from 5 mg/m² to 1 g/m², and particularly preferably from 10 mg/m² to 800 mg/m², for each kind.
Fine particles of the solid-dispersed dye used can be obtained by pulverizing the dye by means of a dispersion machine such as a ball mill or a sand mill, followed by dispersion together with water, a hydrophilic colloid such as gelatin, or a surface active agent such as sodium dodecylbenzenesulfonate, sodium fluorinated octylbenzenesulfonate, saponin or nonylphenoxypolyethylene glycol.
The solid-dispersed dye may include those represented by the formulas described in U.S. Patent No. 4,857,446, etc. For example, those represented by Formulas I to V may preferably be used.
The present invention can be applied to various types of light-sensitive materials for graphic arts, X-ray photography, general-purpose negatives, general-purpose reversals, general-purpose positives and direct positives, and can be particularly remarkably effective when applied to graphic arts light-sensitive materials for which a very high dimensional stability is required.
The light-sensitive silver halide photographic material according to the present invention may preferably be developed at a temperature of 50°C or below, and particularly preferably from about 25°C to about 40°C. It is common for its photographic processing to be completed within 2 minutes. In particular, it is preferable to carry out 5 to 60 second rapid processing.

EXAMPLES

Example 1

Synthesis of latex La:

To a solution prepared by adding 0.125 kg of dextran sodium sulfate KMDS, produced by Meito Sangyo Co., Ltd., and 0.05 kg of ammonium persulfate to 40 lit. of water, a solution comprising a mixture of components (a) to (c) as shown below was added with stirring at a liquid temperature of 80°C over a period of 1 hour in an atmosphere of nitrogen, followed by stirring for 1.5 hours. Thereafter, 1.25 kg of KMDS and 0.005 kg of ammonium persulfate were added, followed by stirring for 1.5 hours. After the reaction was completed, steam distillation was further carried out for 1 hour to remove remaining monomers, followed by cooling to room temperature and then adjustment of pH to 6.0 using ammonia. The latex thus obtained was made up to 50.5 kg by adding water.

(a) n-Butyl acrylate 4.51 kg
(b) Styrene 5.49 kg
(c) Acrylic acid 0.1 kg

Thus, a monodisperse latex with an average particle diameter of 0.25 µm and Tg of about 0°C was obtained.

Preparation of emulsion:

A silver nitrate solution and an aqueous solution of sodium chloride and potassium bromide, in which a rhodium hexachloride complex was added so as to be in a concentration of 8 x 10⁻⁵ mol/mol·Ag, were simultaneously added to a gelatin solution while controlling flow rates, followed by desalting to give a cubic, monodisperse silver chlorobromide emulsion having a grain size of 0.13 µm and containing 1 mol% of silver bromide.
This emulsion was subjected to sulfur sensitization by a conventional method, and 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added as a stabilizer. Thereafter, gelatin was added so as to be in an amount of 1.2 g/m² when the coat amount of the emulsion was 3.5 g/m² in terms of silver, followed by addition of additives shown below. An emulsion coating solution E-O was thus prepared. Subsequently, an emulsion protective layer coating solution P-O, a backing layer coating solution B-O and a backing protective layer coating solution BP-O were prepared to have the composition shown below.

Preparation of emulsion coating solution E-0:

Compound (a)	1 mg/m²
NaOH (0.5N)	adjusted to pH 5.6
Compound (b)	40 mg/m²
Compound (c)	30 mg/m²
Saponin (20%)	0.5 cc/m²
Sodium dodecylbenzene sulfonate	20 mg/m²
5-Methylbenzotriazole	10 mg/m²
Compound (d)	2 mg/m²
Compound (e)	10 mg/m²
Compound (f)	6 mg/m²
Latex La	1.0 g/m²
Styrene/maleic acid copolymer	90 mg/m²
(thickening agent)

A 50:46:4 mixture of (A):(B):(C)

Emulsion protective layer coating solution P-O:

Backing layer coating solution B-O:

Gelatin	1.0 g/m²
Compound (j)	100 mg/m²
Compound (k)	18 mg/m²
Compound (l)	100 mg/m²
Saponin (20%)	0.6 ml/m²
Latex (m)	300 mg/m²
5-Nitroindazole	20 mg/m²
Styrene/maleic acid copolymer	45 mg/m²
(thickening agent)
Glyoxal	4 mg/m²
Compound (n)	10 mg/m²
Compound (p)	10 mg/m²
5-Methylbenzotriazole	20 mg/m²

Backing protective layer coating solution BP-O:

Gelatin 0.5 g/m²

Compound (g) (1%) 2 ml/m²

Spherical polymethyl methacrylate (4 µ) 25 mg/m²

Sodium chloride 70 mg/m²

Glyoxal 22 mg/m²

Compound (o) 100 mg/m²

Compound (p)

${H-(-OH₂CH₂-)}_{n} -OH Mw: 1,600$

Added in the form of a solution prepared by dissolving in a pH12 aqueous NaOH solution in a concentration of 5% and adjusted to pH 6 using acetic acid. (Solid-dispersed dye)
A polyethylene terephthalate base with a thickness of 100 µm, having been subbed on its emulsion layer side according to the subbing as shown in Japanese Patent O.P.I. Publication No. 19941/1984, was subjected to corona discharging thereon at 10 W/m²·min, followed by coating with a solution having the following composition, using a roll-fit coating pan and an air knife coater. Drying was carried out for 30 minutes under parallel-flow drying conditions of 90°C and an overall heat transfer coefficient of 25 kcal/m²·hr·°C, and then at 140°C for 90 seconds. After dried, this layer had a layer thickness of 1 µm, and a surface specific resistivity of 1 x 10⁸ Ω at 23°C and 55%RH.
On this base, using the emulsion coating solution and emulsion protective coating solution described above, an emulsion layer and an emulsion protective layer as layers on the emulsion layer side were provided in this order from the side close to the support, by simultaneous multi-layer coating by a slide hopper system while maintaining the temperature at 35°C and while adding formalin as a hardening agent in an amount of 30 mg per gram of gelatin, and the material thus coated was passed through a cold-air set zone (5°C). Thereafter, to form a backing layer and a backing coating layer, the backing layer coating solution and the backing protective layer coating solution were coated also by a slide hopper system while adding a hardening agent, followed by cold-air setting (5°C). At the time when passed each set zone, the coatings were satisfactorily set. Subsequently, in a drying zone, the coated material was dried simultaneously on its both sides under drying conditions shown below. After the coating on the backing layer side, the coated material was transported completely without contact with rollers and other members until it was wound up. In this instance, the coating was carried out at a speed of 150 m/min.

Drying conditions:

The coatings were dried with 30°C air until the weight ratio of H₂0 to gelatin came to be 800%, and dried with 35°C and 30%RH dry air until it came to be more than 800% to 200%. Keeping them subjected to that air until they came to have a surface temperature of 34°C (regarded as "drying completed"), and 30 seconds after this time of point the coatings were further contacted for 1 minute with air under conditions shown in Table 1 later. Here, the drying from its initiation until the H₂0/gelatin ratio came to be 800% was carried out for 50 seconds; until more than 800% to 200%, for 35 seconds; and from 200% until "drying completed", for 5 seconds.
The light-sensitive material thus obtained was wound up in an environment of 23°C and 40%RH, subsequently cut in the same environment, and then sealed in a barrier bag having been moisture-conditioned for 3 hours in the same environment, together with thick paper having been moisture-conditioned for 8 hours in an environment of 40°C and 10%RH and thereafter moisture-conditioned for 2 hours in an environment of 23°C and 40%RH.
The light-sensitive material thus produced had a coated silver weight of 3.5 g/m².
On the evaluation sample thus prepared, its dimensional stability was evaluated in the following way.

Dimensional stability:

The sample was cut in a size of 30 cm × 60 cm, imagewise exposed so as to form two thin lines at an interval of 56 cm using a light-room printer P-627M (manufactured by Dainippon Screen Mfg. Co., Ltd.), and then photographically processed. The resulting sample was used as an original. This original, an unexposed sample having the same size as the original, the printer and an automatic processor were moisture-conditioned for 2 hours in an environment of 23°C and 5%RH. Thereafter the original and the unexposed sample ware subjected to contact (face-to-face) exposure, and then photographically processed using the automatic processor. The sample having been processed was moisture-conditioned for 2 hours, and thereafter superposed on the initial original to measure any difference in configuration of the thin lines from the original ones, using a magnifier with scale.
The measurement was made at n = 6, and an average value was determined, which was represented by (a).
A similar experiment was also made in an environment of 23°C and 60%RH, and the resulting value was represented by (b).
The difference between (a) and (b), dependence on environmental humidity, was also determined, and the resulting value was represented by (c).
When the value (a) or (b) exceeds ±20 µm, a difference from original configuration is perceivable. When the value (c) is 20 µm or less, the difference in dimensions before and after processing is at the level almost unrecognizable over the range of 5 to 60%RH.

Standard processing conditions:

- Formulation of developing solution -
(Composition A)
Pure water (ion-exchanged water)	150 ml
Disodium ethylenediaminetetraacetate	2 g
Diethylene glycol	50 g
Potassium sulfite (aqueous 55% w/v solution)	100 ml
Potassium carbonate	50 g
Hydroquinone	15 g
5-Methylbenzotriazole	200 mg
1-Phenyl-5-mercaptotetrazole	30 mg
Potassium hydroxide
in an amount necessary to adjust to 10.9 the pH of the solution used.
Potassium bromide	4.5 g

(Composition (B)
Pure water (ion-exchanged water)	3 ml
Diethylene glycol	50 g
Disodium ethylenediaminetetraacetate	25 mg
Acetic acid (aqueous 90% solution)	0.3 ml
5-Nitroindazole	110 mg
1-Phenyl-3-pyrazolidone	500 mg

When the developing solution was used, the composition A and the composition B were dissolved in this order in 500 ml of water, and made up to 1 liter for its use.

- Formulation of fixing solution -
(Composition A)
Ammonium thiosulfate (aqueous 72.5 w/v solution)	230 ml
Sodium sulfite	5.6 g
Sodium acetate trihydrate	27.8 g
Boric acid	9.8 g
Sodium citrate dihydrate	2.0 g
Acetic acid (aqueous 90% w/v solution)	6.4 ml

(Composition B)
Pure water (ion-exchanged water)	28 ml
Sulfuric acid (aqueous 50% w/v solution)	6.7 g
Aluminum sulfate	25.31 g
(aqueous solution with a content of 8.1% w/v in terms of Al₂O₃)

When the fixing solution was used, the composition A and the composition B were dissolved in this order in 500 ml of water, and made up to 1 liter for its use. This fixing solution had a pH of about 4.4.

Results obtained are shown in Table 1.

Table 1

No.	Dry air contacted after completion of drying			Difference in dimensions before and after processing (µm)			Invention
	Temp.	Relative humidity	Absolute humidity	(a)	(b)	(c)
	(°C)	(%)	(%)
1	30	12	0.31	+20	-8	28	Yes
2	"	6	0.16	+18	-7	25	Yes
3	"	3	0.08	+9	-6	15	Yes
4	40	12	0.55	+60	-10	70	No
5	"	8	0.36	+19	-14	33	Yes
6	"	6	0.27	+17	-17	34	Yes
7	"	3	0.14	+8	-12	20	Yes
8	"	1	0.05	+6	-14	20	Yes
9	50	12	0.92	+65	-10	75	No
10	"	8	0.61	+55	-13	68	No
11	"	6	0.46	+20	-9	29	Yes
12	"	3	0.23	+7	-12	19	Yes
13	"	1	0.08	+3	-14	17	Yes
14	66	6	0.97	+45	-20	65	No
15	"	3	0.48	+12	-6	18	Yes
16	"	1	0.16	+3	-14	17	Yes
17	77	6	1.17	+43	-17	60	No
18	"	3	0.58	+18	-9	27	Yes
19	"	1	0.19	+10	-5	15	Yes

As is seen from the results shown in Table 1, a good dimensional stability can be exhibited over the range of 5 to 60%RH when the drying of the present invention is carried out.

Example 2

Experiments were made in the same manner as in Example 1 except that the light-sensitive material as used in Example 1 was made to have a gelatin weight on the emulsion layer side as shown in Table 2. Flow rate of air for drying each sample was controlled so that the drying was carried out under the conditions corresponding to those for No. 13 in Table 1.

Results obtained are shown in Table 2.

Table 2

	Amount of gelatin (g/m²)		Difference in dimensions before and after processing			Invention
No.	Protective layer/emulsion layer	Total	(a)	(b)	(c)
20	0.25/0.25	0.5	+10	+5	5	Yes
21	0.5/0.5	1.0	+11	+4	7	Yes
22	0.6/0.6	1.2	+9	+1	8	Yes
23	1.0/1.0	2.0	+9	±0	9	Yes
24	1.1/1.2	2.3	+7	-5	12	Yes
25	1.2/1.3	2.5	+5	-10	15	Yes
26	1.3/1.4	2.7	+6	-14	20	Yes
27	1.4/1.5	2.9	+6	-19	25	Yes
28	1.5/1.5	3.0	-3	-27	30	No
29	1.6/1.6	3.2	-5	-40	45	No
30	2.0/2.0	4.0	-10	-45	55	No

As is seen from the results shown in Table 2, the difference in dimensions before and after processing is not more than ±20 µm over the range of 5 to 60%RH when the amount of gelatin is not more than 2.9 g/m², showing good results. The value (c) in the difference in dimensions before and after processing is within 20 µm over the range of 5 to 60%RH when the amount of gelatin is not more than 2.7 g/m², showing very good results.

Example 3

As the latex stabilized with gelatin, Lb was prepared in the manner shown below. With regard to sample No. 24 used in Example 2, La was removed and Lb was added as shown in Table 3 below to prepare samples. The dimensional stability was evaluated in the same manner as in Example 2.

Synthesis of latex Lb:

To a solution prepared by adding 0.125 kg of gelatin and 0.05 kg of ammonium persulfate to 40 lit. of water, a solution comprising a mixture of components (a) to (d) as shown below was added with stirring at a liquid temperature of 50°Cin an atmosphere of nitrogen, followed by stirring for 1.5 hours. Thereafter, 1.25 kg of gelatin and 0.005 kg of ammonium persulfate were added, followed by stirring for 1.5 hours. After the reaction was completed, steam distillation was further carried out for 1 hour to remove remaining monomers, followed by cooling to room temperature and then adjustment of pH to 6.0 using ammonia. The latex thus obtained was made up to 50.5 kg by adding water.

(a) Ethyl acrylate 5.0 kg
(b) Styrene 3.0 kg
(c) Methyl methacrylate 1.4 kg
(d) Sodium acrylamido-2-methylpropanesulfonate 0.6 kg

Thus, a monodisperse latex with an average particle diameter of 0.1 was obtained.

Results obtained are shown in Fig. 3.

Table 3

	Amount of Lx (g/m²)	Difference in dimensions before and after processing
No.	Protective layer/emulsion	(a)	(b)	(c)
31	0/1.0	+8	±0	8
32	0/0.5	+8	-8	16
33	0/0.3	+8	-12	20
34	0/0.1	+7	-13	20
35	1.0/1.0	+7	±0	7
36	0.5/0.5	+8	-9	17
37	0.3/0.3	+8	-10	18
38	0.1/0.1	+7	-13	20

As is seen from the results shown in Table 3, the comparison of No. 24 in Table 2 with No. 31 in Table 3 proves that the use of the latex polymerized in the presence of gelatin brings about a more improvement in the dimensional stability. As is also seen therefrom, the latex polymerized in the presence of gelatin may be added in an mount of 0.1 g/m² at least in the emulsion layer and may also be added in a non-sensitive hydrophilic colloid layer.

Claims

A process for producing a light-sensitive silver halide photographic material comprising steps of
coating one or more layers including at least one silver halide emulsion layer on a support,
drying said one or more layers, and
winding up said support with said dried coating layers,
wherein the total amount of gelatin provided on the emulsion coated side of the support is 0.5 g to 2.9 g per square meter, and the surface of said coating layers is contacted to air having an absolute humidity of not higher than 0.5 % or a relative humidity of not higher than 5 % for a time not shorter than 5 seconds at a time after completion of drying step and before start of winding up.
The process of claim 1, wherein the amount of gelatin provided on the emulsion coated side of the support is 0.5 g to 2.7 g per square meter.
The process of claim 1, wherein said air to be contacted to said coating layers has an absolute humidity of 0.01 % to 0.5 % or a relative humidity of 0.1 % to 5 %.
The process of claim 1, wherein at least one of layers provided on the emulsion coated side of the support contains a latex polymerized in the presence of gelatin.
The process of claim 3, wherein the weight ratio of gelatin to polymer, gelatin/polymer, at the time of polymerization of said latex is 1/100 to 2/1.
The process of claim 5, wherein the weight ratio of gelatin to polymer, gelatin/polymer, at the time of polymerization of said latex is 1/50 to 1/2.
The process of claim 4, wherein weight of polymer of said latex in the layer to which said latex is added is 20 % to 200 % by weight of gelatin contained in said layer.
The process of claim 4, wherein the coating amount of polymer of said latex is 0.05 g to 5 g per square meter.
The process of claim 1, wherein air to be contacted to the surface of said coating layers after completion of drying thereof has an absolute humidity of not higher than 0.5 % and a relative humidity of not higher than 3 %.
The process of claim 1, wherein said air having an absolute humidity of not higher than 0.5 % or a relative humidity of not higher than 5 % is contacted to the surface of said coating layers at a time within 5 minutes after completion of drying of said layers.
The process of claim 1, wherein the surface of said coating layers were contacted to air having a relative humidity of not higher than 50 % after contacting said air having an absolute humidity of not higher 0.5 % or a relative humidity of not higher than 5 %.
A process for producing a light-sensitive silver halide photographic material comprising steps of
coating one or more layers including at least one silver halide emulsion layer on a support,
drying said one or more layers, and
winding up said support with said dried coating layers,
wherein the total amount of gelatin provided on the emulsion coated side of the support is 0.5g to 2.7 g per square meter, and the surface of said coating layers is contacted to air having an absolute humidity of from 0.01 % to 0.5 % and a relative humidity of 0.1 % to 3 % for a time not shorter than 5 seconds at a time with in 5 minutes after completion of drying step and before start of winding up and at least one of said layers contains a latex polymerized in the presence of gelatin in a ratio of from 20 % to 200 % by weight of gelatin contained in said layer.