JPH06175252A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material excellent in dimensional stability, high in drying property after processing and having high speed processing aptitude. CONSTITUTION:In the silver halide photographic sensitive material having at least one layer of a silver halide emulsion layer on a supporting body, a water soluble or dispersible reactive compound made by containing at least two free isocyanate groups, blocking at least >=2 free isocyanate groups with bisulfite and furthermore blocking the residual all free isocyanate groups with another blocking agent and a polymer latex stabilized by gelatin are contained in at least one layer in the layers constituting the silver halide photographic sensitive material.

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 silver halide photographic light-sensitive material having excellent dimensional stability and good drying property even in rapid processing.

[0002]

2. Description of the Related Art Generally, gelatin is often used as a binder in silver halide photographic light-sensitive materials. Gelatin has high swelling property and gelling ability, and can be easily cross-linked with various hardeners.By adjusting the physical properties of the coating liquid, materials such as photosensitive silver halide that do not accept high temperatures can be used to cover a large area. It is a binder having extremely excellent properties for uniform application over the entire area.

[0003]

In the silver halide photographic light-sensitive material, the silver halide grains change into extremely hard metallic silver in the state where the gelatin layer absorbs water sufficiently and swells during development. For this reason, the emulsion layer does not return to its original state even after drying, and there is a phenomenon that the dimensions of the same light-sensitive material are different before and after processing.

On the other hand, a technique for improving the physical properties of a light-sensitive material by incorporating a polymer latex in a silver halide emulsion layer and a backing layer is well known.

Examples of these techniques include Research Disclosure 19951, Japanese Patent Publication Nos. 39-4272 and 39-17702.
No. 43-13482, U.S. Patent No. 2376005, No. 2763625, No. 27.
No. 72166, No. 2852386, No. 2853457, No. 3397988, etc. In addition, JP-A-59-38741, JP-A-61-296348,
No. 61-284756, No. 61-285446 and the like disclose a method of incorporating fine oil droplets of paraffin or vinyl polymer. However, it is still insufficient, and further improvement has been desired. This is because in the case of the conventional latex, adding a large amount to gelatin causes the latex to form a film (aggregate), and even if it is added more than that, the effect does not appear, and in this state it is not sufficient as an effect of improving dimensional stability. Therefore, it is desired to develop a means for improving the phenomenon that the dimensional difference before and after the treatment largely changes depending on the environmental humidity.

Further, when a large amount of latex is added to gelatin, the degree of swelling in the vicinity of the area where the latex is added is increased, which adversely affects the drying property after processing.

It is known to harden gelatin using various compounds to improve the drying property after the treatment. Techniques for hardening such gelatin include US Pat. No. 3,642,486, Japanese Patent 37-33792, Japanese Patent 49-13563, and Japanese Patent 5
It is proposed to 2-31737.

In order to improve the drying property of the silver halide photographic light-sensitive material after processing, it is effective to add a large amount of a hardener to suppress wetting of the binder layer. It has a drawback that it becomes slower and the maximum concentration lowers, and it has been the reality that only a certain amount can be added.

On the other hand, US Pat.
There is disclosed a patent such as -86821 in which a film hardener having an isocyanate blocked is added to a light-sensitive material to cause a film hardening reaction during development processing.

When these compounds were added to a silver halide photographic light-sensitive material in combination with a conventionally known hardener, the drying property in a system using a large amount of polymer latex was at an insufficient level. .

With respect to the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material having excellent dimensional stability, high drying property after processing and suitability for rapid processing. .

[0012]

The above-mentioned object of the present invention is to provide a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, and to form a constituent layer of the silver halide photographic light-sensitive material. Among them, at least one layer contains at least two free isocyanate groups, and at least two or more of the free isocyanate groups are blocked with bisulfite, and all remaining free isocyanate groups are other blocking agents. It is achieved by a silver halide photographic light-sensitive material characterized in that it contains a water-soluble or water-dispersible reactive compound which is blocked and a polymer latex stabilized with gelatin.

The total amount of gelatin in the hydrophilic colloid layer coated on the support is preferably 2.7 g / m ² or less on each side.

The present invention will be described in more detail below.

The gelatin-stabilized polymer latex that can be used in the present invention is characterized in that the surface and / or the inside of the polymer latex is dispersion-stabilized with gelatin. It is particularly desirable that the polymer constituting the latex and gelatin have some kind of bond. In this case, the polymer and gelatin may be bound directly or may be bound via a crosslinking agent.

The gelatin-stabilized polymer latex of the present invention has a polymer latex after the polymerization reaction of the polymer latex is completed.
It can be obtained by adding a gelatin solution to the reaction system and reacting. It is preferable to react the polymer latex synthesized in a surfactant with gelatin using a crosslinking agent. Further, it can be obtained by a method in which gelatin is present during the polymerization reaction of the polymer, which gives more preferable results than the above method. Further, in this case, it is preferable not to use a surfactant during the polymerization reaction of the polymer, but when the surfactant is used, the addition amount thereof is 0.1 to 3.0%, particularly preferably 0.1 to 1.5% based on the polymer component. . The present inventor has found that, in the process of continuing to improve the physical properties of the light-sensitive material, there is a specific boundary in the ratio of the added amounts of gelatin and latex.

The ratio of gelatin to polymer at the time of synthesis is 1:
100 to 2: 1 is preferable, and 1:50 to 1: is particularly preferable.
It is 2.

The preferable range of the average particle size of the gelatin-stabilized polymer latex used in the present invention is 0.00.
It is 5 to 1 μm, preferably 0.02 to 0.5 μm. Examples of the polymer latex stabilized with gelatin of the present invention include, for example, U.S. Patents 2,772,166 and 3,325,286,
3,411,911, 3,311,912, 3,525,620, Research Disclosure
No. 195 19551 (July 1980) and the like, acrylates, methacrylic acid esters, hydrates of vinyl polymers such as styrene, and the like.

The polymer latex portion of the gelatin-stabilized polymer latex preferably used in the present invention includes a homopolymer of a metaalkyl acrylate such as methyl methacrylate or ethyl methacrylate, a homopolymer of styrene, or a metaalkyl acrylate. Styrene and acrylic acid, N-methylol acrylamide,
Copolymers with glycidol methacrylate, etc., homopolymers of alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, etc. or copolymers of alkyl acrylate with acrylic acid, N-methylol acrylamide, etc. Polymerization component is up to 30% by weight), butadiene homopolymer or copolymer of butadiene and styrene, butoxymethyl acrylamide, one or more of acrylic acid, vinylidene chloride-methyl acrylate-acrylic acid terpolymer, etc. Can be mentioned.

In the case of binding with gelatin via a crosslinking agent, the monomers constituting the polymer latex include
Carboxyl group, amino group, amide group, epoxy group, hydroxyl group, aldehyde group, oxazoline group, ether group, active ester group, methylol group, cyano group, acetyl group,
It is desirable to include those having a reactive group such as an unsaturated carbon bond. Further, when a cross-linking agent is used, those used as a cross-linking agent for ordinary gelatin can be used. For example, aldehyde type, glycol type,
Crosslinking agents such as triazine-based, epoxy-based, vinylsulfone-based, oxazoline-based, methacrylic-based, and acrylic-based crosslinking agents can be used. Furthermore, in order to further enhance the dispersion stability of the gelatin-stabilized polymer latex of the present invention, 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof can be used as a monomer constituting the polymer latex. The amount of the above-mentioned monomer added is preferably 0.5 to 20% by weight based on the total weight of the constituents.

Examples of gelatin used for stabilizing the latex of the present invention include gelatin and gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers,
Other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used in combination.

Examples of gelatin include lime-treated gelatin, acid-treated gelatin, Bulletin of Society of Japan (Bull.Soc.Sci.Phot.Japan) No. 16, page 30 (196)
You may use the acid-processed gelatin as described in 6),
Also, a hydrolyzate or an enzymatic hydrolyzate of gelatin can be used. Examples of the gelatin derivative include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkyleonoxides, and epoxy compounds in gelatin. What is obtained by reacting is used. Specific examples thereof are U.S. Patents 2,614,928 and 3,132,9.
45, 3,186,846, 3,312,553, British Patent 861,41
No. 4, No. 1,033,189, No. 1,005,784, Japanese Patent Publication No. 42-26845
No. etc.

Examples of proteins include albumin, casein,
As the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, a sulfuric acid ester of cellulose, or as the sugar derivative, sodium alginate or a starch derivative may be used in combination with gelatin.

The gelatin-stabilized polymer latex used in the present invention may be added to at least one hydrophilic colloid layer. A preferable result is obtained when it is added in both layers of the non-photosensitive hydrophilic colloid layer. It may be contained on only one side of the support, or may be contained on both sides. The effect of dimensional stabilization becomes remarkable when the amount of latex added is 30% or more based on the gelatin in each hydrophilic colloid layer, particularly preferably 30% to 200%. The effect could be clarified by using the latex of the present invention. A conventionally known latex may be added to the layer to which the latex of the present invention is added and / or not added. When included on both sides of the support, the type and / or amount of polymer latex included on each side may be the same or different.

Next, some specific examples of the latex that can be used in the present invention are shown. The specific examples of the latex shown in the present specification also represent a latex having any composition ratio of the latex composed of the constituent components. Of course, the specific examples of the latex shown here are typical examples of the latex that can be used, and it goes without saying that the constituent components (not only the composition ratio) of the latex used in the present invention are not limited to these specific examples. Yes.

[0026]

[Chemical 1]

[0027]

[Chemical 2]

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

[0031]

[Chemical 6]

[0032]

[Chemical 7]

As the blocking agent used in the present invention, a compound having at least one active hydrogen capable of reacting with a free isocyanate group and an anionic group in the same molecule, for example, oxybenzoic acid, phenolsulfonic acid, glycolic acid. , Lactic acid, malic acid, bisulfite, bicarbonate and the like are used.

Examples of the reactive compound containing a free isocyanate group used in the present invention include those obtained from an excess amount of a polyisocyanate of a compound having two or more active hydrogen groups. Examples of the compound having two or more active hydrogen groups include those having two or more hydroxyl groups, carboxyl groups, amino groups, or mercapto groups at the end or in the molecule, and further polyether, polyester, polyether ester, etc. Is mentioned.

Examples of the polyether include alkylene oxides such as ethylene oxide and propylene oxide,
Alternatively, a polymerization product such as styrene oxide or epichlorohydrin and a random or block copolymer thereof, or an addition polymer to a polyhydric alcohol, etc. may be mentioned.

Polyesters and polyether polyesters include polyvalent saturated and unsaturated carboxylic acids such as succinic acid, adipic acid, phthalic acid and maleic anhydride or their acid anhydrides and ethylene glycol, diethylene glycol, 1,3. -And polyhydric saturated and unsaturated alcohols such as 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, polyethylene glycol of relatively low molecular weight , Mainly linear or branched condensates obtained from polyalkylene ether glycols such as polypropylene glycol and mixtures thereof,
In addition, polyesters made from lactones and hydroxy acids, and further polyether esters obtained by adding ethylene oxide, propylene oxide or the like to polyesters produced in advance are also included.

Polyisocyanates for obtaining urethane compounds by reacting with a compound having two or more active hydrogen groups include tolylene diisocyanate isomers,
Aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, araliphatic diisocyanates such as xylylene diisocyanate, isophorone diisocyanate, alicyclic diisocyanates such as 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,2 Examples thereof include aliphatic diisocyanates such as 1,4-trimethylhexamethylene diisocyanate.

Specific examples (structural formulas) of these polyisocyanates are given below.

[0039]

[Chemical 8]

[0040]

[Chemical 9]

[0041]

[Chemical 10]

Examples of hydroxyl group, amino group or mercapto group are ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol,
Neopentyl glycol, 1,4-cyclohexanedimethanol, glycols such as ethylene oxide adduct of bisphenol A, glycerin, trimethylolpropane,
Mention may be made of polyhydric alcohols such as pentaerythritol, diamines such as ethylenediamine, hexamethylenediamine and piperazine, amino alcohols such as monoethanolamine and diethanolamine, thiodiglycols such as thiodiethylene glycol and water. .

Examples of the carboxy group include succinic acid, adipic acid, sebacic acid, isophthalic acid, terephthalic acid,
5-sulfoisophthalic acid etc. can be mentioned.

The urethane type compound containing at least two free isocyanate groups used in the present invention can be easily synthesized by a conventionally known polyaddition method. In this case, however, the molar ratio of isocyanate group / active hydrogen group can be freely selected to be 1 or more, but it is preferable that the content of free isocyanate group in the obtained urethane compound is 1 to 30% by weight.

Next, the free isocyanate groups of the synthesized urethane compound are blocked with an aqueous bisulfite solution. In addition, examples of the bisulfite salt that is blocked with a compound having one or more active hydrogen groups and anionic salts in the same molecule as necessary include sodium bisulfite, potassium bisulfite, ammonium bisulfite, and the like. Examples of compounds having one or more and anionic salt-like groups or anionic salt-forming groups in the same molecule include amino groups and hydroxyl groups such as aminosulfonic acids, aminocarboxylic acids and hydroxyacetic acid as described above. Sulfonic acid groups, those having two types of groups of carboxylic acid groups are mentioned, as the aminosulfonic acids sulfanilic acid, N-phenylaminomethanesulfonic acid, Taunrin methyl taurine, as the aminocarboxylic acids, glycine, alanine, Glutamic acid, aminobenzoic acid, diaminobenzoic acid and The Dorokishi acid, glycolic acid, lactic acid, malic acid, salicylic acid and the like. Since they are used as a mixture with the bisulfite, they are used as lithium salt, sodium salt, potassium salt, ammonium salt and the like.

Specific synthetic methods for blocking are described, for example, in JP-B-55-39254 and JP-B-53-17642. The reactive urethane compound used in the present invention is commercially available, for example, from Daiichi Kogyo Seiyaku Co., Ltd. under the trade name of Elastron. For example, the following products are available depending on the type of raw material polyol (polyester polyol, polyether polyol, etc.).

Elastron H-3, E-37 (polyester type), Elastron C-9, F-29, C-52, CT-
7, H-38, A-42, BAP, W-11, (polyether type), and Elastron R-24, S-24, KS-18, etc., and in addition, Coronate from Nippon Polyurethane Industry Co., Ltd. 25072515, AX-35, 36 from Koyo Sangyo Co., Ltd. and K-1000 series from Nippon Shokubai Chemical Co., Ltd. Next, specific compound examples will be given, but the present invention is not limited to these.

[0048]

[Chemical 11]

[0049]

[Chemical 12]

[0050]

[Chemical 13]

[0051]

[Chemical 14]

[0052]

[Chemical 15]

Examples of commercially available compounds include:
There are the following.

Elastron H-3 (Daiichi Kogyo Seiyaku Co., Ltd.) Elastron E-37 (〃 〃) Elastron H-38 (〃 〃) Elastron A-42 (〃 〃) Elastron C-9 (〃 〃) Elastron W-11 (〃〃) The amount of the compound used in the present invention can be arbitrarily selected according to the purpose. Usually 0.01 for dry gelatin
Can be used in proportions ranging from 1 to 40% by weight. Particularly preferably, it is used in a proportion in the range of 1 to 30% by weight.

The silver halide photographic light-sensitive material of the present invention may contain a hardener other than the above compounds in at least one of the constituent layers. As the hardener used in the present invention, Research Disclosure Vol. 176 Item 17643 (December 1978)
26) and Vol. 187, Item 18716 (November 1979), page 651, left column.

The hydrophilic colloid layer in the present invention means a layer containing gelatin as a main binder.
As gelatin, the same gelatin as that used for stabilizing the latex of the present invention can be used.

The total amount of gelatin in the hydrophilic colloid layer coated on the support may be 4 g / m ² or less on each side including gelatin in the polymer latex stabilized with gelatin. , 2.7 g / m ² or less, the effect is particularly remarkable.

Known general additives can be used in the emulsion according to the present invention, and the method for producing silver halide grains, the method for sensitizing, etc. are not particularly limited, and are, for example, JP-A-63-230035. , Japanese Patent Application No. 1-266640 can be referred to.
It is preferable to add at least one known contrast enhancer such as a tetrazolium compound or a hydrazine derivative.

In the present invention, one or more antistatic layers can be provided on the backing side and / or emulsion layer side of the support for the purpose of antistatic property which is another physical property of the light-sensitive material.

In this case, the surface resistivity on the side provided with the antistatic layer is preferably 1.0 × 10 ¹¹ Ω or less at 25 ° C. and 50%, and particularly preferably 8 × 10 ¹¹ Ω or less.

The antistatic layer is preferably an antistatic layer containing a water-soluble conductive polymer, hydrophobic polymer particles and a reaction product of a curing agent, or an antistatic layer containing a metal oxide.

Examples of the water-soluble conductive polymer include polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric ester group, a quaternary ammonium salt, a tertiary ammonium salt, and a carboxyl group polyethylene oxide group. . Of these groups, a sulfonic acid group, a sulfuric acid ester group and a quaternary ammonium salt group are preferred. The conductive group needs to be 5% by weight or more per molecule of the water-soluble conductive polymer.

Further, the water-soluble conductive polymer contains a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinyl sulfone group and the like. Of these, a carboxyl group, a hydroxy group, an amino group, an epoxy group, an aziridine group, and an aldehyde group are preferably contained. 5% by weight of these groups per polymer molecule
The above must be included. The number average molecular weight of the water-soluble conductive polymer is 3,000 to 100,000, preferably 3500 to 50,000.

As the above-mentioned metal oxide, tin oxide, indium oxide, antimony oxide, zinc oxide, vanadium oxide, or those obtained by doping these metal oxides with metal silver, metal phosphorus or metal indium is preferably used. To be The average particle size of these metal oxides is from 1 μm to
0.01μ is preferable.

When the lower layer is an emulsion layer, the matting agent enters the emulsion layer by pressure because it is still soft,
Partial destruction of the emulsion layer occurred, causing a coating failure. The winding tension also causes the same.

Any known matting agent can be used in the present invention. For example, silica described in Swiss Patent 330,158, French Patent 1,296,9
Glass powder described in No. 95, alkaline earth metal or cadmium described in British Patent No. 1,173,181, inorganic particles such as zinc carbonate; starch described in US Pat. No. 2,322,037,
Starch derivatives described in Belgian Patent 625,451 or British Patent 981,198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3644, polystyrene or polymethylmethacrylate described in Swiss Patent 330,158, U.S. Patent
Polyacrylonitrile described in US Pat. No. 3,079,257, US patent
Organic particles such as the polycarbonate described in 3,022,169 may be included. These matting agents may be used alone or in combination. The shape of the matting agent is preferably spherical as a regular matting agent, but may be other shapes such as flat plate and cubic. The size of the matting agent is represented by the diameter when the volume of the matting agent is converted into a spherical shape. In the present invention, the matte particle size refers to the spherically converted diameter.

In a preferred embodiment of the present invention, the outermost layer on the emulsion surface side preferably contains 4 to 80 mg / m ² of at least one regular and / or irregular matting agent having a matting particle size of 4 μm or more. . More preferably, 4 mg of at least one fixed and / or irregular matting agent having a particle size of less than 4 μm is used.
/ m is ² to 80 mg / m ² combined contain it.

The fact that the matting agent is contained in the outermost layer means that
At least one part of the matting agent is preferably contained in the outermost layer, and one part of the matting agent may reach a layer below the outermost layer.

In order to fulfill the basic function of the matting agent,
It is desirable that a part of the matting agent is exposed on the surface.
Further, the matting agent exposed on the surface may be a part of the added matting agent or all. The method of adding the matting agent is
It may be a method of dispersing in a coating liquid in advance and coating, or a method of spraying a matting agent after coating the coating liquid and before completion of drying. When adding a plurality of different matting agents, both methods may be used in combination. Manufacturing techniques for more effectively adding these matting agents to the light-sensitive material are described in Japanese Patent Application No. 1-228762.

As the undercoat layer that can be used in the present invention, an undercoat layer containing an organic solvent system containing polyhydroxybenzenes described in JP-A-49-3972, JP-A-49-11118.
No. 52, No. 52-104913, No. 59-19941, No. 59-19940, No. 5
9-18945, 51-112326, 51-117617, 51-5846
No. 9, 51-114120, 51-121323, 51-123139,
51-114121, 52-139320, 52-65422, 52-1
09923, 52-119919, 55-65949, 57-128332
No. 59-19941 and the like water-based latex undercoating layer described, but also U.S. Patent Nos. 2698235, 2779684,
Examples thereof include vinylidene chloride-based undercoating described in No. 425421 and No. 4645731.

The surface of the undercoat layer can be chemically or physically treated. Examples of the treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and surface activation treatment such as ozone oxidation treatment. . The undercoat layer is distinguished from the coating layer according to the present invention, and there is no limitation on the coating time or conditions.

However, the embodiments of the present invention exhibit a more remarkable effect when coated on a polyester support provided with a vinylidene chloride subbing.

In the present invention, in addition to the usual water-soluble dye, a solid-dispersed dye may be contained in any of the hydrophilic colloid layers. The layer may be the outermost layer on the emulsion surface side, or may be added below the emulsion layer and / or on the backing surface side for the purpose of preventing halation. Further, an appropriate amount may be added to the emulsion layer for adjusting the irradiation. Of course, plural kinds of solid disperse dyes may be contained in plural layers.

The amount of the solid disperse dye added is preferably 5 mg / m ^{2 to 1} g / m ² , and particularly preferably 10 mg / m ^{2 to 1} g / m ^2.
a ^{mg / m 2 ~800mg / m 2} .

The fine particles of the solid dispersion used are obtained by crushing the dye with a dispersing machine such as a ball mill or a sand mill, and then water or a hydrophilic colloid such as gelatin, sodium dodecylbenzenesulfonate, sodium fluorinated octylbenzenesulfonate. , Saponin, nonylphenoxy polyethylene glycol and the like can be dispersed and obtained.

Examples of the general formula of the dye used in the present invention include those described in US Pat. No. 4,857,446 and the like, and those represented by the general formulas [I] to [V] are preferably used.

The present invention can be applied to various photosensitive materials for printing, X-ray, general negative, general reversal, general positive, direct positive, etc., but requires extremely high dimensional stability. When it is applied to a photosensitive material for printing, a particularly remarkable effect is obtained.

The development temperature of the silver halide photographic light-sensitive material according to the present invention is preferably 50 ° C. or lower, more preferably about 25 ° C. to 40 ° C., and the development processing time is generally completed within 2 minutes. However, more preferable results can be obtained by performing rapid processing for 5 to 60 seconds.

[0079]

EXAMPLES Examples of the present invention will be specifically shown below, but it goes without saying that the present invention is not limited to these examples.

Example 1 (Synthesis of Comparative Latex A) To a solution prepared by adding 0.01 kg of sodium dodecylbenzenesulfonate and 0.05 kg of ammonium persulfate to 40 liters of water was stirred at a liquid temperature of 60 ° C. under a nitrogen atmosphere. ) Styrene 3.0 kg (a) Methyl methacrylate 3.0 kg and (c) Ethyl acrylate 3.2 kg and (d) 2-acrylamido-2-methylpropanesulfonic acid
0.8Kg was added over 1 hour, then stirred for 1.5 hours and then 1 more
After steam distillation to remove residual monomer, cool to room temperature and adjust the pH to 6.0 with sodium hydroxide.
Adjusted to. The obtained latex liquid was adjusted to 55 kg with water. As described above, a monodisperse latex having an average particle size of 0.11 μm was obtained.

(Latex Lx-8) 1.0 kg of gelatin in 60 liters of water 0.01 K of sodium dodecylbenzenesulfonate
g and ammonium persulfate 0.05Kg were added to the solution at a temperature of 60
(A) Styrene 3.0K under nitrogen atmosphere while stirring at ℃
g, (a) 3.0 kg of methyl methacrylate, and (iii) 3.2 kg of ethyl acrylate, and 2-acrylamido-2-
0.8 kg of sodium salt of methyl propane sulfonic acid was added over 1 hour, and after stirring for 1.5 hours, steam distillation was performed for 1 hour to remove residual monomer, and after cooling to room temperature, pH was adjusted to 6.0 with ammonia. Adjusted to. The obtained latex liquid was adjusted to 75 kg with water. As described above, a monodisperse latex having an average particle size of 0.1 μm was obtained.

(Latex Lx-17) To a solution prepared by adding 0.01 kg of sodium dodecylbenzenesulfonate and 0.05 kg of ammonium persulfate to 40 liters of water while stirring at a liquid temperature of 80 ° C.
(A) Ethyl acrylate 9.3Kg under nitrogen atmosphere,
(A) Reaction product of epichlorohydrin and acrylic acid 0.4K
g and (c) A mixture of 0.3 kg of acrylic acid was added over 1 hour, then stirred for 1.5 hours, 1.0 kg of gelatin and 0.005 kg of ammonium persulfate were added and stirred for 1.5 hours, and steam was further added for 1 hour after the reaction was completed. After distilling to remove residual monomer, cool to room temperature and adjust the pH with ammonia.
Adjusted to 6.0. The obtained latex liquid was adjusted to 55 kg with water. As described above, a monodisperse latex having an average particle size of 0.12 μm was obtained.

(Preparation of emulsion) A silver sulfate solution and an aqueous solution of sodium chloride and potassium bromide were mixed with 8 × of rhodium hexachloride complex.
The solution added to 10 ^-5 mol / Ag mol was simultaneously added to the gelatin solution while controlling the flow rate, and after desalting, the particle size was adjusted to 0.
A cubic crystal, monodisperse, silver chlorobromide emulsion containing 13 μm and 1 mol% of silver bromide was obtained.

This emulsion was subjected to sulfur sensitization by a conventional method, 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer, and then the following additives were added to coat the emulsion. Liquid E
-1 to 10 are adjusted, and then emulsion protective layer coating solution P-0, backing layer coating solution B-0, backing protective layer coating solution BP-0.
Was prepared with the following composition.

(Preparation of Emulsion Coating Solutions E-1 to 10) Potassium bromide 5 mg / m ² compound (a) 1 mg / m ² NaOH (0.5N) adjusted to pH 5.6 Compound (b) 40 mg / m ² saponin (20%) 0.5 cc / m ² sodium dodecylbenzenesulfonate 20 mg / m ² 5-methylbenzotriazole 10 mg / m ² compound (d) 2 mg / m ² compound (e) 10 mg / m ² compound (f) 6 mg / m ² Latex LX Amount shown in Table 1 Styrene-maleic acid copolymerizable polymer (thickener) 90 mg / m ²

[0086]

[Chemical 16]

(Emulsion protective layer coating liquid P-0) Gelatin Amount shown in Table 1 Compound (g) (1%) 25 cc / m ² compound (h) 40 mg / m ² compound (k) 100 mg / m ² spherical monodispersion Silica (8μ) 20mg / m ² 〃 (3μ) 10mg / m ² Compound (i) 100mg / m ² Compound (o) 1.5mg / m ² Citric acid Adjusted to pH 5.8 Latex LX of the present invention Amount shown in Table 1 Styrene-maleic acid copolymer (thickener) 50 mg / m ² Formaldehyde (curing agent) 10 mg / m ² Isocyanate block compound of the present invention Amount shown in Table 1 (Backing layer coating solution B-0) Gelatin 1.0 g / m ² compound (j) 80 mg / m ² compound (k) 15 mg / m ² compound (l) 150 mg / m ² calcium chloride 0.3 mg / m ² saponin (20%) 0.6 cc / m ² citric acid pH adjusted to 5.5 5 - methyl benzotriazole 10 mg / m ² 5-nitroindazole 20 mg / m ² of polyethylene glycol (molecular 1540) 10mg / m ² Styrene - maleic acid copolymer (thickener) 45 mg / m ² Glyoxal 4 mg / m ² Compound (n) 80mg / ^{m 2} (Backing protective layer coating solution BP-0) shown in gelatine Table 1 Quantity Compound (g) (1%) 2cc / m ² Compound (j) 20mg / m ² Compound (k) 4mg / m ² Compound (l) 50mg / m ² Spherical polymethylmethacrylate (4μ) 25mg / m ² Sodium chloride 70 mg / m ² compound (o) amounts indicated in isocyanate blocking compound of table 1 1.5 mg / m ² glyoxal 22 mg / m ² bisvinylsulfonylmethylether 5 mg / m ² the invention

[0088]

[Chemical 17]

[0089]

[Chemical 18]

[0090]

[Chemical 19]

Each coating solution prepared as described above was used in
-After applying corona discharge at 10 W / (m ² · min) on the 100 μm-thick polyethylene terephthalate base with undercoating shown in 19941, use a roll-fit coating pan and air knife with the following composition. 10 cc / m
^It was applied so as to be ² . Drying was performed at 90 ° C for 30 "under parallel flow drying conditions with an overall heat transfer coefficient of 25 Kcal (m ² · hr · ° C), and then at 140 ° C for 90 seconds. The thickness of this layer after drying was 1
μ, and the surface resistivity of this layer was 1 × 10 ⁸ Ω at 23 ° C. and 55%.

[0092]

[Chemical 20]

Ammonium sulfate 0.5 g / l Polyethylene oxide compound (average molecular weight 600) 6 g / l Curing agent 12 g / l

[0094]

[Chemical 21]

[0095]

[Table 1]

On this base, the emulsion layer and the emulsion protective layer were sequentially coated from the side closer to the support as the emulsion surface side in this order at 35.degree. After passing through the zone (5 ° C.), the backing layer and the backing protective layer were coated by the slide hopper while adding the hardening agent, and set with cold air (5 ° C.). The coating liquid showed sufficient setting properties when passing through each set zone. Subsequently, both sides were simultaneously dried in the drying zone under the following drying conditions.
After coating both sides of the backing, it was conveyed until it was wound up with a roller and without contact with anything else. At this time, the coating speed was 100 m / min.

(Drying conditions) After setting, the product was dried with a dry air at 30 ° C. until the weight ratio of H ₂ O / gelatin reached 800%, and then 800 to 20.
0% was dried with 35 ° C (30%) dry air, and the air was blown as it was, and after 30 seconds from the time when the surface temperature reached 34 ° C (which is considered as the end of drying), it was dried with 48 ° C 2% air for 1 minute. . At this time,
Drying time is 50 seconds from the start of drying to 800% of H ₂ O / Gel, 800
% -200% is 35 seconds and 200% -drying is 5 seconds.

This light-sensitive material was wound up at 23 ° C. and 40%, then cut under the same environment, and put into a barrier bag conditioned under the same environment for 3 hours.
It was sealed with cardboard (which was conditioned at 40 ° C. 10% for 8 hours and then at 23 ° C. 40% for 2 hours).

In the light-sensitive material produced as described above, the coated silver amount was 3.5 g / m ² .

Evaluation sample Nos. 1 to 10 produced as described above
Was evaluated for dimensional stability and dryness in an automatic processor as follows.

(Dimensional stability) The obtained sample was 30 cm × 60 cm
The image was exposed to light using a bright room printer P-627FM (manufactured by Dainippon Screen Co., Ltd.) at a distance of about 56 cm, and developed.

The original, the unexposed sample (the same size as the original), the printer and the automatic developing machine were conditioned at 23 ° C. and 20% for 2 hours, and then the original was exposed to the exposed (face-to-face) exposure.
Processed in an automatic processor. After humidity control of the developed sample for 2 hours, the sample was overlaid on the original document and the distance between the fine lines was measured with a loupe with a scale. The measurement was performed at n = 6, and the average was taken. [(A) value] The same experiment was conducted at 23 ° C. and 60%, and the difference from the value of the dimensional difference before and after the treatment at 20% (showing the dependency on environmental humidity) was taken. [(B) value] (a) value is ±
If it exceeds 20μ, dimensional deviation will be noticed, and (b) value will be 20μ.
When it exceeds, it is conscious that the dimensional difference before and after processing has changed,
It is a level at which it is necessary to change the setting of some work conditions.

(Evaluation of Drying Property) After the above-mentioned development, a sample of 30 cm × 60 cm in size was treated with a fixing solution using an automatic developing machine and the dried state was observed. The line speed of the automatic processor was changed and the number of drying seconds when the processed film was dried was measured.

(Standard processing conditions) Development 28 ° C. 30 seconds Fixing 28 ° C. 21 seconds Washing with water Room temperature 17 seconds Squeeze 2 seconds Drying 50 ° C. 19 seconds [Developer formulation] (Composition A) Pure water (ion exchange water) 150 ml Ethylenediaminetetraacetic acid Disodium salt 2g Diethylene glycol 50g Potassium sulfite (55% W / V aqueous solution) 100ml Potassium carbonate 50g Hydroquinone 15g 5-Methylbenzotriazole 200mg 1-Phenyl-5-mercaptotetrazole 30mg Potassium hydroxide Amount to bring the pH of the solution to 10.9 Odor Potassium iodide 4.5g (Composition B) Pure water (ion exchanged water) 3ml Diethylene glycol 50mg Ethylenediaminetetraacetic acid disodium salt 25mg Sulfuric acid (90% aqueous solution) 0.3ml 5-Nitroindazole 110mg 1-Phenyl-3-pyrazolidone 500mg Use of developer Sometimes the above composition A and composition B in 500 ml of water
Were melted in this order and finished to 1 liter before use.

[Fixing liquid formulation] (Composition A) Ammonium thiosulfate (100% conversion) 168.2 ml Pure water 5.0 g Sodium sulfite 5.63 g Sodium acid trihydrate 37.8 g Boric acid 9.78 g Sodium citrate dihydrate 2 g Acetic acid (90% W / W aqueous solution) 6.4g (Composition B) Pure water (ion exchanged water) 2.82g Sulfuric acid (50% W / V aqueous solution) 6.6g Aluminum sulfate (Al ₂ O ₃ equivalent content is 8.1% W / V) 26.3 g of the fixing solution was dissolved in 500 ml of water in the order of the above composition A and composition B to 1 liter. The pH of this fixer is approximately
It was 4.38.

The results are shown in Table 2.

[0107]

[Table 2]

From the results in Table 2, it can be seen that the samples of the present invention have good dimensional stability and dryability.

[0109]

According to the present invention, a silver halide photographic light-sensitive material having excellent dimensional stability and rapid drying property can be provided.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support,
At least one free isocyanate group is contained in at least one of the constituent layers of the silver halide photographic light-sensitive material, and at least two or more free isocyanate groups are blocked by bisulfite, and all the remaining residual groups are present. A silver halide photographic light-sensitive material comprising a water-soluble or water-dispersible reactive compound obtained by blocking the free isocyanate group with another blocking agent and a polymer latex stabilized with gelatin.