JPH0318696B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material with improved photographic processing characteristics. Usually, a silver halide photographic material (hereinafter referred to as a "photosensitive material") is subjected to a development process after being photographed. For example, in the case of a color negative photosensitive material, the development process usually includes a color development process - a bleaching process - a fixing process -
It consists of a water washing step, and in the color development step, stirring is generally performed using a nitrogen burst or the like. On the other hand, the developer is circulated through a circulation pump-filter system, and when air bubbles due to nitrogen burst enter this circulation system, even finer air bubbles are generated. Furthermore, photosensitive materials contain a wide variety of surfactants for various purposes, and since these are generally water-soluble, they flow into the developer and promote the formation of bubbles. Furthermore, since the photosensitive material contains gas or a substance that generates gas in the developer, bubbles may be generated from the photosensitive material itself. Microscopic bubbles generated by these causes alone or in combination tend to adhere to the solid surface, but especially when they adhere to the surface of a photosensitive material, those areas are not developed and are left blank, reducing the value of the photosensitive material. This can cause serious damage that can result in complete loss. Several studies have been carried out to solve this problem. These methods mainly involve incorporating a certain type of surfactant into the photosensitive material in order to improve wetting of the surface of the photosensitive material.
-3219, JP-A-51-32322, etc. However, these methods have the disadvantage that the amount of surfactant added is limited and sufficient effects cannot be obtained because the surfactant flows into the treatment liquid and promotes the foaming properties of the treatment liquid. Furthermore, these methods achieve their effects by orienting the surfactant on the surface of the photosensitive material in a preferred manner for wetting, but the preferred orientation changes due to heat, humidity, or time, and the initial effect may be lost. It also had the essential drawback that it could not be displayed. Therefore, the first object of the present invention is to produce stable photographs that have good wettability to photographic processing solutions, are free of bubbles, and are free of unevenness, even during automatic development processing at high speeds. The object of the present invention is to provide a novel photosensitive material having processing characteristics. The second object is to provide a photosensitive material whose photographic processing characteristics are free from deterioration due to heat, humidity, and time. Thirdly, it is an object of the present invention to provide a photosensitive material that does not increase the foaming properties of a processing solution and has excellent photographic processing characteristics as mentioned above. Fourth, it is an object of the present invention to provide a photosensitive material that exhibits the above-mentioned target photographic processing properties without impairing other physical properties such as adhesion resistance. As a result of various studies, the present inventors have found that the above-mentioned objects can be achieved by providing a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid outer surface layer on the same side of a support. , wherein the outer surface layer consists of two layers, an outer inner layer and an outer outer layer, the outer inner layer contains an alkali-soluble polymer having an anionic group, and the outer surface layer does not contain a carboxylic acid activated condensing agent. It has been found that this can be achieved by using a silver halide photographic light-sensitive material. In the present invention, the outer surface layer on the same side as the photosensitive silver halide emulsion layer (hereinafter referred to as emulsion layer) refers to the outer surface layer that is on the same side as the photosensitive silver halide emulsion layer (hereinafter referred to as emulsion layer) when the photosensitive material is finished as a product.
It refers to a non-photosensitive hydrophilic colloid layer located further outside the emulsion layer when viewed from the support, and is referred to as a so-called protective layer (hereinafter, the outer surface layer will be referred to as a protective layer). Therefore, a non-photosensitive hydrophilic colloid layer sandwiched between the support and the emulsion layer and between the emulsion layers is not included. Further, when the emulsion layers are on both sides of the support, the protective layer may be provided on the outside of the emulsion layers on both sides. Therefore, in the photosensitive material of the present invention, there are the following three possible embodiments regarding the layer structure position of the protective layer. That is, (1) when the protective layer of the present invention is provided on the outer surface of a photosensitive material that has an emulsion layer on one side of the support; (2) when the protective layer of the present invention is provided on the outer surface of a photosensitive material that has emulsion layers on both sides of the support; (3) In the case of a light-sensitive material having emulsion layers on both sides of the support, when the protective layer of the present invention is provided only on the outer surface of both sides (3)
That's right. The alkali-soluble polymer having an anionic group used in the present invention is not particularly limited, but monopolymers or copolymers of monomers having a carboxylic acid group, monomers having a sulfonic acid group, and monomers having a phosphoric acid group may be used. Useful. As these monomers, the following are particularly preferably used. Acrylic acid, methacrylic acid, maleic anhydride (maleic acid, half ester, half amide, etc. derived therefrom), cinnamic acid, crotonic acid, citraconic acid, p-carboxystyrene, vinyl-α-carboxymethyl ether, etc. Also vinyl sulfone acid,
These include styrene sulfonic acid and phosphoric acid alkyl acrylate. Monomers copolymerizable with the above monomers include ethylenically unsaturated monomers such as ethylene, vinyl acetate, styrene, alkyl vinyl ethers such as methyl vinyl ether, acrylic esters (such as ethyl acrylate, butyl acrylate, phenyl acrylate, etc.), and the like. Examples include methacrylic acid esters, acrylamide derivatives such as acrylamide acryloylmorpholine, methacrylamides, vinylpyrrolidone, and the like.
The proportion of alkali-soluble monomer in the copolymer varies depending on the type of polymer, but it is preferably at least 5 mol%. In addition, the molecular weight of the alkali-soluble polymer used in the present invention varies depending on the type of polymer, but generally
5000-500000, preferably 10000-200000. The alkali-soluble polymer can be used after being neutralized with an alkali, if necessary. The term "alkali" as used herein refers to salts of alkali metals, alkaline earth metals, and basic bases that provide an alkaline aqueous solution, preferably salts such as Na ⁺ , K ⁺ , Li ⁺ , NH ⁺ ₄ and the like. Further, the degree of neutralization may be set to any level as required, but the alkali-soluble polymer should be 1% or more.
It is preferable to adjust the pH between 5.0 and 8.5 in an 8% aqueous solution. Specific compounds advantageously used in the present invention include the following. The amount of the alkali-soluble polymer used in the present invention varies depending on the type and molecular weight of the polymer, but is preferably 0.05 g/m ² to 2.0 g/m ² , more preferably 0.1 g/m ² to 1.0 g. /m ² is preferred. In addition, the polymer is supplementarily added not only to the layer in contact with the emulsion layer (protective inner layer) of the protective layer consisting of the protective inner layer and protective outer layer, which follow the names of the outer surface inner layer and outer layer, but also to the outer protective layer. You may. Further, the amount of the alkali-soluble polymer added to the binder is preferably 1 or less, more preferably 0.5 or less in terms of dry weight ratio. The amount of binder in the protective outer layer is 0.1 to 1.0g/
m ² preferably 0.3 to 0.8 g/m ² and in the protective inner layer 0.2 to 4.0 g/m ² preferably 0.3 to 3.0
g/ ^m2 . It was not previously known that anionic alkali-soluble polymers enhance the wettability of photosensitive materials with developing solutions, and this is a new discovery. Moreover, unlike surfactants, the technology improves wetting by aligning to the surface of the photosensitive material, but by adding it to the inner layer rather than the surface layer that is in direct contact with the processing solution, it improves wetting at the same time. The present invention is novel and different from previous technologies in that it improves retention of properties and adhesion resistance. By adding the polymer to the protective inner layer described above in the present invention, the following effects can be obtained. That is, if it is added to the protective outer layer instead of the protective inner layer, there is a large risk that surface properties such as adhesion resistance will deteriorate first. Development called adhesion occurs between photographic materials or between photographic materials and other objects that come into contact with them during the production, processing, or storage of photosensitive materials, and often causes various inconveniences. This is development. In order to make the hydrophilic colloid layer difficult to adhere to (in the industry this is referred to as "improving adhesion resistance", the term adhesion resistance will be used hereafter), the layer has an average particle size of 1 to 1. 5μ fine powder (hereinafter referred to as
A technique is known in which the roughness of the surface of the colloid layer is increased by making the colloid layer surface rougher by making it so-called matte by making the colloid layer have fine particles such as silica, magnesium oxide, or polymethyl methacrylate (hereinafter referred to as a matting agent). If a matting agent is further added to improve the adhesive resistance that has deteriorated as described above, after the development process,
It is said to have undesirable side effects such as reducing the transparency of the formed image, impairing the graininess of the image, and worsening the slipperiness of the surface of the photosensitive material, making the image surface more prone to scratches. produce defects. The second problem is the outflow of the polymer into the processing solution. The outflow into the processing solution causes undesirable effects such as formation of scum in the processing solution or deterioration of membrane strength. Of course, even if it is added to the protective inner layer, the outflow will not be completely eliminated, but the amount of outflow will be considerably smaller than when the alkali-soluble polymer is exposed on the surface of the photosensitive material. Next, if it is added to a layer further below the protective inner layer, such as an emulsion layer or other intermediate layer, the expected effect will not be obtained even if the amount added is increased considerably because the distance from the surface of the photosensitive material is long. There is a drawback. Therefore, a protective inner layer is particularly preferred as the layer to which the alkali-soluble polymer is added, and when the light-sensitive material is wetted with an alkaline processing liquid, it rapidly diffuses to the outer surface and improves wetting. Furthermore, it can be added as an auxiliary to the protective outer layer if necessary. In the present invention, surfactants may be used alone or in combination. They are generally used as coating aids, but as mentioned above, they are used to improve the wetting characteristics of photosensitive materials to processing solutions, emulsification and dispersion, sensitization, improvement of photographic properties, antistatic properties, and prevention of adhesion. Applicable for such reasons. These surfactants include natural surfactants such as saponins,
Nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkyl amines, quaternary ammonium salts, pyridine and other heteros, cationic surfactants such as phosphonium or sulfonium salts, carboxylic acids, sulfonic acids, There are anionic surfactants containing acidic groups such as phosphoric acid, oxalate ester groups, and sulfate ester groups; amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino acids, aminosulfonic acids, and amino alcohols; There are also fluorine-based surfactants. Among these, for example, JP-A-51-3219, JP-A-51-
The compounds described in No. 32322 and the like are surfactants preferably used in the present invention. Other examples of surfactants that may be used include U.S. Pat.
No. 2271623, No. 2240472, No. 2288226, No.
No. 2739891, No. 3068101, No. 3158484, No.
No. 3201253, No. 3210191, No. 3294540, −48−
No. 15649, No. 3441413, No. 3442654, No. 3475174
No. 3545974, West German Patent Publication (OLS)
It is described in British Patent No. 1942665, British Patent No. 1077317, British Patent No. 1198450, etc. Examples of fluorine-based surfactants include British Patent No. 1330356, British Patent No. 1524631, and U.S. Patent No.
No. 3666478, No. 3589906, Special Publication No. 52-26687,
It is described in JP-A-49-46733, JP-A-51-32322, etc. Representative compounds, for example, N-
Perfluorooctylsulfonyl-N-propylglycine potassium salt, 2-(N-perfluorooctylsulfonyl-N-ethylamino)ethyl phosphate, N-[4-(perfluorononenyloxy)benzyl]-N,N- Dimethylammonioacetate, N-[3-N',N',N'-trimethylammonio)propyl]perfluorooctylsulfonamide iodide, N-(polyoxyethylenyl)-N-propylperfluorooctylsulfonamide ( _{C8F17SO2N ) ( C3H7 )}
(CH ₂ CH ₂ O) _o H) and fluorine-containing succinic acid compounds. The binder used in the protective layer of the present invention can be any of those commonly used in the art, such as alkali-treated gelatin, acid-treated gelatin, and enzyme gelatin, as well as derivative gelatin such as phthalated gelatin and malonated gelatin. can. In addition to the above-mentioned derivative gelatin and ordinary photographic gelatin, if necessary, colloidal albumin, agar, gum arabic, dextran, alginic acid, cellulose such as cellulose acetate hydrolyzed to an acetyl content of 19 to 26% may be used. derivatives, polyacrylamides, imidized polyacrylamides, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol-vinyl cyanoacetate copolymers, polyvinyl alcohol-polyvinyl pyrrolidone, hydrolyzed polyvinyl acetate, proteins or saturated Polymers obtained by polymerizing an acylated protein and a monomer having a vinyl group, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. can also be used. The protective layer in the present invention can be hardened using a conventionally well-known hardening agent.
Examples of hardening agents include ketone compounds such as diacetyl, diclopentanedione, bis(2-chloroethylurea), 2-hydroxy-4,6-di-chloro-1,3,5-triazine, U.S. Pat.
No. 3288775, No. 2732303, British Patent No. 974723,
Compounds containing reactive halogens, divinyl sulfone, 5-
Acetyl-1,3-diacryloylhexahydro-
1,3,5-triazine and the like can be used. A matting agent may be used in the present invention. Examples include inorganic substances such as silica, magnesium oxide, titanium dioxide, calcium carbonate, etc., polymethyl methacrylate, cellulose acetate propionate, or acrylic acid and acrylic acid as described in JP-A-51-135958. There are organic substances such as alkali-soluble porous polymer particles made of methyl, and the particle size is 0.1μ to 20μ.
A thickness of approximately 0.5 to 10 μm is particularly preferred. In the present invention, the protective outer layer may include colloidal silica. A specific example is EIdu Pont.
Ludox AM from de Nemours & Co. (USA),
Ludox AS, Ludox LS, Ludox TM, Ludox
HS, etc., and from Nissan Chemical Co., Ltd. (Tokyo, Japan) with product names such as Snowtex 20, Snowtex C, Snowtex N, Snowtex O, etc.
SytonC−30 from Monsanto Co. (USA),
With product names such as Syton200, and Nalco Chem.Co.
(USA) Nalcoag 1030, Nal−coag
Examples include those commercially available under trade names such as 1060 and Nalcoag ID-21-64. The protective outer layer of the present invention may also contain a slip agent. Useful materials include higher alkyl sodium sulfates, higher fatty acid higher alcohol esters, carbo waxes, higher alkyl phosphate esters, and silicone compounds. Especially US patent no.
The compounds described in No. 2882157, No. 3121060, No. 3850640, and JP-A No. 141623/1988 are particularly effective when used alone or in combination of two or more. The light-sensitive material of the present invention has at least one emulsion layer supported on a support, and includes an emulsion layer, a support, and optional auxiliary layers (an antihalation layer, a filter layer, an intermediate layer, a subbing layer, etc.). etc.), all known ones can be used. The silver halide used in the emulsion layer of the present invention is
Generally, silver halide particles are dispersed in a hydrophilic colloid, and silver halides include silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide. Ammonia method, neutral method, acid method, British Patent No. 635841, U.S. Patent No.
It can be produced by various methods such as the so-called convergence method and simultaneous mixing method described in No. 3622318. Furthermore, as the hydrophilic colloid in which silver halide is dispersed, the same binder as used in the non-photosensitive hydrophilic colloid layer described above can be used. The silver halide emulsion described above can also be chemically sensitized by conventional methods. Furthermore, these silver halide emulsions can be subjected to spectral sensitization or superchromatic sensitization, if necessary, by using cyanine dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or in combination with styryl dyes, etc. You can do the feeling. Various known photographic additives may be added to the above-mentioned photographic emulsion for various purposes, such as to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material. For example, as an antifoggant, 4-hydroxy-6-methyl-1,3,3a,7
- Many heterocyclic compounds, mercury-containing compounds, including tetrazaindene, 3-methylbenzothiazole, 1-phenyl-5-mercaptotetrazole,
A large number of compounds such as mercapto compounds and metal salts have been known for a long time. The following couplers can be used in the color photosensitive material of the present invention. As the yellow coupler, an open chain ketomethylene compound has conventionally been used, and the generally widely used benzoylacetanilide type yellow coupler and pivaloylacetanilide type yellow coupler can be used. Furthermore, a two-equivalent type yellow coupler in which the carbon at the coupling position is substituted with a substituent that can be removed during the coupling reaction is also usefully used. These examples are from U.S. Patent No.
No. 2875057, No. 3265506, No. 3664841, No. 3408194, No. 3447928, No. 3277155,
No. 3415652, Special Publication No. 13576, No. 13576, No. 48-
No. 29432, No. 48-66834, No. 49-10736, No. 49
It is described in No.-122335, No. 50-28834, No. 50-132926, etc. Examples of magenta couplers that can be used in the present invention include compounds such as pyrazolone, pyrazolotriazole, pyrazolinobenzimidazole, and indazolone. As a pyrazolone magenta coupler, U.S. Patent No.
No. 2600788, No. 3062653, No. 3127269, No. 3311476, No. 3419391, No. 3519429,
Same No. 3558318, Same No. 3684514, Same No. 3888680,
JP-A-49-29639, JP-A No. 49-111631, JP-A No. 49-
Compounds described in Japanese Patent Publication No. 129538, No. 50-13041, No. 51-105820, Japanese Patent Publication No. 53-47167, and Japanese Patent Publication No. 55-30615; as pyrazolotriazole magenta couplers, British Patent No. 1247493, Compounds described in Belgian Patent No. 792525; Also, as pyrazolinobenzimidazole magenta couplers, compounds described in U.S. Patent No. 3061432, West German Patent No. 2156111, and Japanese Patent Publication No. 46-60479; Examples of indazolone magenta couplers include compounds described in Belgian Patent No. 769116. Next, as the cyan coupler used in the present invention, phenol or naphthol derivatives are generally used. For example, U.S. Patent No. 2423730;
No. 2474293, No. 2801171, No. 2895826, No. 3476563, No. 3737316, No. 3758308,
No. 3839044, JP-A-47-3742, JP-A No. 50-10135
No. 50-25228, No. 50-112038, No. 50-
It is described in No. 117422, No. 50-130441, etc. In addition to the above-mentioned couplers, colored magenta couplers and colored cyan couplers can also be advantageously used in the light-sensitive material of the present invention, and any photosensitive materials such as so-called DIR compounds, dye fading inhibitors, stain inhibitors, etc. additives may be included. In the present invention, the support on which the protective layer, emulsion layer, and other auxiliary layers according to the present invention are coated includes cellulose ester films such as cellulose nitrate and cellulose acetate, polyester films such as polyethylene terephthalate, polyvinyl acetal films, and polyester films. Vinyl chloride film, polystyrene film, polycarbonate film, baryta paper,
Polyethylene coated paper, polypropylene synthetic paper, etc. are preferably used. In the present invention, the selection of coating methods for the protective layer, emulsion layer and other constituent layers of the light-sensitive material is important in order to ensure uniform quality and productivity. For example, you can choose from dip coating, double roll coating, air knife coating, extrusion coating, and curtain coating, among which extrusion coating and curtain coating can apply two or more layers at the same time. is particularly useful. Also, the coating speed can be selected arbitrarily, but from the viewpoint of productivity
30/min or more is preferable. Also, because of its fast reactivity, such as hardening agents,
For substances that may cause gelation if added to the coating liquid in advance, it is preferable to mix them using a static mixer immediately before coating. The photosensitive material of the present invention can be any type of photosensitive material processed with an alkaline processing liquid, such as general black and white, X-ray, printing, micro, electron beam recording, infrared recording, and color. It's okay. Next, the present invention will be explained in detail with reference to Examples, but the embodiments of the present invention are not limited thereto. Example 1 Containing 300 g of gelatin per mole of silver halide and containing α-pivaloyl-α-(1-benzyl-2,4-dioxyimidazolin-3-yl)-2-chloro-5[r] as the yellow coupler. −(2,
2.5×10 ⁻² mol of 4-tert-amylphenoxy)butyramide]acetanilide and as a hardening agent,
1,2-bis(vinylsulfonyl)ethane 0.02
A color blue-sensitive silver iodobromide (silver iodide 7 mol %) emulsion containing g/1 g gelatin was prepared. Along with this emulsion, the compound P-1,1,2-bis(vinylsulfonyl) of the present invention was used for the protective layer.
A gelatin solution containing ethane, polymethyl methacrylate with an average particle size of 4 μm as a matting agent, and a coating aid was poured onto a pre-subbed cellulose triacetate film support using a slide hopper method so as to have the composition shown in Table 1. Starting from the support, an emulsion layer, a protective inner layer, and a protective outer layer were simultaneously coated in three layers at a coating speed of 50 m/min. The thickness of the protective layer after drying is based on the thickness of the protective outer layer.
The thickness of the inner layer was 0.5μ, and the inner layer was 1.0μ. After drying, coated samples No. 1 to No. 4 were each 3.5 cm x 14
Cut into cm-sized pieces and store for 1 day at 23℃ and 55% RH (RH represents relative humidity. The same applies below), then vertically immerse in a developer having the following composition.
After 3 minutes, the number of bubbles attached to the sample surface was counted. Color developer composition: 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1, Adjust to PH10.0.

【table】

[Table] In addition, two pieces of 5 cm square each were cut from Samples No. 1 to No. 4, and each piece was stored in an atmosphere of 23°C and 80% RH for one day without touching each other. The protective layers of the samples are brought into contact with each other.
A load of 800 g was applied and the sample was stored in an atmosphere of 40° C. and 80% RH, and then the sample was peeled off and the area of the bonded portion was measured to measure adhesiveness. The evaluation criteria were based on the following method. Rank A adhesive area area 0-20% Rank B 21-40% Rank C 41-60% Rank D 61-80% Rank E 81% or more The results are shown in Table 2.

[Table] In the comparison of samples No. 1 to No. 4 in Table 2, No. 2 to No. 4 containing compound P-1 are No.
It can be seen that the number of attached bubbles is significantly reduced compared to No. 1. Moreover, in the comparison of No. 2 to No. 4, adding Compound P-1 to the outer layer deteriorates the adhesion resistance, whereas adding it to the inner layer does not deteriorate the adhesion resistance, which is the superiority of the present invention. I understand that. Example 2 The following layers were provided on the subtracted triacetic acid base from the base side. 1st layer Antihalation layer containing black colloidal silver (dry film thickness 1μ) 2nd layer 1-hydroxy-N-{r-(2,4-di-tert-
amylphenoxy)-butyl}-2-naphthamide
6.8×10 ^-2 mol, 1-hydroxy-N-{δ-(2,4-di-tert-amylphenoxy)-butyl}-4-(2-ethoxycarbonylphenylazo)-2-naphthamide 1.7 as colored coupler ×
10 ^-2 mol, 2-(1
-phenyl-5-tetrazolylthio)-4-(2,
4-di-tert-amylphenoxyacetamide)
-1-Red-sensitive silver iodobromide emulsion layer containing 4×10 ^-3 mol of indanone (silver iodobromide emulsion containing 8 mol% silver iodide, dry film thickness 6μ) Third layer per mol of silver halide 1-(2,4,6-trichloro)phenyl-3 as magenta coupler
-[3-(2,4-di-tert-amylphenoxy)
Acetamide] benzamide-5-pyrazolone
5.8×10 ^-2 mol, 1- as a colored coupler
(2,4,6-trichlorophenyl)-3-[3-
(octatecenylsarcinimide)-2-chloro]anilide-4-(r-naphthylazo)-5-pyrazolone 1.7×10 ^-2 mol and 2-(1-phenyl-5-tetrazolylthio) as a development inhibitor-releasing substance. )-4-(2,4-di-tert-amylphenoxyacetamide)-1-indanone 7×10 ⁻³ mol green-sensitive low-sensitivity silver iodobromide emulsion layer (silver iodide 8
(silver iodobromide emulsion containing mol %, dry film thickness 3.5 μm) 4th layer The same compound as the magenta coupler, colored coupler, and development inhibitor-releasing substance in the 3rd layer was added per mole of silver halide at 1.1×10 ^{- 2} moles, 5
Green-sensitive high-sensitivity silver iodobromide emulsion layer containing ×10 ^-3 mol and 2 × 10 ^-2 mol (silver iodobromide emulsion containing 6 mol of silver iodide, dry film thickness 2.5μ) 5th layer Yellow colloidal silver and a gelatin layer containing 2,5-di-tert-octylhydroquinone (dry film thickness
1 μ) 6th layer Contains 350 g of gelatin per mole of silver halide, and as a yellow coupler α-vivaloyl-α-(1-benzyl-2-phenyl-3,5-
dioxo-triazolidin-4-yl)-5′-[α
-(2,4-di-tert-amylphenoxy)butyramide]-2'-chloroacetanilide 3×10 ^-1
Blue-sensitive silver iodobromide emulsion layer containing 1,2-bis(vinylsulfonyl)ethane as mol and hardener (silver iodobromide emulsion containing 7 mol % silver iodide, dry film thickness
6μ) Protective layers having the compositions shown in Table 3 below were coated thereon as the seventh and eighth layers.

[Table] The thickness of the protective outer layer after drying was approximately 0.6μ, and the thickness of the protective inner layer was approximately 1.2μ. Regarding the sample coated and dried as above,
The tests described in (1) to (4) below were conducted. (1) Samples No. 5 to No. 10 after drying, each 3.5 cm x 14 cm
Cut into pieces and store in an atmosphere of 23℃ and 55%RH.
After storage for a day, the sample was immersed vertically in a developer having the composition shown below, and the number of air bubbles attached to the sample surface was counted after 3 minutes. Color developer composition: (development temperature 38°C) 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfate
4.75g Anhydrous sodium sulfite 4.25g Hydroxylamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Sodium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5g Potassium hydroxide 1.0g Add water to make 1, Adjust to PH10.0. (2) Also, cut samples No. 5 to No. 10 into 3.5 cm x 14 cm pieces and place them in an atmosphere of 40°C and 80% RH.
The sample was stored for a week, and then stored in an atmosphere of 23° C. and 55% RH for 1 day, and then subjected to the same treatment using the developer described above, and the number of air bubbles attached to the sample surface was counted. (3) Also, cut two pieces of each sample No. 5 to No. 10 into 5 cm square pieces, and place them in an atmosphere of 23°C and 80% RH without touching each other.
After storing for several days, the protective layers of the same samples were brought into contact with each other, a load of 800 g was applied, and the temperature was 80% at 40°C.
The sample was stored in an RH atmosphere, and then the sample was peeled off and the area of the adhesive part was measured to measure the adhesion. Note that the evaluation criteria were based on the method described in Example 1. (4) Next, samples No. 5 to No. 10 were cut into 3.5 cm x 100 cm.
We prepared 20 bottles of each sample, treated them with a developer solution according to sample number, and examined the foaming properties of these developers. For foaming properties, collect 200c.c. of each developer in a cylinder,
They were aerated for 1 minute and the height of the bubbles generated was taken as a measure. The above results are shown in Table 4.

[Table] In Table 4, it can be seen that the number of attached bubbles decreases significantly when Exemplified Compound P-6 is added. Moreover, the results do not change whether it is added to the protective outer layer or the inner layer. Furthermore, it can be seen that when added to the outer layer, the adhesion resistance deteriorates significantly, whereas when added to the inner layer, it does not deteriorate. Also, comparative compound S-1
In comparison with Sample No. 9, the number of bubbles adhering rapidly increased after heating, humidification, and treatment, whereas in No. 7, the number of bubbles adhering did not change even after heating and humidification, indicating the superiority of the present invention. I understand that. Example 3 A high-sensitivity silver iodobromide emulsion containing 2.0 mol% of silver iodide was chemically ripened and then 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene was added as a stabilizer in an amount of 2.0 g per mole of silver halide, and saponin as a coating aid and formalin as a hardening agent were added in predetermined amounts. This emulsion contained 60 g of gelatin per mole of silver halide. Along with this emulsion, the compounds P-1, P- of the present invention
6 and formalin as a hardening agent, saponin or sodium di-2-ethylhexylsulfosuccinate as a coating aid, and polymethyl methacrylate as a matting agent. Coating the emulsion layer, protective inner layer, and protective outer layer in order from the support onto a polyethylene terephthalate film support at a coating speed of 50 m/s.
Three layers were applied simultaneously in minutes.

[Table] The thickness of the protective layer of the coated sample after drying was 0.7μ for the outer layer and 1.3μ for the inner layer. After drying, coated samples No. 11 to No. 15 were each 3.5 cm x 14
Cut into cm-sized pieces, store for 1 day at 23℃ and 55% RH, then immerse in a developer having the following composition.
After seconds, the number of bubbles attached to the sample surface was counted. Developer composition (development temperature 35°C) Hydroquinone 10g Anhydrous sodium sulfite 70g Boric anhydride 1g Sodium carbonate (monohydrate) 20g 1-phenyl-1,3-pyrazolidone 0.35g Sodium hydroxide 5g 5-methylbenzotriazole 0.05g Odor Potassium chloride 5g Glutaraldehyde bisulfite 15g Glacial acetic acid 8g Add water to make 1. In addition, two pieces of No. 11 to No. 15 were cut into 5 cm square pieces each, and after storing them for one day in an atmosphere of 23°C and 80% RH, the protective layer surfaces of each sample of the same type were brought into contact with each other, and 800 g 40℃, 80℃ with a load of
Store under an atmosphere of %RH and then peel off the sample.
The area of the bonded portion was evaluated according to the criteria shown in Example 1. The above results are shown in Table 6.

Table 6 shows that the present invention is effective against foam adhesion and also has excellent adhesive resistance. Comparative Example 1 Samples 16 to 20 were prepared exactly as in Example 3, but each outer layer and inner layer contained N-methylsulfonyloxy-2,6-dioxo-piperidine.
24 mg/m ² were added. The obtained sample is Example 3
The same evaluation as above was carried out, and the results are shown in Table 7.

[Table] From Table 7, the carboxylic acid activated condensing agent,
The addition of N-methylsulfonyloxy-2,6-dioxo-piperidine improves adhesion resistance, but
It turns out that it is harmful to foam adhesion.

Claims (1)

[Claims] 1 In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and a non-light-sensitive hydrophilic colloid outer surface layer on the same side of the support, the outer surface layer is composed of two layers: an outer surface inner layer and an outer surface outer layer. 1. A silver halide photographic material comprising: an alkali-soluble polymer having an anionic group in the outer and inner layers; and a carboxylic acid-activated condensing agent is not contained in the outer surface layer.