JPS5814131A - silver halide photographic materials - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly to a hydrophobic support having a coating layer with good coating stability and a sufficiently cured antistatic coating layer. The present invention relates to a silver halide photographic material comprising a body and a silver halide photographic constituent layer.

Usually, a silver halide photographic material is composed of a support and a silver halide photographic constituent layer provided on the support. Such silver halide photographic constituent layers include a silver halide photographic emulsion layer, a protective layer, a subbing layer, an intermediate layer or anti-wrapping layer, an antihalation layer or filter layer, an ultraviolet absorbing layer, etc., and combinations thereof. It is what was done. For example, a single silver halide photographic material has a silver halide photographic emulsion layer and its protective layer on a support. In addition, multilayer silver halide photographic materials have a multilayer arrangement in which a real emulsion layer and an intermediate layer, a green emulsion layer and an ultraviolet absorbing layer, a red emulsion layer and a protection layer, etc. are sequentially provided on a support. It is something.

By the way, conventional supports for silver halide photographic materials include films such as polyethylene terephthalate film J1, cellulose acetate film, polystyrene film, and polycarbonate film, paper as a substrate, and resins with film-forming ability on both sides, often polyolefins. Hydrophobic supports such as resin-coated papers coated with resins are well known. In particular, polyolefin resin-coated paper is increasingly being used as a support for photographic paper in place of the conventionally used baryta paper. The reason for this is that polyolefin resin-coated paper used as a photographic support is hydrophobic, so processing liquids penetrate into the base paper layer during the development and fixing process of photographic paper, compared to baryta paper. This is because there is an advantage that processing times such as washing and drying are shortened.

However, these photographic hydrophobic supports have several drawbacks. The well-known shortcomings are:
These hydrophobic supports and silver halide photographic materials having hydrophobic supports become electrostatically charged during handling and tend to attract dirt, dust, etc., resulting in various problems such as water repellency, desensitization, capri In addition to causing spots, especially as a result of the discharge of accumulated static electricity, unpleasant partial caps may be formed in the photographic layer called static marks in the silver 14 true emulsion layer. It may occur. Furthermore, silver halide photographic materials having these hydrophobic supports tend to curl in the direction of the photographic layer plane, making their use inconvenient. On the back side of this thinned silver halide photographic material, that is, on the surface of the support that is not coated with the silver halide layer, a hydrophilic colloid layer called an antistatic and anticurl back coat layer is formed. It is known to install a fabric layer t-.

It is also known to provide an entire coating layer consisting of a hydrophilic colloid layer called antistatic sublayer J- on the side of the support on which the constituent layers are coated.

However, if the antistatic coating layer consisting of the hydrophilic colloid layer for the barafco-l layer phase and the subbing layer is not sufficiently adhered to and cured on the hydrophobic support, it may cause oxidation. During the handling of silver copies, especially during the development process, film peeling becomes a problem.

In order to solve the above-mentioned problems of silver halide photographic materials having hydrophobic supports, various coating layers for back coat layers or subbing layers have been proposed. for example,
JP-A-55-32009 proposes a back coat layer or undercoat layer containing as main components a styrene-maleic anhydride copolymer, colloidal silica, and a specific curing agent. In addition, Japanese Patent Application Laid-open No. 55-69139 describes carbon number 4
A back coat layer has been proposed whose main components are a water-soluble polymer compound obtained by copolymerizing the above ethylenically unsaturated copolymerizable monomer with maleic anhydride and a specific curing agent. These coating layers have the following advantages;
5 - It is excellent. First, since it is a single coating layer, the coating process is simple. Second, since the coating layer is cured by fully contacting the hydrophobic support, the silver halide consisting of the hydrophobic support with the coating layer and the silver halide photographic constituent layer. Photographic materials do not suffer from problems such as film peeling during the development process. Thirdly, because the coating layer has excellent antistatic and anti-curl properties, it is a static mark for silver halide photographic materials consisting of a hydrophobic support with a coated coating layer and/or a silver halide photographic constituent layer. and significantly reduces the tendency of curling. Fourthly, it is a coating layer that does not have an adverse effect on the emulsion. Although these coating layers are quite excellent in the above points, it has become clear that they have some serious problems.

In the first place, as a result of studies conducted by the present inventors, it has become clear that another type of drawback of hydrophobic supports for photography also appears during the development of silver halide color photographic materials. recent years,
Silver halogenide color 6- Development processing systems for photographic materials are either continuous replenishment systems or continuous systems for processing solutions aimed at reducing costs. In color photographic processing solutions such as developing solutions and bleach-fix solutions, oxidation products such as developing agents, development accelerators, etc.) and organic compounds eluted from silver rhodanide color photographic materials into processing solutions and oxidative polymerization. There is a tendency for contaminants from the products to build up and to stick to the hydrophobic surfaces of the supports of color photographic materials, especially on the opposite side of the support from which the emulsion layer has been fully coated. By the way, when a silver halogenide photographic material consisting of a hydrophobic support having a coating layer as already exemplified and described and a silver halogenide photographic constituent layer is subjected to development processing, particularly color processing processing, It has become clear that these coated layers have the disadvantage of being resistant to adhesion of contaminants, in other words, that these coated layers have no ability to prevent contamination. Furthermore, the fabric layer consisting of a hydrophilic colloid applied adjacent to a hydrophobic support can have multipurpose functions such as antistatic properties, anti-curling properties, adhesion properties, and anti-staining properties when coated in a single layer. And often,
There is also a serious problem in that, especially when colloidal silica is present, the stability of the coating liquid stabilizer deteriorates, and coating liquid components tend to settle, separate, or coagulate. For this reason, it is desired to develop a coating layer consisting of a hydrophilic colloid layer for a back coat layer and/or an undercoat layer, which has multi-purpose functions and particularly has excellent stability of the coating solution fc.

Therefore, the purpose of the present invention is, firstly, to improve the stability of the coating liquid;
It consists of a hydrophobic support with a coating layer that is sufficiently cured and has excellent antistatic properties, and a silver halide photographic constituent layer. An object of the present invention is to stably provide an excellent /S silver halide photographic material that does not cause the problem of film peeling during processing and has a reduced tendency to generate static marks.

Second, the stability of the coating solution is good, and the excellent coating composition consisting of a hydrophobic support and a silver halide photographic constituent layer, which is equipped with a back coat layer that has multipurpose functions in a single coating layer, is excellent. There are several things that the Silver Photographic Materials Association provides. Thirdly, a hydrophobic support having a backcoat layer with good coating liquid stability, a sufficiently cured coating layer, and excellent antistatic performance and excellent antifouling performance; It consists of a silver chloride color photographic constituent layer, therefore, it does not cause problems of film peeling and contamination during the processing of silver chloride color photographic materials, and reduces the tendency for static marks and curls to occur. The purpose of the present invention is to stably provide excellent silver halide color photographic materials. Another object of the present invention is to provide an excellent silver halogenide photographic material comprising a hydrophobic support and a silver halogenide photographic constituent layer, which is provided with a coating layer having a multipurpose function that does not have an adverse effect on the emulsion. The goal is to provide the following. Other objects of the invention,
Features, advantages, etc. will be understood from the description of Specification 1 below.

As a result of extensive studies, the present inventors have found that the object of the present invention is to provide a silver halide photographic material consisting of a hydrophobic support and a silver halide photographic layer, in which a silver halide film is formed on one or both sides of the support. , (a) a water-soluble polymer compound or a salt thereof obtained by copolymerizing an ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms and maleic anhydride; This is achieved by applying a coating layer comprising at least 1 flt of a curing agent having phtyleneimino groups or ≠lysyl ether groups and (C) colloidal silica and (d) at least one of oxidized starch or phosphoesterified starch. I understand.

More specifically, even if a water-soluble polymer other than oxidized starch or phosphated starch is used as component (d) of the coating layer of the present invention, the effects of the present invention cannot be obtained at all. In particular, even if starches other than natural starches such as wheat starch and corn starch, oxidized starches such as starch derivatives such as cationized starch and hydroxyethylated starch, or starches other than phosphoric acid esterified starches are used, the stability of the coating liquid is poor. It is also noteworthy that natural starch does not have the ability to prevent contamination. Even if gelatin such as gelatin-conductors such as lime-treated gelatin, acid-treated gelatin, phthalated gelatin, and acylated gelatin is used, rapid aggregation and precipitation will occur, and the stability of the coating solution will deteriorate. In addition, even if polyvinyl alcohol kf is used, for example, i'VA-1lo, PVA-1l 7, PVA manufactured by Kuraray@
-HCXPVA-2t o h Regardless of the tosonoken degree and the degree of polymerization, the stability of the coating solution cannot be improved, and on the contrary, the adhesion to the hydrophobic support becomes worse. When carboxy-modified polyvinyl alcohol is used, rapid aggregation and precipitation occur, which actually worsens the stability of the coating liquid. Also,
Water-soluble polymeric polysaccharides other than oxidized starch or phosphoric acid starch, such as Xanthen
gum) (for example, KIZAN, Zanflow (HaNli'LO), etc. released by Mishima), modified guar gum (.argum) (for example, Maproid (MMYPL't1MD) released by Mishima)5
200.7700, etc.), the stability of the coating liquid is poor. Furthermore, even if cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, or polyvinylpyrrolidone are used, the stability of the coating solution is poor, and when polyacrylamide is used, the coating layer will not be sufficiently cured. As described above, (d) of the coating layer in the present invention
Even if a water-soluble polymer other than oxidized starch or phosphated starch is used as a component, the effects of the present invention cannot be obtained at all. The present invention is based on the new fact that the unique effects of oxidized starch or phosphated starch significantly improve the stability of the coating liquid and also provide anti-fouling properties without impairing the properties and curing performance. It is something.

The water-soluble polymer compound or its salt obtained by copolymerizing an ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms and maleic anhydride used in the practice of the present invention is an α-olefin having 4 or more carbon atoms. It is obtained by hydrolyzing a copolymer of an ethylenically unsaturated copolymerizable monocap such as , alkyl vinyl ether, or styrene with maleic anhydride, optionally with an alkali such as sodium hydroxide, potassium hydroxide, or ammonia. . For information on ethylenically unsaturated copolymerizable monomers and maleic anhydride copolymers and their production methods,
It is described in U.S. Special Fraud No. 2.047,398, etc. Preferred ethylenically unsaturated copolymerizable monomers include α-olefins having 4 or more carbon atoms, alkyl vinyl ethers, styrene, more preferably α-olefins having 5 or more carbon atoms, and alkyl groups t-if having 3 or more carbon atoms. Examples include alkyl vinyl ether and styrene, but the present invention is not limited to these. *9. The molecular weight of the ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms and the maleic anhydride copolymer is preferably 2,000 to 150,000. Specific examples of water-soluble polymer compounds or salts thereof obtained by copolymerizing an ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms with maleic anhydride include isobutylene, 1-pentene, and butyl vinyl ether. Alternatively, the pH of the solution obtained by hydrolyzing styrene and maleic anhydride copolymer with an alkali such as total sodium hydroxide or potassium hydroxide is 5. Examples include reaction products with Q~9.0.

In addition, the curing agent having an ethyleneimino group or a glycyl ether group used in the practice of the present invention has an ethyleneimino group or a glycyl ether group in its molecule.
Representative examples are shown below,
The present invention is not limited to these. Furthermore, it is advantageous to dissolve these curing agents in a suitable solvent such as water, methanol, ethanol, N,N-dimethylformamide, acetone, ethyl acetate, etc., and then incorporate them into the hydrophilic colloid layer.

-14- Ct ■ Na CH2-CH2 -17- (18) Colloidal silica used in the practice of the present invention is ultrafine particles (average particle size 5 to 60 mμ) of silicic anhydride (8102) mainly using water as a dispersion medium. It is a colloidal solution dispersed in water. Further, the dispersion medium is generally water, but methanol or the like may be used in some cases. In addition, in the colloid solution,
Contains alkaline components for purposes such as colloid stabilizers.

For example, it may contain Na2O, NF13, formamide, ethylamine, morpholine, etc.

A commercially available product of colloidal silica preferably used in the present invention is Snowtick-18-s manufactured by Nissan Chemical.

Furthermore, the oxidized starch used in the practice of the present invention is obtained by treating starch with various oxidizing agents to change its physical and chemical properties to some extent, and generally contains hypochlorous acid.
j1 or persulfate t? As the oxidizing agent, those produced by a wet method or a dry method under various oxidizing conditions are advantageously used. As the oxidized starch particularly preferably used in the present invention, the temperature of sap of 10% by weight of oxidized starch is 95°C.
After stirring and gelatinizing at 300 rpm for 30 minutes, the sap was
Cool to 0°C and use Brookfield Viscometer 6 Orp.
The viscosity measured at m is from several centimeters to 50 centimeters.

Commercially available products include M8-#3 manufactured by Nihon Shokuhin Kako@
400, MS-#3600, MS-4#3800, Oji Ace A manufactured by Tamako National, etc.

In addition, the phosphoric acid esterified starch used in the practice of the present invention can be obtained by treating starch with various types of phosphoric acids, such as h#''t phosphates, to phosphorylate the starch to a total degree of substitution of 0.2 or less. orthophosphoric acid, hydrogen phosphate, phosphate, metaphosphoric acid, metaphosphate, polymetaphosphate, birophosphoric acid, pyrophosphate, polyphosphate, etc. as phosphoric acid or phosphate. Then, various conditions (for example, PH1 heating temperature,
Those produced by heating time, etc.) are advantageously used. As the phosphoric acid esterified starch particularly preferably used in the present invention, after gelatinizing a 20-tx size solution of esterified starch at a temperature of 95°C for 20 minutes, cooling the size liquid to 50°C, The viscosity measured by Orpm is from 10 centivoise to 500 centivoise. Commercially available products include M8 manufactured by Nihon Shokuhin Kako ■.
-44400, MS-1600, MS-#4800
and so on.

The amount of each component applied to the hydrophobic support or the amount used in carrying out the present invention is obtained by copolymerizing an ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms with maleic anhydride. The coating amount of the water-soluble polymer compound or its salt is usefully in the range of 0.01 f/- to 10 f/-, preferably 0.1 t/rr? ~5. Of/nl
is within the range of The usage amount of a curing agent having an ethyleneimino group or a glycyl ether group is ``ICkU2'', which is +U by copolymerization of an ethylene-based non-ja 4-1 copolymerizable monomer with 4 or more carbon atoms and maleic anhydride. 0.5 weight-jtX for water-soluble polymer compound or its Jl
A range of 100'i to 100'i% is useful, and a particularly preferred range is 2-electrotX to 501iJiX. The application t of colloidal silica and oxidized starch or phosphated starch is usefully in the range of 0-01 f/II/ to 10 t/-, preferably 0.1 f/- to 5.0 f/-.
1, which must be within the range of
The starting point j is not limited to these ranges.

Furthermore, various types of hydrophobic supports can be used in the present invention. For example, synthetic paper such as polypropylene, polystyrene, film such as cellulose acetate, cellulose nitrate 2 l-lenterephthalate, polyvinyl acetate, polystyrene, polyamide, polycarbonate,
In addition, α-olefin polymers, especially polyethylene, polypropylene, ethylene-butene copolymers, etc. with 2 carbon atoms
Paper coated or laminated with ~10 α-olefin polymers is advantageously used. These thermoplastic resin films or polyolefin resins contain white pigments such as titanium oxide, zinc oxide, talc, and calcium carbonate, and blue pigments such as cobalt blue, navy blue, gunyoi, cerianpuru, and phthalocyanipple. pigments and dyes, cobalt violet, fast violet,
Magenta pigments and dyes such as manganese and purple, dispersants of fatty metal salts such as zinc stearate, calcium stearate, and calcium balmitate, stabilizers, antioxidants, band 1 inhibitors, and plasticizers that are usually mixed with resins. Additives such as agents, RLT agents, fluorescent agents, and ultraviolet absorbers may also be added.

Further, the thickness of the polyolefin layer of the polyolefin-coated paper according to the present invention is not particularly limited, but is generally 5.
Extrusion coatings to thicknesses on the order of microns to 50 microns are advantageous.

The silver halide photographic emulsion layer according to the present invention includes various types. Examples include a photographic emulsion layer for enlarged positives, a photographic emulsion layer for contact positives, a photographic emulsion layer for negatives, a color photographic emulsion layer, a photographic emulsion layer for printing, a photographic emulsion layer for direct positives, a photographic emulsion layer for diffusion transfer method, etc. . In addition, such photographic emulsion layers contain binders such as gelatin and gelatin derivatives, chemical sensitizers such as hypo, noble metal sensitizers such as gold salts and platinum salts, hexahalogenoiridium (shoulder bodies, hexahalogenorhodium ( HI) High contrast agents such as complexes, nucleic acid decomposition products, JP-A-50-147925, JP-A-51-1071
Crystal adjustment of silver halide grains such as mercap) & ring compounds described or exemplified in No. 29, 1st floor Kaisho 52
-65432, color sensitizers, stabilizers, antifoggants, color photographic couplers, hardeners, dihydroxybenzene compounds, coating aids, etc. cited or exemplified in the specification of No. 52-88340. Capsule agents, additives for direct positive photographic emulsions such as direct positive photographic dyes, dye developer 111I
#&, other additives, etc. can all be included.

In the present invention, the stability of the coating liquid is good, and by incorporating another kind of antistatic agent, gold, into the cured coating layer with antistatic and antifouling properties, the antistatic effect of the coating layer is even more noticeable. Sulfur rfR cellulose alkali metal salts such as (trade name), polystyrene sulfonic acids such as Oligo-Z (trade name of Tomoe Paper Manufacturing Co., Ltd.), Chemistatsu) 6120 (trade name of Sanyo Chemical Industries, Ltd.) alkaline salts, sodium polyacrylates (e.g., sodium salts of polyacrylic acid, polymethacrylic acid, polyα-ethyl acrylic acid, etc.), potassium polyacrylates, sodium salts of acrylic acid and methyl acrylate copolymers, etc. These include alkali salts of polymerized acrylic acids and acrylic copolymers. The amount of these antistatic agents to be used is based on the composition of the coating layer in the present invention (for example, the type of constituent polymer, the amount of coating, the type and amount of the curing agent, the pH of the coating layer, etc.) Although it varies depending on the situation, 0.01F/-~3
A range of 1/n- is preferred.

In addition, the coating layer of the present invention may contain various matting agents to completely eliminate adhesion between silver halide photographic materials or between silver halide photographic materials and objects that come into contact with them. preferable. As these matting agents, fine particles of water-insoluble inorganic or organic compounds with a particle size of 0.2 to 5 μ (particularly 0.5 to 3 μ) are useful. As the inorganic compound, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate, calcium carbonate, kaolinite clay, glass, etc. can be preferably used. Examples of organic compounds include water-dispersible vinyl polymers such as polymethyl acrylate, polymethyl methacrylate, polystyrene, styrene and divinylbenzene copolymer, polyvinyl acetate, polyethylene carbonate, and polytetrafluorocarbon. As examples of cellulose derivatives such as ethylene, methyl cellulose, ethyl cellulose, starch granules, etc. can be preferably used. These matting agents can be used in combination with different types of substances, if necessary.

The coating layer in the present invention may contain various additives. Examples of surfactants include anionic surfactants such as alkylbenzene sulfonates and sulfosuccinates, nonionic surfactants such as saponins and alkylene oxide compounds, and amphoteric surfactants such as amino acids, aminosulfonic acids, and amino alcohol esters. agents, fluorine-based surfactants as exemplified in JP-A No. 50-99529;
Compounds described or exemplified in No. 068, JP-A No. 54-94318, and copolymers of varnish-26-tyl acrylate, vinyl ester, etc. and other ethylene group-containing monomers as film property improvers. Additives such as a latex consisting of a copolymer of diene monomers, a latex consisting of a copolymer of diene monomers, and a carboxy-modified latex of these can be contained singly or in combination.

In the coating material of the present invention, the water-soluble polymer of the present invention and the oxidized starch may be combined with other polymers to the extent that the effects of the present invention are not impaired.

Examples of these polymers include polyvinyl alcohol, polyacrylamide, poly-N-vinylpyrrolidone, agar, and sodium alginate.

When coating the coating layer of the present invention on one or both sides of a hydrophobic support, surface activation such as corona discharge, glow discharge, other electron impact, flame treatment, surface roughening, ultraviolet irradiation, ozone oxidation, etc. Preferably, the coating is applied after the treatment. Further, the coating can be performed using a squeeze coater, a bar coater, a blade coater, a Krachia coater, an air knife coater, a slide hopper coater, or a combination thereof.

Drying after application can be performed by various methods such as hot air, infrared rays, heated dryer, and microwave.

The silver halide photographic material of the present invention can be exposed, developed, and processed as described in "Photographic Light-sensitive Materials and Handling Methods" (Kyoritsu Shuppan, Miyamoto Gobuchi, Photographic Technology Course 2) in accordance with the photographic material. Processes such as stopping, fixing, bleaching, and stabilization are performed,
In particular, multilayer silver halide color photographic materials that undergo a bath white fixing process after color development include CD-1 [, CD-■ (the above two compounds are trade names of Kodak Company), droxychrome (May and Baker Company) It can be processed with any main type of color developer such as (trade name). Benzyl alcohol, thallium salt, or phenidone may be added to the developing solution containing such crude drugs. A useful one-bath bleach-fix solution is a solution of a metal salt of an aminopolycarboxylic acid (for example, a ferric complex salt such as ethylenediaminetetraacetic acid or propylenediaminetetraacetic acid); , sodium thiosulfate, ammonium thiosulfate, and the like are useful. Such -bath bleach-fix solutions can contain various additives. For example, desilvering accelerators (e.g., mercaptocarzonic acid as described in U.S. Pat. No. 3,512,979,
Mercapto as described in Belgian Patent No. 682,426
Containing a combination of various compounds such as polycyclic ring compounds, etc.), antifouling agents, pH regulators or pH buffering agents, hardening agents (for example, magnesium sulfate, aluminum sulfate, potassium alum, etc.), and surfactants. It's colored. Also, although such -bath bleach-fix solutions may be used at a variety of PH, useful PH ranges are P)Ie, o to 8.0.
It is.

Next, examples will be described in order to explain the present invention more specifically.

[Example 1] An antistatic composition as shown in Table 111 was applied as a coating liquid for the back coat layer to the back side of a polyethylene coated paper which had been previously subjected to a corona discharge treatment. & (moisture) and dried. The polyethylene coated paper used is polyethylene 10
A photographic paper with a basis weight of 160 tons/- containing a sizing agent and a wet strength agent is coated with soft polyethylene containing titanium dioxide, an appropriate amount of an antioxidant, and a bluing agent, and then subjected to a corona discharge treatment to a thickness of 30 μm. The back side is extrusion coated with polyethylene containing an appropriate amount of antioxidant in a ratio of 7 parts of soft polyethylene and 3 parts of hard polyethylene. Further, the surface of the polyethylene WU was processed into a completely flat so-called glossy surface, and the surface quality of the back polyethylene was processed into a matte surface.

-30- Table 1 After applying corona discharge to the surface of the polyethylene coated paper coated with these back coat layers, a silver chlorobromide gelatin emulsion containing a yellow coupler and its protective layer were coated using an extrusion-shore method. Dried silver halide color photographic material 4+
It was created.

The stability of the coating liquid for the back coat layer was evaluated by the method described below.

[Evaluation of the stability of the coating liquid for the back coat layer] Take the same amount of each coating liquid into a test tube, store it in a constant temperature bath at 40°C for 1 day, then observe the state of the coating liquid and evaluate the stability. do. that time,
The evaluation criteria are: ○ mark (good), Δ mark (fairly good), × mark (
(not allowed).

In addition, each sample obtained as described above was heated at 50°C and 60°C.
After being stored in a constant temperature and humidity chamber at RH for one day, it was evaluated by the method described below. In this case, the evaluation standard for the antistatic performance of the back coat layer is numerical value, and the evaluation standard for the treatment resistance, lead-oxidation resistance, back stain prevention property, and photographic properties of the back coat layer is O mark ( Good), Δ mark (slightly good), and × mark (poor).

[Evaluation of antistatic performance of back coat layer] 20°C, 35
9g 'Surface specific resistance of sample in IH'f: 1 t
Measurements were made using electrodes with a length of 10 cm placed at a distance of ts.

[Evaluation of processing resistance strength of back coat layer] 2 in color developer
After dipping at 0° C. for 3 minutes, make a cross-shaped scratch on the back coat layer and rub the scratched area with your fingertips to check the peeling condition.

[Additional df value of back coat layer]

Write with pencils of different hardness, observe the recording state on the surface, and judge effectiveness.

[Bonding value of the back stain prevention performance of the back coat layer] In the color developing solution over time - Adsorption: Polyethylene is adsorbed in advance to uncoated photographic paper, and the thus obtained film is attached to the photographic paper. When the stain and the back coat layer surface of the sample are brought into pressure contact in a color developing solution, the degree of dislocation of the blackish brown stain to the back coat layer surface is observed and judged.

[Photography aptitude]

The entire surface of the photographic emulsion layer and bank coat layer were kneaded together, rolled into a roll, and stored in a constant temperature and humidity bath at 50°C and 80% I for 2 days, followed by color development (30°C, 5 minutes) and -bath bleaching. Perform a fixing process and perform a fog determination.

The results obtained are shown in Table 2.

Table 2-34- As can be seen from Table 2: In the case of a back coat layer that does not have Iroidal silica (Ui 3, Ugly 4), the instability of the coating solution is not caused, but the pencil retouchability is This is a problem because it is defective and its antistatic performance is poor. In addition, in the case of a back coat layer without oxidized starch (Na 2 , Nil 4 )%
The back stain prevention performance is poor, and if colloidal silica is present, the stability of the coating solution is also poor, which is a problem. However, the back coat layer (magnetic layer) in the present invention is good in all evaluation criteria. It is an excellent silver halogenide color photographic material that can satisfy all the performance requirements, such as particularly good antistatic performance and ease of writing with a pencil, as well as good back stain prevention performance and coating liquid stability. I understand that very well.

[Example 2] Coating liquid No. 1 of Example 1? The water-soluble polymers (5) to (20) listed in Table 3 were added to the formulation t listed in the table (indicated as parts by weight of solid content) in place of the oxidized starch quadruple part (solid) of the blend and Nll blend. It was carried out in the same manner as in Example 1 except that it was used in Example 1.

As a result, the stability of coating solutions containing oxidized starch or phosphated starch was good, but the stability of coating solutions containing other water-soluble polymers was poor, and The usefulness of the invention is well understood.

Table 3

Claims (1)

[Claims] l Consisting of a hydrophobic support and a silver halide photographic constituent layer, on one or both sides of the support (a) an ethylenically unsaturated copolymerizable monomer having 4 or more carbon atoms and maleic anhydride; A water-soluble polymer compound or a salt thereof obtained by copolymerization with an acid, (b) at least one curing agent having two or more ethyleneimino groups or glycyl ether groups in the molecule, and ((+) colloidal A silver halide photographic material characterized in that it has a coating layer containing silica and (d) at least one of oxidized starch or phosphate esterified starch.2 The silver halide photographic constituent layer is silver halide color. The silver halide photographic material according to claim 1, which is a photographic constituent layer.3 The unsaturated copolymerizable monomer having 4 or more carbon atoms is styrene. Or the silver halide photographic material according to item 2.