JPS60185947A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material sufficiently antistaticized, prevented from sticking of processed prints to each other, and staining of a processing bath, a printer, etc., and capable of clearly retaining types formed on the surface of a backing layer even after development processing, by specifying the compsn. of the polymer latex of the backing layer. CONSTITUTION:The backing layer of a silver halide photosensitive material contains colloidal silica and a polymer latex. This latex is an emulsion of a copolymer or this copolymer neutralized with an acid, obtained by copolymerizing (a) acrylic acid or methacrylic acid in an amt. of 1.0-5.0wt% of the total monomers, (b) 5.0-20wt% styrenesulfonic acid, and (c) lower alkyl acrylate, and (d) styrene both weighing the rest in a c/d weight ratio of 1.0/1.0-2.0/1.0. As such a polymer latex, an aq. dispersion of a water-insoluble polymer, such as acrylic or vinyl acetate type latex, having an average particle diameter of 20-200mum can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved silver halide photographic material, and more particularly to coatings with antistatic properties and pencil retouchability.
The present invention relates to a silver halide photographic material with improved printability, which comprises a hydrophobic support having VI 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 is
It consists of a silver halide emulsion layer and its protective layer on the support. A multilayer silver halide color photographic material is a multilayer arrangement in which a blue-sensitive emulsion layer and an intermediate layer, a green-sensitive emulsion layer and an ultraviolet absorbing layer, a red-sensitive emulsion layer and a protective layer, etc. are sequentially provided on a support. Yellow, magenta, and cyan color-forming couplers are all contained in each color-sensitive emulsion layer.

By the way, conventional supports for halogen 11Z silver photographic materials include films such as polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film, paper as a substrate, and resins capable of forming films on both sides, often polyolefins. Hydrophobic supports such as resin-coated papers coated with resins are well known. In particular, as a support for photographic paper,
Polyolefin resin-coated paper is increasingly being used in place of the traditionally used baryta paper. The reason for this is that the polyolefin resin-backed paper used as a photographic support is hydrophobic, so compared to the case of baryta paper, processing liquid is applied to the base paper layer during the development and fixing processes of photographic paper. This is because it is difficult to penetrate and therefore has the advantage of shortening processing times such as washing with water and drying.

However, these photographic hydrophobic supports have several drawbacks. The well-known shortcomings are:
Silver halogenide photographic materials containing these hydrophobic supports become electrostatically charged during handling, and tend to attract dirt, dust, etc., resulting in the formation of various spots such as water repellency, desensitization, and capricity. Particularly, as a result of discharging the accumulated static electricity, a partial capri, called a state ink mark, which is extremely unpleasant in terms of photographic properties, may be produced in the silver halide photographic emulsion layer. Furthermore, silver halide photographic materials with these hydrophobic supports do not have the ability to write on the back surface, especially with a pencil, so consumers who have become familiar with conventional silver halide photographic materials that use baryta paper as a support This has become extremely inconvenient for people.

Therefore, on the back side of a silver halide photographic material containing a hydrophobic support, that is, on the surface of the support that is not coated with the silver halide photographic constituent layer, is called an antistatic and pencil-resistant back coat layer. It is known to install a coating layer.

For example, in order to provide antistatic performance,
Colloidal silica described in No. 98, Special Publication No. 52
The use of colloidal alumina described in Japanese Patent Publication No. 18020 and various carboxyl group-containing compounds described in Japanese Patent Publication No. 5.8-9408 is known.

In addition, ethylene maleic anhydride copolymer described in Japanese Patent Publication No. 57-129'80, Japanese Patent Publication No. 55-6913
A water-soluble polymer compound or a salt thereof obtained by copolymerization of an ethylenically unsaturated monoelectrolyzable monomer having 4 or more carbon atoms and maleic anhydride as described in No. It is also known to use organic polymeric antistatic agents such as the water-soluble film-forming polymeric anionic polymers described in No. 53,940.

In addition, in order to improve the power of writing with a pencil, for example, barium sulfate as described in Japanese Patent Publication No. 57-53940, silicon dioxide as described in Japanese Patent Application Publication No. 57-118241, calcium carbonate, etc. , magnesium carbonate, titanium oxide, aluminum nitride, barium sulfate fine particles, glass powder, etc. are known.

However, these silver halide photographic materials comprising a hydrophobic support with a bank coat layer and silver halide photographic constituent layers have had one or more serious drawbacks in their use.

For example, when used in a silver halide photographic material with a high sensitivity, static marks may not be sufficiently prevented, or after processing.
The anti-corrosion performance may deteriorate and the prints will stick to each other, making handling inconvenient. Some of the ingredients may be released in the treatment bath, resulting in the accumulation of sludge that does not weigh the vehicle. The back coat layer may be weak. Due to the weak adhesion with hydrophobic resins, the inside of the printer may be contaminated with powder from the back coat layer during exposure of silver halide photographic materials, and silver halide photographic X
In some cases, the coating equipment became contaminated during the coating of the constituent layers.

In recent years, cutting has been carried out in printers for the purpose of automatically cutting roll-shaped silver halide photographic materials by clearly marking the boundaries between the screens, or for the purpose of writing information about the screens. In some cases, the type may be printed on the bank coat layer on the back side of the silver halide photographic material, but this type ink may be washed away in the processing bath, or the color may become diluted and the function cannot be fully demonstrated. Occurred. In particular, in the case of multilayer silver halide color photographic paper, most of which is automatically printed and cut in roll form, the printability on the back coat layer inside the printer is an important characteristic. There has been a strong demand for a multilayer silver halide color photographic paper that can be clearly printed on the bank coat layer surface even after development. By the way, type printing as referred to in Mei 411 refers to printing in which ink or a substrate such as a type ribbon bearing ink is interposed between the bank coat layer surface of the silver halide photographic material and the type consisting of dots or student discounts. , which indicates that the ink is printed in the form of a type on the surface of the back coat layer by pressure bonding, preferably by an impact method.

Furthermore, as already mentioned, silver halide photographic materials having a hydrophobic support are characterized by so-called rapid processing, which shortens the processing time.

However, the back coat layer with type imprint (
i-If a silver halide photographic material having a hydrophobic support is developed after 60 minutes or more, especially 3 hours or more, after type printing, the type will be clearly visible even after processing. Even though it is possible to obtain a printed print within 60 minutes after type printing, especially the shorter the time since type printing, the type printing after processing is possible. In extreme cases, very little of the type impression remains, which is a serious problem that is completely contrary to the rapid processability benefits of silver halide photographic materials having hydrophobic supports. I understand.

In addition, it is possible to add notes using single lead (hereinafter simply referred to as pencil addition notes).
In a silver halide photographic material having a hydrophobic support provided with a back coat layer containing fine particles, especially inorganic fine particles, in order to have a This may result in uneven gloss.

Accordingly, a first object of the present invention is to provide an improved silver halide photographic material having a hydrophobic support provided with a backcoat layer. υ1] It is sufficiently antistatic and therefore prevents the generation of static marks and prevents prints from sticking to each other after processing, and does not cause contamination to the processing bath, printer, etc. Furthermore, a silver halide photographic material having a hydrophobic support comprising a bank coat layer, in which type impressions made on the surface of the back coat layer are clearly present even after development, and a method for processing the phenomenon. It is to provide. The second object of the present invention is to provide a hydrophobic coating with a back coat layer, which has a clear type impression on the bank coat layer surface in the printer even after development processing, and which has excellent rapid processing properties. The object of the present invention is to provide a multilayer silver halide color photographic material having a support. A third object of the present invention is to have a hydrophobic support provided with a back coat layer that allows writing with a pencil on the back coat layer surface without causing unpleasant gloss unevenness on the surface of the silver halide 4-filled constituent layer. An object of the present invention is to provide a silver halide photographic material. Other objects, features, advantages, etc. of the present invention are described in the following specification 1.
This can be understood from the description.

As a result of intensive studies, the present inventors have found that the first and second objects of the present invention are to have a silver halide photographic constituent layer on one side of a hydrophobic support, and to have a silver halide photographic constituent layer on the opposite side of the support. at least a)
A polymer latex and b) a back coat layer containing colloidal silica, and as the polymer latex, (a) 1.0 to 5.0% by weight of acrylic acid or methacrylic acid based on the total amount of monomers and (b) 5. obtained by copolymerizing 0 to 20 weight percent weight ratio of sulfonic acid and the remaining weight percent of (c) acrylic acid lower alkyl ester and (c) styrene, and (c) acrylic acid lower alkyl ester pair) weight composition of styrene. is 1.0 vs. 1.0 to 2.0
It has been found that this can be achieved by using an emulsion of a copolymer or its acid-neutralized product with a ratio of 1.0 to 1.0.

Furthermore, it has been found that the third object of the present invention can be achieved by further incorporating C) a matting agent into the back coat layer containing the above-mentioned a)'; El) marlatex and b) colloidal silica.

The silver halide photographic material 4A according to the present invention does not produce unpleasant partial fog called static marks. Further, even if the sheets are stacked after development, fixing (or bleach-fixing), washing, and drying, they will not stick to each other due to static electricity and become difficult to handle.

The silver halide photographic material according to the present invention does not contaminate processing baths, printers, etc. with back coat coating.

In the silver halide photographic material of the present invention, the type imprint made on the surface does not disappear or become thinner during processing so that it no longer plays its role, and even after processing, the type imprint is clearly visible. An impression is obtained.

Furthermore, the silver halide photographic material according to the present invention containing a capping agent in the back coat layer has excellent pencil retouchability of 14 Vr. Since only a small amount of matting agent is required, there is no unpleasant gloss unevenness on the front surface.

Examples of the polymer latex used in the practice of the present invention include Cevian-A46704, Cevian-A46739 (
Known product names include Daicel Chemical Industries, Ltd.). The amount of application is 1 mf/+r in terms of solid content? from 30θ■
7'n? The range is preferably 7.5m2? From 75
mf//n? The range is wide. When the coating amount is as small as 9, the necessary antistatic performance cannot be obtained, and when it is too large, the condition of the coated surface deteriorates.

The colloidal silica used in the practice of the present invention is a colloidal bath liquid in which ultrafine particles of anhydrous silicon (SiO2) are dispersed in water mainly using water as a dispersion medium. Further, the dispersion medium is generally water, but methanol or the like may be used in some cases.

Further, the colloid solution contains an alkaline component for purposes such as a colloid stabilizer. For example, Na2O and other N
It may also contain H5, formamide, ethylamine, morpholine, etc.

The colloidal silica preferably used in the practice of the present invention is preferably colloidal silica with an average particle size of 5 mμ to 100 mμ, and the coating amount is preferably in the range of 10 μm to 1.0 μm in solid content. .03ff/rr? from 0
．． A range of 3f/d is good. If the particle size of colloidal silica is too small, it will easily become kelp, and if it is too large, the silica particles will settle and cannot be stably obtained as colloidal silica. If the coating amount is too small, the necessary antistatic performance will not be obtained, and if the coating amount is too large, the scratch resistance and printability of the film will be insufficiently improved.

A specific example of colloidal silica is Snowtex manufactured by Hinami Kagaku ■.

Powders having an average particle size of 0.2μ to 10μ, preferably 0.3μ to 5μ are useful as matting agents preferably used in the practice of the present invention. Specific examples include silicon dioxide, calcium carbonate, magnesium carbonate,
+1 ratio titanium, precipitated aluminum hydroxide, barium sulfate, strontium sulfate, acrylic resin)] fine particles such as toy, polystyrene, and rice starch.

If the particle size of the matting agent is too small or the amount applied is too small, the pencil retouchability will be insufficient, and if the particle size is too thick or the amount applied is too large, the texture will be can be unpleasant and result in undesirable scratches on the surface. Therefore, the coating amount is preferably in the range of 5mg/m'' to 500η.
A range of 2 ng/- to 1501 ng/- is preferable.

In the bank coat layer according to the present invention, a compound having two or more ethyleneimino groups or glycidyl ether groups in the molecule is contained as a curing agent for the purpose of improving the hardness or scratch resistance of the layer. is advantageous.

Specific examples of those curing agents are shown below. Moreover, 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 bank coat layer.

t Na , JU Furthermore, the content of these curing agents is usefully in the range of 2.0 to 100% by weight, particularly preferably 10 to 50% by weight, based on the polymer latex.
is within the range of

In carrying out the present invention, different latexes can be used in combination as appropriate for various purposes such as adjusting the physical properties of the film and improving the direction of adhesion to the support. Such polymer latexes are aqueous dispersions of water-insoluble polymers with an average particle size of 20 mμ to 200 mμ, and include various types including acrylic latex, vinyl acetate latex, styrene-butadiene latex, acrylonitrile-butadiene latex, etc. are available.

In addition, in carrying out the present invention, polyvinyl alcohol, polyvinylpyrrolidone,
It can be used in combination with various water-bathable polymers such as starch paste, lintel derivatives, cellulose derivatives, Guams, and polymers having sulfone groups or carboxyl groups. However, it is undesirable to use a large amount of these water-soluble polymers since they deteriorate the strength of the film and the printability of the type.

In particular, water bathing polymers having sulfone groups or carboxyl groups and water-soluble polymers commonly called antistatic agents cause significant deterioration in film strength and type printability. Since the antistatic effect of the present invention is excellent, not only is it not necessary to use a water-soluble antistatic agent in combination for normal purposes, but it is also not necessary to use a water-soluble antistatic agent at all, or in the case where it is used in combination, the amount used is as low as possible. It is desirable to keep it in small amounts.

As a preferred embodiment of the separate building of the present invention, a) 1.0 to 5.0% by weight of acrylic acid or methacrylic acid out of the total amount of monomers, (b) 5.0 to 20% by weight of styrene sulfonic acid, and the remaining weight%. A copolymer obtained from (C) acrylic acid lower alkyl ester and (c) styrene and having a weight composition of (c) acrylic acid lower alkyl ester and (c) styrene from 1.0:1.0 to 2.0:1.0. There is still a silver halide photographic material which has a bank coat layer consisting of a polymer latex, which is a neutralized form thereof, b) colloidal crystallinity, e) gelatin, and f) a non-formalin-based gelatin hardening agent.

Gelatin has high reactivity with various crosslinking agents, and various special hardening agents have been designed for use in photographic emulsions. When this gelatin is used in combination with a special hardening agent, water resistance can be dramatically improved compared to other water-grade polymers, without causing well damage like other water-grade polymers. Can be used. However, among gelatin hardening agents, aldehyde-based ones have some drawbacks, such as contamination of the bank coat layer. In particular, formalin or a compound that liberates formalin cannot be used because it will fog the photographic emulsion or, if the silver halide photographic material is a color photographic material, it will react with the coupler and cause unpleasant discoloration.

As the hydrophobic support used in carrying out the present invention, those of each building are used. 10) Synthetic papers such as polypropylene and polystyrene, films such as cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyvinyl acetate, polystyrene, polyamide, and polycarbonate, and polyolefin, polystyrene, and polysalts on both sides of paper as a substrate. Examples include resin-coated paper coated with a film-forming resin such as f-vinyl, often a polyolefin resin. In particular, polyolefin resin-coated paper is used as a support for photographic paper, especially color photographic paper, which requires good type printability and stain resistance, in that the effects of the present invention are more clearly demonstrated. Used to advantage.

1.The resin layer of these thermoplastic resin films or resin-coated papers contains titanium oxide, zinc oxide, talc,
White pigments such as calcium carbonate, fatty acid amides such as stearinamide and araxinamide, dispersants such as fatty acid metal salts such as zinc stearate, magnesium stearate and calcium palmitate, pigments and dyes such as ultramarine blue and cobalt violet, Antioxidants, fluorescent brighteners,
It is preferable to contain a combination of various additives such as ultraviolet absorbers.

The polyolefin resin-coated paper which is advantageously used in the practice of the present invention is manufactured by extrusion coating a molten polyolefin resin onto a running base paper through a slit die.

At that time, prior to melt extrusion coating, the base paper surface is subjected to corona treatment.
It is desirable to activate it by flame treatment or the like. There is no particular limit to the thickness of the coating resin, but it is generally 5.
A value of about μ to 50 μ is advantageous. The side of the polyolefin resin-coated paper on which the silver halide photographic constituent layer is provided has a glossy surface, matte surface, silky surface, etc. depending on the purpose, and the back surface is usually a matte surface.

The polyolefin resin for coating the polyolefin resin-coated paper that is advantageously used in the practice of the present invention includes homopolymers of olefins such as low density polyethylene, high density polyethylene, polyglobylene, polybutene, and polypentene, or double polymers such as ethylene-propylene copolymers. Examples include copolymers consisting of more than one type of olefin and mixtures thereof, and those having various densities and melt viscosity indexes (hereinafter simply referred to as MI) can be used alone or in mixtures. The base paper for the polyolefin resin-coated paper may be ordinary natural pulp paper, synthetic fiber paper, or so-called synthetic paper made of synthetic resin film, but wood pulp such as softwood pulp, hardwood pulp, or mixed softwood and hardwood pulp may be used. Natural pulp paper based on is advantageously used. There are no particular restrictions on the thickness of the base paper, but paper with good surface smoothness is preferred, and its basis weight is 5.
A height of 0 seconds to 250 seconds is preferred. Furthermore, the base paper mainly composed of natural pulp can contain various submolecular compounds and additives. For example, starch derivatives, polyacrylamides, polyvinyl alcohol derivatives, dry paper strength agents such as gelatin, fatty acid salts, rosin derivatives, sizing agents such as dialkyl ketene dimer emulsions, wetting agents such as melamine resins, urea resins, epoxidized polyamide resins, etc. Paper strength agents, stabilizers, pigments, dyes, fluorescent whitening agents, latex, inorganic electrolytes, P)I regulators, etc. can be contained in appropriate combinations.

The back coat layer according to the present invention can contain various polymer compounds and additives.

Water-soluble polymers include starch derivatives such as oxidized starch and phosphated starch, polyvinyl alcohol, polyacrylamide, poly-N-vinylpyrrolidone, agar, and sodium alginate; surfactants include alkylbensulfone modified salts and sulfosuccinic acid. Anionic surfactants such as ester salts, nonionic surfactants such as saponin and alkylene oxide compounds, amphoteric surfactants such as amino acids, aminosulfonic acids, and amino alcohol esters, as exemplified in JP-A-50-99529. Fluorine surfactants, etc., as fluorescent whitening agents,
No. 8, JP-A No. 54-94318, etc., compounds described or exemplified may be included.

In carrying out the present invention, an air knife coater, a roll coater, a bar coater, a blade coater, a slide hopper, and a slide hopper are used to apply the back coat coating liquid onto the surface of the hydrophobic support opposite to the surface on which the silver halide photographic constituent layer is provided. coaters, gravure coaters, flexogravure coaters, combinations thereof, etc. Before coating, the hydrophobic surface is subjected to corona treatment,
It is desirable to activate it by flame treatment or the like.

Drying devices for the applied coating liquid include hot air dryers such as straight tunnel dryers, arch dryers, air loose dryers, sine curve air float dryers, infrared rays,
Various drying devices such as a heating dryer, a dryer using microwaves, etc. can be mentioned.

The silver halide photographic emulsion layer according to the present invention includes those of various types of yuzu. 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, binders such as gelatin and gelatin derivatives are contained in the photographic emulsion layer.
Chemical sensitizers such as hypo, noble metal sensitizers such as gold salts and platinum salts, high contrast agents such as hexahalogenorhodium (III) complexes and hexahalogenorhodium (I[l) complexes, nucleic acid decomposition products, JP-A-Sho No. 50-147925, Kaikai 51-1
Crystal habit modifier for silver halide grains such as mercapto heterocyclic compounds described or exemplified in No. 07129, JP-A-52
-65432, color sensitizers, stabilizers, antifoggants, color photographic couplers, hardeners, dihydroxybenzene compounds, coating aids cited or exemplified in the specification of No. 52-88340, Further, a capsulant, additives for direct positive photographic emulsions such as dyes for direct positive photographs, dye developers, and other additives can be contained.

The silver halide photographic material according to the present invention may be subjected to exposure and development as described in "Photographic Light-sensitive Materials and Handling Methods" (Kyoritsu Shuppan, written by Gobe Miyamoto, Photographic Technology Course 2). , stopping, fixing, bleaching, stabilizing, etc., but the multilayer silver halide color photographic material that undergoes a bath bleach-fixing process after color development is CD-1 [, C1)-1V.
It can be processed with any crude drug color developer such as (the above 211fl product is a Kodak brand name), droxychrome (May & Bee Co., Ltd. brand name). Benzyl alcohol, thallium salt,
Phenidone or the like may also be included. Also, 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), and as a fixing agent,
Sodium thiosulfate, ammonium thiosulfate, and the like are useful. Such a bath bleach-fix solution can contain a variety of additives. For example, desilvering promoters (e.g., mercaptocarboxylic acids as described in U.S. Pat. No. 3,512,979, mercapto heterocycles as described in Belgian Patent No. 682,426), stain inhibitors, Pal modifiers or PH Various compounds such as a slowing Yfaj agent, a hardening agent (for example, magnesium sulfate, aluminum sulfate, potassium alum, etc.), and a surfactant can be contained in combination. 1, such a bath bleach-fix g can be used at a range of pH, but the useful P)l region, the area P, H6,0 =
j3.0.

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

Example 1 Basis weight 160? /n? #; runs at 80 m/min,
After corona discharge treatment on the back side in the first zone, low density polyethylene (@ degree 0.918, MI5) 5
0 parts, high density polyethylene (density 0.965, MI7)
A resin composition consisting of 50 parts was coated by bath melt extrusion to a resin thickness of 30 μm, resulting in a matte surface resin)v! form. After corona discharge treatment on the cover surface in the second zone, low density polyethylene (f; 0°918, MI 8.5) was prepared using a melt extruder.
30 parts of a masterbatch kneaded with 30% by weight of titanium oxide, low density polyethylene (density 0.918
, MI5.0) 45 parts, high density polyethylene (density 0.
965, Ml 7.0) was applied by melt extrusion to a resin thickness of 30 μm to form a glossy resin layer. In the third zone, after corona discharge treatment is applied to the back resin surface, a rotating 140-mesh gravure roll is immersed in the coating liquid listed in Table 1, the excess coating liquid is scraped off with a blade, and the coating liquid is kept constant. A photographic support with antistatic properties was produced by transferring the mixture onto a surface and drying it. The coating amount of the aqueous coating liquid was: l/m'' (moisture).

After corona discharge treatment was applied to the surface of the polyethylene paper coated with these backcoats (i.e., the side of the support opposite to the side on which the backcoat layer was applied), yellow couplers were sequentially applied adjacent to the support. A blue-sensitive silver chlorobromide gelatin emulsion layer and an intermediate layer containing a blue-sensitive silver chlorobromide gelatin emulsion layer containing a magenta coupler, an ultraviolet absorption layer containing an ultraviolet absorber and a red-sensitive silver chlorobromide gelatin emulsion layer containing a cyan coupler. and its protective layer were applied using an extrusion method and dried to create multilayer silver halide color photographic paper.

Each sample obtained as described above was heated at 50℃ and 60℃RH.
After being stored in a constant temperature and humidity chamber for one day, it was evaluated by the method described below. At that time, the antistatic performance and film strength of the bank coat layer are expressed in numerical values, and the evaluation criteria for the pencil retouchability of the back coat layer, cloudiness on the photographic paper surface, and type printability are ○ mark (good), Δ Indicated by a mark (slightly good) or an x mark (unsatisfactory).

[Evaluation of antistatic performance of bank coat layer] The surface resistivity of the sample was measured at 20° C. and 354 RH for a sample before color development and a sample after color development using a roll processor using the following processing method.

Color development (30℃, 3 minutes 30 seconds) → Bleach fixing (30℃,
1 minute 30 seconds) - +Washing (30℃, 3 minutes) → Drying (45℃
, 1 minute) [Evaluation of the film strength of the bank coat layer] After immersing the sample in a color developing solution at 20°C for 3 minutes, a ball point needle with a sphere diameter of 1 mm was placed perpendicular to the film surface of the back coat layer, and the sample surface was The load of the ball point needle that causes damage to the back coat film (hereinafter referred to as film strength) is measured when the back coat film is moved in parallel at a fast speed.

[Evaluation of pencil retouchability of back coat layer] Write with an HB pencil, observe the recording state on the surface, and judge the effectiveness.

[Evaluation of cloudy surface of photographic paper]

The sample was cut into a total size of 8.25 cIn x 8.25 crn, and 10 sheets were stacked so that the back coat layer and the silver halide photographic constituent layer were in contact with each other. This was heated to 40 degrees Celsius and 80 degrees H.
The device is placed under a 4.5 kg load and left for 24 hours. Thereafter, it is taken out, the sample is peeled off, and the degree of haze on the surface of the photographic paper is visually determined.

[Evaluation of type printability of bank coat layer] Using an impact printer installed in an automatic printer, a type ribbon (for Kodak back printer manufactured by Easman Kodatsu Co., Ltd.) was placed between the bank coat layer surface of the paper stock and the type.
Information consisting of numbers, letters, a, etc. was printed in the form of a type on the surface of the bank coat layer. At 1 minute, 50 minutes, and 1.3 hours after type printing, the sample with type printing is processed with a roll processor, and the disappearance state of the type printing is observed and judged.

The results obtained are shown in Table 2.

As can be seen from Table 2, the sample CmA ) which does not contain latex specified in Table 1 (Note 2) and the sample which does not have colloidal silica (A B ) are different from the other samples (AC~&M
), it can be seen that the antistatic performance is insufficient. Furthermore, it can be seen that even in the present invention, the greater the amount of colloidal silica and the greater the amount of latex defined in (Note 2), the better the banding and warping prevention performance. The sample (iF') with the largest amount of colloidal silica showed a slight deterioration in film strength and type printability, indicating that it is unsuitable when such performance is particularly important. Although it is unclear from Table 2, in the sample (Ya H) containing the largest amount of latex as specified in (Note 2), coating streaks occurred during coating. Therefore, it is unsuitable for those who do not have relevant oiling techniques. Samples (AI to M) show that addition of a matting agent imparts pencil writing performance. Sample (AK-M)
shows that the film frequency is enhanced by cooling a compound 12+ having two or more ethyleneimino groups or two or more epoxy groups in the molecule. Sample (AM)
shows that the film strength can also be strengthened by using different types of latex together.

Example 2 The same procedure as in Example 1 was carried out except that the coating liquid shown in Table 3 was used instead of the coating liquid shown in Table 1 of Example 1.

The results obtained are shown in Table 4.

As can be seen in Table 4, samples outside the present invention (boiled).

No. 0) tends to cause clouding on the front side of the photographic paper when trying to obtain the same lead-phobic attachability as the present invention. On the other hand, in the samples of the present invention (AP, Q), sufficient pencil fibrillation properties were achieved with a small amount of inorganic pigment, so that the front side of the photographic paper did not become cloudy all over.

In the present invention, the sample (&Q) in which a water-bathable polymer was used in combination showed some improvement in anti-waking performance and film strength, but showed deterioration in type printing.

It can be seen that the combined use of such water bathing polymers may be disadvantageous depending on the application.

Example 3 The same procedure as in Example 1 was carried out except that the coating liquid described in Table 5 was used instead of the coating liquid described in Table 1 of Example 1.

All results are shown in Table 6.

When the sample (AR) using formalin was developed immediately after preparation, capri was observed. In addition, discoloration of cyan, magenta, and yellow layers was observed after storage at 35°C for one month.
In particular, the magenta layer showed significant discoloration. Contamination was also observed on the back side.

The sample using glyoxal (As) was also 35℃1
Upon observation after storage, contamination was found on the back side of the Chikaragetsu.

From Table 6, samples using gelatin (JPfx R, S,
It can be seen that the film strength of sample T) is improved compared to the sample (AU) in which neither sample was used.

However, the use of formalin glyoxal as a curing agent is not suitable for the purpose of the present invention for the reasons mentioned above.

Example 4 N,N'-ethylenebis(vinylsulfonylacetamide), 1,3.5-)lyacryloyl-hexahydro was added to the substitute hl of the breaking agent INE-010 during the formulation of sample AT in Example 3. -8-)Ryazine, 2,4-dichloro-6-hydroxy-8-)riazine sodium salt, and 1,6-hexamethylene diisocyanate were used in the same manner as in Example 3. As a result, exactly the same results as in Example 3 were obtained.

Claims (7)

[Claims] (1) A resin-coated paper-type photographic support in which both sides of a base paper are coated with resin gold has a 7 silver halide photographic constituent layer on one side, and at least (a) on the opposite side of the support. A silver halogenide photographic material having a back coat layer containing a polymer latex and (b) colloidal silica,
The polymer latex contains (a) 1 with respect to all monomers.
．． 0 to 5.0% by weight of acrylic acid or methacrylic acid, (b) 5.0 to 20% by weight of styrene sulfonic acid, and the remaining weight -m% of (c) acrylic acid lower alkyl ester, and (b) styrene. obtained by copolymerization, and (
c) A copolymer or an emulsion thereof having a weight composition of styrene in a lower alkyl ester pair of acrylic acid in a range of 1.0:1.0 to 260:1.0. Chemical silver photographic materials. (2) The content of the polymer latex is 1.0 my/lri to 300 η as a polymer content, and the content of the colloidal glue is 10 m/lri as a solid content. /
- to 1.02 to 1.02. (3) The silver halide photographic material according to claim 1 or 2, wherein the back coat layer contains (C) a matting agent. (4) The content of the matting agent is from 5 mf/d to 500 mf/d.
7f1g/silver silver halogenide photographic material according to claim 3. (5) The back coat layer contains (d) a compound having two or more ethyleneimino groups or glycidyl ether groups in the molecule/) Claim 1;
Silver halide photographic material according to item 2, 3 or 4. (6) A patent in which the content of a compound having two or more ethyleneimino groups or glycidyl ether groups in the molecule is from 2.0 to 50% by weight based on the polymer content of the polymer latex. A silver halide photographic material according to claim 5. (7) Claims 1, 2, 3, or 4, wherein the back coat layer contains (e) gelatin and (f) a non-formalin gelatin hardening agent. Silver halogenide photographic material.