JPS6135441A - Silver halide photographic material - Google Patents

Abstract

PURPOSE:To prevent electrostatic charging and static marks and sticking of prints by forming a silver halide photographic constituent layer on one side of a hydrophobic support and a back coat layer contg. an inorg. antistatic agent, a multivalent metal salt or complex on its opposite side. CONSTITUTION:The silver halide photographic constituent layer is formed on one side of the hydrophobic support and on its opposite side the back coat layer is formed contg. an inorg. antistatic agent, such as montmorrilonite clay or colloidal silica or their combination, and a salt or complex of a multivalent metal, such as Cr or Zr, used in an amt. of 1X10<-2>-10mg metal/m<2>, and it is formed by using a coating fluid having a pH of >=6.0. As a result, static marks and sticking of prints to each other can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved silver halide photographic material, and more particularly to a hydrophobic support having an antistatic and water-resistant coating layer and a silver halide photographic constituent layer. The present invention relates to a silver halide photographic material having improved tape adhesion.

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.

A silver halide emulsion layer and its protective layer are provided on a support. In addition, multilayer silver halide color photographic materials are
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 the support to form a multilayer arrangement. It contains all cyan coloring couplers.

By the way, conventional supports for silver halide photographic materials include films such as polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film, as well as resins capable of forming films on both sides as paper substrates, often polyolefin resins. Hydrophobic supports such as resin-coated papers coated with In particular, as a support for photographic paper, polyolefin resin-coated paper is increasingly being used instead 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 processes of photographic paper, compared to baryta paper. This is because the processing time for washing, drying, etc. can be shortened.

However, these photographic hydrophobic supports have some drawbacks. l[is doing. A well-known disadvantage of these hydrophobic supports is that silver halide photographic materials become electrostatically charged during handling and tend to attract dirt and dust, resulting in poor water repellency and desensitization. In addition to causing the occurrence of various spots such as capricivity, in particular, as a result of the discharge of accumulated static electricity, areas called static marks in the silver halide photographic emulsion layer, which are extremely unpleasant due to the electromagnetic characteristics. Capri' may be caused.

For this purpose, a coating layer called an antistatic back coat layer is provided on the back side of the silver halide photographic material that is attached to the hydrophobic support, that is, on the surface of the support that is not coated with the silver halide photographic constituent layer. It is known to do.

For example, antistatic performance? To give special public service 1977-302
Colloidal silica described in No. 98, Special Publication No. 52
It is known to use colloidal alumina described in Japanese Patent Publication No. 18020, and compounds containing carboxyl groups of foodstuffs described in Japanese Patent Publication No. 58-9408.

In addition, ethylene maleic anhydride copolymer described in Japanese Patent Publication No. 57-12980, Japanese Patent Publication No. 58-56859
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 as described in the Japanese Patent Publication No. 1983
It is also known to use M-type polymeric antistatic agents, such as the water-soluble film-forming polymeric anionic polymer electrolyte described in No. 53940.

However, these silver halide photographic materials comprising a hydrophobic support with a backcoat layer and a silver halide donor layer suffer from one or more serious drawbacks in their use. had.

For example, when used in high-sensitivity silver halide photographic materials, static marks may not be sufficiently prevented, or the antistatic performance may deteriorate after processing, resulting in prints sticking to each other and making handling inconvenient71. Some of the components may detach inside the printer, resulting in undesirable sludge buildup, or the back coat layer may be weak or have weak adhesion to the hydrophobic resin, causing the inside of the printer to be damaged. There have been cases where the backcoat layer has been contaminated with powder, or the coating equipment has been contaminated during the coating process where the silver halogenide photographic constituent layer is missing.

Also, in the case of roll-shaped silver chloride photographic paper (hereinafter simply referred to as roll photographic paper), roll photographic paper? When developing in a roll processor after exposure, the end of the leader film or leader paper meets the beginning of the roll of photographic paper to be developed, or the end and the next part of the roll of photographic paper being developed. The first part of the pre-roll photographic paper to be developed is often bonded and connected by R-glaze layer tape or pressure-sensitive adhesive tape, so-called leader-edge Indian adhesive tape.

A single-sided adhesive tape or a double-sided adhesive tape is used as the glaze layer tape for this purpose. At that time, when using the single-sided glazed layer tape 2, it is necessary to use a roll processor (hereinafter simply referred to as processor) to ensure that the end of the leader film or photographic paper that is passing through it and the leading edge of the photographic roll that is to be developed next. At the center of the seam, there is an adhesive layer of single-sided adhesive tape on the back side of the roll of photographic paper, and the adhesive layer is glued and connected with an appropriate length of single-sided adhesive tape. Also, double-sided adhesive tape? When used, (a) an adhesive layer of double-sided adhesive tape is placed between the end of the front surface of the leader film or roll of photographic paper that is passing through the processor and the beginning of the back of the roll of photographic paper that is to be processed next; (b) Double-sided adhesive tape is placed between the end of the back of the leader film or roll of photographic paper that is passing through the processor and the beginning of the front of the roll of photographic paper that is to be processed next. or (c) the joint between the end of the leader film or roll of photographic paper passing through the processor and the leading edge of the roll of photographic paper that is to be developed next. Use a type of double-sided adhesive tape that has an adhesive between the seam on the back side of the photographic paper and another hydrophobic patch or film, and use double-sided adhesive tape of an appropriate length. Glued/connected.

In this way, the exposed rolls of photographic paper are successively developed in a processor one after another. In any of the adhesion methods using adhesive tape, the adhesive layer of the adhesive tape is present on the back side of the roll photographic paper, and the back coat layer of the roll photographic paper has a bank coat layer. It will pass.

When the adhesive/connection area passes through Procera Surf in such a state, in the case of a roll of photographic paper without a puncture coat layer, the adhesive tape may be applied to the entire adhesive/connection area during the development process or drying of the roll of photographic paper. Strong adhesion and support, smooth transport and development of rolled photographic paper. However, in the case of roll photographic paper with a puncture coat layer, sometimes the adhesive tape completely peels off from the adhesive/connection part or partially peels off during the development process or subsequent drying of the roll photographic paper. To ensure normal transportation as soon as possible ↓
This sometimes caused problems such as the development process not being carried out. By the way, in this specification, the adhesive tape firmly adheres and supports all adhesive/connected parts during the developing process of the roll photographic paper and furthermore during drying, so that the transport and development process of the roll photographic paper are carried out smoothly. I'll just call it good tape adhesion, but during the development process of roll photographic paper, during the subsequent drying process, the adhesive tape would completely peel off from the adhesive/connection area, or it would peel off quite a bit in some areas. Therefore, the failure to carry out normal conveyance and development processing is simply referred to as poor tape adhesion.

As a result of the investigation, it was found that the peeling of adhesive tape depends on the properties and type of the back coat layer, the properties and type of the adhesive tape, the method of adhesion of the adhesive tape, the processing conditions in the processor, etc.
It was found that in most cases, punctures occur at the interface between the puncture coat layer and the adhesive layer of the adhesive tape. However, halogenated tapes have good tape adhesion regardless of the nature and type of adhesive tape, adhesive tape adhesion method, processor processing conditions, etc., and have strong film strength and a back coat layer with excellent antistatic performance. The development of silver photographic materials is strongly desired.

Therefore, the first object of the present invention is to provide a hydrophobic support with a backcoat layer. It is an object of the present invention to provide an improved silver halogenide photographic material. That is.

It is sufficiently anti-static and therefore prevents the formation of static marks, prevents prints from sticking to each other after processing, and does not contaminate noise in the processing bath, printer, etc.; It is an object of the present invention to provide a silver halogenide photographic material having a hydrophobic support having good tape adhesion and therefore excellent suitability for processing in a processor and having a back coat layer. The second object of the present invention is to provide a hydrophobic support with a back coat layer that has good tape adhesion and is therefore suitable for continuous development in a roll processor. It is to provide paper.

A third object of the present invention is to provide a silver halide photographic material tray provided with a bank coat layer which has excellent water resistance, especially resistance to developing solutions for silver halide photographic materials, and which is suitable for processing. It is an object of the present invention to provide a silver halogenide photographic material free from detachment of back coat components during fuchu. Other objects, features, advantages, etc. of the present invention will be understood from the description below.

As a result of intensive studies by the present inventors, the object of the present invention is to provide a silver halide photographic constituent layer on one side of a hydrophobic support,
On the opposite support surface, (A) an inorganic antistatic agent and (B)
) It has been found that this can be achieved by providing a back coat layer containing a polyvalent metal or a complex and having a coating liquid pH of 6.0 or higher.

In other words, a hydrophobic support with a back coat layer! There has been a fundamental technical conflict between sufficiently improving the antistatic properties of the backcoat layer and achieving good tape adhesion in silver halide photographic materials. That is, when trying to improve the tape adhesion of a back coat layer containing a known antistatic agent, the antistatic performance deteriorates.
On the other hand, it was found that an attempt to improve antistatic performance 2 resulted in a serious contradiction in that tape adhesion deteriorated. In particular, water-soluble polymers obtained by copolymerization of conventionally known organic or inorganic antistatic agents, such as polystyrene/sulfonic acid, polyvinylsulfonic acid, polyacrylic acid, polymethacrylic acid, vinyl methyl ether, and maleic anhydride. Ornaments, water-soluble polymer compounds obtained by the copolymerization of styrene and maleic anhydride, copolymers of itaconic acid and styrene, copolymers of citraconic acid and methyl acrylate, polyvinylphosphor/relatives, etc. A back coat layer containing an organic polymeric antistatic agent such as a salt, or an inorganic antistatic agent such as a colloid or fine 1118a of montmorillo/stone group minerals such as bentonite or synthetic hectoride, or colloidal silica is sufficient. It has been extremely difficult to achieve both good antistatic performance and good viewing ability.

Therefore, the inventors of the present invention have conducted extensive studies.

(g) Inorganic antistatic agent and (B) polyvalent metal salt'! It goes without saying that the above-mentioned technical contradiction can be solved by a back coat layer containing a compound or a complex and having a coating liquid pH of 6.0 or more, and it is possible to obtain good tape adhesion and good antistatic performance. This discovery led to the present invention.

Furthermore, the present invention is the first to reach a practical level as a back coat layer containing gelatin and a non-aldehyde organic gelatin curing agent. That is, in a bank coat layer containing an inorganic antistatic agent, especially colloidal silica, gelatin, and a non-aldehyde organic gelatin hardener, although antistatic performance can be achieved by modifying the formulation, tape adhesion is poor. was still very bad. The tape has poor adhesion.

No improvement was observed regardless of the type or content of the non-aldehyde organic gelatin hardener. However, by incorporating a polyvalent metal salt or complex into the back coat layer and increasing the PHy of the coating liquid to 6.0 or higher, excellent tape adhesion and good antistatic performance were achieved for the first time. .

The silver halide photographic material according to the invention does not produce unpleasant partial capri, so-called static marks. Also,
Development, fixing (or bleach-fixing).

Even if they are piled up after drying, they will not stick to each other and become difficult to handle.

The silver halide photographic materials according to the present invention are free from contamination with processing baths, printers, etc. t-bank coat coating components.

In the silver halide photographic material according to the present invention, the adhesive tape has good adhesion to the back surface of the material, and the adhesive tape does not peel off from the adhesive/connection portion during the development process and subsequent drying of the silver halide photographic material. Therefore, continuous development processing is possible.

The inorganic antistatic agents used in the practice of this invention are selected from clay minerals and colloidal silica of which colloidal or finely divided aqueous dispersions thereof can be prepared in water. Particularly, from the standpoint of performance and economy of backcoat J-, inorganic antistatic agents that are advantageously used in the practice of the present invention include montmorillonite clay, hectorite clay, colloidal silica, and combinations thereof. I can give it to you.

The montmorillonite clay advantageously used in the practice of the present invention is an idealized clay containing small amounts of alkali or alkaline earth metals such as sodium, potassium, lithium, calcium, etc. together with associated impurities such as iron, titanium% zinc, silica, etc. W3. H((At515 Mg IA)
It is a complex hydrated magnesium aluminum silicate represented by 8 i 401o(OH) 2 (where W represents an interlayer ion such as sodium, potassium, lithium, calcium, etc.). A typical example of montmorillonite clay is called be/tonite. Specific examples of be/tonite include Bengel S and Pengel FW manufactured by Toyojun Yoko ■.

Bengel HV, Bengel Φ15. Examples include Bengel I) 23, Be/Gerna 31, and Kunigel VA manufactured by Kunimine Toka Kogyo ■.

Hectorite clays advantageously used in the practice of the present invention include:
Small amounts of alkali or alkaline earth metals such as lithium, sodium, potassium, calcium, etc., and associated impurities such as titanium/zinc.

Ideal formula W 115 (Mga
y's Li 1/s ) 8 i4010(OH,F
) 2 (Here, W can also be replaced with lithium, sodium, potassium, or calcium atoms?
It is a complex hydrated lithium magnesium silicate represented by: Specific examples of hectorite clay include Laponite S and Laponite B manufactured by Labaut Industries ■ (UK).
I can give it to you.

Colloidal or fine particles of clay mineral used as an inorganic antistatic agent in the practice of the present invention In order to incorporate them into the back coat layer coating solution, an aqueous dispersion of colloidal or fine particles of clay mineral is prepared, and the dispersion is It can be added to the back coat layer coating liquid components, or it can be contained by adding the back coat layer coating liquid components to the dispersion to form a coating. How to prepare an aqueous dispersion of clay minerals is to prepare a predetermined amount of water. A preferred method is to add and disperse the clay mineral little by little while stirring with a high-speed stirrer, such as a homomixer, while sufficiently shearing the mineral. When preparing the dispersion, use polysulfate salts such as sodium pyrophosphate and sodium hexametaphosphate, and polyhydric alcohols such as trimethylolethane and trimethylolpropane.

1fi- It is preferable to add a dispersant such as a nonionic polymer such as polyethylene glycol alkyl ester as appropriate. Also, the amount of clay mineral used is 5 q/rr in terms of solid content.
~80υν range, preferably 15111f/rr
It is preferable to use the range of 1 to 3001-.

Colloidal silica is particularly advantageously used as an inorganic antistatic agent in the practice of this invention. The colloidal silica is a colloidal solution in which ultrafine particles of silicic anhydride (8i02) are dispersed in water, mainly using water as a dispersion medium. Also 1
The dispersion medium is generally water, but methanol or the like may also be used. In addition, the colloid bath liquid contains an alkaline component for purposes such as a colloid stabilizer. For example, Na2O,
In addition to K2O, it may also contain NH3, formamide, ethylamine, morpholine, etc.

The colloidal silica used particularly advantageously in the practice of the present invention has an average particle size of 5 mμ to 120 mμ.
The range of f/m' is preferably 0.05fβ to 0.5f
/rr? Good range. Specific examples of colloidal silica and 1
ff-riA
7. Snowtex 20 made by Nikkata Kagaku ■. Snowtex 30, Snowtex 40, Snowtex C,
There are Snowtex series such as Snowtex N, Snowtex 0°Snowtex 20L, Snowtex OL, and Snowtex ZLi.

The polyvalent metal salts or complexes used in the practice of the present invention are selected from magnesium, calcium, barium, zinc, aluminum, chromium, zirconium and tin salts or complexes, preferably chromium or tin salts. Zirconium salts or complexes are good. Preferred examples include salts of magnesium, calcium, barium, zinc, aluminum, chromium tin and organic acids such as acetic acid and citric acid, and non-+1A acids such as hydrochloric acid, carbonic acid, nitric acid, and sulfuric acid. and as a complex.

It can be complexed with a complexing agent such as ethylenediaminetetraacetic acid. Particularly preferred examples include chromium alum, chromium sulfate, zirconyl nitrate, zirconyl sulfate, and zirconyl acetate.

In order to incorporate the polyvalent metal salt or complex used in the practice of the present invention into the backcoat layer coating solution, an aqueous solution or dispersion of the polyvalent metal salt or complex is prepared in advance, and the aqueous solution or aqueous dispersion is prepared in advance. Dispersion liquid? It can be added to the backcoat layer liquid components, or the backcoat layer coating liquid components can be added to the aqueous solution or aqueous dispersion to prepare a coating liquid. In addition, a water bath liquid or aqueous dispersion of a salt or complex of a polyvalent metal may have an alkaline water bath liquid such as sodium hydroxide or potassium hydroxide or hydrochloric acid in its P)I of 6.0 to 9.5.
After preparation with an aqueous acid solution such as sulfuric acid, sulphur/acid, etc.

Including M ’+! 5. It's ugly. When colloidal silica is used as an inorganic antistatic agent, it may be added to a polyvalent metal salt or an integrated aqueous solution or aqueous dispersion, or after being combined with an aqueous dispersion of colloidal silica. The content of the polyvalent metal salt or complex is calculated from the weight of the polyvalent metal in the range of 1×10'η to 10 gin♀, preferably in the range of 5×10-2 FW/q to 1η arm. Good.

In the present invention, the bank coat layer has a coating liquid with a pH of 16
The sound effect of the present invention is produced only when the coating is adjusted to 0 or higher. That is, even if the back coat layer contains an inorganic antistatic agent and a polyvalent metal salt or complex,
If the back coat layer is applied with a coating liquid having a pH of less than 6.0, the effect of improving tape adhesion will be extremely insufficient.

Good tape adhesion can be obtained only when the pH of the coating liquid for the back coat layer is adjusted to 6.0 or higher, and when applied after adjusting the pH of the coating liquid to 7.0 or higher. In this case, very good tape adhesion is obtained. In addition, coating liquid P
The upper limit of H is not particularly limited, but considering the influence of the bank coat layer on the silver halide emulsion layer, the upper limit of PH
9.5 or less is desirable. When adjusting the pH of the coating liquid for the back coat layer, if the pH of the coating liquid is low, use an inorganic alkaline bath solution such as IJum or potassium hydroxide.

On the other hand, if the pH of the coating solution is too high, it is desirable to adjust it with an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid, or phosphoric acid or an aqueous solution of an organic acid such as acetic acid or citric acid.

The back coat layer in the present invention is J! When it contains gelatin and a non-aldehyde organic gelatin hardening agent,
The abrasion resistance of the bank coat coating layer has been improved for even better fc
Become something. That is, the poor antistatic properties and tape adhesion of the back coat layer, which are extremely difficult to improve, are caused by the bank coat layer containing gelatin and a non-aldehyde type M gelatin hardener. contains an inorganic antistatic agent and a polyvalent metal salt or complex, and the pH of the coating liquid is adjusted to 6.0 or higher before coating.
The first time it is fully improved. And at that time.

This allows the back coating layer to have good abrasion resistance.

However, formalin is used as a hardening agent for gelatin, and as a decomposition product of dimethylurea, trimethylolmelamine, etc.? Compounds such as those occurring, also mucochloric acid,
mucobromic acid, mucophenoxiftetralic acid, glyoxal, 2,3-dihydroxy-1,4-dioxane, 2,
If aldehydes such as 5-dimethoxytetrahydrofuran and glutaraldehyde are used, will they cause adverse effects on photographic properties, such as generation of 2O-IJ' in photographic emulsions? In addition, it also causes unpleasant coloring and contamination of the bank coat layer and photographic emulsion layer, and in the case of color photographic paper, it also causes discoloration of dye images. cannot be used.

Gelatin preferably used in the practice of the present invention includes:
So-called lime-treated gelatin, acid-treated gelatin, and groups that can react with amino groups, imino groups, hydroxyl groups, or carboxyl groups as functional groups contained in gelatin molecules? gelatin derivatives, modified gelatin, etc. treated with reagents such as phthalic anhydride, succinic anhydride, trimellidic anhydride, etc. that increase the carboxyl group in the gelatin side chain. Any of those commonly used in the art, such as phthalated gelatin, succinated gelatin, and trimeridated gelatin, can be used. The content of gelatin preferably used in the implementation of the present invention is not particularly limited, but from the viewpoint of the balance of various properties of the coating layer,
The range is preferably from 150 to 150, and more preferably 7/? y
A range of 1" to 60 .mu./R is particularly preferred.

Curing agents preferably used in the practice of the present invention include divinylsulfone, N,N'-ethylenebis(vinylsulfonylacetamide), i,3-bis(vinylsulfonyl)-2-7'lovanol, methylenebismaleimide. , 5
-acetyl-1,3-diacryloyl-hexahydro-
Active vinyl compounds such as 8-triazine/, 1°3.5-)lyacryloyl-hexahydro-8-triazine-1,3,5-)IJ vinylsulfonyl-hexahydro-8-)lyazine.

2.4-dichloro-6-hydroxy-8-) riazine
Sodium salt, 2,4-dichloro-6-medoxy8-
) ryazine/, 2,4-dichloro-6-(4-sulfoanilino)-8-) riazine-sodium salt, 2,4-dichloro-6-(2-sulfoethylamino)-8-) riazine, N, N '-bis(2-prolloethylcarbamyl)
An active halogen compound like piperazine.

Diethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerol diglycidyl ether, glycerol triclycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl Epoxy compounds such as ether, diglycerol triglycidyl ether, and sorbitol tetraglycidyl ether.

2,4.6-)diethylene-8-)riazine, 1゜6
-Hexamethylene y-N,N'-bisethylene urea.

Etele/imino compounds such as bis-β-ethyleneiminoether thioether.

1.2-(methanesulfonoxy)ethane, 1゜4-
Methanesulfonic acid ester compounds such as di(methanesulfonoxy)butane and 1,3-di(methanesulfo/oxy)pentene.

Dicyclohexylcarbodiimide, 1-cyclohexyl-3-(3-)limethylaminoprobyl)carbodiimide P-1-luenesulfo/acid, 1-ethyl-3-(
Carbodiimide compounds such as 3-dimethylaminoglopyru)carbodiimide hydrochloride.

Inoxazole compounds such as 2,5-dimethylisoxazole perchlorate, 2-ethyl-5-phenylisoxazole-3-sulfonate, and 5,5'-(halapenylene)bisisoxazole.

N-carboethoxy-2-impropoxy-1゜2-dihydroquinoline, N-(1-morpholinocarboxy)-
Dehydrated peptide reagents such as 4-methylpyridinium chloride; Active ester compounds such as N,N'-aziboyldioxydisuccinimide and N,N'-terephthaloyldioxydisuccinimide.

In cyanurate compounds such as toluene-2,4-diisocyanurate and 1,6-hexamethylene diyne cyanurate can be mentioned.

In addition, as for the content of the gelatin hardening agent preferably used in carrying out the present invention, an optimum addition amount of 7 may be selected depending on the performance of the back coat layer. The range of 0.2% to 50% by weight is preferred, and the range of 2% to 15% by weight is particularly preferred. Further, it is advantageous to dissolve the curing agent in a suitable solvent such as water, methanol, ethanol, N,N-dimethylformamide, acetone, ethyl acetate, etc. and then incorporate it into the back coat layer.

Various types of hydrophobic supports can be used in the practice of the present invention. For example, synthetic papers such as polypropylene and polystyrene, films such as cellulose acetate, cellulose nitrate, polyethylene terephthalate, polyvinyl acetate, polystyrene, polyamide, and polycarbonate, and films made of paper such as polyolefin, polystyrene, polyvinyl chloride, etc. Resin-coated paper coated with film-forming resins, often polyolefin resins? I can give it to you. especially,
Polyolefin resin-coated paper is advantageously used as a support for photographic paper, especially roll photographic paper, which requires good tape adhesion and antistatic properties, since the effects of the present invention are more prominently exhibited. It will be done.

Also, these thermoplastic resin films or

The resin layer of the resin-coated paper contains white pigments such as titanium oxide, zinc oxide, Merck, and calcium carbonate, fatty acid amides such as stearic acid amide, arachidi/acid amide, zinc stearate, magnesium stearate, calcium palmitate, etc. It is preferable to contain a dispersant such as a fatty acid metal salt, a pigment such as ultramarine, cobalt violet, a dye, an antioxidant, a fluorescent whitening agent, an ultraviolet absorber, and various other additives in an appropriate combination.

The polyolefin resin-coated paper advantageously used in the practice of the present invention is produced by extrusion coating onto a running base paper from a bath melt polyolefin/resin slit die in the form of a film.

At that time, prior to bath melt extrusion coating, corona treatment on the base paper surface,
It is desirable to activate it by flame treatment or the like. There is no particular limit to the thickness of the coating resin layer, but it is generally 5 μm.
~50μ is advantageous. The side of the polyolefin resin-coated paper on which the silver halide photographic constituent layer r is provided should be a glossy side, a matte side, or a silky side depending on the purpose. The long side is usually matte.

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, polypropylene, polybutene, and polype/thene, or air v y -7' Copolymers consisting of two or more olefins such as O-pyrene copolymers and mixtures thereof? The melt viscosity index (melt index; hereinafter abbreviated as MI) of each density can be used alone or in combination. The base paper for the polyolefin resin-coated paper may be ordinary natural pulp paper, synthetic fiber paper, or so-called finished paper made of synthetic resin film, but it may also be made of softwood pulp, hardwood pulp, or wood mixed with softwood and hardwood pulp. Natural pulp paper based on par2 hoolp 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 50 t/lr? ~2
509/rr? is preferred. Furthermore, the base paper containing natural pulp as a main component can contain % kinds of polymerization adducts 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 brighteners, latex,
A suitable combination of fish electrolytes, pH adjusters, etc. can be included.

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

Water-bathable polymers include oxidized starch, starch-containing conductors such as phosphated starch, cellulose sulfate ester salts, hydrolysates of methyl vinyl ether and maleic anhydride copolymers or their salts, styrene and maleic anhydride copolymers. gelatin thickeners such as hydrolysates or salts thereof and reaction products of their maleic acid copolymers with polyvinyl alcohol, polyacrylamide, poly N-vinylpyrrolid/, sodium alginate, etc., alkylbenzene sulfones as surfactants. Anionic surfactants such as acid salts and sulfosuccinate salts.

Nonionic surfactants such as saponin and alkylene oxide compounds, 1% amphoteric surfactants such as amino acids, aminosulfonic acids, and amino alcohol esters + fluorine-based surfactants as exemplified in 1982-99529, etc.
As a fluorescent brightener, compounds such as those described or exemplified in Japanese Patent Publication No. 45-24068, Japanese Patent Application Laid-Open No. 54-94318, etc. can be included.

In carrying out the present invention, a back coat coating is applied on the opposite side of the hydrophobic support surface on which the silver halide layer is provided.
Examples of the coating device include an air knife coater, a roll coater, a bar coater, a blade coater, a slide hopper coater, a glaminator, a flexogravure coater, and combinations thereof. Prior to coating, it is desirable to activate the hydrophobic support surface by corona treatment, flame treatment, or the like. The coating can also be applied by using an on-machine device on a laminator immediately after coating the base paper with a film-forming resin.

So-called off-machine coating may be performed using a separate coating device. Various types of drying equipment for the applied coating liquid include hot air dryers such as straight tunnel dryers, arch dryers, air loose dryers, sine curve air float dryers, dryers using infrared rays, heated dryers, microwaves, etc. equipment can be provided.

The silver halogenide photographic emulsion layer according to the present invention includes various types. Examples include black and white photographic emulsion layers, color photographic emulsion layers, photographic emulsion layers for printing, photographic emulsion layers for direct positive use, and the present invention is particularly useful in the case of emulsion layers for roll photographic paper. In addition, such photographic emulsion layers contain gelatin ζ゛, binders such as gelatidi derivatives, chemical sensitizers such as hypo, noble metal sensitizers such as gold salts; High contrast agents such as hexahalogenorhodium (III) complexes, nucleic acid decomposition products,
Japanese Patent Publication No. 50-147925, 1977-107129
Crystal habit modifier for silver halide grains such as mercapto heterocyclic compounds described or exemplified in JP-A-52-6543
No. 2, color sensitizers, stabilizers, antifoggants, color photographic couplers, hardeners, dihydroxybenzene compounds, coating aids, etc. cited or illustrated in the specification of No. 52-88340, and Additives for direct positive photographic emulsions such as caplace agents, dyes for direct positive floaters, dye developers, and other additives can be contained.

The silver halide photographic material according to the present invention, together with its floating material, can be exposed to light as described in "Photographic Light-sensitive Materials and Handling Methods" (Kyoritsu Shuppan, written by Gobe Miyamoto, Photographic Technology Course 2). , developing, stopping, fixing, bleaching.

Stabilization and other treatments are carried out, but multi-layer nologe/silver oxide color yoshin materials undergo gradual bath bleaching treatment after color development.
It can be processed with any crude drug color developer such as CD-1 [, CD-IV (the above two compounds are trade names of Kodak Co.), and droxychrome (trade name of May and Baker Co.). Does the developer containing such main chemicals include benzyl alcohol, thallium salt, phenidone, etc.? It may be included. 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 the fixing agent is sodium thiosulfate. , ammonium thiosulfate, and the like are useful. Are there any additives in the single-bath bleach-fix solution? It can be included. For example, desilvering accelerators (e.g., mercaptocarboxylic acids described in U.S. Pat. No. 3,512,979, Belgian Patent No. 682,4
mercaptoheterocyclic compound described in No. 26), a contamination preventive agent.

PHp moderating agent or PH buffering agent, hardening agent (fc, for example,
Various compounds such as magnesium sulfate, aluminum sulfate, potassium alum, surfactants, etc. can be contained in combination. Also, the 32-bath bleach-fix solution can be used at various pH values, but the useful pH range is PH 6.0 to PH 8.0.

Next, the present invention will of course be explained more specifically.

Example full speed.

Example 1 Paper with a basis weight of 160 f/m' is run at 80 m/min.

After corona discharge treatment on the back side in the first zone, low density polyethylene (density 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 with a resin thickness of 30 μm to form a resin layer with a matte surface. After corona discharge treatment on the cover surface in the second zone, low density polyethylene (density 0.918, MI 8.5)
30 parts by weight of a masterbatch with titanium oxide sonic beams incorporated, low density polyethylene (density 0.913, MI
5.0) 45 parts, high density polyethylene (density 0.
A resin composition consisting of 25 parts of 9651Ml (7.0) was coated by bath melt extrusion to a resin thickness of 30 μm to form a resin layer with a glossy surface. In the third zone, is the back resin surface? After corona discharge treatment.

The rotating 140-mesh gravure roll is completely immersed in the coating liquid listed in Table 1, the excess coating liquid is scraped off with a blade to make the coating liquid constant, and the coating liquid is transferred to the back resin surface and dried to obtain antistatic performance. A photographic support with sound manufactured. The amount of water-based coating liquid applied was 3:3 (moisture).

In preparing the coating solution, a 2-liter aqueous solution of chromium alum and a 1N aqueous solution of caustic soda were mixed in advance and then added together. In addition, the pH of the coating solution was adjusted to 8.1±0.2 with a 1N aqueous solution of caustic soda or hydrochloric acid before combining the entire amount with water.
further adjusted. Also, the organic and inorganic antistatic agents listed in Table 1 are those listed in Table 2? I used it as a toilet.

(Note 2) Does a 5-inch aqueous dispersion of clay have sufficient shearing force for 95 parts by weight of water? While stirring with a homo mixer, add 5 parts by weight of clay. It was prepared by adding it little by little and dispersing it.

The surface of the polyethylene-coated paper coated with these backcoats (i.e., the side of the support opposite to the side on which the backcoat layer is coated) is treated with a corona discharge, and then a yellow coupler superimposed layer is applied adjacent to the support. A blue-sensitive silver chlorobromide gelatin emulsion layer and an intermediate layer, a green-sensitive silver chlorobromide gelatin emulsion layer superimposed on a magenta coupler, an ultraviolet absorbing layer containing an ultraviolet absorber, and a red-sensitive silver chlorobromide gelatin emulsion layer containing a cyan coupler. The protective layer was applied using an extrusion method and dried to produce a multilayer silver halide color photographic paper.

Each sample obtained in the above manner was heated at 50°C and 60cm
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 back coat layer are numerical values, and the evaluation criteria for the tape adhesion of the back coat layer are ○ mark (good without peeling), ■
Mark (slight peeling, no practical problem), △ mark (peeling,
(Practical impossibility), marked with an x mark (large or complete peeling, practically impractical).

[Evaluation of antistatic performance of back coat layer] The surface resistivity of the sample at 20t and 35SRH was measured 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 with water (30℃, 3 minutes) → Drying (45℃,
1 minute) [Evaluation of the film strength of the back coat layer] After immersing the sample in a color developing solution at 20°C for 3 minutes, a ball point needle with a ball diameter of 1 mm was placed perpendicular to the film surface of the bank coat layer, and the sample surface was f2 cm/ The load (hereinafter referred to as film strength) of the ball void/toe needle that causes damage to the back coat film when the back coat film is moved in parallel at a speed of sec (hereinafter referred to as film strength) 2 is measured.

[Evaluation of tape adhesion of bank coat layer] An adhesive layer of double-sided adhesive tape exists between the end of the leader film and the beginning of the back coat surface of the sample cut into a roll with a width of 82 mm. Model like this, length 15cm
The samples were adhered and connected using a double-sided adhesive tape (Nitto Tape A300 (manufactured by Nitto Electric Industry Co., Ltd.) with a width of 75 mm, developed using the sample processor, and the appearance of peeling of the adhesive tape was observed and judged.

The results obtained are shown in Table 3.

Table 3 As hardening agents, formalin (Ban 7), glyoxal (A
8) The sample used was stored at 35°C for one month. After storage, contamination was observed on the back side of the sample using glyoxal (flat 8). In addition, a sample containing formalin (A 7)
In this case, discoloration of cyan, magenta, and yellow coloring pigments was observed, and the magenta coloring pigment was particularly markedly discolored. Indicated.

In addition, capri was observed in this sample (A7) from the beginning.

As can be seen from Table 3, according to the present invention, chromium myopon is used as an inorganic antistatic agent and a polyvalent metal salt. Added sample (
A9.10.11.12) has excellent antistatic performance, film strength, and tape adhesive properties. On the other hand, chrome alum? The sample without it (A5゜6) had poor tape adhesion and was a practical problem, and the sample (AI, 2, 3.4) with the well-known 7'C shoulder polymer antistatic agent had poor tape adhesion. Not only is the strength weak and the tape adhesion is poor, but the antistatic performance is also inferior to that of dud 8A.

As described above, according to the present invention, antistatic performance, film strength, and tape adhesion can be achieved in a well-balanced manner, and therefore, the present invention provides a silver halide roll photographic paper with excellent continuous processability. It is clear that it is useful. On the other hand, in other cases, the antistatic performance, film strength, or tape adhesion may be poor, or the emulsion layer may be contaminated with discolored gold, or the emulsion layer may contain capri gold.

Example 2 In the formulation of sample A9 of Example 1, the amount of caustic soda 1N water bath solution? A coating liquid that has been prepared with different PH' values as listed in Table 4? It was carried out in the same manner as in Example 1 except for using.

Results obtained? It is shown in Table 4.

Table 4 As can be seen from Table 4, even if the coating solution contains an inorganic antistatic agent and a polyvalent metal salt, the pH of the coating solution is less than 6.0 (
A13) had poor tape adhesion and somewhat weak film strength.

On the other hand, according to the present invention, 5 samples in which the pH of the coating liquid is 6.0 or more (
A14 to A18) have excellent antistatic performance, film strength, and tape adhesion. From the viewpoint of tape adhesion, it can be seen that the pH of the back coat coating liquid is particularly preferably in the range of 7 to 10.

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

The results obtained are shown in Table 6.

Table 6 As shown in Table 6, inorganic antistatic agents and polyvalent metal salts? Samples according to the invention (A23-26), including M, have excellent antistatic performance and tape adhesion. Also, gelatin and non-aldehyde 'fV4M hardening agent? Furthermore, it can be seen that samples (425, 26) containing the above-mentioned materials have strong film strength and are preferable. On the other hand, a sample that does not contain polyvalent metal salt (A19
It can be seen that samples 21) to 21) are problematic due to poor tape adhesion.

Example 4 - To A - rsrr With the formulation of sample 10 of Example 1, as shown in Table 7, the amount of chromium alum 2-chi aqueous solution and the pH of the coating solution were 8.1±0. How much is the 1N aqueous solution of caustic soda so that the amount is 2? Is the coating solution prepared differently? It was carried out in the same manner as in Example 1 except for using.

The results obtained are shown in Table 7.

Table 7 As can be seen from Table 7, tape adhesion improves as the content of polyvalent metal salt increases.

However, if the content was 1 q/m or more, the coating liquid would thicken, which was not preferable.

Example 5 N,N'-ethylenebis(vinylsulfonylacetamide), 1,3.5-)lyacryloyl-hexahydro was substituted for the blending agent NBR-010 of sample A9 in Example 1. -8-)Ryazine, 2,4-dichloro-6-hydroxy-8-)Ryazine sodium salt, 1,6-hexamethylene diisocyanate? The same procedure as in Example 1 was carried out except that each was used. As a result, exactly the same results as in Example 1 were obtained.

Example 6 Example 4 was carried out in the same manner as in Example 4, except that zirconyl acetate, zirconyl sulfate, or magnesium chloride was used instead of chromium alum as the polyvalent metal salt. As a result, the same results as in Example 4 were obtained.

December 1, 1980 (January 3, 1981) Relationship with the case of the person making the amendment Patent Applicant 4, Agent residence Mitsubishi Paper Mills Co., Ltd., 3-4-2 Marunouchi, Chiyoda-ku, Tokyo 100, by amendment. (Increasing number of inventions) 7. Detailed explanation of the invention in the specification subject to amendment 8, Contents of amendment Table 1 on page 36, Table 2 on page 37, Table 3 on page 40
The tables, Table 4 on page 42 and Table 7 on page 46 of Pg, are amended as follows.

Claims (4)

[Claims] (1) Having a silver halide photographic constituent layer on one side of a hydrophobic support, and having (A) an inorganic antistatic agent and (B) a polyvalent metal salt or complex on the opposite side of the support. What is claimed is: 1. A silver halide photographic material comprising a backcoat layer containing a coating liquid having a pH of 6.0 or more. (2) The silver halide photographic material according to claim 1, wherein the polyvalent metal is chromium or zirconium. (3) The back coat layer further includes (C) gelatin and (D)
) The silver halide photographic material according to claim 1 or 2, which contains a non-aldehyde organic gelatin hardening agent. (4) The silver halide photographic material according to claim 1, 2 or 3, wherein the pH of the coating liquid is 7.0 or more.