JPS62192738A - Silver halide photographic emulsion improved in antistaticness and the like - Google Patents

Abstract

PURPOSE:To improve antistatickness, releasability of an emulsion layer from a reverse layer, and adhesion between a backing layer to a support by coating the reverse side with a layer containing a water-dispersible binder and at least one of specified salts. CONSTITUTION:At least one layer containing photosensitive silver halide emulsion is formed on a hydrophobic paper base, and the reverse side of the base is coated with the layer containing the water-dispersible binder and at least one of the salts represented by formula I-IV is which M is an alkali metal, alkaline earth metal, or NH4; l is 1 when M is an alkali metal or NH4, and it is 2 when M is an alkaline earth metal; each of m and n is a positive integer satisfying the following relationship: m=2n+k, where k=1, -1, or -3. The salt of formula I, II, III or IV may be added alone or in combination with other one or more, in an amount not especially limited, but preferably, in an amount of 1-80wt% of the total weight of the backing layer. The polyolefin resin coated paper base is formed by, preferably, treating the surface of the paper base with corona discharge, flame, or the like in advance to activate the surface, and then, extruding the melted polyolefin resin through a slit die in the form of a film onto a traveling paper base.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an improved silver halide photographic material, and in particular, improves antistatic properties, sticking properties between the emulsion side and the back side, and the properties of the back coat layer. This invention relates to a silver halide photographic material with improved adhesion to a support.

[Prior Art] 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 a color clouding prevention layer, an antihalation layer or filter layer, an ultraviolet absorbing layer, etc., and combinations thereof. It is something that For example, a single silver halide photographic material is
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. Each contains a cyan coloring coupler.

By the way, supports for silver halide photographic materials have conventionally been made of films such as polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film, and paper substrates with resins capable of forming films on both sides, often polyolefin resins. Hydrophobic supports such as resin-coated papers coated with

However, these photographic hydrophobic supports have several drawbacks. The well-known shortcomings are:
Silver halide photographic materials having these hydrophobic supports become electrostatically charged during handling and tend to adsorb dirt, dust, etc., leading to the generation of various spots such as water repellency, desensitization, and capriness. Particularly, as a result of the discharge of accumulated static electricity, partial fog called static marks, which is extremely unpleasant from a photographic perspective, may occur in the silver halide photographic emulsion layer. For this reason, the back side of a silver halide photographic material having a hydrophobic support,
That is, it is known to provide an antistatic coating layer called a bank coat layer on the surface of the support that is not coated with silver halide photographic constituent layers.

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. 58-9408 are known.

In addition, ethylene maleic anhydride copolymer described in Japanese Patent Publication No. 57-12980, Japanese Patent Publication No. 55-69189
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 organic polymer antistatic agents such as the water-soluble film-forming polymeric anionic polymer electrolytes described in No. 58,940.

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

For example, when used in high-sensitivity silver halide photographic materials, it may not be possible to sufficiently prevent static marks, the antistatic performance may deteriorate after processing and prints may stick to each other, making handling inconvenient; Some particles may detach, resulting in undesirable accumulation of sludge, or the adhesive strength between the backcoat layer and the hydrophobic resin may be weak, causing the interior of the printer to be contaminated with powder from the backcoat layer components during exposure of the silver halide photographic material. , or the coating equipment may be contaminated during the coating stage of the silver halide photographic constituent layer.

In addition, in the case of a multilayer color film, since the production process involves a plurality of coatings, failures are likely to occur due to sticking between the surface of the emulsion layer or intermediate layer during coating and the back surface of the support.

On the other hand, the expansion of the use and processing methods for photographic materials, such as rapid shooting and rapid processing, and the diversification of the environments in which they are used, such as in high-temperature, high-humidity environments, are making photographic materials more harsh than they have been in the past. will be handled,
Sticking failures involving the outermost layer of the photographic material as described above are more likely to occur.

In order to solve these problems, it is necessary to improve the clinging properties of the outermost layers such as the surface of the emulsion layer and the back surface of the photographic material.

OBJECTS OF THE INVENTION 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. i.e., it is sufficiently antistatic, thus preventing the formation of static marks, and improving the adhesion between the backcoat layer and the support, yet causing contamination of processing baths, printers, etc. The object of the present invention is to provide a silver halide photographic material having a hydrophobic support with a free backcoat layer.

A second object of the present invention is to provide a silver halide photographic material in which the sticking property between the surface of the emulsion layer and the surface of the backcoat layer is improved.

[Structure 1 of the Invention] As a result of intensive studies, the present inventors have found that the object of the present invention is to provide a photographic material having at least one layer containing a photosensitive silver halide on a hydrophobic support, a water-dispersible binder and a water-dispersible binder. This is achieved by a silver halide photographic material characterized in that a layer containing at least one of the salts represented by the following general formulas (I) to <rv> is coated on the back surface.

General formula (I) M (BF4) General formula CM)
M(PFsn also general formula (III) (Cn FICoo)I
M general formula (IV) (Cn FI SO3)I
In the formula M, M is an alkali metal, an alkaline earth metal, and N
Represents H4. 2 is 1 when M is an alkali metal or NH4, and 2 when M is an alkaline earth metal. Also n,
m represents a positive integer satisfying tn-2n +k (k represents 1, -1, or -3).

The back side herein refers to the side opposite to the layer containing silver halide with respect to the support in a silver halide photographic material.

The back coat layer is a layer having antistatic properties that is coated on the back surface of a silver halide photographic material, and is located as the outermost layer on the back surface.

Water-dispersible binders include U.S. Pat. No. 4,241.
No. 169, No. 4,307,174, No. 4,193
, No. 803, No. 4,252,885, European Patent No. 5
No. 8.737, No. 29.620, No. 78,559
No., JP-A-58-169145, JP-A No. 56-95959
No. 53-119024, No. 5g-5338,
No. 58-5227, No. 59-19941, No. 59-
No. 77439, No. 57-128332, Special Publication No. 1977-
No. 3976, No. 4g-3564, No. 56-21769
An aqueous dispersion of a water-insoluble polymer described in No. 1, etc. is preferably used.

The content of the water-dispersible binder used in the implementation of the present invention is not particularly limited, but from the balance of various performances of the back coat layer, it is preferably in the range of 8ff1g/f to 150I1g/f, and more preferably 7 mQ/f. 1' ~60II
A range of g/f is particularly preferred.

Among the salts represented by the following general formulas (I) to (IV) used in the present invention, n in general formulas (T1) and (IV) is not particularly limited, but is preferably 1 to 4.

General formula (I) M(BF4>J General formula (II) M(PFs)1 General formula (I[[) (Cn Fm Coo)I
M general formula (IV) (Cn Fm SOs ) I
In the formula M, M is an alkali metal, an alkaline earth metal, and N
Represents H4. represents 1 when M is an alkali metal or NH4, and represents 2 when M is an alkaline earth metal. Also n,
m represents a positive integer satisfying m=2n 10k (k represents 1, -1, or -3).

The salts of general formulas (I) to <rv> may be used alone or may contain two or more types. The amount of these salts added is not particularly limited, but it is preferably added in an amount of 1 to 80% by weight based on the total weight of the back coat layer. Representative examples of these salts are shown below, but the present invention is not limited to the following examples.

Li BF Gin, KBF4, C3BF4.

Ca (BF+)2, l'Ja 8F+
, KPFs.

Rb PFs, MO (PF6) 2.

lea (PF8)2, Na PFs, CFa
SOa K.

C4Fs SO3Na.

CFa SOs Lf, (CFa803)2C
a.

Ca　F7　C00K, CFa　COONa　.

C4F9 GOONH4, (03F7 Coo)2
Ca.

CaF+yCOONa, CF2-CF2-GOOK
.

CFa-CF=CF2-COONa The polyolefin resin-coated paper 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 in the form of a film.

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 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 is provided has a glossy surface, matte surface, grained 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, polypropylene, polybutene, and polybentene, or double polymers such as ethylene-propylene copolymers. Examples include copolymers consisting of more than 1 species of olefins and mixtures thereof, and those having various densities and melt viscosity indexes (melt index 2 or less simply abbreviated as MI) can be used alone or in mixtures. M paper for polyolefin resin-coated paper may be ordinary natural pulp paper, synthetic fiber paper, or so-called synthetic paper made of artificial paper made of synthetic resin film. 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.
0g/ to 250g// is preferable. Furthermore, the base paper containing natural valve as a main component can contain various polymeric compounds and additives. For example, starch derivatives, polyacrylamides, polyvinyl alcohol derivatives, dry paper strength agents such as gelatin, sizing agents such as fatty acid salts, O-zine derivatives, dialkyl ketene dimer emulsions,
Wet paper strength agents such as melamine resin, urea resin, epoxidized polyamide resin, stabilizers, pigments, dyes, optical brighteners,
Latex, inorganic electrolytes, I)H regulators, etc. can be contained in appropriate combinations.

Furthermore, the thermoplastic resin film support that is advantageously used in carrying out the present invention is made by melting a composition consisting of titanium oxide, a fluorescent brightener, and a polyethylene terephthalate resin, extruding it through a slit die, and rapidly cooling it to form an amorphous sheet. , manufactured by sequentially stretching in the vertical and horizontal directions and heat-setting.

There is no particular limit to the content of titanium oxide, but it is between 10 and 2.
A content of the order of 5% by weight is advantageous.

There is no particular limit to the content of the optical brightener, but it is 0.01
~1% by weight is advantageous.

Although there is no particular restriction on the stretching ratio in the longitudinal and lateral directions, it is advantageous to set the stretching ratio in the longitudinal and lateral directions to about 2 to 4 times.

The thickness of the thermoplastic resin film support made of this polyethylene terephthalate resin composition is not particularly limited, but is preferably about 50 to 300 μm.

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 as a substrate and polyolefin, polystyrene, polyvinyl chloride, etc. Examples include resin-coated paper coated with a film-forming resin, often a polyolefin resin. especially,
Polyolefin resin-coated paper is advantageous as a support for photographic paper, especially color photographic paper, which requires good type printability and antistatic properties, in that the effects of the present invention are more prominently exhibited. used.

In addition, 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 stearic acid amide and alaxic acid amide, 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, optical brighteners,
It is preferable to contain a suitable combination of various additives such as ultraviolet absorbers.

The back coat layer according to the present invention may contain additives such as a surfactant, a matting agent, a lubricant, a crosslinking agent, and other known antistatic agents, if necessary.

Further, the effects of the present invention are more significantly exhibited when the back coat layer of the silver halide photographic material according to the present invention contains colloidal silica.

Colloidal silica preferably used in the practice of the present invention is mainly composed of silicic anhydride (Si 02 ) using water as a dispersion medium.
It is a colloidal solution made by dispersing ultrafine particles in water.

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, Na
In addition to 2O, it may also contain NHa formamide, ethylamine, morpholine, etc.

The colloidal silica preferably used in the practice of the present invention preferably has an average particle size of 511 Iμ to 120 mμ,
The coating amount is 0.05!7/f~1.0g/f in solid content.
The range of is preferably 0.1111/f −0,51
A range of 7/f is good. A specific example of colloidal silica is Snowtex manufactured by Yasan Kagaku Co., Ltd.

Examples of the surfactant used in the present invention include alkyl carbon salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, and sulfosuccinic acid. Anionic compounds containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkylphenyl ethers, and polyoxyethylene alkyl phosphate esters. surfactant,
Amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides, etc., alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium , heterocyclic quaternary ammonium salts such as imidazolium, and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings, e.g. saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol algyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicone) , nonionic surfactants such as glycidol derivatives (eg, alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, and the like are preferably used.

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,
Titanium oxide, precipitated aluminum hydroxide, barium sulfate, strontium sulfate, acrylic resin, polystyrene,
Fine particles such as rice starch can be cited.

The w cloth m and r are 5m! ]/n' to 500 rag
/f preferably ranges from 12mo/y to 150
Good ma/f range.

In addition, in the back coat layer of the present invention, U.S. Patent No. 2,91
No. 7,480, No. 4,272,616, No. 4.0
It is also preferable to use polymeric additives having surface activity as described in Japanese Patent Application No. 47,958, Japanese Patent Application No. 55-70837, and Shu 52-16224.

In addition, for the purpose of improving the film strength of the bank coat layer, a curing agent of an active halogen compound, for example 2, is used.

4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-6-methoxy-S-triazine, 2,4-dichloro-6-(2-sulfoethylamino)-S-triazine, N- It is desirable to use N'-bis(2-chloroethylcarbamyl)piperazine or the like.

In carrying out the present invention, an air knife coater, a roll coater, a percoater, a blade coater, and a slide hopper coater 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. , a gravure coater, a flexogravure coater, and a combination thereof. 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 loop 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 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, 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 (1) complexes and hexahalogenorhodium (I) complexes, nucleic acid decomposition products, JP-A-1987- No. 147925, surrounding area 51-10712
Crystal habits of silver halide grains such as mercapto heterocyclic compounds described or exemplified in No. 9! Regulatory preparation, JP-A-52-65
No. 482, color sensitizers, stabilizers, antifoggants, color photographic couplers, hardeners, dihydroxybenzene compounds, coating aids, and caplase cited or illustrated in the specification of No. 52-88340. It may contain additives for direct positive photographic emulsions such as dyes for direct positive photographs, dye developers, and other additives.

The silver halide photographic material according to the present invention can be exposed and developed 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. Multilayer silver halide color photographic materials that undergo bath bleach-fixing treatment after color development are CD-I, CD-IV (the above two compounds are It can be processed with any herbal color developer such as Kodak (trade name), droxychrome (May & Baker). Benzyl alcohol, thallium salt, phenidone, etc. may be added to the developer containing such a main agent.

Additionally, useful one-bath bleach-fix solutions are solutions of metal salts of aminopolycarboxylic acids (e.g., M iron t# salts such as ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, etc.), and fixing agents include sodium thiosulfate, Thio III! Ammonium and the like are useful.

Such a bath bleach-fix solution can contain various additives. For example, desilvering promoters (e.g., mercaptocarboxylic acids as described in U.S. Pat. No. 3,512,979, mercapto-heterocyclic compounds as described in Belgian Patent No. 682,426), antifouling agents, pH! 1 moderator or pH 1lt! Various compounds such as i-agent, hardener (for example, Ta''*magnesium, aluminum sulfate, potassium alum, etc.), surfactant, etc. can be contained in combination. various pH
The useful pH range is pH 6.0-8.
It is 0.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited by the Examples.

Example 1 The back side of a 160 μm thick base paper made of wood valves as the main raw material was coated with polyethylene having a density of 0.930 a l amj to a thickness of about 30 μm, and the surface contained 10% by weight of titanium oxide. Density 0.960 (
J/CIl! '17) A support for photographic paper was obtained by coating polyethylene to a thickness of about 30 am.

After the back surface of this support was subjected to a corona discharge treatment, a coating liquid having the following composition (Table 1) was applied at 20 ij2 per 1f by a wire bar code method. Subsequently, the surface was subjected to a corona discharge treatment, and then a black and white photographic emulsion was coated to obtain photographic paper samples 1 to 12.

The resulting photographic paper was evaluated for antistatic properties on the back side, stickability on the emulsion side and back side, and dry film adhesion properties of the back coat layer using the following test methods. The results obtained are summarized in Table 2.

<Antistatic property evaluation> The sample was heated at 23°C under 20% R and l-1 for 12 hours. The sample was moistened and the amount of peeling charge against neoprene rubber was measured under the same conditions. Measurement is a sample! This was done after I adjustment, before image processing, and after development processing.

Evaluation of stickiness〉 Two pieces of 5 cm square were cut from each sample after drying, and they were heated at 23°C for 80 minutes without touching each other.
0% RH (RH stands for relative humidity.

The same applies hereinafter) After storing for one day in an atmosphere of The area of the adhesive part was measured to measure the stickiness.

Note that the evaluation criteria were based on the method shown below.

Area of rank A adhesive part: 0 to 20% Area of rank B adhesive part: 21 to 40% Area of rank C adhesive part: 41 to 60% Area of rank D adhesive part 6
1-80% Rank E Area of bonded part: 81% or more If rank A is practically acceptable, there is no problem.

<Dry film attachment test> A shallow scratch is made on the back coated surface of the sample with a razor in the shape of the substrate, and then cellophane adhesive tape is pressed onto the scratch, and then the tape is suddenly peeled off. The remaining rate of the coating layer is expressed as a percentage.

In practice, there is no problem if this percentage is 80% or more.

From the results in Table 2 in the margin below, it is clear that the photographic paper sample of the present invention has antistatic properties.
It is clear that the stickability between the emulsion side and the backcoat side and the dry film adhesion to the support are good.

Example 2 80 parts by weight of polyethylene terephthalate and 2 parts of titanium oxide
A white opaque support having a thickness of about 125 μm was obtained by melt extrusion and two-wheel stretch molding of a resin composition consisting of 0 parts by weight. After corona discharge treatment on the back side of this support, a polymer undercoat layer was provided, and after further corona discharge treatment, a coating liquid of the formulation shown in Table 1 was applied by slide hopper coating at a rate of 20% per 1f.
0n12 was applied. Subsequently, after corona discharge treatment on the surface, a polymer undercoat layer was applied, and after further corona discharge treatment,
Samples 13 to 24 were obtained by applying a color emulsion for printing polish.

Table 3 summarizes the results of evaluating the antistatic properties of the back surface, the adhesion between the emulsion surface and the back surface, and the dry film adhesion properties of the back coat layer for the obtained samples.

From the results shown in Table 3 below, it is clear that the samples of the present invention have good antistatic properties, good adhesion between the emulsion side and the back coat side, and good dry film adhesion to the support.

Further, the samples of the present invention did not generate static marks and did not cause any contamination of the developing bath.

Patent applicant Konishiroku Photo Industry Co., Ltd. Procedural amendment (method) May 13, 1988 Patent application tjS35496 No. 2, Title of invention Silver halide photographic material with improved antistatic properties, etc. 3, Amendment Relationship with the case of a person who does
27) Konishi Roku Photo Industry Co., Ltd. Representative Director Keio Ide 4, Agent 102 Address Kudan-Rosaka Building, 4-1-1 Kudan 4-t, Chiyoda-ku, Tokyo Telephone 263-9524 (Shipping date) April 22, 1986 6. Clean the entire specification subject to amendment! (Change the content, shi)-.

Claims (1)

[Claims] A photographic material having at least one layer containing photosensitive silver halide on a hydrophobic support, comprising a water-dispersible binder and a salt represented by the following general formulas (I) to (IV). A silver halide photographic material characterized by having a layer containing at least one of: coated on the back side. General formula (I) M(BF_4)_l General formula (II) M(PF_6)_l - General formula (III) (CnFmCOO)_lM General formula (IV) (CnFmSO_3)_lM In the formula, M is an alkali metal, alkaline earth Metal and NH_
Represents 4. l represents 1 when M is an alkali metal or NH_4, and represents 2 when M is an alkaline earth metal. Further, n and m represent positive integers satisfying m=2n+k (k represents 1, -1, or -3).