JPH0419641A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve dryability without impairing covering property of a coating film by specifying a weight ratio of silver to be used to the binder of an emulsion and incorporating a polymer latex in the emulsion layer. CONSTITUTION:At least one silver halide emulsion layer formed on a paper base has a weight ratio of the coated silver to the binder of the emulsion of >=1, and the emulsion contains the polymer latex. It is prepared by mixing a solution of a water-soluble silver salt, such as silver nitrate, with a solution of a water-soluble halide salt, such as potassium bromide, in the presence of a water-soluble polymer, such as gelatin, thus permitting the obtained reflection density type silver halide photographic sensitive material to be superior in the covering property of the coating film and dryability.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic material, and in particular, a silver halide photographic material with improved drying properties without impairing covering power in reflection density. It is related to.

(Prior art) In commonly used reflection density type silver halide photographic materials, it is necessary to increase the weight of the binder in the emulsion layer relative to the weight of the silver of the coated silver halide in order to improve the covering power. Are known.

However, by increasing the weight of the binder in the emulsion layer in this manner, the amount of liquid carried by the binder layer to the drying section of the developing machine increases, resulting in poor drying and tends to cause density unevenness after processing.

(Object of the Invention) Therefore, the object of the present invention is to improve the drying properties of a reflective density type silver halide photosensitive material without impairing the covering power.

(Disclosure of the Invention) An object of the present invention is to provide a silver halide photosensitive material having at least one silver halide emulsion layer on a paper support, in which the weight ratio of the coated silver to the binder of the emulsion layer is is 1 or more, and the emulsion layer contains a polymer latex.

A water-soluble silver salt (for example, silver nitrate) solution and a water-soluble rogone salt (for example, potassium bromide) solution are mixed in the presence of a water-soluble polymer solution such as gelatin. Examples include silver chloride, silver bromide, and mixed silver halides such as silver chlorobromide.

Silver iodobromide, silver chloroiodobromide, etc. can be used.

Average grain size of silver halide grains (grain diameter for spherical or approximately spherical grains; grain size for cubic grains, wavelength, average based on projected area)
is preferably 2μ or less. The particle size distribution may be narrow or wide.

The shape of these silver halide grains may be cubic, octahedral, or a mixed crystal thereof. Preferably it is monodisperse, more preferably regular.

Alternatively, two or more types of halogenated photographic emulsions formed separately may be mixed. Furthermore, even if the crystal structure of the silver halide grains is similar even to the inside.

It also has a layered structure with different interior and exterior.

It may also be of a so-called conversion type as described in British Patent No. 635,841 and US Pat. No. 3,622,318. It may be of the type J) in which a latent image is mainly formed on the surface or the internal latent image type in which it is formed inside one particle.

These photographic emulsions were developed by Meesi, l The Theo
ryof the Photography Pro
cess j 4th. tentative.

Published by MacMillan (1976) -P, Gr.
Written by afkidea.

[Chimie at Photography
j, published by Paul Mon-te1 (1957)
S.G., F. Duffin, [Pho-togr.
aphic emulsion chernistry
Published by J-The Fo-eaI Press (1966
]; V, L, Zelikman atal'
li rMaki+＞g and Coating P
Photographic Emulsion J, T
It can be adjusted using the method described in He Focal Press (1964, 2, etc.).
Any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble chlorine salt may be one-sided mixing method, simultaneous mixing method, or a combination thereof. It's okay.

It is also possible to use a method in which silver ions are formed in excess of particulate silver ions (so-called back mixing method).

One type of simultaneous mixing method is a method of keeping the pAge constant in the liquid phase in which silver halide is produced.

A so-called Chondrold double jet method may also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halogenide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, cadmium salt, zinc salt, lead salt, thallium salt.

Iridium salt or its complex salt, rhodium salt or its complex salt,
Iron salts or iron complex salts or the like may also be present.

It is preferable to coexist with the thioether compound described in US Pat. No. 3,574,628.

The ciT pouring salts are usually removed from the emulsion after precipitation or physical ripening.As a means for this purpose, the Tardel water washing method, which is performed by gelatinizing gelatin, which has been known for a long time, may also be used. Inorganic salts consisting of polyvalent anions 1 For example, sodium sulfate anionic surfactants, anionic polymers (such as polystyrene sulfonic acid λ, or gelatin derivatives (such as aliphatic acylated gelatin,
A sedimentation method (flocculation) using aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) may also be used. In addition, after the silver halide grains in the emulsion solution are precipitated by natural sedimentation or centrifugation, a part of the dispersion medium is removed as a supernatant liquid by decantation, suction, etc., and if necessary, water is added and removed. Natural sedimentation (or centrifugation)/decantation method in which the steps are carried out once or several times, or Japanese Patent Publication No. 10957-1983, Japanese Patent Application Laid-Open No. 1983-1987-
No. 209823, U.S. Pat. No. 4,334,012.

An ultrafiltration method may be used in which the dispersion medium is removed through an ultrafiltration membrane as described in Japanese Patent Nos. 4,336,328 and 3,782,953, while supplying water if necessary. The process of removing soluble salts may be omitted.

The silver halide emulsion is a so-called unripened emulsion that is not chemically sensitized (Zorimi tape emulsion can also be used, but it is usually chemically sensitized. For chemical sensitization, #I Glafkides or the book by Zelikman et al.
Or f(, Fr1eaer[, “Die Gru-
ndlagan der Photography
han Prozessewit 5ilb@rhal
ogenid@n J , AkademischeVe
The method described in Rlagggea@1lachaft (1968) can be used.

In other words, sulfur-containing compounds that can react with active gelatin or silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines), sulfur sensitization methods, reducing substances (
For example, reduction sensitization using metal salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds), noble metal compounds (e.g. gold compounds, and periodic group II metals such as platinum, iridium palladium, etc.). A noble metal sensitization method using complex salts of 1 to 4 can be carried out alone or in combination.

The photographic emulsion used in the present invention has the purpose of preventing capri during the manufacturing process, storage, or photographic processing of light-sensitive materials, or for stabilizing photographic performance.

Various compounds can be included. Azoles (e.g. benzothiazolium salts, nitroimidazoles, nitrobenzimidazole gQ, rio o
Hensuimidazoles, bromobenzimidazoles,
nitroindazoles, benzotriazoles, aminotriazoles]; mercapto compounds (e.g. mercaptothiazoles, mercagutobenzothiazoles, mercaztobe/zimidazoles, mercagutothiadiazoles, mercaptotetrazoles (1-phenyl -5-mercaptotetrazoles, mercaptopyrimidines, mercaptotriazines, etc.]: thioketo compounds such as oxadrinthione; azaindenes (e.g. 1,3,3m,
7) Tetraazaindenes].

Compounds known as anti-capri agents or stabilizers such as pentaazaindenes, etc.); benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. can be added.

In particular, mercapto compounds such as those described in US Pat. No. 3,295,976, US Pat. No. 3,397,987, US Pat. No. 3,266,897 and US Pat.

2933388 and IW13202512, especially [-phenyl-5-
Mercaptotetrazole and 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene are preferred.

For more detailed examples of these and how to use them, see, for example, U.S. Pat.
No. 47, t￥! The material described in Japanese Patent Publication No. 52-28660 can be used.

The anti-capri agent may be present in any layer contained in the light-sensitive material of the present invention. It may also be added at any stage during emulsion production that can be normally employed.

Bay that can be used in the emulsion layer of the light-sensitive material of the present invention>
Gelatin is most commonly used as 9'2, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, cardoxymethyl cellulose, cellulose sulfate esters, and sodium alginate.

Sugar derivatives such as starch derivatives; single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyvinylimidazole, polyvinylpyrazole, etc. A wide variety of synthetic hydrophilic polymeric materials can be used, such as.

In addition to lime-processed gelatin, gelatin includes acid-processed gelatin and "Bull, Soe, Set, Phot,"
Enzyme-treated gelatin as described in Japan JN1116.30 (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

Examples of gelatin derivatives include gelatin and various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, and epoxy compounds. The product obtained by reacting is also used.

The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methyloldimethylhydantoin, etc.).

Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-8-triazine.

1.3-vinylsulfonyl-2-propatol, etc.),
Active halogen compounds (2,4-dichloro-6-hydroxy-3-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), etc. are used alone.
or in combination.

Among these, active vinyl compounds and active halogen compounds are particularly preferred.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

For example, nabonine (steroids), alkylene oxide derivatives (e.g. polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethinone glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alkynylsuccinic polyglycerides, alkylphenol polyglycerides), fatty ieR esters of polyhydric alcohols, alkyl esters of sugars Nonionic surfactants such as: alkyl calzenates, alkyl sulfonates, alkylbenzene sulfonates, alkyl carbenes, etc.
onic acid salts, alkyl sulfates, alkyl phosphate esters 5j (, N-aclu N-alkyltafrines,
Sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkylphenyl ethers.

Calxoxy group, sulfo group, phospho group, such as polyoxythythere/alkyl phosphate esters.

Anionic surfactants containing acidic groups such as sulfate ester groups and phosphate ester groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl @ fine or phosphate esters, alkyl betaines, and amine oxides. ;alkylamine salts, aliphatic or aromatic quaternary
Cationic surfactants such as complex quaternary ammonium salts, pyridinium, imidazolium, etc., and phosphonium or sulfonicum salts containing aliphatic or bicyclic rings can be used.

Among these, 1% fluorine-containing surfactants (described in Japanese Patent Publication No. 80849/1984) and polyoxyethynone nonionic surfactants are preferred.

The photographic emulsions used in the present invention may be spectrally sensitized by dyes, dyes, etc. The dyes to be used include
Cyanine pigment, melonanine pigment.

Included are complex cyanine dyes, complex melonanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioquinonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, melonani/dyes, and complex merocyanine dyes. For these pigments, any of the methods commonly used for cyanine pigments as basic heterocyclic nuclei can be applied. Ding, vilorin nucleus,
Oxazoline nucleus, thiazoline nucleus, virol nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; Nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei: and aromatic to these nuclei A nucleus of fused hydrocarbon rings.

Immediately, indorenin cough, benzindo V nin nucleus.

Indole nucleus, benzoxadol cough, su7oxazole cough, benzothiazole cough, naphthothiazole nucleus, penzose V nazole nucleus, benzimidazole cough, quinoline nucleus, etc. can be applied. These coughs may also be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include pyrazolin-5-one, thiohydantoin, 2-thioxazolidine-2,
5- to 6-membered expressions such as 4-dione, thiazolidine-2,4-dione, rhodanine, and thiobarbic acid nuclei!
JI cough can be applied.

The photographic emulsion layer of the photographic light-sensitive material of the present invention is used for the purpose of increasing sensitivity, increasing contrast, or promoting development.

For example, polyalkylene oxide or its ether,
Derivatives such as esters and amines, thioether compounds,
Thiomorpholines, quaternary ammonium salt compounds, RiV
It may also contain tantalum conductors, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. For example, U.S. Patent 24
No. 00532.

No. 2423549, No. l'812716062, No. 3
No. 617280, No. 3772021, No. 380800
No. 3, British Patent No. 1488991, etc. can be used.

In the present invention, the silver halide photographic emulsion solution prepared as described above is prepared by a coating method commonly used in this field.
For example, dip-type coating in which the support is dipped into the emulsion and pulled up along a coating roller.
Extrusion type coating in which the coating liquid is extruded through a slit and applied (for example, Japanese Patent Publication No. 44-23758, U.S. Patent No. 3474758, and U.S. Patent No. 399688)
No. 5), curtain flow type coating to stabilize liquid pools in extrusion type (e.g. US Pat. No. 3,632,374 and US Pat. No. 35,089)
47) etc. on the support or other layers (
(undercoat layer, other emulsion layer, etc.).

By drying the emulsion coating layer thus obtained as described above, a photographic material containing an emulsion layer in which silver halide grains are sufficiently precipitated can be obtained.

In the present invention, it is preferable to use polymer latex as the binder. Examples of preferred polymer latexes include alkyl, hydroxyalkyl or glycidyl esters of acrylic acid;
It is a polymer having an alkyl ester, a hydroxyalkyl ester, or a glycidyl ester of methacrylic acid as a monomer unit and having an average molecular weight of 100,000 or more, particularly preferably 300,000 to 500,000, and specific examples include the following formula % formula % This invention The polymer latex used in
An aqueous dispersion of a water-insoluble polymer of 0 mμ to 200 mμ,
The preferred amount of other binders, such as gelatin, is 1.
The dry weight ratio is 0°01 to 1. 0, particularly preferably 0.1 to 0.8.

Furthermore, regarding polymer latex, the above-mentioned
No. 5-5331, U.S. Pat. No. 2,852.386, U.S. Pat. No. 3,062,674, U.S. Pat.
, 411,912 can be referred to.

Further, the ratio of the weight per unit area of the coated silver to the weight of the binder is 1 or more, preferably 1.2 or more. Generally, the ratio of the weight of silver to the weight of the binder in photographic paper and industrial material paper is 0.4 or less, and this is intended to improve covering power, but this results in poor drying properties and curling properties.

Here, the covering power is defined as Cp=D/M (D is the optical density, measured as the reflection density in the case of the present invention, and M is the amount of silver per unit area, usually expressed in g/bo).

The greater the covering power, the more a certain optical density can be achieved with a smaller amount of silver, and therefore silver savings can be achieved.

The "reflective support" used in the present invention refers to a material that enhances the reflectivity and makes the image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing dispersed light-reflecting substances such as titanium, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing dispersed light-reflecting substances as a support. For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate,
Examples include polyamide film, polycarbonate film, polystyrene film, and vinyl chloride resin.

A particularly preferably used support for the present invention is polyethylene coated paper.

In particular, polyethylene-coated paper having a layer containing a dye or pigment such as fluorescent dye or ultramarine blue is preferred. Furthermore, it is preferable to provide an antistatic layer on the opposite side of the support used in the present invention to the side on which the emulsion layer is provided. For details of such supports, see, for example, JP-A-61-210346 and JP-A-63-24.
No. 247, No. 63-24251 and No. 63-24255
It is written in the number etc.

(Examples) The present invention will be illustrated below with examples, but the scope of the present invention is not limited by these descriptions.

Silver nitrate aqueous solution (A) was added to gelatin aqueous solution (A) kept at 50°C.
B) and sodium chloride potassium bromide aqueous solution (C) were simultaneously mixed to increase the potential by +5 for an addition time of 0 to 12'.
The voltage was controlled at 0 mV.

After removing soluble salts from this emulsion by a conventional method well known in the art, gelatin was added thereto and sensitized with gold and sulfur, and then 0.1 mmol of the antifoggant 1-phenyl-5-mercaptotetrazole was added. . At the time of coating, this emulsion was coated with dilute gelatin or polymer latex; polyethyl acrylate and coated on a paper support and a polyethylene phthalate film to obtain samples 1 to 7 as shown in Table 1.

All of the above samples were coated on paper supports.

Samples 1 to 3 in Table 1 were exposed to 400 lux tungsten light for 1 second through an optical wedge, and then developed for 10 minutes at 20°C with a surface developer having the following composition.

<Developer composition> N-methyl-p-aminophenol sulfate 2.3g ascorbic acid 10.0g potassium metaborate
35.0g potassium bromide
Add 1.0g water
11 The maximum density and drying property of the image obtained by stopping, fixing and washing with water were measured according to a conventional method. The results are shown in Table 2.

As is clear from the above results, according to the present invention, a reflection density type silver halide photosensitive material having excellent covering power and drying properties can be produced.

Claims (1)

[Claims] In a silver halide photosensitive material having at least one silver halide emulsion layer on a paper support, the ratio of the weight of the coated silver to the weight of the binder of the emulsion layer is 1 or more, and the emulsion layer A silver halide photosensitive material containing polymer latex.