JPS5830752A - Photographic material - Google Patents

Abstract

PURPOSE:To prevent discoloration of a photographic material and to obtain an image high in whiteness, by providing a layer containing a silver halide developing agent on a support of paper base treated with hydroxymethanesulfinic acid or its salt and coated with a resin capable of forming a film. CONSTITUTION:A resin, such as polyolefin is coated on the surface of a support of paper base impregnated with an aq. soln. of hydroxymethanesulfinic acid or its salt and dried. One surface of this support is treated by corona discharge, and photographic constituent layers are formed on the support. At that time, a silver halide developing agent or its precursor is added to at least one of these layers, preferably to a silver halide emulsion layer, thus permitting a photographic paper obtained by this process not to discolor to yellow or yellowish red during long term storage, especially in high temp. and high humidity, and to have high operability in development processing, and high whiteness and superior quality.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a photographic field containing a halogenated chain constructor in a photographic constituent layer formed on a support coated with a certain resin as a film forming part, and more specifically to a photographic field containing a halogenated chain constructor. The variation of photographic materials under the influence of image agents is that photographic materials are composed of a support and photographic constituent layers provided on the support. Such photographic constituent layers include a silver halide photographic emulsion layer, a protective layer, a subbing layer, an intermediate layer between the emulsion layers, or a layer (6), a fat-holding layer, a fatty acid layer or a filter layer, UV collecting layer containing UV absorbing agent, product for diffusion transfer method ig+
10, usually composed of n*-containing images, layers, etc., and combinations thereof. 4IK, the photographic constituent layer O in which at least one of the photographic constituent layers is a silver halide photographic emulsion layer is referred to as a silver halide photographic constituent layer, and is a photographic material in which a silver halide photographic constituent layer is provided on a support. For example, a single silver halide photographic material is one in which a silver halide photographic emulsion layer and seven protective layers are provided on a support. In addition, the multilayered chain photo material can be used on a support. A multilayer arrangement in which a real-sensitivity halide chain photographic emulsion layer and an intermediate layer, a green-sensitivity silver halide photographic emulsion layer and an ultraviolet collecting layer, a red-sensitivity silver halide photographic emulsion layer and a protective layer, etc. are provided in the application. It is.

In addition, certain photographic materials, such as special public @311-1109
No. 1, Kosho 5s-zysss, 'f#1k1851
In the case of photographic material 140 for the diffusion@1 method, which uses a pair of silver halide photographic materials and an image-receiving material as described in No.
A support has photographic constituent layers, one of which is an image-receiving layer. More must! Depending on the photographic material oam, m photographic constituent layers, in most cases supports without silver halide photographic constituent layers, a hydrophilic colloid called a back coat layer with anti-curl and anti-curl properties. Although it is known to provide coating layers consisting of layers, they are not included in the photographic constituent layers referred to herein.

Photos of improved durability of 4611 liquid, etc. Jl & Market OII
There are efficient photographic materials that can be improved from 02 to 4 in terms of photographic properties, such as acceleration of the development properties of silver halide photographic emulsions, improved sensitivity, increased gradation, sharpness R%, and improved resolution. It's becoming more and more necessary.

As a photographic material that can meet these demands, a resin-coated paper coated with a film-forming resin, often a polyolein resin, is used as a photographic support using a paper mainly composed of natural pulp as a substrate. Many photographic materials have come to be manufactured which are provided with a photographic constituent layer containing a chain a-containing image agent. The reason for this is, firstly, that such photographic materials already contain a silver halide developer in the photographic constituent layers, so compared to photographic materials that do not contain a silver halide developer, it is difficult to develop from the early stage of development of the photographic material. This is because an efficient developing effect can be obtained with quick cleaning. Secondly, because the tree-coated paper used as a photographic support is hydrophobic, it is difficult to develop 1% of the photographic material compared to the case of baryta paper, which is conventionally used as a photographic support. This is because the silver layer i permeates into the base paper layer during fixing and processing, so there is an advantage that the time required for washing, drying, etc. is shortened.

However, a tree coated paper made of paper mainly composed of natural pulp and coated with film-forming lll5.
- It has become clear that photographic materials used as zero-photo supports and containing silver halide AS agents in the photographic constituent layers stamped onto said supports have serious drawbacks.

That is, if this photographic material is stored for a long period of time after its manufacture, or if it is stored in a bag under high temperature and high humidity, the color of the underarm material may change to yellow, yellowish brown, or yellowish red. Due to the problem of color change, discoloration is often observed when viewing this photographic material from the side opposite to the photographic constituent layers. As a result of the studies conducted by the present inventors, it has become clear that ζO discoloration occurs in the following mysterious situation.

In addition, the photographic constituent layers containing silver halide developer are discolored, and the base paper layer mainly composed of natural pulp is also discolored. *jgiz,
If the photographic constituent layer does not contain a silver halide agent, substantially no discoloration is observed.Thirdly, a so-called synthetic paper is used as the first support, and a silver halide developer is placed on the support. It has become clear that no discoloration of the support is observed in photographic materials in which the photographic constituent layer containing the compound is soft.

As mentioned above, this discoloration is caused by the interaction between the resin-coated paper using M-paper as a support and the silver halide IA agent contained in the O photographic constituent layer on the support. Few,
Also, in such an action,
1Mt), which is thought to be due to the influence of
The exact mechanism of action is not yet clear. However, in any case, the discoloration of ζ causes deterioration of the white background, 1lriOfIg dyeing, and photographic properties of the photographic material, which seriously impairs its commercial value.

Therefore, the purpose of Zero Development@O is to prevent discoloration of a photographic material containing a silver halide developer in the photographic constituent layers provided on a paper-based support coated with a film-forming resin. Therefore, it is an object of the present invention to provide an excellent photographic material 01111J, which is efficient and easy to work with, has improved photographic properties, and has a high degree of whiteness.

As a result of intensive studies, the present inventors have found that the object of the present invention is to provide a photographic material in which a photographic constituent layer is provided on a support, in which at least one of the photographic constituent layers contains at least one type of silver halide iI*ytso. #
It has been found that this can be achieved by using IRN-covered paper coated with a film-forming resin using recycled paper as a substrate.

Moreover, in the photographic material of the present invention, not only the discoloration of the base paper layer of the resin-coated paper serving as the support is significantly prevented, but also the discoloration of the photographic constituent layer containing the halogenated *** agent is also significantly prevented. The present invention is based on these completely new facts.

EXAMPLES OF THE INVENTION 11 IAK Examples of the salts of hydroxymethanesulfinic acid used include alkali metal salts, alkaline earth metal salts, ammonium salts, etc., and the sodium salt is generally known as Rongalite.

Hydroxymethanesulfinic acid and its salts used in the practice of the present invention can be added to the paper base material at the time of rolling out the paper stock. Advantageously, it is added during the papermaking stage, such as by spraying. In addition, Ik coating may be performed using an air knife coater, a roll coater, a gravure coater, a blade coater, etc.Although the amount of the compound represented by the general formula (I) to be treated is not limited to 41Kl, it is preferably paper-based. It is preferable to add io4 or more per material 1+/.

What is the silver halide fA imager used in the present invention @C)? Am activator, for example, contains an alkaline solution. Specific examples of silver halide 116 agents include hydroquinone, 2-methylhydroquinone, λ5-dimethylhydroquinone, trimethyl^hydroquinone, 2-chloro-hydroquinone, 2-phenyl-hydroquinone,
2-t@rt-butylhydroquinone, 2.5-di-1・rt-butylhydroquinone, λ5-di-t@rt
- O-hydroquinone compounds such as octylhydroquinone: polyhydric phenol compounds such as catechol, 4-1ar&-butyl-catechol, and pyrogallol 11-phenyl-3-pizzolidone (7E9t), l-(zen-tolyl)-3-pyrazolidone , l-7E-2-acetyl-
3-bi? ' / 9 F, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-44-dimethyl-
3-pyrazolidone, l-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p-chlorophenyl-4-methyl-4-hydroxy-3-pyrazolidone, 1-('p-tolyl)-44- 3-pyrazolidone compounds such as dihydroxymethyl-3-pyrazolidone, l-phenyl-4-hydroxymethyl-3-pyrazolidone) p-amino-phenol, 2-amino-4-methyl-phenol, metol, 4-hydroxyphenyl Amino-phenol compounds such as amino-acids; aminohexone-reductone compounds such as dimethylaminohexose reductone, dimaro-butylaminohexose reductone, morpholinohexose reductone, piperazinohexose reductone 7; 4-amino-1,4
- Amino-naphthalene diol compounds such as dihydro-sinaphthalene, 2"re-N-dihydroxynaphthalene; p-phenylenediamine, 4-(N,N-diethyl)aminoaniline, 4-(N-Zf-N-hydroxyethyl) A11; Middle Hi≠1≠4Uki4=(N-X, f-N-β-methylsul7onaminoethyl)amino-2-methylaniline 1.
4-(N-ethyl-N-hydroxyethyl)amino-2
- Methylaniline, etc. and their hydrochlorides, sulfates,
4-aminoaniline compounds such as salts such as diphenylboron salt; hydrazine, hydroxyethylene, naphthalene diol, etc. can be used. Also, IAg
Specific examples of the II main drug-body substance include 4-chloroacetyloxy-hydroquinone, hydroquinone monoatrate, L4-dichloroacetyloxyhydroquinone, l,4-=neat, etc. % limited to these silver halide developers
Not 0. Further, a herogenated compound or a combination thereof may be contained. For example, a combination of a hydroquinone compound and a 3-pyrazolidone compound is useful.

In addition, the silver halide developer used in the practice of the present invention includes a silver halide photographic emulsion layer, a protective layer, a subbing layer, an intermediate layer, a color spread stopping layer, and an antihalation layer formed on a support. It is sufficient if it is contained in at least 41 layers of photographic constituent layers consisting of a layer or a filter layer, an ultraviolet-1LLL layer, a receiver layer, etc., and combinations thereof.
From the viewpoint of the photographic material 01111 effect, it is particularly useful to incorporate the halogenated am toner into the silver halide emulsion layer of the silver halide photographic material, and it is essential! Depending on the situation, they may be contained in combination in photographic constituent layers other than the silver halide photographic emulsion layer. On the other hand, J! In the case of specific photographic materials, such as photographic materials for diffusion transfer method O, a 3-pyrazolidone compound is contained in the photographic constituent layers of the silver halide photographic material, and a hydroquinone compound is contained in the photographic constituent layers of the image-receiving material. It may be contained separately, as in the following. Halogenation*
*In order to incorporate the agent into the photographic constituent layer, it is advantageous to add a silver halide developer to the OIL aqueous colloid for the photographic constituent layer during the production of the four-layer material. As for the method of adding O, add silver halide developer to water, methanol,
A method in which a solvent such as ethanol, gropanol, inglobanol, acetone, methyl alcohol ketone, benzene, dioxane, etc. is dissolved and added to the coating 11 for the four true constituent layers, and a silver halide developer is mixed with dibutyl heptalate, phthalate, etc. High-boiling point solvents such as di-normalnonyl acid and tricresyl phosphate are a must! Depending on the situation, mix them with a low boiling point I medium such as ethyl acetate or hequinane and an O mixed solvent.
mlEK for one true constituent layer as an emulsion dispersed in the presence of a surfactant in another hydrophilic colloid solution.
It is advantageous to use an oil protection method in which silver particles have a low boiling point of 11mK11 and occlude them in a resin latex for use in photographic constituent layers.

In addition, the amount of halogenated *m* agent to be included in the photographic constituent layer, the type of silver halide 1111180 steel, the type of photographic material, its use, and the composition and crystal habit of silver halide in the silver emulsion layer. , Grain size, crystal form, etc., 1m class of silver halide, silver ion negativity in emulsion, PH, emulsion properties such as binder, stabilizer for silver halide emulsion, fog suppression, sensitizing dye, hardening film. It is actually determined by additives such as agents, etc., and is not determined by f#Km@, but the content is less than or equal to overcharge@f/d〉, and II# is preferably a hydroquinone compound. In the case of the O content, the O content is less than st/-, and in the case of the 3-biracidatone compound, the O content is less than 11/d.

Photographic materials to which the present invention is effective include silver halide black and white photographic materials, silver halide 2-photographic materials, multilayer silver halide 2-photographic materials, silver halide photographic materials for diffusion transfer methods, and image-receiving materials ( For example, 譬A@1g-11093, 4Ikai 1972-zysis, *Kin@s*-4377
Direct positive lid silver halide photographic materials, for general photographic paper, for typesetting photographic paper, for copying photographic paper, for block preparation materials, for printing (e.g., Special Publication No. 48-30
(Including materials such as S 62), etc. Types and uses are @
Not determined.

This invention is 0! J! The filter paper base material (hereinafter simply referred to as base paper) used for Maro is mainly composed of Fi natural parg, but if necessary, paper made of a mixture of synthetic pulp and threat fiber other than natural pulp may be used. Also, natural pulp can be bleached with chlorine, hypochlorite, chlorine dioxide, the usual bleaching tin layer and alkaline extraction or partial layer and must! Depending on the situation, wood pulps such as softwood sulfur, hardwood pulp, and softwood pulp with a combination of hydrogen peroxide, peracetic acid, etc., and a combination layer of these are advantageously used. In addition, various materials such as kraft pulp, sulfide pulp, soda pulp, etc., and pulp using an anthraquinone compound as a cooking aid can be used.

For example, dry paper strength can be increased by adding a polymeric compound or an additive to the base paper, which is made of natural pulp and is used in the practice of the present invention, when forming a paper stock slug. - As cationized starch, cationized Iv acryland, anionized polyacrylamide, carboxy-modified polyvinyl alcohol, gelatin, etc. As sizing agents, fatty acid salts, rosin, rosin conductors such as maleated rosin, alkenyl or alkyl succinic acids, Those salts are also acidic anhydrides, sials, and lucetendai! = Emulsions, petroleum resin emulsions, etc. Fillers: clay kaolin, calcium carbonate, barium sulfate, titanium dioxide, aluminum hydroxide, magnesium hydroxide; wet paper strength agents: melamine resin, urea resin, epoxy Chemical I
Lyamide resin, etc., may be used as a fixing agent, polyvalent metal salts such as al-1-um sulfate, caustic soda, soda carbonate, etc. as a PH@@ agent, and mulberry and fluorescent brighteners, etc. may be added as appropriate. It's advantageous. In addition, for making the base paper, a paper machine that is over-energized, such as a fourdrinier paper machine or a circular wire paper machine, is used.

Advantageously, the paper used in the practice of the present invention is sprayed, tab-sized or size-pressed with a pulp containing various water-soluble polymeric compounds and additives, which is mainly composed of natural pulp.

Examples of such aquatic polymer compounds and additives include:
As water-soluble polymer compounds, cationized polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethylcellulose, droxyethylcellulose, cellulose sulfate, gelatin, casein, sodium polyatarylate, styrene-maleic anhydride copolymer sodium Sizing agents include petroleum resin emulsions, ammonium salts of styrene-maleic anhydride copolymer alkyl esters, alkyl ketene dimer emulsions, styrene-butadiene copolymers, ethylene-vinyl acetate copolymers, etc. As latex such as polymers, polyethylene, and vinylidene chloride copolymers, dilutions, and inorganic electrolytes,
Thermoabsorbing substances such as common salt and mirabilite, glycerin and polyethylene glycol, pigments such as clay kaolin, talc, iin barium, and titanium oxide, and PH regulators such as hydrochloric acid, phosphoric acid, electrolytic soda, and soda carbonate.
It is advantageous to use a combination of additives such as dyes and pyrophores.

There is no acid 41K limit regarding the base paper 0111II, which is mainly composed of natural pulp, and its thickness, but the base paper is compressed by applying ``'C pressure to a calender after making the base paper wiO i-based paper is preferred because of its smoothness;
The basis weight is preferably 401/d to 21kOfld.

Film-forming resins used in zero-start @O implementation include polyolefins, polystyrene, polyvinyl chloride, polyacrylic esters, linear polyesters such as polyethylene terephthalate, polycarbonates, polyamides such as nylon, cellulose, polyacrylonitrile, and O homopolymers. In addition, the Mori copolymer f1 may be any resin as long as it is capable of coating a resin A1 film on a base paper such as ethylene-vinyl acetate copolymer and mixtures thereof, and is not limited to 41, but may be a polyolefin resin. is particularly advantageous in terms of extrusion coating properties, good adhesion to the base paper, and cost. The polyolefin resin in the present invention refers to low-density polyethylene high 1! Homopolymers of olefins such as modified polyethylene, polypropylene, polybutene, polybentene, copolymers of two or more olefins such as ethylene-propylene copolymers, and hot metal products thereof], various 01! Melt index (melt index; hereinafter simply referred to as MI) can be used alone or in combination.

Among the film-forming layers used in the practice of this invention are:
White pigments such as titanium oxide, TL complex oxide, Merck, and calcium carbonate, 11 fatty acids such as stearin amide, alaxin amide, and stearic acid! Lead, stearic acid metal salts such as stearic acid, aluminum stearate, stearic acid calcicum, octyl zirconicum, sodium palmitate, calcium palmitate, sodium laurate, tetrakis [methylene-S (λS-zi-butylene) 4-Hydroxyphenyl)propionate] Mechita, antioxidants such as λ6-di-t@rt-butyl-4-methylphenol, cobalt blue, navy blue, reviews! , O-blue pigments and dyes such as cerulean blue and phthalocyanine blue, magenta OII pigments and dyes such as cobalt violet, fast violet, and manganese violet, bis(t@rt-butylbenzoquinazole)thiophene, bis(methylbenzoxazole)naphthalene, etc. EOII whitening agent, Tenuvin 320
It is preferable to add various additives such as 1 Tinuvin 32@, Tinuvin 328 (trade name of Ciba Geigy)' and any ultraviolet absorber in an appropriate combination.

These O additives are added to a resin, preferably a polyolefin**
The best way to add the ingredients is by melt-mixing using a heated wire crawler, Banbury mixer, kneader-1 kneading extruder, etc., and add all the ingredients from the beginning! You can create and use a compound with a high IO composition ratio, or create a masterbatch containing high K for each component and mix them in the desired ratio. You may.

The 5uii coated paper used in the practice of the present invention G is usually manufactured by the so-called extrusion coating method in which 1liN in a heating bath is polished on a running base paper, and preferably both surfaces thereof are coated with resin. In addition, it is preferable to apply IIIK coating of the base paper with resin, and to apply activation treatments such as corona discharge treatment and flame irradiation to the base paper. The emulsion side surface of the resin-coated paper may be glossy, i) 1m, or i
The back side is usually matte, and the front side or the surface angle FiAK as required is corona senden am, etc.
Be able to discuss activation escape methods such as flame treatment. Additionally, the thickness of the resin-coated paper 011 layer is not limited to 41, but it is generally advantageous to extrusion coat it to a thickness of 5 tons to 50 microns.

Various types of silver halide photographic emulsions can be used as silver halide photographic constituent layer O silver halide photographic emulsions which are advantageously used in zero-start embroidery. For example, as a halide composition, for example silver chloride, silver bromide, chlorobromide chain Shiozawa silver bromide! - Emulsions made of silver iodochloride, silver iodobromide, etc., or their O-temperature mixtures, emulsions of silver halide grains with parent-like shapes such as cubic grains, or silica In an emulsion consisting of a group of grains having a crystalline structure and a tk shape (LO
, O)L (1,1,1)lit, etc., or their Oa particles, for example (L to O)
Emulsions consisting of mixed crystal grains having (1, Ll) and (1, Ll), etc., have fine-grained emulsions or ti@grain-like emulsions with a wide range of grain size distribution.
As an emulsion or a monodisperse emulsion, the K11 degree distribution is narrow.
As an OPH in an emulsion, for example, dP H4L O
! t, apn & o O@IIK certain emulsion, O in emulsion
As the chain ion concentration, for example, ・PAtILO or P
As a binder for emulsions and silver halide grains in Category 1 of JJP I L., hydrophilic binders such as polyvinyl alcohol, poly(N-vinyl vinylidene), acrylic acid-acrylic ester-acrylamide O copolymer are used. Various types of O such as emulsions using polymers such as
Things can be used. It is also possible to use negative silver halide photographic emulsions or, if desired, direct positive silver halide photographic emulsions. Furthermore, it is a must! Depending on the situation, it may be used either as a surface SISNM silver halide photographic emulsion in which the image is formed mainly on the surface of the silver halide grains, or as an internal aSS halide steel photographic emulsion.

Furthermore, it is possible to use emulsions in which silver halide photographic emulsions have been produced, dispersed, and first ripened under various methods and conditions. @), *Full-open 4 @-777!
Conversion silver halide method, ammonia method, acidic or neutral method) alkaline method, O iodized steel core described in No. 4111-1979-@59z s, etc. Emulsions simulated by various methods and conditions can be used, including methods and combinations thereof. Further, it is particularly advantageous to use emulsions containing various types of at agents during the production and dispersion of these silver oxide photographic emulsions, during or after the a' first ripening. For example, water-soluble rhodium compounds such as rhodium trichloride and hexahalogenorhodate; hexahalogenoiridium complex salts such as hexahalogenoiridium ([V)]; and iridium chloride (■X iridium bromide). ff
*Soluble iridium compounds such as lλ, gold halides,
Water-soluble gold compounds such as total acid salts, halogenated hydroacids, and hydrogenated gold salts, water-soluble platinum compounds such as tetrachloroplatinates, JP-A No. 11sd-14r9ts, 4$1
Mercapto-complex concentrated compounds described or exemplified in No. 1 Sho 5l-1071ffi 1, etc., 4HIi@54-103
The diazaindolizine compound described in No. 018,
Emulsions containing water-soluble salts, inorganic and organic metal salts such as lithium and nickel, and appropriate combinations thereof are useful. After these ill-ripened silver halide emulsions are precipitated and dehydrated, the desired electrical conductivity is achieved.
It is preferable to wash with water until the chain ion concentration is reached, but a non-washable method is also used. Things slow down.

These silver halide 1 true emulsions are usually used after being subjected to various chemical sensitizations. These chemically sensitized emulsions include, for example, sensitized layer gelatin containing an active sulfur compound;
Emulsions sensitized with sulfur sensitization using thiosulfates and active sulfur compounds, emulsions sensitized with seleno compounds such as N,N-dimethylselenourea, iridium, gold,
Emulsions sensitized with noble metals using water-soluble noble metal compounds such as platinum, and emulsions 1i11 sensitized with polyethylene oxide conductors are useful.

Spectral sensitization and supersensitization can be combined with chemical sensitization by using polymethine sensitizing dyes II such as polymethane, cyanine, merocyanine, and carbocyanine alone or in combination, or by using them together with styryl dye and Oa1 season. Emulsions which have been applied can be used advantageously.

Further, in the practice of the present invention, silver halide 2-photographic emulsions may also be used. That is, it reacts with the oxidation product of the am base agent to form a dye. The use of an emulsion containing a compound (coupler, -) results in slowness. For this purpose El! A representative example of Kab2- that can be used is Cbiparoylacetani9V11.
Examples include benzoylacetanilide mow chain ketomethylene couplers, pyrazolone magenta couplers, phenolic or narratol couplers, mixtures thereof, and black couplers.
In accordance with the structure of these couplers, the active sites of the development inhibitor release layer Kabutsu (DIR Kagutsu) and Kabu2- are respectively 10-allyl substituted, -0-acyl substituted, hydantoin compound substituted, and 2-sol substituted. Two-equivalent Kagufu, etc., which have been subjected to compound substitution, phosphoric acid ionic acid compound substitution, mono-oxinoindo compound substitution, pyridazone compound substitution, etc., can be prepared.

Various binders or protective colloids can be used as the binder or protective colloid in the first constituent layer used in the present invention @OSA Maro. Namely, lime-treated gelatin, acid-treated gelatin, gelatin derivatives, such as heptadated gelatin, acylated gelatin, etc., cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, and boripinyl alcohol. , Po9-N-ni'
Nylpyrrolidone, acrylic acid-acrylic ester copolymer 1 Synthetic layer aqueous binder such as acrylic acid-acrylamide copolymer, acrylic acid-acrylic ester-acrylamide copolymer, and as a thickening agent for gelatin and gelatin derivatives Natural or synthetic polymer substances having hydroxyl groups such as cellulose, dext2), dext, phosphorus, alginic acid, starch, polyvinyl alcohol, preferably polysaccharide III sulfate ester compounds, styrene-maleic acid copolymers , poly! such as alkyl vinyl ether-maleic acid co-X combination! - AA 11K
Or use them in combination.Ik◆.

It is advantageous to contain various O capri Rm agents or cane stabilizers in the four true constituent layers used in the practice of the present invention, particularly in the saponified IIm'4 true emulsion layer. 0
G4, for example, U.S. ate license No. 1'fl (No. 082, same No. L9)
44104) etc. & and droxy-azaine 1'9 dine compound, 1lillllas-
1021621, Oka 11sx-107129, etc.) 7 heteroconcentrated compounds, 2-thione heterocyclic compounds, benzimidazole, benzotriazole, l-phenyl-tetrazole, benzoxitnol, guanazolized gold 411F & any mercapto It is advantageous to contain groups such as complex compounds and combinations thereof.

In addition, various additives can be contained in the photographic constituent layer used in the present invention. For example, as a hardening agent, 1 lumaline, formaldehyde, and reaction products such as melamine, halogen carboxylic acid, vinyl sulfone compounds, aziridine compounds, epoxy compounds, active halogen compounds, acrylic compounds, Organic a film agents such as isocyanate compounds, inorganic hardeners such as chromium alum and zirconyl carbonate, and surfactants such as anionic interfaces such as alkylbenzene, K k 7 , f phosphates, and sul 7 ocuccinate salts. Active agents, naponin, nonionic surfactants such as alkylene salt compounds, amino acids, aminosulfonic acids,
Aminosulfonic acids, esters of aminoarsul 1
Hydroxy-dialkyl-phenyl Mttt41tK-4 as a UV absorber such as WQ surfactant
As a fluorescent whitening agent, such as a 1-sulfur benzotriazole compound, 41kai1@415-! No. 4/68, Kaisho 14-1
No. 141111, etc., and exemplified Compound 1, food red No. 2, 4IM@47-1 as a sharpness improving dye.
Acidic dyes such as those exemplified in No. 47!1, sequestering agents such as ethylenediaminetetra-acid, mordants such as N-guanyl hydrazone compounds, quaternary onium salt compounds, antistatic agents, cellulose dyes, etc. Antistatic agents, alkali salts of polystyrene sulfonic acid, alkali salts of acrylic acids and acrylic acid copolymers to be polymerized, matting agents such as polymethyl methacrylate, polystyrene, methacrylic acid-methacrylate copolymers, A latex made of a copolymer of acrylic stirrup ester, methacrylate, A-acid ester, etc. and another monomer having an ethylene group can be contained as a film property improving agent such as colloidal silicon oxide. Furthermore, the image-receiving layer for the diffusion transfer method according to #4 can contain fAII nuclei for a silver complex suitable for promoting the formation of a chain-containing diffusion transfer image. Examples of these development nuclei include chains, metal sulfides such as gold, platinum, and palladium, heavy metal sulfides such as bismuth, cobal F1, nickel, and zinc, and capped silver halides. Colloidal noble metal sulfides are preferred. Furthermore, the electrically bonded positive silver halide emulsion layer according to the present invention can contain additives for positive true emulsions such as capacitance agents and intensifying dyes for direct positive photographic emulsions.

To improve the photographic material o&ti, i.e., the support that does not have a photographic constituent layer, often a silver halide photographic constituent layer, a back coat is used to prevent curling, prevent charging, prevent adhesion, and prevent slipping. It is possible to install m fabric layers leading from an aqueous cokioid layer, referred to as a layer. Paraparakko according to the present invention. In this specification 2.! Pages to S: Binders or protective colloids, curing agents, antistatic agents, surfactants, matting agents, as described on pages
This is slowed down by the inclusion of latex, etc. Further, it is desirable that the pH of the back coat layer be 9 or less, preferably 7.0 or less.

For coating a photographic constituent layer on a support, there are generally four methods used to coat a photographic constituent layer on a support: the dilag CDip) method, the meniscus (M axis 1 mm') method, and the air knife (Air knife) method.
&st*) method, slide hollover (goatH@yν
tr ) method or extrusion version ('lx
'trm@l@m bar) method, curtain 70-(
It is advantageous to apply the coating by a method such as ``Certain fl/W'' or a combination thereof, and then dry it.

′ ゛From the book I! Silver halide photographic materials at jlK are divided into ``Photographic Light-sensitive Materials and Electrical Methods'' depending on the type, use, purpose, etc.
OJ and sanding such as exposure, development, stopping, fixing, bleaching, and stabilization are performed as described in (Kyoritsu Publishing, Gobe Miyamoto, Photographic Technology 2).

For example, a general-purpose Hakushima silver halide zero-value material typically has less than V silver halide after exposure! It is developed by processing with St which combines crude drug and burqa suer, but in some cases, an alkaline active solution containing all (or substantially no) silver halotanide aS main matrix is used. 3J images are fixed and stabilized with an acidic solution containing a small amount of a fixing agent such as sodium thional 7ate or sodium thiocyanate. Photographic material for diffusion transfer method OiA image @ The typical 46ml used in 3! consists of at least a silver halide complexing agent such as thiosulfate, an alkaline agent, a preservative such as sulfite, and a silver halide sII main chestnut. Lord 1
An active solution containing no or substantially no [[] may also be used. In addition, halogenated-force 2-photographic materials are
The exposure is usually carried out in an alkaline active bath containing or substantially free of a color developing agent to develop the color, and the metal salt of the smoked aminopolycarboxylic acid (e.g., ethylvindiaminetetraacetic acid, II&F in a one-bath bleach-fix solution containing at least a fixing agent such as a thiosulfate and a fixing agent such as a thiosulfate. The one-bath bleach-fix solution may contain additives such as a desilvering accelerator and a fluorescent brightener. ``Next, in order to explain the present invention in more detail, the actual details will be omitted.

(!I!III) Canadian Standard 7 Leeness S 101ml 1g KIQ is mixed with MUJI Bleach Shoes 7 TOPARG SO weight part and HISHI SHOHASHI FIL 7 ITOPALG SO weight iI, and the following composition is 150f/ Paper d was made.

(The numerical weight expansion part in the blend is shown.) Pulp 1.0 cationization #I
I2 Anionic polyacrylamide oil 4Ls Sodium stearate α2 Sulfur 7”! Dry on a hot plate.

This paper was soaked with an impregnating solution of the following formulation for 2017d, and 1
It was dried in a constant hot air dryer at 10°C.

(Numbers in islands indicate parts by weight.) Gelatin 1 Diaminostilbendisulfoic acid fluorescent brightener aOS Blue dye α002 Citric acid
0.10 ngaritsu
Add varying amounts of water Zo
.

After the impregnated and dried substrate was subjected to supercalender treatment at a linear pressure of IJO4/cm, both sides of the substrate were subjected to corona discharge treatment. Next, on the other side, there is a high school student! degree polyethylene (density 0
．． A 1:1 mixture of 9@f/cd1 (melt index S) and low density polyethylene (density O, S f/j, melt index S) was melt-extruded to a thickness of 207 m at a resin temperature of 330°C using a melt extrusion coating machine. I coated it. Next, low-density polyethylene containing anata-vIl titanium oxide 12X on the surface (pigment-added polyethylene has a density of 1111!o, 112f/j, and a melt index of S).
was coated to a thickness of 208 mm at a resin temperature of 330°C.

Next, polyethylene o'ara containing titanium oxide was subjected to a corona discharge treatment, and then the following emulsion was coated and dried.

Hequinachlororhodium(III)il potassium 6×1o
19.2F with nitric acid chains in gelatin 144F in the presence of
Mufar produced by producing and dispersing silver halide grains of
/AfC4! Average particle with helogne composition of 45/55 @ & I Substantial K sulfur sensitized to true optimum sensitivity
An acidic silver halide emulsion consisting of (1,0,0) kabura was added and dissolved in 420f of an aqueous solution of 8 to 17 cutin,
Sensitizing dye represented by the following formula [TI] ・Shim 1-phenyl-b-kabutorchi) 2 sol 1x Plasma 1111 Drop-111 citrate methanol 1iii exposure 4I@ is added, and then 1Ox dodecylbecycore sulfonic acid No seeoo
Add an aqueous solution of 12 N formalin 111118- to the substituted cyanostilbendisulpta-onate brightener Ql, and add methylhydroquinone But as a silver chloride II* agent to Improvil. Dissolve in alcohol Kame 4@ and add. Further, an emulsion to which no silver halide developer is added is also prepared separately.

Then adjust the emulsion OPH to Table 6 & 1Ill using a PH adjuster.
L,, -Adjust the total amount by adding water to *001. These O emulsions were coated at a rate of 75 f/s/(@min) on the polyethylene-coated paper described below together with a protective layer of the O emulsion layer.
Fabricate 11 layers using combinations of IK and O.

10JI after 4199nBO1t water SOO@K11jl
7-on iron saw/4L#f, 12 on F deklebenzens
N*lew 9 N water IFm! 1 sactmt, and the entire volume is diluted with 4 ootKIIl of water. The ζ0 wave is applied as a protective layer on the emulsion layer at a coating weight of 401/dCII.

The coated and dried sample was kept at room temperature for 2 days and 2 days.
c. After storage for 4 days with sow, D-7zllillez
After O'CK and i+n for se seconds, it was stopped, fixed, washed with water, dried, and the whiteness of the front and back sides of the printing paper was examined using a color difference meter. Also,
The stored samples were exposed to 1-second exposure for cytometry and then subjected to IA imaging to measure their photographic durability and to test their storage stability.

The obtained results are shown in IIIK.

Fix table (Note 1) J I8 Z8? :10 C) Color 1Ell
Expression method K [h, 6 lines ILX a, bo Expressed as three numbers. L represents f14 degrees, and a large value 'I#i@t' indicates a high degree.

Hatake represents redness, and the larger the number, the stronger the redness, negative numbers represent stronger greenness, b represents yellowness, and the larger the value, the stronger the yellowness. A negative number indicates a strong blue tint.

Book@Detailed Book Nori, *, b value is Nippon Electric and industrial worker ND-
101DC! Based on measurements with a single color difference meter. ΔL
is according to the formula below.

AL-L (SO'C3GX4a)-L (Touon Tonada 2 days)
(Nouri Abmb (5OCR084th)-1 (Toontono 2
(Note 3) F (gamma) is a well-known index in the Todoroki industry that represents the hardness of a photosensitive material, and is given by the formula Δr.

Δr-rtsocsoxa days)-1 (temperature 12 days) (
Note 4) Turnip 9F is undew t, #I is D-7! ill statue moat 1
Fi! O reflex when diluted with lA for 3 minutes at SO℃
1lI station, and ΔP#i is based on the following formula.

at-F(secs@*4a)-FClllltllna
) 11KF (當當當112113alIifJ&':)
Ta.

As can be seen from the IEI table, if #C Longadat is added in the layer, yellowing and fading is significant compared to %/% IDK, and the present invention is IIIA.
When exposed to heat, the yellowing and discoloration are destroyed by the virtually harmless AM exposure, and the RtioL value decreases.

Zero-shot 80911m has no negative impact on photos.

[Tsubagi Tsuba 2] In Example I, methylhydroquinone λ2t and 1-722-3-pyrazolidone a, oat
om hardware, hydroquinone 12t% λ5-G tar
The procedure was carried out in the same manner as in 111 except that t-phthylhydroxyphenol 2t14-benzoyloxyphenol λ2t was used, and the same results as in the case of using methyl hydride non-alcoholic acid were obtained.

Claims (1)

[Scope of Claims] l At least % of the photographic constituent layers provided on the support contain at least one type of halogenated chain *tis*o;
A photographic material characterized in that the support is coated with a film-like resin using a substrate layered with at least one hydroxymethanesulfinic acid or a salt thereof. Photographic constituent layers t))lk A photographic material described in Section 111 of the Patent Claim, in which at least one layer is a silver halide photographic emulsion layer. afy
The range of tatami claims that is a chain photographic emulsion layer
Photographic material 1). 4 Photographic material in which the layer of the film is polyolein. S The backing material according to Patent Claim O@Kuniyoshi Item 4, wherein the boda olefin resin Il is polyethylene.