JPS62235940A - Photosensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material capable of controlling generation of fog by incorporating a hydrolysate compd. of a quaternary chalcogen azolium salt contg. a specific quaternary group to the photographic material. CONSTITUTION:The photographic material contains the hydrolysate of the quaternary chalcogen azolium salt (A) having a quaternary group shown by formula I. In the formula, L is a bivalent binding group, T is -CO- or -SO2-, V and W are each an electron attractive group. A preferable salt A comprises the compd. shown by formula II wherein R<1> is H or 1-8C an alkyl group, etc., R<2> and R<3> are each H, halogen atom, etc., Q is an quaternary group shown by formula I, X is a middle chalcogen such as S or Se, etc., Y<1> is a pair ion, (n) is 0 or 1. Salt A shown by formula II is a compd. shown by formula III capable of ring-opening by hydrolysis. The titled material having a less tendency for generating fog during storage is obtd. Y<2> in formula III, is a pair ion, another groups are the same to those shown by formula II.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic light-sensitive material, and particularly to a silver halide photographic light-sensitive material in which fogging is prevented during storage of the light-sensitive material over time. It's about materials.

[Prior Art] Silver halide photographic materials tend to produce fog due to the presence of nuclei that can be developed even without exposure, and especially during storage over time, the occurrence of fog may result in a decrease in sensitivity or It is extremely common for problems such as deterioration of gradation to occur.

Since it is desirable to minimize such undesirable phenomena, it has been known to add antifoggants, stabilizers, etc. to silver halide emulsions. For example, U.S. Patent No. 2,403.927;
1-phenyl-5-mercaptotetrazoles, 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene, etc. described in Japanese Patent Publication No. 804,633, Japanese Patent Publication No. 39-2825, etc. are used as fog suppressants. has been used.

However, these compounds do not necessarily have a sufficient fog-inhibiting effect during storage over time, and have drawbacks such as a decrease in sensitivity and softening of gradation, so that they have not yet reached a level of satisfaction.

In addition, in the case of color photosensitive materials, an antifoggant that not only has good storage stability over time but also does not delay the bleaching time is required. When the conventionally known 1-phenyl-5-mercaptotetrazole was used as an antifoggant in a silver halide emulsion, it tended to deteriorate the desilvering and bleaching properties.

Therefore, there is a desire for a fog suppressant that does not deteriorate the desilvering bleaching properties and does not cause the aforementioned deterioration of photographic performance during storage over time.

[Object of the Invention] Therefore, the present invention has been made in view of the above-mentioned circumstances, and its first object is to prevent deterioration of photographic performance during storage of silver halide photographic sensitizers over time. In particular, it is an object of the present invention to provide a silver halide photographic material in which the occurrence of fog is suppressed.

be.

A second object of the present invention is to provide a silver halide photographic material containing a fog inhibitor that is less likely to cause a decrease in sensitivity or softening of gradation due to development inhibition.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material stabilized by a fog inhibitor that less inhibits desilvering and bleaching properties during color development.

We have found that the above objects can be achieved using a photographic material having the following structure.

A photographic material comprising a photosensitive silver halide emulsion layer and a hydrolyzed compound of a quaternary chalcogen azolium salt containing a middle chalcogen atom as a ring-constituting atom and having a quaternizing group of the following formula.

■ -L -T -N H-CI-1 = divalent bonding group T-Go- or -S○2- V, W: electron-withdrawing group, respectively Among the above quaternary chalcogen azolium salts, preferred are It is expressed by the following formula.

R+, hydrogen, alkyl group having 1 to 8 carbon atoms, 6 carbon atoms
~10 aryl groups R2, R3: hydrogen, halogen, aliphatic or aromatic hydrocarbon group bonded to the above ring directly or via -〇- or -S-, -CN, amino group, amide group, sulfone Amide group, sulfamoyl group, ureido group, thioureido group, -OH, -COM.

-8O2M (M is an atom or group that forms an aldehyde, ketone, acid, ester, thioester, amide or salt with -Co- or GL-8O2-), or a ring in which R2 and R3 are jointly fused to the above ring may be formed.

Q: Quaternized group represented by the above formula X: middle chalcogen Yl: counter ion n: O or 1 The above formula will be explained in detail.

The king is preferably a carbonyl group.

L is preferably an alkylene group having 1 to 8 carbon atoms (ie, an alkanediyl group). Particularly preferred in the present invention is methylene group (-CH2-) or ethylene i (
-CH20H2-).

Examples of electron-withdrawing groups represented by v and W include sulfonyl groups (methanesulfonyl, p-toluenesulfonyl, benzenesulfonyl, trifluoromethanesulfonyl, etc.), sulfamoyl groups (sulfamoyl, N, N-
dimethylaminosulfonyl, N-phenylaminosulfonyl, N-amylaminosulfonyl, etc.), carbonyl group (acetyl, propionyl, benzoyl, p-methylbenzoyl, etc.), carbamoyl group (carbamoyl, N,N-diethylamino carbonyl, N-methylaminocarbonyl, N-hexylaminocarbonyl, etc.), alkoxysulfonyl groups (methoxysulfonyl, butoxysulfonyl, etc.), aryloxysulfonyl groups (tolyloxysulfonyl, phenyloxysulfonyl, etc.) group), alkoxycarbonyl group (ethoxycarbonyl, methoxycarbonyl, n-butoxysulfonyl, etc.), aryloxycarbonyl group (p-
tolyloxycarbonyl, phenoxycarbonyl, etc.), nitro group, cyano group, truxy group (e.g. methyl,
(propyl) or alkoxy (for example methoxy, ethoxy, butroxy).

As R1, hydrogen, a methyl group, and an ethyl group are preferable, and hydrogen and a methyl group are particularly preferable.

The middle chalcogen represented by X refers to each atom of sulfur, selenium, or tellurium.

The aliphatic hydrocarbon group represented by R2 and R3 (including those bonded directly to the ring and those bonded via -〇-1-S-) is preferably an alkyl group, and the alkyl also includes aralkyl. do.

The aromatic hydrocarbon groups represented by R2 and R3 also include alkaryl.

The alkyl group and the alkyl moiety of aralkyl or alkaryl are preferably those having 1 to 8 carbon atoms (for example, methyl, ethyl, propyl, butyl, amyl, hexyl, octyl), and particularly preferably those having 1 to 4 carbon atoms. . These alkyls include those having 8 substituents such as halogen, cyano, aryl, carboxy, alkylcarbonyl, arylcarbonyl, and aminocarbonyl.

Further, the aryl group and the aryl moiety of aralkyl or alkaryl preferably have 6 to 10 carbon atoms (eg, phenyl, naphthyl), and include those having substituents.

Examples of the substituent include halogen, cyan, alkyl, carboxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, and aminocarbonyl.

The amino groups represented by R2 and R3 include primary to tertiary amines, the amide groups include acetamide and butyramide, and the sulfonamide groups include alkylsulfonamide,
Arylsulfonamide is the sulfamoyl group, alkylsulfayl, arylsulfamoyl,
As the ureido group, 1-ureido, 3-phenyl-1-
Examples of the thioureido group include ureido and 3-methyl-1-ureido, and examples of the thioureido group include 1-thioureido, 3-phenyl-1-thioureido, and 3-methyl-1-thioureido.

Examples of the ring formed jointly by R2 and R3 include aromatic hydrocarbon rings such as benzene and naphthalene. These rings may have substituents. Examples include those shown above as examples of R2 and R3 when X is sulfur or selenium, and when X is tellurium, substitution is made directly or via -〇-1-8-. Aliphatic or aromatic group, amino group, amide group, sulfonamide group, sulfamoyl group, ureido group, thioureido group, OH.

C0M1802 M (M represents an atom or group necessary to form an acid, ester, thioester or salt.

).

Particularly preferable substituents for the ring formed by R2 and R3 are alkyl groups, alkoxy groups, alkylthio groups, and OH. Those with numbers 1 to 8 are preferred, and those with numbers 1 to 4 are particularly preferred.

Yl is a counter ion to make the quaternary chalcogen azolium salt electrically neutral, and Yl is a counter ion for making the quaternary chalcogen azolium salt electrically neutral, and
! Examples include anions such as 04e or p-toluenesulfonate.

When the quaternary chalcogen azolium salt is of the betaine type, n is O.

The chalcogen azolium salt described above is ring-opened in advance or by hydrolysis in a light-sensitive material to form a compound of the following formula, which produces the effects of the present invention.

Here, R'%R2, R3, Q, X and nLtM are as described above. Y2 is a counterion.

Y2 is a counter ion for making the hydrolyzed compound electrically neutral, and includes cations such as alkali, alkaline earth, ammonium, and cations generated due to the base used for hydrolysis. When the hydrolyzed compound is of the betaine type, n is 0.

The compound according to the present invention can be prepared by combining a chalcogenide azole compound represented by the general formula [A] and a quaternizing reagent represented by the general formula [G] without a solvent or in an appropriate solvent (e.g. phenol, m- It can be obtained by heating in a high boiling point solvent such as cresol.

In addition, the quaternizing reagent represented by the general formula [G] is generally prepared by combining an acid chloride [D] having an alkylation reaction deffi group at the terminal with a corresponding amine compound [E] in an aprotic solvent. [D] [E] [G] Obtained by reaction.

Next, specific synthesis examples will be shown, but other compounds according to the present invention can also be synthesized according to the following methods.

Reference synthesis example-1 N-(3-bromopropionyl)aminomalonic acid dimethyl ester malonic acid dimethyl ester 40o vinegar fa 60 *Q
While keeping the solution at 15-20°C, 75 g of an aqueous solution of 51 g of sodium nitrite is added dropwise while stirring. After the addition was completed, stirring was continued for 4 hours, and the mixture was further left overnight at temperature V.

The reaction solution is extracted using ether, and the extracted solution is water,
Wash with dilute alkaline aqueous solution and then with water.

After drying using anhydrous sodium sulfate, the solvent was distilled off to obtain isonitrosomalonic acid dimethyl ester 309.

30 g of isonitroso is dissolved in 90v12 dry methanol, 3 g of 20% palladium-carbon catalyst are added and hydrogenated in an autoclave. The catalyst is filtered off and the filtrate is distilled off under reduced pressure while keeping the temperature low. Methanol is replaced with dry ether and hydrochloric acid gas is blown in to precipitate the hydrochloride.

It was collected by filtration and washed with dry ether to obtain 26 (J) of aminomalonic acid dimethyl ester hydrochloride.

17 g of 3-bromopropionic acid chloride is dissolved in dry ether 701Q and stirred while cooling with ice.

While keeping the reaction temperature below 15°C, 701 g of a dry ether solution of 1.05 equim of aminomalonic acid dimethyl ester was added.
dropwise reaction. Subsequently, 100 g of an aqueous solution of 10,70 g of sodium carbonate was gradually added dropwise to neutralize the mixture, and the reaction product was collected by filtration. The filtered material is purified by dispersion washing using a dilute alkaline aqueous solution and water. After drying, 1'l of the desired product was obtained as a colorless powder.

Reference synthesis example-2 N-bis(N'-methylcarbamoyl)methyl-3-
Iodopropio, acid amide N, N'-dimethylmalonic acid amide 48.6 g vinegar F
While keeping the i701Q solution at 15-20°C, an aqueous solution 801Q containing 51% of sodium nitrite is added dropwise. After the dropwise addition was completed, stirring was continued for an additional 4 hours to complete the reaction. - After standing overnight at room temperature, extract with ether and wash the extract with water. Further, it is washed with a dilute aqueous alkaline solution, washed with water, and dried with anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain 349 isonitrosomalonic acid amide. Isonitroso body 34
Dissolve g in 1201Q dry methanol, add 3 g of 20% palladium-carbon catalyst, and reduce by hydrogenation. Methanol is removed under reduced pressure, diluted with ether, and dried hydrochloric acid gas is blown in to form a salt. Filter the precipitate and wash thoroughly with ether.

Amino-N,N-dimethylmalonic acid amide hydrochloride at 28
! Ill? Ta.

3-iodo-propionic acid chloride 21.8! 70 minutes into the ether solution of II while keeping the reaction temperature below 15°C.1.
05 equivalents of amino-N,N-dimethylmalonic acid amide in ether solution 1001 (2) are added dropwise to react.

After neutralizing the reaction solution, the ether is volatilized and stirred, and the precipitate is collected by filtration. The filtered material is washed by dispersion in dilute alkaline water and water, purified, and dried.

Target object i9. I got sg.

Synthesis Example 1 (Exemplary Compound No. 5) 1.5 g of 2-methylbenzothiazole and N-(3-bromopropionyl)aminomalonic acid dimethyl ester 17
(Mix +, add 30d of ■-cresol and
Heat and stir at 0°C for 4 hours. After cooling to 80° C., 200 ij2 of acetone was added to stir and crystallize.

The crude crystals were purified by recrystallization from methanol to obtain 8 g.

Synthesis Example 2 (Exemplary Compound 12) 5-methoxy-2-methylbenzothiazole 9) and 3-
16.3 g of iodo-N-bis(N'-methylcarbamoyl)methylpropionic acid amide was mixed, 301 g of m-cresol was added, and the mixture was heated and stirred in an oil bath at 140° C. for 4 hours.

Lower the temperature to 80°C and add ethanol-acetone (1:2).
> Add mixed solution 12011Q and perform heating rapid flow crystallization.

After cooling sufficiently, the crystals were collected by filtration and recrystallized from a mixed solvent of ethanol and water to obtain 9.2 g.

The hydrolyzed compound of the present invention is preferably added to a photosensitive silver halide emulsion layer, and the addition port thereof is preferably 0.01 to 10 mmol, particularly 0.01 to 10 mmol per mol of silver halide in the emulsion layer. 0.015 to 2 mmol is preferred.

The silver halide emulsions used in the photographic elements of this invention include:
Any silver halide used in conventional silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, can be used as the silver halide.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Further, while taking into consideration the critical growth rate of silver halide crystals, halide ions and limiting ions may be generated by sequentially and simultaneously adding the halide ions and limiting ions while controlling the pH 10AQ in the mixing pot. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained.

Silver halide emulsions are manufactured by adjusting the grain size of silver halide grains using a silver halide solvent as necessary.
Particle shape, particle size distribution and particle growth rate can be controlled.

In the process of forming and/or growing the grains, silver halide grains are produced using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (complex salts containing), rhodium salts (complex salts containing), and iron salts (complex salts containing). A metal ion is added using at least one selected from complex salts containing
Alternatively, these gold layer elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained. When removing the salts, Research Disc
Losure) No. 17643.

The silver halide grains used in silver halide emulsions may have a uniform silver halide composition distribution within the grain, or they may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain. good.

The silver halide grains used in the silver halide emulsion may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grains.

Silver halide grains used in silver halide emulsions may have regular crystal shapes such as cubes, octahedrons, and dodecahedrons, or irregular crystal shapes such as spherical or plate shapes. It can be something you have. In these particles, (100)
Any ratio between the plane and the (111) plane can be used. Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 5 μm or less, and particularly preferably 3 μl or less.

The silver halide emulsion of the present invention may have any grain size distribution. Emulsions with a wide grain size distribution may be used, or emulsions with a narrow grain size distribution may be used alone or in combination.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, a sulfur sensitization method, a selenium sensitization method, a metal bottom sensitization method using gold or other noble metal compounds, etc. can be used alone or in combination.

The silver halide emulsion of the present invention can be optically sensitized to a desired wavelength range using dyes known as sensitizing dyes in the photographic industry. Sensitizing dyes may be used alone, but
You may use two or more types in combination. Along with the sensitizing dye, the emulsion contains a dye that itself does not have a spectral sensitizing effect, or a supersensitizer, which is a compound that does not substantially absorb visible light and enhances the sensitizing effect of the sensitizing dye. Good too.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, at the end of chemical ripening, and/or after the end of chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to keep photographic performance stable. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
Although it is advantageous to use gelatin, gelatin derivatives, graft polymers of gelatin and other polymers,
Hydrophilic colloids such as other proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can also be used.

When gelatin is used as a binder for a silver halide emulsion, the jelly strength of the gelatin is not limited, but it is preferably a jelly strength of 2509 or more (value measured by the baggy method).

The photographic emulsion layer and other hydrophilic colloid layers of photographic elements using the silver halide emulsion of the present invention contain one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution.
It is also possible to add a hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a photographic element using the silver halide emulsion of the present invention for the purpose of increasing flexibility.

The photographic emulsion layer and other hydrophilic colloid layers of the photographic element using the silver halide emulsion of the present invention contain a dispersion (latex) of a water-insoluble or M-soluble synthetic polymer for the purpose of improving dimensional stability. can be done.

The emulsion layer of the photographic element of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-phenylenediamine derivative, aminophenol derivative, etc.) during color development to form a dye. A dye-forming coupler is used.

The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, these dye-forming couplers require only two silver ions to be reduced, even though four silver ions need to be reduced in order to form one molecule of dye. Either equivalence is acceptable. Dye-forming couplers can be used as development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, capri agents, antifoggants, and chemical sensitizers by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments can be included, such as spectral sensitizers, spectral sensitizers, and desensitizers. Colored couplers that have a color correction effect on these dye-forming couplers, or DIR that releases a development inhibitor during development and improves image sharpness and image graininess.
A coupler may also be used in combination. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor.

A colorless coupler that undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied, and the boiling point is usually about 150°C.
Dissolve the above-mentioned high-boiling point organic solvent in combination with a low-boiling point and/or water-soluble organic solvent as necessary, add a surfactant to a hydrophilic binder such as an aqueous gelatin solution, and stir with a stirrer.
After emulsifying and dispersing it using a dispersing means such as a homogenizer, colloid mill, 70-jit mixer, or ultrasonic device, it may be added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid and sulfonic acid, they can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent migrates between the emulsion layers (same-color-sensitive layers and/or between different color-sensitive layers) of the photographic element of the present invention, causing haze or deterioration of sharpness. A color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

Image stabilizers can be used in the silver halide photographic elements of this invention to prevent degradation of the dye image.

The hydrophilic colloid layers such as the protective layer and intermediate layer of the photographic element of the present invention are made of photosensitive material FJ! It may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging with 5ij, etc., and to prevent deterioration of the image due to U2 light.

Formalin scavengers can be used to prevent degradation of magenta dye-forming couplers and the like by formalin during storage of the photographic element.

In the photographic elements of this invention, when the hydrophilic colloid layer contains dyes, ultraviolet absorbers, etc., they may be mordanted with a mordant such as a cationic polymer.

Compounds that alter developability, such as development accelerators and retarders, and bleach accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the photographic elements of this invention. Compounds that can be preferably used as development accelerators include:
Research Disclosure - (Research
Disclosure) A compound described in Section XXI B-0 of No. 17643, and the development retardant is
This is a compound described in Section XXI, Section E of No. 3. A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The photographic emulsion layer of the photographic element of the present invention may contain polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urethane derivatives, urea derivatives, imidazole derivatives, and the like.

In the photographic element of the present invention, an optical brightener can be used for the purpose of emphasizing the whiteness of the white background and making the coloration of the white background less noticeable.

Photographic elements of the present invention can be provided with auxiliary layers such as filter layers, antihalation layers, and/or antiirradiation layers. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the photographic element of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from scratching each other.

Slip of photosensitive materials +! A lubricant can be added to reduce J-rubbing.

Antistatic agents can be added to the photographic elements of this invention for antistatic purposes. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and the protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated with respect to the emulsion layer and/or the support. May be used for.

The photographic emulsion layer and/or other hydrophilic colloid layer of the photographic elements of this invention may include coatability-improving, antistatic, slippery-improving,
Various surfactants can be used for the purpose of emulsification dispersion, adhesion prevention, improvement of photographic properties (development acceleration, film hardening, sensitization, etc.).

You may be

Supports used in the photographic elements of this invention include cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride,
Films made of semi-synthetic or synthetic polymers such as polyethylene terephthalate, polycarbonate, polyamide,
These films include flexible supports provided with reflective layers, glass, metal, ceramics, and the like.

The photographic element of the present invention can be produced directly or after subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., as necessary, or to improve the adhesion, antistatic property, dimensional stability, abrasion resistance, etc. of the support surface. It may be applied through one or more subbing layers to improve hardness, antihalation, eta properties, and/or other properties.

Thickeners may be used in coating the photographic elements of this invention to improve coating properties. Also, for example, as a hardening agent,
For substances that have a fast reactivity and may cause gelation before coating if added to the coating solution in advance, it is preferable to mix them using a static mixer or the like immediately before coating.

In preparing the photographic elements of this invention, the silver halide emulsions and other protective colloid layers are disclosed in Research Disclosure.
It can be applied by the method described in Section A of Xv of No. 17463 and dried by the method described in Section B of the same.

The photographic elements of this invention can be exposed with electromagnetic radiation in the region of the spectrum to which the constituent emulsion layers are sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps,
Light emitted from phosphors excited by mercury lamps, xenon arc lamps 1, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, gamma rays, alpha rays, etc. Any known light source can be used.

The exposure time is not only the 1 millisecond to 1 second exposure time normally used in cameras, but also the exposure shorter than 1 microsecond, for example, 100 nanoseconds to 1 microsecond exposure using a cathode ray tube or xenon flash lamp. However, exposures longer than 1 second are also possible.

The exposure may be carried out continuously or intermittently, and any known method may be used for developing the photographic element of the present invention. This development process may be either a process for forming a silver image (black and white development process) or a process for forming a color image, depending on the purpose. If an image is to be produced by the reversal method, a black and white negative development process is first carried out, and then a color development process is carried out by applying a white exposure or processing with a bath containing a capri agent. Alternatively, silver dye bleaching may be used, in which a dye is contained in a photosensitive material, and after exposure, a black and white development process is performed to form a silver image, and this is used as a bleaching catalyst to bleach the dye.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but it can also be carried out using other methods, such as a spray method that supplies the processing solution in the form of a spray, or by bringing it into contact with a carrier impregnated with the processing solution. A web method, a method of viscous development processing, etc. may be used.

The black and white development process includes, for example, a development process, a fixing process, and a water washing process. Alternatively, a developing agent or its precursor may be incorporated into the sensitive material, and the developing process may be carried out using only an alkaline solution.

A development process using a lithium developer as a developer may be performed.

The color development process includes a color development process, a bleaching process, a fixing process, and if necessary, a water washing process, or a stabilization process accompanied by water washing. Instead of a liquid treatment process,
A bleach-fixing process can be carried out using a one-bath bleach-fix solution, or a monobath process can be carried out using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be carried out in one bath. You can also do that.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, an activator treatment step in which a color developing agent or its precursor is contained in the material and development is performed with an activator solution may be performed instead of the coloring ring/image processing step, or an activator treatment step may be performed in place of the monobath treatment. The activator treatment and the bleaching and fixing treatments may be performed simultaneously. Representative treatments among these treatments are shown below. (These treatments are carried out as a final step, for example, either a water washing process or a stabilization process accompanied by a water washing process.) Color development process - Bleaching process Constant fixation process Color development process - Bleach-fixing process/Pre-hardening process - Neutralizing process - Color development process - Stop-fixing process - Washing process - Bleaching process Constant coloring process - Washing process - Post-hardening process/Color development Development process - Water washing process - Supplementary coloring ring I & Processing process - Stop process - Bleach process Constant fixation process / Monobath process / Activator process - Bleach-fix process / Activator process - Bleaching process constant In addition to these treatments, there are methods in which the developed silver produced by color development is subjected to halogenation bleaching and then color development is performed again, and various intensification treatments (amplification treatments) described in JP-A-58-154839. ), etc. Example-1 High-sensitivity silver iodobromide emulsion for negatives (silver iodide 2 4-hydroxy-6=methyl-1,3,
1.0 g of 3a,7-chitrazainean was added per mole of silver halide.

A portion of this emulsion was used as a blank (comparison) sample, and the compounds according to the present invention and comparative compounds as shown in Table 1 below were added to the remaining emulsion and sufficiently adsorbed, and then saponin was added as a coating aid. An appropriate amount of formalin was added as a film agent to prepare an emulsion.

The obtained emulsion was uniformly coated onto a subbed polyester base so that the silver ratio was 30/12, and dried to obtain a sample according to the present invention.

The sample prepared in this way was left at room temperature for 3 days as a fresh sample, at a temperature of 50°C and a relative humidity of 80°C.
% for 3 days, temperature 55℃, relative humidity 7
% for 3 days to prepare samples with forced deterioration.

Next, exposure was performed using a conventional sensitometric wedge, and development was performed at 35° C. for 30 seconds using the following developer [A]. After fixing, the film was washed with water and dried, and the sensitivity was measured.

Developer [A] 1-phenyl-3-pyrazolidone 1.5 g Hydroquinone 30 (J5-nitroindazole 0.25 () Potassium bromide 5.0 g Anhydrous sodium sulfite 55 () Potassium hydroxide
300Ta acid
10 g glutaraldehyde (25%>
5 (Add water to bring the total volume to 1.

The results obtained are shown in Table 1 below.

However, the fog value is the value obtained by subtracting the base density, the sensitivity value is expressed as a relative sensitivity from the sensitivity at the fog value + 0.5 position, with the comparison sample set as 100, and gamma is the linear portion on the characteristic curve. It is shown by the slope of .

As is clear from Table 1 above, sample N according to the present invention
o, Nos. 2 to 9 have improved stability during film storage by suppressing fogging, decrease in sensitivity, and deterioration of gamma despite the harsh storage conditions compared to comparative samples. I understand.

Example 2 A silver iodobromide emulsion containing 7 mol % of silver iodide and having an average grain size of 1.2 μm was chemically ripened with gold and sulfur sensitizers to the highest sensitivity, and then a green-sensitive sensitizing dye of 5.5 μm was used as a green-sensitive sensitizing dye. '-diphenyl-9-
An appropriate amount of ethyl-3,3'-di-γ-sulfopropyloxacarbocyanine sodium salt was added to prepare a green-sensitive silver halide emulsion.

Then, per mole of silver halide, 1-(2,4,6-dolichlorophenyl)-
80 g of 3-[3-(2,4-di[-amylphenoxyacetamide)benzamide]-5-pyrazolone and 1-(2,4,6-
Dolichlorophenyl)-4-(1-naphthylazo)-3
Weigh out 2.5 g of -(2-chloroo-5-octadecenylsuccinimidoanilino)-5-pyrazolone, then 120 g of tricresyl phosphate and 2.5 g of ethyl acetate.
401j2 was mixed and dissolved by heating, and then a coupler solution emulsified and dispersed in a solution of 5 g of sodium triisopropylnaphthalene sulfonate and 550 iQ of a 7.5% aqueous gelatin solution was added to the above emulsion.

This emulsion was divided into 15 parts, the compound according to the present invention and the comparative compound were added thereto as shown in Table 2 below, and after sufficient adsorption, 2 parts were added as a gelatin hardener.
An appropriate amount of sodium -hydroxy-4,6-cyclotriazine was uniformly added to form a silver halide emulsion.

This emulsion was uniformly coated and dried on a subbed triacetate film so that the silver content was 3.0 g/m', and a sample was prepared.

The obtained film sample was subjected to the same forced deterioration test as in Example 1, then wedge exposed in the usual manner and color developed according to the following color processing steps.

The color sensitometry results obtained from the obtained pieces are shown in Table 2 below.

The fog in the table is the value after subtracting the base concentration, and the sensitivity is based on the blank sample left for 3 days (sample No. 1).
6) is expressed as 100. Also, gamma is expressed by the slope of the straight line.

Treatment process [Processing temperature 38℃] Processing time 8 for color development
Bleach for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stabilized for 3 minutes and 15 seconds
Drying for 1 minute and 30 seconds The composition of the treatment liquid used in each treatment step is as follows.

[Color developer] 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)-aniline sulfur'PIi salt 4.759
Anhydrous sodium sulfite 4.25 (1 hydroxylamine 1/2 sulfate 2. OQ anhydrous potassium carbonate 37.5 (J sodium bromide 1.3 g nitrilotriacetic acid
3 Sodium salt (1 water m) 2.5a Potassium hydroxide Add 1.0g water and 1
! shall be.

[Bleach solution] Ethylenediaminetetraacetic acid at ammonium salt 100.0 (]
Ethylenediaminetetraacetic acid 2 ammonium salt io, o g ammonium bromide 150.0! I + glacial acetic acid 10.0ml 12 Add water to make 11, and adjust to pH 6.0 using aqueous ammonia.

[Fixer] Ammonium thiosulfate 175.0 (1
Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make one volume, and adjust to I) 86.0 using acetic acid.

[Stabilizer] Formalin (37% aqueous solution) 1.5 year old Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.> 7.5.2
As is clear from Table 2, compared to the comparative samples, the samples according to the present invention suppress the occurrence of fog, decrease in sensitivity, and decrease in gamma under severe storage conditions, and have improved stability during storage. I understand that.

Example 3 A multilayer color photosensitive material sample (comparison) was prepared by sequentially providing each layer having the composition shown below on a cellulose triacetate film support.

1st layer: Antihalation layer Black gelatin layer containing colloidal silver 2nd layer: Intermediate gelatin layer 3rd layer: Red-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5 mol% Average grain size 0.5μ - Silver coating amount...1.79+If/t' sensitizing dye process...
...6X10-5 mole sensitizing dye per mole of silver■...3X10-5 per mole of silver
Molar coupler A: 0.06 mol per mol of silver. Coupler C: 0.003 mol per mol of silver. Coupler D: 0.06 mol per mol of silver. 003
Moltricresyl phosphate coating ffi 0.3mf
f1/v 4th layer: Red-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% Average grain size 0.1 μm Silver coating amount...1.4 g/f Sensitizing dye I... ...3 x 10 per mole of silver
-5 mole sensitizing dye■...1.2X 1 per mole of silver
0-5 mole coupler F...0.0125 per mole of silver
Molar coupler C...0.0016 per mole of silver
Moltricresyl phosphate application 0.2mN/12
5th layer: Intermediate layer Same as 2nd layer 6th layer: Green-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 4 mol% Average grain size 0.5 μm Silver coating amount...1-00/+2 Sensitizing dye ■・・・3X10-5 per mole of silver
Molar sensitizing dye ■・・・1X10-5 per mole of silver
Molar coupler B...0.08 mole per mole of silver Coupler M...0,008 per mole of Ki
Molar coupler D...0,0015 per mole of silver
Moltricresyl phosphate coating ω1.4vl/11' 7th layer: Green-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide: 5T nil% Average grain size 0.75 μm Silver coating amount...1. lp/u2 Sensitizing dye ■・・・2.5X l per mole of silver
'Q-5 mol sensitizing dye■...0.8X 1 per mol of silver
0-5 mole coupler 8...0.02 mole per mole of silver Coupler M...0.003 mole per mole of silver Tricresyl phosphate coating m O,8iN/
v' 8th layer: Yellow filter single layer gelatin layer containing yellow colloidal silver in an aqueous gelatin solution.

9th layer: Blue-sensitive low-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide 6 mol% Average grain size 0.70 μm Silver coating amount...0.5 g/m' Coupler Y...1 mol silver 0.125 molar tricresyl phosphate application a O, hQ/v'
10th layer: Blue-sensitive high-sensitivity emulsion layer Silver iodobromide emulsion Silver iodide 6 mol% Average grain size 0.8 μm Silver coating amount...0.60/i2 Coupler Y... 1 mol of silver 0.04 molar tricresyl phosphate application m 0.1 mN/x
'11th layer: Protective layer Apply a gelatin layer containing polymethyl methacrylate particles (1.5 μm in diameter).

The couplers in each layer are prepared by adding the couplers to a solution of tricresyl phosphate and ethyl acetate, adding sodium p-dodecylbenzenesulfonate as an emulsifier and dissolving them by heating.
The mixture was mixed with a heated 10% gelatin solution and emulsified using a colloid mill.

In addition to the above composition, a gelatin hardening agent and a surfactant were added to each layer.

Compound used to make the sample.

Sensitized image material: anhydro-5,5'-tsuk0ro 3.3
'-di(γ-sulfopropyl)-9-ethylruthylpocyanine hydroxide pyridium salt sensitizing dye ■: Anhydro-9-ethyl-3°3'-di(
γ-sulfopropyl)-4,5,4'.

5'-dibenzothiacarbocyanine hydroxide/triethylamine salt sensitizing dye ■: Anhydro-9-ethyl-5゜5'-dichloro-3,3'-di(γ-sulfopropyl)oxacarbocyanine hydroxide/sodium salt increase Sensitive dye ■: anhydro-5,6,5',6'-tetrachloro-1,1'-diethyl-3,3'-di(β-[
β-(γ-sulfoboxy)ethoxy]ethylimidazolupocyanine hydroxide coupler A coupler C CH.

The third and fourth red-sensitive layers and the sixth and seventh green-sensitive layers of the above-mentioned silver halide emulsion are prepared by adding a sensitizing dye and then adding a known stabilizer. as 4-hydroxy-6
-Methyl-1,3,38.

3 g of 7-chitrazaindene per mole of silver halide
and 10111 g of 1-phenyl-5-mercaptotetrazole per mole of silver halide were added for stabilization.

No. 9 Ji of the next blue-sensitive emulsion layer! In the 10th layer, before adding coupler Y, the comparative compound and the compound of the present invention were added as shown in Table 3 below, and the mixture was adjusted and coated in multiple layers.

The obtained multilayer color photosensitive material was subjected to high-temperature, high-humidity processing for the storage test in the same manner as in Example 1, and then subjected to normal wedge exposure, and then subjected to the same color processing as in Example 2. . Sensitometric results are shown in Table 3.

Table 3 above shows that the samples according to the present invention have excellent storage stability over time even in the case of photosensitive forest materials for multilayer coloring.

It is shown that.　　　　　　′□　　・□　.

In addition, regarding the desilvering bleaching performance when the bleaching fR interval was shortened, the samples of the present invention showed less deterioration than the comparative samples.

Example 4: A silver halide color photographic/photographic light-sensitive material of the present invention was prepared by coating the following layers on a paper bundle/body whose both sides were coated with polyethylene resin.

Layer 1: Blue-sensitive emulsion layer.

Silver chlorobromide emulsion containing 20 mol% silver chloride (0.28
Q, containing 1.2 g of gelatin) was sulfur sensitized and then blue sensitizing dye (BSD-1) was added to 5.5
One mole of silver genide was added to prepare a blue-sensitive silver genide emulsion. After this emulsion was dispersed, comparative compounds and compounds according to the invention were added as shown in Table 4 below. After sufficient adsorption, the following solution was added as a coupler solution.

Coupler solution / Amount per 1f Yellow coupler (Y-1> 0.751J
2.5-di-1 ritylhydroquinone 0.0150 dioctyl phthalate 0.4 g Next, the following layer 2 was coated as a protective layer on this emulsion layer to prepare a sample according to the present invention.

・ 11 12: 'gelatin protective layer 1f gelatin
1.4g hardener (bisvinylsulfonyl methyl ether) 0.1(1(
BSD-1) (Yellow coupler Y/1) The obtained color photosensitive material was subjected to a forced deterioration test in the same manner as in Example-1, and then wedge exposed in the usual manner, and color development was performed according to the following color processing steps. did.

The color sensitometry results obtained from the obtained samples are shown in Table 4 below.

The sensitivities in the table are relative sensitivities when the comparison sample (blank) of each layer left for 3 days is set as 100.

Processing process Temperature Time (1) Color development 33℃ 3 minutes 30 seconds (2) Bleach fixing 33℃ 1 minute 30 seconds (3) Washing with water
30-34℃ 3 minutes (4) Drying 60-9
0°C - The composition of the treatment liquid used in each step is as follows.

(Color developer) Pure water 800 vQ ethylene glycol 121Q benzyl alcohol 121Q anhydrous potassium carbonate 300 anhydrous potassium sulfite
2gN-ethyl-N-(β-methanesulfonamido)ethyl-3-methyl-4-amineaniline sulfur! I salt 4.5g Sodium chloride 1. Add O0 water and 1f
Set it to L.

pH=10 with 10% potassium hydroxide or 20% VAvi
．． Adjust to 2.

(Bleach-fix solution) Pure water 75 ha (2
Iron (1) ethylenediaminetetraacetate Sodium 501J Ammonium thiosulfate 85g Sodium bisulfite 100 Sodium metabisulfite 2g Ethylenediaminetetraacetate'fa disodium 20g Sodium bromide
Add 3.0 g of pure water to make 12, and adjust the pH to -7.0 with 20% ammonia water or 20% sulfuric acid.

The results in Table 4 also show that the compounds according to the present invention do not cause deterioration of photographic properties even in color light-sensitive materials and can provide a capri suppressing effect with less desensitization.

Patent applicant: Konishiroku Photo Industry Co., Ltd. Representative Patent Attorney Miyao Ichinose Procedure NeIll device (voluntary) June 13, 1986

Claims (1)

[Scope of Claims] A photosensitive silver halide emulsion layer and a hydrolyzed compound of a quaternary chalcogen azolium salt containing a middle chalcogen atom as a ring-constituting atom and having a quaternizing group of the following formula. photographic materials. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ L: Divalent bonding group T: -CO- or -SO_2- V, W: Each electron-withdrawing group