JPH01300245A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the initial sensitivity of the title material, and to lessen the sensitivity change of the material with lapse of time by incorporating a prescribed amount of the fine particle of a sulfur crystal in the silver halide emulsion layer contd. in the photosensitive material. CONSTITUTION:The photosensitive material comprises at least one layer of the silver halide emulsion layers, and the fine particle of the sulfur crystal is incorporated in the emulsion layer in an amount of 1X10<-5>-5X10<-3>g/AgNO3 mol. The period of adding the sulfur crystal to the emulsion layer is preferably the step of finishing an emulsion preparation keeping step with the period of adding various kinds of additive agents. The temp. of finishing the emulsion preparation at the time of adding the sulfur crystal to the emulsion is not specified, and preferably <=50 deg.C. Thus, the initial sensitivity of the photosensitive material immediately before applying the emulsion on the material is improved, and the sensitivity change of the material during preserving the material is reduced.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic material, and particularly to a silver halide photographic material having excellent stability over time.

(Prior Art) Conventional silver halide photographic light-sensitive materials contain various compounds for the purpose of preventing fog and sensitivity fluctuations during the manufacturing process, storage, or photographic processing of the light-sensitive materials. Ta.

That is, the compounds to be contained include, for example, azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles,
Mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazole R (especially l-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines ; mercaptotriazines; thioketo compounds such as, for example, oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy substituted (1,3,3a);

7) Tetrazaindenes), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
Antifoggants or stabilizers such as benzenesulfonic acid amides and the like are known.

(Problems to be Solved by the Invention) However, these conventional techniques are insufficiently effective in preventing sensitivity fluctuations of 1 degree during storage of silver halide photographic materials, and problems arise in use for each photographic material. It is used with an expiration date set within a range that does not include.

Furthermore, if an attempt is made to prevent fluctuations in sensitivity during storage by increasing the amount of a conventionally used stabilizer added, the sensitivity immediately after application decreases, resulting in a problem of low sensitivity stability.

An object of the present invention is to provide a silver halide photographic material that has high initial sensitivity immediately after coating, has small sensitivity fluctuations during storage, and can maintain its initial high sensitivity.

(Means for Solving the Problems) The above object of the present invention is to have at least one layer of a silver halide emulsion, and to have sulfur crystal fine particles in the emulsion layer.
This can be achieved by containing 5 Xl0-'g/3 mol of AgNO.

There is no particular restriction on the timing of adding sulfur crystal fine particles to the emulsion layer, but it is preferable to add them at the same time as various additive chemicals at the stage of preparing the complete milk. Furthermore, there is no particular restriction on the temperature of the complete milk at the time of addition, but it is preferably 50°C or lower.

Furthermore, when an emulsion that is not subjected to chemical ripening is used as the silver halide photographic light-sensitive material, it can be more significantly stabilized.

The meaning of ``no chemical ripening'' refers to the use of sulfur aggravating agents that react with silver salts to form silver sulfide, reduction aggravating agents such as stannous salts and amines, etc., for the purpose of conventional chemical aging. Adding agents, noble metal aggravating agents such as chloroauric acid and gold trichloride, or using activated gelatin containing sulfur-containing compounds, and at a predetermined temperature, p! (This means not performing a process that worsens the condition over time, and the degree of sensitization due to minute amounts of sensitizing substances contained in gelatin, which is usually referred to as inert gelatin, is ignored.)

The sulfur crystal particles to be added can be produced by oxidizing hydrogen sulfide or by decomposing an aqueous solution of sodium thiosulfate by oxidation. This may be finely pulverized in a mortar to make it into finer particles, or the finer particles may be dissolved in a potassium hydroxide solution and added to the emulsion to form microcrystals in the emulsion.

The size of the sulfur crystal fine particles is preferably 100 μm or less, more preferably 10 μm or less.

The silver halide of the silver halide photographic light-sensitive material used in the present invention is not particularly limited, but it is preferably silver bromide or silver iodobromide having an iodine content of 5 mo1% or less.

The average grain size of the silver halide is preferably 1n or less, particularly preferably 0.2 to 0.5-.

Average grain size is a term commonly used and easily understood by experts in the field of silver halide photographic science. means the particle diameter.If the particle is cubic, the edge length x
,〃1- is the particle size.

The average particle projected area is also determined by algebraic mean or geometric mean. For more information on how to determine average grain size, see The Theory of the Photographic Process by C.E. Mees and T.H. James (11. (Th
e theory of the photograp
hic process), 3rd edition, pp. 36-43 (1
966, published by McMillan).

There are no restrictions on the shape of the silver halide grains, and they may be tabular, spherical, cubic, octahedral, or any other shape.It is also preferable that the grain size distribution be narrow, especially within ±40% of the average grain size. 90 of the total number of particles within the particle size range
%, preferably 95%, so-called monodispersed emulsions are preferred.

In the present invention, the soluble root salt and the soluble halogen salt may be reacted by any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

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

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method. According to this method, the crystal form is regular and A silver halide emulsion with nearly uniform grain size can be obtained.

The silver halide emulsion in the light-sensitive material used in the present invention is
One kind may be used alone, or two or more kinds (for example, those having different average particle sizes or different halogen compositions) may be used in combination.

The number of silver halide emulsion layers may be one, but two or more layers may also be provided. The amount of coated silver is preferably in the range of Ig/rrr to 8g/rd.

The hydrophilic colloid layer of the photographic material of the present invention may contain various dyes (for example, ultraviolet absorbing dyes) for the purpose of preventing irradiation, imparting safelight suitability, and the like.

The photographic emulsions and non-photosensitive hydrophilic colloids of the present invention may contain inorganic or organic hardeners.

For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes @ (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.)
, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-8-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-
[β-(vinylsulfonyl)propionamide], etc.)
, active halogen compounds (2,4-dichloro-6-hydroxy-3-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazine, etc. Azinylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-412
Preferred are the active vinyl compounds described in US Pat.

The photosensitive emulsion layer and/or non-photosensitive hydrophilic colloid layer of the present invention may contain various known interfaces for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties. An activator may be used, and for the purpose of preventing static electricity, a fluorine-containing surfactant described in JP-A-60-80849 is preferred.

As binder or protective colloid for photographic emulsions it is advantageous to use gelatin, but other hydrophilic colloids can also be used. For example, gelatin derivatives,
Graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; II derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

The silver halide emulsion layer and other layers of the photographic light-sensitive material of the present invention preferably contain a compound having an acid group. Examples of the compound having an acid group include organic acids such as salicylic acid, acetic acid, and ascorbic acid, and acrylic acid. Polymers or copolymers having acid monomers such as , maleic acid, phthalic acid as repeating units may be mentioned. Regarding these compounds, Japanese Patent Application No. 60-66179 and No. 60-60-
No. 68873, No. 60-163856 and No. 60-1
The description in the specification of No. 95655 can be referred to.

Particularly preferred among these compounds is ascorbic acid as a low molecular compound, and ascorbic acid as a high molecular compound, and acid monomers such as acrylic acid and crosslinking monomers having two or more unsaturated groups such as divinylbenzene. It is a water-dispersible latex of copolymer.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for purposes such as improving dimensional stability. For example, alkyl (meth)acrylate, alkoxy acrylate (meth)acrylate, glycidyl (
Polymers containing meth)acrylate alone or in combination, or combinations thereof with acrylic acid, methacrylic acid, and the like as monomer components can be used.

The light-sensitive material of the present invention relates to a white/male photographic light-sensitive material, particularly a lithographic light-sensitive material.

Further, although the light-sensitive material of the present invention contains fine sulfur crystal particles, it does not have the effect of improving sensitivity like conventional sulfur sensitization.

(Example) The present invention will be specifically explained below using Examples.

However, the present invention is not limited only to these examples.

Example Commercially available alkali-treated gelatin was used to obtain cubic particles with an average particle size of 0.3 using the controlled double jet method.
An emulsion of n silver iodobromide (1=1 molχ) was prepared. This emulsion was precipitated by a flocculation method, washed with water, and then redispersed.

This emulsion was divided into two halves, and one half was used as is without chemical ripening. This emulsion is designated as A.

The other sample was subjected to gold-sulfur sensitization using a conventional method. Gold chloride was used as a gold sensitizer. Hypo was also used as a sulfur sensitizer. Let this milk M be B.

Spectral sensitizing dye, surfactant, thickener, sulfur crystal fine particles, 4-hydroxy-1°3.3a were added to emulsion A at 38°C.
, 7-titraazaine, hypo, and hydrazine derivatives were added and coated on the support so that the Ag amount was 3.5 g/%.

Sulfur crystal fine particles, 4-hydroxy-1,3,3a,7
- Samples 1 to 5 were prepared with the added amounts of chitraazaindene and hypo as shown in Table 1. Coating was completed within 30 minutes after each chemical was added.

Samples 6 to 10 were prepared in the same manner as Samples 1 to 5, except that Emulsion A used in Samples 1 to 5 was changed to Emulsion B.

After coating the prepared sample, 25°C 160%?
■ Save it for 2 days, 10 days, 30 days, 100 days, 300 days.
Sensito exposure was carried out on the same day, the image was developed with a developing machine GR-D-1 (manufactured by Fuji Photo Film), and a fixing machine G11-F-1 (manufactured by Fuji Photo Film ■) was used.
The film was fixed with a photo film (manufactured by Shishi Photographic Film ■) and washed with water, and the change in sensitivity over time was examined.

As shown in Table 1, Sample 2.3 of the present invention did not have higher sensitivity two days after application than Sample 1 of the comparative example.
[It can be seen that no chemical ripening was performed.]

Sample 2.3 of the present invention is also sample 1.3 of the comparative example.
It can be seen that the sensitivity fluctuation over time is significantly smaller than in Example 4.

As seen in sample 5, conventional 4-hydroxy-1,
If an attempt is made to increase the amount of 3,3a,7-titraazaindene added to achieve stability over time, the sensitivity will become low two days after application.

Therefore, by the method of the present invention, it is possible to supply a photosensitive material with high initial sensitivity and small change in sensitivity over time, which could not be achieved using conventional techniques.

As shown in Table 2, it can be seen that the effects of the present invention are exhibited even in chemically ripened emulsions.

(Effects of the Invention) According to the present invention, it is possible to provide a photosensitive material that has high initial sensitivity and shows little change in sensitivity over time. The light-sensitive material obtained according to the present invention is of practical use because its sensitivity hardly decreases over time.

-Ding-wagong city, ■ Mi H! V 1. Indication of 1 fl 1986 ≦ T Special Edition ■ 1 No. 130213 2, Name of the invention C [1 Silver Genide Photography (Photographic Materials 3, Ministry of Amendment) Relationship: Name of Special Edition Applicant Name: (!+2017;\t-Photo Film Co., Ltd. 14, Agent (1 location: 〒100 Tokyo T-dai [[18 Kasumigaseki 3-2-2 May 29th floor Kasumigaseki Building Kasumigaseki Building Mail 1.1J
P.O. Box No. 49'), ll1hH to i (number of claims to be added by 1 - 06, amendment against Australia: Specification 51-1)
Contents of Column 7, Supplement 1 of ``Invention, Jada na1lI2 Akira'':
The [Detailed Description of the Invention] column of Specification-: shall be amended as follows.

(1) 1'100μ or less j on page 5, line 5 for specification submission is "1"
0 μ or less”.

(2) Line 566 of the same book: “10μ or less J is 10.1μ
"That's all," he said.

Claims (2)

[Claims] (1) It has at least one silver halide emulsion layer, and the emulsion layer contains 1 x 10^-^5 x 10^- fine sulfur crystal particles.
A silver halide photographic material containing ^3g/AgNO_3mol. (2) The silver halide photographic material according to claim 1, which uses an emulsion that is not subjected to chemical ripening.