JPH1165011A - Silver halide photosensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photosensitive material excellent in development, suitable for quick photographic processing and excellent in pressure resistance (scratches and blackening do not generate). SOLUTION: This material is composed by including at least four or more layers of a hydrophilic colloid layer containing silver halide emulsion layers on both sides of a transparent supporting body. In this case, the quantity of gelatin in the hydrophilic colloid layers is to be 1.0 to 2.2 g/m<2> per side and oil is to be contained in at least one layer among the hydrophilic colloid layers. It is preferable with this material to have a polymer latex, whose glass transition point (Tg) is -30 deg.C to +90 deg.C, contained in the hydrophilic colloid layers. It is also preferable to have oil contained in the photosensitive material containing a silver halide particle of 10 to 80 mole % silver chloride content and an aspect ratio of 3 to 15.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material having improved developability and abrasion resistance and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, the market for silver halide photographic light-sensitive materials (hereinafter simply referred to as light-sensitive materials) has
Low replenishment is rapidly advancing. Therefore, photosensitive materials are required to have further improved developability.

Hitherto, as a means for improving the developability of a light-sensitive material, for example, a method of reducing the amount of silver in a thin film or flattening or forming fine particles to improve the covering power of silver halide grains has been known. ing.

However, the reduction in the amount of the binder and the reduction in the thickness of the silver halide grains or the flattening of the silver halide grains cause deterioration of the pressure resistance during handling and automatic conveyance of the photosensitive material, and the problem that pressure fog is easily generated. Had.

Particularly, in the case of a photosensitive material for medical use, the support is 17
Since the thickness is 0 to 180 μm as compared with others, in a roller conveyance system in a medical device, an automatic developing machine, or the like, pressure blackening due to abrasion easily occurs, and further, in the case of a medical photosensitive material having a photosensitive layer on both surfaces, There are many opportunities. Further, in recent X-ray films for direct photography, there is a tendency to improve the image quality by providing a crossover cut layer below the emulsion layer. Therefore, it is necessary to further reduce the thickness of the emulsion layer and the protective layer so as not to increase the drying load in the rapid processing.
The abrasion resistance is not preferred because it results in further deterioration.

Hitherto, various techniques have been disclosed as methods for preventing pressure fog of silver halide photographic materials. However, many of the known techniques can increase the pressure resistance, but impair the developability in many cases, and are not enough to obtain rapid processing suitability, and further solutions have been strongly desired.

Hitherto, various techniques have been disclosed as methods for preventing pressure fog of silver halide photographic materials. However, although many of the known techniques can increase the pressure resistance, they often impair the developability of the light-sensitive material, which is not enough to obtain rapid processing suitability, and further improvement techniques have been desired.

[0008]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a silver halide photographic material having good developability, rapid processing suitability, and excellent pressure resistance (without generation of abrasion blackening). Is to provide.

[0009]

The object of the present invention has been attained by the following.

In a silver halide photographic material comprising at least four hydrophilic colloid layers including a silver halide emulsion layer provided on both sides of a transparent support, the amount of gelatin in the hydrophilic colloid layer is reduced per one side. 1.0 to 2.2 g /
m is ² and at least one layer of said hydrophilic colloid layer, a silver halide photographic light-sensitive material characterized by containing an oil.

The silver halide photographic material as described in the above item, wherein said hydrophilic colloid layer contains a polymer latex having a glass transition point (Tg) of -30 ° C to + 90 ° C.

The silver halide photographic material as described in the above item, wherein the content of the polymer latex is 0.1 to 1.5 g / m ² per one side.

In a silver halide photographic light-sensitive material comprising a transparent support and a hydrophilic colloid layer including at least one silver halide emulsion layer, the silver halide grains of the emulsion layer have a silver chloride content of 10%. Silver halide photographic light-sensitive silver halide grains comprising tabular silver halide grains having an average aspect ratio of 3 to 15 at ８０80 mol%, and wherein at least one of the hydrophilic colloid layers contains an oil. material.

A method for processing a silver halide photographic light-sensitive material, characterized in that the silver halide photographic light-sensitive material described above is processed after imagewise exposure for a total processing time of 10 to 45 seconds.

Hereinafter, the present invention will be described in detail.

The hydrophilic colloid layer of the silver halide photographic material of the present invention contains oil dispersed therein. Here, the oil includes those having a solubility in water of not more than 10% by weight at 25 ° C. and being liquid at 25 ° C.

The average particle size of the oil droplets to be dispersed may be as wide or narrow as the individual particle size distribution.
A case where the size of about 0.4 μm occupies 75% or more of the whole is effective in generating fingerprint marks or silver tone. Various surfactants can be used for dispersion. For example, anionic surfactants described in U.S. Pat. Nos. 2,332,027, 2,801,170 and 2,801,171, and anionic and nonionic surfactants described in JP-B-48-9979. Etc. can be used.

Hereinafter, typical specific examples of the oil that can be used in the present invention will be described.

Diethyl adipate, dibutyl adipate, diisobutyl adipate, di-n-hexylethyl adipate, dioctyl adipate, dicyclohexyl azelate, di-2-ethylhexyl azelate, dioctyl sebacate, diisooctyl sebacate, dibutyl succinate, octyl Stearate, dibenzyl phthalate, tri-o-cresyl phosphate, diphenyl-mono-p-tert-butylphenyl phosphate, monophenyl-di-o-chlorophenyl phosphate, monobutyl-dioctyl phosphate, 2,4-di-n- Amylphenol, 2,4-di-tert-amylphenol, 4-n-nonylphenol, 2-methyl-4-n-octylphenol, N, N-diethylcaprylamido, N, N- Ethyl lauramide, glycerol tripropionate, glycerol tributyrate, glycerol mono lactate acetate, tributyl citrate, acetyl triethyl citrate, di -2
-Ethylhexyl adipate, dioctyl sebacate,
Diisooctyl azelate, diethylene glycol dibenzoate, dipropylene glycol benzoate, triethyl citrate, tri (2-ethylhexyl) citrate, acetyl tri-n-butyl citrate, di (isotesyl) 4,5-epoxytetrahydrophthalate,
Oligovinyl ethyl ether, dibutyl phthalate, diisodecyl phthalate, polyethylene oxide (n>
16), glycerol tributyrate, ethylene glycol diprolobionate, di (2-ethylhexyl) isobutyrate, butyl laurate, tri- (2-ethylhexyl) phosphate, triphenyl phosphate,
Tricresyl phosphate, silicone oil, dimethyl phthalate, diethyl phthalate, dipropyl phthalate,
Dibutyl phthalate, isooctyl phthalate, diamino phthalate, di-n-octyl phthalate, diamyl naphthalene, triamyl naphthalene, monocaprin, monolaurin, monomyristin, monopalmitin, monostearin, monoolein, dicaprin, diproline, dimyristine, dipalmitine , Distearin, diolein, 1-stearo-2-palmitin, 1-palmit-3
-Stearin, 1-palmito-2-stearin, triacetin, tricaprin, trilaurin, trimyristin, tripalmitin, tristearin, triolein,
Tripetroserin, trielsin, triricinolein,
Linoleodiestearin, Oleodiesercin, Linoleoziercin, Palmito oleolinorenin, Paraffin, Linseed oil, Soybean oil, Eno oil, Kiri oil, Asami oil, Kaya oil,
Drying oils such as walnut oil, soy sauce oil, poppy oil, sunflower oil, azusa oil, kwai oil, safflower oil; cottonseed oil, corn oil, sesame oil, rapeseed oil, rice bran oil, lotus oil, mustard oil, pumpkin oil, Semi-dry oils such as dehydrated castor oil; peanut oil, olive oil, camellia oil, sasanqua oil, tea oil, castor oil, hydrogenated castor oil, almont oil, bundling oil, ben oil,
Oyster oil and the like can be mentioned. Further, compounds represented by the following general formula can also be used as the oil of the present invention.

[0020]

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In the formula, R represents an alkyl group having 1 to 8 carbon atoms.

Others JP-A-50-23823, 50
-62632, 51-26035, 51-26
Compounds other than those described in JP-A Nos. 036 and 51-26037 can be used in the same manner.

Among these, adipic acid, phthalic acid, sebacic acid, succinic acid, citric acid, fumaric acid, esters such as mazeleiic acid, isophthalic acid and phosphoric acid, glycerin esters and paraffin have no adverse effect on photographic light-sensitive materials. It can be conveniently used because it is easily available, chemically stable and easy to handle. Further, dibutyl phthalate, diisodecyl phthalate, di-n-octyl phthalate, glycerol tripropionate, dioctyl sebacate, paraffin and silicone oil are particularly preferred oils in the present invention.

In the present invention, when the oil is contained in the non-photosensitive hydrophilic colloid layer provided between the silver halide emulsion layer and the uppermost layer, a water-soluble or water-insoluble organic low-boiling compound may be used, if necessary. No problem. After the photographic light-sensitive material is coated and dried, it evaporates and almost no longer exists in the layer. Specific examples of these include methanol, ethanol, propyl alcohol, fluorinated alcohol, acetonitrile, dimethylamide, dioxane,
Methyl isobutyl ketone, diethylene glycol monoacetate, chloroform, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexynol, cyclohexanetetrahydrofuran and the like are mentioned.

In the present invention, the oil droplets are mainly composed of the above-mentioned oils. The lipophilic photographic coupler, ultraviolet absorber, development inhibitor releasing compound, hydroquinone derivative,
An image fading inhibitor or the like may be contained in the oil droplets. However, when a large amount of lipophilic photographic additive is used, the pressure resistance of the silver halide photographic light-sensitive material is deteriorated.

The oil used in the present invention is one which can be dispersed in a coating solution without being mixed with the solution and which does not lose oil droplets even when the coating solution is coated and dried under ordinary conditions. To be elected. Of these, preferred are those having a melting point of 25 ° C. or less when used alone or in combination of two or more.
Those that are liquid at 5 ° C. are more preferred.

In the present invention, one or more oil droplets may be formed at the same time by using oil.
You may mix and use what was separately emulsified and dispersed.

The following are specific examples of oil dispersions.

Exemplary Oil Dispersion Dispersion Particle Size (μm) O-1: Tris (isopropylphenyl) phosphate 0.20 O-2: Trixyleryl phosphate 0.25 O-3: Tributyl phosphate 0.15 O-4 : Dioctyl phthalate 0.15 O-5: dibutyl phthalate 0.20 O-6: dihexyl phthalate 0.15 O-7: tricresyl phosphate 0.20 O-8: o-acetyltriethyl citrate 0.15 O- 9: N, N-dimethyllaurylamide 0.10 O-10: diisodecyl phthalate 0.20 The amount of the oil of the present invention is preferably 10 mg to 1000 mg, more preferably ²⁰ mg to 1 m2 per side of the photosensitive material as an oil component. 300 mg is preferred. The layer to which the oil is added is preferably an emulsion layer or a layer farther from the support than the emulsion layer. Most preferably, it is contained in an intermediate layer provided between the emulsion layer and the surface protective layer.

The hydrophilic colloid layer of the silver halide photographic light-sensitive material of the present invention preferably contains a polymer latex.

As the polymer latex used in the present invention, a polymer latex generally used for a photosensitive material can be used. That is, it is a polymerizable ethylene-based compound or a polymerizable diolefin-based compound, and these are roughly classified into a hydrophobic monomer and a hydrophilic monomer. As the hydrophobic monomer, for example, methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, alkyl acrylates such as t-butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, Alkyl methacrylates such as 2-ethylhexyl methacrylate, t-butyl methacrylate and iso-propyl methacrylate; glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; alkenyl benzenes such as styrene, vinyl toluene, α-methyl styrene and chloromethyl styrene Kind,
Vinyl esters such as vinyl acetate and vinyl propionate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and phenyl vinyl ether; vinyl halides such as vinyl chloride, vinyl bromide and vinylidene chloride; acrylic amides and methacrylic amides Examples thereof include amides and diene monomers such as butadiene.

Examples of the hydrophilic monomer include hydroxyalkyl acrylates such as hydroxyethyl acrylate and hydroxypropyl acrylate; hydroxyalkyl methacrylates such as hydroxyethyl methacrylate and hydroxypropyl methacrylate; tetraethylene glycol; Ethylene glycol (meth) acrylates such as methacrylate, acrylic acid, methacrylic acid, itaconic acid, α-acrylamide-
An ionic monomer such as 2-methylpropanesulfonic acid is exemplified. These monomers may be used alone, or two or more kinds may be used in combination.When a hydrophilic monomer is used, it is preferable to use the monomer together with a hydrophobic monomer to obtain a stable latex. It is better not to use a hydrophilic monomer.

The polymer latex used in the present invention may be obtained by an emulsion polymerization method or a suspension polymerization method in which the polymer is polymerized in a dispersion medium from the beginning, or may be separately polymerized to take out a polymer.
This may be redispersed to obtain a latex, but an emulsion polymerization method is preferred from the viewpoint of production cost, dispersion stability and the like.

The polymer latex used in the present invention has a polymer Tg (glass transition temperature) of -30 ° C. to 90 ° C.
It is. More preferably, it is 10 ° C to 70 ° C.

The Tg of many polymers of the ethylenic monomers used in the present invention is described in "Polymer Handbook" by Brand Wrap et al., Pages III-139 to 179 (19).
1966 (Wiley & Sons), and the Tg (° K) of the copolymer is represented by the following formula.

Tg (copolymer) = V ₁ Tg ₁ + V ₂ Tg ₂
+ ... + V _w in Tg _W However Ueshiki, V _1, V ₂ is ... V _W represents the weight fraction of the monomer in the _{copolymer, Tg 1, Tg 2 ... Tg} W each monomer in the copolymer Represents the Tg (° K) of the homopolymer. Tg calculated according to the above equation has an accuracy of ± 5 ° C.

Hereinafter, preferred examples of the polymer latex used in the present invention will be shown, but the present invention is not limited thereto.

(P-1) St (20) MMA (70) MA (10) (P-2) St (15) MMA (75) MA (10) (P-3) St (50) MMA (35) MA (15) (P-4) St (25) MMA (70) MA (15) (P-5) St (40) MMA (55) AA (15) (P-6) St (20) EMA (70) ) AA (10) (P-7) St (10) MMA (75) AA (15) (P-8) St (10) MMA (80) acryloyloxyethyl orthophthalic acid (10) (P-9) St (15) MMA (75) acryloyloxyethyl succinate (10) (P-10) St (18) MMA (75) acryloyloxyethyl succinate (7) (P-11) CHMA (60) AIN (30) GMA
(10) (P-12) CHMA (80) AIN (15) GMA
(5) (P-13) CHMA (80) GMA (20) (P-14) CHMA (80) EMA (15) GMA
(5) (P-15) CHMA (65) EMA (25) GMA
(10) (P-16) n-butyl acrylate (10) t-butyl acrylate (35) styrene (25) hydroxyethyl methacrylate (30)

[0039]

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St: styrene, MMA: methyl methacrylate, EMA: ethyl methacrylate, MA: methacrylic acid, AA: acrylic acid, CHMA: cyclohexyl methacrylate, GMA: glycidyl methacrylate,
AIN: represents —CH ₂ —C (COOC ₉ H ₁₉ iso) H— (the composition indicates a weight fraction).

Comparative Latex 1 St (15) Ethyl Acrylate (85) Tg-6 ° C. Comparative Latex 2 CHMA (30) AIN (55) GMA (15) Tg-21 ° C. 0.1 to 1.5 g / m ² per one side of the material. More preferably, it is 0.2 to 1.0 g / m ² . The addition layer is not particularly limited as long as it is a hydrophilic colloid layer of the light-sensitive material of the present invention, but is preferably an emulsion layer.

The silver halide photographic light-sensitive material of the present invention is a light-sensitive material provided with at least four hydrophilic colloid layers on a support coated with an undercoat layer. Preferably, the photosensitive material is provided with 4 to 8 hydrophilic colloid layers. Most preferably, there are four to six layers. Here, the hydrophilic colloid layer in the present invention includes a photosensitive or non-photosensitive silver halide emulsion layer, an intermediate layer, a protective layer, a dye layer, an undercoat layer (not an undercoat layer), and the like.

In the light-sensitive material of the present invention, a non-light-sensitive hydrophilic colloid layer can be provided between the support and the emulsion layer, and the undercoat layer can contain a polymer latex or a filter dye. .

In the light-sensitive material of the present invention, the amount of gelatin in the hydrophilic colloid layer is contained in the range of 1.0 to 2.2 g / m ² per one side. More preferably, the content is 1.5 to 2.0 g / m ² , and if it is less than this, the scratch resistance is not improved.

The silver halide grains used in the light-sensitive material of the present invention are silver halides such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, silver iodochloride, silver chloroiodobromide and the like. Can be. The content of silver iodide is preferably 1.0 mol% or less, more preferably 0.5 mol% or less, as the average silver iodide content in the whole silver halide grains.

The light-sensitive material of the present invention has a silver chloride content of 10 to 80 mol%, preferably 10 to 80 mol%, as a silver halide composition.
Silver halide emulsions of .about.60 mol% are preferred. The emulsion may contain 1 mol% or less of silver iodide, and the silver halide grains are preferably silver chlorobromide and silver chloroiodobromide grains.

The silver halide grains of the light-sensitive material of the present invention are:
The particles have an average aspect ratio of 3 to 15, and more preferably 3.5 to 8.0.

Tabular silver halide grains can be prepared, for example, by the method described in US Pat. No. 5,320,938. That is, it is preferable to form nuclei with low pCl in the presence of iodine ions under conditions that facilitate formation of the (100) plane. After nucleation, Ostwald ripening and / or growth is performed to obtain tabular silver halide grains having a desired grain size and distribution. The tabular silver halide grains used in the present invention may be so-called halogen conversion type (conversion type) grains. The halogen conversion amount is preferably from 0.2 mol% to 0.5 mol% with respect to the silver amount, and the conversion may be performed during physical ripening or after completion of physical ripening.

In the process of forming and / or growing the silver halide grains, cadmium salts, zinc salts,
Lead salts, thallium salts, iridium salts (including complex salts), rhodium salts (including complex salts), ruthenium salts (including complex salts),
It is preferable to add a metal ion using at least one selected from an osmium salt (including a complex salt) and an iron salt (including a complex salt), and to include these metal elements inside the particle and / or on the surface of the particle.

In the present invention, it is preferable to add a silver halide solvent before the desalting step in order to accelerate the developing speed. For example, a thiocyanate compound (potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, etc.) is used in an amount of 1 × 10 ⁻³ mol or more and 3 × 10 ³ mol or more per mol of silver.
It is preferable to add ^-2 mol or less.

In the present invention, gelatin is preferably used as a dispersion medium for the protective colloid of the silver halide grains. As the gelatin, alkali-treated gelatin, acid-treated gelatin, low-molecular-weight gelatin (molecular weight: 20,000 to 10)
And modified gelatin such as phthalated gelatin. Other hydrophilic colloids can also be used. Specifically, Research Disclosure Magazine (hereinafter abbreviated as RD), Vol. 17643 (December 1978
Month). As for the amount of gelatin, the amount of gelatin in the entire hydrophilic colloid layer per one surface of the photosensitive material is 1.0 to 2.5 g / m ² .

In the present invention, unnecessary soluble salts may be removed during the growth of silver halide grains, or they may be kept contained. When removing the salts, see RD Vol. It can be carried out based on the method described in 17643, Section II.

The silver halide grains of the present invention can be subjected to chemical sensitization. The conditions of the process of chemical ripening or chemical sensitization,
For example, the pH, pAg, temperature, time and the like are not particularly limited, and the reaction can be performed under conditions generally performed in the art. For chemical sensitization, sulfur sensitization using a compound containing sulfur that can react with silver ions or active gelatin, selenium sensitization using a selenium compound, tellurium sensitization using a tellurium compound, using a reducing substance A reduction sensitization method, gold or a noble metal sensitization method using a noble metal or the like can be used alone or in combination. Among them, a selenium sensitization method, a tellurium sensitization method, a reduction sensitization method, etc. are preferably used.

The silver halide emulsion used in the practice of the present invention may be spectrally sensitized with a cyanine dye or the like. The sensitizing dye may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for supersensitization.

In the light-sensitive material using the silver halide emulsion of the present invention, various photographic additives can be used before and after physical ripening or chemical ripening of the emulsion.

Compounds that can be used in such a step include, for example, (RD) 17643 and 18716 (1
November 997) and 308119 (January 1989)
(February). The types and locations of the compounds described in these three (RD) are described below.

[0057]

[Table 1]

As the support used in the light-sensitive material of the present invention, those described in the above RD can be mentioned. Suitable supports include a polyethylene terephthalate film or a polyethylene naphthalate film and the like. In order to improve the adhesiveness of the coating layer, a subbing layer may be provided, or corona discharge or ultraviolet irradiation may be applied. Then, the constituent layer according to the present invention can be applied to both surfaces of the support thus treated.

In the light-sensitive material of the present invention, the silver halide emulsion layer and other hydrophilic colloid layers can be coated on a support or other layers by various coating methods. For the coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, a slide hopper method, or the like can be used. For details, see (RD) 17643, p. The method described in the section "Coating procedures" of 27-28 can be used.

The processing of the light-sensitive material of the present invention is carried out, for example, in the manner described in RD-17643, pages XX to XXI, pp. 29 to 30 or 3 above.
Treatment with a processing solution as described in 08119, XX to XXI, pp. 1011 to 1012 may be performed.

Examples of the developer for black-and-white photographic processing include dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-aminophenol), and reductone. Can be used alone or in combination. In the developer, a known agent such as a preservative, an alkali agent, a pH buffer, an antifoggant, a hardener, a development accelerator, a surfactant, an antifoaming agent, a color tone agent, a water softener, and a dissolution aid can be used. A viscosity imparting agent may be used as necessary.

The fixing solution contains a fixing agent such as thiosulfate and thiocyanate, and may further contain a water-soluble aluminum salt such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

The silver halide photographic light-sensitive material of the present invention can perform ultra-rapid processing with a total processing time (Dry to Dry) of 10 to 45 seconds. Preferably it is in the range of 10 to 30 seconds. Here, the total processing time refers to the time from when the leading end of the photosensitive material to be processed is immersed in the developing tank solution of the automatic developing machine until it is dried through the squeeze roller.

In the silver halide photographic light-sensitive material of the present invention, the replenishment amount of the developing solution and the fixing solution is 35 to 40 per m ^{2 of the} light-sensitive material.
It can be processed with 0 ml. Examples of the replenishment method include replenishment by width and feed rate described in JP-A-55-126243, area replenishment described in JP-A-60-104946, and area controlled by the number of continuously processed sheets described in JP-A-1-149156. It may be supplemented.

[0065]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 <Preparation of Seed Emulsion-1> [A ₁ ] Ossein gelatin 24.2 g Distilled water 9657 ml Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous methanol solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml [B ₁ ] 2.5N AgNO ₃ aqueous solution 2825 ml [C ₁ ] Potassium bromide 841 g Finish with water to 2825 ml [D ₁ ] 1.75 N KBr aqueous solution Nos. 58-58288 and 58-5828
Using a mixing stirrer described in the specification of No. 9, 464.3 ml of each of the solution B ₁ and the solution C ₁ was added to the solution A ₁ by a simultaneous mixing method over 1.5 minutes to form nuclei.

After stopping the addition of the solution B ₁ and the solution C ₁ ,
Over a period of 40 minutes of time to raise the temperature of the solution A ₁ to 50 ° C., after adjusting the pH to 5.0 with 3% KOH, the solution again B ₁ and solution C ₁ simultaneous mixing method, each 55 0.4 ml /
Min was added at a flow rate of 42 minutes. From this 42 ° C to 50
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature rise to 0 ° C. and re-mixing with the solutions B ₁ and C ₁ was +8 mV and +16 mV respectively using the solution D _1. It controlled so that it might become.

After the addition was completed, the pH was adjusted to 6 with 3% KOH, and immediately, desalting and washing were performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.045 μm. It was confirmed by an electron microscope that the average particle size (circular diameter conversion) was 0.42 μm. The variation coefficient of the thickness was 42%, and the variation coefficient of the distance between twin planes was 45%.

<Preparation of Tabular Silver Bromide Emulsion> A tabular pure silver bromide emulsion was prepared using Seed Emulsion-1 and the following three kinds of solutions.

[A ₂ ] Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous methanol) 2.25 ml Seed emulsion-1 1.218 mol equivalent Equivalent to 3669 ml with water [B ₂ 1747 g of potassium bromide Finish to 3669 ml with water [C ₂ ] 2493 g of silver nitrate Finish to 4193 ml with water In a reaction vessel, stir vigorously while keeping solution A ₂ at 50 ° C., and add the total amount of solution B ₂ and solution C ₂ there. It was added by a double jet method over 100 minutes. During this time, the pH was kept at 9.0 with the KOH solution, and the pAg was kept at 8.6 throughout. Here, the addition rates of the solution B ₂ and the solution C ₂ were changed functionally with respect to time so as to match the critical growth rate. That is, they were added at an appropriate addition rate so that no small particles were generated except for the seed particles that were growing, and that they did not become multicomponent due to Ostwald ripening.

After completion of the addition, the emulsion was cooled to 40 ° C., and 1800 ml of an aqueous solution of 13.8% (by weight) of a modified gelatin modified with a phenylcarbamoyl group (substitution rate: 90%) was added as an aggregating polymer. Stir for 3 minutes. Thereafter, a 56% (by weight) aqueous solution of acetic acid is added to adjust the pH of the emulsion.
Was adjusted to 4.6 and stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.
1.25 l was added, and after stirring and standing, the supernatant was drained.

Subsequently, an aqueous solution of gelatin and sodium carbonate 1
A 0% (by weight) aqueous solution was added to adjust the pH to 5.80, followed by stirring at 50 ° C. for 30 minutes to redisperse. After redispersion, the pH was adjusted to 5.80 and the pAg to 8.06 at 40 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, it was found that the average grain size was 0.84 μm, the average thickness was 0.16 μm, the average aspect ratio was about 5.3, and the grain size distribution was 20%. Tabular silver halide grains were obtained. The amount of gelatin at the end of physical ripening was 15.9 g per mol of silver halide.

After the emulsion prepared above was heated to 55 ° C., the following spectral sensitizing dye (A) 450 per mole of silver halide was used.
mg, and 45 mg of the spectral sensitizing dye (B).
100 mg of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. After 10 minutes, 3.5 mg of chloroauric acid, 10 mg of sodium thiosulfate,
100 mg of ammonium thiocyanate was added. 4 more
0 minutes later, 0.3 mol of the following silver iodide fine grains was added,
After another 10 minutes, 5 m of triphenylphosphine selenide
g, and after 40 minutes, 500 mg of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added. After 5 minutes, 13 g of trimethylolpropane and 30 g of gelatin were added. After cooling, the emulsion gelled to complete the chemical sensitization.

<Preparation of Silver Iodide Fine Particles> [A ₃ ] Ossein gelatin 100 g KI 8.5 g Make up to 2000 ml with distilled water [B ₃ ] AgNO ₃ 360 g Make up to 605 ml with distilled water [C ₃ ] KI 352 g distilled water The solution A ₃ was added to the reaction vessel, and the solution B ₃ and the solution C ₃ were added at a constant speed by a simultaneous mixing method over 30 minutes while stirring at 40 ° C. The pAg during the addition was kept at 13.5 by a conventional pAg control means. The formed silver iodide was a mixture of β-AgI and γ-AgI having an average grain size of 0.06 μm. This emulsion is called a silver iodide fine grain emulsion.

(Spectral sensitizing dye) Sensitizing dye (A): 5,5'-di-chloro-9-ethyl-
Anhydride of sodium 3,3'-di- (3-sulfopropyl) oxacarbocyanine Sensitizing dye (B): 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3 Anhydrous sodium salt of '-di- (4-sulfobutyl) benzimidazolocarbocyanine <Preparation of Subbed Support> Both sides of polyethylene terephthalate (PET) base having a thickness of 175 μm and a blue coloration of 0.17 in concentration After a corona discharge treatment of 8 Wmin / m ² , the following undercoating lower layer was applied,
For 1 minute. Then, after performing the same corona discharge treatment again, the following undercoating upper layer coating solution was applied,
Drying at 1 ° C. for 1 minute gave a subbed support.

(Undercoat lower layer) Latex: St (15) EA (85) 200 mg / m ² Compound A 5.0 mg / m ² Hexamethylene-1,6-bis (ethyleneurea) 5.0 mg / m ² SnO ₂ (Solid content) 300 mg / m ² (undercoating upper layer) n-butyl acrylate (10), t-butyl acrylate (35), styrene (25), hydroxyethyl methacrylate (30) 10 mg / m ² Compound L-1 30 mg / m ² Compound A 5.0 mg / m ² Acetic acid 2.0 mg / m ² Silica having an average particle size of 3 μm 3.0 mg / m ² Compound S 5.0 mg / m ²

[0078]

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<Preparation of Photosensitive Material> The undercoated support obtained above was coated on both sides with the layer composition shown in Table 2 below, and the first layer was formed from the side closer to the support (intermediate layer 1). . The following coating amount is an attached amount per one side.

(Intermediate layer 1) Lime-treated inert gelatin 0.2 g / m ² Filter dye F (solid dispersion) 30 mg / m ² Sodium-i-amyl-n-decylsulfosuccinate 2.5 mg / m ² Polymer latex See Sample No. 3. Only 7 was added (emulsion layer) The additives added to the emulsion were as follows. The amount of addition other than gelatin is indicated by the amount per mol of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg Polyvinylpyrrolidone (molecular weight 10,000) 0.7 g Styrene-maleic anhydride copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.0 g 1-phenyl-5-mercaptotetrazole 8.5 mg Colloidal silica (Ludox AM manufactured by Dupont) 85 mg Lime-treated inert gelatin Amount shown in Table 2 t -Butylcatechol 150 mg Compound Z 1.7 g KBr 200 mg Thallium nitrate 55 mg Trimethylolpropane 6.5 g Dextran (average molecular weight 40,000) 10 g Compound B 150 mg Dextrin (average molecular weight 1000) 10 g Polystyrene sulfo Per amount sided sodium acid (average molecular weight 300,000) 1.3 g polymer latex Table 3, wherein amount of silver was coated to a 1.4 g / m ^2.

(Intermediate layer 2) Amount per m ² per side Gelatin (lime-treated inert gelatin) Amount shown in Table 2 Polymer latex Amount shown in Table 3 Oil Amount shown in Table 3 Sodium polystyrene sulfonate (average molecular weight 300,000) 5.5 mg / m ² (protective layer) Next, the following was prepared and applied as a coating solution for the upper layer of the protective layer. It represents the m amounts with ² per one surface below.

Lime-treated inert gelatin Amount shown in Table 2 Sodium-i-amyl-n-decylsulfosuccinate 18 mg Polymethyl methacrylate (a matting agent having an area average particle size of 3.5 μm) 28 mg Silicon dioxide particles (area average particle size 1) .2 μm matting agent) 14 mg (CH ₂ ＣＨCHSO ₂ CH ₂ ) ₂ (curing agent) 10 mg C ₇ F ₁₅ CH ₂ (CH ₂ CH ₂ O) ₁₃ H 10 mg C ₈ F ₁₇ SO ₃ K 2 mg Activator S 13 mg Hardener H 135mg Preservative 0.1g

[0084]

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[0085]

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The following characteristics of the obtained sample were evaluated.

<Evaluation of Scratches> Two samples each were prepared, cut into 30 cm pieces, and conditioned at 23 ° C. and 60% RH for 3 hours. This sample is overlaid and 500 on one end
g of the weight, the other hand was held by hand, and only the upper film was pulled horizontally at a speed of 5 seconds / m. After this operation was repeated twice, development processing was performed without exposure, and the obtained sample was visually evaluated according to the following criteria. The larger the value, the better the abrasion resistance.

[0088] 4. 2. There is almost no abrasion (rubbing fog). Scratches (rub-like fog) are present, but acceptable for practical use. Many scratches (rubbing fog) make it impractical. Extremely abrasions (rubbing fog) <Evaluation of developability> Using a cassette for medical X-ray photography, combining the front side and the back side of radiation-sensitized Skrlen SRO-250 (manufactured by Konica Corporation) X-ray photography was carried out by a distance method, and a total processing time of 45 seconds and 25 seconds was performed by the following developing system. The gamma value of the obtained sample was determined by the following method,
The developability was evaluated from the gamma reduction width of the 5-second processing.

Gamma was determined from the slope of a straight line connecting the density of fog + 0.25 and the density of fog + 2.0, and evaluated according to the following four grades.

A. Good with little decrease in gamma. Although there is a slight decrease in gamma, practically acceptable level C.I. Impaired due to reduced gamma. Table 3 shows the obtained results.

<Developing process> The developing process is performed by an automatic developing machine SRX.
-502 (manufactured by Konica Corporation) with a line speed of 1.8
It was modified so that it could be doubled and processed using a developer and a fixer having the following formulation.

(Developer Formulation) Part-A (for finishing 12 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraaminepentaacetic acid 120 g Sodium bicarbonate 132 g 5-methylbenzotriazole 1.2 g 1- Phenyl-5-mercaptotetrazole 0.2 g 1,4-dihydroxybenzene 340 g Add water to make 5000 ml. Part-B (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-phenyl-3-pyrazolidone 22 g 5-nitro Indazole 0.4g Starter solution formulation (for 1 liter finishing) Glacial acetic acid 120g Potassium bromide 225g Add water to make up to 1000ml (Fixing solution formulation) Part-A (for 18 liter finishing) Thio Ammonium sulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-dimethylamino) -ethyl-5-mercaptotetrazole U 18 g Part-B Aluminum sulfate 800 g (Preparation of developer) The developer was prepared by adding P to about 5 liters of water.
Art-A and Part-B were added simultaneously, and water was added while stirring and dissolving to make up to 12 liters.
It was adjusted to 0.40 and used as a developer.

20 ml of a starter solution was added per liter of the developing solution, and the pH was adjusted to 10.40 to obtain a working solution.

(Preparation of Fixing Solution) The fixing solution was prepared by simultaneously adding Part-A and Part-B to about 5 liters of water, adding water while stirring and dissolving to make up to 18 liters, and adding sulfuric acid and sodium hydroxide. The pH was adjusted to 4.4 using this solution, which was used as a fixer solution and a fixer replenisher.

The processing temperatures were 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing and 50 ° C. for drying, respectively. The obtained results are shown in Tables 2 and 3 below.

[0096]

[Table 2]

[0097]

[Table 3]

As is clear from Table 3, the sample of the present invention
It can be seen that the decrease in gamma is small and the developability is excellent. Further, it can be seen that the abrasion resistance performance was improved and the abrasion blackening was smaller than that of the comparative sample. Example 2 (Preparation of Comparative Emulsion Em-1)
6 g was dissolved in a vessel heated to 50 ° C., and 0.4 g of potassium bromide, 6 g of sodium chloride and 10 g of sodium polyisopropylene-polyoxyethylene-disuccinate were added.
After adding 0.8 ml of a 20% ethanol solution,
One liter of an aqueous solution containing 0 g of silver nitrate and 1 liter of an aqueous solution containing 84 g of potassium bromide and 28 g of sodium chloride were added by a double jet method over about 55 minutes. After desalting, 20 g of gelatin was added and stirred at 50 ° C. for 30 minutes to perform redispersion. Observation of the obtained Em-1 with an electron microscope showed that the mean particle size was 0.40 μm and the silver chloride content was 4
It was 0 mol% silver chlorobromide cubic grains.

(Preparation of Comparative Emulsion Em-2) Em-2 was prepared in the same manner as in Em-1, except that the aqueous solution was changed to 28 g of potassium bromide and 56 g of sodium chloride in the process for producing Em-1. Observation of the obtained Em-2 with an electron microscope showed that the average particle size was 0.40 μm and the silver chloride content was 8
It was 0 mol% silver chlorobromide cubic grains.

(Preparation of Em-3) 24 g of gelatin was dissolved in 400 ml of water, and a pAg was adjusted to 9.0 by using an aqueous solution containing 11.2 M of sodium chloride and 1.8 M of potassium bromide as a mother liquor. Sodium chloride 10.8
A halide solution containing M and potassium bromide 1.2M, and a 2M silver nitrate aqueous solution at a constant flow rate (5 ml
/ Min) for 30 minutes. During the addition, the temperature of the mother liquor was kept at 40 ° C., the pH was kept at 7.0 and the pAg was kept at 9.0.
After desalting, 17 g of gelatin was added, and the mixture was stirred at 50 ° C. for 30 minutes to perform redispersion. Observation of the obtained Em-3 with an electron microscope revealed silver chlorobromide tabular grains having an average particle diameter of 0.40 μm, an average aspect ratio of 4.0, and a silver chloride content of 40 mol%.

(Preparation of Em-4) In the same manner as in the preparation of Em-3, except that the molar ratio of sodium chloride and potassium bromide in the mother liquor and the halide liquid was 8: 2 and the pAg was kept at 8.1. Em-4 was prepared.

Observation of the obtained Em-4 with an electron microscope revealed that the average particle diameter was 0.40 μm and the average aspect ratio was 4.0.
0, silver chlorobromide tabular grains having a silver chloride content of 80 mol%.

(Preparation of Em-5)
Em-5 was prepared in the same manner except that Ag was kept at 9.5. Observation of the obtained Em-5 with an electron microscope revealed silver chlorobromide tabular grains having an average particle diameter of 0.40 μm, an average aspect ratio of 10.0, and a silver chloride content of 40 mol%.

(Preparation of Em-6) In the preparation of Em-3, the mother liquor and the halide liquor were prepared in the same manner except that the molar ratio of sodium chloride to potassium bromide was 8: 2 and the pAg was kept at 8.8. Em-6 was prepared.

When the obtained Em-6 was observed with an electron microscope, the average particle diameter was 0.40 μm and the average aspect ratio was 10.
0, silver chlorobromide tabular grains having a silver chloride content of 80 mol%.

(Chemical sensitization of emulsion) Next, the emulsion Em-
After the temperature of 1 to 6 was brought to 60 ° C., the following spectral sensitizing dye was added as a dispersion in the form of solid fine particles so as to have a concentration of 0.7 mmol per mol of silver, and then potassium thiocyanate, chloroauric acid and sodium thiosulfate were added. A mixed aqueous solution and a dispersion of triphenylphosphine selenide were added, and aging was performed for a total of 2 hours. At the end of ripening, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) was added as a stabilizer.

Sensitizing dye (A): 5,5'-dichloro-9
-Ethyl-3,3'-di- (3-sulfopropyl) -oxacarbocyanine sodium salt anhydrous Additives and their amounts (per mole of AgX) are shown below.

Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.0 mg Triphenylphosphine selenide 0.2 mg in terms of powder 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (TAI) 280 mg The solid dispersion of the sensitizing dye was prepared by adding a predetermined amount of the dye to water previously adjusted to 27 ° C., and adding 3,5,
Obtained by stirring at 00 rpm for 30-120 minutes.

The above triphenylphosphine selenide was prepared as follows. That is, 120 g of triphenylphosphine selenide was added to 30 k of ethyl acetate at 50 ° C.
g, and dissolved completely by stirring. On the other hand, 3.8 kg of photographic gelatin was dissolved in 38 kg of pure water, and this was added to a 25 wt% aqueous solution of sodium dodecylbenzenesulfonate 9.
3 g were added. Then, these two liquids are mixed and the diameter 1
Using a high-speed stirring type disperser having a 0 cm dissolver, dispersion was performed at 50 ° C. for 30 minutes at a peripheral speed of the dispersion blade of 40 m / sec. Thereafter, ethyl acetate was removed while rapidly stirring under reduced pressure until the residual concentration of ethyl acetate became 0.3 wt% or less. Thereafter, this dispersion was diluted with pure water to finish up to 80 kg. A part of the dispersion thus obtained was fractionated and used in the above experiment.

The same support as used in Example 1 was used.

<Preparation of Photosensitive Material> Coating was carried out with the following layer composition to obtain a film sample.

First Layer (Intermediate Layer 1) Same as in Example 1 Second Layer (Emulsion Layer) Except for gelatin, it is represented by the amount added per mol of silver halide.

Lime-treated inert gelatin 0.9 g / m ² polyvinylpyrrolidone (molecular weight 10,000) 0.7 g C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.0 g 1-phenyl- 5-mercaptotetrazole 8.5 mg colloidal silica (Ludox AM manufactured by DuPont) 50 g / mol Ag t-butylcatechol 150 mg compound Z 1 g KBr 100 mg thallium nitrate 30 mg trimethylolpropane 3.0 g dextran (average molecular weight 40,000) 10 g dextrin (average) Molecular weight 1000) 10 g Sodium polystyrenesulfonate (average molecular weight 500,000) 1.5 g Polymer latex (Example P-11) 20 g The emulsion layer was coated so that the silver amount per side was 1.3 g / m ² .

Third layer (middle layer 2) Amount per one side, m ² Lime-treated inert gelatin 0.3 g Oil Amount shown in Table 4 Sodium polystyrene sulfonate (average molecular weight 300,000) 4 mg Fourth layer (protective layer) The following was prepared and applied as a coating liquid for a protective layer. Shown sided, m quantity with ² per below.

Lime-treated inert gelatin 0.4 g Sodium-i-amyl-n-decylsulfosuccinate 20 mg Polymethyl methacrylate (matting agent having an area average particle diameter of 6 μm) 30 mg Hardening agent H 135 mg C ₇ F ₁₅ CH ₂ (CH ₂ CH ₂ O) ₁₃ H 20 mg C ₈ F ₁₇ SO ₃ K 2 mg Activator S 1 mg Preservative 100 mg The obtained sample was evaluated in the same manner as in Example 1, and the following Table 4 was obtained.

[0116]

[Table 4]

As apparent from FIG. 4, according to the present invention, abrasion blackening was reduced, developability was excellent, and rapid processing suitability was obtained.

[0118]

According to the present invention, it has been possible to provide a silver halide photographic light-sensitive material having excellent scratch resistance, improved developability and rapid processing suitability.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03C 1/76 G03C 1/76 5/26 5/26

Claims (5)

[Claims] 1. A silver halide photographic material comprising at least four hydrophilic colloid layers including a silver halide emulsion layer on both sides of a transparent support, wherein the amount of gelatin in the hydrophilic colloid layer is: 1.0 to 2.2 g / per side
m ^2, and and the silver halide photographic light-sensitive material characterized by containing an oil with at least one layer of a hydrophilic colloid layer. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the hydrophilic colloid layer contains a polymer latex having a glass transition point (Tg) of -30 ° C. to + 90 ° C. material. 3. The silver halide photographic material according to claim ² , wherein the content of the polymer latex is 0.1 to 1.5 g / m ² per one side. 4. A silver halide photographic material comprising a transparent support and a hydrophilic colloid layer comprising at least one silver halide emulsion layer, wherein the silver halide grains in the emulsion layer contain silver chloride. Silver halide grains comprising tabular silver halide grains having a ratio of 10 to 80 mol% and an average aspect ratio of 3 to 15, wherein at least one of the hydrophilic colloid layers contains an oil. Photosensitive material. 5. A method for processing a silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material according to claim 4 is processed for a total processing time of 10 to 45 seconds after imagewise exposure.