JP2699003B2 - Processing method of silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide photographic light-sensitive material.

[Background of the Invention]

Attempts have been made to capture a radiation image for medical diagnosis as a digital value, perform image processing using a computer to make the image more suitable for diagnosis, and then expose the image with a laser beam to reproduce the image. In particular, argon, helium-neon, helium-cadmium and the like have been put to practical use as lasers for these scanning exposure apparatuses. However, all of these lasers have shortcomings such as a short lifetime, a large size, and a complicated device for modulating the light emission intensity.

On the other hand, in recent years, research on semiconductor lasers has progressed, and power-up and longer life have been realized. Semiconductor lasers have the advantages of being inexpensive, having a long life, being small in size, and capable of direct modulation as compared with conventional argon and helium-neon lasers, and requiring no modulator.

However, since the emission wavelength of the semiconductor laser having the above characteristics is in the near infrared region of 750 to 1,500 nm, a recording material having a photosensitive region in the near infrared region is required as a recording material.

As a method of spectrally sensitizing silver halide to the near infrared region, for example, the Theory of The Photographic Process
ss) Third edition, published by Macmillan (1966), 1
As described on pages 98 to 201, a method using a long-chain cyanine dye is known.

On the other hand, for the performance of silver halide photographic materials,
Various demands have been made, and in particular, a highly sensitive silver halide photographic light-sensitive material having stable photographic performance has been demanded.

In silver halide photographic materials, the sensitivity is generally increased by increasing the size of silver halide emulsion grains. However, according to this method, the blackening density per unit developed silver decreases, and γ (gradient of the linear portion of the characteristic curve) decreases. To improve these, it was necessary to increase the amount of silver per unit area of the photosensitive material.

On the other hand, as one method of sensitizing without increasing the amount of silver, the use of a polyoxyethylene compound has been proposed.
No. 27065. However, according to this method, although the sensitivity is increased, it is also known that there are many adverse effects on photographic characteristics, such as an increase in fog and a yellow tone of the developed silver color. In particular, when a polyoxyethylene compound is used for the purpose of sensitization, the silver tone after development is significantly yellowed, and it is extremely difficult to achieve both sensitization and improvement of the silver tone yellowing within the practical range. Yes, measures were desired.

[Disclosure of the Invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material which can be sensitized without increasing fog and in which the silver tone after development does not deteriorate due to the sensitization.

The object is that at least one photosensitive silver halide emulsion layer provided on a support contains at least one selected from the group of compounds represented by the following general formula [I]; A silver halide photographic material comprising at least one compound selected from the group consisting of compounds represented by the following general formula (II) in at least one of the hydrophilic colloid layers on the same side as the photosensitive silver halide emulsion layer is provided. A compound selected from the group consisting of the following 3-pyrazolidone compounds:
This is achieved by a method for processing a silver halide photographic light-sensitive material, which is processed with a developer containing 1.2 g / g or more.

General formula [I] (In the general formula [I], Z ₁ and Z ₃ represent a non-metal atom group necessary for forming a benzothiazole nucleus, a benzoxazole nucleus, a naphthothiazole nucleus, or a naphthoxazole nucleus which may have a substituent. Z ₂ represents a 5- or 6-membered carbon atom ring, and R ₁ and R ₂ represent a saturated or unsaturated aliphatic group.

(However, R ₅ and R ₆ represent an alkyl group which may have a substituent, an alkoxycarbonyl group or an allyl group, and R ₇ represents an alkyl group which may have a substituent, an allyl group or an alkoxycarbonyl group. Represents a group) or a hydrogen atom.
X ^- represents an anion. n represents 1 or 2 (however, 1 when an inner salt is formed). ) General formula [II] (In the general formula [II], R ₁₀ represents an alkoxy group having 1 to 5 carbon atoms, an alkyl group, or an aryl group; R ₁₁ represents an alkylene group having 2 to 5 carbon atoms or a divalent aromatic group; a, b,
c, d, e are integers, a + e is 5-70, b + d is 5-50, c
Represents an integer of 0 to 30. 1) 1-phenyl-5-methyl-3-pyrazolidone 1-phenyl-2-hydroxymethyl-4-methyl-3-pyrazolidone 1-phenyl-5,5-dimethyl-3-pyrazolidone 1-phenyl-2-morpholinomethyl -4-Methyl-3-pyrazolidone 1-phenyl-2-morpholinomethyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone 1-p-tolyl-4,4 -Dihydroxymethyl-3-
Pyrazolidone 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-2-hydroxy-4,4-dimethyl-
3-Pyrazolidone When Z ₂ is a 5-membered ring, [I] is represented by the following [Ia].

[I-a]

R ₃ and R ₄ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom, or an alkoxy group having 1 to 4 carbon atoms.

When Z ₂ is a 6-membered ring, [I] is represented by the following [Ib].

General formula [1-b] In the formula, R ₈ represents a hydrogen atom or a methyl group, R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monocyclic allyl group.

Hereinafter, the infrared sensitizing dye represented by the general formula [I] will be described.

In the general formula [I], Z ₁ and Z ₃ each represent a nonmetallic atomic group necessary for forming a benzothiazole nucleus, a benzoxazole nucleus, a naphthothiazole nucleus, and a naphthoxazole nucleus which may have a substituent. The substituent includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms.

R ₁ and R ₂ are each a saturated or unsaturated aliphatic group, for example, a methyl group, an ethyl group, a 2-hydroxyethyl group,
-Methoxyethyl group, 2-acetoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobunyl group,
There are 4-sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group, p-sulfophenethyl group, n-propyl group, isopropyl group, n-butyl group and the like.

R ₅ and R ₆ each represent an alkyl group which may have a substituent, particularly an alkyl group having 1 to 12 carbon atoms, an alkoxycarbonylalkyl group which may have a substituent (for example, methoxycarbonylmethyl group, ethoxy An optionally substituted allyl group (eg, phenyl group, m-tolyl group, p-tolyl group, m-chlorophenyl group, p-chlorophenyl group, alkoxy group having 1 to 4 carbon atoms) And R ₇ is an alkyl group which may have a substituent, particularly an alkyl group having 1 to 12 carbon atoms, an allyl group, particularly 6 to 10 carbon atoms.
Allyl group, alkoxycarbonyl group, especially having 1 to 1 carbon atoms
Represents an alkoxycarbonyl group having 4 alkoxy groups.

In the general formula [Ib], R ₈ represents a hydrogen atom or a methyl group, R ₉ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a monocyclic allyl group.

X ^- is an anion such as chlorine ion, bromine ion, iodine ion, perchlorate, benzenesulfonate, p- toluenesulfonate, methylsulfate, ethylsulfate, tetrafluoroethane borate.

Next, typical specific examples of the compound represented by the general formula [I] will be described.

4 The amount of the compound represented by the general formula [I] of the present invention to be used is preferably 0.003 g to 0.3 g, more preferably 0.005 g to 0.15 g, per mol of silver halide.

Incidentally, these compounds represented by the general formula [I] of the present invention,
It can be easily synthesized according to the methods described in U.S. Pat. Nos. 2,734,900, 3,482,978, and 3,758,461.

The compound of the present invention represented by the general formula [I] can be directly dispersed in an emulsion. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a complex solvent thereof, and added to the emulsion in the form of a solution. It is also possible to mix with a solvent using ultrasonic waves. Further, as a method for adding the compound of the present invention, as described in the specification of U.S. Pat.No. 3,469,987, the compound is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and the dispersion is dispersed in an emulsion. Method of adding to the inside, Tokiko 46
A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it as described in -24185 and adding the dispersion to an emulsion, as described in U.S. Pat. A method in which a dye is dissolved in an emulsion, and the solution is added to the emulsion, as described in JP-A-51-74624. As described in JP-A-50-80826, a method of dissolving a dye in an acid substantially free of water and adding the solution to an emulsion is used. Other additions to emulsions include U.S. Pat.Nos. 2,912,343, 3,342,605, and 2,986,28
Nos. 7, 3,429,935 and the like can also be used.

The compound represented by the general formula [I] of the present invention may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support. Of course, it can also be dispersed.

Next, the polyethylene oxide compound represented by the following general formula [II] to be contained in the layer on the same side as the silver halide emulsion layer spectrally sensitized by the above general formula [I] will be described.

General formula (II) (Wherein, R ¹⁰ represents an alkoxy group or an alkyl group having 1 to 5 carbon atoms, or an aryl group, and R ¹¹ represents an alkylene group or a divalent aromatic group having 2 to 5 carbon atoms, a, b , c, d, e are integers, and a + e is 5-7
0, b + d is 5 to 50, and c is 0 to 30. Incidentally, specific examples of the compound represented by the general formula [II] include those shown in the following table.

The polyethylene oxide compound of the present invention represented by the general formula (II) is a polyethylene glycol, a polypropylene glycol, a polyol such as a polyoxytetramethylene polymer, an aliphatic alcohol, an aromatic alcohol,
It can be synthesized by dehydrating and condensing aliphatic mercaptan, ethylene oxide, propylene oxide and the like.

In order to incorporate the polyethylene oxide compound of the present invention, the polyethylene oxide compound of the present invention is dissolved in water, an organic solvent miscible with water, or a mixture thereof to form a silver halide emulsion layer and / or an adjacent layer thereof. May be added to a coating solution for forming a silver halide emulsion layer, and particularly preferably to a coating solution for forming a silver halide emulsion layer.

The addition amount of the polyethylene oxide compound of the present invention,
10 mg to 5 g is preferable per 1 mol of silver halide, especially 100 m
g to 2 g are preferred.

The timing of adding the polyethylene oxide compound of the present invention can be selected at any time during the process of producing a light-sensitive material. For example, when the polyethylene oxide compound is added to a silver halide emulsion layer, it is added after chemical ripening. Is preferred.

In the present invention, on one side of the support, the average particle size is
An emulsion layer of light-sensitive silver halide grains of 0.1 μm to 1.0 μm, preferably 0.05 μm to 0.3 μm is provided.

Here, the average particle diameter indicates the diameter of a spherical particle when its diameter is converted into a circular image of the same area when the projected image is converted into a circular image of the same area.

It is preferable that 60% or more of the total number of particles have a particle size in the range of ± 10% of the average particle size.

In the silver halide emulsion used in the present invention, silver halides such as those commonly used in silver halide emulsions such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride are used. Any silver halide may be used, but silver halides containing silver iodide, such as silver iodochloride, silver iodobromide, silver iodobromochloride, and particularly silver iodobromide are preferred. Incidentally, AgI is preferably in the range of 0.5 to 10 mol%.

The silver halide grains used in the silver halide emulsion are:
The grains may have a uniform silver halide composition distribution within the grains, or may be core / shell grains having different silver halide compositions between the inside of the grains and the surface layer.

The silver halide grains used in the silver halide emulsion are:
The particles may be such that the latent image is mainly formed on the surface, or may be the particles that are mainly formed inside the particle.

The silver halide grains used in the silver halide emulsion are:
It may have a regular crystal form such as a cube, an octahedron, or a tetrahedron, or may have an irregular crystal form such as a sphere or a plate.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be used as a mixture.

Silver halide emulsions, for example, British Patent No. 618,061,
1,315,755, 1,396,696, JP-B-44-15748,
U.S. Patent Nos. 1,574,944, 1,623,499, 1,673,522
No. 2,278,947, 2,399,083, 2,410,689,
No. 2,419,974, No. 2,448,060, No. 2,487,850, No. 2,5
18,698, 2,521,926, 2,642,361, 2,694,63
No. 7, 2,728,668, 2,739,060, 2,743,182,
No. 2,743,183, No. 2,983,609, No. 2,983,610, No. 3,0
21,215, 3,026,203, 3,297,446, 3,297,44
No. 7, 3,361,564, 3,411,914, 3,554,757,
3,565,631, 3,565,633, 3,591,385, 3,6
56,955, 3,761,267, 3,772,031, 3,857,71
No. 1, 3,891,446, 3,901,714, 3,904,415,
3,930,867, 3,984,249, 4,054,457, 4,0
67,740, Research Disclosure
closure) 12008, 13452, 13654, Theory of the Photographic Process (THJa
The Theory of the Photographic Process.4th.E by mes
d. Macmillan. 1977) It is preferable to sensitize using a chemical sensitizer or a sensitization method described in pp. 67 to 76 and the like.

The silver halide emulsion used in the light-sensitive material according to the present invention is one which is chemically sensitized to a required wavelength region using the dye represented by the general formula [I]. The emulsion may contain a supersensitizer which is a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye.

The silver halide emulsion used in the present invention is subjected to chemical ripening for the purpose of preventing fogging during the production process, storage, or photographic processing of the light-sensitive material, or for maintaining photographic performance stably, and at the end of chemical ripening. And / or after the completion of chemical ripening and before coating the silver halide emulsion, compounds known as antifoggants or stabilizers in the photographic industry can be added.

In addition, various photographic additives such as gelatin plasticizers, hardeners, surfactants, image stabilizers, ultraviolet absorbers, antioxidants, etc. may be added to all the hydrophilic colloid layers of the light-sensitive material used in the present invention, if necessary. Stain agents, pH adjusters, antioxidants, antistatic agents, thickeners, granularity improvers, dyes, morphants, brighteners, development speed adjusters, matting agents, etc., within the range where the effects of the present invention are not impaired Can be used within.

Examples of the hardener include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-
Methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxy dioxane, etc.), active halogen compounds (2,4-
Dichlor-6-hydroxy-3-triazine, etc.) and mucohalic acids (mucochloric acid, mucophenoxycyclolic acid, etc.) are used, and vinyl sulfone hardeners are preferably used.

The vinyl sulfone hardener is a compound having a vinyl group bonded to a sulfonyl group or a group capable of forming a vinyl group, and preferably has at least two vinyl groups bonded to a sulfonyl group or a group capable of forming a vinyl group. Is a compound having For example, a compound represented by the following general formula [VS-I] is preferably used.

Formula [VS-I] L- (SO ₂ -X) m In formula [VS-I], L is an m-valent linking group, X is -CH = CH ₂ or -CH ₂ CH ₂ Y And Y represents a salt capable of leaving in the form of HY by chlorine, for example, a halogen atom, a sulfonyloxy group, a sulfooxy group (including a salt), a tertiary amino residue, and the like.

m represents an integer of 2 to 10, and when m is 2 or more, -SO _2-
Xs may be the same or different from each other.

The m-valent linking group L is, for example, an aliphatic hydrocarbon group (for example, alkylene, alkylidene, alkylidine or the like or a group formed by combining them), an aromatic hydrocarbon group (for example, arylene or the like, -O-, -NR'- (R 'represents a hydrogen atom or an alkyl group having preferably 1 to 15 carbon atoms), -S-, -CO -, - SO -, - SO 2 - or -SO ₃ - in an m-valent group formed by combining one or more of the bond shown, they may include a -NR'- two or more R '
Combinations may combine to form a ring. The linking group L further comprises
Also includes those having a substituent such as a hydroxy group, an alkoxy group, a carbamoyl group, a sulfamoyl group, an alkyl group or an aryl group.

Examples of X, -CH = CH ₂ or -CH ₂ CH ₂ Cl and the like are preferable.

Hereinafter, typical specific examples of the vinyl sulfone hardener will be described.

_{VS- 1 H 2 C = CHSO 2} CH 2 SO 2 CH = CH 2 VS- 2 H 2 C = CHSO 2 (CH 2) 2 SO 2 CH = CH 2 VS- 3 H 2 C = CHSO 2 (CH 2) _{3 SO 2 CH = CH 2 VS-} 4 H 2 C = CHSO 2 CH 2 OCH 2 SO 2 CH = CH 2 VS- 5 H 2 C = CHSO 2 (CH 2) 2 O (CH 2) 2 SO 2 CH = CH ₂ VS− 8 H ₂ C = CHSO ₂ CH ₂ CONHCH ₂ NHCOSH ₂ SO ₂ CH = CH ₂ VS− 9 H ₂ C = CHSO ₂ CH ₂ CONH (CH ₂ ) ₂ NHCOCH ₂ SO ₂ CH = CH ₂ VS−10 H ₂ C = CHSO ₂ CH ₂ CONH (CH ₂ ) ₃ NHCOCH ₂ SO ₂ CH = CH _{2 VS-20 [(H 2 C} = CHSO 2) 3 CCH 2 SO 2 (CH 2) 2 SCH 2] 2 CO VS-22 (H ₂ C = CHSO ₂ CH ₂ ) ₄ C VS-24 (H ₂ C = CHSO ₂ CH ₂ ) ₃ CC ₂ H ₅ VS−30 H ₂ C = CHSO ₂ (CH ₂ ) ₂ SO ₂ (CH ₂ ) ₂ SO ₂ CH = CH ₂ VS−31 H ₂ C = CHSO ₂ (CH ₂ ) ₂ O (CH ₂ ) ₂ NHONH (CH ₂ ) ₂ O
(CH ₂ ) ₂ SO ₂ CH = CH ₂ VS−35 (H ₂ C = CHSO ₂ NH) ₂ CH ₂ VS−36 H ₂ C = CHSO ₂ (CH ₂ ) ₂ NH (CH ₂ ) ₂ NH (CH ₂ ) ₂ SO ₂ C
H = CH ₂ VS−41 C ₈ H ₁₇ C (CH ₂ SO ₂ CH = CH ₂ ) ₃ VS−44 CH ₂ (CONHCH ₂ SO ₂ CH = CH) ₂ VS-46 C (CO (CH 2) 2 SO 2 CH = CH 2) 4 VS-48 NH [(CH ₂ ) ₂ SO ₂ CH = CH ₂ ] ₂ VS-49 CH ₃ C (CH ₂ OCH ₂ SO ₂ CH = CH ₂ ) ₃ VS-50 C (C ₂ OCH ₂ SO ₂ CH = CH ₂ ) ₄ VS-51 N [(CH ₂ ) ₂ OCH ₂ SO ₂ CH = CH ₂ ] ₃ VS-52 (CH ₂ = CHSO ₂ CH ₂ ) ₃ CCHSO ₂ (CH ₂ ) ₂ Cl VS-53 H ₂ C = CHSO ₂ CH = CH ₂ VS−54 H ₂ C = CHSO ₂ CH ₂ C (CH ₂ SO ₂ CH ₂ CH ₂ OSO ₃ ⁻ Na ⁺ ) ₃ VS−55 CH ₃ SO ₃ (CH ₂ ) ₂ SO ₂ (CH ₂ ) ₂ OSO ₂ CH ₃ Vinyl sulfone hardeners used in the present invention include, for example, aromatic compounds described in German Patent No. 1,100,942 and U.S. Patent No. 3,490,911, JP-B-44-2962.
No. 2, No. 47-25373, No. 47-24259, etc., alkyl compounds linked by a hetero atom,
Sulfonamides and ester compounds described in 47-8736 and the like, and 1,3,5-tris [β- (vinylsulfonyl) -propionyl]-described in JP-A-49-24435 and the like. Hexahydro-s-triazine or alkyl compounds as described in JP-B-50-35807 and JP-A-51-44164, and compounds described in JP-A-59-18944 and the like are included.

These vinyl sulfone hardeners are dissolved in water or an organic solvent and added to a binder (eg, gelatin) in an amount of 0.001%.
It is used in an amount of 5 to 20% by weight, preferably 0.02 to 10% by weight.

For the addition to the photographic layer, a batch method or an in-line addition method is employed.

The layer in which these hardeners are added to the photographic layer is not particularly limited, and may be added, for example, to the uppermost layer, the lowermost layer, or all layers.

When a vinyl sulfone-based hardener is used in the light-sensitive material of the present invention and is treated with the developer of the present invention, so-called color contamination due to the dye remaining on the light-sensitive material after processing is reduced. Has few features.

Filter dyes or dyes used for various purposes such as prevention of irradiation include oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among them, oxanol dyes; hemioxanol dyes and merocyanine dyes are useful. Specific examples of the dye to be used are West German Patent No. 616,007, British Patent Nos. 584,609 and 1,177,429.
No., JP-B-26-7777, 39-22069, 54-38129
No., JP-A-48-85130, JP-A-49-99620, JP-A-49-114420
Nos. 49-129537, 50-28827, 52-108115
Nos. 57-185038; U.S. Pat.Nos. 1,878,961 and 1,88
4,035, 1,912,797, 2,098,891, 2,150,695
No. 2,274,782, 2,298,731, 2,409,612,
No. 2,461,484, No. 2,527,583, No. 2,533,472, No. 2,8
Nos. 65,752, 2,956,879, 3,094,418, 3,125,44
No. 8, No. 3,148,187, No. 3,177,078, No. 3,247,127,
3,260,601, 3,282,699, 3,409,433, 3,5
Nos. 40,887, 3,575,704, 3,653,905, 3,718,47
No. 2, 3,865,817, 4,070,352, 4,071,312,
Each specification No. PB Report 74,175, Photographic Abstract (Photo.Abstr.) Are those described in 1 28 ('21), and the like.

Further, a technique of improving the dimensional stability by incorporating a polymer latex in a silver halide emulsion layer and a backing layer can also be used.

Gelatin is used as a binder of the light-sensitive material used in the present invention. Examples of such binders include gelatin derivatives, cellulose derivatives, graft polymers of gelatin and other polymers, and other proteins, sugar derivatives, cellulose derivatives, and homo- or copolymers. A hydrophilic colloid such as a synthetic hydrophilic polymer can be used in combination.

The support used in the light-sensitive material of the present invention may be a flexible reflective support such as paper laminated with an α-olefin polymer (eg, polyethylene / butene copolymer) or the like, synthetic paper, cellulose acetate, cellulose nitrate, polystyrene. ,
Examples include films made of semi-synthetic or synthetic polymers such as polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, flexible supports having a reflective layer provided on these films, and metals.

 Among them, polyethylene terephthalate is particularly preferred.

The undercoat layer that can be used in the present invention is disclosed in
JP-A-49-11118, an undercoating layer in an organic solvent system containing polyhydroxybenzenes described in JP-A-49-3972, etc.
No. 52-104913, No. 59-19941, No. 59-19940, No. 59
-18945, 51-112326, 51-117617, 51-5
No. 8469, No. 51-114120, No. 51-121323, No. 51-1231
No. 29, No. 51-114121, No. 52-139320, No. 52-65422
Nos. 52-109923, 52-119919, 55-65949
And the aqueous latex undercoating layers described in JP-A Nos. 57-128332 and 59-19941.

Next, a developer for a silver halide photographic material containing the above general formulas [I] and [II] will be described.

In the present invention, a compound selected from the following group of 3-pyrazolidone compounds is used for the developer.

1-phenyl-5-methyl-3-pyrazolidone 1-phenyl-2-hydroxymethyl-4-methyl-3-pyrazolidone 1-phenyl-5,5-dimethyl-3-pyrazolidone 1-phenyl-2-morpholinomethyl- 4-methyl-3-pyrazolidone 1-phenyl-2-morpholinomethyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone 1-p-tolyl-4,4- Dihydroxymethyl-3-
Pyralidone 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrrolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-2-hydroxy-4,4-dimethyl-
3-Pyrazolidone The developing agent used in the development of the silver halide photographic light-sensitive material according to the present invention is as described above, but the developing solution used in the development contains, as a preservative, for example, sodium sulfite,
Even if a sulfite such as potassium sulfite is used, the effect of the present invention is not impaired. Hydroxylamine and hydrazide compounds can also be used as preservatives. In this case, the amount used is preferably 5 to 500 g, more preferably 20 to 200 g per developer.

The developing solution may contain glycols as an organic solvent. Examples of such glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol, and 1,5-pentanediol. However, diethylene glycol is preferably used. The preferred usage of these glycols is 5 to 500 g per developer.
More preferably, it is 20 to 200 g. These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material according to the present invention can be subjected to a development treatment using a developer containing a development inhibitor, whereby an extremely excellent light-sensitive material can be obtained.

The silver halide photographic material according to the present invention can be processed under various conditions. As for the processing temperature, for example, the developing temperature is preferably 50 ° C. or lower, particularly preferably about 25 ° C. to 45 ° C., and the developing time is 9 to 50 seconds, but less than 20 seconds, for example.
It is effective even when ultra-rapid processing of less than 19 seconds is performed.

Processing steps other than development, such as washing, stopping, stabilizing,
It is optional to employ steps such as fixing and, if necessary, forehardening and neutralization, and these steps may be omitted as appropriate.

In addition, the present invention exhibits a great advantage even when ultra-rapid processing such as a processing time of 20 to 60 seconds is applied. The ultra-rapid processing referred to in this specification means that the leading edge of the film is inserted into the automatic developing machine and then passed through a developing tank, a transfer section, a fixing tank, a transfer section, a washing tank, a transfer section, and a drying section. Is the total time it takes to come out of the dry area (in other words, the quotient obtained by dividing the total length of the processing line by the line transport speed is
A process that is between 20 seconds and 60 seconds. Here, the reason why the time of the transition portion should be included is well known in the art. However, since the liquid of the previous process swells in the gelatin film also at the transition portion, it is substantially treated. This is because the process can be regarded as progressing.

〔Example〕

Hereinafter, the present invention will be further described with reference to Examples, but it goes without saying that the present invention is not limited to these Examples.

Example 1 A solution containing 0.5 mol of ammonium silver nitrate while stirring a solution 1 containing 130 g of potassium bromide, 2.5 g of potassium iodide, 30 mg of 1-phenyl-5-mercaptotetrazole and 15 g of gelatin at 40 ° C. 500 ml was added in 1 minute and 2 minutes after the addition, acetic acid was added to bring the pH to 6.0.

One minute later, 500 ml of a liquid containing 0.5 mol of silver nitrate was added over 1 minute, and after stirring for 15 minutes, an aqueous solution of formalin condensate of sodium naphthalenesulfonate and magnesium sulfate was added to coagulate the emulsion. After removing the supernatant, warm water at 40 ° C
After stirring for 10 minutes, an aqueous solution of magnesium sulfate was added again to coagulate the emulsion. After removing the supernatant, 300 ml of a 5% gelatin solution was added, and the mixture was stirred at 55 ° C. for 30 minutes to form an emulsion. This emulsion has an average grain size of 0.40 μm, and 0.2 μm to 0.7 μm.
m contained 90% of the total number of particles.

Next, ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added to the emulsion to perform gold-sulfur sensitization.

To the resulting emulsion, a compound represented by the general formula [I] as shown in Table 1 was added as a sensitizing dye, and 4-hydroxy-6 was further added.
1.0 g of -methyl-1,3,3a, 7-tetrazaindene was added per mole of silver halide.

On the other hand, a backing layer solution containing 400 g of gelatin, 2 g of polymethyl methacrylate, 6 g of sodium dodecylbenzenesulfonate, 20 g of the following antihalation dye, and glyoxal was prepared as a solution for forming the backing layer. Then, the copolymer aqueous dispersion obtained by diluting a copolymer comprising three kinds of monomers of glycidyl methacrylate 50% by weight, methyl acrylate 10% by weight, and butyl methacrylate 40% by weight so as to have a concentration of 10% by weight was thinned. On one side of a polyethylene terephthalate base applied as a liquid, the above-mentioned backing layer liquid was applied together with a protective layer liquid consisting of gelatin, a matting agent, glyoxal, and sodium dodecylbenzenesulfonate, to form a backed support. I got Coating amount 2.5 g / m ² the backing layer and the protective layer as respective amounts with gelatin, 2.0 g / m ^2.

(Antihalation dye)

The coating solution and the protective layer solution described below were applied to the backed support prepared as described above to obtain a coated sample.

In addition, the following compounds as protective layer additives per 1 g of gelatin, C ₈ F ₁₇ SO ₃ K 5 mg 7 mg of a matting agent composed of silica having an average particle diameter of 7 μm, 70 mg of colloidal silica having an average particle diameter of 0.013 μm, 2 mg of sodium chloride, etc., and further, formaldehyde and glyoxal as hardening agents were added.

Each layer was simultaneously coated on the backed support at a coating speed of 60 m / min by a slide hopper method to form a silver halide emulsion layer and a protective layer in order from the support, thereby obtaining a sample.
The amount of silver is 2.5 g / m ² , the amount of gelatin is 3 g / m ^{2 for} the emulsion layer,
It was 1.3 g / m ² .

In addition, in the sample Nos. 10 and 11 in Table 1, the compound of the general formula [II] was added to the protective layer.

[Preparation of coating sample]

As emulsion additives, 10 g of trimethylolpropane, 50 mg of nitrophenyl-triphenylphosphonium chloride, 1 g of ammonium 1,3-dihydroxybenzene-4-sulfonate, 1 g of 2-mercaptobenzimidazole-5 per mole of silver halide were used. Sodium sulfonate 10mg, 1,1-dimethylol-1-bromo-1-nitromethane 1
0mg, And a compound of the general formula [II] as shown in Table 1 at the end to prepare an emulsion coating solution.

Evaluation of Coated Sample After the obtained sample was stored in an atmosphere of 23 ° C. and 55% RH for 3 days to stabilize the hardened film, 100,000 minutes per pixel (100 μm ² ) using a semiconductor laser emitting at 800 nm. Exposure with changing the amount of light in 1 second, automatic processing machine for X-ray manufactured by Konica Corporation (trade name: Konica X-ray automatic developing machine SRX-50)
In 1), processing was performed with a total processing time of 45 seconds.

The processing was performed at 35 ° C. using the following five types of processing solutions A to E and the following fixing solutions.

(Adjustment of developer)

 Developers A to E were prepared with the following compositions.

For each sample after development, fog and sensitivity were evaluated.

The sensitivity was determined by the common logarithm of the reciprocal of the amount of exposure required to give a density of “fog +1.0”, and the sensitivity when developing with the developing solution of Sample No. A was 100. It was shown as a relative value.

The silver tone of the sample after development was also evaluated with this sample. 1 was no problem at all, 5 was strong yellow and did not endure the image, and was evaluated on a five-point scale.

 Table 1 shows the above results.

As is clear from Table 1, the present invention is excellent in fog and sensitivity, and has no problem with the silver tone after development.

Example-2 The coating samples Nos. 1, 3, and 6 obtained in Example 1 were
16,17.

Also, the hardening agent of the emulsion protective layer is only glyoxal,
Other than that, coating samples were prepared in the same manner as Sample Nos. 15 to 17, and were named Nos. 18, 19, and 20.

Further, the hardening agents for the emulsion protective layer, the backing layer, and the backing protective layer were vinyl sulfone-based hardeners shown in Table 2, and the other coating samples were prepared in the same manner as in Sample Nos. 15, 16, and 17. Create and No.
21 to 30.

The obtained sample was evaluated for fog, sensitivity and silver tone in the same manner as in Example-1. The sensitivity is represented by a relative sensitivity, where the sensitivity when Sample No. 15 is treated with the developing solution A is 100.

In addition, as an evaluation of color contamination, each coated sample was treated without exposure to obtain a fog sample, and the sample was visually evaluated for the remaining state of the dye according to the following five grades.

 1; no color contamination is felt 2; slight but no problem 3; color contamination is confirmed but acceptable 4; color contamination occurs and cannot be used 5; color contamination is remarkable and cannot be used at all The developers used were A, C and D in Example 1.

 Table 2 shows these results.

As is clear from Table 2, the fog of the present invention is fogged,
It can be seen that the sensitivity is excellent, and there is no problem with silver tone and color contamination after development.

For material No. 22, vinyl sulfone-based hardeners were added to VS-11, VS-13, VS-25, VS-28, VS-29, VS-32,
When the evaluation was performed while changing to VS-38, VS-40, VS-53, VS-54, VS-55, and VS-56, the same effect was obtained for these samples.

Claims (1)

(57) [Claims] At least one photosensitive silver halide emulsion layer provided on a support contains at least one compound selected from the group consisting of compounds represented by the following general formula (I):
A silver halide photograph wherein at least one of the hydrophilic colloid layers on the same side as the photosensitive silver halide emulsion layer contains at least one selected from the group of compounds represented by the following general formula [II]: The photosensitive material comprises a compound selected from the group consisting of 3-pyrazolidone compounds represented by the following formula [III]:
A method for processing a silver halide photographic light-sensitive material, wherein the processing is performed with a developer containing 1.2 g / g or more. General formula [I] (In the general formula [I], Z ₁ and Z ₃ each represent a non-metallic atom group necessary for forming a benzothiazole nucleus, a benzoxazole nucleus, a naphthothiazole nucleus, or a naphthoxazole nucleus which may have a substituent. Z ₂ represents a 5- or 6-membered carbon atom ring, and R ₁ and R _{2 each} represent a saturated or unsaturated aliphatic group. (However, R ₅ and R ₆ represent an alkyl group which may have a substituent, an alkoxycarbonyl group or an allyl group, and R ₇ represents an alkyl group which may have a substituent, an allyl group or an alkoxycarbonyl group. Represents a group) or a hydrogen atom.
X ^- represents an anion. n represents 1 or 2 (however, 1 when an internal salt is formed). ) General formula [II] (In the general formula [II], R ₁₀ represents an alkoxy group having 1 to 5 carbon atoms, an alkyl group, or an aryl group; R ₁₁ represents an alkylene group having 2 to 5 carbon atoms or a divalent aromatic group; a, b,
c, d, and e are 5 to 70 for a + e, 5 to 50 for b + d, and 0 to 30 for c.
Represents an integer. ) Formula [III] 1-phenyl-5-methyl-3-pyrazolidone 1-phenyl-2-hydroxymethyl-4-methyl-3-pyrazolidone 1-phenyl-5,5-dimethyl-3-pyrazolidone 1-phenyl-2 -Morpholinomethyl-4-methyl-3-pyrazolidone 1-phenyl-2-morpholinomethyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone 1-p-tolyl -4,4-dihydroxymethyl-3-
Pyrazolidone 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 1-phenyl-4,4-dimethyl-3-pyrazolidone 1-phenyl-2-hydroxy-4,4-dimethyl-
3-pyrazolidone