JPH0255349A - Silver halide photographic sensitive material and image forming method using this material - Google Patents

Abstract

PURPOSE:To enhance the sensitivity, gamma, and green preservable property of the photosensitive material for an LED light source or He-Ne light source by using a prescribed high-sensitivity emulsion and adding a polyalkylene oxide and specific compd. thereto. CONSTITUTION:The silver halide emulsion layer of the photosensitive material uses the emulsion consisting of a monodisperse silver halide emulsion contg. 0.1-3mol% silver iodide and having <=20% dispersion coefft. The polyalkylene oxide (e.g. the compd. expressed by formula I) having >=1,500mol.wt. and the polyhydroxy benzene compd. (e.g. the compd. expressed by formula II) are added to the emulsion layer or the other hydrophilic colloidal layer. After this photosensitive material is subjected to imagewise exposing, the material is processed by a developing soln. contg. >=0.15mol/l sulfite and a silver halide solvent (A). An imidazole compd., amine compd., etc., are preferably used for the solvent A.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material for printing plate making using a laser or dLED as a light source. It is.

(Prior Art) In recent years, in the field of printing and plate making, one-sided scanner systems have been widely used, and among them, the mainstream has changed to one-sided dot generator systems that directly electrically form halftone dots or characters. Conventionally, a high-output argon laser has been used for this dot generator type scanner light source, but since this light source is bulky and expensive, recently it has been replaced with a compact and inexpensive helium-neon light source. (Al2. I nm
) Alternatively, various companies have developed dot generator type scanner devices using an LED light source (Al0 to Af0 nm). The photosensitive materials used in this scanner are required to have various characteristics.

In other words, it has high spectral sensitivity for each wavelength and 1 at high illuminance.
Since exposure is performed for 0-3 to 10-7 seconds, high sensitivity and contrast are required even under such conditions. Furthermore, in the facsimile field, priority is given to promptness, so it is necessary to withstand high temperature and rapid processing, and in terms of work efficiency, there is a need for safety against bright green safelights.

Silver halide emulsion sensitivity or When this is subjected to spectral sensitization, the spectral sensitivity needs to be high with high illuminance and short exposure. A method often used for this purpose is to increase emulsion sensitivity by introducing an iridium salt into silver halide, as described in JP-A-Shosan I-jOP/r, Ibid.
! -2//7j3, same t/-λyr3'y, same t/-2
It is described in 0/233, or in Japanese Patent Publication No. 4TT-Pco No. 17λ of the Showa era. Regarding spectral sensitizing dyes for obtaining red-sensitive emulsions in general, see Tokuko Shoda t-≠2772, ibid. ! -3 rig, Tokukai ShojO-A bow! No., same J Hiro-
/ is described in No. 726.

A monodisperse gold/sulfur sensitized silver iodobromide emulsion having a cubic or tetradecahedral crystal habit is widely known as a preferable emulsion for obtaining a red-sensitive emulsion.
No. 366, Patent Application No. 63-162j6, No. 43-6il
It is written in the l/ri issue.

However, when using a high-sensitivity silver iodobromide emulsion, there were problems in that the progress of the phenomenon was delayed, or that the sensitivity decreased or the tone became soft due to bromide ions that accumulated in the stock solution when a large amount of film was processed. .

In order to solve this problem, a method of introducing a polymer having a polyalkylene oxide group was proposed in Kentoku 74!24.
/-, but this method reduces sensitivity and fog (especially under high temperature and high humidity) when the film is stored for a long period of time.
) and a decrease in γ, there has been a desire for a silver halide light-sensitive material with high sensitivity and high contrast without any fluctuation in performance over natural aging.

Polymers having polyalkylene oxide groups are introduced into the halogen recording emulsion layer for various purposes, for example, in Japanese Patent Publications Sho≠3-r3λ, Japanese Patent Publication No. 4LP-Ko 36.2r, and J-147-3620. , same to-ii60 Kota issue, same to-ii 0-23230 issue, same! Court tr+2o, same JrJ
-37μ/! No., same jj-+2j727, same ♂-2
No. 71/≠λ, No. 61-λ904t'AI, U.S. Patent Department 331jt7011, No. 3zriirr, No. 3! !
227th issue, 374' Otsu! Hiroj, British special fIf//
It is described in No. 4J7, etc. On the other hand, polyhydroxybenzene compounds are described in JP-A No. 06+22,
Bu-7236, 6λ-27/G3, same tco, 2
6ri No. 737, etc.

(Object of the invention) The first object of the invention is to use an LED light source or a He-Ne light source.
Highly sensitive and hard for laser light sources! The purpose of the present invention is to provide a J1 silver halide photographic material.

A second object of the present invention is to provide a silver halide photographic material that exhibits little decrease in sensitivity and r even when the pH decreases or the bromide ion concentration increases due to processing of a large amount of film. be.

The third object of the present invention is that even if the film is stored for a long time (
It is an object of the present invention to provide a silver halide photographic material that exhibits little fluctuation in sensitivity and fog (especially under high temperature and high humidity conditions).

(Structure of the Invention) The above object of the present invention is to have at least one silver halide emulsion layer on a support, and the silver halide emulsion has a
．． In a silver halide photographic light-sensitive material comprising monodispersed silver halide grains containing 1 mol/3 mol of silver iodide and having a dispersion coefficient of 10 or less, the emulsion layer or other hydrophilic colloid layer contains molecular weights i, zoo. This has been achieved by a silver halide photographic material containing the above polyalkylene oxide compound and polyhydroxybenzene derivative.

The silver halide emulsion used in the present invention will be explained in detail.

The silver halide grains according to the present invention are silver iodobromide or silver iodochlorobromide, and the average silver iodide content is 0°/mo1% to
J, 0 m01 (lb), more preferably 0.
j~λmo1%.

Preferred silver halide grains in the present invention are grains having a core/shell structure, and the average silver iodide content in the core portion is preferably higher than the silver iodide content in the shell portion.

The difference in silver iodide content between the core and shell is 3 molt or more,
Especially from 3! Morti is preferred.

The ratio (mole ratio) of the amount of silver in the core part and the shell part is 1 for the shell to 1 for the core, especially 3! It is preferable that

The shape of the silver halide grains according to the present invention may be, for example, cubic, octahedral, dodecahedral, plate-like, or spherical, but cubic and dodecahedral are preferred.

The size distribution of silver halide grains in the present invention is a monodisperse silver halide emulsion with a coefficient of variation of 20% or less, particularly preferably /j- or less.

Here, the coefficient of variation is is defined as

Photographic emulsion #iP used in the present invention, Glafkid
Chimie at Physique Pho by es
tographique (Paul Monte 1, 1947), G, F.

Duffin llFPhotographjc Em
ulsion Chemistry (The Foca
Press, 1946), V, L, Zel
Written by ikman et alMak1ng and Co
ating Photographic Emulaio
n (Published by The Focal Press, /ri6da9
It can be prepared using the method described in 2010).

That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the formation of the reaction between the soluble silver salt and the soluble halogen salt may be performed using any of the one-sided mixing method, simultaneous mixing method, and a combination thereof. good.

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, a so-called Chondral double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In addition, in order to make the particle size uniform, British patent i,
s3r, oit issue, special public show ψr-34rri θ, same! 2-
/GjAII, a method of changing the addition rate of silver nitrate or alkali halide depending on the grain growth rate, British Patent No. 4t, 2412, 4A4tj, JP-A-13-1973-31/2≠ It is preferable to use a method of changing the concentration of an aqueous solution as described in the above, and to grow rapidly within a range that does not exceed the critical saturation level.

In addition, in the case of tabular grains,
It is preferable to use particles having a uniform particle size and/or thickness as described in Japanese Patent Application No. 14, Japanese Patent Application No. 67-≠ryro, Japanese Patent Application No. 111, Japanese Patent Application No. 1987-1-2, and the like.

In addition, known methods can be used for producing core/shell emulsions; for example, Japanese Patent Publication No. 2/417
No., Tokukai Akira! /-3ri No. 0.27, same j reference-//112
No. 3, same ll-101j21r, same! ter 2 octopus ≠ 3
No., J Turf No. 2237, No. J Turf 11jlIr, No. 6? -//J64<No. 3, jterl≠ri3≠≠, etc. can be referred to.

In the process of silver halide grain formation or physical ripening, it is preferred that cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or iron complex salts, etc. coexist.

In particular, iridium salts have a remarkable effect on increasing sensitivity, increasing contrast, and improving the progression of playability. The preferred range is l×70-8~/
X/0-6-E: ni/mol of silver, and in the present invention, it can be added to the threads of the core and shell or both.

Examples of the silver halide solvent used in the present invention include U.S. Pat. ! 31. ko r
No. y, No. 3. ! 7μ, Otsu- is written in the item, etc. (a)
Organic thioethers, Tokukaisho! 3-l Cog or No., same!
! (b) thiourea derivative described in -777J7,
(e) silver halide solvents having oxygen or carbonyl groups as described in JP-A-13-1007/P; (d) imidazoles as described in JP-A-1007/7; e) Sulfites (f) Thiocyanates.

Among these, thioethers are particularly preferred.

Specific compounds are shown below.

CH2-NHCOC) [2CH2COBCH2-8-C
H2CH2SC2H.

HO-(OH2)2-8-(CH2)2-8-(CH2
)2-OH The silver halide emulsions of the present invention are preferably gold sensitized and sulfur sensitized.

Gold sensitizers used in the present invention include various gold salts, such as potassium chlorooleite, potassium auric thiocyanate, potassium chlorooleate, and auric trichloride.

Specific examples are described in US Patent No. 23 Tata 013 and US Pat.

As the sulfur sensitizer used in the present invention, in addition to the sulfur compounds contained in gelatin, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines, etc. can be used.

Specific examples include US Pat.

J7r, F4'7, same a, uio, try, same J
, 7Jr, jJf, No. 313, J, 4jj, No. 55.

Preferred sulfur compounds are thiosulfates and thiourea compounds.

The preferred amount of the sulfur sensitizer and gold sensitizer added is from io-2 to 10-7 mol, more preferably from 0-3 to 0-5 mol. .

The molar ratio of sulfur sensitizer to gold sensitizer is 1:3 to 3:1.
and preferably Fil:, 2 to Conil.

In the present invention, in addition to gold sensitization, other noble metals, such as complex salts of platinum, palladium, iridium, etc., may be contained.

In the present invention, a reduction sensitization method can be used.

As the reduction sensitizer, stannous salts, amines, formamidine sulfinic acid, silane compounds, etc. can be used.

The polyalkylene oxide compound used in the present invention is an alkylene oxide having 2 to ≠ carbon atoms, such as ethylene oxide, propylene-7,2-oxide, butylene-/, 2-oxide, etc., preferably at least a JO unit of ethylene oxide. Polyalkylene oxide consisting of water, aliphatic alcohol, aromatic alcohol,
It includes condensates with compounds having at least 7 aqueous hydrogen atoms such as fatty acids, organic amines, and hexitol derivatives, and block copolymers of two or more types of polyalkylene oxides. That is, examples of polyalkylene oxide compounds include polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers (alkylaryl), ethers, polyalkylene glycol esters, polyalkylene/glycol fatty acid amides, and polyalkylene glycol amide 7fA. Polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, and the like can be used. It is necessary that the molecular weight is /yo00 or more.

The number of polyalkylene oxides is not limited to one, but may be two or more in the molecule. In that case, the individual polyalkylene oxides are less than 10 7 /l/*L/
The total number of fullylene oxide units in the molecule must be at least 30. When there is more than one polyalkylene oxide in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention preferably has a concentration of 10 or more.
It contains alkylene oxide units up to O.

Specific examples of the polyalkylene oxide compounds used in the present invention are as follows.

Polyalkylene oxide compound example 1-t HO(CH2CH20)40H1-J
HO(CH2CH20)66H(-3HO(CH2
CH20)□5s)11-p HO(CH2CH2
0)2(10H1-z C1aH30(CH2CH
20) 100H1-A C3H17CH==CHC
6H160(CH2CH20)45H■-//I啼子1-/j 1-/ 三C11H23COO(CH2CH20)8oHC11H
23C00(CH2CH20)50α:'ttHz3C
11H23CONH (CH2CH20) 45H1-/j 1-/ buC14H29N(CH2) (CH20H20) 44
H! -27 1-/7 H(CH2CH20) a(CH2H20) b(CH=
CH, O) cHH3 a +b -1-c = 70 b:a-)c=/O: ri b=ta + c = j.

! -7F I-coO HO(CH2CH20), (CH,CH2CH2CC
H2CH2CH20)b(CcHh+c=JO, b=/
Da, etc. JP-A No. 10-114 Hiroshi 23, JP-A No. 1989-114, JP-A No. 114-01
The polyalkylene oxide compounds described in No. 130 and JP-A No. 33-3217 can be used.

These polyalkylene oxide compounds may be used alone or in combination of two or more.

When these polyalkylene oxide compounds are added to a silver halide emulsion, they are dissolved in an aqueous solution of an appropriate concentration or in a low boiling point organic solvent that is miscible with water.
It can be added to the emulsion at an appropriate time before coating, preferably after chemical ripening. It may be added to non-photosensitive hydrophilic colloid layers, such as intermediate layers, protective layers, filter layers, etc., instead of being added to the emulsion. Further, these compounds may be included in the treatment liquid.

The usage amount of these polyalkylene oxides is rmg~jgs, especially 10mg~/7 square meters.
It is preferable that it is g.

The polyhydrobenzene compound introduced into the photographic material of the present invention is preferably a compound having one of the following structures.

X and Y are -H, -OH, halogen atom -0M (
Md alkali metal ion, -alkyl group, phenyl group, amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated alkyl group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group, carboxyalkyl group, carboxy An amino group, a hydroxyphenyl group, a hydroxyalkyl group, an alkyl ether group, an alkylphenyl group, an alkylthioether group, or a phenylthioether group.

More preferably, -H, -OH, α, -Br, -CO
OH, -CH2CH2COOH, -CH3, -CH2C
H3, -CH(CH3)2, -C(CHs)s, -0C
H3, -CHol-8O3Na, 5O3H.

-8CH3, A-(7) A-(8) A - (91 be. X and Y may be the same or different.

Particularly preferable representative compound examples are A-(1) A-(2) A-(3) A-frame A-(11) OH A-(4) A-(5) A-(6) A-α (A-α9 The substituent X1Y and the compound of the present invention are not limited to the above.

The polyhydroxybenzene compound of the present invention may be added to the emulsion layer of the sensitive material, or may be added to a layer other than the emulsion layer. The amount added is preferably in the range of 10-5 to 1 mol, and particularly effective in the range of 10-3 to 10-1 mol.

The light-sensitive silver halide emulsion of the present invention may be spectrally sensitized to relatively long wavelength blue light, green light, red light or infrared light using a sensitizing dye. As the sensitizing dye, cyanine dyes, merocyanine dyes, complex cyanine color L complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes, hemioxonol dyes, etc. can be used.

Useful sensitizing dyes for use in the present invention include, for example, R[! St
! ^RCII DISCLO3URI! ILes+
17 G 43 N -A section (December 1978 P, 2
3), LL@m Section 1831X (August 1979 P,
437) or in the literature published by Ogawa.

In particular, sensitizing dyes having spectral sensitivities that are compatible with the spectral characteristics of various scanner light sources can be advantageously selected.

For example, B) JP-A-50-62425 and JP-A-54-18726 for light sources for helium-neon leather;
For the trinuclear cyanine dyes shown in No. 5.9-102229, and C) for LED light sources,
No. 51-9609, No. 55-39818, thiacarbocyanines described in JP-A-62-284343, D) JP-A-59-Sho.
191032, tricaoorbocyanins described in JP-A-60-80841, JP-A-59-192242
Advantageously, dicarbocyanines containing a 4-quinoline nucleus as described in No.

Representative compounds of those sensitizing dyes are shown below.

Specific compound e of B) [In the formula, Y1 and Y are each a non-containing compound necessary to form a heterocycle such as a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring. Represents a group of metal atoms, and these heterocycles include lower argyl groups, alkoxy groups, hydroxy groups, and aryl groups.
, an alkoxycarbony group, or a halogen atom.

R represents an alkyl group having a lower alkyl group, a sulfo group, or a carboxy group, respectively.

R represents a lower alkyl group, and represents an X anion.

□, 1 represents 1 or 2.

, represents 1 or O, and represents yoO when it is an inner salt,
] Specifically (Cl1g) 5sOJ (CHt)ssO3e 6, n.

I]-5 I]-6 In particular, the combination with the above-mentioned C) sensitizing dye is preferable because it enables a high frequency range.

Specific compound of (CI+ri 5sch e C, 11°D) [)-1 xHs Ct If s These sensitizing dyes may be used alone or in combination. The combination is often used especially for the purpose of supersensitization.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are disclosed in Research Disclosure (Res.
volume 17 of 7
6 Ko 3 (published in February 2007), page 23, Section 5.

The photosensitive material of the present invention preferably contains a polymer represented by the following general formula (n).

General formula (II) +A+-(-B supply → C amount A: <silicary unit (monomer unit)) derived from an ethylenically unsaturated monocarboxylic acid or monocarboxylic acid salt copolymerizable with an ethylenically unsaturated monomer represents.

B: Represents a repeating unit derived from a polyfunctional crosslinking agent.

C: represents an ethylenically unsaturated monomer other than A and B.

X: J□~ioo Morchi Y20~! 0 Mortiz: O~! Examples of A in the QMorch general formula (It) include the following.

Examples of maleic acid and phthalic acid B include divinylbenzene, trivinylcyclohexane, trivinylbenzene, λ, 31j, 6-titrachloro7.4cm divinylbenzene, esters of unsaturated acids and unsaturated alcohols such as vinyl crotonate, allyl Methacrylate, allyl crotonate, esters of unsaturated acids and polyfunctional alcohols such as trimethylolpronon trimethacrylate, neopentyl glycol dimethacrylate, butanediol dimethacrylate 02
H-lylate, 1.6-hexanethiol-diacrylate, 1.5-pentanedio-diacrylate, pentaerythritol-triacrylate, tetraethylene glycol-diacrylate, triethane, lengelicol-diacrylate, unsaturated alcohol and polyfunctional esters with aqueous acids such as diethyl phthalate, unsaturated polyethers such as triethylene glycol-divinyl ether, or aqueous bisacrylamides such as methylene-bis-acrylamide, glyoxal-bis-acrylamide, N,N'-dihydroxyethylene-
Bis-acrylamide, N,N'ciscumine-bis-acrylamide, triacrylyl-diethylenetriamine, acrylic (or methacrylic) esters of polyethers such as polyethylene glycol-diacrylate (or dimethacrylate), divinyl sulfone, and the like.

Particularly preferred component B is divinylbenzene and diethylene glycol dimethacrylate.

Examples of component C include alkyl acrylate, alkyl methacrylate, ethylene, propylene, styrene, acrylamide, methacrylamide, and the like.

Next, specific examples of preferred acid polymers will be shown.

■-1) -+ CIl! -CIl-hn COOI+ ■-2) lh +C1h-C→1 COOII 0OH COOC11゜ Cll5 ■-5) +C11□CH-+TT -ecLcII 10 zHs CO□H "-9) ff-10) CIl.

(C-CIl,) C11゜x:y:z-64:9:27 (mol%) -11
) (C-CI1) L + CM-CI+□± x:y:z-60:10:30 (mol%)ff-1
, 3) x:)':z=64:11:25 (mol%) Synthesis examples of these acid polymers are given in JP-A-62-2.
20947.

The amount of these acid polymers used is 0.000000000000000000000000 per m2
The amount is preferably 0.01 to 10 g, particularly 0.2 to 3 g.

The silver halide emulsion layer is preferred as the place where these acid polymers are added, but other hydrophilic colloid layers may also be used.

The photosensitive material of the present invention preferably contains a polyhydroxybenzene compound, preferably a compound having one of the following structures.

Kill group, sulfonated amino group, sulfonated carbonyl group, carboxyphenyl group, carboxyalkyl group, carboxyamino group, hydroxyphenyl group, hydroxyalkyl group, alkyl ether group, alkylphenyl group,
It is an alkylthioether group or a phenylthioether group.

More preferably, -H, -OH, CI, -Br, -C
ooH, -CHz CHz CooHlCHx, C
Hz CH3, CH(CHs)1°C(CHs)a
, -0CHs , CHOlS Os Na , -
S Ox Hl-3CH,, X and Y are respectively -H,-
Examples include OH, halogen atom -OM (M is an alkali metal ion), -alkyl group, phenyl group, amino group, carbonyl group, sulfone group, sulfonated phenyl group, sulfonated Al, and the like. X and Y may be the same or different.

Particularly preferable representative compound examples include A −+11 A −+21 A −+31 A−■ 8−α罎i1 OH A −(71 il −Ql1 A −+81 OH A −(9) OH −QD OH Substitution of the present invention The groups X, Y and compounds are not limited to those described above.

The polyhydroxybenzene compound of the present invention may be added to the emulsion layer of the sensitive material or to a layer other than the emulsion layer, and the amount added is in the range of 10-' to 1 mol per mol. is effective, and a range of 10-3 mol to 1O-1 mol is particularly effective.

The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fogging or stabilizing photographic performance during the manufacturing process, storage, or photographic processing of the light-sensitive material. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles, mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes (particularly 4-hydroxy 1flA (1,3,3a,
7) Tetrazaindenes), penquazaindenes, etc.; benzenethiosulfonic acid, benzenesulfinic acid,
Many compounds known as anti-capri agents or stabilizers can be added, such as benzenesulfonic acid amides and the like.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include thixonol dye. , hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful.

For the purpose of increasing sensitivity, increasing contrast, or promoting development, the photographic emulsion layer of the photographic window optical material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and class ammonium salt compounds, urethane derivatives,
It may also contain developing agents such as urea derivatives, imidazole derivatives, 3-pyrazolidone aminophenols, and the like.

Among them, 3-pyrazolidones (1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hyroxymethyl-3-pyrazolidone, etc.) are preferred, and usually 5
g/rri and used below 0. 01-0.2
g/n? is more preferable.

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

For example, the active vinyl compounds (1,3,5-)lyacryloyl-hexahydro-S-triazine, bis(vinylsulfonyl)methyl ether, N,N-methylenebis-[β
-(vinylsulfonyl)propionamide], etc.), active halogen compounds (2゜4-dichloro-6-hydroxy-5-)riazine, etc.) (mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium salts 1 ((1
-morpholy)carbonyl-3-pyridinio)methanesulfonate, etc.), haloamidinium salts (1-(nichloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-41220,
53-57257, 59-16254.5, 60
Preferred are the active vinyl compounds described in US Pat. No. 3,325,287 and the active vinyl compounds described in US Pat.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol alkyl ethers, polyalkylene glycols) nonionic compounds such as alcohol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates anionic interfaces containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Active agents: Ampholytic surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amine oxides; Alkylamine salts, aliphatic or aromatic quaternary ammonium salts, pyridinium , heterocyclic quaternary ammonium salts such as imidazolium, and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocycles.

Further, it is preferable to use a fluorine-containing surfactant described in JP-A No. 60-80849 and the like for the antistatic barrel.

The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide, polymethyl methacrylate, etc. in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of dimensional stability. For example, a polymer containing as a monomer component alkyl (meth)acrylate, alkoxy acrylic (meth)acrylate, glycidyl (meth)acrylate, etc. alone or in combination, or a combination of these with acrylic acid, methacrylic acid, etc. is used. be able to.

Gelatin is advantageously used as a condensing agent or protective colloid in photographic emulsions, 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; hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of imidazole, polyvinylpyrazole, and the like.

As for gelatin, in addition to coal sample gelatin, acid-treated gelatin)
Chin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

The silver halide emulsion layer used in the present invention can contain a polymer latex such as an alkyl acrylate.

Supports for the photosensitive material of the present invention include cellulose triacetate, cellulose diacetate, nitrocellulose,
Polystyrene, polyethylene terrestrial paper, baryta coated paper, polyolefin coated paper, etc. can be used.

There are no particular restrictions on the developing agent used in the developer used in the present invention, but it preferably contains dihydroxybenzenes, and dihydroxybenzenes and 1-phenyl-3- A combination of birapritones or a combination of dihydroxybenzenes and p-aminophenols may also be used.

The dihydroxybenzene developing agent used in the present invention includes hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-
Examples include dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, and hydroquinone is particularly preferred.

As the developing agent for 1-niphenyl-3-pyrazolidone or its derivative used in the present invention, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4- Hydroxymethyl-3-birazolitone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5
-Methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone, 1-p-tolyl-4,4-dimethyl-3-pyrazolidone, 1-p-)
Examples include dil-4-methyl-4-hydroxymethyl-3-virapritone.

Examples of the p-aminophenol developing agent used in the present invention include N-methyl-p-aminophenol, p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, and N-(4-hydroxyphenyl)glycine. ,
There are 2-methyl-p-aminophenol-p-benzylaminophenol, among which N-methyl-p-aminephenol is preferred.

The developing agent is preferably used in an amount of usually 0.05 mol/E to 0.8 mol/Il. In addition, when using a combination of dihydroxybenzenes and 1-phenyl-3-pyrazolidones or p-amino-phenols, the former is reduced to 0.
．． 05 mol/f-0゜5 mol/1. Preferably, the latter is used in an amount of 0.06 mol/l or less.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite,
Examples include formaldehyde and sodium bisulfite. The sulfite is preferably 0.3 mol/l or more, especially 0.4 mol/l or more, and the upper limit is up to 2.5 mol/l, especially 1.
It is preferable to set it to 2 or less.

Alkaline agents used to set pH include pH moderators such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, tribasic sodium phosphate, tribasic potassium phosphate, sodium silicate, and potassium silicate. Contains buffering agent.

Additives used in addition to the above components include compounds such as boric acid and borax; development inhibitors such as sodium bromide, potassium bromide, and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosol; Like hexylene glycol, ethanol, and methanol! Organic solvent: l-phenyl! -Mercaptotetrazole, Komerkabutobenzimidazole! - It may contain an antifoggant such as a mercapto compound such as sulfonic acid sodium salt, an indazole compound such as j-nitroindazole, or a penttriazole compound such as j-methylbenttriazole. It may also contain formulation agents, surfactants, antifoaming agents, water softeners, hardeners, phenomenon accelerators, and the like.

Preferred compounds for the silver halide solvent used in the present invention are disclosed in JP-A-Sho! Amino compounds described in 6-/θtλhiro≠, imidazole compounds described in Japanese Patent Publication No. 4tI-374A23, US Pat. No. 3.27/.

Organic thioether compounds described in No. 117, JP-A-Sho! 3
-7≠Thiourea compound described in Kou 3/ri issue, JP-A-Sho re
-ioo'yi'i, and amine compounds, imidazole compounds, and thiocyanate compounds are particularly preferred.

Specific examples of preferred amine compounds and imidazole compounds are shown below.

Examples of amino compounds include J-(,2-aminoethylamino)ethanol, tetramethylammonium acetate, choline, choline chloride, hydroxylamine sulfate, triethanolamine, jetanolamine,
Trimethylamine, λ-diethylamine-7-ethanol, λ-methylamino/-ethanol, 3-dimethylamino-/1,2-propanediol, 3-diethylamino-/-zoO/e-nol,! -amino/-tanol, diethylamine, methylamine, triethylamine, dipropylamine, di-isopropylamine 7.3.
! '-Diaminodiprobylamine, 3-dimethylano/-furonosinol, hydantoic acid, allylamine, ethylamine, dimethylamine, ethylenediamine,
These include λ-dimethylaminoethanol, -monoethylamineethanol, and the like.

Examples of imidazole derivatives include imidazole, co-methylimidazole, ≠-methylimidazole, -, tadimethylimidazole, coethyl-≠-methylimidazole, co-amyl-imidazole, l-inamyl-λ
-Methylimidazole, ≠, j-dimethyl-imidazole, coethyl imidazo, l-methylimidazole, λ
,three.

! -Trimethylimidazole, goohydroxymethyl-
! -Methylimidazole, ≠-(cohydroxyethyl)-! -methylimidazole, /-7lylimidazole, /-vinylimidazole, etc.

The phenomenon liquid used in the present invention contains JP-A-Sho! as a silver stain preventive agent. The compound described in Buichi 2 Ko 74/L7, the compound described in (4I Kaisho tλ-colco, tzi No.) as a phenomenon unevenness preventive agent, the compound described in Patent Application No. 10/1974 as a solubilizing agent.
Compounds described in No. J can be used.

In the phenomenon liquid used in the present invention, a buffering agent is added.
Boric acid described in 7-λr7or, JP-A-10-1979 J4L
Saccharides (e.g. sucrose), oximes (e.g. acetoxime), phenols (e.g.
j-sulfosarcyl (1 ml), tertiary phosphate (eg, sodium salt, potassium salt), etc., and boric acid is preferably used.

The fixing solution is an aqueous solution containing, in addition to the fixing agent, a hardening agent (for example, an aqueous aluminum compound), acetic acid and a dibasic acid (for example, tartaric acid or a salt thereof), and preferably pHi, r or more, more preferably ≠,
0. J, has j'i.

Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The amount of fixing agent used can be changed as appropriate, and is generally about 0. /~approximately 1 lulu/l.

The water-soluble aluminum salt which mainly acts as a hardening agent in the fixing solution is a compound generally known as a hardening agent for acidic hardening fixing solutions, and includes, for example, aluminum chloride, aluminum sulfate, and potassium alum.

As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. These compounds are fixed in fixer/l
Those containing 0.00 j mol or more are effective, especially 0.00 j mol or more.
01morphtto.

0.3 mol/l is particularly effective.

Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate,
Ammonium potassium tartrate, etc.

Examples of citric acid or its derivatives that are effective in the present invention include citric acid, sodium citrate, and potassium citrate.

The fixing solution further contains preservatives (e.g., 4a salts, bisulfite salts), pH buffering agents (e.g., acetic acid, borium acetate, etc.), as desired.
, pH adjuster (e.g. ammonia, sulfuric acid), 1
Preservation improving agents (for example, potassium iodide) and chelating agents may be included. In Konin, the pH buffer is preferably /r, 2jf than to-4L09/11 because the pH of the developer is high.
/l is used.

The fixing temperature and time are the same as for developing, about 20"
C to about j00c and 10 seconds to 1 minute is preferred.

In addition, in the washing water, mold inhibitors (for example, the compounds described in Horiguchi's "Chemistry of Bacteria and Prevention", Japanese Patent Application No. 3107), washing accelerators (such as sulfites), chelates, etc. It may also contain agents such as agents.

According to the above method, the developed and fixed photographic material is washed with water and dried. Washing with water is carried out to almost completely remove silver salts dissolved during fixing, and is carried out at approximately 20°C to approximately IO'c.
Preferably, the time is 3 minutes.

Drying is carried out at about ao'c to about 1000C, and the drying time can be changed as appropriate depending on the surrounding conditions, but is usually about 3 seconds to 3 minutes and 30 seconds.

U.S. Patent 7.1 regarding roller conveyance type automatic developing machine
Specification No. 021779, Reference No. Jj? It is described in the specification of No. 77, etc.9, and is simply referred to as a roller conveyance type processor in this specification. A roller conveyance type processor consists of four steps: development, fixing, washing, and drying, and the method of the present invention also includes other steps (for example, a stopping step) II? Although not excluded, it is most preferable to follow these four steps. Here, in the water washing step, water can be saved by using a two to three stage countercurrent washing method.

The developing solution used in the present invention is a patent application made in 1973? -124,20
It is preferable to store it in a packaging material with low cable permeability as described in No. 0. Further, as the developer used in the present invention, the system described in Japanese Patent Application No. 1.0-232.4t7/1988 can be preferably used.

(Example 1) Emulsion A%B11141! ! Shita.

(Emulsionist) A mixed aqueous solution of potassium iodide and potassium bromide and a gelatin aqueous solution containing a silver nitrate aqueous solution'@i,r-dihydroxy-3,6-cythiaoctane were mixed with vigorous stirring at 7!0.
C/! The average particle size is O, ko! μ iodine content z Molch's monodisperse, octahedral silver iodobromide emulsion? Obtained. This silver iodobromide emulsion has 10-7 mol of 3I per mol of Ag as the core.
Potassium bromide aqueous solution and silver nitrate aqueous solution containing rc16
pAg=7. A core/shell silver iodobromide emulsion was obtained by adding it in a uniform manner. After desalting this emulsion according to a conventional method,
Add /, Yxio-5 moles of sodium thiosulfate and /, λ x 70' moles of chloroauric acid per mole of silver.
Chemical sensitization was performed for 70 minutes at 30°C. Hiro-hydroxy-6-methyl-/,3,33,7- as a stabilizer
/- solution of chitrazaindene at 30 tx per mole of silver
1, and finally the average silver iodide content /, j mole of 0
, 4cjttm monodisperse cubic emulsion (dispersion coefficient/(7%
), i got it.

(Emulsion B) Ag1 mole x10. ``Mole of 3 I rC1
6. Into a mixed aqueous solution of potassium iodide and potassium bromide containing all 6, 2i of a silver nitrate aqueous solution, and a gelatin aqueous solution containing r-dihydroxy-3,6-cythiaoctane, with vigorous stirring, 7
It was added at 00C for ≠Q minutes so that pAg=7°≠, and desalted, chemically sensitized, and stabilizers were added in the same manner as Emulsion A, and the average silver iodide content/! Morchi's o, 4LB
A monodisperse cubic emulsion (dispersion coefficient r) of tm was obtained.

The above spectral sensitizing dye (C-≠) was added to the above emulsion at 70 mf/f per mole of silver, and an anti-capri agent was added.
Phenyl! -Mercaptotetrazole and per mole of silver #) 2j da, hydroquinone/! O~/m2, polyethyl acrylate latex as a plasticizer, coj% of the total gelatin binder, the polyalkylene oxide compound of the present invention added as shown in Table 1, and λ-bis(vinylsulfonylacetamide)ethane klOW/ as a hardening agent. rn2,
Ko.

≠-dichloro-6-hydroxy-8-) riazine Hiroshi Om
9/m2 and ■-t acid polymer latex 200~
/ m” and Ginko-jt/ on the polyester support.
Ischemia was performed to reach m2. Gelatin is J, 197g1
It was 2.

On top of this, gelatin o, 7 y/m2, polymethyl methacrylate 60 with a particle size of 3 to 3 μm as a matting agent.
~/ns 2s Colloidal silica with particle size "~λomμ 70■/m", silicone oil 100■/m
The upper layer of the protective layer to which dodecylbenzenesulfonic acid (IJium salt) and the fluorine-based surfactant of the following structural formula 〇 were added as a coating aid, and ■ Cs F 1
7 S O2N-CH2C00K3H7 Gelatin 00t/m2, polyethyl acrylate latexco 25IQ/m2, dye of the above structural formula 100rny/m2, dye 200rQ/m2 and dotesylbenzenesulfone yl as a coating aid. vinegar)
A lower protective layer containing IJum was applied at the same time.

The base used in this example had a back layer and a pack protective layer having the following compositions.

(Back layer) Gelatin 3.2f/m 2 Sodium dodecylbenzenesulfonate Toda dye a
rosyb
30 da C/jOq) /, 3-divinylsulfonyl-2-propatol 10 da/m"Polyvinylbenzenesulfo/potassium acid 30 da/m"■ (Pack protective layer) Gelatin polymethyl methacrylate (particle size, 7μ ) Sodium dotecylbenzenesulfonate Fluorine surfactant (of the above compound) 7jf/m" 30~/, 2.20 da/.2.21!9/m" 603 people Silicone oil 100 da/m2 Photographic performance The obtained sample was exposed to xenon flash light with an emission time of 10-5 nm through an interference filter having a peak of t at f470 nm and a continuous wedge.

Fuji Photo Film automatic developing machine FG using developer Ak.
310 with ttON (:30 After development, fixer Lp-30
The sample was fixed using No. 15, washed with water, and dried for sensitometry.

Sensitivity is the reciprocal of the exposure amount given to the density J, Ok, and the relative sensitivity is shown in Table 7. (Photographic performance a) r is the characteristic curve,
Concentration 0. This is the slope of the straight line connecting the point J and the point 3.0.

The larger the value, the higher the contrast.

Evaluation of long-term storage stability Film f was left for j days at 10° C. and 70% relative humidity, and then processed under the same conditions as in the above evaluation of photographic performance. (Photographic performance b) (Example 7) Using the samples used in Example 1, 3, 3, 7, r, yt and developers 1 and 2 having the following compositions, Fuji Photo Film ■
automatic developing machine FG-44 (7N, 3j0CJ o//H
After B, fixing using fixing iLF-Jory2,
Furthermore, it was washed with water and dried, and sensitometry was performed. sensitivity,
γ and fog were determined in the same manner as in Example. The results are shown in Table 7 λ. As is clear from Table λ, the samples of the present invention showed a large increase in sensitivity and r, especially in the developer l containing a silver halide solvent (λ-methyl-imidazole).

(Example 3) After the 31r0C30'' phenomenon with the same FG-460F, the sample used in Example 3 was developed using developer 3 with the following composition.
Fix using fixer GR-Fl-, wash with water, dry, and then
Tometori one? and evaluated in the same way. The results are shown in Table 3. As is clear from the table, the samples of the present invention showed a large increase in sensitivity and .gamma., particularly in a developer containing a silver halide solvent (n-butylethanolamine).

(Adjust the pH to ii and t using all the potassium hydroxide.

) Procedural amendment

Claims (1)

[Scope of Claims] 1) having at least one silver halide emulsion layer on a support, the silver halide emulsion containing 0.1 mol% to 3 mol% silver iodide, and having a dispersion coefficient of 20 In a silver halide photographic light-sensitive material comprising monodispersed silver halide grains with a molecular weight of 1% or less, the emulsion layer or other hydrophilic colloid layer has a molecular weight of 1
, 500 or more of a polyalkylene oxide compound and a polyhydroxybenzene compound. 2) An image characterized by processing the silver halide photographic light-sensitive material according to claim 1 with a developer containing at least 0.15 mol/l of sulfite and a silver halide solvent after imagewise exposure. Formation method. 3) An image forming method characterized in that the silver halide solvent according to claim 2 is an imidazole compound, an amine compound, or a thiocyanate compound.