JPH0778608B2 - Silver halide photographic light-sensitive material for black and white - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a microfilm, particularly a COM (Computer Output).
The present invention relates to a micro film (hereinafter referred to as a COM film) used in a Microfilmer system, and particularly to a COM film that forms a positive silver image by reversal development processing.

(Prior art and its problems) As one of the methods of recording and storing a huge amount of information output from a computer at high speed and high density, a system using a so-called COM film is operating all over the world.

A film for COM generally has one or more negative type silver halide emulsion layers on a support, and after the film is imagewise exposed, a negative or positive image is formed by negative development processing or reversal development processing. .

The silver halide emulsion used for such purpose is generally designed to have a high microcontrast so that a microimage composed of a line drawing original can be recorded with high resolution.

In COM applications, high sensitivity is required due to the peculiarity of the light source (CRT), but conventional COM films have insufficient sensitivity.

On the other hand, generally, as a method of increasing the sensitivity of a silver halide photosensitive material, there is a method of increasing the size of silver halide grains, but increasing the grain size of silver halide lowers the resolution of a silver image obtained. Due to the use of microfilm, this reduction in resolution is a fatal drawback.

Therefore, the advent of a high-sensitivity and high-resolution microfilm for COM has been strongly desired.

(Object of the Invention) An object of the present invention is to provide a high-sensitivity and high-resolution COM film.

In particular, it is to provide a COM film capable of forming a positive image by reversal development processing and having high sensitivity and high resolution.

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a black and white silver halide photographic light-sensitive material for forming a positive image by reversal processing, which comprises at least one silver halide emulsion layer on a support. This is achieved by a silver halide photographic light-sensitive material for black and white, which contains a compound represented by the following general formula (I) in a layer or other hydrophilic colloid layer.

In the formula, R ₁ and R ₂ each represent a hydrogen atom or an aliphatic residue,
R ₁ and R ₂ may combine with each other to form a ring.

R ₃ represents a divalent aliphatic group.

M is a hydrogen atom, an alkali metal atom, an alkaline earth atom,
It represents a quaternary ammonium salt, a quaternary phosphonium salt or an amidino group.

Next, the general formula (I) will be described.

In the formula, R ¹ and R ² each represent a hydrogen atom or an aliphatic residue. The aliphatic residue may be an alkyl group having 1 to 12 carbon atoms, an alkenyl group, and an alkynyl group, each of which may be substituted with an appropriate group. As the alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, decyl group, dodecyl group, isopropyl group, sec butyl group,
For example, a cyclohexyl group. Examples of the alkenyl group include allyl group, 2-butenyl group, 2-hexenyl group and 2
An octenyl group and the like. Examples of the alkynyl group include a propargyl group and a 2-pentynyl group. Examples of the substituent include a phenyl group, a substituted phenyl group, an alkoxy group, an alkylthio group, a hydroxy group, a carboxyl group, a sulfo group, an alkylamino group and an amide group. When R ¹ and R ² form a ring, it is a 5- or 6-membered carbon ring or heterocycle consisting of a combination of carbon, nitrogen, and oxygen, for example, And so on. Preferred examples of R ¹ and R ² are a hydrogen atom and an alkyl group having 1 to 3 carbon atoms, and more preferably,
A hydrogen atom, a methyl group and an ethyl group.

The divalent aliphatic residue of R ³ is a saturated or unsaturated linear or branched aliphatic hydrocarbon group having 1 to 6 carbon atoms, for example,
_{-CH 2 -, - CH 2 CH} 2 -, - (CH 2) 3 -, - (CH 2) 4 -, - (CH 2) 6 -, - CH
₂ CH = CHCH _2- , -CH ₂ C ≡ CCH _2- , And so on. As more preferably R ³ in those 2 to 4 as a preferred number of carbon atoms in R ³ -CH ₂ CH ₂ - and -CH ₂ CH ₂ CH ₂ -
Is.

M is a hydrogen atom, an alkali metal [Na ⁺ , K ⁺ , Li ^+, etc.], an alkaline earth metal [Ca ⁺⁺ , Mg ^++, etc.], a quaternary ammonium salt [having 4 to 30 carbon atoms, for example, (CH ₃ ) ₄ N ⁺ , (C
₂ H ₅ ) ₄ N ⁺ , (C ₄ H ₉ ) ₄ N ⁺ , C ₆ H ₅ CH ₂ N ⁺ (CH ₃ ) ₃ , C ₁₆ H ₃₃ N ⁺ (CH ₃ ) ₃ etc.] Quaternary phosphonium salt 〔(C ₄ H ₉ ) ₄ P ⁺ , C ₁₆ H ₃₃ P ⁺ (C
Represent _{H 3) 3, C 6 H} 5 CH 2 P + (CH 3) 3 , etc.], or an amidino group.
Examples of the strong acid salt of the general formula (I) include hydrochloride, sulfate, p-toluenesulfonate, and methanesulfonate.

Next, among the compounds represented by the general formula (I), preferred examples are given.

(1) NH ₂ CH ₂ CH ₂ SH ・ HCl (2) (CH ₃ ) ₂ NCH ₂ CH ₂ SH ・ HCl (3) (CH ₃ CH ₂ ) ₂ NCH ₂ CH ₂ SH ・ HCl (4) (CH ₃ ) ₂ NCH ₂ CH ₂ CH ₂ SH ・ HCl (5) (CH ₃ CH ₂ ) ₂ NCH ₂ CH ₂ CH ₂ SH ・ HCl The compound represented by the general formula (I) may be added at the photosensitive emulsion layer and / or other hydrophilic colloid layer (eg, surface protective layer, intermediate layer, undercoat layer). It is particularly preferably an emulsion layer.

The addition amount of the compound represented by the general formula (I) is preferably 0.05 to 5 mg / m ² , and more preferably 0.1 to 1 mg / m ^2.
Is.

The compound represented by the general formula (I) is described in U.S. Pat. No. 3,893,
As described in No. 858 and No. 3,772,020, it is a compound known as a bleaching accelerator for color light-sensitive materials.
However, it was unexpected that the black and white light-sensitive material exhibited a sensitizing effect.

In particular, it was completely unexpected that the compound of formula (I) exerts a remarkable sensitizing effect in a COM film for reversal development processing.

As the silver halide grains used in the silver halide photographic material of the present invention, the following core / shell type is preferred.

i) The core is AgBr or AgBEI (I Is less than 0.5 mol%)
Nari Ciel is AgBrI (I Is 0.5 to 5 mol%).

ii) The core is AgBr or AgBrI (I Is less than 0.5 mol%)
And AgBrI (I Is 1 to 5 mol%)
The shell of AgBr or Ag on the outside of the shell.
BrI (I Has a second shell consisting of 0.5 mol% or less)
To do.

The total silver iodide content of the core / shell type grains of the present invention is preferably 0.5 to 5.0 mol%, more preferably 1.0 to 3.0 mol%, and the core / shell ratio (silver amount) is 1/1 to
The size is preferably from 1/2 to 6, and the size is preferably from 0.1 to 0.7 μm, particularly preferably from 0.2 to 0.4 μm. The shape of the particles is preferably tetradecahedral or cubic, and so-called monodisperse (dispersion coefficient 5 to 15%) is preferable.

The silver halide emulsion may be a so-called unprimitive emulsion which is not chemically sensitized, but it is usually chemically sensitized. For chemical sensitization, the above Glafkide
s or Zelikman et al. or edited by H. Frieser Die Grun
dlagen der Photographischen Prozesse mit Silberhal
The method described in ogenden, (Akademische Verlagsgesellschaft, 1968) can be used.

In other words, sulfur sensitization using compounds such as thio-soluble salts, thioureas, thiazoles, rhodanins and active gelatin, primary tin salts, amines, hydrazines, formamidine sulfinic acid, silane compounds, etc. In addition to the ring sensitization method used, gold complex salts, the periodic table of platinum, iridium, palladium, etc.
It can be used alone or in combination in a noble metal sensitization method using a complex salt of a Group VIII metal.

Further, for the purpose of increasing sensitivity, increasing contrast, or promoting development, for example, a thioether compound, thiomonufolin, quaternary ammonium salt compound, urethane derivative, urea derivative, imidazole derivative, 3-pyrazolidones and the like may be contained. For example, U.S. Patents 2,400,532 and 2,423,5
No. 49, No. 2,716,062, No. 3,617,280, No. 3,772,021
Nos. 3,808,003 and the like can be used.

In the present invention, it is advantageous to use gelatin as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric substances such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin oxygen-decomposite can also be used.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, coating aids, antistatic agents, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration,
Various known surfactants may be included for various purposes such as increasing contrast and sensitizing.

For example, saponins, glycidol derivatives (eg, alkenyl succinic acid polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, nonionic surfactants such as urethanes or ethers; triterpenoid saponins, alkylcarboxylic acids. Acid salts, alkylbenzene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N
Anionic surfactants such as alkyl taurines, sulfosuccinic acid esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine imides, Amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts,
Heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and cationic surfactants such as aliphatic or heterocycle-containing phosphonium or sulfonium salts can be used. A fluorine-containing surfactant is preferably used for the purpose of antistatic.

The photographic light-sensitive material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth)
Acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) Acrylate,
A polymer having a monomer component of a combination with sulfoalkyl (meth) acrylate, styrene sulfonic acid, or the like can be used.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers.
For example, chromium salts (chrome alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), Active vinyl compounds (1,3,5-triacryloyl-hexahydro-S-triazine, bis (vinylsulfonyl) methyl ether, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.) , Mucohalogen acids (mucochloric acid, mucophenoxycyclo acid, etc.), isoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, etc., can be used alone or in combination.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and the like. The dye used is a cyanine dye,
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. It is a particularly useful dye, a merocyanine dye, and a composite merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon rings fused to the nuclei of indolenin, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, benzimidazole A nucleus, a quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-2,
5- to 6-membered heterocyclic nuclei such as 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus and thiobarbituric acid nucleus can be applied.

In the light-sensitive material of the present invention, a water-soluble dye (such as an oxonol dye, a hemioxonol dye, a styryl dye, a merocyanine dye, a cyanine dye and an azo dye) is used as a filter dye in a hydrophilic colloid layer or for various purposes such as prevention of irradiation. May be included.

The silver halide photographic light-sensitive material of the present invention may contain a known antifoggant or stabilizer. Antifoggants or stabilizers that may be contained include mercaptos, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, aminotriazoles, benztriazoles, nitrobenzes. Triazoles, benzenethiosulfonic acids, benzenesulfinic acids, benzenesulfonic acid amides, azaindenes [eg triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes )〕and so on.

The silver halide photographic light-sensitive material of the present invention may have two or more silver halide emulsion layers, and may further have a surface present invention layer, an intermediate layer, an anti-halation layer, a back layer and the like. Good.

It is particularly preferable to have a gelatin layer containing no dye between the silver halide emulsion layer and the support.

In addition to gelatin, the gelatin layer may contain hydroquinone and its derivatives, resorcin, catechol, DIR-hydroquinones, etc.
It is preferably 0.5 to 1.5 μm.

The back layer of the light-sensitive material of the present invention preferably contains an antistatic agent, a matting agent and the like.

As the antistatic agent, conductive metal oxide fine particles (for example, SnO ₂ doped with antimony), fluorine-containing surfactant, conductive polymer and the like are preferable, and as the matting agent, PMMA or SiO _{2 having a} particle size of 1 to 10 μm is used. Are preferred.

The exposure for obtaining the photographic image in the present invention may be carried out by using a usual method. That is, any of various known light sources such as natural light (sunlight), tungsten lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, and cathode ray tube flying spot can be used. Exposure time is 1/1000 that is usually used in cameras
Of course one second exposure time from seconds shorter exposure than 1/1000 sec, for example 110 ⁴ using xenon flash lamp or a cathode ray tube
Exposures of up to 1/10 ⁶ seconds can be used, and exposures longer than 1 second can be used.

For the photographic processing of the light-sensitive material of the present invention, any known development processing method for forming a silver image by reversal development can be used. A known treatment liquid can be used. The treatment temperature is usually chosen between 18 ° C and 50 ° C.
The temperature may be lower than 0 ° C or higher than 50 ° C.

The reversal development process usually comprises the following steps.

First development-washing-bleaching-cleaning-overall exposure-second development-fixing-washing-drying.

The developing solution used for the black and white photographic processing of the first development may contain a known developing agent. As developing agents, dihydroxybenzenes (eg, hydroquinone), 3
-Pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-
p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in US Pat. No. 4,067,872. Etc. can be used alone or in combination. In particular, it is preferable to use pyrazolidones and / or aminophenols together with dihydroxybenzenes. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants and the like, and further contains a solubilizing agent, a toning agent, if necessary.
A development accelerator, a surfactant, a defoaming agent, a water softening agent, a film hardening agent, a viscosity imparting agent and the like may be contained. The light-sensitive material of the present invention is usually processed with a developer containing 0.15 mol / l or more of sulfite ion as a preservative.

The pH is preferably 9 to 11, and particularly preferably 9.5 to 10.5.

The first developer contains 0.5 to 6g of silver halide solvent such as NaSCN.
/ l used.

As the second developing solution, a general black-and-white developing solution can be used. That is, it has a composition obtained by removing the silver halide solvent from the first developing solution. The pH of the second developer is 9-
A value of 11 is preferable, and a pH of 9.5-10.5 is particularly preferable.

Bleaching agents such as potassium dichromate or cerium sulfate are used in the bleaching solution.

A thiosulfate or thiocyanate is preferably used in the fixing solution, and may contain a water-soluble aluminum salt if necessary.

The present invention will be further described below with reference to examples.

Example An emulsion was prepared by the following method. Solution I, II, III, I
V is prepared and solution I is kept at 70 ° C., where solution II, III,
IV was added by the triple jet method. Solution I was added at a constant flow rate over 40 minutes, solution III was started at the same time as II, and pAg during the addition was 8.7 for the first 5 minutes.
Control the flow rate to 7.2 for the next 35 minutes,
When the addition of Solution II was complete, the addition of Solution III was stopped. The solution IV was added at a constant flow rate 5 minutes after the addition of II and III was started, and the addition of IV was completed in 20 minutes. After the addition was completed, the emulsion was washed with sedimented water for desalting according to a conventional method. Then, 100 g of gelatin was added per mol of silver halide, dissolved at 40 ° C. and p
Ag was adjusted to 8.9 and pH was adjusted to 7.0 with NaOH. Thereafter, the mixture was heated to 75 ° C., and spectral sensitizing dyes I (300 mg) and II (30 mg) were added per mol of silver halide, and further sodium thiosulfate 40 mg and chloroauric acid tetrahydrate 40 mg were added. Then, it was aged for 50 minutes and spectrally and chemically sensitized. The resulting emulsion is a cubic monodisperse emulsion with a side length of about 0.35μ.

Gelatin in the above emulsion, 4-hydroxy-6 as a stabilizer
-Methyl-1,3,3,3a tetrazaindene, 1, as a hardener
3-divinylsulfonyl-2-propanol, p-sodium dodecylbenzenesulfonate as a coating aid were added, and compound (I) was further added, and the conductivity was made of SnO ₂ containing Sb so that the film thickness became 2.6 μ. Thickness with a transparent coating layer
It was coated on a 100 μ polyethylene terephthalate film. At this time, the thickness of the gelatin layer should be between the emulsion layer and the film so that the surface protective layer should be 1.0 μm above the emulsion layer.
Was simultaneously applied so as to have a thickness of 0.5 μ.

The surface protective layer is composed of barium strontium sulfate as a matting agent, liquid paraffin as a sliding agent, in a gelatin aqueous solution,
It was prepared by adding colloidal silica as an anti-scratch agent and sodium p-dodecylbenzenesulfonate as a coating aid.

The gelatin layer was prepared by adding p-sodium dodecylbenzenesulfonate as a coating aid to an aqueous gelatin solution.

The amount of the hardener was changed in order to prepare a sample in which the swelling ratio of the emulsion surface layer (protective layer, emulsion layer, gelatin layer) was changed. Here, the swelling ratio means that the emulsion surface layer swells when the sample is immersed in water at 25 ° C. for 1 minute, but the value obtained by subtracting the film thickness before swelling from the film thickness after swelling (swelled amount) It is the quotient divided by the film thickness.

Evaluation of Coated Sample (Imagewise Exposure) The exposure was carried out by using a MARK-II xenon flash sensitometer manufactured by US EG & G. Through a continuous density wedge for 10 ⁻⁴ seconds.

(Reversal Development Processing) The development processing is carried out by using a commercially available reversal processing solution (FR Chemi
FR-531, FR-532, FR-533, FR-534, FR535 manufactured by cals) were used under the following conditions.

Process Treatment liquid Temperature Time 1 First development FR-531 (1: 3) 35 ℃ 30 seconds 2 Washing water Running water 〃 〃 3 Bleaching FR-532 (1: 3) 〃 〃 4 Clean FR-533 (1: 3) 〃 〃 5 explosive light − − − 6 Second development FR-534 (1: 3) 〃 〃 7 fixed FR-535 (1: 3) 〃 〃 8 water washing water spray 〃 〃 9 dry − − − The exposed and reverse-developed film sample was measured with a densitometer, and characteristic values were read from the characteristic curve of blackening density vs. exposure amount for comparative evaluation.

As the treatment fatigue solution, a commercially available COM film (COM-SE manufactured by Fuji Photo Film Co., Ltd.) was treated in a state of 100 m ^{2 and then} treated.

The results are shown in the table below.

From this, it can be seen that the present invention has high sensitivity and a small decrease in D _{max in} the fatigue solution.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material for black and white, which has at least one silver halide emulsion layer on a support and forms a positive silver image by reversal processing, the emulsion layer or other hydrophilic layer. A silver halide photographic light-sensitive material for black and white, characterized in that the compound represented by the following general formula (I) is contained in the functional colloid layer. In the formula, R ₁ and R ₂ each represent a hydrogen atom or an aliphatic residue,
R ₁ and R ₂ may combine with each other to form a ring. R ₃ represents a divalent aliphatic group. M is a hydrogen atom, an alkali metal atom, an alkaline earth atom,
It represents a quaternary ammonium salt, a quaternary phosphonium salt or an amidino group. 2. The silver halide grains in the silver halide emulsion are core / shell type, the core is substantially silver bromide, and the shell is substantially silver iodobromide. The silver halide photographic light-sensitive material for black and white according to claim 1.