JPH01233449A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (A) Industrial Application Field The present invention relates to a silver halide photographic light-sensitive material and an image forming method, and in particular to a light-sensitive material useful for forming high-contrast images using a hydrazine compound. and methods.

(B) Prior Art The addition of hydrazine compounds to silver halide photographic emulsions and developing solutions is described in US Pat. No. 3,730,727 (developing solution combining ascorbic acid and hydrazine);
No. 3,227,552 (using hydrazine as an auxiliary developer to obtain a direct positive color image), No. 3
, 386,831 (contains β-monophenyl hydrazide of aliphatic carboxylic acid as a stabilizer for silver halide sensitive materials), 2゜419.975, and Me e
“The Theory of Photography” by
phic ProcessJ 3rd edition (1966),
It is known as 281 pages etc.

Among these, US Pat. No. 2,419,975 in particular discloses that a high contrast negative image can be obtained by adding a hydrazine compound.

That is, a hydrazine compound is added to a silver chlorobromide emulsion, and 12
．． It is stated that when developed with a developer having a high pH of 8, extremely high-contrast photographic characteristics with a gamma (γ) of over 10 can be obtained.

However, a strong alkaline developer having a pH close to 13 is easily oxidized in the air, is unstable, and cannot withstand long-term storage or use. The ultra-high contrast photographic characteristics with a gamma value exceeding 10 are extremely useful for photographic reproduction of continuous-tone images using dot images (dot images) useful in printing plate making, and reproduction of line drawings, whether negative or positive images. Useful.

Conventionally, for this purpose, a silver chlorobromide emulsion with a silver chloride content of more than 50 moles, preferably more than 75 moles, is used, and the effective concentration of sulfite ions is kept extremely low (usually 0.1 mole/mol/2). A method of developing with a hydroquinone developer (see below) was commonly used (lith development).

However, in this method, due to the low sulfite ion content in the developer, the developer is extremely unstable and cannot be stored for more than 3 days.

Furthermore, since all of these methods require the use of silver chlorobromide emulsions with relatively high silver chloride contents, high sensitivity cannot be obtained.

Therefore, there has been a strong demand for using a highly sensitive emulsion and a stable developer to obtain ultra-high contrast photographic characteristics useful for reproducing halftone images and line drawings.

For this purpose, U.S. Pat.
No. 269.929, No. 4,272,614, No. 4,
No. 323.643 and other publications disclose silver halide photographic materials that use a stable developer to provide extremely high-contrast negative photographic properties, but these acylhydrazine compounds provide sufficient tone and sensitivity. When used like this, countless circular capris (sand fogs: pe
pper fog) was likely to occur, significantly impairing image quality.

(C) Purpose of the Invention The purpose of the present invention is, firstly, to develop a gamma film using a stable developer.
An object of the present invention is to provide an image forming method capable of obtaining photographic characteristics of extremely high contrast negative gradation in which the contrast ratio exceeds 10.

A second object of the present invention is to provide a negative-working silver halide photographic light-sensitive material containing hydrazines that can provide good image quality without problems with uneven development or sand capri.

A third object of the present invention is to provide a silver halide photographic material that can provide good image quality, especially when used in combination with hydrazines.

(D) Structure of the Invention The present invention is a silver halide photographic light-sensitive material containing at least one compound represented by the following general formula (I), and further comprising hydrazine, especially the following formula (
This is an image forming method in which development is performed in the presence of at least one hydrazine compound represented by II).

Bifurcated formula (I) Ar-0-R [In the formula, Ar represents a substituted or unsubstituted aryl group, and the aryl group specifically represents a phenyl group or a naphthyl group. (Examples of substituents include, for example, alkyl groups, aryl groups, halogen atoms, alkoxy groups, aryloxy groups, carbamoyl groups, acylamido groups, sulfonamide groups, or combinations thereof.) R is hydrated with an alkali. It represents a decomposable group, and typical examples include R,, -Co-, and R11-OCO-.

(Here, R11, R12, RJIS, R14, 几15
may be the same or different, and each represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Also, R15 and 'R15 are mutually V
C-linked and may have a cyclic structure such as a benzene ring 6)] General formula (IF) ArI NH-NH-R1 [In the formula, Ar1 represents a substituted or unsubstituted aryl group; specifically represents a phenyl group or a naphthyl group.

(Examples of substituents include, for example, alkyl groups, aryl groups, halogen atoms, alkoxy groups, aryloxy groups,
Examples include alkenyl groups, substituted amino groups, acylamino groups, sulfonamide groups, alkylidene amino groups, thiourea groups, thioamide groups, heterocyclic groups, and combinations thereof. ) R1 is an alkylsulfonyl group (the alkyl group may be substituted with a halogen atom, etc.), an arylsulfonyl group (the aryl group represents, for example, a phenyl group, a naphthyl group, etc., and as a substituent, for example, an alkyl base,
may be substituted with an alkoxy group, a halogen atom, etc.), or a group represented by formula (III).

] General formula III) +R2 [In the formula, R2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted 1
It represents a alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted amino group, or a heterocyclic group.

n represents a positive integer of l or 2. ]General formula RI)
In the group represented by 几2, the alkyl group is preferably an alkyl group having 30 or less carbon atoms, such as a halogen atom, a cyano group, an alkoxy group, an aryloxy group, an aryl group, a substituted amine group, etc. It may have a substituent.

- In the formula (III), among the groups represented by R2, the aryl group is a 2-enyl group or a naphthyl group which may have a substituent, and examples of the substituent include an alkyl group, an aryl group, and a naphthyl group. group, a halogen atom, an alkoxy group, an aryloxy group, or a combination thereof.

In the general formula (II[), among the groups represented by R2, the alkoxy group is preferably an alkoxy group having 1 to 1 o carbon atoms, and may be substituted with a halogen atom, an aryl group, or the like.

In the general formula (I[I), among the groups represented by R2, the aryloxy group is preferably a monocyclic group, and may be substituted with a halogen atom, an alkyl group, or the like.

In the general formula (III), among the groups represented by R2, substituents for the amino group include an alkyl group, an aryl group, an acyl group, a heterocyclic group, or a combination thereof.

In general formula (1), the heterocyclic group among the groups represented by R2 specifically includes a pyridyl group which may have a substituent, a pyrazinyl group, a pyrimidinyl group, a pyridazinyl group,
Quinolyl group, inquinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, or pteridinyl group, and examples of substituents include alkyl group, aryl group, halogen atom, substituted ami7 group, Examples include a cyan group, an acylamino group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or a combination thereof.

Next, specific examples of the compound represented by general formula (I) are shown below. However, the present invention is not limited to the following compounds.

■-10 ■-20 ■-30 t ■-70 ■-90 The compound represented by U91 (19 (nl), which is a formula CI of the present invention) can be synthesized by various methods.

That is, the corresponding alcohol (Ar-OH) and the corresponding (acid) halide (R-X) or anhydride (几-0-R) are mixed in a suitable solvent (e.g. dioxane, benzene, DMF). It can be easily obtained by reacting in a base catalyzed medium or by simply heating.

Hereinafter, the method for synthesizing the compound represented by the formula CI) of the present invention will be explained by giving specific examples.

<Synthesis Example 1> Synthesis of Exemplary Compound I-3 4-chloro-2
-(dodecylcarbamoyl)-1-naphthol 11.7
After dissolving F in 100ml of dioxane, 4.6rILt of triethylamine was added.

While stirring the reaction solution at room temperature, 3. ethyl chlorocarbonate was added.
2- was added dropwise little by little, and the reaction was carried out at the same temperature for about 1 hour.

After the reaction, crystals precipitate when the reaction solution is poured into water.

After several crystals and washing with water, the obtained crude crystal n-
Recrystallization was performed from hexane to obtain the target exemplary compound I-3.

Yield: 9.5F Melting point near 2-74℃〈Synthesis example 2
> Synthesis of Exemplified Compound I-4 4-Chlo-o-2-(dodecylcarbamoyl)-1-su7toll 11.7 and 3
After adding -Bromophthalide 7 fVCMEK 200-, 4.69 g of potassium carbonate (anhydrous) was added and heated under reflux with stirring for about 3 hours.

After the reaction, the reaction solution was poured into water and extracted with MEK.

The obtained organic layer was washed with water and then dried over Na2SO4.

After drying, Na2SO4 was removed and the solvent was distilled off under reduced pressure, and the resulting precipitate was recrystallized from a mixed solvent of ethyl acetate and benzene to obtain the target exemplary compound I-4.

Revenue: 3.8? Melting point: 219.5-221.
5°C (decomposition point) Next, specific examples of the compound represented by formula (n) are shown below.However, the present invention is not limited to the following compounds.

1[-5 C2H5 ■-11 CH.

■-17 ■-18 ■-20 ■-21 The content of the compound represented by the general formula (1) can be determined depending on the characteristics of the silver halide emulsion used, the chemical structure of the compound, -the formula (n
) The suitable content may vary over a wide range, depending on the nature of the compound and development conditions, but approximately lX per mole of silver in the surface latent image type silver halide emulsion.
A range of 10-' to 1X10-2 moles is useful in practice.

The content of the compound represented by the general formula (U) is also the same as the content of the compound represented by the general formula (U).
Although it may vary depending on the conditions mentioned in the content of I) and the compound represented by the general formula (I) to be combined, it is about 1Xl0 per mole of silver in the surface latent image type silver halide emulsion.
-' to lXl0-'' molar range is practically useful.-
When the compound represented by formula (n) is contained in the developer, the amount is suitably 10-4 to 10-1 mol/l, preferably 5.times.10-' to 5.times.10-2 mol/l.

In the light-sensitive material of the present invention, the compounds represented by the general formulas (1) and (If) are preferably contained in the surface latent image type silver halide emulsion layer. It may be contained in an adjacent hydrophilic colloid layer.

Such layers include subbing layers, interlayers, filter layers, protective layers,
The layer may have any function, such as an antihalation silon layer, as long as it does not prevent the compounds represented by formulas (I) and (n) from diffusing into the silver halide grains.

The compounds represented by formulas (1) and (II) are preferably contained in the same layer, but they can also be contained in different stones.

The silver halide used in the light-sensitive silver halide emulsion layer of the light-sensitive material of the present invention is not particularly limited, and silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide, etc. can be used. However, when silver iodobromide or silver chloroiodobromide is used, the content of silver iodide is preferably in the range of 5 mole or less.

There are no particular limitations on the morphology, crystal habit, size distribution, etc. of the silver halide grains, but grain sizes of 0.7 microns or less are preferred.

Silver halide emulsions are made of gold compounds such as chlorauric acid salts and gold trichloride, salts of noble metals such as rhodium and iridium, sulfur compounds that react with silver salts to form silver sulfide, stannous salts, etc. Sensitivity can be increased by using reducing substances such as amines without making the particles coarser.

Further, salts of noble metals such as rhodium and iridium, and iron compounds such as red blood salts may be present during physical ripening or nucleation of silver halide grains.

In particular, the addition of rhodium salts or complex salts is preferable because it further promotes the effect of the present invention of achieving ultra-high contrast photographic characteristics in a short development time.

In the present invention, a surface latent image type silver halide emulsion refers to an emulsion comprising silver halide grains having surface sensitivity higher than internal sensitivity, and this emulsion is preferably described in US Pat. No. 4,224,
It has a difference between surface sensitivity and internal sensitivity as specified in the specification of No. 401.

It is desirable that the silver halide emulsion be monodisperse, particularly an emulsion having the monodispersity defined in the above-mentioned US Pat. No. 4,224,401.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or others.

The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes,
and hemioxonol dyes.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a pigment belonging to complex merocyanine pigments.

These sensitizing dyes may be used alone or in combination.

Combinations of sensitizing dyes are 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.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

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

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, Sci, Phot,
Enzyme-treated gelatin as described in Japan, A16, P2O (1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance.

That is, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles,
Mercaptotetrazoles; Mercaptopyrimidines;
Many compounds conventionally known as anti-capri agents or stabilizers can be added, such as mercaptotriazines, thioketo compounds; azaindenes;

Among these, particularly preferred are benzotriazoles (eg, 5-methylbenzotriazole) and nitroindazoles (eg, 5-nitroindazole).

These compounds may be included in the treatment liquid.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardening agent in the photographic emulsion layer or other hydrophilic colloid layer.

For example, chromium salts (chromium, aluminum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N
- Methylol compounds, dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-6-hydroxy-8
-) IJ azinato), etc. can be used alone or in combination.

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, non-ionic materials such as saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenylsuccinic acid polyglycerides, etc.), fatty acid esters of polyhydric alcohols, and shield alkyl esters. surfactants; carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate esters, such as alkyl carboxylates, alkyl sulfonates, alkyl sulfate esters, alkyl/L/IJ esters, etc. anionic surfactants containing acidic groups such as amino acids, aminoalkylsulfonic acids, aminoalkyl sulfuric acids or phosphoric acid esters; aliphatic or aromatic quaternary ammonium salts, pyridinium,
Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium can be used.

In the photographic light-sensitive material used in the present invention, in the photographic emulsion layer and other hydrophilic colloid layers, for the purpose of improving dimensional stability, etc.
It may contain a decomposed product of a water-insoluble or poorly soluble synthetic polymer.

For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl acetate, acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α
, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, and the like can be used.

In order to obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, it is necessary to use the conventional Lith developer or the US Pat.
It is not necessary to use a highly alkaline developer with a pH close to 13 as described in No. 9.975, and a stable developer can be used.

That is, the silver halide photographic light-sensitive material of the present invention contains a sufficient amount of sulfite ion as a preservative (particularly 0.15 moh/L).
above) can be used, and also has a pH of 9
, 5% or more, especially 10.5 to 12.3%, can provide a sufficiently high contrast negative image.

There is no particular restriction on the developing agent that can be used in the method of the present invention, and examples include dihydroxybenzenes, 3-pyrazolidones,
Amine phenols and the like can be used alone or in combination.

The developer also contains alkali metal sulfites, carbonates,
Contains pH buffering agents such as borates and phosphates, development inhibitors or anti-capri agents such as bromides, iodides, and organic anti-capri agents (particularly preferably nitroindazoles or benzotriazoles). be able to.

In addition, if necessary, water softeners, solubilizing agents, toning agents, development accelerators, surfactants, antifoaming agents, hardeners, and film silver stain preventive agents (for example, 2-mercaptobenzimidazole sulfonic acid) It may also include.

Specific examples of these additives are described in Research Disclosure No. 176, No. 17643, and the like.

As the fixer, one having a commonly used composition can be used.

As a fixing agent, in addition to thiosulfate and thiocyanate,
Organic sulfur compounds known to be effective as fixing agents can be used.

Further, the fixing solution may contain a water-soluble aluminum salt or the like as a hardening agent.

In the present invention, a method may be adopted in which a developing agent is incorporated into the photosensitive material and the material is processed with an alkaline activator solution.

(Unexamined Japanese Patent Publication No. 57-129436, No. 57-129433
No. 57-129434, No. 57-129435, U.S. Pat. No. 4,323,643, etc.).

The treatment temperature is usually selected between 18°C and 50°C, but 1
The temperature may be lower than 8°C or higher than 50°C.

It is preferable to use an automatic processor for photographic processing.

In the present invention, even if the total processing time from when the photosensitive material is placed in an automatic processor to when it comes out is set to 60 seconds to 120 seconds, sufficient photographic characteristics with ultra-high contrast and negative gradation can be obtained.

(E) Example <Example 1> A silver iodobromide emulsion consisting of cubic streaks with an average grain size of 0.25μ containing 97 molts of AgBr and 3 molts of AgI was prepared by a double jet method, and washed with water by a conventional method. After redissolving, chemical sensitization was performed using sodium thiosulfate.

After dividing this silver iodobromide emulsion into nine parts, compounds (1-1), (1-3), (■-4) of the general formula (1) of the present invention were prepared.
, (1-11), (1-13) and comparative compound (A),
(B) In addition, the general formula (n) is added to each of these in an amount of 4.0 x 10-' mol per mol of silver halide.
Compound (If-4) of 4.0 per mole of silver halide
It was added so that it became X10-' mole.

Each of these was coated onto a polyester film at a silver content of 1.3 x 10'' 2 moles per m''.

After applying wedge exposure to each film sample prepared in this way, using a developer having the composition shown below,
Development was performed at ℃ for 2 minutes, 4 minutes, and 6 minutes, respectively.

<Developer> Comparative compound (A) Comparative compound (B) The results are shown in Table ■.

As is clear from Table 2, the film samples (Film Shops 3 to 7) to which the compound of general formula (1) of the present invention was applied,
It can be seen that the film has sufficiently high sensitivity and gamma even from the early stage of development.

Furthermore, in the film samples (Film Black 8.9) using Comparative Compounds (A) and (B) (where the alcohol component is not protected by a hydrolyzable group), high contrast development with the hydrazine compound was not possible. You can see that it's blocked.

Furthermore, all the film samples to which the compound of the present invention was applied had less capri and no sand fog was observed, whereas the film samples to which the compound of the general formula CI) of the present invention was not applied ( At the film shop 2),
Obvious formation of sand capri was already observed after 4 minutes of development time.

<Example 2> Next, another part of the film sample obtained in Example 1 was used to test the quality of halftone dots.

That is, using a 150 line gray contact screen,
After exposing each film sample to light through the Sensimetry River Fog Light Edge, it was incubated at 38°C with the same developer as before.
Developed for 2 seconds and checked the dot quality.

The results are shown in Table ■.

The halftone dot quality is visually evaluated on a five-level scale, with 5 representing the best quality and 1 representing the worst quality. As a halftone original plate for plate making, 5.4 is practically usable, 3 is poor but barely usable, and 2.1 is of a quality that is practically unusable.

<Table ■> As is clear from Table ■, the film sample to which the compound of general formula CI) of the present invention is applied exhibits good halftone dot quality.

Claims (2)

[Claims] (1) A silver halide photographic material containing at least one compound represented by the following general formula (I) is developed in the presence of at least one hydrazine compound represented by the following general formula (II). image forming method. General formula (I) Ar-O-R (In the formula, Ar represents a substituted or unsubstituted aryl group, and R represents a hydrolyzable group.) General formula (II) Ar_1-NH-NH- R_1 (In the formula, Ar_1 represents a substituted or unsubstituted aryl group, and R_1 represents an alkylsulfonyl group, an arylsulfonyl group, or a group represented by the general formula (III).) General formula (III) ▲ Numerical formula, There are chemical formulas, tables, etc. ▼ (In the formula, R_2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, Represents a substituted or unsubstituted amino group or heterocyclic group. n is
Represents a positive integer of 1 or 2. ) (2) A silver halide photographic material containing at least one compound represented by the following general formula (I). General formula (I) Ar-O-R (wherein, Ar represents a substituted or unsubstituted aryl group, and R represents a hydrolyzable group)