JPH04265971A - Image forming method - Google Patents

Abstract

PURPOSE:To prevent a change in sensitivity and softening in tone with the elapse of time and the increase of black spots occurring in an unexposed part by incorporating a specified compd. into a silver halide emulsion layer and/or a layer adjacent to the emulsion layer. CONSTITUTION:When a silver halide photographic sensitive material having at least one silver halide emulsion layer on the base and contg. a hydrazine deriv. in the silver halide emulsion layer and/or a layer adjacent to the emulsion layer is processed with a developing soln. of pH<11.0 to form a high-contrast black-and-white image having >=8gamma, at least one kind of compd. represented by the formula is incorporated into the silver halide emulsion layer and/or a layer adjacent to the emulsion layer. In the formula, each of R1-R3 is H, alkyl or phenyl and R2 and R3 may bond to each other to form a ring.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method using a silver halide photographic light-sensitive material, and more particularly to an image forming method with high contrast and fewer black spots.

0002

BACKGROUND OF THE INVENTION The photolithography process involves converting a continuous tone original into a halftone image. In this process, contagious development has been used as a photographic technique capable of reproducing ultra-high contrast images.

The lithium-type silver halide photographic material used for infectious development has, for example, an average grain size of about 0.2 μm, a narrow grain distribution and a well-shaped grain, and a high content of silver chloride (at least (50 mol% or more) silver chlorobromide emulsion. By processing this lithium-type silver halide photographic light-sensitive material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lithium-type developer, images with high contrast, high sharpness, and high resolution can be obtained.

[0004] However, these lithium-type developers have extremely poor storage stability because they are susceptible to air oxidation.
It is difficult to maintain constant development quality during continuous use. A method of quickly obtaining a high-contrast image without using the above-mentioned Lith type developer is known. For example, as seen in the specification of JP-A-56-106244, a hydrazine derivative is contained in a silver halide photographic light-sensitive material. According to these methods, high-contrast images can be obtained even by processing with a developing solution that has good preservability and can be processed quickly.

[0005] In these techniques, in order to fully exhibit the high contrast properties of hydrazine derivatives, a pH of 11.0 or higher is required.
had to be processed with a developer containing pH1
In a high pH developer having a pH of 1.0 or more, the developing agent is likely to be oxidized when exposed to air. Although it is more stable than Lith developer, due to oxidation of the developing agent, it is often impossible to obtain ultra-high contrast images. In order to compensate for this drawback, Japanese Patent Application Laid-Open No. 63-29751 and European Patent No. 333,435, European Patent No. 345,025, etc. disclose halogen containing high contrast agents that can increase contrast even in relatively low pH developing solutions. A silver oxide photographic material is disclosed.

However, in the case of an image forming method in which a silver halide photographic light-sensitive material containing a high contrast agent such as these is processed with a developer having a pH of less than 11.0, sensitization and softening of the contrast over time, as well as unresolved problems after development, occur. Currently, there is a problem that sand-like fog, so-called black spots, which occur in exposed areas deteriorate, and it is not possible to obtain satisfactory performance.

[0007] JP-A-2-271351 discloses an example of using an additive to a developer, but no additive has yet been disclosed that exhibits the desired effect when added to a photosensitive material.

[0008]

OBJECTS OF THE INVENTION A first object of the present invention is to provide a method for forming ultra-high contrast images in which sensitivity fluctuations and softening over time and increase in black spots occurring in unexposed areas are prevented.

A second object of the present invention is to provide a method for forming ultra-high contrast images, which prevents changes in sensitivity over time, softening of tone, and increase in black spots in unexposed areas even when processed with a developer having a pH of less than 11. Our goal is to provide the following.

0010

[Structure of the Invention] The above-mentioned object of the present invention is to provide a halogen compound having at least one silver halide emulsion layer on a support, and containing a hydrazine derivative in the silver halide emulsion layer and/or its adjacent layer. In an image forming method in which a silver halide photographic light-sensitive material is processed with a developer having a pH of less than 11.0, the following general formula [1] is contained in the silver halide emulsion layer and/or its adjacent layer.
This is achieved by an image forming method characterized by containing at least one compound represented by:

[0011]

[Case 2]

[In the formula, R1, R2 and R3 each independently represent a hydrogen atom, an alkyl group or a phenyl group. Furthermore, R2 and R3 may be connected to each other to form a ring. ] Hereinafter, the present invention will be explained in detail.

The structure of the hydrazine derivative used in the present invention is preferably the following general formula [H].

[0014]

[Chemical formula 3]

[0015]

[C4]

In the formula, A is an aryl group (for example, phenyl, naphthyl, etc.) or a heterocyclic group containing at least one sulfur atom or oxygen atom (for example, thiophene, furan,
benzothiophene, pyran, etc.).

R1 and R2 each represent a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), or an alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl, etc.) , alkynyl groups (e.g., propargyl, butynyl, pentynyl, etc.), aryl groups (e.g., phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (e.g., unsaturated heterocyclic groups such as pyridine, thiophene, furan, etc.) and saturated heterocyclic groups such as tetrahydrofuran and sulfolane), hydroxy groups, alkoxy groups (e.g., methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy groups (e.g., allyloxy, butenyloxy, etc.),
represents an alkynyloxy group (e.g., propargyloxy, butynyloxy, etc.), an aryloxy group (e.g., phenoxy, naphthyloxy, etc.), or a heterocyclic oxy group (e.g., pyridyloxy, pyrimidyloxy, etc.),
When n=1, R1 and R2 are combined with a nitrogen atom in a ring (for example,
piperidine, piperazine, morpholine, etc.).

However, when n=2, at least one of R1 and R2 is an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or a heterocyclic group. shall represent a group. Specific examples of the alkynyl group and saturated heterocyclic group represented by R3 include those mentioned above.

Various substituents can be introduced into the aryl group represented by A or the heterocyclic group having at least one sulfur atom or oxygen atom. Examples of substituents that can be introduced include halogen atoms, alkyl groups, aryl groups, alkoxy groups, aryloxy groups, acyloxy groups, alkylthio groups, arylthio groups, sulfonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, sulfamoyl groups, Examples include an acyl group, an amino group, an alkylamino group, an arylamino group, an acylamino group, a sulfonamide group, an arylaminothiocarbonylamino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group, and a cyano group. Among these substituents, a sulfonamide group is preferred.

In each general formula, A preferably contains at least one diffusion-resistant group or silver halide adsorption-promoting group. The diffusion-resistant group is preferably a ballast group commonly used in immobile photographic additives such as couplers. The ballast group is a group having 8 or more carbon atoms and is relatively inert to photography, and can be selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group, an alkylphenoxy group, etc. Can be done.

The silver halide adsorption promoting group includes a thiourea group, a thiourethane group, a heterocyclic thioamide group, a mercapto heterocyclic group, a triazole group, etc. in US Pat. No. 4,385,
Examples include the groups described in No. 108.

-NHNH- in general formulas [A] and [B]
H, that is, the hydrogen atom of hydrazine, is a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl, etc.), an acyl group (e.g., acetyl, trifluoroacetyl, ethoxycarbonyl, etc.), an oxalyl group (e.g., ethoxalyl, pyruvoyl, etc.), etc. It may be substituted with a substituent, and the compounds represented by general formulas [A] and [B] also include such compounds.

More preferred compounds in the present invention are compounds of general formula [A] where n=2, and compounds of general formula [B]
It is a compound of

In the compound of general formula [A] where n=2,
R1 and R2 are hydrogen atoms, alkyl groups, alkenyl groups,
Alkynyl group, aryl group, saturated or unsaturated heterocyclic group,
More preferably, the compound is a hydroxy group or an alkoxy group, and at least one of R1 and R2 represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group.

Representative compounds represented by the above general formulas [A] and [B] include those shown below. However, as a matter of course, general formula [A] that can be used in the present invention
, [B] are not limited to these compounds.

[0026] Specific compound examples

[0027]

[C5]

[0028]

[C6]

[0029]

[C7]

[0030]

[Chemical formula 8]

The compound according to the present invention is disclosed in Japanese Patent Application No. 2-3274.
Among H-1 to H-187 described in No. 02, pages 20 to 58, those excluded from the above examples are used. However, the present invention is not limited to these. Next, the compound of general formula [1] used in the invention will be explained.

[In the formula, R1, R2, and R3 each independently represent a hydrogen atom, an alkyl group (preferably a substituted or unsubstituted alkyl group having 10 or less carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, hydroxymethyl group, hydroxyethyl group, etc.) or phenyl group (substituted or unsubstituted phenyl group, such as methoxyphenyl group, p-chlorophenyl group, etc.). Furthermore, R2 and R3 may be connected to each other to form a ring. ] Specific examples of the compound represented by the general formula [1] are listed below, but the present invention is not limited thereto.

[0033]

[Chemical formula 9]

[0034]

[Chemical formula 10]

These compounds are known and can be obtained as commercial products or synthesized by known synthesis methods. For example, Aldrich C.
o. ) in the 1986-1987 catalog.

In the image forming method of the present invention, the compound of the above general formula [1] is used for sensitization and high sensitivity by the hydrazine compound when the silver halide photographic light-sensitive material is exposed to light and developed in the presence of the hydrazine compound. It promotes the contrast effect and shows the effect of shortening the time required for development.

The amount of the compound of general formula [1] to be added is as follows:
1 x 10-2 to 1 x 10-5 per mole of silver halide
mol, preferably 1 x 10-3 to 1 x 10-4 mol.

The silver halide emulsion (hereinafter referred to as silver halide emulsion or simply emulsion) used in the present invention includes silver halide such as silver bromide, silver iodobromide, silver iodochloride, and chloride. Any of those commonly used in silver halide emulsions, such as silver chloride and silver chloride, can be used, but preferably contains silver chlorobromide, silver bromide, or silver iodide in an amount of up to 2 mol %. Silver iodobromide.

Further, monodisperse particles having a coefficient of variation expressed by (standard deviation of particle size)/(average value of particle size) x 100 of 15% or less are preferable.

Various techniques and additives known in the art can be used in the silver halide emulsion of the present invention.

For example, the silver halide photographic emulsion and backing layer used in the present invention contain various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, slip agents, and development inhibitors. Agents, ultraviolet absorbers, irradiation inhibitors, dyes, heavy metals, matting agents, and the like can be further incorporated by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion and backing layer of the present invention.

When the compound of the general formula according to the present invention is added to a hydrophilic colloid layer, gelatin is suitable as the binder for the hydrophilic colloid layer, but hydrophilic colloids other than gelatin can also be used. These hydrophilic binders are preferably coated on both sides of the support at an amount of 10 g/m 2 or less.

Supports that can be used in the practice of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, and polyester films such as polyethylene terephthalate. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

To develop the silver halide photographic material of the present invention, for example, T. H. The Theory of the Photographic Process by James, 4th edition (
The Theory of the Photographer
aphic Process, Fourth Edit
ion) pages 291-334 and Journal of the American Chemical Society (Journal
of the American Chemical
Society) Volume 73, Page 3,100 (195
The developers described in 1) can be effectively used in the present invention.

These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination.

Further, even if a sulfite salt such as sodium sulfite or potassium sulfite is used as a preservative in the developer used for developing the photosensitive material of the invention, the effects of the invention will not be impaired. Furthermore, hydroxylamine and hydrazide compounds may be used as preservatives. In addition, pH adjustment and buffer functions can be provided using caustic alkali, carbonate alkali, or amine, which are used in general black and white developers. The developer used in the present invention has a pH of 11.
It is characterized by the fact that it can be used with less than In addition, the developer contains an inorganic development inhibitor such as bromopotash, 5-methylbenzotriazole, 5-methylbenzimidazole, 5-
Organic development inhibitors such as nitroindazole, adenine, guanine, 1-phenyl-5-mercaptotetrazole, metal ion scavengers such as ethylenediaminetetraacetic acid, development accelerators such as methanol, ethanol, benzyl alcohol, polyalkylene oxide, alkylaryl It is optional to add surfactants such as sodium sulfonate, natural saponins, sugars or alkyl esters of the above compounds, hardening agents such as glutaraldehyde, formalin, and glyoxal, and ionic strength regulators such as sodium sulfate. It is.

The developer used in the present invention may contain glycols such as diethylene glycol and triethylene glycol as an organic solvent. Further, it is preferable not to contain alkanolamines disclosed in JP-A-56-106244 and the like.

[0048]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of silver halide photographic emulsion A) A silver iodobromide emulsion (2 mol % of silver iodide per 1 mol of silver) was prepared using the simultaneous mixing method. During this mixing, K2IrCl6 was added at 8% per mole of silver.
x10-7 mol was added. The obtained emulsion has an average grain size of 0
．． The emulsion consisted of 20 μm cubic monodisperse grains (coefficient of variation 9%). Added modified gelatin, patent application Hei 1-1
It was washed with water and desalted in the same manner as in Example 1 of No. 80787. The pAg at 40°C after desalting was 8.0. Subsequently, a potassium iodide aqueous solution of 0.1 mol% per mol of silver was added to this emulsion to convert the grain surface, and then 15 ml of a 1% aqueous solution of the mixture of compounds [A], [B], and [C] was added. Emulsion A was obtained.

[0050]

[Chemical formula 11]

(Preparation of silver halide photographic light-sensitive material) One side of a 100 μm thick polyethylene terephthalate film coated with a 0.1 μm thick undercoat layer (see Example 1 of JP-A-59-19941) on both sides. On the undercoat layer, apply a silver halide emulsion layer of the following formulation (1) with a gelatin amount of 2.0 g.
/m2, silver amount is 3.2 g/m2, and on top of that, an emulsion protective layer of the following formulation (2) is applied with a gelatin amount of 1.
．． 0g/m2, and on the other undercoat layer on the opposite side, apply a backing layer according to the following recipe (3) so that the amount of gelatin is 2.4g/m2, and On top of that, a backing protective layer of the following formulation (4) was applied so that the amount of gelatin was 1 g/m2. 1 to 18 were obtained.

Prescription (1) (silver halide emulsion layer composition)
gelatin

2.0g/m2 Silver halide emulsion A Silver amount

3.2g/m2

[0053]

[Chemical formula 12]

Stabilizer: 4-methyl-6-hydroxy-1,3,3
a,7-tetrazaindene 30mg/m2
Antifoggant: Adenine

10mg/m2
1-phenyl-5-mercaptotetrazole
5mg/m2 Surfactant: saponin
0.1g/m2

[0055]

[Chemical formula 13]

Hydrazine derivatives according to the present invention and compounds of general formula [1] according to the present invention Amounts shown in Table 1

[0057]

[Chemical formula 14]

Prescription (3) (Backing layer composition)

005
9]

[Chemical formula 15]

Gelatin

2.4g/m2 Surfactant: Saponin
0.1g/m2
:S-1

6mg/m2 colloidal silica
100mg
/m2 prescription (4) [Backing protective layer composition] Gelatin

1g/m2 Matting agent: average particle size 5.
0 μm monodispersed polymethyl methacrylate
50mg/m2 Surfactant: S-2

10mg/m2 Hardening agent: Glyoxal
25mg/m2
:H-1

35mg/m2 The obtained sample was tightly attached with a step wedge and
After exposure to 00K tungsten light for 5 seconds, processing was carried out under the following conditions using a rapid processing automatic developing machine GR-26SR manufactured by Konica Corp., into which a developer and a fixer having the compositions shown below were introduced.

The obtained sample was stored at 23° C. and 50% RH for 24 hours, then sealed and packaged, and left at 55° C. for 3 days as a thermo-treatment for aging. This thermo-treated sample was exposed, developed and fixed in the same manner.

Developer formulation Ethylenediaminetetraacetic acid sodium salt

1g sodium sulfite

60g boric acid


40g hydroquinone

35g
Sodium hydroxide

8g sodium bromide

3
g 5-methylbenzotriazole

0.2g 2-mercabutobenzothiazole
0.1g 2-mercabutobenzothiazole-5-sulfonic acid
0.2g 1-
Phenyl-4,4-dimethyl-3-pyrazolidone
0
．． Add 2g water

Adjust pH with 1l sodium hydroxide
10
．． 5 Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution)

240ml sodium sulfite

17g Sodium acetate trihydrate
6.5
g Boric acid

6.0g Sodium citrate dihydrate

2.0g (composition B) Pure water (ion exchange water)

17ml sulfuric acid (50% W/V aqueous solution)
4.7g aluminum sulfate (AI2O3 equivalent content is 8.1% W/V
26.5 g of aqueous solution) When using a fixer, the above compositions A and B were dissolved in 500 ml of water in that order, and the final volume was made up to 1 liter. The pH of this fixer was adjusted to 4.8 with acetic acid.

(Development processing conditions) (Process) (Temperature) (Time) Development
Fixation at 38℃ for 20 seconds
Wash at 35℃ for 20 seconds
Dry at 30℃ for 15 seconds
The concentration of the sample obtained at 50° C. for 15 seconds was measured using an optical densitometer Konica PDA-65. 1
The sensitivity at a density of 2.5 is expressed as a relative sensitivity of 100, and the gamma is expressed as a tangent between a density of 0.1 and 2.5. Gamma values less than 6 are unusable, and 6
．． A gamma value of 0 or more and less than 10.0 still provides insufficient high contrast performance. A gamma value of 10.0 or more results in an ultra-high contrast image, which is sufficiently practical.

[0064] Also, black spots in unexposed areas were evaluated using a 40x magnifying glass. The highest rank is "5" for those with no black spots, and the ranks are lowered sequentially to "4", "3", "2", and "1" depending on the degree of occurrence of black spots. shall be evaluated. Rank “1” and “2”
”, black spots are also at a level that is not practical.

[0065] The results are shown in Table 1.

[0066]

[Table 1]

As is clear from Table 1, sample No. 1 according to the present invention. It can be seen that samples Nos. 5 to 11 have high sensitivity, high contrast, good black spots, and little change in performance over time compared to the comparison.

[0068]

[Effects of the Invention] According to the present invention, a method for forming ultra-high contrast images that prevents sensitivity fluctuations and softening over time and increase in black spots that occur in unexposed areas even when processed with a developer having a pH of less than 11.0. were able to provide.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support and containing a hydrazine derivative in the silver halide emulsion layer and/or its adjacent layer is prepared at a pH of 11. An image forming method in which the silver halide emulsion layer and/or its adjacent layer contains at least one compound represented by the following general formula [1], in an image forming method in which the silver halide emulsion layer and/or its adjacent layer are processed with a developing solution of less than 0. Formation method. embedded image [In the formula, R1, R2, and R3 each independently represent a hydrogen atom, an alkyl group, or a phenyl group. Furthermore, R2 and R3
may be connected to each other to form a ring. ]