JPH06148781A - Image forming method - Google Patents

Abstract

PURPOSE:To provide the image forming method using a black and white silver halide photographic sensitive material which maintains a high sensitivity and high contrast in spite of processing with a developer of 11.2pH, decreases the black dots to be generated in unexposed parts and decreases the fluctuations in performance with lapse of time. CONSTITUTION:This image forming method consists in forming images by processing the silver halide photographic sensitive material having at least one layer of silver halide emulsion layers on a base and incorporating a hydrazine deriv. into these silver halide emulsion layers and/or the adjacent layers thereof by a developer having <11.2pH. At least one layer among the silver halide emulsion layers have silver halide particles contg. >=20mol% silver bromide in silver halide emulsions and these silver halide particles are the particles prepd. in the presence of 10<-4> to 10<-4> mol per 1mol silver.

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, and more specifically, it has high contrast and suppresses generation of black spots
The present invention relates to an image forming method using a black-and-white silver halide photographic light-sensitive material whose performance does not fluctuate with time.

[0002]

BACKGROUND OF THE INVENTION The photomechanical process involves the conversion of continuous-tone originals into halftone images. In this process, a technique based on infectious development has been used as a photographic technique capable of reproducing an image in ultra-high contrast.

The lithographic silver halide photographic light-sensitive material used for infectious development has, for example, an average particle diameter of 0.2 μm, a narrow particle distribution and a well-shaped particle shape, and a high silver chloride content (at least 50 mol). % Or more) of silver chlorobromide emulsion.
By processing this lith-type silver halide photographic material with an alkaline hydroquinone developer having a low sulfite ion concentration, a so-called lith-type developer, a high cost last,
Images with high sharpness and high resolution can be obtained.

However, since these lith-type developers are susceptible to aerial oxidation, their preservative properties are extremely poor.
It is difficult to keep the development quality constant during continuous use.

There is known a method of rapidly obtaining a high-contrast image without using the lith developer. For example, as can be seen in JP-A-56-106244, a silver halide photographic light-sensitive material contains a hydrazine derivative,
The processing is carried out with an alkali developing solution containing an amino compound. According to these methods, the homeostasis is good,
A high-contrast image can also be obtained by processing with a developer capable of rapid processing.

In these techniques, the hydrazine derivative had to be processed with a developing solution having a pH of more than 11.2 in order to fully exhibit the high contrast property. In a high pH developer having a pH of over 11.2, the developing agent is easily oxidized when exposed to air. It is more stable than the lith developer, but due to the oxidation of the developing agent, an ultrahigh contrast image may not be often obtained.

In order to make up for this drawback, Japanese Patent Laid-Open No. 63-29751 and European Patents 333,435 and 345,025 have comparatively low levels.
There is disclosed a silver halide photographic light-sensitive material containing a contrast-increasing agent that makes the contrast high even with a pH developer.

However, in the case of an image forming method in which a silver halide photographic light-sensitive material containing such a contrast-increasing agent is processed with a developer having a pH of less than 11.0, sensitization or softening with time,
The present situation is that satisfactory performance cannot be obtained due to the problem of deterioration of so-called black spots, which are sand-like fog generated in the unexposed area after development processing.

[0009]

SUMMARY OF THE INVENTION In contrast to the above problems, the object of the present invention is to obtain high sensitivity, high contrast, less black spots on the unexposed area even when processed with a developing solution having a pH of less than 11.2, and to improve with time. An object of the present invention is to provide an image forming method using a black-and-white silver halide photographic light-sensitive material with less fluctuation in performance.

[0010]

SUMMARY OF THE INVENTION The above object of the present invention is to provide at least one silver halide emulsion layer on a support and to contain a hydrazine derivative in the silver halide emulsion layer and / or its adjacent layer. In an image forming method of forming an image by treating a silver photographic light-sensitive material with a developer having a pH of less than 11.2, at least one of the silver halide emulsion layers comprises 20 mol% or more of silver bromide in the silver halide emulsion. Containing silver halide grains containing 10 to ^{9 -9} to 1 mol of silver per 1 mol of silver.
It is achieved by an image forming method using a silver halide photographic light-sensitive material, which is a grain prepared in the presence of 10 ⁻⁴ mol of rhodium salt. Hereinafter, the present invention will be specifically described.

First, the hydrazine derivative preferably used in the present invention is represented by the following general formulas [Hc] and [H-
The compound represented by d] is mentioned.

[0012]

[Chemical 1]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and n represents an integer of 1 or 2. When n = 1, R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, Or a heterocyclic oxy group, R ₁₅ and R
₁₆ may form a ring with a nitrogen atom. When n = 2,
R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkynyloxy group, an aryloxy group, or hetero. Represents a ring oxy group. However, when n = 2, R ₁₅ and R
_At least one of ₁₆ represents 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 oxy group. R ₁₇ represents an alkynyl group or a saturated heterocyclic group.

The compound represented by the general formula [Hc] or [Hd] includes a compound in which at least one H of -NHNH- in the formula is substituted with a substituent.

More specifically, A is an aryl group (eg, phenyl, naphthyl, etc.), or a heterocyclic group containing at least one sulfur atom or oxygen atom (eg, thiophene, furan, benzothiophene, pyran, etc.). Represents

R ₁₅ and R ₁₆ are each a hydrogen atom, an alkyl group (eg, methyl, ethyl, methoxyethyl, cyanoethyl, hydroxyethyl, benzyl, trifluoroethyl, etc.), an alkenyl group (eg, allyl, butenyl, pentenyl, pentadienyl). Etc.), an alkynyl group (eg, propargyl, butynyl, pentynyl, etc.),
Aryl groups (eg, phenyl, naphthyl, cyanophenyl, methoxyphenyl, etc.), heterocyclic groups (eg, unsaturated heterocyclic groups such as pyridine, thiophene, furan and saturated heterocyclic groups such as tetrahydrofuran, sulfolane),
Hydroxy group, alkoxy group (eg, methoxy, ethoxy, benzyloxy, cyanomethoxy, etc.), alkenyloxy group (eg, allyloxy, butenyloxy, etc.), alkynyloxy group (eg, propargyloxy, butynyloxy, etc.), aryloxy group (eg, ,
Phenoxy, naphthyloxy, etc.) or a heterocyclic oxy group (eg, pyridyloxy, pyrimidyloxy, etc.), and when n = 1, R ₁₅ and R ₁₆ together with the nitrogen atom form a ring (eg, piperidine, piperazine, morpholine, etc.) May be formed.

However, when n = 2, at least one of R ₁₅ and R ₁₆ is an alkenyl group, alkynyl group, saturated heterocyclic group, hydroxy group, alkoxy group, alkenyloxy group, alkynyloxy group, aryloxy group or hetero. It represents a ring oxy group.

Specific examples of the alkynyl group and saturated heterocyclic group represented by R ₁₇ 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 the substituent that can be introduced include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, and a sulfamoyl group, Acyl group, amino group, alkylamino group, arylamino group, acylamino group, sulfonamide group, arylaminothiocarbonylamino group,
Examples thereof include a hydroxy group, a carboxy group, a sulfo group, a nitro group and a cyano group. Of these substituents, the sulfonamide group is preferred.

In each general formula, A preferably contains at least one diffusion resistant group or silver halide adsorption promoting group. As the anti-diffusion group, a ballast group commonly used in non-moving photographic additives such as couplers is preferable. The ballast group is a group having a carbon number of 8 or more and relatively inert to photographic properties, and is selected from, for example, an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. You can

Examples of the silver halide adsorption promoting group include groups described in US Pat. No. 4,385,108 such as thiourea group, thiourethane group, heterocyclic thioamide group, mercapto heterocyclic group and triazole group.

--NH in the general formulas [Hc] and [Hd]
H of NH-, that is, the hydrogen atom of hydrazine, is a sulfonyl group (for example, methanesulfonyl, toluenesulfonyl, etc.),
Acyl groups (eg acetyl, trifluoroacetyl,
Ethoxycarbonyl, etc.), an oxalyl group (eg, ethoxalyl, pyruvoyl, etc.) and the like, and the compounds represented by the general formulas [Hc] and [Hd] are such compounds. Also includes.

In the present invention, more preferred compounds are the compounds of the general formula [Hc] when n = 2, and the compounds of the general formula [Hd].

In the compound of the general formula [H-c] with n = 2, R ₁₅ and R ₁₆ are hydrogen atom, alkyl group, alkenyl group, alkynyl group, aryl group, saturated or unsaturated heterocyclic group, hydroxy group, Or an alkoxy group, and R ₃₁
Further, a compound in which at least one of R ₃₂ and R ₃₂ represents an alkenyl group, an alkynyl group, a saturated heterocyclic group, a hydroxy group, or an alkoxy group is more preferable.

Typical compounds represented by the above general formulas [Hc] and [Hd] are shown below.
However, as a matter of course, the specific compounds of the general formulas [Hc] and [Hd] that can be used in the present invention are not limited to these compounds.

Specific compound examples

[0027]

[Chemical 2]

[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

Specific compounds other than the above are disclosed in
2-841 542 (4) to 546 (8) compound examples
There are (1) to (61) and (65) to (75).

The hydrazine derivative in the present invention is disclosed in
It can be synthesized by the method described in No. 2-841, pages 546 (8) to 550 (12). The addition position of the hydrazine derivative of the present invention is the silver halide emulsion layer and / or the adjacent layer. The addition amount is preferably 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver, and more preferably 1 × 10 ^-5 mol to 1 per mol of silver.
× 10 ^-2 mol.

When [Hc] or [Hd] is contained as a hydrazine derivative, it is disclosed in JP-A-4-98239.
(7) at least one of the nucleation promoting compounds described in page 1, lower left column, line 1 to 626 (26), lower left column, line 11 is used in a silver halide emulsion layer and / or a silver halide emulsion layer on a support. It is preferably included in the non-photosensitive layer on the side.

Typical examples of the nucleation accelerator are shown below.

[0035]

[Chemical 6]

[0036]

[Chemical 7]

Still another specific example is JP-A-4-98239.
No. 608 (8), compounds I-1 to I-26, 609
Compounds II-1 to 1-1 described on pages (9) to 610 (10)
II-29, compounds 610 (10) to 611 (11), compounds III-1 to III-25, 611 (11) to 613 (13), compounds IV-1 to IV-41, 613 (13) pages ~ 614 (1
4) Compounds VI-1 to VI-27, 615 (1)
Compounds V-II-1 to V described on pages 5) to 616 (16)
-II-30, Compounds V-III-described on pages 616 (16)-
1-V-III-35, compounds described on pages 618 (18) to 620 (20) VI-I-1 to VI-I-44, 621 (21) to 624 (24)
Compounds described on page VI-II-1 to VI-II-68 and 624
Compounds described in pages (24) to 626 (26) VI-III-
1 to VI-III-35 other than the above representative examples.

The photosensitive material of the present invention is preferably provided with at least one conductive layer on the support. As a typical method for forming the conductive layer, a water-soluble conductive polymer,
There are a method of forming using a hydrophobic polymer and a curing agent and a method of forming using a metal oxide. For these methods, for example, the methods described in JP-A-3-265842, page (5) to page (15) can be used.

In the silver halide emulsion layer used in the present invention, at least one layer has silver halide grains containing 20 mol% or more of silver bromide in the silver halide emulsion, and the silver halide grains. Was prepared in the presence of 10 ⁻⁹ to 10 ⁻⁴ mol of rhodium salt per mol of silver.

Further, (standard deviation of particle size) / (average value of particle size)
Monodisperse particles represented by × 100 and having a coefficient of variation 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 include various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, sliding agents, development inhibitors, and ultraviolet absorbers. , An anti-irradiation dye, a heavy metal, a matting agent and the like can be further contained by various methods. Further, a polymer latex can be contained in the silver halide photographic emulsion of the present invention and the backing layer.

These additives are described in more detail in Research Disclosure Vol. 176 Item / 7643 (December 1978) and Vol. 187 Item / 8716 (November 1979). It is summarized below.

Additive Type RD / 7643 RD / 8716 1. Chemical sensitizer Page 23 Page 648 Right column 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column to supersensitizer, page 649, right column 4. Whitening agent Page 24 5. Antifoggants and stabilizers 24 to 25 pages 649 right column 6. Light absorbers, filter dyes 25 to 26 pages 649 right column ~ ultraviolet absorbers 650 page left column 7. Anti-stain agent page 25 right column page 650 left-right column 8. Dye image stabilizer page 25 9. Hardener 26 pages 651 left column 10. Binder page 26 Same as above 11. Plasticizer, lubricant Page 27 Page 650 Right column 12. Coating aid, surface active agent, pages 26 to 27, same as above 13. Antistatic Agent Page 27 As above As a support which can be used in the silver halide photographic light-sensitive material of the present invention, cellulose acetate, cellulose nitrate,
Examples thereof include polyester such as polyethylene terephthalate, polyolefin such as polyethylene, polystyrene, baryta paper, paper coated with polyolefin, glass and metal. These supports are subjected to a surface treatment if necessary.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing by various methods such as a commonly used method after exposure.

The black-and-white developing solution is an alkaline solution containing a developing agent such as hydroxybenzenes, aminophenols, aminobenzenes, etc., and sulfites, carbonates, bisulfites of other alkali metal salts, and JP-A-56-56. -106244, amino compounds, bromides, iodides and the like can be included. The pH of the developer is preferably less than 11.2.

[0046]

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

Example 1 (Preparation of silver halide photographic emulsions EmA and EmB) A silver iodobromide emulsion (2 mol% of silver iodide per mol of silver) was prepared by the simultaneous mixing method. The hexa bromine rhodium salt potassium salt 8 × 10 ^-8 mol during mixing, and the K ₂ IrCl ₆ was added per mol of silver, respectively 8 × 10 ^-7 mol. The resulting emulsion was an emulsion consisting of cubic monodisperse grains (coefficient of variation 9%) having an average grain size of 0.20 μm. Modified gelatin described in JP-A-2-280139 and G-8 was added, washed with water and desalted. The pAg at 40 ℃ after desalting is
It was 8.0. Subsequently, a 0.1 mol% potassium iodide aqueous solution per mol of silver was added to this emulsion to convert the grain surface, and then the following compounds [A] [B] [C] were used.
EmB was obtained by adding 15 ml of a 1% water drop solution of the mixture.
The emulsion prepared by the same method as above (except that no rhodium salt was added) was designated as EmA.

(Preparation of EmC) A silver iodobromide photographic emulsion (AgI ₂ mol%) was mixed with H ₂ O ₂ 5 × 1 per mol of silver by the simultaneous mixing method.
Prepared in the presence of 0 ^-3 . During this mixing, K ₂ IrCl ₆ was added to AgImol
8 × 10 ⁻⁷ mol was added per unit. Then, it was treated in the same manner as EmA to obtain EmC.

[0049]

[Chemical 8]

(Preparation of silver halide photographic light-sensitive material) One of 100 μm-thick polyethylene terephthalate film having 0.1 μm-thick undercoat layer (see Example 1 of JP-A-59-19941) on both sides On the undercoat layer, a silver halide emulsion layer having the following formulation (1) was used, in which the amount of gelatin was 2.0 g / m ² and the amount of silver was 3.2 g / m ^2.
And an emulsion protective layer of the following formulation (2) so that the amount of gelatin will be 1.0 g / m ^2, and on the other undercoat layer on the opposite side. Is a backing layer coated according to the following prescription (3) so that the amount of gelatin is 2.4 g / m ^2, and a backing protective layer of the following prescription (4) is further applied so that the amount of gelatin is 1 g / m ² . A sample was obtained by applying it to the.

Formulation (1) (composition of silver halide emulsion layer) Gelatin 2.0 g / m ² Silver halide emulsion A Silver amount 3.2 g / m ²

[0052]

[Chemical 9]

Stabilizer: 4-methyl-6-hydroxy-1,3,3a, 7-tetrazaindene 30 mg / m ² Antifoggant: adenine 10 mg / m ² 1-phenyl-5-mercaptotetrazole 5 mg / m ² Surfactant: saponin 0.1g / m ²

[0054]

[Chemical 10]

Hydrazine derivatives according to the present invention and compounds of the general formula [1] according to the present invention

[0056]

[Chemical 11]

Formula (3) (backing layer composition)

[0058]

[Chemical 12]

Gelatin 2.4 g / m ² Surfactant: saponin 0.1 g / m ² : S-1 6 mg / m ² colloidal silica 100 mg / m ² formulation (4) [backing protective layer composition] gelatin 1 g / m ² matting agent average particle size: 5.0μm monodisperse polymethyl methacrylate a cleat 50 mg / m ² surfactant: ^S-2 10mg / m 2 hardener: glyoxal 25 mg / m ^2: the H-1 35mg / m ² obtained sample After adhering a step wedge and exposing it to a tungsten light of 3200K for 5 seconds, the following conditions were measured by an automatic processor GR-26SR for rapid processing manufactured by Konica Co., Ltd. in which a developing solution and a fixing solution having the compositions shown below were added. It was processed in.

The obtained sample was subjected to 24 hours under the condition of 23 ° C. and 50% RH.
After time storage, it is hermetically packaged and thermo-treated for time 55
It was left for 3 days at ℃. The thermoprocessed sample was similarly exposed and developed and fixed.

Developer Formulation Ethylenediaminetetraacetic acid sodium salt 1g Sodium sulfite 60g Boric acid 40g Hydroquinone 35g Sodium hydroxide 8g Sodium bromide 3g 5-Methylbenzotriazole 0.2g 2-Mercaptobenzothiazole 0.1g 2-Mercaptobenzothiazole- 5-Sulfonic acid 0.2g 1-Phenyl-4,4-dimethyl-3-pyrazolidone 0.2g Add water and 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 6.5g 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 Sulfuric acid Aluminum (AI ₂ O ₃ Aqueous solution with a converted content of 8.1% W / V) 26.5g When using the fixer, the above composition A and composition B in 500ml of water in this order
It was dissolved in 1 liter and made up to 1 l for use. The pH of this fixer is vinegar
Adjusted to 4.8 with acid.

[0062] The concentration of the obtained sample was measured with an optical densitometer, Konica PDA-65,
The relative sensitivity was shown with the sensitivity of Sample No. 1 at a density of 2.5 being 100, and gamma was displayed with the tangent of the concentrations of 0.1 and 2.5. Gamma value less than 6 cannot be used, 6.0
If the gamma value is less than 10.0, the contrast performance is still insufficient. With a gamma value of 10.0 or higher, the image becomes ultra-high contrast and can be used sufficiently.

The black spots in the unexposed area were also evaluated with a magnifying glass of 40 times. The highest rank is "5" when black spots are not generated at all, and the rank is gradually lowered to "4", "3", "2", "1" according to the degree of occurrence of black spots. It shall be evaluated. In the ranks "1" and "2", black spots are also levels that are not practically preferable.

The results are shown in Table 1.

[0065]

[Table 1]

From the results shown in Table 1, the sample using the emulsion containing grains prepared in the presence of rhodium according to the present invention has less black spots on the same day and over time, and has little sensitivity and gamma performance variation with time. I understand.

Example 2 EmA of Example 1 except that the silver chloride content was 10 mol% and the silver bromide content was 90 mol%, and that the nucleation accelerator in the additive was removed.
Silver halide emulsions EmD, E, and F were prepared in the same manner as in B and C, and silver halide photographic light-sensitive materials were prepared.

Each of the samples was added to the developer of Example 1 with the following Am.
-1 Compound was treated and evaluated in the same manner as in Example 1 except that 0.5 ml was added.

[0069]

[Chemical 13]

The results are shown in Table 2.

[0071]

[Table 2]

From the results shown in Table 2, as in the case of Example 1, good results were obtained for the light-sensitive material using EmE according to the present invention.

[0073]

INDUSTRIAL APPLICABILITY According to the present invention, a black-and-white silver halide photographic light-sensitive material having high sensitivity, high contrast, little black spots generated in an unexposed area, and little performance variation with time even when processed with a developer having a pH of less than 11.2 It was possible to provide an image forming method using.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Takehiko Ito 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company In-house (72) Mariko Kato 1 Sakura-cho, Hino-shi, Tokyo Konica Stock Company In-house

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 has a pH of 11. In an image forming method of forming an image by processing with a developing solution of less than 2, at least one of the silver halide emulsion layers comprises silver halide grains containing 20 mol% or more of silver bromide in the silver halide emulsion. An image forming method characterized in that the silver halide grains are grains prepared in the presence of 10 ⁻⁹ to 10 ⁻⁴ mol of rhodium salt per mol of silver.