JPH04280245A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To minimize both black dot generation and fogging by containing a hydrazine derivative in a silver halide emulsion layer and/or its adjacent layer, and containing a specified compound therein. CONSTITUTION:A compound having at least one silver halide emulsion layer on a support body, containing a hydrazine derivative in the silver halide emulsion layer and/or its adjacent layer, and represented by the formula I is contained. In this case, R1, R2 each represent a hydrogen atom or an alkoxy group, X represents a divalent group containing oxygen atom or hydrogen atom forming a 15- or 21-membered ring. The addition amount of this compound is within the range of 3X10<-7>X10<-1>, more preferably 3X10<-6>-3X10<-2> per mole of silver halide.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a light-sensitive material for printing plate making.

0002

BACKGROUND OF THE INVENTION In general, high-contrast photographic images are used in the photolithography process to form characters and halftone-resolved photographic images, and in ultra-precision photolithography processes to form fine line images.

It is known that certain types of silver halide photographic materials for this purpose can form photographic images with extremely high contrast.

[0004] Conventionally, for example, a photosensitive material made of a silver chlorobromide emulsion with an average grain size of 0.2 μm, a narrow grain distribution and uniform grain shape, and a high content of silver chloride (at least 50 mol % or more) A method has been used to obtain images with high contrast, high sharpness, and high resolution, such as halftone dot images or fine line images, by treating the image with an alkaline hydroquinone developer having a low sulfite ion concentration.

This type of silver halide photosensitive material is known as a lithium-type photosensitive material.

The photolithography process involves converting a continuous tone original into a halftone image, that is, converting the continuous tone density changes of the original into a set of halftone dots having an area proportional to the density. include.

For this purpose, a dot image is formed by using the above-mentioned lithium-type photosensitive material and photographing an original through an intersection screen or a contact screen, and then performing a development process.

For this purpose, a silver halide photographic material containing a silver halide emulsion with fine grains and a uniform grain size and shape is used, but even when this type of silver halide photographic material is used, When processed with a general black and white developer, the halftone image formation etc. is inferior to when developed with a lithium type developer. Therefore, it is processed with a developer called a Lith type developer, which has an extremely low sulfite ion concentration and uses hydroquinone as a single developing agent.

However, since the Lith type developer is susceptible to auto-oxidation and has extremely poor storage stability, there is a strong need for a control method to maintain constant development quality even during continuous use. Significant efforts have been made to improve the persistence of.

[0010] As a method for improving this, in order to maintain the stability of the above-mentioned Lith type developer, a replenisher (processing fatigue replenishment) is used to compensate for the deterioration in activity due to development processing, and a replenisher is used to compensate for oxidation deterioration over time. A so-called two-liquid separation replenishment system, in which a replenisher and a replenisher (time-related fatigue replenishment) are refilled using separate replenishers, is generally widely adopted in automatic developing machines for photolithography and the like.

However, the above method has the disadvantage that it is necessary to control the replenishment balance of the two liquids, which complicates the apparatus and operation.

[0012] Furthermore, in the Lith type development, since it takes a long time (induction period) until an image appears due to development, an image cannot be obtained quickly.

On the other hand, a method is known for quickly obtaining a high contrast image without using the above-mentioned Lith type developer. For example, U.S. Patent No. 2,419,975, JP-A No. 5
As seen in JP-A-1-16623, JP-A-51-20921, JP-A-56-106244, etc., a hydrazine derivative is contained in a silver halide photosensitive material.

According to these methods, it is possible to maintain a high concentration of sulfite ions in the developer, and it is possible to process with improved preservability.

However, in these methods, in order to fully exhibit the high contrast properties of the hydrazine derivative, it is necessary to process with a developer having a pH of 11 or more. In a developer having a high pH of 11 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.

[0016] In order to compensate for this drawback, Japanese Patent Application Laid-Open No. 63-297
No. 51 and European Patent No. 333,435 disclose a silver halide photographic light-sensitive material containing a contrast-enhancing agent that can achieve high contrast even in a relatively low pH developer.

However, when a silver halide photographic light-sensitive material containing such a high contrast agent is processed with a developer having a pH of less than 11, the high contrast is insufficient and satisfactory halftone dot performance cannot be obtained. This is the current situation.

Furthermore, when a hydrazine derivative is used to obtain a high-contrast image, a problem called sandy black spots tends to occur, but as a means to improve this problem, an acidic substance is added to the image.
It has been proposed to lower the pH of the film surface, but this causes problems such as delaying the hardening of gelatin in the coating film, decreasing the mechanical strength of the coating film, and deteriorating stability over time. do.

[0019]

OBJECTS OF THE INVENTION In order to solve the above-mentioned problems, an object of the present invention is to provide a silver halide photographic material that uses a hydrazine derivative, has ultra-high contrast, has less occurrence of black spots, and has less fog. It is to provide.

[0020]

[Structure of the Invention] The above object of the present invention is to provide a silver halide emulsion layer having at least one silver halide emulsion layer on a support, containing a hydrazine derivative in the silver halide emulsion layer and/or its adjacent layer, and This is achieved by a silver halide photographic material containing a compound represented by the following general formula [I].

[0021]

[Case 2]

[In the formula, R1 and R2 are each a hydrogen atom,
It represents an alkoxy group, and X is a divalent group containing an oxygen atom or a nitrogen atom, forming a 15- or 21-membered ring. ]
The present invention will be explained in detail below.

Specific examples of the compound represented by the general formula [I] of the present invention include, for example, JP-A No. 2-284138 (2).
Compounds 1 to 8 described on page 1 or the following compounds may be mentioned.

The amount of these compounds used in the present invention is 3 x 10-7 to 3 x 10-1 mol, more preferably 3 x 10-1 mol, per mol of silver halide contained in the light-sensitive material.
It is preferable to set it as the range of x10-6 - 3x10-2.

[0025]

[Chemical formula 3]

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

[0027]

[C4]

In the formula, A represents an aryl group or a heterocyclic group containing at least one sulfur atom or oxygen atom, and G represents -[
C(O)]n- group, sulfonyl group, sulfoxy group, -P
(O)(R)- group or iminomethylene group, n is 1
or 2, A1 and A2 are both a hydrogen atom, one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted acyl group, and R is a hydrogen atom or an alkyl group. , aryl group, alkoxy group, aryloxy group, amino group, carbamoyl group,
It represents an oxycarbonyl group or an -O-R3 group, and R3 represents an alkyl group or a saturated heterocyclic group.

Further, the following general formulas [A] and [B] are preferred.

[0030]

[C5]

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, R1 and R2 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 hetero group. Represents a ring oxy group, R1 and R
2 may form a ring together with the nitrogen atom. When n=2,
R1 and R2 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 a heterocyclic group. represents a group. However, when n=2, R1 and R
At least one of 2 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. R3 represents an alkynyl group or a saturated heterocyclic group. General formula [A] or [
The compound represented by B] includes those in which at least one H of -NHNH- in the formula is substituted with a substituent.

A, R1, and R2 have the same meanings as described in Japanese Patent Application No. 2-222638. H in -NHNH- in general formulas [A] and [B], 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.) ), oxalyl group (e.g., ethoxalyl, pyruvoyl, etc.), and the general formula [
The compounds represented by [A] and [B] also include such compounds.

More preferred compounds in the present invention are compounds of the general formula [A] where n=2, and compounds of the 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.

As representative compounds represented by the above general formulas [A] and [B], exemplary compounds (I-1) to (I- 59),
H described in Japanese Patent Application No. 2-222638, pages 20 to 44
-1 to H-130, there are those shown below. However, as a matter of course, general formula [A] that can be used in the present invention,
The specific compounds of [B] are not limited to these compounds.

[0036] Specific compound examples

[0037]

[C6]

[0038]

[C7]

[0039]

[Chemical formula 8]

[0040]

[Chemical formula 9]

The compound according to the present invention is disclosed in Japanese Patent Application No. 2-222
It can be synthesized by the method described in No. 638, pages 59 to 77.

[0042] The silver halide photographic light-sensitive material to which the present invention is applied and which can produce high-contrast images contains at least one hydrazine compound represented by the above general formulas [A] and [B]. However, the amount of compounds of general formulas [A] and [B] contained in the photographic light-sensitive material is 5 x 10 per mole of silver halide contained in the photographic light-sensitive material.
-7 mol to 5 x 10-1 mol is preferred.

[0043] In particular, it is preferably in the range of 5 x 10-6 mol to 1 x 10-2 mol.

The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halides such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any material used in emulsions can be used, and the silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method, and various techniques known in the photographic material industry can be used. can.

Although the photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, Glafkides or Ze
likman et al. or H. Frieser, ed.
Grundlagen d-er Photograp
hischen Prozesse mit Silb
erhalo-geniden, Akademich
e Verlagsgesellschaft, 196
The method described in 8) can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, gold or other noble metal compounds, or a combination thereof can be used.

As the photosensitive emulsion, the above emulsions may be used alone, or two or more types of emulsions may be mixed.

The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure No. 176.
Volume Item 17643 (December 1978) and Item 18
It is described in Volume 7, Item 187166 (November 1979), and the relevant parts are summarized in the table below.

[0049] Additive type
RD17643RD
187161. chemical sensitizer
23 pages
Page 648, right column 2. Sensitivity enhancer
Same as above 3. spectral sensitizer
pages 23-24
Page 648 right column ~ Super sensitizer
Page 649, right column 4. brightener
Page 24 Antifoggant 5.
pages 24-25
Page 649 right column and stabilizers Light absorbers, filters
64
9 Right column~6.
Pages 25-26 Dyes, UV absorbers
650 left column 7. anti-stain agent
Page 25 8. dye image stabilizer
25 pages
9. Hardener
26 pages
Page 651 left column 10. binder
26 pages
Same as above 11. Plasticizer/lubricant
27 pages
650 Right column Coating aid・12.
pages 26-27
Same as above Surfactant Static 13.
27 pages
Same as above Inhibitor In carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic light-sensitive materials. .

Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α -Olefin polymer (
Examples include paper coated with or laminated with polyethylene, polypropylene, ethylene/butene copolymer, or the like.

The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating process is based on JP-A-52-10491.
No. 23, No. 59-18948, No. 59-1994
The treatments described in Publications No. 0 and No. 59-11941 are preferred. In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.

Processing such as development is described in Japanese Patent Application No. 2-2226.
In addition to using the developer shown in No. 38, various methods known in the art commonly used for processing silver halide photographic materials can be used.

[0053]

[Examples] Next, the present invention will be specifically explained with reference to Examples. However, as a matter of course, the present invention is 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%). Modified gelatin (patent application Hei 1-1807)
87 Exemplified Compound G-8) was added, and Patent Application No. 1-1807
It was washed with water and desalted in the same manner as in Example 1 of No. 87. 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 a mixture of compounds [A], [B], and [C] was added to obtain emulsion A. Ta.

[0055]

[Chemical formula 10]

(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 3.2g/m2, and on top of that, an emulsion protective layer of the following formulation (2) is coated so that the gelatin amount is 1.0g/m2, On the other undercoat layer on the opposite side, a backing layer was coated according to the following recipe (3) so that the amount of gelatin was 2.4 g/m2, and on top of that, a backing protective layer according to the following recipe (4) was applied. Sample No. was coated so that the amount of gelatin was 1 g/m2. 1-1
I got 8.

Prescription (1) (Silver halide emulsion layer composition)
gelatin
2.
0g/m2 Silver halide emulsion A amount
3.
2g/m2

[0058]

[Chemical formula 11]

Hydrazine derivatives according to the present invention and compounds of general formula [I] or [II] according to the present invention in amounts shown in Table 1

[0060]

[Chemical formula 12]

Matting agent: monodispersed silica with an average particle size of 3.5 μm
3mg/m2 Hardener: 1,3-vinylsulfonyl-2-propanol 40mg/m2 Prescription (3) (backing layer composition)

[0062]

[Chemical formula 13]

Gelatin

2.4g/m2 Surfactant: Saponin

0.1g/m2 :S-1

6mg/m2 colloidal silica
100mg/m2 Formula (4) (backing protective layer) Gelatin

1mg/m2 Matting agent: Monodispersed polymethyl methacrylate with an average particle size of 5.0μm 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, the following table 1
Processing was carried out under the following conditions using an automatic developing machine GR-26SR for rapid processing manufactured by Konica Corp., which was charged with a developer and a fixer having the composition shown below.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution)
240ml sodium sulfite
17g Sodium acetate trihydrate
6.5g boric acid

6g Sodium citrate dihydrate
2g (Composition B) Pure water (ion exchange water)
17ml
Boric acid (50% W/V aqueous solution)
4.7g Aluminum borate (Al2O3 equivalent content is 8.1% W/V
(aqueous solution) 26.5 g When using the 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 100, and the relative sensitivity is expressed as 100, and G is expressed as the tangent between the densities of 0.1 and 2.5. It cannot be used with a G value of less than 6.0, and 6.0
If the gamma value is less than 10.0, the high contrast performance is still insufficient. A gamma value of 10.0 or higher will result in an ultra-high contrast image,
It becomes fully practical.

Further, black spots in unexposed areas were also evaluated using a 40x magnifying glass. The highest rank is ``5'' when there are no black spots, and the rank is lowered to ``4'', ``3'', ``2'', and ``1'' depending on the degree of occurrence of black spots. shall be evaluated. Rank “1” and “2”
'', the black spots are large and are at a level that is not practical.

The results are shown in Table 1.

[0068]

[Table 1]

From the results in Table 1, it can be seen that the samples of the present invention have fewer black spots and less gamma.

Example 2 Chemically sensitized cubic silver chloride emulsion (average grain size 0.3 μm)
) was coated with the following compound added to give a silver amount of 5 g/m2.

[0071]

[Chemical formula 14]

Compound (I) according to the present invention
51mg/m2
Hydrazine derivative [H] according to the present invention
The samples obtained in the amounts shown in Table 2 were processed and evaluated in the same manner as in Example 1.

[0073]

[Table 2]

From the results in Table 2, the samples of the present invention were able to obtain the same effects as Example 1.

[0075]

Effects of the Invention According to the present invention, it was possible to provide a silver halide photographic light-sensitive material which has ultra-high contrast but has less occurrence of black spots and less fog.

Claims (1)

[Claims] Claim 1: having at least one silver halide emulsion layer on a support, containing a hydrazine derivative in the silver halide emulsion layer and/or its adjacent layer, and having the following general formula [
A silver halide photographic material containing a compound represented by [I]. embedded image [In the formula, R1 and R2 represent a hydrogen atom and an alkoxy group, respectively, and X is a divalent group containing an oxygen atom or a nitrogen atom, forming a 15- or 21-membered ring. ]