JPH03249756A - Ultra-high contrast negative image forming method - Google Patents

Abstract

PURPOSE:To form negative images which are 10 or over in gamma, are extremely high in contrast and lessen pepper generation by processing a photosensitive material in the presence of >=1 kinds of polyalkylene oxides or the derivatives thereof with the developing soln. contg. at least specific two components. CONSTITUTION:The exposed silver halide photographic sensitive material of a substantially surface latent image type is subjected to the development processing in the presence of at least one kind of the polyalkylene oxides or the derivatives thereof with the developing soln. contg. at least an amino phenolic developing agent and reductions. The polyalkylene oxide derivatives used in this embodiment include the addition polymer of polyethylene oxide, etc., and water, one kind of the compds. selected from aliphat. alcohols, etc. The aminophenolic developing agent is particularly preferably 4-(N-methyl) aminophenol sulfate (metol). The negative images which are 10 or over in gamma, are extremely high in contrast and lessen the pepper generation are formed in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method of forming a photographic image using a silver halide photographic material. More specifically, the dispute relates to a method for forming extremely high contrast negative images, which are particularly useful in Graphic Arp's printing photolithography process.

(Prior Art) In the photoengraving process, it is required to form sharp halftone dot images or line images, so an image forming system that exhibits extremely high contrast photographic characteristics (in particular, a gamma of 10 or more) is required.

Conventionally, for this purpose, the content of silver chloride was 50 mol%,
A lithium-type silver halide photographic light-sensitive material comprising a silver chlorobromide emulsion preferably exceeding 70 mol % contains only hydroquinone as a developing agent and has an extremely low free sulfite ion concentration (usually 0.1 mol/l or less). A method of processing with a Lith developer has been used. However, since lithium-type silver halide photographic emulsions require the use of silver chlorobromide emulsions with high silver chloride content, it has been difficult to achieve high sensitivity.

Other methods for obtaining high contrast negative images include US Pat. No. 4.168.977, US Pat. No. 4.224.401,
4.241.164, 4.269.929, 4.311.781, 4.650.746
There is a method using a specific hydrazine derivative as disclosed in No. 1, et al.

According to this method, a surface latent image type silver halide photographic light-sensitive material containing a specific hydrazine derivative (generally an acylphenylhydrazine derivative) as a nucleating agent is prepared at a pH of 11 to 1.
When processed with a 2.3 developer, ultra-high contrast and high sensitivity photographic characteristics with a gamma of over 10 can be obtained. In this method, silver bromide or a silver chlorobromide emulsion with a high silver bromide content can be used, so higher sensitivity can be achieved compared to a lithium-type silver halide emulsion.

However, high contrast imaging systems using the above-mentioned acylhydrazine derivatives have been found to have several drawbacks. In other words, by using the above image forming system, you can obtain a high-contrast negative image and at the same time
This is a major problem in the photolithography process due to the occurrence of black spots.

Pellets are black sesame-like spots that occur in unexposed areas, such as areas between halftone dots that should be undeveloped, and significantly reduce the commercial value of photolithographic materials. cause a malfunction.

Therefore, a great deal of effort has been made to develop techniques for suppressing perturbation, but improvements in perturbation often result in a decrease in sensitivity and gamma, and the development of an image forming system that achieves high sensitivity and high contrast without the occurrence of perturbation. is strongly desired.

A second drawback of conventional high-contrast imaging systems is that large amounts of expensive hydroquinone must be used to maintain a constant developer activity. Since the lithium developer has a low concentration of sulfite ions, it is easily subject to air oxidation, resulting in significant consumption of hydroquinone, the developing agent. Furthermore, although it is permitted to add a high concentration of sulfite to the developer of a high-contrast image forming system that uses hydrazine derivatives, hydroquinone is susceptible to air oxidation due to its high pf ((II~12.3)). Consumption is significant. Therefore,
In order to maintain the development activity of these developers, it is necessary to maintain the amount of hydroquinone in the developer above a certain level by using a large amount of expensive hydroquinone or by replenishing the amount of hydroquinone consumed by air oxidation. Therefore, it is desired to develop a high-contrast image forming system using a developer that consumes less hydroquinone or does not use hydroquinone as a developing agent.

(Problems to be Solved by the Invention) The problems to be solved by the present invention are to achieve extremely high contrast and clear image with a gamma of over 10 by processing a silver halide photographic light-sensitive material with a developer that does not use hydroquinone as a developing agent. An object of the present invention is to provide a method for forming a negative image with less occurrence of negative images.

(Means for Solving the Problems) The above object of the present invention is to provide a developer containing at least (1) an aminophenol developing agent and (2) reductones, and at least one polyalkylene oxide or a derivative thereof ( This was achieved by developing an exposed silver halide photographic material of substantially surface latent image type in the presence of a polyalkylene oxide derivative (hereinafter simply referred to as a polyalkylene oxide derivative).

The polyalkylene oxide derivatives used in the present invention include polyalkylenes such as polyethylene oxide and polypropylene oxide, polyalkylene oxides such as polyethylene oxide and polypropylene oxide, water, aliphatic alcohols, phenols,
Addition polymers with one type of compound selected from the group of glycols, fatty acids, and organic amines, or condensates of polyalkylene oxide and one type of compound selected from the above group of compounds, or various These include mutual block copolymers of alkylene oxide (eg, ethylene oxide and propylene oxide).

Further, the polyalkylene oxide derivative used in the present invention has a number average molecular weight of 500 to 20.000, particularly preferably 1.000 to 10.000.

Next, some specific examples of polyalkylene oxide derivatives used in the present invention will be shown.

P-I HO(CH2CH20),,H(molecular weight 1
．． 000~20.000P-2H(OCH2CH,)
1 (CH2H20). (CH2CH20). HP-a
C+28+10(CH2CH20)z, HP-,
i C+5H3sO(CH2CH2O)zsHP
-5Cl8H330 (CH2CH20),. HP-6C
5H17+0(CH2CH20)20H-9 -f at C*H+s')-0(CH2CH20)+00
8shi-10 Cl 1H23c00 (CH2CH20) 308P-1
3C, H, □CH"CH-C8H160 (CH2CH2
0) 16H) The polyalkylene oxide derivative used in the present invention may be contained in either the photographic material or the developer. However, it is more preferable to incorporate it into the photographic material.

In order to incorporate a polyalkylene oxide derivative into a photographic light-sensitive material, the compound may be added to a surface latent image type photographic emulsion, or a non-photosensitive layer consisting of another hydrophilic colloid layer, such as a protective layer. , an intermediate layer, an antihalation layer, a filter layer, and other layers. Preferably, it is added to the surface latent image type photographic emulsion used in the present invention. In order to add the polyalkylene oxide derivative used in the present invention to a photographic light-sensitive material, water or an organic solvent miscible with water, such as alcohols, ketones, etc.
It may be dissolved in esters, amides, etc. and added to the surface latent image type photographic emulsion or non-photosensitive hydrophilic colloid solution used in the present invention.

The amount of the polyalkylene oxide derivative used in the present invention added to the photographic light-sensitive material is 0 per mole of silver halide.
．． A range of 1 g to 5 g is appropriate, and 0.5 g to 3 g.
A range of g is particularly preferred. Further, the timing of adding these compounds can be selected at any time during the process of manufacturing the photographic material.

For example, when it is added to a silver halide emulsion layer, it is preferably added at any time after the second ripening and before coating.

Note that the polyalkylene oxide derivative used in the present invention is effective even when added to the developer of the present invention, and in this case, it is sufficient to add 0.1 to 5 g per 1 liter of the developer.

An aminophenol developing agent is used in the developer used in the present invention. Examples of aminophenol-based developing agents include 4-aminophenol, 4-(N-methyl)aminophenol, 2,4-diaminophenol, N-(4-hydroxyphenyl)glycine, and 2-(N-2'-hydroxyethyl). Aminophenol, 2-hydroxymethyl-
4-aminophenol, 2-hydroxymethyl-4-(
Examples include N-methyl)aminophenol, hydrochloride and sulfate of these compounds, and 4-(N-methyl)aminophenol sulfate (methol) is particularly preferred. The amount of these developing agents added is 0.5 to 10 g, preferably 1 to 3 g per liter of developer.

The reductones used in the developer used in the present invention are:
Endiol type (Endiol) Enaminol type (En
aminol), -r-diamine type (Endiami
n), thiolenol type (Thiol-EnoJ) and enamine-thiol type (Enamin-Thiol
) is generally known as a compound. Examples of these compounds are U.S. Pat.
It is described in No. 237443. The methods for synthesizing these reductones are also well known, for example in ``The Chemistry of Reductones'' by Danji Nomura and Norifumi Omura (Uchida Rokakuba Shinsha, 1969).

is covered in detail.

Among these, particularly preferred reductones for use in the present invention are 3-carbonyl-enediol type compounds represented by the following general formula [■].

Here, R is a hydrogen atom or a hydroxyl group, and n is 1 to 4.
is an integer.

Next, particularly preferred specific examples of reductones used in the present invention will be given.

■■Kobun-2 ■-4 ■I-1 ■KibunI [-2 1-4 H The reductones used in the present invention can also be used in the form of alkali metal salts such as lithium salts, sodium salts, and potassium salts. These reductones are used in an amount of 1 to 1 per 11 parts of the developer.
It is preferable to use 50 g, preferably 5 to 20 g.

It is desirable that the developer used in the present invention contains a preservative and an alkali in addition to the above-mentioned essential components. Sulfites can be used as preservatives. Sulfites include sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium bisulfite, potassium metabisulfite, and the like. The amount of these sulfites added is preferably 0.2 mol or less, particularly 0.1 mol or less per developer.

The alkali is used to adjust the pH of the developer to 9 or higher, particularly preferably to a pH of 9 or higher.
Added to set to 1o-11. As the alkaline agent used for pH setting, common water-soluble inorganic alkali metal salts such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and tribasic potassium phosphate can be used.

In addition to the above-mentioned components, the developer used in the present invention may optionally contain a water-soluble acid (e.g. acetic acid, boric acid), a pH buffer (
For example, sodium carbonate, potassium carbonate, tribasic sodium phosphate, sodium metaborate), inorganic fog suppressants (
For example, sodium bromide, potassium bromide), organic fog suppressants (for example, l-phenyl-5-mercaptotetrazole), organic solvents (for example, ethylene glycol, diethylene glycol, methyl cellosolve), etc. Depending on the situation, it may contain a toning agent, a surfactant, an antifoaming agent, a water softener, etc.

The developing treatment temperature is selected to be in the range of 18 to 50°C, more preferably in the range of 20 to 40°C.

The development method of the present invention makes it possible to obtain ultra-high contrast and high sensitivity photographic properties with less occurrence of blur without using any expensive hydroquinone as a developing agent.

Next, a silver halide photographic material to which the image forming method of the present invention is applied will be explained.

The silver halide photographic material used in the present invention has at least one emulsion layer consisting essentially of a surface latent image type silver halide emulsion. Here, the term "substantially surface latent image type silver halide emulsion" refers to a type of silver halide emulsion in which a latent image is mainly formed on the grain surface, which is in contrast to an internal latent image type silver halide emulsion. It has the following.

There is no particular limitation on the halogen composition of the silver halide emulsion used, and any composition such as silver chloride, silver chlorobromide, silver iodobromide, silver chloride, etc. may be used.

The content of silver iodide is 5 mol% or less, more preferably 3 mol% or less.

Although the silver halide grains used in the present invention can have a relatively wide grain size distribution, it is preferable to have a narrow grain size distribution, and in particular, the grain size that accounts for 90% of all grains is within ± It is preferable that the emulsion is monodispersed within 40%.

The silver halide grains used in the present invention have an average grain size of 0.
．． The thickness is preferably 7μ or less, particularly preferably 0.4μ or less.

Further, the silver halide grains may have a regular crystal shape such as a cube or an octahedron, or may have an irregular crystal shape such as a spherical shape or a plate shape.

Silver halide grains used in the present invention can be prepared using any known method. i.e. acid method,
Either the neutral method or the ammonia method may be used, and the reaction method for the soluble silver salt and the soluble silver salt may be a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof. As one of the simultaneous mixing methods, a method of keeping the silver ion concentration (pAg) in the liquid phase in which silver halide is produced constant, that is, a 14g Chondrold double jet method (C, D, J method) is used. Monodisperse silver halide grains with uniform crystal shape and nearly uniform grain size can be obtained. In order to increase the contrast of the silver halide emulsion during the process of silver halide grain formation or physical ripening, a cadmium salt, iridium salt or rhodium salt may be present.

The binder contained in the silver halide photographic emulsion layer used in the present invention preferably does not exceed 250 g per mole of silver halide. Gelatin is most preferred as the binder, but hydrophilic colloids other than gelatin can also be used. For example, albumin, casein, graft polymers of gelatin and other polymers, polyvinyl alcohol,
Hydrophilic polymers such as polyacrylamide can be used.

Although the silver halide emulsion used in the present invention does not need to be chemically sensitized, it is usually chemically sensitized.

As the chemical sensitization method, sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used, and particularly preferred chemical sensitization for carrying out the present invention is the sulfur sensitization method or the combination of sulfur sensitization and noble metal sensitization. This method combines one method, gold sensitization.

As the sulfur sensitizer, active gelatin, thiosulfate, thioureas, allylthiocarbamide, etc. can be used. As a gold sensitizer, HAuCl4゜A, (SCN)2-
Salt, skin (S203) 2''-salt, etc. can be used.

The silver halide emulsion used in the present invention is spectrally sensitized using one or more sensitizing dyes in order to impart photosensitivity in a desired wavelength range. Sensitizing dyes include cyanine dyes, merocyanine dyes, styryl dyes, hemicyanine dyes, holopolar dianine dyes, oxytool dyes,
and hemioxonol dyes, etc. can be used. Particularly useful dyes are cyanine dyes and merocyanine dyes. As the basic heterocyclic nucleus of pigments, any nucleus commonly used for cyanine dyes can be used.

Namely, pyrroline nucleus, oxazole nucleus, oxaprine nucleus, thiazole nucleus, thiazoline nucleus, pyrrole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, indole nucleus, benzoxazole, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus. , quinoline nucleus, etc. can be applied.

The silver halide photographic light-sensitive material according to the present invention is formed by coating on a support at least one hydrophilic colloid layer containing a substantially surface latent image type silver halide emulsion, and other non-photosensitive materials. A hydrophilic colloid layer such as a protective layer, an intermediate layer, an antihalation layer, a filter layer, etc. may be coated. These hydrophilic colloid layers may contain inorganic or organic hardeners. Hardeners include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds (
dimethylol urea, methylol dimethyl hydantoin, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-8-triazine, mucochloric acid, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahytrose-s-triazine) etc.), epoxy and aziridine hardeners, and the like can be used.

The hydrophilic colloid layer used in the present invention may optionally contain various photographic additives, such as an emulsion stabilizer (6-hydroxy-4-methyl-1,3,3a).

hydroxytetrazaindene compounds such as 7-tetrazaindene), spreading agents (such as saponins), ceratin plasticizers (such as copolymers of acrylic acid esters), antistatic agents, coating aids, and photographic property improvements (e.g., development acceleration). Various surfactants (cationic, anionic, nonionic, amphoteric surfactants) for various purposes such as (high contrast, high contrast), fog suppressants (hydroquinone, 5-methylbenzotriazole, ■-phenyl-5-mercapto) tetrazole, etc.), matting agents, and water-insoluble or sparingly soluble polymer latexes (homo- or copolymers of alkyl acrylate, alkyl methacrylate, acrylic acid, glycidyl acrylate, etc.) for the purpose of improving the dimensional stability of photographic materials. It can be used as long as the effect of the invention is not impaired.

(Examples) The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.

Examples 1 to 5 and Comparative Example 1.2 A silver nitrate aqueous solution and 7.5×10-” mol of rhodium hexachloride [I
II) While keeping the pAg of a mixed aqueous solution of potassium bromide and sodium chloride containing sodium at 7.2, at the same time 75
By adding the cubic crystal monodisperse silver chlorobromide emulsion CAgCf with an average grain size of 0.28 μm over a period of 1 minute. : 70 mol%) was prepared, and after removing soluble salts by a conventional method,
Add 4X10-5 moles of sodium thiosulfate and 1X10-5 moles of chloroauric acid per mole of silver halide at 48°C.
Chemically aged for 60 minutes. This is called emulsion A. This emulsion contains 80 g of gelatin per mole of silver halide. Emulsion A was prepared in exactly the same manner as Emulsion A, except that potassium iodide was further added to the mixed aqueous solution of potassium bromide and sodium chloride.
Silver iodochlorobromide emulsion B (Ag
C12/AgBr, molar ratio: 70/30) was prepared.

The emulsion thus prepared contains 6X10-3 moles of 6-hydroxy-4-methyl-1 per mole of silver halide,
3,3a,7-tetrazaindene.

After addition of 3.5 x 10-' moles of 3.3'-dimethyltheazolinocarbocyanine methyl sulfate, 5 x 10-2 moles of hydroquinone as a fog inhibitor and the polyalkylene oxide derivatives of the invention as shown in Table 1, respectively. , and coated on a polyethylene terephthalate (PET) base at a silver content of 40 silver per 1000 rj. This emulsion layer was protected by a gelatin protective layer containing formalin and dimethylol urea as hardeners.

The sample of the film produced as described above was LB-
Using a 200 and ND-10 filter, the film was exposed for 10 seconds using a 2666 tungsten light source through a step wedge with a height difference of 0.15, and then developed at 20°C for 5 minutes using a developer with the following composition according to the present invention, and then stopped. , fixed, washed and dried.

Developer solution Metol 2.5g Sodium ascorbate 10.0g (sodium salt of I-1) Potassium bromide 1.0g Sodium metaborate tetrahydrate 35. Add Og water
1.01 pH 10.8 The photographic properties obtained are shown in Table 1. In Table 1, the relative sensitivity is the relative value of the reciprocal of the exposure amount that provides a density of 3.0 excluding fog, and is shown with the value of Comparative Example 1 as 100. Gamma (γ) is expressed as an average slope between blackening density 0.5 and 3.0 excluding fog. In addition, the Peraper evaluation is made by observing the unexposed part of the fill with a 50x magnifying glass and rating it on a 5-point scale.
represents the best quality (substantially no sluggishness), and E represents the worst quality. A and B are suitable for practical use, C is low quality but somehow within the practical tolerance range, D,
E is impractical.

As is clear from Table 1, even when Comparative Examples 1 and 2, to which no polyalkylene oxide derivative was added, were developed with the developer of the present invention, no high-contrast images with low gamma were obtained. On the other hand, Example 1 in which the polyalkylene oxide derivative of the present invention was added. 2. 3°4.5, the developer of the present invention provides extremely high contrast with a gamma of over 10 and high sensitivity, and no occurrence of perturbation is observed.

Examples 6 to 11 and Comparative Examples 3 to 7 The film samples of Example 4 were exposed in the same manner as in Example 4, and then developed at 20°C for 5 minutes with the developer of each Example and Comparative Example shown in Table 2. , photographic characteristic values were determined in the same manner as in Example 4. The results obtained are shown in Table 3. In Table 3, the relative sensitivity is shown with Comparative Example 7 (commercially available developer Kodak D-11) set as 100.

? As is clear from Table 3, in Examples 6 to 11, images with extremely high contrast and high sensitivity with a gamma exceeding 15 and no blurring were formed, and the polyalkylene oxide derivative was also added to the developer. It can be seen that (Example 8) - layer gives favorable results. On the other hand, high-contrast images cannot be obtained even when developed with the developers of Comparative Examples 3 to 7.

(Effects of the Invention) According to the image forming method of the present invention, it is possible to form a negative image with a gamma exceeding 10, extremely high contrast, and less occurrence of blur, and to obtain a high-quality image that is particularly effective for photolithography for printing. I can do it.

Claims (1)

[Scope of Claims] 1. A method for forming an ultra-high contrast negative image by imagewise exposing and developing a substantially surface latent image type silver halide photographic light-sensitive material, which comprises at least one polyalkylene oxide or a derivative thereof. 1. A method for forming an ultra-high contrast negative image, comprising processing with a developer containing at least the following two components in the presence of: 2. The method for forming an ultra-high contrast negative image according to claim 1, wherein: (1) an aminophenol developing agent; (2) a reductone; and the reductone is a compound represented by the general formula [I] or a salt thereof. General formula I ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R represents a hydrogen atom or a hydroxyl group, and n represents an integer from 1 to 4.) 3. Compounds in which reductones are represented by general formula [II] or The method for forming an ultra-high contrast negative image according to claim 1, which is a salt thereof. General formula II▲ Contains mathematical formulas, chemical formulas, tables, etc.▼