JPH02287347A - Silver halide photographic sensitive material for direct positive image - Google Patents

Abstract

PURPOSE:To improve a safe light property and dye clearing by incorporating one kind of specific dyes into at least one layer. CONSTITUTION:At least one kind of the dyes having formula I are incorporated into at least one layer. In the formula I, R1 denotes an alkyl group, aralkyl group; R2 denotes a hydrogen atom, alkyl group, alkoxy group; R3 denotes a sulfoalkyl group, sulfoaryl group; R4 denotes an alkyl group, aryl group, carboxyl group, alkoxycarbonyl group. The photographic influence of this dye on silver halide emulsions for direct positive is less than with the other known dyes. The safe light property is effective in the way and the good dye clearing is attained.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a pre-fogged direct-positive silver halide photographic material, and more particularly to a direct-positive silver halide photographic material for bright room use. This relates to improving the safelight properties of.

[Prior art]

Direct positive silver halide photographic light-sensitive materials are often used primarily in the printing industry for the "turning" process in the photolithography process. In this "returning" process, the original original image is reproduced from positive image to positive image or from negative image to negative image, but the important point in this process is the faithful reproduction of the fine lines and halftone images of the original image. is required.

The photographic properties of the direct positive silver halide emulsion used to meet these requirements are that the tone is high (particularly high contrast in the toe area), the Q high density (Dmax) is high, and the minimum density (Dm
in) is required to be low.

More recently, light sources rich in ultraviolet light, such as xenon,
Direct positive silver halide photosensitive materials for bright rooms (hereinafter referred to as photosensitive materials for bright rooms), which are exposed using metal halides, mercury lamps, or ultra-high pressure mercury lamps and handled under fluorescent lamps that cut ultraviolet light, have been widely used. . This photosensitive material for bright rooms has the advantage of being extremely easy to work with because it can be handled in a bright room compared to conventional photosensitive materials that are handled in a dark room. Such sensitive materials for use in bright rooms are required to have good safelight properties (hereinafter referred to as safelight properties) under fluorescent lamps that block ultraviolet rays.

Conventionally, as a method of improving safelight properties under fluorescent lamps that cut off ultraviolet rays, the addition of dyes that absorb in the 400 to 550 nm range has been carried out to reduce or cut the photosensitivity of the photosensitive area of silver halide. . These dyes include oxonol dyes, azo dyes, benzylidene dyes, merocyanine dyes, styryl dyes, quinoline dyes, etc.
635, 58-215642, 52-20822,
No. 49-5616 discloses the production of direct positive silver halide light-sensitive materials using these dyes. However, although these dyes improve safelight properties, many of them cause deterioration in photographic properties, such as softening of tone, increase in Dmin, and significant decrease in sensitivity.

Furthermore, regarding the reversal characteristics of a direct reversal emulsion, silver chlorobromide or silver bromide is preferable to silver chloride, especially in terms of Dmin, but as silver bromide content increases, the photosensitive range extends to the longer wavelength side. , a large amount of dye must be used. As a result, not only the photographic properties deteriorate, but also the dye removal after photographic processing becomes poor, and the color of the dye remains, impairing the quality of the photosensitive material.

In general, direct positive reversal emulsions whose surfaces are fogged in advance are
Because surface fog nuclei are easily affected by compounds added to the emulsion (e.g., additives, dyes, surfactants, hardeners, etc.), the types and amounts of compounds added are currently limited6. be. Direct positive photosensitive materials use photographic phenomena different from negative photosensitive materials, and are in a field of photographic technology different from negative emulsion technology. Therefore, dyes that have no photographic effect on general negative emulsions cannot necessarily be used directly in positive reversal emulsions, and it is difficult to make predictions from data obtained from negative emulsions.

[Purpose of the invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a direct positive silver halide photographic X-sensitive material for use in a bright room, which has good safelight properties and good dye removal.

[Structure of the invention]

As a result of examining various dyes, the present inventors have discovered a dye that can accomplish the above purpose.

That is, the present invention has been achieved by a direct positive silver halide photographic light-sensitive material, which is characterized in that at least one layer contains at least one dye having the following general formula.

General Formula In the above general formula, R1 is an alkyl group (e.g., lower alkyl group such as methyl, ethyl, propyl, butyl, hydroxyalkyl group such as hydroxyethyl, hydroxypropyl, alkoxyalkyl group such as methoxyethyl, ethoxyethyl, cyanoethyl , cyanoalkyl groups such as cyanopropyl, carboxyalkyl groups such as carboxymethyl, carboxyethyl, carboxypropyl, alkoxycarbonyl groups such as methoxycarbonylmethyl, methoxycarbonylmethyl, ethoxycarbonylethyl,
sulfoalkyl groups such as sulfoethyl, sulfopropyl, sulfobutyl, etc.), aral Φyl groups (e.g. Eva, Hensyl,
7enethyl, chlorobenzyl, methylbenzyl, methoxybenzyl, nitrobenzyl, sulfobenzyl, sulfo7enethyl, etc.).几2 is a hydrogen atom, an alkyl group (for example, a lower alkyl group as mentioned in R1), an alkoxy group (for example, methoxy, ethoxy, propoxy,
(lower alkoxy group such as butoxy). R3 is a sulfoalkyl group (e.g., as mentioned for R1), a sulfoaryl group (e.g., sulfophenyl, disulfo73-
Furthermore, the benzene ring may be substituted with a carboxy group, a hydroxy group, an alkyl group, an alkoxy group, for example, a halogen atom such as chlorine. ) R4 is an alkyl group (for example, a lower alkyl group as described in R1 above), an aryl group (for example, phenyl, tolyl, methoxyphenyl, chlorophenyl, cyano 7enyl, nitrophenyl, carboxyphenyl, sulfophenyl, etc.), or a carboxy group. , represents an alkoxycarbonyl group (for example, as described above for R1). However, the sulfo group, carboxy group, etc. in the dye molecule may form a salt such as an alkali metal salt (eg, sodium, potassium, etc.) or ammonium salt.

The dye of the present invention was published in Japanese Patent Application Laid-open No. 62 (1983) as a dye with good dye shedding.
-133453, which is already a known dye, was found to be an extremely good dye for direct positive silver halide photosensitive materials. That is, even if it is directly added to a positive silver halide emulsion, there is very little adverse effect on its photographic properties, and dye removal after processing is also good. Furthermore, the dye of the present invention has a wide absorption band in the target wavelength range,
Furthermore, since it has a high molecular extinction coefficient, it gives good results in improving safelight properties.

Next, typical examples of the dyes represented by the above general formula of the present invention will be listed.

[Exemplary compounds]

Dye craftsman dye 2 dye 3 dye 4 dye 5 dye 6 dye 11 dye 12 dye 16 dye 17 dye 18 to 803 dye 13 dye 14 dye 19 dye 20 Next, typical examples of dye synthesis methods will be specifically described.

Synthesis of dye 1: 3-methyl-1(4-sulfophenyl)-5-pyrazolone 12.7t and 6-formyl-1-methyl 1.2,3
．． 4-tetrahydroquinoline 8.82 to methanol 10
0- was added thereto, and the mixture was heated under reflux for 30 minutes. The precipitated crude dye was collected by suction in a cold tube. After washing with methanol, the mixture was turbid with methanol, and triethylamine 20- was added to dissolve the mixture, and then insoluble materials were removed.

A solution prepared by dissolving potassium acetate in 100% ethanol was added to Solution F, and the precipitated crystals were collected. After washing with ethanol and drying, an orange powder with a melting point of 288.0°C (decomposed) 18. (lt
-I got it. The maximum absorption value of the aqueous solution was 511 nm.

Synthesis of dye 3: 3-t-butyl-1-(2,5-disulfo-7enyl)-
5-pyrazolone 18.8 F and 1-benzyl-6-formyl-1,2,3,4-tetrahydroquinoline 12.6
200 dt of methanol was added to f, and further 20.0 dt of triethylamine was added, followed by heating under reflux for 3 hours.

Approximately 10 f' of potassium acetate was dissolved in 400 m of ethanol, and after mixing thoroughly, the crude dye was taken out in a suction furnace.

After washing with ethanol and drying, an orange powder 18.2F with a melting point of 300°C or higher was obtained. The maximum absorption value of an aqueous solution is 502 n
It was m.

Other dyes represented by the general formulas of the present invention can also be easily synthesized according to the above synthesis examples. 5-pyrazolo 7, which is one of the intermediate raw materials for dye synthesis of the present invention, is described, for example, in the Journal of Medicinal Che.
mistry Vol. 7, p. 493 (1964), Jour
nalfar praktfshe Chemie W
It can be obtained by a condensation reaction between a β-keto acid ester and a hydrazine derivative, with reference to the method described in Vol. 1139, p. 148 (1934).

On the other hand, 6-formyl-1,2,3,4-tetrahydroquinoline derivatives can be prepared by combining 1,2,3,4-tetrahydroquinolines with a suitable alkylating agent C, such as alkyl iodide, p
- toluenesulfonic acid alkyl ester, benzyl halide, sultone, etc.) and then the so-called Vilsmeyer-Hack reaction with dimethylformamide and phosphorus oxychloride yields 6-formyl-1,2,3,4-tetrahydroquinolines. It will be done.

The absorption maximum value (nm) of the aqueous solution of the representative example of the dye represented by the general formula of the present invention is as follows.

Dye 1 511 Dye 2 533 The dye of the present invention can be dissolved in a suitable solvent such as water, methanol or ethanol and incorporated directly into the layer of a positive silver halide photographic light-sensitive material by a conventional method.

These dyes can be contained in the protective layer, intermediate layer, emulsion layer, and backing layer, and are usually added to a hydrophilic colloid aqueous solution and coated on the support.

The amount of the dye of the present invention to be added may be 5 to 1000 q per dye, particularly preferably 50 to 300 q.

The halide composition of the iron halide used in the present invention is not particularly limited, and includes silver chloride, silver bromide, silver chlorobromide, silver iodobromide,
Ambush silver chloride, etc. The shape of the silver halide grains may be a regular crystal such as a cube or an octahedron, or an irregular shape such as a spherical or plate shape.

In general, direct positive silver halide emulsions can be broadly divided into two types. One is an emulsion of the type (Aa emulsion) consisting of silver halide grains whose surfaces are fogged in advance and which contain an electron-trapping compound said to trap electrons inside the silver halide grains. The other emulsion uses ff1 (which covers the grain surface to create an electron-trapping compound inside the silver halide grains).
Bu emulsion) is first inverted by the addition of an organic desensitizer.

The Affi emulsion is described in U.S. Pat. chemical sensitization treatment such as metals belonging to Group 8 of the periodic table (rhodium, palladium, iridium,
A method is described in which a positive reversal emulsion is directly produced by treating the shell with osmium, platinum, ruthenium, etc.) and then fogging the surface of the shell.

The present invention can be used for both type A and By type emulsions.

The size of the silver halide grains used in the present invention is 0.0
A thickness of 5 to 1 micron is used, but it is preferably 0.25 micron or less for direct positive silver halide photosensitive materials for bright room use. If the size is larger than that, the safe light property will deteriorate and the tone will become soft.

The application of fog to the surface of silver halide grains carried out in the present invention is described in US Pat. No. 3,367,778 and US Pat.
, 340, 3,501,305, Japanese Patent Publication No. 50-681
Fogging can be carried out using a known method such as using a reducing agent alone or a reducing agent and a gold compound, or using light, as described in No. 33.

Reducing agents include aldehydes such as formalin, hydrazine, triethylenetetramine, thiourea dioxide,
Stannous chloride, amine borane, etc. are used.

Gelatin is most preferred as a protective colloid and binder for silver halide grains used in the practice of the present invention, but polymeric compounds other than gelatin (for example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid , polyvinylimidazole, polyethylene glycol, maleic anhydride, polystyrene sulfonic acid.

Cellulose derivatives such as polyvinylpyridine, methylcellulose, hydroxymethylcellulose, carboxymethylcellulose, copolymers of these monomers, etc.) can partially or completely replace the gelatin.

The gelatin used is alkali-treated and acid-treated gelatin C.
Isoionic point 5-9), enzyme-treated gelatin, low calcium content gelatin (content 100 ppm or less), high jelly strength gelatin (PAGI method jelly strength 270 or more),
Gelatin derivatives (for example, chemically modified gelatin such as heptadated gelatin and carbamylated gelatin) are used.

Polymeric latexes can also be used as part of the binder to improve dimensional stability. Examples of the polymer latex include polyacrylic acid types such as polyvinyl acetate, polymethyl acrylate, ethyl, and butyl, polymethacrylic acid types such as polymethyl methacrylate, ethyl, and butyl, polystyrene types, polybutadiene types, and the like. There are copolymers of monomers, etc. Physical properties such as particle size and glass transition point of the polymer latex are not particularly limited, but it is desirable that the particle size is 1 μm or less and the glass transition point is 50° C. or less.

The dye of the present invention can be used in combination with the dye represented by the following general formulas (1) and (II) shown in No. 59-24845. For example, even when the dye of the present invention is used in combination with the dye of general formula (1) and/or the dye of general formula (U) in any proportion, the dye of the present invention remains stable without undergoing any change.

General formula (II) (wherein, Rt represents a group selected from a carboxylic group, an alkyl group, an aryl group, an alkoxycarbonyl group, and an aryloxycarbonyl group, and R2 is a sulfonic acid group or a carboxyl group. Represents a group selected from a substituted alkyl group, a sulfonic acid group, or an aryl group substituted with a carboxyl group, and R5, R4, R5 and R
t6 represents a group and atom selected from a hydrogen atom and a substituted or unsubstituted alkyl group, R7 represents a group selected from a hydrogen atom, a sulfonic acid group, a carboxyl group, a sulfoalkyl group, and an alkoxy group, and R11 represents a sulfonato group. and a sulfonatoalkyl group.

) A typical example of the general formula CI) is A typical example of the general formula (■) is etc.

Known organic desensitizers may also be used in the practice of the present invention. As organic desensitizers, those having a positive sum of oxidation potential and reduction potential are effective, and particularly known desensitizers include binaphthol yellow, binaphthol green, phenosafranine, 5-nitrobenzotriazole, etc. can be.

Also, organic desensitizers described in Jikai 54-115219 and the like can also be used.

Known additives can be added to the direct positive silver halide photosensitive material used in the present invention.

Stabilizers include mercapto compounds, benzotriazole compounds, oxazole compounds, etc. Hardeners are not particularly limited, but include aldehyde compounds, 2-hydroxy 4.
6-dichloro-1,3,5-) riazine, N-methylol compounds, vinyl sulfone compounds, etc. Coating aids include saponin, alkylene oxide type, glycidol type nonionic surfactants, carboxylic acids, sulfonic acids, phosphorus. Anionic surfactants containing acid, sulfuric ester groups, phosphoric ester groups, and other acidic groups, amino acids, amphoteric surfactants such as aminosulfonic acids, and polyalkylene oxide compounds are used.

Supports used in the practice of the present invention include, for example, glass,
Film base, such as cellulose acetate, polyethylene terephthalate, baryta paper, resin coated paper,
Aluminum foil, concrete, etc. can be used.

The direct positive silver halide light-sensitive material of the present invention may contain a brightening agent, an ultraviolet absorber, a matting agent, an antistatic agent, and the like, if necessary.

The direct positive halogenated M light-sensitive material of the present invention can be processed under various conditions, including but not limited to high-temperature rapid automatic processor processing at 30 to 50 DEG C. for 20 to 60 seconds, and blood image processing.

As the developer, either a developer used for general silver halide photographic light-sensitive materials or a Lith developer can be used.

Example 1 A potassium bromide aqueous solution containing lXl0-' mol of potassium hexachloroiridate (IV) per 1 mol of silver nitrate and a silver nitrate aqueous solution were mixed in a gelatin solution by a controlled double jet method, and the average particle size was 120 F? A 1μ silver bromide emulsion was prepared. This emulsion was desalted by the 70 Kiereshi method and the pAg and pH were adjusted to yield Ikg of silver nitrate.
0.5 t of thiourea dioxide was added per sample, and fogging was applied at 60° C. for 70 minutes. The ratio of silver nitrate to gelatin in the emulsion is 2:
It was set to 1. This emulsion was divided into several equal parts, a hardening agent and a surfactant were added to each part, and the amount of silver nitrate was 5f per 100μ thick polyethylene terephthalate film base.
A gelatin solution containing the dye shown in Table 1 was applied thereon as a retention layer.

Comparative samples were prepared by adding dyes represented by the following structural formulas A to E in place of the dyes used in the present invention.

Specific dye: 0sNa Comparative dye B Comparative dye C Comparative dye E Developed with paper manufacturer's Gelacol developer.

Thereafter, it was fixed with an acidic hardening solution (EK Co., Ltd. F-5), washed with water and dried.

The transmission density of each sample was measured using a Macbeth transmission density meter (Model R, D917), and photographic characteristics were calculated.

(Leaving space below) Example 2 Divide the capri-applied emulsion into several equal parts in the same manner as in Example 1, add an appropriate amount of a hardening agent and a surfactant to each, and apply it to a polyethylene terephthalate film. A gelatin solution containing the dye of the present invention shown in is applied as a protective layer. A polyethylene tele-7 talate film paste was used which had been previously coated with a backing layer containing a yellow dye (60 capes per 1 ff 1 inch) having the following <R formula t.

The safelight property of the sample thus obtained was evaluated. Safelight properties were determined by leaving the samples under a UV-cut fluorescent lamp at a light intensity of 200 lux for the time shown in Table 2, and then performing the same development process as in Example 1.

Table 2 Samples 2 to 6 were visually observed for residual color of the dye, and all were good with no difference from the control.

〔Effect of the invention〕

Traps as shown in Tables 1 and 2 of Example 1.2.

The dye of the present invention has very little photographic effect on direct positive silver halide emulsions compared to other known dyes, and is also extremely effective in safelight properties. Dye removal was also very good.

Claims (1)

Claims: A silver halide photographic material for direct positive use, characterized in that at least one layer contains at least one dye having the following general formula. General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 represents an alkyl group or an aralkyl group. R_2 represents a hydrogen atom, an alkyl group, or an alkoxy group. R_3 represents a sulfoalkyl group or a sulfoaryl group. .R_4 represents an alkyl group, aryl group, carboxyl group, or alkoxycarbonyl group.)