JPS5872937A - Spectrally sensitized photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material with high spectral sensitivity to laser light by spectrally sensitizing a silver halide emulsion contg. silver iodide with a specified sensitizing dye. CONSTITUTION:A spectrally sensitized photosensitive silver halide material is obtd. by adding a sensitizing dye represented by general formulaIor II to a silver iodobromide emulsion contg. 0.1-4.0mol% silver iodide by 20mg per 1mol silver halide. Since the dye has high spectral sensitivity to gaseous He-Ne laser light, etc., the absorption wavelength range of the silver halide emulsion layer becomes 400-600nm. This sensitive material is suitable for laser facsimile, etc., has high sensitivity, leaves no dye stain on a film, and can be handled under bright safelight.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a spectrally sensitized silver halide photosensitive material,
Especially if@-Me (helium-neon) gas laser f
t, (632,snm) with high i-spectral WAFI
The present invention relates to a photosensitive material for laser facsimile.

In recent years, it has become very common to use laser light instead of a modulated discharge tube as a 7 ac tV light source. This is because conventional modulated discharge tubes cannot provide a sufficient amount of light and have reached their limits in terms of speed. Another factor that cannot be overlooked is the emergence of extremely compact laser tubes due to the development of radar technology. Currently, the laser oscillator is ruby, H.-
N. (helium-neon: gas), Ar (argon: gas), Kr (krypton: gas)
, carbon dioxide, YAG (yttrium-aluminum-garnet), pigments, etc. are used, but for 7-axe scolding, H.-Gasrape is usually used because it is cheap and compact. It is.

In the case of a facsimile machine using such a single laser beam, various characteristics are required of the photosensitive material used. For example, the emission wavelength of laser light (6 in the case of H-y gas laser)
It is desirable that the silver halide photosensitive material has sufficient photosensitivity for 3L8mm) and that its sensitivity is as high as possible. This is because the load on the laser tube can be reduced as much as possible and the waiting time of the laser tube can be extended. A sensitizing dye with an appropriate sensitizing spectral region is selected and used for this purpose, but the additional requirement is that there is no adverse interaction with other photographic additives;
Examples include not leaving dye stains on the film after processing and not causing capri. In addition, since it is necessary to receive 7 techniques in an extremely short period of time,
The development processing of the photosensitive materials used for this purpose also needs to be done quickly, and its characteristics are also important. Furthermore, in order to improve work efficiency, a safe light as bright as possible is required.

The main purpose of the present invention is to use the N-He laser beam (632
, 8nia), it is an object of the present invention to provide a silver halide photosensitive material which has high sensitivity and high contrast and does not leave dye stains on the film. Another purpose of Me-H is that it is capable of rapid processing and can be handled even under relatively bright safety light.
・Providing silver halide photosensitive materials for laser facsimile.

The above object contains a sensitizing dye represented by the following general formula [I] and a sensitizing dye represented by the following general formula (), and silver iodide containing 0.1 to 4.0 mol% of silver halide. This is achieved by a silver halide photographic light-sensitive material having a silver halide emulsion layer containing.

General Formula [I] General Formula 1 In the formula, Yl and Y each represent a group of nonmetallic atoms necessary to form a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring, or a quinoline ring, These 11-vote rings may be substituted with silver halide, lower alkyl groups, or lower alkoxy groups. and R1 each represent a substituted or unsubstituted alkyl group, i represents a hydrogen atom or a lower alkyl group, and ml, 1 and n represent 1 or 2.

Silver halide in the silver halide emulsion used in the present invention is preferably silver iodobromide or silver iodochlorobromide containing 01 to 4.0 mol % of silver iodide.

Binders for silver halide emulsions include gelatin, hydrolyzed heptalyose acetate, carboxymethyl cellulose, hydroxyethyl cellulose, heptalyrose derivatives such as methyl heptalyose, synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl Acetate, polyacrylamide, polyN, N-dimethylacrylamide, polyy-vinylpyrrolidone, U.S. Pat.
, No. 341,332, No. 3,615,424, No. 3,
Water-soluble polymers such as those described in U.S. Pat. No. 860,428, U.S. Pat.
Gelatin derivatives such as 7-enylcarbamylated gelatin, acylated gelatin, and 7-thallated gelatin as described in U.S. Pat. No. 2,548,520, U.S. Pat.
Acrylic acid esters such as those described in No. 831.761, methacrylic acid (ester), acrylonitrile, and other monomers having a polymerizable ethylene group are combined with gelatin. be able to. The amount of grinder is 40 to 10 per mole of silver halide.
0 Ii is preferred. This means that during rapid processing, the drying property of the binder is 10% per mole of silver tetragenide.
This is because if 09 or more is used, it will be inferior. Further, a polymer latex can also be contained in the emulsion layer. As the polymer latex, an aqueous dispersion of a homo or copolymer of methyl acrylate, methyl methacrylate, acrylic acid, methacrylic acid, glycidyl acrylate, styrene, vinyl chloride, vinylidene chloride, etc. is used.

Specific examples of the compound represented by the above general formula [IF (hereinafter referred to as compound #[■]-) used in the present invention include the following. However, the present invention is not limited thereto.

[IF - (1) [1] - (2) 0] - (3) [IF - (4) [IF - (5) [IF - (6) [IF - (7) [IF - (8) [ IF-(9) [IF-(IF)) Specific examples of the compounds represented by the above general formulas (hereinafter referred to as compound initial compound) used in the present invention include the following. However, the present invention is not limited to these.

rU] -(1) [TI] -(g) [TI] -(3) [ff] -(4) rlI] -(5) [[[] -(6) [Old -(]) [11] -(8) [Old-(9) Compound [I] and compound [IT] are both 600 nm ~
Although it has the ability to sensitize in the wavelength range of 1000 to 1000 nm, it is not possible to obtain a silver halide photographic material with sufficiently high sensitivity, high contrast, and little color patch staining as desired by using only one of them.

The above compounds [I] and [1'] may be added to the silver halide emulsion during the second ripening or after the second ripening, and the amount of addition is 1 mo of silver halide and 5 mo of silver halide, respectively. ~5
A range of 00 # is appropriate, more preferably 10 to 10011, respectively. Also, the absorption wavelength range is 40
It is preferable to add at least one compound having a wavelength of 0 to 600 nm to the halogenating agent of the present invention and/or to a protective layer provided on the layer. Examples of compounds that can be advantageously used with such compounds include compounds represented by -1[1-[IX] below.

General formula [[U] General formula [V] 4. -2. General formula [V [] General formula [[] General formula [(g) represents a group. Q represents an atomic group necessary to form pyrazolone, barbic acid, thioparpi/I/wI or 3-oxythionaphthene. R is a substituted or unsubstituted alkyl group, R, R, and - are each a hydrogen atom,
The alkoxy group, dialkylamino group or sulfone group, R@ represents a hydrogen atom or a hapogen atom. -1R
1,R@,n,,R3・,RIM,Rtl,It,
, % R14, RIM s x, and Rtl are each a hydrogen atom, a chlorine atom, an alkyl group, a hydroxyl group,
Represents an alkoxy group, amino group, acylamino group, carboxyl group or sulfone group. However, R11 and 1'
It may be combined with +s to form a benzene ring.

RIM is a hydrogen atom, an acyl group or an alkoxycarbonyl 4, R1 is a hydrogen atom or an alkyl group, R1゜, R
11 and R□ represent each A hydrogen atom, alkyl group or sulfone group. M is a hydrogen atom, a sodium atom or a potassium atom, X is an anion, m1nl and - each represent 1 or 2. However, when m is 1, an inner salt is formed. Y represents an alkyl group or a carboxyl group
)vinegar.

These compounds can usually be added after the second ripening period when added to the emulsion, and at any time before coating when added to the protective layer.
What is necessary is just to make it contain 100y9-3.0p per gelatin. Next, the compound represented by the general formula [Bai ~ general formula [Oka]
Specific examples of compounds [IIr] to [IX] will be shown below.

However, the present invention is not limited to these specific examples.

Compound [Specific example of IIO [III] - (2) Compound [Specific example of blank [rV] - (3) Compound [Specific example of Vl [Vl - (1) So, H [Vl - (3)] 80. H Specific example of compound [VI] [V[]-(1) [V[1-(2) Ikawa-(3) O1 So, Ha SO3Na[1-(5
) So, K So, β wings - (6) 1i10. K [Wl - (]) Specific example of compound [Vl [] 01 Na - (2) 0-ON ゝN' [■] - (3) Specific example of compound [food] [ff1l - (1) [[ ]-(3) [Vll-(4) H [%fl-(7) H \ 5(11Na Specific example [IX] of compound [[X] X] -(3) 0BNa 11-(4) SO3Na [IX] -(5) Compound [[r'] - [IX] The additive selected from among [[r'] - [IX] has sensitivity in the photosensitive wavelength range (400 - 600 nm) This greatly contributes to the use of bright safety light.

The silver halide photographic emulsion used in the present invention includes commonly used chemical sensitizers, stabilizers, toning agents, hardeners, anti-capri agents, surfactants, thickeners, plasticity 1, slipping agents, Development inhibitor, ultraviolet absorber, erasilon inhibitor dye,
Heavy metals, matting agents, etc. can be further incorporated by a conventional method.

The silver halide photographic emulsion used in the present invention can be applied to a suitable support, such as glass, a cellulose derivative film such as cellulose triacetate, a synthetic resin film such as polyethylene terephthalate, baryta, resin coated paper, synthetic paper, etc. It can be painted in the usual way.

Hereinafter, the present invention will be further explained in detail with reference to Examples.

Example A silver iodobromide emulsion containing 0.5 mol % of silver iodide was sensitized with gold and sulfur, and the sensitizing dyes shown in Table 1 were added, and the compound [■]-('F) 9g per mole of silver halide
Added. Furthermore, a coating aid and a hardening agent were added and coated on the polyethylene terephthalate base.
A14 was created. These samples were exposed to light using a helium neon laser with an output of 1 mW, and developed for 30 seconds at 35°C using Sakura facsimile film developer ODM-all (manufactured by Konishi Roku Photo Industry Co., Ltd.) to determine sensitivity, gamma, and residue. The chromaticity was measured. In addition, the unexposed sample was left for 0 and 5 minutes at a distance of 1 m under the green safelight of an SOW light bulb (Sakurasei 7 Light S5N; manufactured by Roku Konishi Photo Industry Co., Ltd.), and the Capri density was measured.Results [Note] (1) The amounts of compound [I] and compound [II] added are each 20 m9 per mole of silver halide.

(2) II' degree is expressed as relative sensitivity when Tsuta No. 1, which is a comparison product, is taken as 100. Gamma is the tanθ value in the straight line portion on the photographic characteristic curve, and residual color was evaluated using developed unexposed samples.

(3) Regarding color retention, + indicates no residual color, - indicates almost no residual color, and - indicates considerable residual color.

comparative compound 0, H, 0, H.

From Table 1, it can be seen that the sample having the silver halide emulsion layer of the present invention has higher sensitivity and higher gamma value for the helium neon laser source than the comparative sample, and also has almost no residual color. Ru.

Furthermore, when the compound shown in this example [vll-(7) and other [Vrl-(1) and 2.0, whereas when these compounds were added, almost no capri occurred even after being exposed to a safelight for several minutes. These results showed that compound j':[Vl ~[(X]) was clearly effective against 7-7 light fog.

Agent Yoshimi Kuwahara

Claims (1)

[Claims] (1) Contains a sensitizing dye represented by the following general formula [I] and a sensitizing dye represented by the following general box, and contains silver iodide with a silver halide content of 0.1 to 4.0 mol%. 1. A silver halide photographic material for helium neon gas laser imx, characterized by having a silver halide emulsion layer. General formula 11 General formula These heterocycles may be substituted with silver halide, lower alkyl or lower alkoxy groups. R and R each represent a substituted or unsubstituted alkyl group, R represents a hydrogen atom or a lower alkyl group, and nI, - and n represent 1 or 2. ] The silver halide photographic light-sensitive material has a protective layer on the silver halide emulsion layer, and the protective layer or the silver halide emulsion layer contains at least a compound having an absorption wavelength range of 100 to 600 nu. The silver halide photographic material according to claim 1, characterized in that it contains one of the following.