JPH0713288A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photographic sensitive material having sensitivity to different wavelength lights even when exposed to each different lights and characteristic curves different in characteristics. CONSTITUTION:The silver halide photographic sensitive material for a laser imager has at least one photosensitive emulsion layer on a support and it is characterized by containing in the emulsion layer at least 2 kind of silver halide emulsions different in spectral maximum sensitive wavelength and different in each sensitivity ratio or almost equal in the spectral maximum sensitive wavelength but different in sensitivity ratio between the sensitivity at the maximum sensitive wavelength and that at the wavelength by >=20nm apart from it.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material for a laser imager, and more particularly to a silver halide photographic light-sensitive material for a laser imager which can cope with laser light sources having different wavelengths.

[0002]

2. Description of the Related Art In recent years, laser imagers have become very popular with the development of new modalities. Along with this, imagers are becoming more diverse in order to improve various performances. Laser light source is one of them,
Gas lasers such as He-Ne and Ar lasers,
Laser light sources, which have different characteristics such as semiconductor lasers having wavelengths in the red and infrared regions, have been put into practical use.

Therefore, different silver halide photographic light-sensitive materials corresponding to such various exposure wavelengths are required to be used properly.

However, even the same silver halide photographic light-sensitive material can have two spectral characteristics. Further, the same silver halide photographic light-sensitive material can be provided with two spectral characteristics by adding a spectral sensitizing dye suitable for each wavelength. However, in this case, although sensitivity at each wavelength can be obtained, for example, the sensitometric performance represented by the gamma value shows almost no change, and the same silver halide photographic light-sensitive material is used for exposure of two or more types. It was not possible to design a gamma value suitable for each wavelength while having sensitivity to the wavelength.

[0005]

The object of the present invention is to have sensitivity at each wavelength even when exposed at different wavelengths,
Moreover, it is to provide a silver halide photographic light-sensitive material having characteristic curve shapes having different characteristics.

[0006]

The above object of the present invention is to provide at least one photosensitive emulsion layer containing two or more kinds of silver halide emulsions having different spectral maximum wavelengths on a support,
Further, the two or more kinds of silver halide emulsions have different sensitivity ratios of the respective emulsions at respective spectral maximum wavelengths, and two kinds of silver halide photographic light-sensitive materials for a laser imager or a support. In the silver halide photographic light-sensitive material having at least one photosensitive emulsion layer containing the above silver halide emulsion, the respective spectral maximum wavelengths of the respective silver halide emulsions are substantially equal to each other, and the sensitivity at the spectral maximum wavelength is This is achieved by a silver halide photographic light-sensitive material for a laser imager, which is an emulsion having different ratios with respect to the sensitivity at a wavelength 20 nm or more away from the spectral maximum wavelength.

In the present invention, the difference in the sensitivity ratio of each emulsion at each spectral maximum wavelength means, for example, 1
The spectral maximum wavelength of _one silver halide emulsion layer is λ ₁ , the sensitivity at the maximum wavelength is S ₁ , the sensitivity at λ ₂ (described below) is S _3, and the spectral maximum wavelength of the other silver halide emulsion layer is When λ ₂ , the sensitivity at the maximum wavelength is S ₂ , and the sensitivity at λ ₁ is S _4, it means that λ ₁ ≠ λ ₂ and S ₁ / S ₄ ≠ S ₂ / S ₃ .

Emulsions having different sensitivity ratios at wavelengths 20 nm or more away from the spectral maximum wavelength are, for example, the spectral maximum wavelengths of the respective silver halide emulsion layers being λ ₁
And the sensitivities at the maximum wavelength are S ₁ and S ₂ , respectively, and the sensitivities at wavelengths more than 20 nm away from λ ₁ are S ₃ and S ₄ , respectively, then | λ ₁ −λ ₂ | ≧ 20 nm, and S _This means a case where ₁ / S ₃ ≠ S ₂ / S ₄ .

The silver halide composition of the silver halide photographic light-sensitive material of the present invention may be silver bromide, silver iodobromide, or a silver iodochlorobromide emulsion containing a small amount of silver chloride.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is described, for example, in "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coating Photographic Emulsion "can be prepared by the method described in Focal Press (1964).

That is, the mixing conditions such as the forward mixing method, the reverse mixing method, the double jet method and the control double jet method under the solution conditions such as the acidic method, the ammonia method and the neutral method,
It can be produced using a particle preparation condition such as a conversion method, a core / shell method, or a combination thereof.

A preferred embodiment of the emulsion used in the silver halide photographic light-sensitive material of the present invention is a monodisperse emulsion in which silver iodide is localized inside the grains. The monodisperse referred to here, when measuring the average particle diameter by a conventional method,
At least 95% by number or weight of grains are silver halide grains having an average grain size within ± 40%, preferably within ± 30%.

The grain size distribution of silver halide may be a monodisperse emulsion having a narrow distribution, and the crystal structure of silver halide may have a silver halide composition in which the inside and the outside are different, For example, a core / shell type monodisperse emulsion having a clear two-layer structure in which a high silver iodide core portion is covered with a low silver iodide shell layer may be used.

The method for producing the above-mentioned monodisperse emulsion is known, and for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is, for example, a seed crystal as a method for obtaining the above monodisperse emulsion, and the seed crystal is used as a growth nucleus to supply silver ions and halide ions. A grown emulsion may be used.

A method for producing the above core / shell type emulsion is well known, for example, J. Phot. Sci, 24.198. (1976), US Pat.
The methods described in 250, 3,505,068, 4,210,450, 4,444,877 or JP-A-60-143331 can be referred to.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be tabular grains having an aspect ratio of 2 or more. As an advantage of such tabular grains, it is disclosed in, for example, British Patent 2,112,157, U.S. Patents 4,414,310, and 4,434,226, etc., as improvement of spectral sensitization efficiency and improvement of image graininess and sharpness are obtained. And
The emulsion can be prepared by the methods described in these publications.

The above-mentioned emulsion may be either a surface latent image type which forms a latent image on the grain surface, an internal latent image type which forms a latent image inside the grain, or a type which forms a latent image on both the surface and the inside. It may be an emulsion.

These emulsions are used at the stage of physical ripening or grain preparation by using, for example, cadmium salt, lead salt, zinc salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or its complex salt. May be.

The silver halide emulsion of the present invention is spectrally sensitized with a compound selected from the group of compounds represented by the following general formula (I), (II), (III) or (IV).

[0021]

[Chemical 1]

In the formula (I), R ₁ and R ₅ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom or a carboxyl group. R ₂
R ₄ and R ₄ may be the same or different and each represents an alkyl group, and R ₃ represents an alkyl group.

X ₁ and X ₂ may be the same or different and each represents a sulfur atom or a selenium atom. Y ₁ ^- is a counter-ion, if it m ₁ represents 0 or 1 to form an intramolecular salt is m ₁ is 0.

In the formula (II), R ₆ , R ₇ , R ₁₁ and R ₁₂ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, a hydroxyl group or a carboxyl group. Represent R ₈ and R ₁₀ may be the same or different and each represents an alkyl group or an aralkyl group, and R ₉ represents an alkyl group. X ₃ and X ₄ may be the same or different and each represents a sulfur atom or a selenium atom.
Y ₂ ^- is a counter-ion, if it n ₁ represents 0 or 1 to form an intramolecular salt is n ₁ is 0.

In the formulas (III) and (IV), Z ₁ is 5
Represents a nonmetallic atomic group necessary for forming a 6-membered or 6-membered nitrogen-containing heterocycle. Y represents a hydrogen atom, an alkyl group, a substituted alkyl group, an alkoxy group or a halogen atom, and R ₁₁ , R ₁₂
Each represents an alkyl group or a substituted alkyl group. R ₁₃
Represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a benzyl group. X represents a counter ion, and m, n and p represent 1 or 2.

In the formula (III), benzothiazole ring and naphthothiazole ring represented by Z ₁ and Z ₃ (for example, [1,2
d], [2,1d] and [2,3d] naphthothiazole ring),
The benzoxazole ring and naphthoxazole ring (for example, the naphthothiazole ring of [1,2d], [2,1d] and [2,3d]) may each have a substituent, for example, a carbon number of 1 to 4 And an alkyl group having 1 to 4 carbon atoms, a phenyl group, a halogen atom (eg, chlor atom, bromine atom), and the like. R ₁₁ and R ₁₂ are alkyl groups having 1 to 4 carbon atoms and substituted alkyl groups having 1 to 4 carbon atoms, such as methyl group, ethyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-acetoxyethyl group, Carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group, P- Sulfophenethyl group, n-propyl group, isopropyl group, n-butyl group, etc.).

When Z ₂ of the above general formula (III) of the present invention is a 5-membered carbon atom ring, it can be represented by the following general formula (III-a).

[0028]

[Chemical 2]

R ₁₃ and R ₁₄ are each a hydrogen atom and have 1 carbon atom.
~ 4 alkyl group represents an alkoxy group having 1 to 4 carbon atoms, a halogen atom (for example, a chloro atom, a bromine atom, etc.), R ₁₅ and R ₁₆ are each an alkyl group having 1 to 12 carbon atoms,
A phenyl group which may have a substituent (for example, a phenyl group,
m-tolyl group, p-tolyl group, m-chlorophenyl group, p-chlorophenyl group, for example, p-methoxyphenyl group substituted with an alkoxy group having 1 to 4 carbon atoms), alkoxycarbonylalkyl group having 1 to 4 carbon atoms (For example, ethoxycarbonylmethyl group etc.) can be mentioned.

R ₁₇ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, or a phenyl group. Z ₁ , Z ₃ , R ₁₁ , R ₁₂
And X and n have the same meaning as in formula (III).

When Z ₂ of the above general formula (III) of the present invention is a 6-membered carbon atom ring, it can be specifically described by the following general formula (III-b).

[0032]

[Chemical 3]

In the formula, R ₁₈ and R ₁₉ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a phenyl group.

Z ₁ , Z ₃ , R ₁₁ , R ₁₂ , and X and n have the same meanings as in formula (III).

In the formula (IV) of the present invention, the 5- or 6-membered nitrogen-containing heterocycle represented by Z ₁ is, for example, a thiazole ring, a selenazole ring, an oxazole ring or a 3,3-dialkylindolenine ring. , Imidazole ring and the like.

Of these, preferably a thiazole ring,
The oxazole ring is more preferably a benzothiazole ring, a naphthothiazole ring, a benzoxazole ring or a naphthoxazole ring. X, m, n and p
Is synonymous with general formula (III).

The following are general formulas (I) to (IV) according to the present invention.
Specific examples of the compound are shown below, but the present invention is not limited thereto.

[0038]

[Chemical 4]

[0039]

[Chemical 5]

[0040]

[Chemical 6]

[0041]

[Chemical 7]

[0042]

[Chemical 8]

[0043]

[Chemical 9]

[0044]

[Chemical 10]

[0045]

[Chemical 11]

[0046]

[Chemical 12]

[0047]

[Chemical 13]

[0048]

[Chemical 14]

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17]

[0052]

[Chemical 18]

The above general formulas (I) to (IV) according to the present invention
The method of synthesizing the compound represented by
It is described in Chemistry of Heterocyclic Compound Vol.18. The general formulas (I) to (I
The compound represented by V) is preferably added in an amount of 0.003 g to 0.3 g, and more preferably 0.005 g to 0.15 g, per mol of silver halide.

General formulas (I) to (IV) used in the present invention
The compound represented by can be directly added to the emulsion, and these are dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and then added. be able to.
Alternatively, an ultrasonic method may be used as the dissolution method.

The method of addition to the emulsion is, for example, US Pat. Nos. 3,469,987, 3,822,135 and JP-B-46-2418.
No. 5, JP-A-50-80826, JP-A-51-74624 and the like may be used.

In the emulsion according to the present invention, various photographic additives can be used in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure No. 17643 (December 1978), No. 18
716 (November, 1979) and No. 308119 (December, 1989). These three research
The types of compounds shown in the disclosure and the locations where they are listed are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical Sensitizer 23 III 648 Upper right 996 III Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right Fog inhibitor・ Stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006 ~ 7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1009-4 XXII Support 28 XVII 1009 XVII Support that can be used in the photosensitive material according to the present invention Examples of the body include page 28 of RD-17643 and 100 of RD-308119 described above.
Examples of suitable supports include plastic films, and the surface of these supports is provided with a subbing layer to improve adhesion of the coating layer, corona discharge, You may give ultraviolet irradiation.

Photographic processing of the light-sensitive material of the present invention is carried out, for example, by RD-17643, XX-XXI, pages 29-30 or 308119, XX-X.
Treatment with a treatment solution as described in XI, pp. 1011-1012 may be performed. This process may be either a monochrome photographic process for forming a silver image or a color photographic process for forming a dye image. The treatment temperature is usually in the range of 18 ° C to 50 ° C.

Developers for black-and-white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-P-aminophenol). Etc. can be used alone or in combination. In the developer, well-known preservatives, alkali agents, pH buffers, antifoggants, hardeners, development accelerators, surfactants, defoamers, toning agents, water softeners, dissolution aids, etc. You may use an agent, a viscosity imparting agent, etc. as needed.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0061]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the following examples.

Example 1 A monodisperse cubic crystal emulsion of silver iodobromide containing 2 mol% of silver iodide having an average grain size of 0.15 μm by a double jet method while controlling at 60 ° C., pAg = 8 and pH = 2.0 ( A) was obtained. The number of twins in this emulsion was 1% or less from the electron micrograph. This emulsion (A) was used as a seed crystal and grown as follows.

That is, the seed crystal (A) was dissolved in 8.5 l of a solution containing protected gelatin and ammonia as required at 40 ° C., and the pH was adjusted with acetic acid.

Using this solution as a mother liquor, an aqueous 3.2 N ammoniacal silver ion solution was added by the double jet method.

First, pAg was controlled to 7.3 and pH was controlled to 9.7 to form a layer having a silver iodide content of 35 mol%. Next, from pH 9.0
It was changed to 8.0 and pAg was kept at 9.0 to grow it. afterwards,
The potassium bromide solution was added through a nozzle over 8 minutes, the pAg was dropped to 11.0, and mixing was completed 3 minutes after the addition of the potassium bromide was completed. This emulsion was a monodisperse emulsion having an average grain size of 0.3 μm. The average silver iodide content of the entire grain was 1.5 mol%.

Next, a desalting step was carried out in order to remove an excessive soluble salt of this reaction solution. That is, the reaction solution was kept at 40 ° C., formaldehyde condensate of sodium naphthalenesulfonate and magnesium sulfate were added, and the mixture was allowed to stand with stirring to remove excess salts by decantation.

Next, the emulsion after desalting was brought to 55 ° C., ammonium thiocyanate, chloroauric acid and sodium thiosulfate were added to carry out chemical sensitization, and then the general formula ( The compounds I) to (IV) were spectrally sensitized by adding the amounts shown in Table 1. Emulsions 1 to 9 were prepared by adding 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene to 1.2 g per mol of silver halide when the maximum sensitivity was reached.

Next, as an emulsion coating solution, the emulsions were mixed at the emulsion mixing ratio shown in Table 2, and the following additives were added to silver halide 1
Added per mole.

Nitrophenyl-triphenylphosphonium chloride 30 mg, 1,3-dihydroxybenzene-4-
Ammonium sulfonate 1 g, 2-mercaptobenzimidazole-5-sodium sulfonate 10 mg, 2-mercaptobenzothiazole 10 mg, trimethylolpropane 9 g,
1,1-Dimethylol-1-bromo-1-nitromethane 10m
g, C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1g

[0070]

[Chemical 19]

1 g of gelatin as a protective layer liquid for the emulsion layer
The following was added to make a coating solution.

50 mg of sodium chloride, 7 mg of a matting agent composed of polymethylmethacrylate having an average particle size of 5 μm, 70 mg of colloidal silica having an average particle size of 0.013 μm, 2 ml of 35% formalin aqueous solution, 1.5 ml of 40% glyoxal aqueous solution, i-amyl-n- Decyl-sodium sulfosuccinate 7mg

[0073]

[Chemical 20]

Next, as a backing layer, 400 g of gelatin,
A backing layer liquid consisting of 2 g of polymethylmethacrylate, 6 g of sodium dodecylbenzenesulfonate and glyoxal was prepared, and 50 wt% of glycidyl methacrylate, 10 wt% of methyl acrylate and 40 wt% of butyl methacrylate.
The concentration of the copolymer consisting of 3 kinds of monomers is 10wt%
Copolymer aqueous dispersion obtained by diluting so as to be applied on one side of polyethylene terephthalate base coated as an undercoating liquid together with a protective layer liquid consisting of gelatin, matting agent, sodium dodecylbenzenesulfonate and glyoxal. The backed support thus obtained was prepared.

[0075] The coating amount backing layer, 2.5 g / m ² of protective layer as each amount with gelatin was 2.0 g / m ^2.

On the backed base, the emulsion coating solution and the protective layer were simultaneously coated in two layers with a slide hopper to obtain a sample. The coating amount was 3.0 g / m ^{2 in} terms of silver amount, and the total binder amount was 1.2 g / m ² in the emulsion layer 3 g / m ² protective layer.

[Sample Evaluation Method] The obtained film sample was tested by the following method.

The development processing was carried out by using an automatic processor SRX-501 (manufactured by Konica Corporation) at 35 ° C. for 45 seconds. The developer used was XD-SR and the fixer was XF-SR (both manufactured by Konica Corporation).

Exposure Method Wedge exposure was performed at a high illuminance of 10 ⁻⁵ seconds using the interference filters having the respective exposure wavelengths shown in Table 3.

Evaluation of Sensitivity It is a relative sensitivity in which the sensitivity of Sample No. 1 obtained from the exposure amount required to give a density of fog +1.0 is represented as 28.

Evaluation of Gamma (G) Fog was obtained by subtracting the base density from the density of the unexposed portion, and the gamma (G) between the density of Fog + 0.25 and the density of Fog + 2.0 was calculated.

[0082]

[Table 1]

[0083]

[Table 2]

[0084]

[Table 3]

As is clear from Table 3, sample Nos. 1 to 10
From the above, the sample of the present invention containing two or more kinds of silver halide emulsions having different spectral maximum wavelengths and having different sensitivity ratios of the respective emulsions at the respective spectral maximum wavelengths has a difference in sensitivity and gamma between 633 nm and 780 nm. It can be seen that one type can be used for each laser light source of each wavelength.

From sample Nos. 11 to 15, sample Nos. 14 and 15 of the present invention prepared from emulsions having substantially the same spectral maximum wavelength and different sensitivity ratios at wavelengths 20 nm or more away from the spectral maximum wavelength. It can be seen that the above-mentioned effects of the present invention are achieved.

[0087]

Industrial Applicability According to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has sensitivity at each wavelength even when exposed at different wavelengths and has characteristic curve shapes having different characteristics.

Claims (2)

[Claims] 1. A support having at least one photosensitive emulsion layer containing two or more kinds of silver halide emulsions having different spectral maximum wavelengths, and each of the two or more kinds of silver halide emulsions is composed of: A silver halide photographic light-sensitive material for a laser imager, wherein the emulsions have different sensitivity ratios at the maximum spectral wavelength. 2. In a silver halide photographic light-sensitive material having at least one light-sensitive emulsion layer containing two or more kinds of silver halide emulsions on a support, the respective spectral maximum wavelengths of the silver halide emulsions are substantially the same. And a silver halide photographic light-sensitive material for a laser imager, characterized in that the emulsions have different ratios of the sensitivity at the spectral maximum wavelength and the sensitivity at a wavelength 20 nm or more away from the spectral maximum wavelength. material.