JPH0213940A - Silver halide photographic sensitive material for light room with void ability etc. - Google Patents

Abstract

PURPOSE:To obtain the title material with improved workability and a good performance by specifying the gamma value of the photosensitive material in case that the material is subjected to image exposure and development processing. CONSTITUTION:A mat agent having a particle size of 3-10mum is incorporated in a protective layer mounted on the photographic constituting layer which exists in the side contg. a photosensitive silver halide of the photosensitive material. The total gelatin amount contd. in said photographic constituting layer is specified to 2.0-3.5g/m<2>. In case that the photosensitive material is subjected to the image exposure and the development processing, the gamma value defined by optical density of 0.3-3.0 is specified to >=6.0. Thus, the photosensitive material for the light room which is improved the void quality and the workability and has a less tendency for generating a pine hole is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material that can be handled in an environment that can be called a bright room.

[Background of the invention]

In recent years, in the field of printing and plate making, there has been a demand for technology that allows filmmaking, especially the so-called film-returning process, to be performed in a bright room, which was traditionally done in a darkroom, in order to save labor and improve the working environment. Improvements have been made to the equipment and photosensitive materials. Examples of photosensitive materials for use in bright rooms include photosensitive materials that also have spectral sensitivity to light sources rich in ultraviolet light, such as ultra-high pressure mercury lamps, mercury lamps, metal halide lamps, xenon lamps, and halogen lamps. These photosensitive materials can be handled under a general fluorescent lamp or a dedicated fluorescent lamp with a low amount of ultraviolet rays. However, the photosensitive material for bright room use used in the conventional booklet turning process uses a developed film on which characters or halftone images have been formed as an original, and the original and the photosensitive material for turning are exposed in close contact.
It is a photosensitive material used to perform negative image/positive image conversion or positive image/positive conversion, and halftone images, line drawings, and character images are converted into negative images/negative images according to their respective halftone dot areas, line widths, and character images. It has the ability to perform positive image conversion, the tone adjustment of halftone dot images, and the line width adjustment of character line images.
There has been a demand for photosensitive materials for use in bright rooms that meet the demands for such performance. However, in the advanced image conversion work of forming cut-out character images by overlapping and turning, there is a drawback that the quality of the cut-out character images deteriorates compared to a method using a conventional turning step using a darkroom photosensitive material. What is important about this is that the method of forming a cutout character image by overlapping is a negative image/
Ideally, positive image conversion should be performed, but while halftone originals are exposed in direct contact with the emulsion surface of the photosensitive material for return, line art originals are exposed using a pasting base and halftone originals in between. The photosensitive material for return is exposed to light through this process.

For this reason, if you apply an exposure amount that faithfully converts a halftone original from a negative image to a positive image, the line drawing original will be exposed out of focus through the pasted base and the spacer due to the halftone image, resulting in the image of the white missing part of the line drawing being exposed. The middle of the line becomes narrow. This is the cause of the deterioration of the quality of cutout character images, but this phenomenon has a large contribution from the light source system, and the exposure latitude of cutout characters in conventional work is narrower than in general simple inversion. It is well known that adequate exposure control is the basis for stable cutout work. However, expectations were higher for the photographic performance of the photosensitive material itself, rather than for preventing the quality deterioration of cut-out character images, which conventional photosensitive materials for bright rooms have, while maintaining adequate exposure control.

[Purpose of the invention]

The present invention provides a silver halide photographic light-sensitive material for bright rooms that is easy to work with and can provide good performance by solving the problems of the conventional light-sensitive materials for bright rooms as described above. The purpose is to

[Structure of the invention]

The object of the present invention is to provide a silver halide photographic material having main photosensitivity in the wavelength range of 300 nm to 450 nm, in which a protective film layer in the photographic constituent layer on the side having photosensitive silver halide has a grain size of 3 to 10 um. The silver halide photograph contains at least one kind of matting agent, and the total amount of gelatin in the photographic constituent layer on the side having the photosensitive silver halide is in the range of 2.0 to 3.5 g/m'', and the silver halide photograph A silver halide photograph for bright room use, characterized in that when a photosensitive material is subjected to imagewise exposure and development processing, the γ value defined at a density of 0.3 to 3°0 is substantially 6.0 or more. This was achieved using photosensitive materials.In other words, if the precision of cut-out characters is evaluated simply by the light source system, the highest precision will be obtained when the light hits the film perpendicularly, and if diagonal light is mixed in, the accuracy will be the same. It is thought that the accuracy of cut-out characters deteriorates.If we consider this further with respect to light passing through a photosensitive material, the sharpness is reduced due to the so-called irradiation phenomenon in which light reflected by one particle sensitizes adjacent particles. On the other hand, it is known that the rate at which the halftone dot area increases with respect to an increase in the exposure amount (referred to as halftone dot thickening performance) is improved due to the irradiation phenomenon. When exposing a light-sensitive material and an original in close contact with each other in a bright room, the light that passes through the emulsion surface is refracted and scattered by the silver halide emulsion layer of the light-sensitive material, the interior and surface of the support, and the light is scattered. Since it has a large effect on the thickening performance of halftone dots and cutout characters, we are researching methods to improve the halftone dot thickening performance by changing the size of the particles and to prevent the precision of cutout characters from deteriorating due to light scattering effects. As a result, the light scattering effect is influenced by the particle size of the matting agent contained in the protective film layer, which is the uppermost layer on the photosensitive layer side of the silver halide photographic light-sensitive material that is exposed in close contact with the original. It was found that the thickening performance of the matting agent also changes.-As the particle size of the matting agent increases, the light scattering effect increases and pinholes occur frequently, leading to a decrease in photographic performance.Particle size of the narrow matting agent This phenomenon occurs because when the matte agent becomes larger, it becomes easier to move from the surface layer to the emulsion layer side.In order to reduce the mobility of the matte agent in large particles, it is necessary to consider the film thickness, etc. that corresponds to the matte particle size. This change in film thickness also affects the scattering effect of light on the support when light passes through it, so it is related to both the thickening of halftone dots and the accuracy of cut-out characters. In order to improve performance, if a high-contrast technology that can obtain a high γ value is adopted, it will lead to improved character image quality, but on the other hand, it will have the contradictory effect of deteriorating the level of pinholes and pasting marks. It will be done.

From this point of view, we have made extensive studies and have achieved the present invention.

The details of the present invention will be explained below.

One of the important features of the present invention is the high-contrast photographic performance of γ of 6.0, which is specified for a density of 0.3 to 3.0, and is applicable to both negative and positive types. In particular, in a negative photographic material, a tetrazolium compound or hydrazine is contained in at least one of the wood-philic colloid layers containing a photosensitive silver halide emulsion contained in the silver halide photographic material and/or in its adjacent layer. compound or polyalkylene oxide compound,
It is particularly preferable to obtain it by processing with a processing solution containing HQ, alone, PQ, or MO as a developing agent and having a pH of 10''13.

First, a method using a tetrazolium compound will be described. The technique of using a tetrazolium compound in a silver halide photographic material is described, for example, in JP-A-52-18317, JP-A-53-17719, JP-A-53-17719, and JP-A-Sho 6.
1-149946 and the like. Hereinafter, this will be referred to as tetrathulium high contrast technology.

Specific examples of the tetrazolium compound used in the present invention include the general formula (1)-1 described in JP-A-62-11253.
Compounds represented by ■-2 and ■-3 can be mentioned.

[■-1] [■-2] [■-3] In the formula, R,,Ra,Rg,Rs,R+□,R,,,R,4
and R16 are each an alkyl group (eg, methyl group, ethyl group).

group, propyl group, dodecyl group, etc.), allyl group, phenyl group (e.g. phenyl group, tolyl group, hydroxyphenyl group, carboxyphenyl group, aminophenyl group, mercaptophenyl group, methoxyphenyl group, etc.), naphthyl group (e.g. α -naphthyl group, β-7thyl group, hydroxynaphthyl group, carboxynaphthyl group, aminonaphthyl group, etc.), and heterocyclic groups (e.g., thiazolyl group, benzothiazolyl group, oxacyl group, pyrimidinyl group, pyridyl group, etc.) It represents a group, and any of these may be a group that forms a metal chelate or a complex. R6
-R1° and R1□ are allyl group, phenyl group,
naphthyl group, heterocyclic group, alkyl group (e.g. methyl group,
ethyl group, propyl group, butyl group, mercaptomethyl group, mercaptoethyl group, etc.), water aX, alkylphenyl group, alkoxyphenyl group, carbonyl group or its salt, carboxyalkyl group (e.g. methoxycarbonyl group, ethoxycarbonyl group), represents a group selected from an amine group (for example, an amino group, an ethylamino group, an anilino group, etc.), a mercapto group, a nitro group, and a hydrogen atom, D represents a divalent aromatic group, and E represents an alkylene group, an arylene group,
It represents a group selected from aralalkylene groups, Xe represents an anion, and n represents 1 or 2. However, when the compound forms an inner salt, n is l.

Next, specific examples of the cation moiety of the tetrazolium compound used in the present invention will be shown, but the cation moiety of the compound that can be used in the present invention is not necessarily limited to these.

(T-1) 2-(benzothiazol-2-yl)-
3=phenyl-5-dodenru 2H-tetrazolium (T-2) 2.3-diphenyl-5-(4-
octyloquinphenyl)-28-tetrazolium (T
-3) 2,3.5-triphenyl-2H-tetrazolium (T-4) 2,3.5-tri(p-carboxyethyl 7gonyl (T-5) 2-(benzothiazol-2-yl)- 3=7anyru5-(o-chlorphenyl)
-2H-tetrazolium (T-6) 2.3-diphenyl-2H-tetrazolium (T-7) 2.3-diphenyl-5-methyl-2
H-tetrazolium (T-8) 3-(p-hydroxyphenyl)-5-methyl-2-phenyl-2H-tetrazolium (T-9) 2.3-diphenyl-5-ethyl-
2H-tetrazolium (T-10) 2.3-diphenyl-5-n-hexyl-2H-tetrazolium (T-11) 5-cyano-2,3-diphenyl-2H-tetrazolium (T-12) 2-(penz thiazol-2-yl)-5-phenyl-3-(4-tolyl)-2H-tetrazolium (T-13) 2-(benzothiazol-2-yl)-5-(4-chlorophenyl)-3-( 4-nitrophenyl)-2H-tetrazolium (T-14) 5-ethoxycarbonyl-2.3
-di(3-nitrophenyl)-2H-tetrathulium (T-15) 5-acetyl-2,3-di(p-
ethoxyphenyl)-2H-tetrazolium (T-16) 2,5-diphenyl-3-(p-
) Reel) -2H-tetrazolium (T-17) 2.5-diphenyl-3-(p-iodophenyl)2H-tetrazolium (T-18) 2.3-diphenyl-5-(p-diphenyl)-2H-tetrazolium (T-19) 5-(p-bromophenyl)-
2-phenyl-3-(2,4,6-1-lichlorophenyl)-2H-tetrazolium (T-20) 3-(p-hydroxyphenyl)-5-(p-2-lofenyl)-2 -Phenyl-2H-tetrazolium (T-21) 5-(3.4-dimethoxyphenyl)-3-(2-ethoxyphenyl)-2-(4-methoxyphenyl)-2H-tetrazolium (T-22) 5 -(4-cyanophenyl)-
2.3 ~ Diphenyl-2H-tetrazolium (T-23) 3-(p-acetamidophenyl)-2.

5-diphenyl-2H-tetrazolium (T-2
4) 5-acetyl-2,3-diphenyl-2H-
Tetrazolium (T-25) 5-(Flu 2yl)-2.3-
Diphenyl-2H-tetrazolium (T-26) 5-(thiecyl)-2.3
-Diphenyl-2H-tetrazolium (T-27) 2.3-diphenyl-5-(pyrid-4yl)-2H-tetrazolium (T-28) 2.3-diphenyl-5-(quinol-2yl)-2H -Tetrazolium (T-29) 2.3-diphenyl-5-(benzoxazol-2yl)-2H-tetrazolium (T-
30) 2.3-diphenyl-5-nido-2
H-tetrazolium' (T-31) 2.2',3.3'-tetraphenyl-5.

5'-1,4-butylene-di(211-tetrazolium) (T-32) 2.2',3.3'-tetraphenyl-5.

5'-p-phenylene-di(2H-tetrazolium) (T-33) 2-(4.5-dimethylthiazol-2yl)-3.5-diphenyl-2H-tetrazolium (T-34) 3.5- Diphenyl-2-(triazin-2yl-2H-tetrazolium) (T-35) 2-(benzothiazol-2yl)-3-(4-methoxyphenyl)-5-phenyl-2H-tetrazolium (T-36) 2.3-dimethoxyphenyl-5-
Phenyl-2H-tetrazolium (T-37) 2,3,5-tris(methoxyphenyl)-2H-tetrazolium (T-38) 2,3-dimethylphenyl-5-phenyl-2H-tetrazolium (T-39) 2 .3-hydroxyethyl-5-phenyl-2H-tetrazolium (T-40) 2.3-hydroxymethyl-5-phenyl-2H-tetrazolium (T-41) 2.3-cyanohydroxyphenyl-5-phenyl-2H -Tetrazolium (T-42) 2.3-di(p-talolophenyl)-
5-722-2H-tetrazolium (T-43) 2.3-di(hydroxyethoxyphenyl)-5-phenyl-2H-tetrazolium (T-
44) 2,3-di(2-pyridyl)-5-phenyl-2H-tetrazolium (T-45) 2,3,5-tris(2-pyridyl)
-2H-tetrazolium (T-46) 2,3.5-tris(4-pyridyl)
-2H-Tetrazolium When a tetrazolium compound is used as a non-diffusible compound, a non-diffusible compound obtained by appropriately selecting a cation moiety and an anion moiety is used.

Examples of the anion moiety of the tetrazolium compound used in the present invention include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as sulfuric acid, nitric acid, and perchloric acid, sulfonic acid,
Acid groups of organic acids such as carboxylic acids, lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, and higher alkyl sulfate ester anions such as lauryl sulfate anions. , dialkyl sulfosuccinate anions such as di-2-ethylhexyl sulfosuccinate anions, polyether alcohol sulfate ester anions such as cetyl polyethenoxy sulfate anions, higher fatty acid anions such as stearate anions, and polyesters such as polyacrylate anions. Examples include those with an acid radical attached to -.

By appropriately selecting the anion moiety and the cation moiety, the non-diffusible tetrazolium compound according to the present invention can be synthesized. The compounds according to the present invention synthesized in this way include, for example, 2°3.5-triphenyl-2H-tetrazolium-dioctylsuccinate sulfonate, and these are as described in detail in the examples below, respectively. A case in which a soluble salt of is dispersed in gelatin, and then the two are mixed and dispersed in a gelatin matrix;
Crystals of the oxidizing agent may be synthesized in pure form, dissolved in a suitable solvent (eg dimethyl sulfoxide), and then dispersed into a gelatin matrix.

If it is difficult to achieve uniform dispersion, emulsification and dispersion using an appropriate homogenizer such as ultrasonic waves or a Manton-Gorlin homogenizer may give good results. In addition, by finely dispersing it in a high boiling point solvent such as dioctyl 7-talate,
It is also possible to protect it and disperse it in a hydrophilic colloid layer.

Next, hydrazine derivatives (e.g. U.S. Pat. No. 4,166.7)
No. 42, No. 4,168,977, No. 4,221,85
No. 7, No. 4,224゜No. 401, No. 4,243,739
No. 4,272,606, and No. 4,311゜781, a negative type (silver halide photographic light-sensitive material) containing a specific anruhydrazine compound) was prepared at pH 1.
A method (hereinafter referred to as a hydrazine high-contrast developing system) for obtaining high-contrast negative images by processing with a solution containing 0.15 mol/Q or more of a sulfite preservative in the range of 1.0 to 12.3 will be described.

Examples of hydrazine derivatives used in this method include aryl hydrazides in which a sulfinic acid residue is bonded to a hydrazo moiety described in U.S. Pat. No. 4,478,928, as well as the following general formula (I): Examples include compounds represented by:

General formula (H) R, -NHNH-G-R2 In the formula, R1 represents an aliphatic group or an aromatic group, and R2 is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or represents an unsubstituted alkoxy group or a substituted or unsubstituted aryloxy group, G is a carbonyl group, a sulfonyl group, a sulfoxy group,
Represents a phosphoryl group or an N-substituted or unsubstituted iminomethylene group. The hydrazine derivative represented by the general formula (H) is disclosed in JP-A-62-210458, and the specific example compounds described in the same publication can also be used in the present invention.

In the present invention, the hydrazine derivative is used in an amount of 1 x 10-' mole to 5 x 10-' mole per 11 mole of halogenated ff.
It is preferable to add the compound in moles, and particularly the amount added is preferably in the range of I x 10-5 mol to 2 x 10-2 mol.

In the present invention, when a hydrazine derivative is contained in a photographic light-sensitive material, it is used as an aqueous solution if it is water-soluble, or as an alcohol (for example, methanol or ethanol) if it is water-insoluble.
It may be added to a silver halide emulsion solution or a hydrophilic colloid solution as a solution of a water-miscible organic solvent such as an ester (for example, ethyl acetate) or a ketone (for example, acetone).

A hydrazine derivative may be used alone in the present invention,
Two or more types may be used in combination.

In addition, the method of using a polyalkylene oxide compound is known as a lithium-type photographic light-sensitive material, and the lithium-type silver halide light-sensitive material is used as a hydroquinone developer and the sulfite ion concentration is quite high (0.2 mol/Q or more). High pH (
10-5) and a developing solution containing a nitroindazole compound, a system (disclosed in Japanese Patent Application Laid-Open No. 190943/1983) is also known that can obtain a high-contrast image. (Hereinafter, referred to as rapid squirrel technology.) Next, the polyalkylene oxide compound used in rapid squirrel technology will be explained.

The polyalkylene oxide compound used in the present invention is an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-1,
a polyalkylene oxide consisting of at least IO units, such as 2-oxide, preferably ethylene oxide;
It includes condensates with compounds having at least one active hydrogen atom such as water, aliphatic alcohols, aromatic alcohols, fatty acids, organic amines, and hexitol derivatives, or block copolymers of two or more types of polyalkylene oxides. That is, as polyalkylene oxide compounds, specifically polyalkylene glycols polyalkylene glycol alkyl ethers 11
11 Aryl ethers 11 1
1 (Alkylaryl) esters, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, polyalkylene glycol amine acids, polyalkylene glycol block copolymers, polyalkylene glycol craft polymers, and the like can be used.

There is not only one polyalkylene oxide in the molecule,
Two or more may be included. The lateral polyalkylene oxide chains may then consist of fewer than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. If there is more than one polyalkylene oxide in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound used in the present invention preferably contains 14 or more alkylene oxide units.

Specific examples of the polyalkylene oxide compounds used in the present invention are as follows.

Polyalkylene oxide compound example 1 80 (OH2CH20), H 20, □112So (CH, CH20) □5H4CaH
+7CH=CHCsH+aOs(CH2CH20)+5
) I6 C, 1823c00 (CH2CH20)8.
117 C,,H21CONH(CH2CH20)+
31(9 czozsN(cuzXcuzcHzo
)2*n10 1((CH2CH20)a(CH2H2
0)b(CH2C)+20)cHC1]3a+b+c=50 In the present invention, the amount of polyalkylene oxide compound added is preferably IO- to 10-'g1 mol Ag per 1 mol of silver halide, particularly 1O -3~IO'
It is preferable to contain 1 mol of Ag.

Furthermore, the following chemical sensitization may or may not be performed,
Non-chemical sensitization is particularly preferred.

Silver halide emulsions include gold compounds such as chloroauric acids and gold trichloride, salts of noble metals such as iridium, sulfur compounds that react with silver salts to form silver sulfide, stannous salts, and reducing compounds such as amines. Sensitivity can be increased without making the particles coarser with a chemical substance.

Further, iron compounds such as salts of noble metals such as iridium and red blood salts may be present during physical ripening of silver halide grains or during nucleation.

The average grain size of the photosensitive/10-genide silver grains used in the present invention means, in the case of spherical grains, the diameter thereof, and in the case of grains of a shape other than spherical, the projected image of the same area as a circular image. Shows the diameter when converted, average particle size 0.05um - 0.3μm
belongs to.

Method for producing silver halide emulsion used in the present invention, sensitization method,
As for binder additives, etc., techniques known in the photographic industry can be used. For example, research on additives
Disclosure Volume 176, No. 17643 (1
December 978) and Volume 187, No.

18716 (November 1979). −
Silver halide emulsions used in the present invention (hereinafter referred to as silver halide emulsions) include silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, etc. Although any silver halide emulsion commonly used in silver halide emulsions can be used, preferably silver chlorobromide containing 60 mol% or more of silver chloride or positive-working halogen emulsions are used as negative-working silver halide emulsions. These are silver chlorobromide, silver bromide, and silver iodobromide containing 10 mol% or more of silver bromide as a silver emulsion.

Silver halide grains used in silver halide emulsions contain cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (complex salts containing), rhodium salt ( Metal ions can be added using at least one selected from iron salts (complex salts containing) and iron salts (complex salts containing iron salts) to contain these metal elements inside the particles and/or on the particle surfaces. In particular, water-soluble rhodium Preferably, it contains salt. Further, by placing the particles in an appropriate reducing atmosphere, reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

When adding a water-soluble rhodium salt, preferably 1 x 10-
7~1XIO''4 mole/Agx1 mole is better.

As the optical brightener, stilbene-based, triazine-based, pyrazoline-based, coumarin-based, and acetylene-based optical brighteners can be preferably used.

These compounds may be water-soluble, or insoluble ones may be used in the form of a dispersion.

Specific examples of polymer matting agents used in the practice of the present invention include water-dispersible vinyl polymers such as polymethyl acrylate and acrylic acids such as cellulose acetate propionate, methyl methacrylate, grindyl acrylate, and glycidyl methacrylate. Examples include matting agents of water-dispersible vinyl polymers such as homopolymers of esters or copolymers of these acrylic esters with other vinyl monomers. So far, as matting agents, British Patent No. 1,055,713, US Patent No. 1,939,213, US Patent No. 2,221,873, US Patent No. 2,268.662, US Patent No. No. 037, same 2
, No. 376.005, No. 2,391,181, No. 2,
701.245, 2,992.101, 3.0
79°257, 3,262.782, 3,51
No. 6,832, No. 3,539゜344, No. 3,591
, No. 379, No. 3,754,924, No. 3,767゜448, etc., West German Patent No. 2
, 592,321, British Patent No. 760,775, 1, 260.

No. 772, U.S. Patent No. 1,201,905, 2;1
No. 92,241, No. 3,053,662, No. 3,06
No. 2,649, No. 3,257,206, No. 3,322
, No. 555, No. 3,353,958, No. 3,370,
No. 951, No. 3,411,907, No. 3,437,4
No. 84, No. 3,523,022, No. 3,615,55
No. 4, No. 3,635,714, No. 3,769.020
Inorganic matting agents described in Japanese Patent No. 4,021,245, Japanese Patent No. 4,029,504, etc. can be preferably used.

Particularly preferred are commonly used colloidal silicate compounds and polymethyl methacrylate, but the type thereof is not limited. The capping agent is added to the protective layer above the emulsion layer or, for example, to the protective layer on the back side, but in the present invention, the polymer matting agent is added to the emulsion layer side.

Further, a technique for improving dimensional stability by incorporating a polymer latex into a silver halide emulsion layer or a banking layer can also be used in conjunction with the embodiments of the present invention. These techniques are disclosed in, for example, Japanese Patent Publication Nos. 93-4272 and 39-1770.
2, No. 43-13482, U.S. Patent No. 2.376.0
No. 05, No. 2,763,625, No. 2,772.166
No. 2,852°386, No. 2,853,457, No. 3,397,988, etc.

The light-sensitive material of the present invention can be exposed to electromagnetic waves in a spectral region to which the emulsion layer constituting the light-sensitive material has sensitivity. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps, quartz lamps, mercury lamps, microwave UV lamps, xenonark lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, Any known light source can be used, such as light emitted from a phosphor excited by electron beams, X-rays, γ-rays, α-rays, or the like. Especially 450
Favorable results can also be obtained by imagewise exposing the photosensitive layer of the photosensitive material of the present invention, which has a maximum sensitivity below 370 nm, with light that does not substantially contain light below 370 nm. In particular, it is particularly preferable that the sensitivity to light of 400 nm is 30 times or more the sensitivity to light of 360 nm in the case of a light-sensitive material for bright room printing.

Next, methods of [image-sensitizing the photosensitive layer with light that does not substantially contain light of 370 nm or less] include a method of incorporating an ultraviolet absorber into the photosensitive material, a method of using an optical filter that absorbs ultraviolet light, and a method of using an optical filter that absorbs ultraviolet light; There are methods using a light source that does not substantially emit energy as described below.

First, the first method will be explained.

Here, the ultraviolet absorber increases the inherent sensitivity of the silver halide emulsion by 1.
72 or less, and as this ultraviolet absorber, an ultraviolet absorber having a peak in the range of 300 to 400 nm can be used, and more preferably, a UV absorber having a peak in the range of 300 to 38 nm is used.
It is an ultraviolet absorber that has a peak at 0 nm.

As the ultraviolet absorber, for example, a benzotriazole compound substituted with an aryl group, a 4-thiazolidone compound, a benzophenone compound, a cinnamic acid ester compound, a butadiene compound, a benzoxazole compound, and an ultraviolet absorber polymer can be used.

Specific examples of ultraviolet absorbers are given in U.S. Patent No. 3,533,794.
No. 3,314.794, No. 3,352,681, JP-A-46-2784, U.S. Patent No. 3,705.80
No. 5, No. 3,707.375, No. 4,045,229
No. 3,700,455, No. 3,499,762, and West German Patent Application Publication No. 1,547,563.

In the present invention, specific compounds described in JP-A-62-210458 can be used.

In the present invention, the ultraviolet absorber is added so as to make the intrinsic sensitivity of the silver halide emulsion at 360 nm 172 or less, and the amount added is such that the absorbance at 360 nm is 0.3 or more, and more preferably This is the amount at which the absorbance at 360 nm is 0.4 or more.

The strength varies depending on the molar absorption coefficient of the ultraviolet absorber, and usually l
It is added in a range of 0-2g/m2 to 19/m2. Preferably it is 50 mg to 500 mg/m2.

The ultraviolet absorber of the present invention is contained in an emulsion layer, a surface protective layer, an intermediate layer, etc.

The above-mentioned ultraviolet absorber can be dissolved in a suitable solvent [for example, water, alcohol (such as methanol, ethanol, propatool, etc.), acetone, methyl selon rub, etc., or a mixed solvent thereof to form the non-photosensitive material of the present invention. It can be added to the coating solution for the hydrophilic colloid layer.

Two or more of these ultraviolet absorbers can also be used in combination.

In the present invention, the above-mentioned safelight dye and ultraviolet absorber may exist in the same layer or in different layers.Next, the second method will be explained. do. As the optical filter (that is, the light source filter) that absorbs ultraviolet rays, it is preferable to use a 17) filter that hardly transmits light of 370 nm or less, such as Koda Nkura Notin Filter NO-2B. More specifically, the transmittance is 20
% or less, more preferably 10% or less.

Next, a third method will be explained. The light source itself? 370
Examples of light sources that do not substantially emit light energy in the nm or less region include Idol Fin manufactured by Eye Graphics Co., Ltd., and Printer P for plate making manufactured by Dainippon Screen Co., Ltd.
-Light source for 603 (metal halide lamp TYPE 5P
G-2000 (2KW) manufactured by Nippon Battery Co., Ltd.).

The light source used in this third method is 300 to 4
Of the emission energy in the 20 nm region, 300
It is preferable that the emission energy in the region of 370 nm or less is 30% or less, and particularly preferably 20% or less.

Furthermore, commercially available photosensitive materials for bright rooms (for example, Konica Co., Ltd.'s C
RH-100, KUV-1 manufactured by Fuji Photo Film Co., Ltd.
00, etc.) can also be exposed using a light source with a higher capacity than a conventional bright room light source through an optical filter (light source filter) that cuts ultraviolet rays. The high-capacity light source used here is, for example, an ultra-high pressure mercury lamp H-15-L 31 (15KW) manufactured by Eye Graphic Co., Ltd.
etc. can be mentioned.

Optical filter that absorbs ultraviolet rays (filter for light source)
When sensitizing is performed between a light source and a photosensitive material, when a layer containing an ultraviolet absorber, etc. is provided in the photosensitive material so that light that does not substantially contain light of 370 nm or less reaches the photosensitive layer, etc. In this case, conventional known light sources can be used. For example, the light source for plate-making printer P-607 (ultra-high pressure mercury lamp: URT) manufactured by Dainippon Screen Co., Ltd.
-CHM-1000) and P-627FM light source manufactured by the same company.

In the method of the present invention, the exposure time is selected depending on the capacity of the light source used, the sensitivity (including spectral sensitivity) of the photosensitive material, etc., but is usually 60 seconds to 5 seconds. In some cases, exposure may be performed for a long time (2 to 3 minutes).

Exposure times include not only exposure times of 1 millisecond to 1 second commonly used in cameras, but also exposures shorter than 1 microsecond, such as 100 nanoseconds to 100 nanoseconds using a cathode ray tube or xenon flash tube.
Microsecond exposures can be used, or exposures longer than 1 second can be given. These exposures may be performed continuously or intermittently.

Various known methods such as black and white, color, and reversal development can be used to develop the photosensitive material according to the method of the present invention, but it is particularly effective when processing the bulk of the photosensitive material for printing, which provides high contrast. It is.

In the present invention, dyes used for filter dyes, antihalation, and various other purposes include triallyl dyes, oxanol dyes, hemioxanol dyes, merocyanine dyes, cyanine dyes, styryl dyes, and azo dyes. Among them, oxanol dyes: hemioxanol dyes and merocyanine dyes are useful. Furthermore, compounds described in Japanese Patent Application No. 153156/1988 can be used in the present invention.

That is, the desensitizing dye used to achieve the object of the present invention is preferably a compound in which the sum of the anode potential and the cathode potential of the polarogram is positive, and such compounds are described in numerous patents and literature. Although any desensitizing dye can be used, those represented by the following general formulas CI) to [v] shown in the above-mentioned Japanese Patent Application Publication No. 1999-1999 can be preferably used as desensitizing dyes.

These compounds are described in U.S. Patent No. 3,567.456;
No. 3,615,639, No. 3,579,345, No. 3,615,608, No. 3,598,596, No. 3
, No. 598,955, No. 3,592,653, No. 3,
No. 582,343, Special Publication No. 40-26751, No. 40
-27332, 43-13167, 45-88
It can be synthesized with reference to specifications such as No. 33 and No. 47-8746.

General formula [■] General formula [■] p.

In the general formulas [I] and (II), R2 is hydrogen, a halogen atom, a cyano group, or a nitro group, and R3 and R2 may form an aromatic ring.

R1 and R1 each represent an alkyl group, a lower alkenyl group, a phenyl group, or a lower hydroxyalkyl group, and R1
and when R2 is other than a hydrogen atom, it may be an aryl group, n is a positive number of 1 to 4, R5 represents a lower alkyl group or a sulfonated lower alkyl group, and X represents an acid anion.

General formula [■] In the general formula (1), R4 and R2 are each a hydrogen atom or a nitro group, R3 and R3 are a lower alkyl group, an allyl group or a phenyl group, Z is a nitrobenzothiazole nucleus,
Nitrobenzoxazole nucleus, Nitrobenzoselenazole nucleus, Imidazo[4・5-b1 Quinoxaline nucleus, 3・3
-dimethyl-3H-pyrrolo[2,3-b1 pyridine nucleus,
3,3-dialkyl-3H-nitroindole nucleus, thiazoσ[4,5-b]quinoline nucleus, nitroquinoline nucleus, nitrothiazole nucleus, nitronaphthothiazole nucleus, nitrooxazole nucleus, nitronaphthoxazole nucleus, nitroselenazole nucleus , an atomic group necessary to form a nitronaphthoselenazole nucleus or a nitropyridine nucleus, X is an anion, and m and n each represent 1 or 2. However, when the compound forms an inner salt, n represents I.

General formula [■] In the general formula (IV), -R, R2, R, and R3 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, or a nitro group, and R6 is a hydrogen atom, Represents an alkyl group or a nitro group. Z is a thiazole nucleus which is unsubstituted or substituted with a lower alkyl group, a phenyl group, a thienyl group, a halogen atom, an alkoxy group, a hydroxy group, a cyano group, an alkylsulfonyl group, an alkoxycarbonyl group, a phenylsulfonyl group, or a trisulfomethyl group; , benzothiazole nucleus, naphthothiazole nucleus, oxazole nucleus, benzoxazole nucleus,
Naphthoxazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, thiazoline nucleus, pyridine nucleus, quinoline nucleus, isoquinoline nucleus, 3,3-dialkyl-3H-indole nucleus, imidazole nucleus, benzimidazole nucleus or naphthimidazole nucleus , Ll and R2 represent a methine chain that is unsubstituted or substituted with a lower alkyl group or an aryl group, R6 and R7 are each an unsubstituted or substituted alkyl group, alkenyl group, 71J-l group, sulfoalkyl group, or aralkyl group, X represents an anion, and m and n each represent 1 or 2. However, when the compound forms an inner salt, n represents 1.

General formula (V) R2x e General formula [73 In the formula, RI and R3 each represent an alkyl group, and R2 represents an aryl group. Ll and L2 each represent a methine chain unsubstituted or substituted with a lower alkyl group or an aryl group, Z is a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a selenazole nucleus, Benzoselenazole nucleus, naphthoselenazole nucleus, thiazoline nucleus, pyridine nucleus, quinoline nucleus, 3,3-dialkylindolenine nucleus, imidazole nucleus, imidazo [4.
5-b] Atom group necessary to form a quinoxaline nucleus, X represents an anion, m represents a positive integer of 1 to 3, and n represents a positive integer of 1 to 2.

Next, specific examples of the compounds represented by the above general formulas CI) to [■] are shown below. It goes without saying that the present invention is not limited to these compounds. Moreover, in the following exemplified compounds, Pts represents para-toluenesulfonic acid anion.

(Exemplary compound) (I7) (■8) No.

N) ICOCI(3 (2I) 2H5 O2 C2H6 NHCOCH3 zHs ♀83 ♀2115 The amount of the desensitizing dye according to the present invention used is preferably 1 mg to 1,000 mg per mole of silver halide, and is particularly preferable. is selected in the range of 5 mg to 300 mg.The timing of addition is at the time of silver halide formation, at the time of physical ripening, at the time of chemical ripening,
It may be applied either after ripening or during preparation of the coating solution.

Further, the desensitizing dye of the present invention preferably has a low sensitivity of 450 nm or less in order to prevent a decrease in sensitivity, and preferably has a maximum spectral sensitivity wavelength of 500 nm or more.

The silver halide photographic light-sensitive material of the present invention can be processed using any of the usual printing developers, but in particular, among the high contrast agents described in the specification, those using tetrazolium compounds and hydrazine compounds are preferred. (10,0~12.
PQ or M containing 0.5 mol/Q or more sulfite in 9
Particularly favorable results can be obtained by processing with a Q-based developer. When a polyalkylene oxide compound is used, preferable results can also be obtained by using a so-called lithium type developer in addition to the above-mentioned PQ and MQ type developers. However, the present invention is not limited to this combination.

In the present invention, the fixer preferably contains an AR compound in order to improve the hardness of the photosensitive material, and the content thereof is 0.1 to 3 g/Q in terms of i in the solution used. Sometimes more preferred.

The preferred concentration of sulfite contained in the fixer is 0.03 to 0.
The amount is 4 mol/Q, more preferably 0.04 to 0.3 mol/Q.

The preferred pH of the fixer is 3.9 to 6.5;
At H, the fixer gives favorable photographic performance, and at 1, the effects of the packaging material of the present invention become significant. The most preferred solution has a pH of 4.2 to 5.3.

In the present invention, the total processing time of 20' to 60' refers to development 1,
This time includes all the steps of fixing, washing, and drying (all including waving), but the developing seconds and fixing seconds can be set completely independently, and either one can be longer, and of course it is particularly preferable to use the same number of seconds. is development; [Fixing 1: 0.3~l
:3. Further, the developing temperature and the fixing temperature may be set completely independently (whichever is higher), or of course may be the same temperature. Particularly preferably, the fixing temperature is within a range of -15°C to +15°C relative to the developing temperature. Also, it is preferable for the washing water to be at room temperature for equipment reasons.
The temperature may be raised by installing a temperature controller.

The temperature after development and after fixing is preferably 20° C. to 45° C. from the viewpoint of stability and odor of the processing solution.

[Examples] Examples of the present invention will be described in detail below, but it goes without saying that the present invention is not limited thereto.

Example 1 A negative silver halide photosensitive material was prepared as a photosensitive material for bright room reversal in the following manner.

(Preparation of emulsion) A silver chlorobromide emulsion having a silver bromide content of 2 mol % was prepared as follows.

An aqueous solution containing 23.9 mg of pentabromorodium potassium salt, sodium chloride, and potassium bromide per 60 g of silver nitrate and an aqueous silver nitrate solution were simultaneously mixed in an aqueous gelatin solution at 30°C for 25 minutes to form average particles. A silver chlorobromide emulsion with a diameter of 0.15 μm was prepared.

After adding 4-hydroxy-1,3°3a,7-titrazaindene as a stabilizer to these emulsions, they were sensitized with sulfur and further additives were added. In other words, as a fog suppressant, ■-
Phenyl-5-mercaptotetrazole, 5-methylbenzotriazole, nonylphenyloxypolyethylene glycol, and acrylic acid-butyl methacrylate polymer latex were added, and then a polyalkylene oxacite compound (PE0) was added in the amount shown in Table 1, and then saponin was added. ,
Emulsion coating solution A-(1) to (11) was prepared by adding sodium dodecylbenzenesulfonate and further adding acrylic a-butyl methacrylate polymer latex and 280 mg of styrene-maleic acid polymer aqueous polymer as a thickener.
was prepared. In addition, polyalkylene oxide compounds (PE
B(1) to (11) were prepared by adding the tetrazolium compound (T) in the amount shown in Table 1 instead of O).

Further, compounds prepared by adding a hydrazine compound (H) in the amount shown in Table 1 instead of the polyalkylene oxide compound (PE0) are referred to as C(1) to (l l).

These were then deposited on a polyethylene terephthalate film base at a rate of m3 silver per m2. og.

A matting agent (average grain size 5
A layer of gelatin overcoat solution containing polymethyl methacrylate (μm) was applied.

The total amount of gelatin on the silver oxide photosensitive layer coated at this time was also varied as shown in Table 1, and the particle size of the matting agent in the gelatin protective film was varied as shown in Table 1. .

(PE0) COCH.

For each of the samples shown in Table 1, a previously prepared manuscript was brought into close contact with each emulsion surface.
It is said that it is appropriate to carry out image exposure at 7FM in combination with each contrast enhancing agent.

Development processing was performed under standard development conditions. The standard development conditions here are shown in Table 2 (however, the fixing is at the same temperature and the same time as the development), and the combination with the contrast agent is also described in JP-A No. 62-210453, etc. As is well known, samples using a tetrazolium salt as a contrast agent are treated with developer A, samples using a hydrazine compound as a contrast agent are treated with developer B, and samples using a polyalkylene oxide compound as a contrast agent are treated with developer B. , and developer C, the composition of which will be described later. In this way, the γ value at a density of 0.3 to 3.0 after the standard development process was determined for each sample, and the results shown in Table 2 were obtained. Furthermore, each sample was evaluated for pinhole and cutout character image quality, and the results are summarized in Table 2. In the same way, for each sample shown in Table 1, a prepared document was brought into close contact with each emulsion surface, and the image was exposed using light source A, for a total processing time of 50''.
(15" x 15") was rapidly processed.

Then, the γ value defined at a concentration of 0.3 to 3.0 for each sample was determined, and as a result, the values shown in Table 2 were obtained.

Furthermore, each sample was evaluated for pinhole and cutout character image quality, and the results are summarized in Table 2.

[Developer prescription]

Developer solution ■ (Mi composition A) Pure water (ion exchange water) 150m4
Ethylenediaminetetraacetic acid disodium salt 2g Diethylene glycol 50g Potassium sulfite (55% W/V aqueous solution) 100mQ Potassium carbonate 509 Hydroquinone 1595-Methylbenzotriazole 200mg 1-phenyl-5-mercaptotetrasol 30mg Potassium hydroxide Adjust the pH of the working solution to 1O14 gold potassium bromide
4.59 (composition) Pure water (ion exchange water) 3m12
Diethylene glycol 50g Ethylenediaminetetraacetic acid disodium salt 251119 Vinegar M
(90% water RJ liquid) 0.
3mQ5-nitroindazole ll
0Bl-phenyl-3-pyrazolidone 5
When using 00B developer, dissolve the above two compositions A and B in the order of 500 mα of water, and then apply the 17
+Iko.

Developer ■ Hydroquinone 45.09N
-Methyl p-aminophenol 1/2i a salt 0.8
gSodium hydroxide 15.0gPotassium hydroxide 55.0g5・Sulfosalicylic acid 45.0gBoric acid
35.0g Potassium sulfite 110°Og Ethylenediaminetetraacetic acid disodium salt 1.0g Potassium bromide
6.0g 5-Methylbenzotriazole n-butyl jetanolamine 15.0g
Add water and calculate Iff (pH
= 11.6) Developer C Developer solution for quick squirting CDL-271 A manufactured by Konica Corporation
B was used.

[Fixer prescription]

(Composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 23
0m+2 Sodium Sulfite 9.
5g Sodium acetate trihydrate 15.9
g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (9
0% W/W aqueous solution) 8.1 mff
Pure water (ion exchange water) 17mQ sulfuric acid (50% W/W aqueous solution) 5.8
! J aluminum sulfate (aqueous solution with AQ.o3 equivalent content of 8.1% W/W)
When using 26.5 g of the fixer, it was dissolved in 500 mC of water in the order of composition A and composition, and finished to 1Q.

The pH of this fixer was about 4.3.

[Quick development processing conditions]

(Process) (Temperature) (Time) (Tank capacity)
Development 35°C 15 seconds
20 (40α) fixed 34°0
15 seconds 20Q water wash
18°0 10 seconds 10
(20p) Drying 40°0 10
seconds 2Off dryer heat transfer coefficient 180K
caQ/h-m2·°C Furthermore, an explanation of the evaluation method and terminology for evaluating the quality of pinholes and cut-out characters in the present invention will be described below.

■The γ value is determined by the following formula.

3, 0-0.3 γ=---1111---111------ lo
g (exposure amount giving density 3.0) - log (density 0.3
(exposure amount to give) ■ Pinhole: When proper reverse exposure is performed, the number of white microdots that appear is visually evaluated on a five-point scale. The rating was rated as 1, where there were many pinholes and the level was unsuitable for practical use, and 5 was the best level.

■Evaluation of cutout character image quality: 50% as cutout character image quality 5
This refers to the image quality in which characters with a width of 30 μm are reproduced when proper exposure is performed so that the halftone dot area becomes 50% of the halftone dot area on the photosensitive material for return, and it is a very good cutout character image quality. On the other hand, cutout character image quality 1 refers to an image quality in which only characters with a width of 150 μm or more can be reproduced when the same appropriate exposure is applied, and is poor cutout character quality. From the results in Table 2, it can be seen that the present invention is comprehensively superior in terms of pinhole and punched character quality photographic performance in both drifting processing and rapid processing.

〔Effect of the invention〕

According to the present invention, it was possible to provide a silver halide photographic light-sensitive material for bright room use, which has improved cutout character quality and pinhole occurrence, and is excellent in workability.

Claims (1)

[Claims] In a silver halide photographic material having a main photosensitivity in the range of 300 nm to 450 nm, at least one matting agent having a particle size of 3 to 10 μm is provided in the protective film layer of the photographic constituent layer on the side having the photosensitive silver halide. is contained, and the total amount of gelatin in the photographic constituent layer on the side having photosensitive silver halide is in the range of 2.0 to 3.5 g/m^2, and the silver halide photographic light-sensitive material is subjected to imagewise exposure, 1. A silver halide photographic light-sensitive material for bright room use, which has a γ value of substantially 6.0 or more, defined as a density of 0.3 to 3.0, when developed.