JP2700726B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide light-sensitive material exposed with a laser light source, and more particularly to a light-sensitive material suitable for at least two types of laser imagers having different wavelengths of laser light sources.

[0002]

2. Description of the Related Art In recent years, the types of laser light sources have been increasing, such as He-Ne (633 nm) and semiconductor lasers (780-780).
820 nm) and a new semiconductor laser (670-68 nm).
0 nm) is also being used. In response to this, the sensitivity and sensitivity of the light-sensitive materials were set in accordance with the respective light sources, so that the types and numbers of the light-sensitive materials had to be increased.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to reduce the number of light-sensitive materials corresponding to the increase in the number of laser imagers of various laser light sources. An object of the present invention is to provide a photosensitive material that can be used for laser imagers having different light sources.

[0004]

The above object of the present invention According to an aspect of the, H
Laser imager having e-Ne laser light source and
Semiconductor having an emission wavelength between 670 nm and 820 nm
For laser imagers with integrated laser light sources
Medical silver halide photographic materials , at least
And at least one panchromatic sensitizing dye having a spectral absorption peak at 600 nm or more and less than 700 nm, and 700 nm
Panchromatic sensitizing dye or red having a spectral absorption peak above
Spectral sensitized with at least one of the external sensitizing dyes
A silver halide emulsion layer , substantially silver bromide, on only one side of the support, having an antihalation layer underneath the emulsion layer or on the other side of the support; The combined transmission density of the He-Ne laser
Attained by a silver halide photographic light-sensitive material for medical use, wherein the emission wavelength of each of the laser light source and the semiconductor laser light source is 0.4 or more and 0.9 or less .

The light-sensitive material of the present invention preferably has a back layer on the side opposite to the light-sensitive emulsion layer. It is preferable to contain an antihalation dye therein. An antihalation layer may be provided between the emulsion layer and the base.

The type of the silver halide emulsion used in the present invention may be any type of silver halide emulsion such as a negative type and an internal latent image type autopositive using a nucleating agent. The photosensitive silver halide used in the present invention may be, for example, silver bromide, silver iodobromide, silver chloride, silver chlorobromide, silver chloroiodide, silver chloroiodobromide and the like. Silver iodobromide, silver chlorobromide and silver chloroiodobromide are preferred. Silver iodide in the silver halide is preferably 0 to 4 mol%,
2 mol% is particularly preferred. Silver chloride in silver halide is 8
It is preferably at most 0 mol%, more preferably at most 40 mol%.

These emulsions have an average particle size of about 0.2 (measured by, for example, a projected area method or a number average method).
And 0.6 μm of emulsion grains are preferred. An average particle size of 0.25 to 0.5μ is more preferable. The emulsion may be a mixture of coarse particles and fine particles. The particle shape is cubic, octahedral, tetrahedral, potato-like, spherical, plate-like, and the particle system is a plate-like shape with a particle size of 5 times or more (see RESEARCHDISCLOSURE Item No. 2253
4p. 20 to p. 58 (described in January, 1983)). Substantially non-light-sensitive emulsions (for example, fine-grained emulsions with internal fogging) may be mixed with these light-sensitive emulsions. Of course, they may be separately applied to different layers.

Further, even if the crystal structure of the silver halide grains is uniform up to the inside, the silver halide grains may have a layered structure in which the inside and the outside are different from each other, as well as British Patent 635,841 and US Pat. A so-called conversion type as described in Japanese Patent No. 622,318 may be used. At the time of forming the silver halide grains, in order to control the growth of the grains, as a silver halide solvent, for example, ammonia, rodankari, rodanammon, thioether compound (for example, US Pat. Nos. 3,271,157 and 3,574)
No. 628, No. 3,704, 130, No. 4, 29
7,439, 4,276,374 and the like) thione compounds (for example, JP-A-53-144319,
3-82408, 55-77737, etc.), amine compounds (for example, JP-A-54-100717)
Etc. can be used. In addition to the silver halide solvent, a compound that controls the crystal habit by adsorbing on the grain surface, for example, a cyanine-based dye, a tetrazaindene-based compound, a mercapto compound, or the like can be used during grain formation. The silver halide emulsion used in the present invention may be monodispersed or polydispersed, but is preferably monodispersed. Two or more kinds of monodispersed emulsions having different grain sizes may be mixed and used. The emulsion of the present invention may be either a negative type or an auto positive type (internal latent image type using a nucleating agent).

The silver halide emulsion of the light-sensitive material of the present invention may contain a metal ion such as iridium ion. For example, in order to contain iridium ions, it is common to add a water-soluble iridium compound (for example, hexachloroiridium (IV) salt) in the form of an aqueous solution when preparing a silver halide emulsion. It may be added in the form of the same aqueous solution as the halide for grain formation, or may be added before grain formation, added during grain formation, or added after grain formation to chemical sensitization, but is particularly preferred. Is addition at the time of particle formation.

The negative emulsion used in the present invention can be prepared by a conventional chemical sensitization method such as sulfur sensitization (US Pat. Nos. 1,574,944 and 2,278,947;
Nos. 3,021,215 and 3,635,717), reduction sensitization (US Pat. No. 2,518,698,
Research Disclosure
Vol. 176 (1978.12) 17643, paragraph 3, etc.), sensitization with thioether compounds (for example, U.S. Pat. Nos. 2,521,926 and 3,021,215)
No. 3,046,133 and 3,165,55
No. 2, No. 3,625,697, No. 3,635,7
No. 17, No. 4,198,240), or a combination of various sensitization methods. More specific chemical sensitizers include sulfur sensitizers such as sodium thiosulfate, allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine;
Reduction sensitizers such as tin chloride, phenylhydrazine and reductone can be exemplified.

Furthermore, the negative working emulsion used in the present invention can be prepared by gold sensitization (for example, US Pat. No. 2,540,085).
No. 2,399,083). Specific examples of the gold sensitizer include potassium chloroaurate, aurasthiosulfate, and potassium chloroparadate. These gold compounds may be added before or after the sulfur sensitizer. It can be added simultaneously with the sulfur sensitizer. The amount of the gold sensitizer used in the present invention is 10 mol / mol of silver halide.
^It is preferably used in a ratio of ^-7 to 10 ^-3 mol, and
It is particularly preferred to use it in a proportion of 0 ^-6 to 10 ^-4 mol.

In order to make both the He-Ne laser (633 nm) and the semiconductor laser (780 nm) suitable for sensitivity, it is preferable to use a panchromatic sensitizing dye and an infrared sensitizing dye in combination. In order to provide both He-Ne laser (633 nm) and semiconductor laser (678 nm) with appropriate sensitivity, 2
It is preferable to use various types of panchromatic sensitizing dyes. Examples of the spectral sensitizer used in the present invention include infrared, panchromatic, ortho, and regular. In the present invention
Sensitization with a spectral absorption peak above 700 nm
Dyes (what are called infrared spectral sensitizers)
For example, as described in JP-A-63-89838.
Tricarbocyanine dye and / or 4-quinoline
Nucleus-containing dicarbocyanine dyes, and specific examples
Is from (I-1) described in the lower column of page 7 of the patent publication.
The compound of (I-4) is mentioned. Further, for example,
JP-A-59-192242, page 6, lower right column to page 7
Conversion of (I-12) to (I-16) described in the upper left column
Compounds. Furthermore, in addition to the above,
JP-A-91032 also discloses specific compounds.
However, the infrared spectral sensitizer used in the present invention is not limited to these.
It is not something to be done. In addition, 600 nm or more and 700 nm or less
Spectral sensitizing dye having a full spectral absorption peak ( panchromatic component
Photosensitizing dyes) include, for example,
JP-A-3-4933, page 2, right column describes (I-
A) to (IC). Further analogy
For example, it is described on page 7 of JP-B-60-45414.
And the compounds of (1-6) to (I-10).
However, the panchromatic spectral sensitizer used in the present invention is not limited to these.
It is not specified. The above-mentioned spectral sensitizing dye used in the present invention is contained in a silver halide photographic emulsion at a ratio of 10 ^-7 to 10 ^-2 mol, preferably 10 ^-6 to 10 ^-3 mol, per mol of silver halide. The above-mentioned spectral sensitizing dye used in the present invention can be directly dispersed in an emulsion. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. The dye is usually added after chemical sensitization in many cases, but may be in the form of grains or before chemical sensitization. Ultrasound can also be used for dissolution.
U.S. Pat. Nos. 2,912,343, 3,342,605 and 2,996,287 for addition to emulsions,
No. 3,429,835 can also be used. The above-mentioned spectral sensitizing dyes may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but may be dispersed in any step of the preparation in the silver halide emulsion as described above. can do. Still further, other sensitizing dyes can be used in the present invention. For example, U.S. Patent Nos. 3,703,377 and 2,688,545,
No. 3,397,060, No. 3,615,635
No. 3,628,964 and British Patent No. 1,24.
No. 2,588, No. 1, 293, 962, Japanese Patent Publication No. 43
No.-4936, No.44-14030, No.43-107
No. 73, U.S. Pat. No. 3,416,927, JP-B-43
No. 4,930, U.S. Pat. Nos. 3,615,613, 3,615,632, 3,617,295, and 3,635,721. The above-mentioned infrared sensitizing dyes and these spectral sensitizing dyes can be used in combination.

In the present invention, together with the sensitizing dyes described above, the compounds described in JP-A-63-89838 can be used for the purpose of further enhancing the supersensitizing effect. Further, the sensitizing dye described in JP-A-63-89838 is used.
The storage stability improver described in the above item can be used in an amount of about 0.01 to 5 g per mol of silver halide in the emulsion. The supersensitizer or storage improver used in the present invention may be directly dispersed in the emulsion,
Further, it may be dissolved in an appropriate solvent (for example, water, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone or the like) or a mixed solvent using a plurality of these solvents, and added to the emulsion. The sensitizing dye can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding the sensitizing dye. The supersensitizer and the preservability improver may be added to the emulsion prior to the addition of the spectral sensitizing dye described above, or may be added later. These may be dissolved separately from the spectral sensitizing dyes and may be separately and simultaneously added to the emulsion, or may be mixed and then added to the emulsion.

The photographic light-sensitive material of the present invention comprises
Various compounds can be added in order to prevent a decrease in sensitivity or fogging during storage or processing. These compounds include nitrobenzene imidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene, 1-phenyl-
Very many compounds such as 5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts have been known for a long time. One example of a compound that can be used is C.I. E. FIG. K. “The Thoery” by Mees
of the Photographic Process "(Third Edition, 1966
Years), pages 344 to 349, with the original documents listed.
For example, US Patent Nos. 2,131,038 and 2,6
Thiazolium salts described in U.S. Pat. Nos. 2,886,437 and 2,444,60.
No. 5, azaindenes described in US Pat. No. 3,287,135, etc .; sulfocatechols described in US Pat. No. 3,236,652, etc .; UK Patent No. 623,448
Oximes described in US Pat.
No. 03,927, No. 3,266,897, No. 3,
Nos. 397,987, mercaptotetrazoles, nitrones and nitroindazoles; US Pat. No. 2,839,405; polyvalent metals salts; US Pat.
No. 0,839, and the like.
iuronium salts); U.S. Pat. No. 2,566,263;
Palladium, platinum and gold salts described in JP-A-2,597,915 and the like.

The silver halide crystal plane of the emulsion used in the present invention may be either the (100) plane or the (111) plane, but the (100) / (111) plane ratio is preferably 1 or more. Monodispersed silver halide emulsion grains having a (100) plane / (111) plane ratio of 1 or more can be prepared by various methods. The most common method is to reduce the pAg value during particle formation to 8.1.
This is a method in which a silver nitrate aqueous solution and an alkali halide aqueous solution are simultaneously added at a constant value of 0 or less at a rate higher than the dissolution rate of the particles and at a rate at which renucleation is not large (so-called control double jet method). More preferably p
Ag value is 7.80 or less, more preferably pAg value is 7.80.
It is better to be 60 or less. When the formation of silver halide grains is divided into two processes, nucleation and growth, the pAg value during growth is particularly 8.10 or less, more preferably 7.8.
0 or less, more preferably 7.60 or less.
As a method of reacting the soluble silver salt and the soluble halide, a one-sided mixing method may be used, but a simultaneous mixing method is preferable in order to obtain good monodispersibility.

The silver halide emulsion used in the present invention is:
(100) face / (111) face ratio is 1 or more, preferably 2
And more preferably 4 or more silver halide grains in 50
It is preferably contained in an amount of not less than 60 wt%, more preferably not less than 60 wt%, and particularly preferably not less than 80 wt%. Incorporation of iridium ions is achieved by adding an aqueous iridium compound (for example, hexachloroiridium (III) or hexachloroiridium (IV)) in the form of an aqueous solution during the preparation of the silver halide emulsion. It may be added by being contained in the same aqueous solution as the halide for grain formation, or may be added before grain formation, added during grain formation, or added after grain formation to washing with water,
Preference is given to addition during grain formation. Particularly preferred is embedding inside the particles. In the present invention, it is necessary to use iridium ions in an amount of 10 ^-7 to 10 ^-3 mol per mol of silver halide for the preparation of the emulsion, but preferably 5 × 10 ^{-7 to} 5 × 10 ⁴ mol.

The silver halide emulsion of the present invention can contain various other commonly used photographic additives. As a stabilizer, for example, triazoles, azaindenes, quaternary benzothiazolium compounds, mercapto compounds, or water-soluble inorganic salts such as cadmium, cobalt, nickel, manganese, gold, thallium, and zinc may be contained. Further, as a hardening agent, for example, aldehydes such as formalin, glyoxal, and mucochloric acid, S-triazines, epoxies, aziridines, vinylsulfonic acid, etc. Alternatively, oleyl monoether, amylated alkyl taurine, fluorine-containing compounds, and the like may be contained. Further, a color coupler can be contained. In addition, if necessary, a whitening agent, an ultraviolet absorber, a preservative, a matting agent, an antistatic agent, and the like can be added.

A dye, a so-called filter dye, can be incorporated in the silver halide emulsion of the present invention.
The dye used in the present invention has a main absorption in the visible wavelength region of the inherent photosensitive wavelength region of the silver halide emulsion used. Above all, λmax is 450 nm to 600
Dyes in the nm range are preferred. There is no particular restriction on the chemical structure of the dye, and oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes, azo dyes, etc. can be used, but water-soluble dyes are useful in terms of eliminating residual color after treatment. It is. Specifically, for example,
Pyrazolone dyes described in U.S. Pat.
Pyrazolone oxonol dyes described in 274,782, diarylazo dyes described in U.S. Pat. No. 2,956,879, and styryls described in U.S. Pat. Nos. 3,423,207 and 3,384,487. Dyes and butadienyl dyes; merocyanine dyes described in U.S. Pat. No. 2,527,583; and U.S. Pat. Nos. 3,486,897, 3,652,284, and 3,718,472. Merocyanine dyes and oxonol dyes, enaminohemioxonol dyes described in U.S. Pat. No. 3,976,661 and British Patent Nos. 584,609 and 1,1.
Nos. 77 and 429, and JP-A-48-85130 and 49
-99620, 49-144420, U.S. Pat. Nos. 2,533,472, 3,148,187, 3,177,078, 3,247,127,
No. 3,540,887 and No. 3,575,704
No. 3,653,905.

In the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention, a coating aid, an antistatic agent, an improvement in slipperiness,
Various surfactants may be included for various purposes such as emulsification / dispersion, prevention of adhesion and improvement of photographic properties (for example, acceleration of development, contrast enhancement, sensitization). For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol) Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Agent: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group or a phosphate group, such as acid esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or phosphoric acid Amphoteric surfactants such as esters, alkylbetaines and amine oxides; alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocycles such as pyridinium and imidazolium,
Cationic surfactants such as quaternary ammonium salts and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. The polyalkylene oxide compound used in the present invention is an alkylene oxide having 2 to 4 carbon atoms,
For example, polyalkylene oxide such as ethylene oxide, propylene-1,2-oxide and butylene-1,2-oxide, which is preferably composed of at least 10 units of ethylene oxide, and water, aliphatic alcohol, aromatic alcohol, fatty acid, organic It includes a condensate with a compound having at least one active hydrogen atom such as an amine or a hexitol derivative or a block copolymer of two or more polyalkylene oxides. When these polyalkylene oxide compounds are added to the silver halide emulsion, they are dissolved in an aqueous solution of an appropriate concentration or in a low-boiling organic solvent miscible with water, at an appropriate time before coating, preferably It can be added to the emulsion after chemical ripening. In addition to the emulsion, it may be added to a non-photosensitive hydrophilic colloid layer, for example, an intermediate layer, a protective layer, a filter layer and the like.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability and the like. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate,
(Meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile and the like can be used alone or in combination.

The emulsion used in the present invention mainly uses gelatin as a protective colloid, and it is particularly advantageous to use inert gelatin. Instead of gelatin, a photographically inert gelatin derivative (for example, phthalated gelatin) or a water-soluble synthetic polymer such as potavinyl acrylate, polyvinyl alcohol, polyvinylpyrrolidone, dextran, or polyacrylamide is used. Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as the plasticizer. As the support of the present invention, for example, a film base such as cellulose acetate, cellulose acetate butyrate, polyester [for example, poly (ethylene terephthalate)] or the like is used.

The surface of the support is preferably subjected to a corona discharge treatment, a glow discharge treatment, or an ultraviolet irradiation treatment in order to improve the adhesion to the hydrophilic colloid layer. Alternatively, styrene butadiene latex,
An undercoat layer made of vinylidene chloride-based latex or the like may be provided, and a gelatin layer may be further provided thereon. Further, an undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion to the hydrophilic colloid layer can be further improved.

The silver halide emulsion of the present invention contains a developing agent such as hydroquinone; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones and phenylenediamines; A combination of developing agents can be included. The developing agent is a silver halide emulsion layer and / or another photographic layer (for example, a protective layer, an intermediate layer, a filter layer,
Antihalation layer, back layer, etc.). The developing agent is dissolved in a suitable solvent, or as disclosed in US Pat. No. 2,592,368 and French Patent 1,50.
It can be added in the form of a dispersion as described in US Pat.

In the present invention, matting agents such as those described in US Pat. Nos. 2,992,101, 2,701,245, 4,142,894, and 4,396,706 are used. Homopolymer of methyl methacrylate or polymer of metal methacrylate and methacrylic acid, organic compounds such as starch, silica, titanium dioxide, sulfuric acid,
Fine particles of an inorganic compound such as strontium and barium can be used. 1.0 to 10μ as particle size
m, particularly preferably 2 to 5 μm. U.S. Pat.
No. 76, 4,047,958 and colloidal silica described in JP-B-56-23139, as well as paraffin wax, higher fatty acid esters, and starch powder derivatives.

For the photographic processing of the light-sensitive material prepared by applying the present invention, any known method can be used. Known treatment liquids can be used. The processing temperature is usually chosen between 18 ° C and 50 ° C. Depending on the purpose, any of a developing process for forming a silver image (black-and-white photographic process) and a color photographic process including a developing process for forming a dye image can be applied. For details, see Research Disclosure, Vol. 176, No. 17643, pp. 28-29, ibid.
Development processing can be performed by the method described in the left column and the right column of page 871, vol. 87, No. 18716. In the ultra-rapid processing of the present invention, it is preferable to include an organic substance which flows out in the developing step in the emulsion layer and / or the other hydrophilic colloid layer. When the substance to be discharged is gelatin, a gelatin species which is not involved in the cross-linking reaction of gelatin by a hardener is preferable. For example, acetylated gelatin and phthalated gelatin correspond to these, and those having a small molecular weight are preferable. On the other hand, as a polymer substance other than gelatin, polyacrylamide as described in U.S. Pat. No. 3,271,158, or alternatively, polyvinyl alcohol, a hydrophilic polymer such as polyvinylpyrrolidone can be effectively used, Sugars such as dextran, soccer rose, and pullulan are also effective.
Among them, polyacrylamide and dextran are preferable,
Polyacrylamide is a particularly preferred substance. The average molecular weight of these substances is preferably 60,000 or less, more preferably 40,000 or less.

The light-sensitive material of the present invention is applied to a He-Ne laser
(633 nm) and semiconductor laser (780 nm)
In order to be suitable for
Good selection of sensitizing dye to impart photosensitivity
633nm and 780n to give images with great sharpness
m to prevent halation caused by the laser beam
It is necessary to provide. As a means for this,
Providing an appropriate antihalation layer on the optical material
Can be prevented. That is, the antihale
The absorption layer has sufficient absorption at 633 nm and 780 nm.
Prevents halation by absorbing stray light
Can be An that gives an image with good sharpness
633 nm and 780 nm laser light of the tihalation layer
Transmission density for lines should be 0.4 or higher
is required. Here, the transmission density is, for example, a spectrophotometer (component
(Specifically, a spectrophotometer U-3210 manufactured by Hitachi, which will be described later.)
Is measured. Anti-halation layer provided on photosensitive material
The position may be between the emulsion layer and the support.
May be provided opposite to the emulsion layer. Similarly, He
-Ne laser (633 nm) and semiconductor laser (678n)
m) to have suitability for both.
633 nm and 678 in the antihalation layer of the photosensitive material
Give a transmission density of 0.4 or more to a laser beam of nm
It is necessary to From a semiconductor laser (780 nm)
Absorb infrared rays like to prevent halation
For the antihalation layer, infrared (780 nm)
Includes an infrared absorbing dye that absorbs light. Similarly, He
-Ne laser (633 nm) or semiconductor laser (678 n
m) to absorb light rays such as from
In order to achieve this, the antihalation layer needs to be
(78 nm) containing an absorbing dye that absorbs light.
This is a tihalation layer. As an infrared absorbing dye,
62-123454 and JP-A-62-181381.
The dyes described are good. Also, as a dye that absorbs visible light
Preferred are those described in JP-A-61-174540.
Exposure light source (He ) for the dye-containing layer (antihalation layer)
-Ne laser or semiconductor laser) has a transmission density of 0.4 to 1.5, preferably 0.45 to 1.2. The method of adding the dye includes aqueous solution addition, micelle dispersion addition, solid dispersion addition, and the like, depending on its properties.

Specific examples of the antihalation dye of the light-sensitive material exposed with a light source of 360 nm to 700 nm include:
The following compound examples can be given.

[0028]

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As the antihalation dye and / or antiirradiation dye used in the present invention when the exposure light source is in the infrared region, a dye having substantial absorption at a long wavelength of 750 nm or more is used. Here, the antihalation dye is used for an intermediate layer, an undercoat layer, an antihalation layer, a back layer, an emulsion layer and the like, and the anti-irradiation dye is used for an intermediate layer and the like in addition to the emulsion layer. These dyes are preferably used in an amount of 10 ^{-3 to 1} g / m ² , more preferably 10 ^{-3 to} 0.5 g / m ² . For example, U.S. Patent Nos. 2,895,955 and 3,177,
Nos. 078 and 4,581,325, JP-A-50-10
0,116, JP-A-62-123454, JP-A-62-123454
Dyes described in JP-A-181381, JP-A-63-23
No. 148 and JP-A-63-89838 are preferably used. These dyes may be used alone or in combination of two or more. Also,
Instead of the above dyes, or these dyes and other dyes may be used in combination. Alternatively, or as a dye to be used in combination, for example, US Pat. No. 2,274,78
No. 2, pyrazolone oxonol dyes described in US Pat. No. 2,956,879, diarylazo dyes described in US Pat. Nos. 3,423,207 and 3,384,48.
No. 7, styryl dyes and butanedienyl dyes, U.S. Pat. No. 2,527,583, merocyanine dyes, U.S. Pat. Nos. 3,486,897 and 3,65.
Nos. 2,284 and 3,718,472, merocyanine dyes and oxonol dyes described in U.S. Pat.
No. 6,661, enaminohemioxonol dyes and the like. Also, JP-A-61-17454.
The present invention will be further described with reference to the following examples in which the dyes described in No. 0 can be mentioned.

[0030]

【Example】

Example 1 Preparation of silver halide emulsion (A). 40 g of gelatin was dissolved in 1 liter of water, and 3 g of potassium bromide and compound [I] were placed in a container heated to 55 ° C.

[0031]

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After adding 60 mg of an aqueous solution containing 200 g of silver nitrate while maintaining the pAg value in the reaction vessel at 7.0.
000 ml and 1080 ml of an aqueous solution of 140 g of potassium bromide containing potassium hexachloroiridate (III) at a molar ratio of 10 ^-7 were added by the double jet method to obtain a cubic monodisperse bromide having an average particle size of 0.35 μm. Silver particles were prepared. After desalting this emulsion, gelatin 71 g
And adjusted to pH 6.0, pAg 8.5, 3 mg of sodium thiosulfate, 4 mg of chloroauric acid and 4-hydroxy-6-
0.2 g of methyl-1,3,3a, 7-tetrazaindene
To give emulsion (A) chemically sensitized at 60 ° C.

2. Preparation of Emulsion Coating Solution A container in which 850 g of Emulsion A was weighed was heated to 40 ° C., and additives were added by the following method to prepare an emulsion coating solution.

(Emulsion coating liquid formulation A) Emulsion (A) 850 g b. Spectral sensitizing dye [II] 1.2 × 10 ^-4 mol c. Supersensitizer [XVI] 0.8 × 10 ^-3 mol d. Preservability improver [VI] 1 × 10 ^-3 morpho. 7.5 g of polyacrylamide (molecular weight: 40,000) Trimethylolpropane 1.6 g g. 2.4 g of sodium polystyrene sulfonate 16 g of poly (ethyl acrylate / methacrylic acid) latex 16 g N, N'-ethylenebis- (vinylsulfoneacetamide) 1.2 g

(Emulsion coating liquid formulation B) Emulsion (A) 850 g b. Spectral sensitizing dye [III] 1.1 × 10 ⁻³ mol c. Supersensitizer [XVI] 0.8 × 10 ^-3 mol d. Preservability improver [VI] 1 × 10 ^-3 morpho. 7.5 g of polyacrylamide (molecular weight: 40,000) Trimethylolpropane 1.6 g g. 2.4 g of sodium polystyrene sulfonate h. Poly (ethyl acrylate / methacrylic acid) latex 16 g N, N'-ethylenebis- (vinylsulfoneacetamide) 1.2 g

[0036]

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(Emulsion coating liquid formulation C) Emulsion (A) 850 g b. Spectral sensitizing dye [II] 1.2 × 10 ^-4 mol c. Spectral sensitizing dye [III] 1.1 × 10 ⁻³ mol d. Supersensitizer [XVI] 0.8 × 10 ^-3 morpho. Preservability improver [VI] 1 × 10 ⁻³ mol f. 7.5 g of polyacrylamide (molecular weight: 40,000) g. Trimethylolpropane 1.6 g h. 2.4 g of sodium polystyrene sulfonate Poly (ethyl acrylate / methacrylic acid) latex 16 g N, N'-ethylenebis- (vinylsulfoneacetamide) 1.2 g

3. Preparation of Coating Solution for Surface Protective Layer of Emulsion Layer A container was heated to 40 ° C., and additives were added according to the following formulation to prepare a coating solution.

(Formulation of Coating Solution for Surface Protective Layer of Emulsion Layer) Gelatin 100g b. Polyacrylamide (molecular weight: 40,000) 10 g c. Sodium polystyrene sulfonate (molecular weight: 600,000) 0.6 g d. N, N'-ethylenebis- (vinylsulfoneacetamide) Adjust e. 2.2 g of polymethyl methacrylate fine particles (average particle size: 2.0 μm) Sodium t-octylphenoxyethoxyethanesulfonate 1.2 g g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 2.7g Ji. Sodium polyacrylate 4g C ₈ F ₁₇ SO ₃ K 70mg j. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70mg Le. NaOH (1N) 4 ml III. 60 ml of methanol

4. Preparation of Back Layer Coating Solution The container was heated to 40 ° C., and additives were added according to the following formulation to obtain a back layer coating solution. (Formulation of back layer coating solution (i)) a. Gelatin 80g b. Dye [VIII] 1.0 g c. Polystyrene sodium sulfonate 0.6 g d. Poly (ethyl acrylate / methacrylic acid) latex 15 g e. N, N'-ethylenebis- (vinylsulfoneacetamide) 4.3 g

[0041]

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(Back layer coating solution formulation (ii)) 1.0 g of dye [VIII] of back layer coating solution formulation (i)
Was changed to 1.7 g of dye [VII]. (Formulation of back layer coating solution (iii)) A solution obtained by adding 1.7 g of dye [VII] to back layer coating solution formulation (i). (Formulation of back layer coating solution (iV)) 1.0 g of dye [VIII] of back layer coating solution formulation (i)
Was changed to 0.7 g, and 1.7 g of dye [VII] was further added .

5. Preparation of Coating Solution for Back Surface Protective Layer The container was heated to 40 ° C., and additives were added according to the following formulation to obtain a coating solution.

(Formulation of Coating Solution for Back Surface Protective Layer) Gelatin 80 g c. Polystyrene sodium sulfonate 0.3 g d. N, N'-ethylenebis- (vinylsulfoneacetamide) 1.7 g e. Polymethyl methacrylate fine particles (average particle size: 4.0 μm) 4 g He-t-octylphenoxyethoxyethaneethanesulfonate 3.6 g g. NaOH (1N) 6 ml h. 2 g of sodium polyacrylate _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.6g j. C ₈ F ₁₇ SO ₃ K 50 mg _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 50mg Wo. 130 ml of methanol

6 Preparation of Coating Sample The above-mentioned back layer coating solution and polyethylene terephthalate blue colored support together with the back layer surface protection coating solution
(D ₆₃₃ = 0.2, D ₆₇₈ = 0.02, D ₇₈₀ =
0), the total amount of gelatin applied was 3.5 g / m ²
It applied so that it might become. Subsequently, the above-mentioned emulsion coating solution and surface protective layer coating solution were coated on the opposite side of the support by coating Ag.
2.5 g / m ² and the amount of gelatin applied to the surface protective layer is 1
A coating sample of g / m ² was made as follows. Hardener N,
N'-ethylenebis- (vinylsulfone acetamide)
The amount was adjusted to 2.3% of the total gelatin amount. The transmission density of the combination of the back layer and the base was measured without a reference using a spectrophotometer U-3210 manufactured by Hitachi, Ltd.

Sample a): Back layer of back layer coating solution formulation (i), emulsion layer of emulsion coating solution formulation A. The transmission density of the back layer and the base together is 633 nm.
0.20 and 0.5 at 780 nm. Sample b): Back layer of back layer coating solution formulation (ii), emulsion layer of emulsion coating solution formulation B. The transmission density of the combination of the back layer and the base was 0.88 at 633 nm and 0.0 at 780 nm. Sample c); back layer of back layer coating solution formulation (iii),
Emulsion layer of emulsion coating solution formulation C. The combined transmission densities of the back layer and the base were 0.88 at 633 nm and 0.5 at 780 nm. Sample d): Back layer of back layer coating solution formulation (iV), emulsion layer of emulsion coating solution formulation C. The combined transmission densities of the back layer and the base were 0.88 at 633 nm and 0.35 at 780 nm.

7. Sensitometry Method The coated samples a) to d) thus prepared were subjected to sensitometry by the following method to measure the sensitivity. Coated sample a)
To d) at a temperature of 25 ° C. and a humidity of 60%, left for 7 days after application, and at room temperature, FCR-70 manufactured by Fuji Photo Film Co., Ltd.
Exposure was performed using a 780 nm semiconductor laser exposure section of No. 00. Exposure conditions were the same as for CR-780 film. 633nmH of AC-1 manufactured by Fuji Photo Film Co., Ltd.
Exposure was performed using an e-Ne laser exposure unit. Exposure conditions were the same as those for CR-633A. The development processing was performed for 45 seconds using RD-7 and Fuji F with FPM-9000 manufactured by FUJIFILM Corporation.

The logarithm of the reciprocal of the exposure amount indicating D = 1.0 was taken as the sensitivity. In the case of 780 nm semiconductor laser exposure, the sensitivity of the coated sample a) was ± 0, and the other values were indicated by relative sensitivity. In the case of 633 nm He-Ne laser exposure, the sensitivity of the coated sample b) was ± 0, and the others were indicated by relative sensitivity.

The CTF showing sharpness was determined by exposing a pattern for CTF measurement with the above-mentioned two types of laser exposure parts, treating for 45 seconds, and measuring the density with a microdensitometer. 1 line /
CTF in mm was displayed.

Test Results The relative sensitivity of the FCR-7000 exposed area by 780 nm semiconductor laser exposure and the CTF and AC-1 exposed area of 63 were measured.
Relative sensitivity and CTF by 3nm He-Ne laser exposure
Are shown in Table 1.

[0051]

[Table 1]

Only the present invention has no substantial reduction in sensitivity and no reduction in CTF for the two laser imagers.

Embodiment 2 1. Preparation of silver halide emulsion (A) Same as emulsion (A) of Example-1.

2. Preparation of emulsion coating solution (Emulsion coating solution formulation B) Same as (Emulsion coating solution formulation B) in (Example-1).

(Emulsion coating liquid formulation D) Emulsion (A) 850 g b. Spectral sensitizing dye [IV] 1.2 × 10 ^-3 mol c. Spectral sensitizing dye [V] 1.3 × 10 ^-3 mol d. Preservability improver [VI] 1 × 10 ^-3 morpho. 7.5 g of polyacrylamide (molecular weight: 40,000) Trimethylolpropane 1.6 g g. 2.4 g of sodium polystyrene sulfonate h. Poly (ethyl acrylate / methacrylic acid) latex 16 g N, N'-ethylenebis- (vinylsulfoneacetamide) 1.2 g

[0056]

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Preparation of Coating Solution for Surface Protective Layer of Emulsion Layer A container was heated to 40 ° C., and additives were added according to the following formulation to prepare a coating solution.

(Formulation of Coating Solution for Surface Protective Layer of Emulsion Layer) Gelatin 100g b. Polyacrylamide (molecular weight: 40,000) 10 g c. Sodium polystyrene sulfonate (molecular weight: 600,000) 0.6 g d. N, N'-ethylenebis- (vinylsulfoneacetamide) 1.5 g e. 2.2 g of polymethyl methacrylate fine particles (average particle size: 2.0 μm) Sodium t-octylphenoxyethoxyethanesulfonate 1.2 g g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 2.7g Ji. Sodium polyacrylate 4g C ₈ F ₁₇ SO ₃ K 70mg j. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 70mg Le. NaOH (1N) 4 ml III. 60 ml of methanol. Dye [IX] 2g

[0059]

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Preparation of Back Layer Coating Solution The container was heated to 40 ° C., and additives were added according to the following formulation to obtain a back layer coating solution.

(Formulation of Coating Solution for Back Layer (ii)) Gelatin 80g b. Dye [VII] 1.7 g c. Polystyrene sodium sulfonate 0.6 g d. Poly (ethyl acrylate / methacrylic acid) latex 15 g e. N, N'-ethylenebis- (vinylsulfoneacetamide) 4.3 g

(Preparation of Coating Solution for Back Layer (V)) Dye [VII] in (Prescription of Coating Solution for Back Layer (ii)) was adjusted to 1.0 g.

Preparation of Coating Solution for Back Surface Protective Layer The container was heated to 40 ° C., and additives were added according to the following formulation to obtain a coating solution.

(Formulation of Coating Solution for Back Surface Protective Layer) Gelatin 80g b. Polystyrene sodium sulfonate 0.3 g c. N, N'-ethylenebis- (vinylsulfoneacetamide) 1.7 g d. 4 g of polymethyl methacrylate fine particles (average particle size: 4.0 μm) 3.6 g of sodium t-octylphenoxyethoxyethanesulfonate f. NaOH (1N) 6 ml g. Sodium polyacrylate 2g h. C ₁₆ H ₃₃ O- (CH ₂ CH ₂ O) ₁₀ -H 3.6 g C ₈ F ₁₇ SO ₃ K 50mg j. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 50mg

Preparation of Coating Sample The above-mentioned back layer coating solution was applied together with the back layer surface protection coating solution to the same polyethylene terephthalate blue coating as in Example 1.
3.5 g total gelatin coverage on one side of the colored support
/ M ² . Subsequently, on the opposite side of the support, the above-mentioned emulsion coating solution and surface protective layer coating solution were applied so that the coating amount of Ag was 2.5 g / m ² and the gelatin coating amount of the surface protective layer was 1 g / m ² . It applied so that it might become. Hardener N,
N'-ethylenebis- (vinylsulfone acetamide)
The amount was adjusted to 2.3% of the total gelatin amount.

Sample e); (Formulation of coating solution for back layer (i
i)) Back layer, (Emulsion coating liquid formulation B) Emulsion layer. The transmission density of the combination of the back layer and the base is 0.3 at 633 nm.
It was 0.45 at 88 and 678 nm. Sample f): a back layer of (back layer coating solution formulation (ii)) and an emulsion layer of (emulsion coating solution formulation D). The transmission density of the combined back layer and base is 0.88, 678 n at 633 nm.
m was 0.45. Sample g); back layer of (back layer coating solution formulation (V))
Emulsion layer of (Emulsion coating liquid formulation D). The combined transmission densities of the back layer and the base were 0.60 at 633 nm and 0.30 at 678 nm.

Sensitometry Method The coated samples e) to g) thus prepared were subjected to sensitometry by the following methods to measure the sensitivity and CTF. The coated samples e) to g) were kept at 25 ° C. and 60% temperature and humidity, left to stand for 7 days after the coating, and exposed using a 633 nm He-Ne laser exposure unit of AC-1 manufactured by Fuji Photo Film Co., Ltd. . Also, FCR-70 manufactured by Fuji Photo Film Co., Ltd.
The 780 nm semiconductor laser light emitting part of No. 00 was remodeled and manufactured by NEC Corporation, AlGaInP 5 mW, 678 nm.
Exposure was performed using a semiconductor laser emitting portion.
The development process is FPM-90 manufactured by Fuji Photo Film Co., Ltd.
00 to RD-7, dry to dry 4 using Fuji F
Treated for 5 seconds.

The logarithm of the reciprocal of the exposure amount indicating D = 1.0 was taken as the sensitivity. In the case of 633 nm He-Ne laser exposure, the sensitivity of the coated sample e) was set to ± 0 and the others were indicated by relative sensitivity. In the case of 678 nm semiconductor laser exposure, the sensitivity of the coated sample f) was set to ± 0 and the others were indicated by relative sensitivity.

The sharpness was determined by exposing the CTF to a pattern for CTF measurement with the above-described two types of laser exposure sections, treating the CTF for 45 seconds, and measuring the density with a microdensitometer. 1 line /
CTF in mm was displayed.

Test Results Relative sensitivity and CTF and AC-1 633 nm H by FCR-7000 modified 768 nm semiconductor laser exposure
Table 2 shows the sensitivity and CTF obtained by e-Ne laser exposure.

[0071]

[Table 2]

Only the light-sensitive material of the present invention shows no substantial reduction in sensitivity and no reduction in CTF in the two types of laser imagers.

 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-2545 (JP, A) JP-A-2-39042 (JP, A) JP-A-2-302752 (JP, A) JP-A-63- 115160 (JP, A) JP-A-50-62425 (JP, A) JP-A-63-56652 (JP, A) JP-A-2-297541 (JP, A) JP-A-1-191133 (JP, A)

Claims (1)

(57) [Claims] 1. A laser having a He-Ne laser light source
-Imager and emission between 670nm and 820nm
Laser image with semiconductor laser light source having wavelength
Oh medical silver halide photographic light-sensitive material of Ja for the corresponding
Thus, at least one panchromatic sensitizing dye having a spectral absorption peak at 600 nm or more and less than 700 nm
Panchromatic with species and spectral absorption peak above 700nm
A silver halide emulsion layer , substantially silver bromide, spectrally sensitized with at least one of a sensitizing dye or an infrared sensitizing dye on only one side of a support, or on the other side of the support having an antihalation layer, transmission density of the combined support and an antihalation layer, said
He-Ne laser light source and semiconductor laser light source
A silver halide photographic light-sensitive material for medical use , which has an emission wavelength of 0.4 or more and 0.9 or less .