JPS6319652A - Method for exposing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the image having a high image quality by constituting a silver halide emulsion layer from the silver halide emulsion layers of R', O' and P', by exposing the silver halide emulsion layers composed of R' and O' with the 2nd higher harmonics, and exposing the emulsion layers composed of P' with a semiconductor laser ray, respectively. CONSTITUTION:The plural layers of the silver halide emulsions are composed of the R' silver halide emulsion layer having the max. photosensitive wavelength of 400-500nm, the O' silver halide emulsion layer having the max. photosensitive wavelength of 600-750nm, and the P' silver halide emulsion layer having the max. photosensitive wavelength of 800-1,000nm. The R' silver halide emulsion layer is exposed with the 2nd. higher harmonics which is obtd. by using the semiconductor laser rays 1, 7, 13 and the SHG 3, 9 elements, and the R' silver halide emulsion layer is exposed with the semiconductor laser ray or said higher harmonics. The P' silver halide emulsion layer is exposed with the semiconductor laser ray. The semiconductor laser is exemplified by GaAs, GaAlAs and GaInAsP laser, etc. Thus, the image having a high sharpness and an excellent color reproducibility is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an exposure method for silver halide photographic materials,
More specifically, the present invention relates to a method of converting infrared light into visible light for exposure using a nonlinear optical element.

[Prior Art] As a means for obtaining a hard copy image from an image information signal, there is a method of writing onto a silver halide photosensitive material using various light sources. Among them, narrowband medium light sources (e.g. lasers,
Methods using semiconductor lasers, light emitting diodes) as light sources are becoming widely used because of their high energy concentration density, high speed writing, and high image quality.

However, the wavelengths of these light sources often do not match the photosensitive range of silver halide photosensitive materials, and various efforts have been made to solve this problem. The photosensitive areas of silver halide photosensitive materials are usually a blue-sensitive area, a green-sensitive area, and a red-sensitive area, but since there is no practical light source that corresponds to the blue-sensitive area, for example, silver halide A method has been proposed in which the light-sensitive areas of a photosensitive material are used as a green-sensitive area, a red-sensitive area, and an infrared-sensitive area.

However, silver halide photosensitive materials having green, red, and infrared light-sensitive regions have the disadvantage that there is no suitable safelight during their manufacture or use.

[Object of the present invention] Therefore, an object of the present invention is to provide an exposure method that allows easy writing on a silver halide photosensitive material from a narrow band medium light source.

Another object of the present invention is to provide a method for exposing a silver halide photosensitive material by which high-quality images can be obtained by the method of the present invention.

Still another object of the present invention is to provide a method for exposing silver halide photosensitive materials that is easy to manufacture and use.

[Structure of the Invention] The above object of the present invention is to expose a silver halide photographic material having a plurality of silver halide emulsion layers having three different maximum sensitivity wavelength ranges on a support using three different laser beams. In the method for exposing a silver halide photographic light-sensitive material, each of the plurality of silver halide emulsion layers has an
Silver halide emulsion layer having a photosensitive maximum wavelength range of ~500 nm (referred to as R' silver halide emulsion layer), 600 to 75
A silver halide emulsion layer having a maximum photosensitive wavelength range of 0 nm (
O′ silver halide emulsion layer) and 800 to 100
This is a silver halide emulsion layer (referred to as a P' silver halide emulsion layer) having a photosensitive maximum wavelength range of 0r+m, and the R' silver halide emulsion layer is a second emulsion layer obtained using a semiconductor laser, - and an SHG element. The O' silver halide emulsion layer is exposed to the second harmonic, and the O' silver halide emulsion layer is exposed to the semiconductor laser light or the semiconductor laser and the semiconductor laser.
This is achieved by an exposure method for a silver halide photographic light-sensitive material in which the P' silver halide emulsion layer is exposed to the second harmonic obtained using HGm radiation and is exposed to semiconductor laser light.

A nonlinear optical element is used as an element that converts the light source wavelength (λ0). Generally, when a substance is irradiated with light (electromagnetic waves), polarization P is induced in the substance by the electric field E of the incident light.
Vibrate. By photographing the polarization, electromagnetic waves are generated using the same principle as in the case of antennas. Polarization P and incident optical electric field E
Generally speaking, P=XE (1+ ai E+a 2 E2+
->-...Equation (1) (in the equation, X represents an arbitrary coefficient 6) In many cases, there is a nonlinear relationship as shown in 1/2λ0.1/3λ0 for light (wavelength λ0),...
Output light having a wavelength of 1/NλO can be obtained. The above harmonics are sequentially converted into second harmonic, third harmonic, etc.
・It is called the Nth harmonic, but the order of the harmonic that is strengthened by different materials is different. Among the nonlinear elements, for example, the SHG element (3econd)-1a is used as an element that strengthens the second harmonic.
rmonic Generator).

The SHG element is an element that halves the wavelength of laser light, and generates a second harmonic of 172 wavelengths with respect to the light incident on the element. A preferred method with high conversion efficiency is to heat a lithium niobate substrate in an acidic solution to replace lithium ions with acid hydrogen ions to create an optical waveguide, and make the refractive index of the optical waveguide higher than that of its surroundings. It is something.

Other useful materials include 3a2NaNbs○15, NH4H2PO4, ZnT
e, CdTe, GaSb, CdSe, [3
aTi○3, Ks Li 4 Nb 03, 8g3A
Examples include SS3, barium oxalate, 2-methyl-4-nitroaniline, and the like.

The SHG element used in the present invention is generally placed outside the laser oscillator, but in the present invention, it may be placed inside the laser oscillator, that is, between the laser oscillator and the mirror.

Temperature control means may be used to stabilize the characteristics of the SHG element used in the present invention. In other words, temperature detection means such as a thermistor resistor, heat generation means (or cooling means using the Beltier effect) such as a resistor, and electric signals received from the temperature detection means are used to control the heat generation means (or cooling means) according to the value of the electric signal. ) The SHG element can be maintained within a constant temperature range by the temperature control means consisting of a temperature control circuit that controls the power supplied to the SHG element.

5) For writing on silver halide color photosensitive materials
(The semiconductor laser light source used in combination with the G element is basically twice the maximum sensitivity wavelength of the photosensitive material.

Examples of semiconductor lasers used in the present invention include:
GaAs, GaAlAs, GaInAsPl Qa
(ASX PI-X), CdTe,
I n P, I nXGa1-KAS, I n
Examples include PX ASI-X.

In the present invention, SHG is added to the blue-sensitive part of the silver halide photosensitive material.
A combination of an element and the semiconductor laser light source is used, a combination of an SHG element and a semiconductor laser, or only a semiconductor laser is used for the red sensitive part, and a semiconductor laser is used for the infrared sensitive part.

Note that in the present invention, the blue light source and the infrared light source can be used together. That is, with one semiconductor laser,
This is a method of using the semiconductor laser as two light sources: infrared light emitted by itself and second harmonics obtained by combining the semiconductor laser with an SHG element. Specifically, for example, the resonant wavelength 8
In the optical path of the semiconductor laser of 00 to 900 nm, SHG
By making the elements automatically attachable and detachable,
As a blue light source of 400 to 450 na+ when put on, and 8 when taken off
It can be used as an infrared light source of 00 to 900 nl.

The light generated by the SHG element and the semiconductor laser light source contains optical harmonics and other impurity light, such as the original incident laser light (λ0), so when writing on the silver halide photosensitive material, it is necessary to It is preferable to use a suitable optical filter. Examples of optical filters include interference filters used for photography, gelatin filters (eg, Eastman Kodak's Wratten filter), colored glass filters, and infrared filters.

In the exposure method of the present invention, various modulation means can be used. For example, in the case of a light source that combines a semiconductor laser and an SHG element, there are modulation by the semiconductor laser, modulation by the SHG element, and modulation by an added modulator, which can be used depending on the purpose.

Silver halide light-sensitive materials to which the exposure method of the present invention can be applied include light-sensitive materials for color negative films, light-sensitive materials for color reversal, direct positive color light-sensitive materials, light-sensitive materials for color photographic paper, heat-developable color light-sensitive materials, and light-sensitive materials for printing plate making. materials, medical photosensitive materials, and diffusion transfer type color photosensitive materials.

The silver halide emulsion used in the light-sensitive material of the present invention includes silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride, which are commonly used in silver halide emulsions. Any one can be used.

The silver halide grains used in the silver halide emulsion may be obtained by any of the acid method, neutral method, and ammonia method. The grains may be grown all at once or after forming seed grains. The method of creating and growing the zero-species particles that may be grown may be the same or different.

Silver halide emulsions can be prepared by mixing halide ions and silver ions at the same time, or by mixing one in a solution where the other is present. , halide ions and silver ions were mixed simultaneously while controlling the pH and pAg in the mixing pot.
It may also be produced by adding it to. By this method, silver halide grains having a regular crystal shape and a nearly uniform grain size can be obtained. After growth, the halogen composition of the particles may be changed using the funversion method.

In the process of grain formation and/or growth, silver halide grains are produced using cadmium salts, zinc salts, lead salts, kuriram salts, iridium salts (including complex salts), kuriram salts (including complex salts), and iron salts ( metal ions are added using at least one selected from the group consisting of complex salts), and metal ions are added inside the particles and/or
Alternatively, these metal elements can be contained on the particle surface, and reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface by placing the particle in an appropriate reducing atmosphere.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or they may be left contained.

The silver halide grains may have a uniform silver halide m composition distribution within the grain, or may be core/shell grains in which the halide am composition differs between the inside of the grain and the surface layer.

The silver halide grains may be grains in which latent images are mainly formed on the surface, or grains in which latent images are mainly formed inside the grains.

The silver halide grains may have a regular square crystal shape such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical or plate shape. In these particles, any ratio of the (1101 plane to the tril1 plane) can be used. Also, they may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The silver halide emulsion may have any grain size distribution, but in the present invention, it has been found that high quality images can be obtained by using a monodisperse emulsion in the silver halide photosensitive material.

In the present invention, the monodispersed emulsion is defined as ±
The ratio of the weight of silver halide grains within the 20% grain size range to the weight of all silver halide grains (the ratio of grains within the IA circle is 50% or more, preferably 70% or more).

Here, the average particle size r is the frequency ni of particles having particle size ri.
The particle size r when the product n1Xri' of and ri' is maximum
Defined as i (3 significant digits, minimum digits are 5 people to the nearest 4).

The grain size ri here means the diameter in the case of spherical silver halide grains, and in the case of grains having a shape other than spherical, the diameter when the projected image is converted into a circular image of the same area.

This particle size can be determined, for example, by observing the particles using an electron microscope.
Take a photo at magnification of 50,000 times to 50,000 times, and calculate the particle diameter on the print or the area of the projected image to 3 significant digits (
It can be obtained by actually measuring the 4th digit (4th to 5th person). (The number of particles to be measured is assumed to be 1,000 or more at random.)

Further, in the monodispersed emulsion of the present invention, the preferred particle size range is 0.1 μva-0.35/j m and 0.1 μva-0.35/j m.
It is 5μaI to 260μm. Further, a polydisperse emulsion and a powder emulsion may be mixed and used.

The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

In the present invention, the maximum sensitivity wavelength range is 400 for the blue-sensitive emulsion layer.
-500nm, red-sensitive emulsion layer should be 600-750nva, infrared-sensitive emulsion layer should be 800-1000r+m,
Preferably, the blue-sensitive emulsion layer has a thickness of 410-4 nm, the red-sensitive emulsion layer has a thickness of 630-69 nm, and the infrared-sensitive emulsion layer has a thickness of 810-9 nm.
It is 2Onm.

Silver halide emulsions can be optically sensitized to a desired wavelength range using dyes known in the photographic industry as sensitizing dyes. The sensitizing dye may be used alone or in combination of two or more, and together with the sensitizing dye, it may be a dye that itself does not have a spectral sensitizing effect, or a compound that does not substantially absorb visible light. In addition, a supersensitizer that enhances the sensitizing action of the sensitizing dye may be included in the emulsion.

Sensitizing dyes include cyanine dyes, merocyanine dyes,
Composite cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxal-7yl dyes are used.

Particularly useful dyes include cyanine dyes, merocyanine dyes,
and a complex merocyanine pigment.

In the present invention, an infrared sensitizing dye is used in the layer having a maximum sensitivity wavelength range of 800 to 1000 nm+.

Infrared sensitizing dyes used in the present invention include! II
No. 58-145936, No. 59-180553,
No. 59-191032, No. 59-192242, No. 60-196757, No. 61-65232, No. 61
Preferred are those shown in US Pat. No. 4,584,258 and US Pat. No. 4,584,258.

Silver halide emulsions are used during the manufacturing process of photosensitive materials, during storage,
Alternatively, for the purpose of preventing capri during photographic processing or maintaining stable photographic performance, photographic Compounds known in the art as anti-capri agents or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsions
As a material, gelatin is advantageously used, but synthetic hydrophilic materials such as gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single or copolymers, etc. Hydrophilic colloids such as polymeric substances can also be used.

The photographic emulsion layer of a light-sensitive material using a silver halide emulsion and other hydrophilic fluid layers can be formed by using one or more hardeners to bind binder (or protective colloid) molecules and increase film strength. Can be hardened. The hardening agent can be added in an amount sufficient to harden the light-sensitive material without adding or depleting the hardening agent to the processing solution, but it is also possible to add the hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility.

A dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer can be contained in the photographic emulsion layer or other water-based colloid layer of a light-sensitive material for the purpose of improving dimensional stability.

The emulsion layer of the light-sensitive material undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (e.g., p-7-nylene quamine derivative, 7-m/7-er/-el derivative, etc.) during color development processing. Pigment-forming couplers that form pigments are highly regarded. The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

It is desirable that the dihalogen dye-forming coupler has a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. Furthermore, even though these dye-forming couplers are 4-equivalent, in which 4 ions need to be reduced to form one molecule of dye, only 2 silver ions need to be reduced. Either is acceptable. The dye-forming coupler has a color correction effect, and by coupling with the oxidized form of the developing agent, it can be used as a development inhibitor, development accelerator, bleach accelerator, developer, silver halide solvent, and toning agent. Included are photographically useful fragment releasing compounds such as agents, hardeners, capri agents, anti-capri agents, chemical sensitizers, spectral sensitizers, and desensitizers. Among these, couplers that release a development inhibitor during development and improve image sharpness and image graininess are called DIR couplers. In place of the DIR coupler, a DIR compound which undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time releases a development inhibitor may be used.

The DIR couplers and DIR compounds used include those with an inhibitor directly attached to the coupling position and those with an inhibitor attached to the coupling position.
It is bonded to the coupling position via a valent group, and the inhibitor is bonded in such a way that the inhibitor is released by an intramolecular nucleophilic reaction within the group separated by the coupling reaction, an intramolecular electron transfer reaction, etc. (referred to as timing DIR couplers and timing DIR compounds). Also, inhibitor L@
One that is diffusible after removal and one that is not so diffusible can be used alone or in combination depending on the purpose. A colorless coupler (also called a competitive coupler) which undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer but does not form a dye can also be used in combination with a dye-forming coupler.

As the inilaw dye-forming coupler, known 7-syl acetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

As the magenta dye-forming coupler, known 5-pyrazolone couplers, pyrazolobenzimidazole couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, ingzolone couplers, and the like can be used.

As cyan dye-forming couplers, phenol or 7-tole couplers are generally used.

Dye-forming couplers, colored couplers, DIR couplers that do not need to be adsorbed on the silver halide crystal surface, I)I
Among R compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc., hydrophobic compounds can be processed using various methods such as solid dispersion method, latex dispersion method, oil-in-water type':fL dispersion method, etc. This method can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler. For the oil-in-water emulsion dispersion method, conventionally known methods for dispersing hydrophobic additives such as couplers can be applied.
High boiling point of approximately 150℃ or higher 8! If necessary, the solvent may have a low boiling point and/or water solubility. Dissolve using a solvent and use a surfactant in a hydrophilic binder such as an aqueous gelatin solution using a stirrer, homogenizer, colloid mill, etc.
- using dispersion means such as knot mixers, ultrasonic devices, etc.
After being emulsified and dispersed, it may be added to the desired hydrophilic colloid liquid. A step of removing the low boiling point organic solvent may be included simultaneously with the dispersion or dispersion.

Examples of high boiling point solvents include phenol t-forms, phthalate alkyl esters, phosphate esters, citric acid esters, benzoate esters, alkylamides, fatty acid esters, trimesic acid esters, etc., which do not react with the oxidized form of the developing agent, with a boiling point of 150. An organic solvent having a temperature of ℃ or higher is used.

Low boiling or water-soluble organic solvents can be used in conjunction with or in place of high boiling solvents. Examples of organic solvents with low boiling points that are substantially insoluble in water include ethyl acetate, propyl acetate,
Examples include butyl acetate, butanol, chloroform, carbon tetrachloride, nitromethane, nitroethane, benzene, etc. Water-soluble organic solvents include acetone, methyl isobutyl ketone, β-ethoxyethyl acetate, methoxyglycol acetate, methanol, ethanol, Examples include acetonitrile, dioxane, dimethylformamide, trimethylsulfoxide, hexamethylphosphonylamide, noethylene glycol monophenyl ether, phenoxyethanol, and the like.

When dye-forming couplers, DIR couplers, colored couplers, DIR compounds, image stabilizers, color antifoggants, ultraviolet absorbers, optical brighteners, etc. have acid groups such as carboxylic acid or sulfonic acid, they may be treated with an alkaline aqueous solution. It is also possible to introduce one part of the hydrophilic colloid.

Anionic surfactants, /
Ionic surfactants, cationic surfactants and amphoteric surfactants can be used.

The oxidized form of the developing agent or the electron transfer agent may migrate between the emulsion layers of the light-sensitive material (between the same color-sensitive layer or between different color-sensitive layers), causing color turbidity or deterioration of sharpness. In addition, a color antifoggant can be used to prevent graininess from becoming noticeable.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

An image stabilizer can be used in the photosensitive material to prevent deterioration of the dye image.

The protective layer of the photosensitive material and the hydrophilic colloid layer such as the intermediate π layer may contain an ultraviolet absorber to prevent fogging due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to ultraviolet rays. good.

In order to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of the light-sensitive material, a formalin scavenger can be used in the light-sensitive material.

When containing dyes, ultraviolet absorbers, etc. in the hydrophilic colloid layer of a photosensitive material, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or the hydrophilic colloid layer of the photosensitive material.

The emulsion layer of photographic light-sensitive materials is made of polyalkylene oxide or its derivatives such as ethers, esters, and amines, 1,000-onythyl compounds, thiomol-7-olins, quaternary ammonium compounds, and urethane derivatives for the purpose of increasing sensitivity, increasing contrast, or accelerating development. A fluorescent whitening agent can be used in a 1° photosensitive material containing urea derivatives, imiguzol derivatives, etc., for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background less noticeable.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out of the light-sensitive material or bleached during the development process.

Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, azo dyes, and the like. A matting agent can be added to the silver halide emulsion layer and V/or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together.

A lubricant can be added to the photosensitive material to reduce sliding friction.

An antistatic agent can be added to the photosensitive material for the purpose of preventing static electricity. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and may be used in the protective colloid layer other than the emulsion layer of the image where the emulsion layer is laminated on the emulsion layer and/or the support. May be used for.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material may be coated with coating properties, antistatic properties, slipperiness properties, emulsification dispersion,
Various surfactants can be used for the purpose of preventing adhesion and improving photographic properties (development acceleration, hardness, film formation, sensitization, etc.).

The support used in the photosensitive material of the present invention includes paper laminated with α-thin polymer (e.g., polyethylene, polypropylene, ethylene/butene copolymer), etc.
Reflective layers can be applied to flexible reflective supports such as synthetic paper, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and films of Nirira. Provided visibility support, glass, metal,
Includes pottery, etc.

After subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc. as necessary, the photosensitive material can be subjected to M-contact or support surface adhesion, antistatic property, dimensional stability, -=, - property, and abrasion resistance. It may be coated through one or more subbing layers to improve properties such as hardness, hardness, antihalation, frictional properties, and/or other properties.

When coating the photosensitive material, a thickener may be used to improve coating properties. Also, for things like hardeners, which are so reactive that if added to the coating solution in advance, they will cause delta before coating, it is best to mix them using a static mixer or the like just before coating. preferable.

As coating methods, extrusion coating and curtain coating, which allow two or more types of layers to be applied simultaneously, are particularly useful, but packet coating may also be used depending on the purpose. Further, the coating speed can be arbitrarily selected.

To obtain a dye image using the light-sensitive material of the present invention, color photographic processing is performed after exposure. Color processing includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process, but instead of the process using a bleach solution and the process using a fixer. In addition, a bleach-fixing process can be carried out using a one-bath bleach-fixing solution, or a monobath processing process using a one-bath developing, bleach-fixing solution that allows color development, bleaching, and fixing to be performed in one bath. You can also do

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, a color developing agent or its precursor is contained in the material and the development process is performed using an activator solution.

A 7-activator treatment can be applied to the monobath treatment. During these processes,
Typical treatments are shown below: (These treatments include a washing process, a washing process, or a stabilization process as the final process.) Color development process - Bleaching process Constant fixation process - Color development process - Bleach-fixing process - Pre-hardening process - Color development process - Stop-fixing process - Water washing process - Bleaching process - Constant fixation process - Water washing process - Post-hardening process - Color development Development process - Water washing process - Supplementary color development process - Stop process - Bleach process Constant fixation process/Activator process - Bleach-fix process/Activator process - Bleach process Constant fixation process/Monobath Processing Steps Processing temperatures are usually selected in the range of 10°C to 65°C, but temperatures above 65°C may also be used. Preferably 25
Processed between °C and 45 °C.

A color developing solution generally consists of an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes amide 77 ether derivatives and l1l-phenylenone amine derivatives. These color developing agents can be used as salts of organic and inorganic acids;
For example, salt salts, sulfates, p-)luenesulfonates, sulfites, chefate salts, benzenesulfonates, etc. can be used.

These compounds are generally about 0 per color developer 11.
．． Concentration of 1 to 30 Fl, more preferably color developer 1
Used at a concentration of about 1 to 15 g per 1 g.

Examples of the above-mentioned amyl/7-el type developer include 0-7
Mi/phenol, p-7 Mi/phenol, 5-amino-
These include 2-year-old pheasant-toluene, 2-ami7-3-oxy-toluene, 2-oxy-3-ami/-1,4-tumethyl-benzene, and the like.

Particularly useful primary aromatic amine color developers include N, N-
A noalxy p-phenylene diamine compound,
Alkyl and phenyl groups may be substituted or unsubstituted. Among them, N is an example of a particularly useful compound.

N-dimethyl-p-7 enylennoamine hydrochloride, N-methyl-p-7 enylennoamine hydrochloride, N,N-trimethyl-p-7 enylennoamine hydrochloride, 2-ami/5
(N-ethyl-N-dodecylamino)-)lunin, N-ethyl-N-β-methanesulfuramide nityl-3-methyl-4-aminoaniline sulfate, N-ethyl-
N-β-hydroxyethylaminoaniline, 4-ami/
-3-methyl-N, N-noethylaniline, 4-ami/
-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate and the like can be mentioned.

Further, the above color developing agents may be used alone or in combination of two or more. Furthermore, the above color developing agents may be incorporated into color photographic materials.

In this case, it is also possible to treat the silver halide color photographic light-sensitive material with an alkaline solution (activator solution) instead of a color developing solution, and the bleach-fixing process is carried out immediately after the alkaline solution treatment.

The color developing solution may contain alkaline agents commonly used in developing solutions, such as sodium hydroxide-1 potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate, or borax. Various additives, such as benzyl alcohol,
It may contain an alkali metal halide such as potassium bromide or potassium chloride, a development regulator such as citradinic acid, and a preservative such as hydroxylamine or sulfite. Furthermore, various antifoaming agents and surfactants, and silica such as methanol, trimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

The pH of the color developer is usually 7 or higher, preferably about 9.
~13.

In addition, the color developing solution used in the present invention may contain antioxidants as necessary, including diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, hydroxamic acid, Pentose or hexose, pyrogallol-1
, 3-methyl ether, etc. may be contained.

In the color developing solution, various chelating agents can be used in combination as metal ion sequestering agents. In the case of sidelight, the chelating agent may be amine polycarboxylic acids such as ethylenediaminetetraacetic acid or noethylenetriaminopentaacetic acid, saturated phosphonic acids such as 1-hydroxyethylidene-1,1'-diphosphonic acid, or amide/tri(methylene phosphonic acid). acids) or amine/polyphosphonic acids such as ethylenediaminetetraphosphoric acid; oxycarboxylic acids such as citric acid or gluconic acid; Examples include polyphosphoric acid and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed separately.

Metal complex salts of organic acids are used as bleaching agents, such as evapolycarboxylic acid, aminopolycarboxylic acid, or R acids such as oxalic acid and citric acid, coordinated with metal ions such as iron, cobalt, and copper. used. Among the above t91 acids, the most preferred W1 acids include carboxylic acid and aminopolycarboxylic acid. Specific examples of these include ethylenenoaminetitraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxydiethyl)-N,N',N')acetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, Examples include iminodiacetic acid, dihydroxynitylglycine citric acid (or tartaric acid), ethyl ethercyamine tetraacetic acid, glycol ethernoamine thitraacetic acid, ethylenediaminetetrapropionic acid, phenylenenoamine thitraacetic acid, and the like. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

These i-whitening agents are preferably used in an amount of 5 to 450 g/l, more preferably 20 to 250 g/l.

In addition to the above bleaching agent, the bleaching solution may contain a sulfite as a preservative, if necessary. Alternatively, it may be a white liquor containing an ethylenediaminetetraacetate iron (1) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. In addition, hydrochloric acid,
Hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, and the like can also be used.

Various bleach accelerators can be added to the bleach solution.

The pH of the bleaching solution used is 2.0 or higher, but generally it is 4.
．． Used from 0 to 9.5, ? It is preferably used in a range of 4.5 to 8.0, most preferably in a range of 5.0 to 7.0.

A fixer having a commonly used composition can be used. As fixing agents, compounds that react with silver halide to form water-soluble complex salts, such as those used in ordinary fixing processes, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium periosulfate, and thiocyanic acid are used. Typical examples include potassium, thiocyanate salts such as sodium thiocyanate and ammonium thiocyanate, thiourea, and thionithyl. These fixing agents are used in an amount of 5Fi71 or more, within the range that can be dissolved, but are generally used in an amount of 70 to 250 g/1. Incidentally, a part of the fixing agent can be contained in the bleaching tank, or conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and/or fixing solution may contain various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. These agents may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, hydrazine, and bisulfite adducts of aldehyde compounds, chelating agents such as aminopolycarboxylic acids, stabilizers such as nitro alcohol and nitrates, and hardening agents such as water-soluble aluminum salts. ,methanol,
Organic solvents such as dimethyl sulfamide and dimethyl sulfoxide may be appropriately contained.

The pl-( of the fixer) is used at a value of 3.0 or more, generally from 4.5 to 10, preferably from 5 to 9.5, and most preferably from 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the group t complex salts of carrier acids described in the above bleaching process, and preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetate iron (I [ A bleach-fix solution containing a large amount of halides such as iron ethylenediaminetetraacetate (
A special bleach-fix solution having a composition consisting of a combination of a complex salt bleach and a large amount of a halide such as ammonium bromide can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

Examples of the /N silver halide fixing agent that can be included in the bleaching constant N solution include the fixing agents described in the above fixing process. The degree of immersion of the fixing agent and the pH buffer and additives that can be included in the bleach-fixing solution are the same as in the above-mentioned fixing process.

The bleach-fix solution is used at a pH of 4.0 or higher, but is generally used at a pH of 5.0 to 9.5, preferably 6.0 to 8.
5, most preferably 6.5-8.5.

The heat-developable photosensitive material can be applied to any photosensitive material that forms an image by heat development. Examples include black-and-white types that form a silver image by heat development, and color types that include a dye-providing substance. In this latter color type, there are further monochromatic materials having a single color, for example, a black dye-providing substance or any other monochrome dye-providing substance, and multicolor, for example, heat-developable color photosensitive materials with yellow, cyan, and magenta color development. can be mentioned. In the color type, a method is usually used in which only the developed dye is transferred to the image receiving member.

The present invention exhibits particularly favorable effects when applied to the latter color type.

In heat-developable photosensitive materials, various standard silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability.

Examples of organic silver salts used in heat-developable photosensitive materials include silver salts of aliphatic carboxylic acids and silver salts of imino groups, with silver salts of imino groups being preferred, and silver salts of bencitriazole derivatives being more preferred. Silver salts of methylbenzotriazole and sulfobenzotriazole derivatives are preferred.

These organic silver salts may be used alone or in combination of two or more, and isolated ones may be used after being dispersed in a binder by an appropriate means, or they may be used after being dispersed in a binder in a suitable binder. The silver salt may be isolated and used as is without isolation.

The amount of the organic silver salt used is preferably 0.01 to 500 mol, more preferably 0.1 to 100 mol, per 1 mol of photosensitive silver halide.

As the reducing agent used in the heat-developable photosensitive material, those commonly used in the field of heat-developable photosensitive materials can be used, such as p-phenylenediamine-based and p-aminephenol-based developing agents, phosphoroamide phenol-based and sulfonate-based developing agents. Amidophenol-based developing agents, hydrazone-based color developing agents, color developing agent precursors, and the like can also be advantageously used, but particularly preferable reducing agents include compounds of the following general formula (1) described in JP-A-56-146133. ) are mentioned. .

General formula (1) In the formula, R1, J: and R2 represent a hydrogen atom or an alkyl group having 1 to 30 carbon atoms (preferably 1 to 4) which may have a substituent, and R1, R2, etc. may be closed to form a heterocycle. R3, R4R5 and R6 each have a hydrogen atom, a halogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or a carbon atom number 1 which may have a filling.
~30 (preferably 1 to 4) alkyl groups, R
3 and R1 and R5 and R2 may each be ring-closed to form a heterocycle. M represents an alkali diabetic atom, an ammonium group, a nitrogen-containing free base, or a compound containing a quaternary nitrogen atom.

On the other hand, the dye-donating substance is disclosed in JP-A No. 57-179840,
In the case of a compound that releases a dye upon oxidation, a compound that loses the ability to release a dye upon oxidation, a compound that releases a dye upon reduction, as shown in No. 58-58543, No. 59-152440, and No. 59-154445, Alternatively, when obtaining only a silver image without containing a dye-providing substance, a reducing agent as described below can also be used.

For example, phenols, sulfonamide phenols,
Mention may be made of polyhydroxybenzenes, naphthols, hydroxynaphthyls and methylene naphthols, methylenebisphenols, ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones and paraphenylenediamines.

These reducing agents can be used alone or in combination of two or more. The amount of the reducing agent used depends on the type of photosensitive silver halide, type of IIM silver salt, and other additives used, but it is usually 0 per mol of photosensitive silver halide. The amount ranges from .01 to 1500 mol, preferably from 0.1 to 200 mol.

Binders used in heat-developable photosensitive materials include synthetic or natural polymeric substances such as polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, xerulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin, and phthalated gelatin. One or more can be used in combination.

In particular, it is preferable to use gelatin or a derivative thereof in combination with a hydrophilic polymer such as polyvinylpyrrolidone or polyvinyl alcohol, and more preferably
It contains the gelatin and vinylpyrrolidone polymer described in No. 4249.

In the above binder, gelatin preferably accounts for 10 to 90% of the total binder amount, more preferably 20 to 60%, and vinyl and lolidone account for 5 to 90%.
It is preferably 10 to 80%, more preferably 10 to 80%.

The amount of binder used is usually - 112 o per layer.
, osg ~ 50 (l, preferably 0.1 g ~ 1
0 (l.

Supports used in heat-developable photosensitive materials include, for example, polyethylene film, cellulose acetate film, polyethylene terephthalate film, synthetic plastic films such as polyvinyl chloride, and papers such as photographic base paper, printing paper, baryta paper, and resin coated paper. Examples include a support, a support formed by providing a reflective layer on the above-mentioned synthetic plastic film, and the like.

When the photothermographic material is a color type, a dye-providing substance is used.

As a dye-donating substance, it participates in the reduction reaction of photosensitive silver halide and/or organic silver salt used as necessary,
Any material that can form or release a diffusible dye as a function of the reaction may be used. (i.e., to form a negative dye image when using negative-working silver halide) and a positive-working dye-donor that acts on a negative function (i.e., to form a positive dye image when using negative-working silver halide). It can be used depending on the situation.

These dye-providing substances may be used alone or in combination of two or more. The amount used is not limited and is determined depending on the type of dye-providing substance, whether it is used alone or in combination, or whether the photographic constituent layer of the light-sensitive material is a single layer or a multilayer of two or more layers. For example, the usage amount is 1
0.005g to 50g per f, preferably 0.1g to
10g can be used.

The image-receiving member used in the heat-developable photosensitive material only needs to have the function of receiving the dye released or formed by heat development, and the image-receiving member used in the photothermographic material may be a mordant used in the dye diffusion transfer type photosensitive material or as described in JP-A No. 57-207250. It is preferable to use a heat-resistant organic polymer material having a glass transition temperature of 40° C. or higher and 250° C. or lower.

Particularly useful mordants are polymers containing ammonium salts,
Polymers containing quaternary amine groups as described in US Pat. No. 3,709,690.

A typical image-receiving layer for dye diffusion transfer is obtained by coating a polymer containing an ammonium salt mixed with gelatin on a support.

Particularly preferred examples of the heat-resistant polymeric substance include:
Examples include a layer made of polyvinyl chloride described in Japanese Patent Application No. 58-97907 and a layer made of polycarbonate and a plasticizer described in Japanese Patent Application No. 5111-128600.

The above polymer is used by dissolving it in a suitable solvent and coating it on a support to form an image receiving layer, or by laminating a film-like image receiving layer made of the above polymer on a support, or by coating it on a support. It is also possible to constitute the image-receiving layer by a member (for example, a film) made of the above-mentioned polymer alone (receiving layer/layer support type).

Furthermore, the image-receiving layer may be constructed by providing an opaque layer (reflective layer) containing titanium dioxide or the like dispersed in gelatin on the image-receiving layer on a transparent support. This opaque layer receives the transferred color image and provides a reflective dye when viewed from the customer's side of the transparent support.

Various exposure means can be used for the heat-developable photosensitive material. The m-image is obtained by imagewise exposure to radiation, including visible light. Generally, light sources used for ordinary color printing, such as tungsten lamps, mercury lamps, xenon lamps, laser beams, CRT beams, etc., can be used as the light source.

As the heating means, all methods applicable to ordinary heat-developable photosensitive materials can be used, such as contacting with a heated block or plate, contacting with a heated roller or drum, passing through a high-temperature atmosphere, etc. Alternatively, it is also possible to use high frequency heating, or furthermore, to provide a conductive layer in a photosensitive material or an image receiving member for thermal transfer, and to utilize Joule heat generated by electricity or a strong magnetic field. There are no particular restrictions on the heating pattern, including methods of preheating (breheating) and then reheating, heating at a high temperature for a short time, or at a low temperature for a long time, continuously increasing, decreasing, or repeating, and even discontinuously. Although heating is possible, a simple pattern is preferred. Alternatively, a method in which exposure and heating proceed simultaneously may be used.

If the heat-developable photosensitive material is a black and white type that forms a silver image,
After imagewise exposure of the heat-developable photosensitive material, the temperature is usually 80°C to 250°C.
C., preferably in the temperature range of 100.degree. C. to 200.degree. C., for a period of 1 second to 240 seconds, preferably 1.5 seconds to 120 seconds. Also, before exposure,
Preheating may be performed in a temperature range of 00°C.

The heat-developable photosensitive material on which a silver image has been formed can be displayed and stored as is, but if a longer storage period is required, unreacted silver salt is preferably removed.

Removal of unreacted silver salts can be carried out using bleach baths, fixing baths, or bleach-fixing baths (for example, JP-A-5
No. 0-54329, No. 50-77034, No. 51-3
No. 28, processing of No. 51-80226, etc., JP-A-59
-136733, Research Disclosure No.
, 16407, same No., 16408, same No. 16
Bleach-fix sheets such as those described in US Pat.

In addition, when the heat-developable photosensitive material is a color type using a dye-providing substance, which is a preferred embodiment, the image receiving member and the photosensitive layer side of the heat-developable photosensitive material in the exposure method are placed in a stacked relationship, and the temperature is usually 80°C to 200°C. °C, preferably 120 °C to 170 °C
at a temperature range of 1 to 180 seconds, preferably 1.
By heating for 5 seconds to 120 seconds, the image is transferred to the image receiving member simultaneously with color development. Also, before exposure, 70℃~1
80° C. temperature box 128 The attached drawing is a block diagram showing an embodiment of an exposure apparatus to which the exposure method of the present invention is applied.

The signal B corresponding to blue is input to the semiconductor laser modulation circuit 27, and the semiconductor laser 1 is modulated by the output signal 31. Light 34 modulated and output from the semiconductor laser 1
is converged by lens 2 and input to SHG element 3,
Light 37 containing the second harmonic component is output. Thereafter, the light 37 becomes light 40 containing only the second harmonic component with the main wavelength component removed by the filter 4. After being converged by the lens 5, only the blue component is reflected by the dichroic mirror 6 in the direction of the polygon mirror 19. Ru.

Similarly, the laser beam 35 modulated by the signal R passes through the path of the lens 8, the SHG element 9, the filter 10, and the lens 11, and only the red component light is reflected by the dichroic mirror 12.
The light 44 is mixed with the blue component light 43 that has passed through the light source 2, and is input to the dichroic mirror 18. moreover,
Similarly to the above process, the laser beam 36 modulated by the signal IR passes through the path of the lens 14, filter 16, and lens 17, and only the near-infrared component light is reflected by the dichroic mirror 18, and the blue light is reflected by the dichroic mirror 18. The mixed light 44 with the red component and the red component becomes light 45 and is guided to the polygon mirror 19. polygon mirror 19
The light scanned by is subjected to fθ conversion by an fθ lens 20, passes through a mirror 21 and a cylindrical lens 22, and is imaged onto a photosensitive material 23. As a result of the above, signal B,
The photosensitive material is exposed to light whose intensity is modulated corresponding to R and IR.

The stage 24 supporting the photosensitive material 23 is installed to be capable of translational movement by the mutual movement of a spur gear 30 provided on the side and a gear 25 provided on the motor 26, thereby transmitting the rotational motion of the motor 26.

Further, the polygon mirror 19 is installed so as to be driven by a polygon mirror drive section 47.

Therefore, the input S Y N is synchronized with the signal B, RS IR.
The motor drive circuit 46 is operated by the signal outputted from the control signal generator 48 in response to the C signal to drive the motor 26 and transport the stage 24. Also, polygon mirror 1
9 is also rotationally controlled. As described above, a two-dimensional image is exposed on the photosensitive material 23.

[Effect of the invention 1] The present invention provides a blue-sensitive emulsion layer (maximum sensitivity wavelength range 400 to 500
nm), red-sensitive emulsion layer (maximum sensitivity wavelength range 600-7500
m), infrared-sensitive emulsion layer (maximum sensitivity wavelength range 800-1000
An exposure method using a silver halide photosensitive material having a unique photosensitive range due to the combination of -nra), which combines a semiconductor laser and an SHG element as a light source for a blue-sensitive emulsion layer, and a light source for a red-sensitive emulsion layer. By using a semiconductor laser or a combination of a semiconductor laser and an SHG element as a light source, and a semiconductor laser as a light source for an infrared-sensitive emulsion layer, it is possible to not only obtain images with high sharpness and excellent color reproducibility. It has the advantage that a green light source of 500 to 600 nm can be used as a safe light in the production and handling of photosensitive materials.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to specific examples.
The present invention is not limited to these embodiments.

The exposure apparatus used in the examples is shown below.

(Exposure device-1) GaAS (oscillation wavelength, approximately 900 nm) as a blue light source
and 3a NaNb 50Ss SHG element, InGaAS as a red light source (oscillation wavelength, approximately 1300 nm)
Exposure device that combines a BaNaNb5o+s SHG element and a GaAIAS (oscillation wavelength, approximately 830 nm) as an infrared light source.

(Exposure device-2) The red light source in exposure device-1 is InGaASP and Ba.
Exposure equipment replaced with a Na Nb s○15 SHG element.

(Exposure device-3) An exposure device in which the red light source in exposure device-1 was replaced with a CdSe light source.

(Exposure device-4) Semiconductor laser HL 8311 E (
850nm, Hitachi) and SHG element (LiIOa,
Semiconductor Ray IJ”-1 as a red light source
1L P 5600 (1300 nm, Hitachi) Dos + - + Gi (LilO3, Gugenger), semiconductor laser light source L 8311E (8
50nm, Hitachi, Ltd.).

(Exposure device-5) The blue light source in the exposure device-2 is InP (oscillation wavelength, about 910 nm) and S of [3a Na Nb s OSs.
Exposure device changed to one with l-IG element.

(Exposure device-6) [3a Na Nb s 0+5 in exposure device-2
Replace the SHG element with a 1-iNbo3 SHG element.
[Exposure equipment.

(Exposure device for comparison) Using a halogen lamp as a light source, as a filter for color separation - Color glass filter 3-46 for blue light (Toshiba Glass) -
Exposure device example 1 using colored glass filter R-64 for red light (Toshiba Glass) and Wratten filter 88A for infrared light (Eastman Kodak Company) (Example of color photographic paper) 1701; l/l' The following layers were sequentially coated on the titanium dioxide-containing polyethylene side of a paper support laminated with polyethylene on one side and polyethylene containing 11% by weight of anatase titanium dioxide on the other side (simultaneous coating), A silver halide color photographic material was prepared.

Layer 1...1.2 g of gelatin, 0.32 () of blue-sensitive silver chlorobromide emulsion (emulsion of note-1), and 1.2 g of gelatin
x 10-3 mol of the following yellow coupler (Y-1>,
0.020 diffusion-resistant hydroquinone compound (HQ-1
) was dissolved. , a layer containing dinonyl phthalate of sog.

Flower 2...0.7g of gelatin, 1,5mg of anti-irradiation dye (△l-1)\10mo of anti-irradiation dye (AI-2) and 0.05(l)
of HQ-1 was dissolved. , a layer containing DOP of osg. Layer 3...1.25g gelatin, 0.
16 g of a red-sensitive cubic silver chlorobromide emulsion (Note-2) and 0.459 of the following magenta couplers M-1 and O,
A layer containing DOP in which 01 g of HQ-1 was dissolved.

Layer 4...1.2g of gelatin and o, 0
A layer containing 0.6 g of DOP in which 0.2Q of 80 HQ-1 and each of the following ultraviolet absorbers UV-1 to UV-4 were dissolved.

Layer 5...1.4g gelatin, 0.201;l
Infrared-sensitive cubic silver chlorobromide emulsion (Note-3) and 0.
A layer containing 24Q of cyan coupler C-1 below and 0.28 g of DOP dissolved in 0.20 (l) of cyan coupler C-2 and 0.01 () of HQ-1.

Layer 6...1.69 gelatin and 0.04 g H
0, in which 0.1 g each of Q-1 and UV-1 to 4 were dissolved;
A layer containing a DOP of 39.

Layer 7: A layer containing 1.1 g of gelatin and o, oig hydroquinone.

As a hardening agent, 0.04 il of sodium 2,4-dichloro-6-hydroxy-s-triazine was added to each of the layers 4 and 7 immediately before coating.

(Note-1) Blue-sensitive silver chlorobromide emulsion 60°C, pAg' = 8 Nikontro) Li Shita same rp!
Average particle size 0.69 μm, Ag5r prepared by mixing method
Monodisperse with a content of 90 mol% (particle ratio within the range 82%)
substantially octahedral emulsion of 2.8X 10-5 moles of sodium thiosulfate, 4 to 1 mole of silver halide, respectively.
．． Chemical ripening and optical sensitization were performed to the optimum sensitivity using 5 x 10-4 moles of a 4-hydroxytetrazaindene compound (HT AZ) and 5.5 x 10-moles of the following blue sensitizing dye (A-1). After, 4.5X 1 (13
-Eru (7) HTA Zwoka, tJ=.

(Note-2) Red-sensitive silver chlorobromide emulsion silver bromide 70 mol% (average grain size 0.53 μm, grain ratio within range 84%) Sodium thiosulfate was added at 3 SX per 1 mol of silver halide.
Chemical sensitization was carried out by adding 10 -5 mol of the mixture, and optical sensitization was carried out using the following red sensitizing dye A-2. Furthermore, a 4-hydroxy-tetraazaindene compound was added as a stabilizer in an amount of 4.5×10 −3 mol per mol of silver halide.

(Note-3) Infrared-sensitive silver chlorobromide emulsion 60 mol% silver bromide (average grain size 0.47 μm, grain ratio within range 82%) Sodium thiosulfate was added at 3.5X per mol of silver halide.
Chemical sensitization was performed by adding 10 −3 mol, and optical sensitization was performed using the following infrared sensitizing dye A-3. Further, as a stabilizer, 4-hydroxytetrazaindene-based compounds were added at 4.5X 10-3 mol and 2X 10-6 mol per mol of silver halide.
Mol of 2-mercapto-1-methyl-5-acetamido-1,3,4-doria-I A-nihydroquinone compound (1-IQ-1) 8 1-1 l-2 I; 1! V-1 υV-2 n++ C(C11,).

V-4 ll The above color photographic paper was subjected to image exposure using the above exposure device-1 and the comparative exposure device, and then processed in the following processing steps: Bleach and fixation at 38°C for 3 minutes and 30 seconds
Wash with water at 38℃ for 1 minute and 30 seconds
30-34℃ 3 division drying
60-80°C 2 minutes - The composition of each treatment liquid is as follows.

[Color developer pure water 800 vQ benzyl alcohol 15-triethanolamine 10g hydroxylamine sulfate 2.0g potassium bromide
1.5g sodium chloride
1.09 Potassium sulfite 2.
Oi; IN-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.591-hydroxyethylidene-1,1-diphosphone! (60%0% aqueous solution 1.5vQ
Potassium carbonate 32 (IWhi
tex B B (50% aqueous solution) 21g (fluorescent brightener, manufactured by Sumitomo Chemical Co., Ltd.) Add pure water to make 11, and add 20% potassium hydroxide or 10
Adjust pl-11Q to 1 with dilute sulfuric acid.

[Bleach-fix solution] Pure water 600 ethylenediaminetetraacetic acid iron (II [)] Ammonium 659 ethylenediaminetetraacetic acid 2-sodium salt g Ammonium thiosulfate 85g Sodium bisulfite 10 (1 Sodium metabisulfite 2g ethylenediaminetetraacetic acid 2-sodium sodium bromide
10 (J color developer 200) Add pure water to 12 and adjust the pH to -7.0 with dilute sulfuric acid.

The density of the yellow image area corresponding to blue light exposure, the magenta image area corresponding to red light exposure, and the cyan image area corresponding to infrared light exposure of the obtained image was measured using a Sakura densitometer PDA-65. did.

Table-1 *B-Light centered at 436nm G...546nllll Light R...644
Light centered on nm () The relative concentration ratio at each wavelength is shown in parentheses.

As is clear from Table 1, according to the present invention,
It can be seen that a dye image with low density at other wavelengths than the maximum density, that is, with high color purity, is obtained, and the color reproducibility is excellent.

Furthermore, in order to evaluate the sharpness, exposure was performed using the exposure apparatus of the present invention and the comparative exposure apparatus using a rectangular wave chart. The response function (
MODULATION TRANSRER FUNC
tion (hereinafter referred to as MTF value) was determined.

Table 2 below shows the M table for frequencies of 5 lines per 1 mn+.
2 From the results in Table 2, it can be seen that exposure apparatus 1 of the present invention has excellent sharpness.

Example 2 Instead of the silver halide emulsion used in layer 1 of Example 1, various grain sizes and grain size distributions as shown in Table 3 were created by changing the amount and speed of addition during simultaneous mixing. Silver halide emulsions with different values were prepared and used in Example-
Sample table 3 was obtained in the same manner as in Example 1. To evaluate the sharpness, each sample obtained was exposed using exposure device 1 and developed in the same manner as in Example 1. The MTF value of the image was measured. The results are shown in Table 4.

Table 4 In Table 4, it can be seen that the average grain size is preferably 0.5 μm or more, and monodispersed emulsions are superior.

Example-3 Instead of sensitizing dye A-1 used in layer 1 of Example-1,
Samples were prepared in the same manner as in Example-1, except that the following compounds A-4 to A-7 were used, respectively.

Further, the same samples as in Example-1 were prepared except that the following compounds A-8 to A-20 were used in place of the sensitizing dye A-2 used in layer 3 of Example-1.

Furthermore, the same samples as in Example-1 were prepared except that the following compounds A-21 to A-2S were used in place of the sensitizing dye A-3 used in layer 5 of Example-1.

These samples were evaluated in the same manner as in Example 1. As a result, the exposure method of the present invention had better sharpness and color reproducibility than exposure methods other than those of the present invention.

8-4 A-ta 1″″q 8-1g A-16 8-20 Ikin-Yoshiro He A-shio Example-4 Exposure device @ instead of exposure device-1 in Example-1
The same operations as in Example-1 were carried out using -4, -5, and -6, and as a result, all of them had superior color reproducibility and sharpness compared to the comparative exposure apparatus.

Example-5 (Example of heat-developable photosensitive material) [Preparation of silver iodobromide emulsion] At 50°C, JP-A No. 57-92523, No. 57-
92524, an aqueous solution 500iR containing 11.6g of potassium iodide and 130g of potassium bromide in solution A prepared by dissolving 20g of ossein gelatin, 1000g of distilled water, and ammonia was prepared. Solution B, an aqueous solution containing 1 mol of silver nitrate and ammonia 50
0 and C solution were added at the same time while keeping I) A (L and pH constant. Furthermore, by controlling the addition speed of B solution and C solution, a silver iodide content of 7 mol% and a regular hexahedron were added. A core emulsion with an average grain size of 0.25 μm was prepared.Next, in the same manner as described above, a silver halide shell having a silver iodide content of 1 mol% was coated by simultaneous mixing. A core/shell type silver halide emulsion with a face shape and an average grain size of 0.30 μm (shell thickness 0.05 μm) was prepared. (Grain ratio within the range 80%) The above emulsion was washed with water and desalted to obtain an i.
1 [obtained. Furthermore, three types of photosensitive silver halide emulsions were prepared using the silver halide prepared above in the following compositions.

a) Infrared sensitive silver iodobromide emulsion [7 Said silver iodobromide emulsion 700iQ4-hydroxy-6-methyl-1°3.3a,7-chitrazaindene 0.4g gelatin
32g sodium thiosulfate
10mg Sensitizing dye (a) below 1% methanol solution 801Q distilled water
1200d sensitizing dye (a) b) Preparation of red-sensitive silver iodobromide emulsion The above silver iodobromide emulsion 700d 0.4g gelatin 32 (J Sodium thiosulfate 10mg sensitizing dye (b) below 1% methanol solution 80g distilled water
1200 m12 sensitizing dye (b
) (UtL2)3δU11111 N((2115)1C
) Preparation of blue-sensitive silver iodobromide emulsion The silver iodobromide hole ^It 70 Q,
Q4-Hydroxy-6-methyl-1゜3.3a, 7-titrali4inane 0.4g Gelatin 320 Soluium thiosulfate 10mg The following sensitizing dye (C) 1% methanol solution 80% distilled water
1200 Sensitizing dye (C) <Preparation of organic silver salt dispersion> 5-Methylbenzo-1-lyazole and silver nitrate were reacted in a water-alcohol mixed solvent to produce 19 5-methylbenzo-1-lyazole 1428.81J and 16.0 g of poly(N-vinylpyrrolidone) were dispersed in an alumina ball mill and adjusted to pH 5.5 to give 20Q kg.

A photothermographic material sample having the following configuration was prepared.

Write in order from top layer to bottom layer. The amount of each ingredient is per 112 pieces.

Protective layer: Gelatin 0.42L SiO20,36 (
1, Safron i, og, hardener 20mq Infrared sensitive layer: methylbenzotriazole silver 1.6g, reducing agent (R-11) 0.57g, cpm -ItO,
8q, the infrared-sensitive silver halide emulsion was converted to silver equivalent to 0.5
8g, the following compound <HQ-1) 60ma, gelatin 0.
75g, phthalated gelatin 0.75Q, polyvinylpyrrolidone o,sg, 3-methylpentane-1,,3,
5-triol 0.38 (1, polyethylene glycol 1.1 g, AI K-XC (see note 1) 80 ma,
The following compound (B-1) 0.52g, hardener 60mg
.

Intermediate layer: gelatin o, sg, the following compound (SC-'1
') 0.4 (1, methylbenzotriazole silver 1
．． 2(], 20 mg of hardener.

Red-sensitive layer: cpm -I 1.3+J, the red-sensitive silver halide emulsion converted to silver @ 76 (+, methylbenzotriazole silver 2.7Q, reducing agent (R-11)
0.76 g, @compound (day Q-1 > 90 mg, gelatin 10. phthalated gelatin 1 g, polyvinylpyrrolidone 0.66 g, 3-methylpentane-1,3°5-triol o,sg, polyethylene glycol 1.5 (1,
A I K-XCO, olg, the following compound (B-1>0, 68 fJ, hardener 80II 1 g.

Intermediate layer: Y-filter dye (Y-1) o4g, 5C-
10.4g, methylbenzotriazole silver 1.2CI
, gelatin 0.5g, hardener 20mg.

Blue-sensitive layer: cpm -m 1.40, the above blue-sensitive silver halide emulsion (I conversion -0.97 g), methylbenzotriazole silver 2.7 g, i base agent (R-11) 0.97a, the above compound ( HQ-1)
90mo, Seratin 1.26g, Phthalated Gelatin 1.
26(], polyvinylpyrrolidone 0.84g, 3-methylpentane-1,3,5-triol 0.63(1,
Polyethylene glycol 1. Fishing, AIK-XC0,1
4 (1, 0.87 g of the following compound (B-1), hardener 0.
I.Q.

Gelatin layer: 2.5 g gelatin Support 180 μm thick polyethylene phthalate film with Nilatex subbing.

Image-receiving element image-receiving layer: polycarbonate "toq", 1 of the following compounds (1
) 0.5 (1, the following compound (2>0.5 Support: Baryta paper - ~ ゜ 3. - ■ 1l ep theory - ■ Q-1 υ1z 5C-1 CIl.

After exposing the above-mentioned heat-developable photosensitive material using exposure device-2 and comparative exposure device, it is superimposed on an image-receiving element.
Heat development was carried out at 50° C. for 1 minute and an image was obtained on the image receiving element upon immediate peeling.

The density of the yellow image area corresponding to blue light exposure, the magenta image area corresponding to red light exposure, and the cyan image area corresponding to infrared light exposure of the obtained image was measured using a Sakura densitometer PDA-65. did.

5 White Emi h (p L7 people Q Table-5 * B...Light centered at 436 nm G...546
Light R centered at nm...Light centered at 644r+m () The relative concentration ratio at each wavelength.

As is clear from Table 5, according to the present invention,
It can be seen that a dye image with low density at other wavelengths relative to the maximum density, that is, with high color purity, was obtained, and the color reprintability was excellent.

In order to roughly evaluate the sharpness, exposure was performed using the exposure apparatus of the present invention and the comparative exposure apparatus using a rectangular wave chart. The response function (
ModulationTransfer Funct
ion (hereinafter referred to as MTF value) was calculated.

Table 6 below shows NITF at a frequency of 5 trees per 1 mm.
The value was shown.

Table 6 From the results in Table 6, it can be seen that exposure apparatus 2 of the present invention has excellent sharpness.

Example 6 Instead of the silver halide emulsion used in the blue-sensitive layer of Example 5, various emulsions as shown in Table 7 were prepared by changing the amount and rate of addition during simultaneous mixing during shell coating. A silver halide emulsion with a certain grain size and grain size distribution is prepared,
Using this, a sample was prepared in the same manner as in Example-5.

Table-7 MTF values of images obtained by exposing each sample obtained using exposure bag @-2 and developing in the same manner as in Example-5 in order to evaluate sharpness. was measured. The results are shown in Table-8.

Table 8 As is clear from Table 8, monodispersed emulsions are preferred.

Example 7 A sample similar to Example 5 was prepared, except that each of the aforementioned compounds A-4 to A-7 was used instead of the sensitizing dye (C) used in the blue-sensitive layer of Example 5. Created.

Further, the same samples as in Example-5 were prepared except that the above-mentioned compounds A-8 to Δ-20 were used in place of the sensitizing dye (b) used in the red-sensitive layer of Example-5.

Furthermore, the sensitizing dye (a) used in the infrared sensitive layer of Example-5
Samples were prepared in the same manner as in Example 5, except that the compounds A-21 to Δ-2 were used in place of each of the compounds A-21 to Δ-2.

These samples were evaluated in the same manner as in Example 5. As a result, the exposure method of the present invention had better sharpness and color reproducibility than exposure methods other than those of the present invention.

Example-8 Exposure device instead of exposure device-2 in Example-5
When the same operation as in Example 5 was performed except for using No. 3, the sharpness and color reproducibility were all better than the exposure method outside the present invention.

Example-9 Exposure device instead of exposure device-2 in Example-5
When the same operations as in Example 5 were carried out except for using No. 4, the sharpness and color reproducibility were all better than the exposure method outside the present invention.

Example-10 Exposure was carried out in the same manner as in Example-1, except that the silver halide photosensitive material in Example-1 was changed to the following color diffusion transfer photosensitive materials ■, ■, and ◎, and development was performed in the prescribed manner. As a result of the processing, the exposure method of the present invention was found to have better sharpness and color reproducibility than exposure methods other than those of the present invention.

■ Kodak In5tant Co1or
Film Print (H8144-10)
■ Fuji I n5tant Co1or
Film (F l -Qc Polaloid
13o.

[Brief explanation of drawings]

The accompanying drawing is a block diagram showing an embodiment of an exposure apparatus to which the exposure method of the present invention is applied. 1.7.13... Semiconductor laser 2.8.14... Converging lens 3.9... SHG element 4.10, 16... Filter 5.11.17... Lens 6.12. 18...One dichroic mirror...
Polygon mirror 20...f-theta lens 21...Mirror 22...Cylindrical lens 23...Photosensitive material 24...Stage 25...1'' 26...Motor 30...Spur gear 27. 28.29...Semiconductor seat 1F-modulation circuit 46
...Motor drive circuit 47...Polygon mirror drive section 48...Control signal generation section

Claims (1)

[Claims] In a method for exposing a silver halide photographic light-sensitive material, the silver halide photographic light-sensitive material having a plurality of silver halide emulsion layers having three different maximum sensitivity wavelength ranges on a support is exposed using three different laser beams. , the plurality of silver halide emulsion layers each include a silver halide emulsion layer (referred to as R' silver halide emulsion layer) having a maximum photosensitive wavelength range of 400 to 500 nm, and a halogen emulsion layer having a maximum photosensitive wavelength range of 600 to 750 nm. a silver halide emulsion layer (referred to as O' silver halide emulsion layer) and a silver halide emulsion layer (referred to as P' silver halide emulsion layer) having a photosensitive maximum wavelength range of 800 to 1000 nm; The silver emulsion layer is exposed to second harmonic light obtained using a semiconductor laser and an SHG element, and the O' silver halide emulsion layer is exposed to second harmonic light obtained using a semiconductor laser light or a semiconductor laser and an SHG element. 1. A method for exposing a silver halide photographic material, characterized in that the P' silver halide emulsion layer is exposed to a semiconductor laser beam.