JPH05113629A - Image forming method - Google Patents

Abstract

PURPOSE:To obtain a high quality image free from unevenness when an image is formed with a silver halide photosensitive material by exposure with vertical single mode type semiconductor laser. CONSTITUTION:The gamma of a photosensitive layer exposed with vertical single mode type semiconductor laser is regulated to >=1.5 and the dynamic range is preferably regulated to <=2.0. The wavelength of light emitted during exposure is set within a wavelength range in which DELTAlog (spectral sensitivity) per 1nm of the photosensitive layer becomes -0.015 to +0.015 and/or the range of the max. spectral sensitivity wavelength (nm) of the photosensitive layer + or -10nm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method for exposing an image signal, which is an electric signal, to a silver halide light-sensitive material through a light emitting element of a semiconductor laser, and particularly, it has less unevenness of exposure. The present invention relates to an image forming method.

[0002]

2. Description of the Related Art Light sources for scanning exposure, such as LEDs and LDs
As a light-sensitive material for recording the output such as, a silver halide light-sensitive material is widely used in both black and white images and color images, and in both halftone dots and continuous gradation. The reason for this is that since a silver halide light-sensitive material has high sensitivity and is excellent in gradation and sharpness, a high-quality system can be designed. In particular, in recent years, as the processing steps of silver halide light-sensitive materials have been simplified and speeded up, scanning exposure type high-quality image forming systems using silver halide light-sensitive materials have been developed more and more.

With this development, the output stability of the scanning exposure light source has become a problem. For example, it is well known that when the temperature of an LED becomes higher, the emission wavelength becomes longer and the power continuously decreases, which causes uneven image density. On the other hand, it has been found that the peak wavelength of the spectral sensitivity of the light-sensitive material can be improved by setting it to a wavelength longer than the wavelength of the light source (JP-A-61-52642). This method is also effective for improving image unevenness caused by the droop of the semiconductor laser.

However, semiconductor lasers, particularly vertical single mode (vertical single mode) type semiconductor lasers, further have a so-called hopping phenomenon in which the emission wavelength fluctuates discontinuously, which is undesirable image unevenness. Was found to occur.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a scanning exposure type image forming method using a vertical single mode type semiconductor laser which is capable of obtaining a high quality image having no exposure unevenness by using a silver halide photosensitive material. To provide.

[0006]

The above objects are achieved by the present invention described in (1) to (4) below. (1) In an image forming method in which at least one photosensitive layer of a photosensitive material having at least one photosensitive layer containing a photosensitive silver halide on a support is imagewise exposed using a light source that can be modulated, The exposure light source is a vertical single-mode type semiconductor laser whose emission wavelength can fluctuate discontinuously with changes in temperature or the amount of emitted light, and the emission wavelength during exposure is the spectral per 1 nm of the photosensitive layer. An image characterized in that the logarithmic variation in sensitivity [Δlog (spectral sensitivity) / nm] is within a wavelength range of ± 0.015 and gamma (γ) of the photosensitive layer is 1.5 or more. Forming method.

(2) Image formation in which at least one photosensitive layer of a photosensitive material having at least one photosensitive layer containing a photosensitive silver halide on a support is imagewise exposed by using a light source that can be modulated. In the method, the exposure light source is a vertical single-mode semiconductor laser in which the emission wavelength can change discontinuously with changes in temperature or the amount of emitted light, and the emission wavelength during exposure is the maximum of the photosensitive layer. An image forming method, wherein the spectral sensitivity wavelength (nm) is within ± 10 nm and the photosensitive layer has a gamma (γ) of 1.5 or more.

(3) Further, the emission wavelength during exposure is within a wavelength range in which the logarithmic variation of spectral sensitivity per nm of the photosensitive layer [Δlog (spectral sensitivity) / nm] is within ± 0.015. The image forming method according to (2) above.

(4) The image forming method as described in any one of (1) to (3) above, wherein the exposure range (E) of the photosensitive layer has a dynamic range of 2.0 or less in log E unit.

Incidentally, Japanese Patent Application Laid-Open No. 2-34445 discloses that
"In a silver halide photographic light-sensitive material exposed by a light source in which the maximum wavelength of the emission spectrum fluctuates due to variations in temperature and manufacturing, the spectral sensitivity distribution of the silver halide photographic light-sensitive material is within ± 25 nm of the standard value of the light source. , 0.2
A silver halide photographic light-sensitive material characterized by being within (log E). Is disclosed.

On the other hand, the present invention selectively uses a vertical single-mode type semiconductor laser as an exposure light source, which is different from the invention disclosed in the above publication. Therefore, the above publication does not suggest the mode hopping phenomenon peculiar to the vertical single mode semiconductor laser. Further, there is no description about γ and dynamic range (DR) of the photosensitive layer.

Therefore, as will be described in detail later, it has been found that the exposure unevenness caused by the mode hopping phenomenon depends on γ of the photosensitive layer and further on DR, and based on this finding, it is attempted to improve the exposure unevenness. The effect is obviously different from the invention.

[0013]

[Specific Structure] The specific structure of the present invention will be described in detail below. In the image forming method of the present invention, at least one photosensitive layer of a silver halide photosensitive material is imagewise exposed using a semiconductor laser as an exposure light source, which is easily modulated.

Such an image forming method is effective in both the black and white field and the color field. It is also effective in both the printing field using halftone dots and the continuous tone photographic field. Therefore, a wide variety of silver halide photosensitive materials can be used in the present invention, and they can be applied to any of negative type photosensitive materials.

The exposure light source in the present invention uses a semiconductor laser (LD) as a light emitting element. Since the LD, which is a semiconductor element, can control the intensity of radiated light by controlling the current flowing to the light emitting element, it does not require an external modulator and can be exposed at low cost, compact size, and high efficiency.

Further, the LD has an advantage that a large amount of exposure can be obtained because the emitted light can be condensed into a parallel beam with high efficiency by a collimator lens.

In such an LD, since the current-light output characteristic has a high temperature dependency, it is indispensable to control the light quantity in order to expose a high quality image.

In order to solve this problem, a light amount detecting photodiode (PD) usually incorporated in an LD package is used, and an automatic power control (controlling the current to the LD so that the light amount emitted from the LD is constant ( APC) is used. A photodiode provided outside may be used as the light amount detection element.

The emission wavelength of the semiconductor light emitting device has temperature dependence. For example, in AlGaAs LD, 0.
It has a temperature coefficient of 23 to 0.27 nm / ° C.

In particular, in the present invention, in order to perform digital exposure with a single wavelength, a vertical single mode type LD is used.
However, the vertical single-mode LD has a characteristic that wavelength changes occur discontinuously. This is called a mode hopping phenomenon.

Here, the single mode means that there may be a plurality of peaks of the oscillation wavelength, but the intensity of one or a plurality of sub-peaks is 1/5 or less, preferably 1/10 or less of the main peak. Say.

Mode hopping is easily visible on an image when recording an image whose density continuously changes in the scanning direction of the raster. This is because mode hopping occurs when the light intensity of the LD continuously changes, and at this time, the light intensity changes and the wavelength changes. Moreover, since the position where this variation occurs varies depending on the raster, it is visually recognized as a light and shade striped pattern.

Mode hopping also occurs when the temperature of the LD during light emission changes. Therefore, mode hopping occurs due to self-heating of the LD during exposure of one raster, which may cause unevenness on the image.

The LD is used by being housed in an LD package, and in this case, temperature control is performed using a heater inside the package. However, it is still difficult to control the temperature to be constant, and fluctuations of several degrees cannot be denied. The oscillation wavelength changes by about 1 nm due to the change of several degrees.

FIG. 1 shows the mode hopping due to this temperature change. The temperature at this time is the temperature of the package.

As described above, in the vertical single mode LD, the emission wavelength can change discontinuously with the change in temperature or the amount of light emission, and this mode hopping phenomenon causes a change in image density. Become.

For example, assume that the wavelength of the light source changes from λ ₁ nm to λ ₂ nm discontinuously. The spectral sensitivity of the photosensitive layer corresponding to this light source is S ₁ and S ₂ for incident light λ ₁ and λ ₂ , respectively.
Then, when the wavelength of the light source changes discontinuously, the spectral sensitivity of the photosensitive layer substantially changes by ΔS = S ₂ / S ₁ . Therefore, the image density changes by γ × log ΔS (γ = gamma of the photosensitive layer).

Here, γ is a point on the characteristic curve that gives the minimum density (Dmin) +0.5 in the characteristic curve as shown in FIG. 2, and point a ₁ corresponding to a on the log E axis. From log E (= a ₁ +) shifted 0.5 to the right on the log E axis
0.5) When the point on the characteristic curve corresponding to the point b ₁ is b, it is defined as the average value of the inclination of the straight line connecting a and b. That is, the point on the D axis corresponding to b is (D
min) + 0.5 + x, it is represented by (x / 0.5).

From the above relationship, the greater the wavelength variation due to the mode hopping of the light source, and the same wavelength variation, the wavelength dependence of the spectral sensitivity of the photosensitive material and γ
Is larger, the density difference is larger and the image quality is deteriorated.

At least one light-sensitive layer of the silver halide light-sensitive material in the present invention is exposed by the LD, and such a light-sensitive layer has a γ of 1.5 or more, preferably 2.0. That is all. By setting the γ value to 1.5 or more, the dynamic range of the photosensitive material can be made smaller than that of the exposure system,
System design becomes easy and sufficient image density can be obtained. On the other hand, when γ is less than 1.5, system design becomes difficult, the ability of the photosensitive material cannot be fully utilized, and only low density images can be obtained. The upper limit of γ is usually about 12.

The dynamic range (DR) of the photosensitive layer is preferably 2.0 or less in log E unit, and particularly preferably 1.8 or less. With such a DR, the exposure light source L having a narrow DR can be used.
It is suitable for D. On the other hand, when the DR exceeds 2.0, it becomes impossible to utilize the entire concentration range of the photosensitive material. Further, from the viewpoint of reducing the change in image density, the lower limit of DR is preferably about 0.3. Here, the dynamic range (DR) refers to a characteristic curve as shown in FIG. 3, in which the minimum density (D _min ) +0.1 which is the logE point that gives a density of 0.1 is shifted to the left by 0.2 on the logE axis. He lo
gE (= M-0.2) point is A, and the maximum concentration ( _Dmax )-
Let B be the logE point that gives a concentration of 0.1, and mean the one defined by BA.

The definition of DR in such a format is as follows.
This is because the density range actually used is from D _min to D _max −0.1. In other words, the front portion of D _max is generally soft and a slight difference in density is produced in the design of the exposure apparatus, so that the light amount must be greatly changed, and this portion is often not used.

With respect to such a photosensitive layer, in the present invention, the emission wavelength during exposure is set as follows: 1) The variation of the logarithm of the spectral sensitivity S per nm of the photosensitive layer (Δlog S / nm) is within ± 0.015, It is preferably within the wavelength range of substantially 0, or 2) ± 1 of the maximum spectral sensitivity wavelength λ _max (nm) of the photosensitive layer.
Within or within 0 nm, preferably within ± 7 nm.

As a result, even if γ of the photosensitive layer is a value of 1.5 or more and the dynamic range (DR) is 2.0 or less, it is possible to prevent the occurrence of image density unevenness. Then, γ is 1.5 or more, and DR is 2.
Since it is 0 or less, a high image density (Dmax) can be obtained and a high quality image can be obtained.

Further, in the present invention, the above 1), 2).
May be applied in combination.

In the present invention, for imagewise exposure using an LD, the construction described in Japanese Patent Application No. 2-318351 by the present applicant may be used. Further, the following method is used to form an image on the photosensitive material with the LD light.

The laser light emitted from the LD is made into a substantially parallel beam by the collimator lens. This beam is further linearly imaged on a polygon mirror which is a deflector by using a cylindrical lens having a power only in the sub-scanning direction. Although the beam rotates at a constant angular velocity as the polygon mirror rotates, the beam is imaged by the f.theta. Further, the fθ lens and the cylindrical mirror correct the pitch unevenness between rasters due to the surface tilt of the polygon mirror.

The configuration of the optical system used at this time is as described in Japanese Patent Laid-Open No.
-77018 and 1-81926.

When the laser beam is deflected by the polygon mirror, jitter occurs in the rotation of the motor that rotationally drives the polygon mirror, and there is an angular error between the adjacent surfaces of the polygon mirror.
The scanning start timing on the sensitive material of each raster will change.

Therefore, by providing a sensor for detecting the scanning start timing in the optical system and synchronizing the image modulation signal of each raster with the timing of the detection signal from the sensor, there is no fluctuation and no fluctuation. The image can be exposed.

The scanning start timing detection sensor is provided at a position corresponding to the image exposure area on the photosensitive material in the optical system.

Since the modulation signal of each pixel is supplied to the LD drive circuit in synchronization with the scanning start timing detection signal, a fixed frequency clock signal which is an integral multiple of the pixel repetition period is divided in synchronization with the scanning start timing detection signal. Has a counter that starts a lap. By using the output of this counter as a pixel synchronization signal, a highly accurate image can be exposed without being affected by raster fluctuation.

The following method is used to modulate the LD light.

This modulation method includes a method of directly modulating an LD to imagewise expose an image, a method of modulating the intensity of light for each pixel by changing a passing current (intensity modulation), and an L method.
As a method for modulating D, there is a method in which the light intensity is constant and the light emission time is controlled for each pixel (time modulation).

In the case of the former intensity modulation method, in the LD, a range in which the light output is linear with respect to the energizing current, that is, the ratio of the maximum light amount and the minimum light amount for laser oscillation is usually about 10 and thus a sensitive material is required. It is not possible to cover the dynamic range with the laser light alone. Also LD
In order to obtain a wide dynamic range, it is possible to use a non-linear region, that is, LED light.
Since the D beam and the LED beam have different image forming beam shapes on the photosensitive material, density variations occur due to the multiple exposure effect of the photosensitive material, resulting in poor image quality.

On the other hand, in the case of the latter time modulation method, since the LD can be switched at high speed, it is possible to modulate a wide dynamic range with laser light.

Mode hopping can occur in any of the above modulation methods, but the present invention is effective in any of them, and in particular, mode hopping occurs remarkably in the intensity modulation method, and the effect of the present invention becomes remarkable. ..

Examples of the negative photosensitive material used in the present invention include black and white photosensitive materials such as black and white photographic paper, black and white negative film and black and white positive film, and color photosensitive materials such as color photographic paper, color negative film and color positive film. Further, it may be a black and white or color photothermographic material.

Among them, in the color light-sensitive material,
The present invention may be applied to at least one photosensitive layer, and preferably two or more layers.

The photosensitive material which can be used in the present invention can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer and a back layer in addition to the photosensitive layer. Further, various filter dyes for improving color separation and anti-irradiation dyes for improving sharpness can be added.

Among such light-sensitive materials, the color field, particularly color photographic paper and heat-developable color light-sensitive materials will be described in detail below, but the present invention is not limited thereto.

As a light-sensitive material used in the image forming method of the present invention, it is also preferable to apply a photographic material which forms a color image by ordinary color development, such as general color photographic paper. The light-sensitive material used at this time contains silver halide grains as a light-sensitive element and a color coupler as a dye-forming element. A color coupler is a compound capable of forming a dye by coupling with an oxidized product of an aromatic primary amine developing agent generated during development of a photosensitive silver halide grain, and a compound having an active methylene position is usually Used. The configuration of the color photographic paper applicable to the present invention will be described below.

The silver halide color photographic light-sensitive material as a color printing paper used in the present invention has at least three silver halide emulsion layers on a support, at least one of which has a maximum spectral sensitivity of 700 nm or more. It is preferable to have Further, a light-sensitive material in which at least two layers are composed of emulsion layers having a maximum spectral sensitivity of 670 nm or more can also be preferably used.

The light-sensitive layer of these silver halide color photographic light-sensitive materials preferably contains at least one coupler capable of forming a color by a coupling reaction with an oxidation product of an aromatic amine compound. For full-color hard copy, at least three types of silver halide photosensitive layers having different color sensitivities are provided on a support, and each layer is yellow by a coupling reaction with an oxidant of an aromatic amine compound. It preferably contains either a magenta or a coupler capable of forming a cyan color. These three different spectral sensitivities can be arbitrarily selected depending on the wavelength of the light source used for digital exposure within the range satisfying the requirements of the present invention, but the closest spectral sensitivity maximum is at least from the viewpoint of color separation. It is preferable that they are separated by 30 nm or more. There is no particular limitation on the correspondence relationship with the color forming couplers (Y, M, C) contained in the photosensitive layers (λ ₁ , λ ₂ , λ ₃ ) having at least three different spectral sensitivities. That is, 3 × 2 = 6 combinations are possible. Also, there is no particular restriction on the coating order from the support side of the photosensitive layers having at least three different spectral sensitivity maxima, but the photosensitive layer containing silver halide grains having the largest average size is the most preferable from the viewpoint of rapid processing. In some cases, it is preferable to come to the upper layer. Therefore, there are 36 possible combinations of the three different spectral sensitivities, the three color forming couplers and the layer order. The present invention can be effectively used for all the 36 types of light-sensitive materials. In the present invention, a semiconductor laser is used as a light source for digital exposure. In this case, at least one of at least three types of silver halide photosensitive layers having different color sensitivities is used.
It is preferable that the photosensitive layer of one kind has a spectral sensitivity maximum at 700 nm or more, and that at least two layers have a spectral sensitivity maximum in a long wavelength region of 670 nm or more. Also in this case, there are no restrictions on the spectral sensitivity maximum, the color forming coupler, and the layer order. Table 1 shows specific examples of a digital exposure light source using a semiconductor laser, a spectral sensitivity maximum, and a color forming coupler, but the present invention is not limited thereto.

[0055]

[Table 1]

The film thickness of the photographic constituent layers (eg, emulsion layer, intermediate layer, surface layer, etc.) of the color photographic paper used in the present invention is preferably 6 to 20 μm, more preferably 7 to 12 μm. The method of the present invention as described above is particularly effective for multi-layer color light-sensitive materials.

As the silver halide emulsion used in the present invention, those composed of silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. Here, “containing substantially no silver iodide” means that the silver iodide content is 1 mol%.
Hereafter, it means preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, and the core and the surrounding inside the silver halide grains A so-called layered structure particle having a halogen composition different from that of a shell [one or more layers] or a structure having a non-layered portion having a different halogen composition inside or on the surface (edge of the particle when present on the particle surface) , Particles having a structure in which different composition portions are joined to the corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two particles rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. Alternatively, it may be one that positively has a continuous structural change.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. In the present invention, the silver chloride content of the high silver chloride emulsion is preferably 90 mol% or more, more preferably 95 mol% or more.

In such a high silver chloride emulsion, a structure having a localized silver bromide phase in the inside and / or on the surface of the silver halide grains as described above is preferable. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content,
More preferably, it is more than mol%. These localized phases can be present inside the particles, on the edges, corners, or on the surface of the particles, and one preferable example thereof is that epitaxially grown on the corners of the particles.

On the other hand, in order to suppress the sensitivity decrease when the light-sensitive material is subjected to pressure as much as possible, even in a high silver chloride emulsion having a silver chloride content of 90 mol% or more, a uniform structure having a small distribution of halogen composition in the grain is obtained. It is also preferable to use the particles.

It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of the circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable.

The particle size distribution is preferably so-called monodisperse with a coefficient of variation (standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodisperse emulsion by blending it in the same layer, or to perform multi-layer coating.

The shape of the silver halide grains contained in the photographic emulsion has a regular crystal form such as a cube, a tetradecahedron or an octahedron, a spherical or plate-like shape. Those having an irregular crystal form or those having a composite form of these can be used.
It may also be a mixture of those having various crystal forms. Among these, 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained.

In addition to these, an emulsion in which tabular grains having an average aspect ratio (circular equivalent diameter / thickness) of 5 or more, preferably 8 or more exceeds 50% of the total grain as a projected area is also preferably used. it can.

The silver chlorobromide emulsion used in the present invention is P. Glafk
by ides Chimie at Phisique Photographique (Paul Mont
published by el, 1967), by GF Duffin Photographic
Emulsion Chemistry (Focal Press, 1966
, VL Zelikman et al Making and Coating Pho
tographic Emulsion (Focal Press, 1964
Year) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a format for reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

In the silver halide emulsion used in the present invention, various polyvalent metal ion impurities can be introduced in the process of emulsion grain formation or physical ripening. Examples of compounds used include salts of cadmium, zinc, lead, copper, thallium, etc., or salts or complex salts of Group VIII elements iron, ruthenium, rhodium, palladium, osmium, iridium, platinum and the like. it can.
Particularly, the above Group VIII elements can be preferably used.
The addition amount of these compounds is wide depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol with respect to the silver halide.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized.

In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. .. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity and a spectral sensitizing dye. The spectral sensitizing dye used at this time is, for example, Heterocycl by FM Harmer.
ic compounds-Cyanine dyes and related compounds (J
ohn Wiley & Sons New York, London, 1964
Year)). Specific examples of the compound and the spectral sensitization method are described in the above-mentioned JP-A-6-63.
Those described on page 22, upper right column to page 38 of JP-A-2-215272 are preferably used.

The silver halide emulsion of the present invention is preferably subjected to gold sensitization known in the art. By performing gold sensitization, it is possible to further reduce fluctuations in photographic performance during scanning exposure with laser light.

To perform the gold sensitization referred to in the present invention, compounds such as chloroauric acid or a salt thereof, gold thiocyanate or gold thiosulfate can be used. The addition amount of these compounds may vary in a wide range depending on the case, but it is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per mol of silver halide. Is. These compounds are added until the chemical sensitization used in the present invention is completed.

In the present invention, gold sensitization is performed by another sensitization method,
For example, it is also preferably combined with sulfur sensitization, selenium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound.

The silver halide emulsion used in the present invention includes various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of Japanese Patent No. 15272 are preferably used.

The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface.

In the present invention, since a semiconductor laser is used as a light source for digital exposure, it is necessary to efficiently spectrally sensitize the infrared region.

In particular, for spectral sensitization in the region of 700 nm or more, a sensitizing dye represented by the general formulas (QI), (Q-II) and (Q-III) shown in Chemical formula 1 is selected and used. be able to. These sensitizing dyes are relatively stable chemically, are relatively strongly adsorbed on the surface of silver halide grains, and are strongly resistant to desorption by a coexisting dispersion such as a coupler.

[0078]

[Chemical 1]

The general formulas (Q-I) and (Q-
The sensitizing dyes represented by II) and (Q-III) will be described in detail.

In formula (Q-I), Z ₆₁ and Z ₆₂ each represent an atomic group necessary for forming a heterocyclic nucleus.

The heterocyclic nucleus is a 5- or 6-membered ring nucleus containing a nitrogen atom as a hetero atom and optionally a sulfur atom, an oxygen atom, a selenium atom or a tellurium atom (these rings may be further bonded with a condensed ring). May be present, and further may have a substituent bonded thereto).

Specific examples of the above-mentioned heterocyclic nucleus include thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus and imidazole. Nucleus, benzimidazole nucleus, naphthimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus,
Examples thereof include a benzindolenine nucleus, an indole nucleus, a tellurazole nucleus, a benzoterrazole nucleus, and a naphthotellurazole nucleus.

R ₆₁ and R ₆₂ are each an alkyl group,
It represents an alkenyl group, an alkynyl group or an aralkyl group. Each of these groups and the groups described below is used in the meaning including the substituted form. For example, when an alkyl group is taken as an example, it includes an unsubstituted alkyl group and a substituted alkyl group, and these groups may be linear, branched or cyclic. The alkyl group preferably has 1 to 8 carbon atoms.

Specific examples of the substituent of the substituted alkyl group include halogen atom (chlorine, bromine, fluorine, etc.), cyano group, alkoxy group, substituted or unsubstituted amino group, carboxylic acid group, sulfonic acid group, hydrogen. A group and the like may be mentioned, and one or more of these may be combined and substituted.

A specific example of the alkenyl group is a vinylmethyl group.

Specific examples of the aralkyl group include a benzyl group and a phenethyl group.

M ₆₁ represents a positive number of 1, 2 or 3.

R ₆₃ represents a hydrogen atom, R ₆₄ represents a hydrogen atom,
In addition to representing a lower alkyl group or an aralkyl group, it can be linked to R ₆₂ to form a 5- to 6-membered ring. Also R
_{When 64} represents a hydrogen atom, R ₆₃ may _combine with another R ₆₃ to form a hydrocarbon ring or a heterocycle. These rings are preferably 5- or 6-membered rings. j ₆₁ and k ₆₁ represent 0 or 1, X ₆₁ represents an acid anion, and n ₆₁ represents 0 or 1.

In the general formula (Q-II), Z ₇₁ and Z ₇₂ have the same meanings as Z ₆₁ and Z _{62 in} the general formula (Q-I).

R ₇₁ and R ₇₂ are R _{61 of} the general formula (QI),
It is synonymous with R ₆₂ and j ₇₁ , k ₇₁ , X ₇₁ and n ₇₁ are synonymous with j ₆₁ , k ₆₁ , X ₆₁ and n _{61 of the} general formula (Q-I), respectively. R ₇₃ represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group (eg, a substituted or unsubstituted phenyl group). m ₇₁ represents 2 or 3. R ₇₄ represents a hydrogen atom, a lower alkyl group or an aryl group, and R ₇₄ and another R ₇₄ may be linked to each other to form a hydrocarbon ring or a heterocycle. These rings are preferably 5- or 6-membered rings.

Q ₇₁ represents a sulfur atom, an oxygen atom, a selenium atom or = N-R ₇₅ , and R ₇₅ has the same _meaning as R ₇₃ .

In the general formula (Q-III), Z ₈₁ represents an atomic group necessary for forming a heterocycle. As this heterocycle, Z
₆₁ and Z ₆₂ , and specific examples thereof include other thiazolidine, thiazoline, benzothiazoline,
Cores such as naphthothiazoline, selenazolidine, selenazoline, benzoselenazoline, naphthoselenazoline, benzoxazoline, naphthoxazoline, dihydropyridine, dihydroquinoline, benzimidazoline, and naphthoimidazoline can be mentioned.

Q ₈₁ has the same meaning as Q ₇₁ . R ₈₁ has the same _meaning as R ₆₁ or R ₆₂ , and R ₈₂ has the same _meaning as R ₇₃ . m ₈₁ is 2
Or represents 3. R ₈₃ has the same _meaning as R _74, and R ₈₃ may _combine with another R ₈₃ to form a hydrocarbon ring or a heterocycle. j ₈₁ is synonymous with j ₆₁ .

In the general formula (QI), Z ₆₁ and /
Alternatively, a sensitizing dye whose Z ₆₂ heterocyclic nucleus has a naphthothiazole nucleus, a naphthoselenazole nucleus, a naphthoxazole nucleus, a naphthimidazole nucleus, and a 4-quinoline nucleus is particularly preferable. Z ₇₁ and / or Z in the general formula (Q-II)
_The same applies to ₇₂ and the general formula (Q-III). Further, a sensitizing dye in which a methine chain forms a hydrocarbon ring or a heterocycle is preferable.

Since infrared sensitization uses sensitization of the sensitizing dye in the M band, the spectral sensitization distribution is generally broader than that in the J band. Therefore, it is preferable to provide a coloring layer containing a dye in the colloid layer on the photosensitive surface side of the predetermined photosensitive layer to correct the spectral sensitivity distribution. This colored layer is effective in preventing color mixing due to the filter effect.

As the sensitizing dye for infrared sensitization, a compound having a reduction potential of -1.05 (VvsSCE) or a base value lower than that is preferable, and a reduction potential of -1.
Compounds with a value of 10 or less are preferred. The sensitizing dye having this property is advantageous for high sensitivity, particularly for stabilizing sensitivity and latent image.

The reduction potential can be measured by phase discrimination type second harmonic alternating current polarography. The working electrode is a mercury dropping electrode, the reference electrode is a saturated calomel electrode, and the counter electrode is platinum.

Further, the measurement of the reduction potential by the phase discrimination second harmonic AC voltammetry using platinum as the working electrode is performed in “Journal of Imaging Science” (Jou
rnal of Imaging Science), Vol. 30, pp. 27-35 (1986).

Specific examples of the sensitizing dye that can be used in the present invention include JP-A-2-157749, page 8, lower left column, first column.
From line 1 to page 13, right lower column, second line. In addition to those described here, the compounds shown in Chemical formulas 2 to 19 can also be used.

In Chemical Formulas 2 to 19, Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group, and PT
S ⁻ represents a paratoluenesulfonate ion.

[0101]

[Chemical 2]

[0102]

[Chemical 3]

[0103]

[Chemical 4]

[0104]

[Chemical 5]

[0105]

[Chemical 6]

[0106]

[Chemical 7]

[0107]

[Chemical 8]

[0108]

[Chemical 9]

[0109]

[Chemical 10]

[0110]

[Chemical 11]

[0111]

[Chemical 12]

[0112]

[Chemical 13]

[0113]

[Chemical 14]

[0114]

[Chemical 15]

[0115]

[Chemical 16]

[0116]

[Chemical 17]

[0117]

[Chemical 18]

[0118]

[Chemical 19]

To incorporate these spectral sensitizing dyes in the silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. In addition, Japanese Patent Publication No.
No. 389, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 57-2
As described in 2089 or the like, an acid or a base is allowed to coexist to prepare an aqueous solution, or as described in US Pat. No. 3,822,135 or US Pat. You may add things to an emulsion. Alternatively, the emulsion may be dissolved in a solvent which is substantially immiscible with water such as phenoxyethanol and then dispersed in water or a hydrophilic colloid to add to the emulsion.
JP-A-53-102733, JP-A-58-10514
Direct dispersion in hydrophilic colloid as described in No. 1,
The dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of chemical sensitization and before coating, but as described in US Pat. Nos. 3,628,969 and 4,225,666, the chemical sensitizer is added at the same time as the spectral sensitization. It is also possible to carry out the sensation simultaneously with the chemical sensitization.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. It is also possible to add the spectral sensitizing dyes separately, as taught in U.S. Pat. No. 4,225,666, i.e. some prior to chemical sensitization and the rest after chemical sensitization. It is possible and can be at any time during silver halide grain formation including the method taught in US Pat. No. 4,183,756. Among these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 * 10 < ^-6 > mol to 5.0 * 10.
^-3 mol range.

In the red or infrared sensitization of the present invention, M band type sensitization is particularly described in JP-A-2-157749, page 13, lower right column, line 3 to page 22, lower right column, lower line 3. Supersensitization with the compounds described is effective.

In the light-sensitive material of the present invention, it is preferable to use a color image preserving improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or after the color development processing. It is possible to use the compound (G), which is chemically bonded to the remaining oxidant of the aromatic amine color developing agent to form a chemically inactive and substantially colorless compound, simultaneously or alone, for example, after processing. Is preferable in preventing stain generation and other side effects due to the formation of a coloring dye by the reaction of the coupler with the color developing agent remaining in the film or the oxidant thereof during storage.

Further, in the light-sensitive material of the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the mold-proofing as described in JP-A-63-271247. It is preferable to add an agent.

In the present invention, dyes may be used for improving the image quality such as sharpness. Specific examples of such dyes include the compounds shown in Chemical formulas 20 to 34.

[0126]

[Chemical 20]

[0127]

[Chemical 21]

[0128]

[Chemical formula 22]

[0129]

[Chemical formula 23]

[0130]

[Chemical formula 24]

[0131]

[Chemical 25]

[0132]

[Chemical formula 26]

[0133]

[Chemical 27]

[0134]

[Chemical 28]

[0135]

[Chemical 29]

[0136]

[Chemical 30]

[0137]

[Chemical 31]

[0138]

[Chemical 32]

[0139]

[Chemical 33]

[0140]

[Chemical 34]

As the support used in the present invention, a transparent film such as a cellulose nitrate film or polyethylene terephthalate, which is usually used in a photographic light-sensitive material, or a reflective support can be used. For the purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention is one which enhances the reflectivity to make the dye image formed on the silver halide emulsion layer clear, and such a reflective support includes
A support coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate, or a support using a hydrophobic resin containing a light-reflecting substance dispersed therein. Is included. For example, baryta paper, polyethylene-coated paper, polypropylene-based synthetic paper, a transparent support provided with a reflective layer or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, polyester film of cellulose triacetate or cellulose nitrate, polyamide There are films, polycarbonate films, polystyrene films, vinyl chloride resins and the like.

As the other reflection type support, a support having a specular reflection or type II diffuse reflection metal surface can be used. The metal surface preferably has a spectral reflectance in the visible wavelength range of 0.5 or more, and the metal surface is preferably roughened or made to be diffuse reflective by using a metal powder. Aluminum, tin, silver, magnesium, or an alloy thereof is used as the metal, and the surface may be the surface of a metal plate, metal foil, or metal thin layer obtained by rolling, vapor deposition, or plating. Of these, it is preferable to obtain the metal by vapor deposition on another substrate. It is preferable to provide a water resistant resin, particularly a thermoplastic resin layer, on the metal surface. An antistatic layer may be provided on the side of the support opposite to the side having the metal surface. Details of such a support are described in, for example, JP-A-61-161.
No. 210346, No. 63-24247, No. 63-24
251 and 63-24255.

These supports can be appropriately selected depending on the purpose of use.

As the light-reflecting substance, it is preferable to sufficiently knead a white pigment in the presence of a surfactant, and it is preferable to use a pigment particle whose surface is treated with a divalent to tetravalent alcohol.

The occupied area ratio (%) of the white pigment fine particles per defined unit area is most typically the observed area is divided into contiguous 6 μm × 6 μm unit areas,
Occupied area ratio of fine particles projected on the unit area (%)
(R _i ) can be measured and obtained. The variation coefficient of the occupied area ratio (%) is R _i with respect to the average value (R) of R _i.
Can be obtained by the ratio s / R of the standard deviation s of.
The number (n) of the target unit areas is preferably 6 or more.
Therefore, the variation coefficient s / R can be obtained by the equation 1.

[0147]

[Equation 1]

In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is preferably 0.15 or less, more preferably 0.12 or less. When it is 0.08 or less, the dispersibility of the particles can be said to be “uniform”.

The support used in the light-sensitive material of the present invention is a support in which a white polyester support or a layer containing a white pigment is provided on the support having a silver halide emulsion layer for display. The body may be used. Further, in order to improve the sharpness, it is preferable to coat an antihalation layer on the side of the support coated with the silver halide emulsion layer or on the back surface. In particular, the transmission density of the support is set to 0. so that the display can be viewed with both reflected light and transmitted light.
It is preferably set in the range of 35 to 0.8.

The exposed light-sensitive material can be subjected to a conventional color development process. The color development process of the present invention is preferably a rapid process, and more preferably an ultra rapid process. In the case of a color photographic light-sensitive material, it is preferable to perform bleach-fixing after color development for the purpose of rapid processing. Particularly when the above-mentioned high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied to the light-sensitive material in the present invention, and the processing method applied for processing the light-sensitive material, Examples of the processing additive include the patent publications shown in Tables 2 to 6, particularly European Patent EP 0,355,660A.
What is described in the specification of No. 2 (Japanese Patent Application No. 1-107011) is preferably used.

[0152]

[Table 2]

[0153]

[Table 3]

[0154]

[Table 4]

[0155]

[Table 5]

[0156]

[Table 6]

Further, as a cyan coupler, JP-A-2-
In addition to the diphenylimidazole type cyan coupler described in Japanese Patent No. 33144, European Patent EP 0,333,185
The 3-hydroxypyridine type cyan couplers described in A2 specification (among these, couplers (42) listed as specific examples, which are 4-equivalent couplers with a chlorine leaving group to make them 2-equivalent, couplers (6) and (9) is particularly preferable) and cyclic active methylene cyan couplers described in JP-A-64-32260 (coupler examples 3, 8, and 34 listed as specific examples are particularly preferable) are also preferably used. ..

The processing temperature of the color developing solution applicable to the present invention is 20 to 50 ° C, preferably 30 to 45 ° C.
The processing time is preferably substantially 20 seconds or less. It is preferable that the amount of replenishment is small, but 20 per 1 m ^{2 of} light-sensitive material
~ 600 ml is suitable, preferably 50-300 ml. It is more preferably 60 to 200 ml, most preferably 60 to 150 ml.

In the present invention, the development time is preferably 45 seconds or less. Further, it can be preferably applied to a rapid processing which is substantially within 20 seconds. The term "substantially 20 seconds" as used herein means that when the photosensitive material enters the developer tank,
It refers to the time until the photosensitive material enters the next tank, and includes the transit time in the air from the developer tank to the next tank.

The pH of the washing step or stabilizing step is preferably 4-10, more preferably 5-8. Although the temperature can be set variously depending on the use and characteristics of the light-sensitive material, it is generally 30 to 45 ° C, preferably 35 to 42 ° C. The time can be set arbitrarily, but a shorter time is preferable from the viewpoint of reducing the processing time. It is preferably 10 to 45 seconds, more preferably 10 to 40 seconds. The smaller the replenishment amount, the more preferable from the viewpoints of running cost, reduction of discharge amount, handling and the like.

A specific preferable amount of replenishment is 0.5 to 50 of the amount carried from the prebath per unit area of the light-sensitive material.
Times, preferably 2 to 15 times. Or photosensitive material 1 m ²
It is 300 ml or less, preferably 150 ml or less.
The replenishment may be performed continuously or intermittently.

The liquid used in the washing and / or stabilizing step can be further used in the previous step. An example of this is that the overflow of washing water reduced by the multi-stage countercurrent method is caused to flow into the bleach-fixing bath of the preceding bath, and the bleach-fixing bath is replenished with a concentrated liquid to reduce the amount of waste liquid.

Next, the drying process usable in the present invention will be described.

A drying time of 20 to 40 seconds is desired in order to complete an image by the ultra-rapid processing of the present invention. As a means for reducing the drying time, as a means on the side of the light-sensitive material, it is possible to improve by reducing the amount of water taken into the film by reducing the amount of a hydrophilic binder such as gelatin. Further, from the viewpoint of reducing the carry-on amount, it is possible to accelerate the drying by absorbing the water with a squeeze roller or a cloth immediately after leaving the washing bath. As a means of improvement from the dryer, it is a matter of course that the drying can be accelerated by increasing the temperature or increasing the drying air. Further, the drying can be accelerated by adjusting the blowing angle of the drying air to the photosensitive material and the method of removing the discharged air.

Although the color photographic paper has been described above, it is also preferable to apply a heat-developable color photosensitive material as the photosensitive material used in the image forming method of the present invention. The constitution of the heat-developable color photosensitive material applicable to the present invention will be described below.

The heat-developable color light-sensitive material which can be used in the present invention basically has a light-sensitive silver halide, a dye-donor compound and a binder on a support. These components are often added to the same layer, but if they are in a reactive state, they can be added separately to separate layers. For example, when the dye-donating compound in the case of being colored is present below the silver halide emulsion-containing layer, the reduction in sensitivity can be prevented.

In order to obtain a wide range of colors on the chromaticity diagram by using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are used in combination. .. For example, a combination of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer, a combination of a green-sensitive layer, a red-sensitive layer and an infrared-sensitive layer, or a red-sensitive layer, a first infrared-sensitive layer,
For example, there is a combination of the second infrared sensitive layers. Each of the light-sensitive layers can take various arrangement orders known in a normal color light-sensitive material. Further, each of these photosensitive layers may be divided into two or more layers if necessary.

The silver halide usable in the heat-developable color light-sensitive material which can be used in the present invention is silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, chloroiodobromide. Any of silver may be used.

The silver halide emulsion used in the present invention may be either a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or an optical fogging. Further, it may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases. The silver halide emulsion may be monodisperse or polydisperse, and monodisperse emulsions may be mixed and used. The particle size is preferably 0.1 to 2 µ, and particularly preferably 0.2 to 1.5 µ. The crystal habit of the silver halide grains may be cubic, octahedral, tetrahedral, flat with a high aspect ratio, or any other form.

Specifically, US Pat. No. 4,500,626, column 50, US Pat. No. 4,628,012, Research Disclosure (hereinafter abbreviated as RD) 17029 (19).
1978), any of the silver halide emulsions described in JP-A No. 62-253159 and the like can be used.

The silver halide emulsion may be used as it is in an unripened state, but it is usually used after being chemically sensitized. The known sulfur sensitizing method, reduction sensitizing method, noble metal sensitizing method and the like can be used alone or in combination for the emulsion for a conventional type light-sensitive material.
These chemical sensitizations can also be carried out in the presence of a nitrogen-containing heterocyclic compound (JP-A-62-253159).

The coating amount of the photosensitive silver halide used in the present invention is in the range of 1 mg / m ² to 10 g / m ^{2 in} terms of silver.

The silver halide used in the present invention may be spectrally sensitized with methine dyes and the like. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes.

Specifically, US Pat. No. 4,617,257
No. 59-180550, 60-14033.
No. 5, RD17029 (1978) pages 12 to 13 and the like.

Further, the sensitizing dye described in the above-mentioned constitution of the color photographic paper can be mentioned as a specific example.

These sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization.

Along with the sensitizing dye, a dye having no spectral sensitizing effect by itself or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Patent No. 3615641, Japanese Patent Application No. 6
No. 1-222694, etc.).

These sensitizing dyes may be added to the emulsion at the time of chemical ripening or before or after the chemical ripening, or before or after the nucleation of silver halide grains according to US Pat. Nos. 4,183,756 and 4,225,666. The addition amount is generally about 10 ^-8 to 10 ^-2 mol per mol of silver halide.

In the heat-developable color light-sensitive material used in the present invention, an organic metal salt can be used as an oxidizing agent together with the light-sensitive silver halide. The use of an organic metal salt is particularly preferable in the photothermographic element. Among such organic metal salts, organic silver salts are particularly preferably used.

Organic compounds that can be used to form the above organic silver salt oxidizing agent include those described in US Pat. No. 4,500,626.
There are benzotriazoles, fatty acids and other compounds described in Nos. 52 to 53 and the like. In addition, JP-A-60-1132
No. 35, a silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate, and JP-A-61-249.
Acetylene silver described in No. 044 is also useful. Two or more kinds of organic silver salts may be used in combination. The above organic silver salt is used in an amount of 0.01 to 10 mol per mol of photosensitive silver halide.
Preferably 0.01 to 1 mol can be used in combination. The total coating amount of the photosensitive silver halide and the organic silver salt is preferably 50 mg / m ² to 10 g / m ² in terms of silver.

Various antifoggants or photographic stabilizers can be used in the invention. Examples thereof include azoles and azaindenes described on pages 24 to 25 of RD17643 (1978), JP-A-59-1684.
42-containing nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, mercapto compounds and metal salts thereof described in JP-A-59-111636, acetylene compounds described in JP-A-62-87957 and the like can be used.

As the reducing agent used in the present invention, those known in the field of diffusion transfer type color light-sensitive materials can be used. Further, a dye-donor compound having a reducing property described later is also included (in this case, other reducing agents can be used together). Further, a reducing agent precursor which has no reducing property by itself but exhibits a reducing property by the action of a nucleophile, an alkali or heat during the development process can be used.

Examples of the reducing agent used in the present invention include:
U.S. Pat. No. 4,500,626, columns 49-50, 44
No. 83, col. 30, columns 31-43617;
No. 4,590,152, JP-A No. 60-140335, pages (17) to (18), Nos. 57-40245, 56.
-138736, 59-178458, 59-
No. 53831, No. 59-182449, No. 59-18
No. 2450, No. 60-119555, No. 60-128
436 to 60-128439, 60-1
No. 98540, No. 60-181742, No. 61-25.
9253, 624244044, 62-131
From 253 to 62-131256, there are reducing agents and reducing agent precursors described in EP 220746A2, pages 78 to 96, and the like.

Combinations of various reducing agents such as those disclosed in US Pat. No. 3,039,869 can also be used.

When a diffusion resistant reducing agent is used, if necessary, an electron transfer agent and / or an electron transfer agent may be added in order to promote electron transfer between the diffusion resistant reducing agent and the developable silver halide.
Alternatively, an electron transfer agent precursor can be used in combination.

The electron transfer agent or its precursor can be selected from the above-mentioned reducing agents or its precursors. It is desirable that the electron transfer agent or the precursor thereof has a mobility higher than that of the diffusion resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3-
It is a pyrazolidone or an aminophenol.

The diffusion-resistant reducing agent (electron donor) used in combination with the electron transfer agent may be any of those reducing agents which do not substantially move in the layer of the photosensitive element.
Hydroquinones, sulfonamide phenols, sulfonamide naphthols, JP-A-53-11 are preferred.
Examples thereof include compounds described as electron donors in No. 0827, and dye-donating compounds having diffusion resistance and reducing properties described below.

In the present invention, the reducing agent is added in an amount of 0.001 to 20 mol, and particularly preferably 0.1 to 20 mol, based on 1 mol of silver.
It is from 01 to 10 mol.

As an example of the dye-donating compound used in the heat-developable color light-sensitive material which can be used in the present invention, first, a compound (coupler) which forms a dye by an oxidative coupling reaction can be mentioned. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. A 2-equivalent coupler having a diffusion resistant group as a leaving group and forming a diffusible dye by an oxidative coupling reaction is also preferable. This nondiffusible group may form a polymer chain. For specific examples of color developers and couplers, see TH James “The Theory of the
Photographic Process ", 4th edition, pages 291-334, and pages 354-361, JP-A-58-123533, 58-149046, 58-149047, 5;
9-111148, 59-124399, 59
-174835, 59-231539, 59-
231540, 60-2950, 60-295.
1, No. 60-14242, No. 60-23474,
No. 60-66249 and the like.

As another example of the dye-donating compound,
Examples thereof include compounds having a function of releasing or diffusing a diffusible dye imagewise. This type of compound can be represented by the following general formula [LI].

(Dye-Y) n-Z [LI]

Dye represents a dye group, a temporarily shortened dye group or a dye precursor group, Y represents a simple bond or linking group, and Z represents a photosensitive silver salt having an imagewise latent image. Or, conversely, a difference is caused in the diffusivity of the compound represented by (Dye-Y) n-Z, or Dye is released and the released Dye and (Dye-Y) n-Z Represents a group having a property of causing a difference in diffusibility between them, n represents 1 or 2, and when n is 2, two Dye-Y may be the same or different.

Specific examples of the dye donating compound represented by the general formula [LI] include the following compounds (1) to (4). The following items (1) to (5) are for forming a diffusible dye image (positive dye image) in the opposite manner to the development of silver halide, and "and" are the diffusible dye image (corresponding to the development of silver halide). To form a negative dye image).

US Pat. Nos. 3,134,764 and 336.
2819, 3597200, and 3544545.
No. 3,482,972 and the like, a dye developer in which a hydroquinone-based developer and a dye component are linked. This dye developing agent is diffusible in an alkaline environment, but becomes non-diffusible when it reacts with silver halide.

As described in US Pat. No. 4,053,137, a non-diffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. Examples thereof include compounds that release a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, and US Pat. No. 4,199.
Compounds that release a diffusible dye by an intramolecular rewinding reaction of the isoxazolone ring described in JP-A No. 354, etc.

US Patent No. 4,559,290, European Patent No. 220746A2, US Patent No. 4,783,396,
As described in Published Technical Report 87-6199, a non-diffusible compound which releases a diffusible dye by reacting with a reducing agent left unoxidized by development can also be used.

As an example thereof, US Pat. No. 4,133,938.
No. 9, 4139379, JP-A-59-185333.
Nos. 57-84453 and the like, which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction, US Pat. No. 4,232,107, JP-A-59
No. 101649, No. 61-88257, RD240
25 (1984) and the like, which release a diffusible dye by intramolecular electron transfer reaction after reduction, West German Patent No. 3008588A, JP-A-56-14.
2530, US Pat. Nos. 4,343,893 and 4619.
Compounds which release a diffusible dye by cleavage of a single bond after reduction as described in US Pat.
Examples thereof include nitro compounds described in U.S. Pat. No. 223 and the like that release a diffusible dye after electron acceptance, compounds described in U.S. Pat. No. 4,609,610 and the like that release a diffusible dye after electron acceptance.

Further, as more preferable ones, European Patent No. 220746A2, Kokai Giho No. 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-201653.
No. 63, 2016-654, etc.
A compound having an -X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, Japanese Patent Application No. 62-106885.
No. ₂ within one molecule of SO ₂ -X (X is as defined above)
And a compound having an electron-withdrawing group, JP-A-63-2713
A compound having a PO-X bond (X has the same meaning as described above) and an electron-withdrawing group in one molecule described in JP-A-44-
The compound having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule described in No. 271341.

Of these, a compound having an N—X bond and an electron-withdrawing group in one molecule is particularly preferable. Specific examples thereof include the compound (1) described in EP 220746A2.
~ (3), (7) to (10), (12), (13),
(15), (23) to (26), (31), (32),
(35), (40), (41), (44), (53)-
(59), (64), (70), Public Technical Report 87-619
No. 9 compounds (11) to (23) and the like.

A compound (DDR coupler) which is a coupler having a diffusible dye as a leaving group and which releases the diffusible dye by a reaction with an oxidized form of a reducing agent. Specifically, British Patent No. 1330524, Japanese Patent Publication No. 48-39165, US Patent Nos. 3443940, 4474867, and 448.
3914 and the like.

A compound (DRR compound) which is reducible to a silver halide or an organic silver salt and releases a diffusible dye when its partner is reduced. Since this compound does not need to use any other reducing agent, it is preferable because there is no problem of image contamination due to oxidative decomposition products of the reducing agent. Typical examples thereof are U.S. Pat. Nos. 3,928,312, 40,53312, and 405.
No. 5428, No. 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113, and 3,443.
939, JP-A-58-116537, and JP-A-57-17.
9840, U.S. Pat. No. 4,500,626 and the like. Specific examples of the DRR compound include the compounds described in the above-mentioned U.S. Pat. No. 4,500,626, columns 22 to 44. Among them, the compounds (1) to (3) described in the above-mentioned U.S. Pat. (10) to (13), (1
6) to (19), (28) to (30), (33) to (3
5), (38) to (40) and (42) to (64) are preferable. The compounds described in US Pat. No. 4,639,408, columns 37 to 39 are also useful.

Other than the above-mentioned couplers and dye-providing compounds other than the general formula [LI], dye silver compounds in which an organic silver salt and a dye are bound (Research Disclosure, May 1978, pp. 54-58). , Etc., azo dyes used in the heat-development silver dye bleaching method (US Pat.
957, Research Disclosure, 1976.
April issue, pages 30 to 32), leuco dyes (US Pat. Nos. 3,985,565 and 4,022,617), and the like can be used.

Hydrophobic additives such as dye-donor compounds and antidiffusive reducing agents can be incorporated into the layer of the photographic material by known methods such as the method described in US Pat. No. 2,322,027. In this case, JP-A-59-83154,
59-178451, 59-178452, 59-178453, 59-178454, 5
9-178455, 59-178457 and the like, a high boiling point organic solvent, if necessary, a boiling point of 50 ° C.
It can be used in combination with an organic solvent having a low boiling point of up to 160 ° C.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, relative to 1 g of the dye-donor compound used. Also, 1 cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less is suitable for 1 g of the binder.

JP-B-51-39853, JP-A-51-
A dispersion method using a polymer described in 59943 can also be used.

In the case of a compound which is substantially insoluble in water, fine particles can be dispersed and contained in a binder in addition to the above method.

When the hydrophobic compound is dispersed in the hydrophilic colloid as the binder, various surfactants can be used. For example, the surfactants listed on pages (37) to (38) of JP-A-59-157636 can be used.

In the present invention, a compound capable of activating development and stabilizing an image at the same time can be used in the light-sensitive material. The specific compounds preferably used are described in US Pat. No. 4,500,626, columns 51 to 52.

In the present invention, in the case of a system for forming an image by diffusion transfer of a dye, a dye fixing material is used together with the light-sensitive material. The dye fixing material may be applied separately on a support different from the photosensitive material, or may be applied on the same support as the photosensitive material. The relationship between the light-sensitive material and the dye-fixing material, the relationship with the support, and the relationship with the white reflective layer are described in US Pat.
The relationships described in column 7 can be applied to the present application.

The dye fixing material preferably used in the present invention has at least one layer containing a mordant and a binder. As the mordant, those known in the photographic field can be used, and specific examples thereof include US Pat. No. 4,500,626, columns 58 to 59 and JP-A No. 61-88256 (32).
The mordant described on page (41), JP-A-62-244043.
No. 62-244036 and the like. Further, a dye-receptive polymer compound as described in US Pat. No. 4,463,079 may be used.

If necessary, the dye fixing material may be provided with auxiliary layers such as a protective layer, a peeling layer and an anti-curl layer. In particular, it is useful to provide a protective layer.

A hydrophilic binder is preferably used as the binder of the constituent layers of the light-sensitive material and the dye-fixing material. As an example thereof, pages (26) to (2) of JP-A-62-253159.
8) The thing described in page is mentioned. Specifically, a transparent or translucent hydrophilic binder is preferable, and for example, gelatin, proteins such as gelatin derivatives or cellulose derivatives, natural compounds such as polysaccharides such as starch, gum arabic, dextran and pullulan, and polyvinyl alcohol, Examples thereof include polyvinylpyrrolidone, acrylamide polymer, and other synthetic polymer compounds. Furthermore, superabsorbent polymers described in JP-A-62-245260, i.e. -COOM or -SO ₃ M (M is a hydrogen atom or an alkali metal) homopolymer or a vinyl monomer together or with other vinyl monomers with A copolymer with a vinyl monomer (for example, sodium methacrylate, ammonium methacrylate, Sumika Gel L-5H manufactured by Sumitomo Chemical Co., Ltd.) is also used. These binders can be used in combination of two or more.

When a system in which a small amount of water is supplied for thermal development is adopted, it becomes possible to quickly absorb water by using the above superabsorbent polymer.
Further, when the super absorbent polymer is used in the dye fixing layer or its protective layer, the dye can be prevented from being retransferred from the dye fixing material to another after the transfer.

In the heat-developable color light-sensitive material which can be used in the present invention, the coating amount of the binder is ² per 1 m 2.
It is preferably 0 g or less, particularly 10 g or less, and more preferably 7 g or less.

As the hardener used for the constituent layers of the light-sensitive material and the dye-fixing material, US Pat. No. 4,678,739, No. 41
Column, JP-A-59-116655 and JP-A-62-24526.
The hardeners described in No. 1 and No. 61-18942 are listed. More specifically, aldehyde hardeners (formaldehyde etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide)) Ethane), N-
Examples thereof include methylol type hardeners (such as dimethylol urea) and polymer hardeners (compounds described in JP-A-62-234157).

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye-fixing material.
The image forming accelerator includes a redox reaction between a silver salt oxidizing agent and a reducing agent, a reaction such as generation of a dye from a dye-donor substance, decomposition of the dye or release of a diffusible dye, and a light-sensitive material layer. Has a function of promoting the transfer of the dye from the dye to the dye fixing layer, and from the physicochemical function, it is a base or a base precursor, a nucleophilic compound, a high boiling organic solvent (oil), a thermal solvent, a surfactant, silver. Alternatively, they are classified into compounds that interact with silver ions. However, these substance groups generally have a composite function, and usually have some of the above-mentioned accelerating effects together. These details are described in US Pat. No. 4,678,739, columns 38 to 40.

Examples of the base precursor include salts of organic acids and bases that are decarboxylated by heat, compounds that release amines by intramolecular nucleophilic substitution reaction, Rossen rearrangement or Beckmann rearrangement. A specific example is US Pat. No. 45114.
93, JP-A-62-65038 and the like.

In a system in which heat development and dye transfer are carried out simultaneously in the presence of a small amount of water, it is preferable to add a base and / or a base precursor to the dye-fixing material in order to improve the storability of the light-sensitive material.

In addition to the above, European Patent Publication 210660
And US Pat. No. 4,740,445, a combination of a sparingly soluble metal compound and a compound capable of complex-forming reaction with a metal ion constituting the sparingly soluble metal compound (referred to as a complex-forming compound), and JP-A-61-232451. Compounds that generate a base by electrolysis as described in No. 1 can also be used as the base precursor. The former method is particularly effective. It is advantageous to add the hardly soluble metal compound and the complex-forming compound separately to the light-sensitive material and the dye-fixing material.

In the heat-developable color light-sensitive material and / or dye-fixing material of the present invention, various development stoppers may be used for the purpose of always obtaining a constant image against variations in processing temperature and processing time during development. it can.

The term "development terminator" used herein means, after proper development,
A compound that rapidly neutralizes or reacts with a base to lower the concentration of the base in the film to stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples thereof include acid precursors that release an acid upon heating, electrophilic compounds that undergo a substitution reaction with a coexisting base upon heating, or nitrogen-containing heterocyclic compounds, mercapto compounds and precursors thereof. For more details, see JP-A-62-2531.
No. 59 (31) to (32).

The constituent layers (including the back layer) of the light-sensitive material or the dye-fixing material are used for the purpose of improving physical properties of the film such as dimensional stabilization, curl prevention, adhesion prevention, film cracking prevention and pressure increase / decrease prevention. Various polymer latices can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, 62-110066 and the like can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used in the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used in the back layer, a curl preventing effect can be obtained. ..

In the constituent layers of the light-sensitive material and the dye-fixing material, a high-boiling organic solvent can be used as a plasticizer, a slipping agent, or an agent for improving the releasability of the light-sensitive material and the dye-fixing material. Specifically, JP-A-62-253159, (2
5), No. 62-245253 and the like.

Further, various silicone oils (all silicone oils from dimethyl silicone oil to modified silicone oil obtained by introducing various organic groups into dimethylsiloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in “Modified Silicone Oil” technical data P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name X-22-3710) are effective.

Further, JP-A-62-215953 and 63
The silicone oil described in JP-A-46449 is also effective.

An anti-fading agent may be used in the light-sensitive material and the dye-fixing material. As the anti-fading agent, there are, for example, an antioxidant, an ultraviolet absorber, or a metal complex of some kind.

The antioxidants include, for example, chroman compounds, coumaran compounds, phenol compounds (eg hindered phenols), hydroquinone derivatives, hindered amine derivatives and spiroindane compounds. The compounds described in JP-A-61-159644 are also effective.

As the ultraviolet absorber, benzotriazole compounds (US Pat. No. 3,533,794, etc.), 4-
Thiazolidone compounds (US Pat. No. 3,352,681, etc.), benzophenone compounds (JP-A-46-2784)
Etc.) and others, JP-A-54-48535 and JP-A-62-
There are compounds described in Nos. 136641 and 61-88256. Further, the ultraviolet absorbing polymer described in JP-A-62-260152 is also effective.

As the metal complex, US Pat.
55, 42425018, columns 3 to 36, 4254.
195, columns 3 to 8, JP-A-62-174741, JP-A-61-88256, pages (27) to (29), and JP-A-63-1.
No. 99248, Japanese Patent Application Nos. 62-234103 and 62-
There are compounds described in No. 230595 and the like.

Examples of useful anti-fading agents are disclosed in JP-A-62-21.
5272 (125)-(137).

The anti-fading agent for preventing the fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing material in advance, or may be supplied to the dye-fixing material from the outside such as a light-sensitive material. May be.

The above-mentioned antioxidant, ultraviolet absorber and metal complex may be used in combination.

A fluorescent whitening agent may be used in the light-sensitive material and the dye-fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent in the dye fixing material or supply it from the outside such as a light-sensitive material. For example, see “The Chemis” edited by K. Veenkataraman.
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
The compound described in 143752 etc. can be mentioned. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds and the like can be mentioned.

The fluorescent whitening agent can be used in combination with an anti-fading agent.

In the constituent layers of the light-sensitive material and the dye-fixing material, various surfactants can be used for the purpose of coating aid, improvement of releasability, improvement of sliding property, prevention of electrification, acceleration of development and the like. Specific examples of the surfactant are disclosed in JP-A-62-173463.
No. 62-183457 and the like.

The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving slipperiness, preventing electrification, improving releasability and the like. Typical examples of the organic fluoro compounds include Japanese Examined Patent Publication No. 57-9053, columns 8 to 17,
Fluorine-based surfactants described in JP-A Nos. 61-20944 and 62-135826, oil-based fluorine-based compounds such as fluorine oil, and solid fluorine-containing compound resins such as tetrafluoroethylene resin. Hydrophobic fluorine compounds may be mentioned.

A matting agent can be used in the light-sensitive material and the dye-fixing material. Matting agents such as silicon dioxide, polyolefins, polymethacrylates, etc.
Japanese Patent Application No. 62-110064, such as benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like, in addition to the compounds described on page 1-88256 (29).
No. 62-110065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a thermal solvent, a defoaming agent, a fungicide / antifungal agent, colloidal silica and the like. Specific examples of these additives are described in JP-A No. 61-88256, pages (26) to (32).

As the support for the photothermographic material and dye fixing material of the present invention, those which can withstand the processing temperature are used. Generally, paper, synthetic polymer (film)
Is mentioned. Specifically, polyethylene terephthalate (PET), polycarbonate, polyvinyl chloride, polystyrene, polypropylene, polyimide, celluloses (for example, triacetyl cellulose) or those films containing pigments such as titanium oxide, and polypropylene. Film method synthetic paper made from etc., mixed paper made from synthetic resin pulp such as polyethylene and natural pulp, Yankee paper, baryta paper, coated paper (especially Cascote paper), metal, cloth, glass etc. Used.

These can be used alone or
It can also be used as a support having one or both sides laminated with a synthetic polymer such as polyethylene.

In addition, the supports described in JP-A-62-253159, pages (29) to (31) can be used.

On the surface of these supports, a hydrophilic binder and a semiconductive metal oxide such as alumina sol or tin oxide,
You may apply carbon black and other antistatic agents.

When the heat development color light-sensitive material which can be used in the present invention is subjected to the heat development, the heating temperature in the heat development step is about 50 ° C. to about 250 ° C., and the development can be performed at about 80 ° C. About 180 ° C is useful. The dye diffusion transfer process may be performed simultaneously with the heat development, or may be performed after the end of the heat development process. In the latter case, the heating temperature in the transfer step can be transferred in the range from the temperature in the heat development step to room temperature, but it is more preferably 50 ° C. or higher and about 10 ° C. lower than the temperature in the heat development step.

In such a heat-developable color light-sensitive material, the total film thickness of each layer coated on the support is 15 in terms of dry film thickness.
It is preferably μ or less. With such a film thickness, dye transfer is promoted, and an effect of forming an image with excellent sharpness can be obtained.

In the present invention, a solvent may be used to promote dye transfer.

In addition, JP-A-59-218443 and JP-A-6-218443.
As described in detail in No. 1-238056 and the like, for a photothermographic material, a method of performing development and transfer simultaneously or continuously by heating in the presence of a small amount of solvent (particularly water) is also useful.
In this method, the heating temperature is preferably 50 ° C. or higher and not higher than the boiling point of the solvent. For example, when the solvent is water, the temperature is preferably 50 ° C or higher and 100 ° C or lower.

Examples of the solvent used for accelerating the development and / or transferring the diffusible dye to the dye-fixing layer include water or a basic aqueous solution containing an inorganic alkali metal salt or an organic base (these bases). Examples thereof include those described in the section of the image formation accelerator). Further, a low boiling point solvent, or a mixed solution of a low boiling point solvent and water or a basic aqueous solution can be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound, etc. may be contained in the solvent.

These solvents can be used by a method of applying them to the dye fixing material, the photosensitive material or both.
The amount used may be as small as the weight of the solvent corresponding to the maximum swelling volume of the entire coating film or less (particularly the amount of the solvent corresponding to the maximum swelling volume of the entire coating film less the weight of the total coating film).

As a method of applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, the method described in JP-A-61-147244, page (26). Further, the solvent may be contained in a microcapsule or the like in advance and incorporated in the light-sensitive material or the dye-fixing material or both.

Further, in order to promote dye transfer, a method in which a hydrophilic thermal solvent which is solid at room temperature and dissolves at high temperature is incorporated in the photosensitive material or the dye fixing material can also be adopted. The hydrophilic thermal solvent may be incorporated in either the light-sensitive material or the dye fixing material, or may be incorporated in both. The layer to be incorporated may be any of an emulsion layer, an intermediate layer, a protective layer and a dye fixing layer, but it is preferably incorporated in the dye fixing layer and / or its adjacent layer.

Examples of hydrophilic thermal solvents include ureas, pyridines, amides, sulfonamides, imides, alcohols, oximes, and other heterocycles. Further, in order to promote dye transfer, a high boiling point organic solvent may be contained in the photosensitive material and / or the dye fixing material.

As a heating method in the developing and / or transferring step, a heated block or plate is brought into contact, or a hot plate, a hot presser, a heat roller, a halogen lamp heater, an infrared or far infrared lamp heater or the like is contacted. Or passing through a high temperature atmosphere. Further, a resistance heating element layer may be provided on the photosensitive material or the dye fixing material, and the resistance heating element layer may be energized and heated. As the heating element layer, those described in JP-A-61-145544 can be used.

The light-sensitive material and the dye-fixing material are superposed,
For the pressure condition and the method of applying the pressure for the close contact, see Japanese Patent Laid-Open No.
The method described in page 1-147244 (27) can be applied.

Any of various developing devices can be used for processing the light-sensitive material of the present invention. For processing a heat-developable color light-sensitive material, see, for example, JP-A-59-75147 and 59-75.
177547, 59-181353, 60-1
Apparatuses described in No. 8951, No. 62-25944, etc. are preferably used.

[0255]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited thereto.

Example 1 A method for preparing emulsions (1) to (3) will be described. Solution I and solution II having the composition shown in Table 8 were added over 15 minutes to an aqueous solution having the composition shown in Table 7 which was well stirred, and thereafter, Table 8
Solution III and solution IV having the composition shown in (3) were added over 35 minutes.
After washing with water and desalting, 25 g of gelatin was added to pH = 6.2, pA
After adjusting to g 8.2, chemical sensitization was performed at 60 ° C. Chemical sensitization was performed using triethylthiourea and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene,
The highest point of sensitivity was optimally chemically sensitized as obtained by 10 ^-4 second exposure.

The yield, grain size and crystal habit of the obtained emulsions are shown in Table 9 and each was a monodisperse emulsion.

The chemical (A) in Table 7 is shown in Chemical formula 35.

[0259]

[Table 7]

[0260]

[Table 8]

[0261]

[Table 9]

[0262]

[Chemical 35]

Next, a method for preparing a gelatin dispersion of zinc hydroxide will be described.

12.55 g of zinc hydroxide having an average particle size of 0.25 μm, 1 g of carboxymethyl cellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of 4% gelatin aqueous solution, and the average particle size was 0.75 mm with a mill.
The glass beads were crushed for 30 minutes. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

Next, a method for preparing a gelatin dispersion of the hydrophobic additive will be described.

The oil phase components shown in Table 10 were each dissolved in 250 cc of ethyl acetate to obtain a uniform solution at 60 ° C. An aqueous phase component heated to 60 ° C. was added thereto, and dispersed by a dissolver having a diameter of 8 cm of a disperser for 30 minutes at 5000 rpm. To this was added post-hydration and stirred to form a uniform dispersion. This is referred to as the hydrophobic additive gelatin dispersion.

[0267]

[Table 10]

A heat developable color light-sensitive material 101 having a multilayer structure as shown in Tables 11 and 12 was prepared from these materials.

[0269]

[Table 11]

[0270]

[Table 12]

In Tables 10 to 12, the yellow dye-donor compound (1), the magenta dye-donor compound (2), the cyan dye-donor compounds (3) and (4) are shown in Chemical formulas 36 and 34, respectively. 37, 38, and 39. Further, the filter dye (5) is converted to Chemical formula 40, the auxiliary developing agent (6) is converted to Chemical formula 41, and the antifoggant (7) is converted to Chemical formula 42.
, Respectively. Further, the water-soluble polymer (8) is converted into Chemical formula 43, and the surfactants (9) and (10) are converted into Chemical formula 4
4, the sensitizing dyes (12), (13) and (14) are
, Respectively. Also, an antifoggant (1
5), (16), and (17) are compounds of
8), (19) and surfactants (20), (21),
(22) is shown in Chemical formula 47.

The hardener (11) is 1,2-bis (vinylsulfonylacetamide) ethane.

[0273]

[Chemical 36]

[0274]

[Chemical 37]

[0275]

[Chemical 38]

[0276]

[Chemical Formula 39]

[0277]

[Chemical 40]

[0278]

[Chemical 41]

[0279]

[Chemical 42]

[0280]

[Chemical 43]

[0281]

[Chemical 44]

[0282]

[Chemical 45]

[0283]

[Chemical 46]

[0284]

[Chemical 47]

In the photosensitive material 101, the emulsion (1),
A light-sensitive material 102 was prepared in exactly the same manner as the light-sensitive material 101 except that the emulsions (4), (5) and (6) prepared as described below were used instead of (2) and (3), respectively. ..

In the light-sensitive material 101, instead of using the sensitizing dye (12) 1.3 mg / m ² in the fifth layer, the sensitizing dye (1
2) 0.68 mg / m ² sensitizing dye (34) 0.6
5 mg / m ² in combination, and the sensitizing dye (13) 0.
Sensitizing dye of Chemical formula 48 instead of using 06 mg / m ² (35)
A light-sensitive material 103 was prepared in the same manner as the light-sensitive material 101 except that 0.07 mg / m ² was used.

[0287]

[Chemical 48]

In the light-sensitive material 103, the emulsion (1),
Emulsions (4), (5), (6) instead of (2), (3)
A light-sensitive material 104 was prepared in exactly the same manner as the light-sensitive material 103 except that each of the above was used.

Preparation method of emulsions (4), (5) and (6) Emulsion (4) 25 g of gelatin in the aqueous solution of Table 7 and 0.02 g of KI,
The emulsion was prepared in exactly the same manner as the emulsion (1) except that the temperature was changed to 60 ° C. and the addition time of the solutions I and II in Table 8 was shortened to 3 minutes.

Emulsion (1) with an average grain size of 0.41 μm
And the yield was almost the same as 605 g. However, the crystal habit was potato-like with a slightly rounded cube.

Emulsion (5) Emulsion (2) except that chemical sensitization was carried out at pH = 6.9, pAg = 8.8, and temperature of 72 ° C., and the chemical sensitization was changed to sodium thiosulfate. An emulsion (5) was prepared in exactly the same manner as in ().

The resulting emulsion had an average grain size of 0.20.
μ, yield 631 g, and crystal habit was octahedron.

Emulsion (6) The temperature of the aqueous solution shown in Table 7 was lowered to 41 ° C., and during the chemical sensitization, sodium thiosulfate, chloroauric acid, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaine was added. An emulsion (6) was prepared in exactly the same manner as the emulsion (3) except that den was used.

The obtained emulsion had an average grain size of 0.27.
μ, the yield was 621 g, and the crystal habit was cubic.

Next, the dye fixing material R-1 having the constitution shown in Table 13 is used.
made.

[0296]

[Table 13]

In Table 13, the silicone oil (23), the surfactants (24) and (25), the mordant (2
8), the high boiling point solvent (29) is shown in Chemical formula 49, and the surfactant (31) and the hardener (32) are shown in Chemical formula 50. Further, the surfactant (9) is represented by the chemical formula 44, and the water-soluble polymers (26), (27),
The fluorescent whitening agent (30) and the matting agent (33) are shown below.

Water-soluble polymer (26): Sumika gel L5
-H (Sumitomo Chemical Co., Ltd.) Water-soluble polymer (27): Dextran (molecular weight 70,000) Optical brightener (30): 2,5-bis (5-tert-butylbenzoxazole (2)) thiophene Matting agent (33): benzoguanamine resin (average particle size 1
5 μm)

[0299]

[Chemical 49]

[0300]

[Chemical 50]

Japanese Patent Application No. 2-
Exposure was performed using the semiconductor laser exposure device described in No. 318351. The exposure conditions were as shown in Table 14.

[0302]

[Table 14]

When 10 sheets of A4 size photosensitive material were continuously exposed under the exposure conditions of Table 14, the emission wavelength was 5th.
It varies from 672 nm to 675 nm for the layer and from 755 nm to 758 nm for the third layer, and it is considered that the mode hopping phenomenon due to temperature variation as shown in FIG. 1 occurs. Such a phenomenon is caused by the photosensitive materials 101 to 104.
The same was observed in any of the above, and was also observed in any of the time and intensity modulation methods.

12 ml / m ² of water was supplied to the emulsion surface of the exposed light-sensitive material exposed under the conditions shown in Table 14, and immediately thereafter, they were superposed so that the image-receiving material and the film surface were in contact with each other. Use a heat roller to adjust the temperature of the absorbed film to 90 ° C.
Heated for 2 seconds. Next, when the image receiving material was peeled off from the light-sensitive material, transfer images of magenta, cyan and yellow were obtained on the image receiving material.

The presence / absence of density unevenness in the magenta and cyan transferred images was visually determined.

The transferred image was measured by a self-recording densitometer to determine the maximum density (Dmax) and the minimum density (Dmin) at each exposure.

Further, in the above, instead of laser exposure, the density is continuously changed to 670 nm, 750 nm, 8
1 with a high-intensity photometer (made by EG & G) using a three-color separation filter wedge that mainly transmits light with a wavelength of 10 nm
0 ^-3 seconds after exposure, the same operation (development, transfer, concentration measurement)
Then, the dynamic range (DR) and gamma (γ) were determined.

The results are summarized in Table 15.

Further, the spectral sensitivity of the light-sensitive materials 101 to 104 was obtained. The result is shown in FIG. As the spectral sensitivity, the relative sensitivity with the spectral sensitivity of the third layer of the photosensitive material 103 at 755 nm being 10 is used.

For the fifth layer (magenta) and the third layer (cyan) of the light-sensitive materials 101 to 104, variation of log (relative sensitivity) per nm in the emission wavelength range [Δlog (relative sensitivity) / nm], And deviation of emission wavelength (λ) from the maximum spectral sensitivity wavelength (λmax) [λmax −λ]
I asked. This is also shown in Table 15.

The emission wavelength range of the fifth-layer exposure semiconductor laser is 672 to 675 nm, and the emission wavelength range of the third-layer exposure semiconductor laser is 755 to 758 nm, as described above.

Further, λmax for the light-sensitive materials 101 to 104 is as follows.

Photosensitive materials 101 and 102 Fifth layer: λmax 686 nm Third layer: λmax 737 nm

Photosensitive materials 103 and 104 Fifth layer: λmax 673 nm Third layer: λmax 752 nm

[0315]

[Table 15]

From the above results, it can be seen that an image having high Dmax and no unevenness can be obtained by the image forming method of the present invention.

Example 2 A silver halide color photographic light-sensitive material (color photographic paper) as shown below was prepared and used as a sample 201.

The silver halide emulsion used in each layer was as shown below.

Cyan coupler-containing layer emulsion Lime-treated gelatin (32.0 g) was added to distilled water (1000 ml) and dissolved at 40 ° C., and the pH was adjusted to 3.8 with sulfuric acid.
5.5 g of sodium chloride and 0.02 g of N, N-dimethylimidazolidine-2-thione were added to adjust the temperature to 52.5.
The temperature was raised to ℃. A solution of 62.5 g of silver nitrate in 750 ml of distilled water and 21.5 g of sodium chloride were added to 5 parts of distilled water.
The solution dissolved in 00 ml was added at 52.5 ° C. with vigorous stirring in 40 minutes. Furthermore, silver nitrate 62.5g
Solution of distilled water in 500 ml of distilled water and sodium chloride 2
52.5 with a solution of 1.5 g dissolved in 300 ml of distilled water
It was added at 20 ° C. over 20 minutes with vigorous stirring. In the aqueous sodium chloride solution to be added, 1 × 10 ⁻⁸ mol of potassium hexachloroiridate (IV) was added per mol of silver nitrate.

Observation of the obtained emulsion by an electron microscope revealed that the average grain size of silver halide grains was 0.46.
It was found that the particles consist of monodisperse cubic particles having a coefficient of variation of 0.0 and a particle size distribution variation coefficient of 0.09.

After washing this emulsion with demineralized water, 0.2 g of nucleic acid was added.
, A monodisperse bromide emulsion having an average grain size of 0.05μ (1.2 × 10 ^-5 mol of iridium hexachloride (I
V) containing dipotassium acid) was added as silver halide in an amount of 1.0 mol%, and triethylthiourea was added in an amount of about 2 × 10
Chemical sensitization was carried out with ^-6 mol / mol Ag, and the compound of formula 51 (V-6) was 7 × 10 ^-6 mol / mol Ag and the compound of formula 51 (F-1) was 5 × 10 ^-3 mol / An emulsion containing mol Ag was prepared and used.

[0322]

[Chemical 51]

Emulsion for Layer Containing Magenta Coupler In the preparation of the above emulsion grains, the temperature at the time of silver halide grain formation was changed to 50 ° C. to obtain an average grain size side length of 0.44 μm and a grain size variation coefficient of 0.08. An emulsion consisting of monodisperse cubic grains was obtained.

After washing this emulsion with demineralized water, 0.2 g of nucleic acid was added.
, A monodisperse silver bromide emulsion having an average grain size of 0.05 μ (1.8 × 10 ⁻⁵ mol of iridium hexachloride per mol of silver bromide)
(IV) containing dipotassium acid) as silver halide of 0.5
Add mol% equivalent, and further add triethylthiourea about 2.5
Chemical sensitization with × 10 ^-6 mol / mol Ag gives
Compound (V-3) of 1 × 10 ⁻⁵ mol / mol Ag,
An emulsion prepared by adding 5 × 10 ⁻³ mol / mol Ag of the compound (F-1) of 1 was prepared and used.

[0325]

[Chemical 52]

Yellow coupler-containing layer emulsion In the preparation of the above magenta coupler-containing layer emulsion, instead of the compound of formula 52 (V-3), the compound of formula 53 (V
-7) and the compound (V-8) are added at 1.2 × 10 ⁻⁴ mol / mol Ag and 0.2 × 10 ⁻⁴ mol / mol Ag, respectively, and the compound (F-1) of Chemical formula 51 is added. Emulsions were prepared and used which differed only in that they were not added.

[0327]

[Chemical 53]

Compounds (D-1) and (D-) shown in Chemical formulas 54 and 55 were applied to the coated samples for the purpose of improving the safety against safelight and further improving the sharpness of images.
2), (D-3), (D-4), (D-5) and (D
-6) respectively ^{16.0mg / m 2, 6.0mg / m} 2, 8.
0 mg / m ² , 20.0 mg / m ² , 4.0 mg / m ² and 22.
It was added so as to be 0 mg / m ² .

Compound D-3 of Chemical Formula 54 is the same as that of (A-2) of Chemical Formula 20 in the above-mentioned specific examples of the dye.
The compound D-4 of is a compound (A-1) of the formula 20 and a D- of the formula 55.
Compound 5 is the same as (A-27) in Chemical Formula 28, and compound D-6 in Chemical Formula 55 is the same as that in Chemical Formula 33 (A-42).

[0330]

[Chemical 54]

[0331]

[Chemical 55]

When preparing a multilayer color light-sensitive material,
After the corona discharge treatment is applied to the surface of the paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate is provided, and various photographic constituent layers are further coated to form a multilayer color having the layer constitution shown below. A photographic paper was prepared. The coating liquid was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY: Chemical formula 58) 19.1 g and color image stabilizer (Cpd-1: Chemical formula 60) 4.4 g and color image stabilizer (Cpd-7: Chemical formula 63) 0 0.7 g of ethyl acetate 2
7.2 cc and 4.1 g each of the solvent (Solv-3: Chemical formula 65) and (Solv-7: Chemical formula 66) were added and dissolved, and this solution was dissolved in 10% gelatin aqueous solution containing 10% sodium dodecylbenzenesulfonate (8 cc). 185 cc was emulsified and dispersed to prepare an emulsified dispersion. This was combined with the previously prepared emulsion for a yellow coupler-containing layer, mixed and dissolved, and a first coating solution was prepared so as to have the composition shown below.

Coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used.

Further, the total amount of Cpd-10 and Cpd-11 shown in Chemical Formula 56 was 25.0 mg / m ² and 50.
The amount added was 0 mg / m ² .

[0336]

[Chemical 56]

1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the yellow color forming layer, the magenta color forming layer and the cyan color forming layer in an amount of 8.0 × 10 ⁻⁴ per mol of silver halide. Added in moles. Furthermore, in the magenta coloring layer and the cyan coloring layer,
The compound of Chemical formula 57 was added in an amount of 2.0 × 10 ⁻³ mol.

[0338]

[Chemical 57]

Tables 16 and 17 show the layer constitution of Sample 201 and the composition of each layer. The numbers in the table represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

[0340]

[Table 16]

[0341]

[Table 17]

The compounds in Tables 16 and 17 constituting Sample 201 are those shown in Chemical Formulas 58 to 66, including those mentioned above in the first layer coating solution.

[0343]

[Chemical 58]

[0344]

[Chemical 59]

[0345]

[Chemical 60]

[0346]

[Chemical formula 61]

[0347]

[Chemical formula 62]

[0348]

[Chemical 63]

[0349]

[Chemical 64]

[0350]

[Chemical 65]

[0351]

[Chemical 66]

In the preparation of the emulsion for each layer of Sample 201,
Emulsions were prepared which differed only by the addition of 20 μg of rhodium chloride to the aqueous sodium chloride solution that was first added during the formation of silver halide grains, and a multilayer color light-sensitive material using these emulsions was prepared in the same manner as in Sample 201. This was designated as Sample 202.

Next, with respect to Sample 201, the spectral sensitizing dye of the silver halide emulsion used in the third layer was changed to V-9 of Chemical Formula 67, and the addition amount was 1.4 × 10 ^-5 mol / mol Ag. A sample was prepared which was different only in that the above was used, and this was designated as sample 203.

Further, with respect to Sample 202, the spectral sensitizing dye of the silver halide emulsion used in the third layer was changed to V-9 of Chemical Formula 67, and the addition amount was 1.4 × 10 ⁻³ mol / mol Ag. A sample different in that only the above was used was prepared, and this was designated as sample 204.

[0355]

[Chemical 67]

These samples were subjected to spectrally resolved exposure using a spectral sensitivity sensitometer manufactured by Fuji Photo Film Co., Ltd. and processed in the processing steps shown in Table 18.

The color developing solutions and the bleach-fixing solutions used in the processing steps of Table 18 are shown in Table 19 and Table 20, respectively. Further, the following rinse solution was used.

[0358]

[Table 18]

[0359]

[Table 19]

[0360]

[Table 20]

Rinse solution Ion-exchanged water (calcium ion 3 ppm or less, magnesium ion 2 ppm or less) Sample 2 thus treated
Spectral sensitivity was obtained for each of 01 to 204.
The obtained results are shown in FIG. As the spectral sensitivity, the relative sensitivity with the spectral sensitivity of the fifth layer at 830 nm being 40 is used.

For the third layers (magenta) of these samples 201 to 204, the emission wavelength range (7
Δlog (relative sensitivity) / nm at 50 to 753 nm) and λmax−λ were determined. The λmax of the third layer is as follows.

Samples 201 and 202 Third layer: λmax 733 nm Samples 203 and 204 Third layer: λmax 748 nm

Photographic properties of the samples 201 to 204 were determined by the same method as that used in Example 1. That is, through an optical wedge and a decomposition filter that transmits light of a specific wavelength, an EG & G Xenon flash sensitometer is used to expose for 10 ⁻³ seconds, and then each layer is processed by the following processing steps. A corresponding characteristic curve (color density-exposure curve) was prepared. However, the transmission wavelength of the decomposition filter was changed to 670 nm, 750 nm and 830 nm.

From the obtained characteristic curve, the γ value and dynamic range of each layer were determined by the same method as in Example 1. That is, as described above, with respect to the γ value, the point corresponding to the density 0.5 higher than the fog density (Dmin) on the characteristic curve and the curve corresponding to the exposure amount 0.5 higher than the corresponding exposure amount The dynamic range corresponds to a value 0.2 smaller than the exposure amount corresponding to a density 0.1 higher than the fog density and a density 0.1 lower than the maximum density (Dmax) for the dynamic range. It is expressed as a difference (Δlog E) from the value of the exposure amount (see FIGS. 2 and 3).

The results are summarized in Table 21.

[0367]

[Table 21]

Next, the same semiconductor laser exposure device as that used in Example 1 was used to perform a color density unevenness test. However, the oscillation wavelength of the semiconductor laser is 672 nm, 7
Changed to 50 nm and 830 nm. Further, the image pattern was changed so that three layers were exposed at the same time to obtain a gradation adjusted so that the three colors of cyan, magenta and yellow were balanced in gray. For the treatment of the exposed sample, the same treatment step and treatment liquid as those used for the sensitometry were used. The results of evaluating the density unevenness of the obtained image are summarized in Table 22.

In the above exposure with the semiconductor laser, color printing paper (100 mm width, 148 mm width)
(Length) was continuously exposed, the oscillation wavelength for magenta layer exposure varied from 750 nm to 753 nm, and it is considered that the mode hopping phenomenon due to temperature variation as shown in FIG. 1 has occurred. Be done. Such a phenomenon was the same in any of Samples 101 to 104, and was also observed in any of the time and intensity modulation methods.

[0370]

[Table 22]

As is clear from the above results, by applying the present invention, it is possible to obtain a high-quality scanned image with high maximum color density even in the laser scanning exposure method using color printing paper. it can.

[0372]

According to the present invention, it is possible to obtain a high-quality image having sufficient image density without causing image unevenness due to exposure unevenness.

[Brief description of drawings]

FIG. 1 is a graph for explaining a mode hopping phenomenon due to temperature fluctuation in the present invention.

FIG. 2 is a graph for explaining γ in the present invention.

FIG. 3 is a graph for explaining a dynamic range (DR) in the present invention.

FIG. 4 is a graph showing the spectral sensitivity of the heat-developable color photosensitive material in Example 1.

FIG. 5 is a graph showing the spectral sensitivity of color photographic paper in Example 2.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] June 30, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0016

[Correction method] Change

[Correction content]

Further, the LD has an advantage that a large exposure amount can be obtained because the emitted light can be condensed with a collimator lens with high efficiency.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction content]

The temperature of the LD is controlled from the outside of the LD package by using a heater, a Peltier element or the like. However, it is still difficult to control the light emitting portion of the LD, that is, the active layer, at a constant temperature, and a fluctuation of several degrees cannot be denied. The oscillation wavelength changes by about 1 nm due to the change of several degrees.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0028

[Correction method] Change

[Correction content]

Here, γ is a point on the characteristic curve that gives the lowest density (Dmin) +0.5 in the characteristic curve as shown in FIG. 2, and point a corresponding to a on the logE axis.
LogE (= 0.5 on the logE axis shifted from ₁ to the right)
a ₁ +0.5) When the point on the characteristic curve corresponding to the point b ₁ is b, it is defined as the slope of the straight line connecting a and b. That is, the point on the D axis corresponding to b is (Dm
In) + 0.5 + x, it is represented by (x / 0.5).

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0033

[Correction method] Change

[Correction content]

With respect to such a photosensitive layer, in the present invention, the emission wavelength during exposure is set as follows: 1) The variation of the logarithm of the spectral sensitivity S per nm of the photosensitive layer (ΔlogS / nm) is within ± 0.015, preferably. Is within a wavelength range of substantially 0, or 2) within ± 10 nm, preferably within ± 7 nm of the maximum spectral sensitivity wavelength λ _max (nm) of the photosensitive layer.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0066

[Correction method] Change

[Correction content]

The silver chlorobromide emulsion used in the present invention is described in P. Gl
by afkides chimieet Phisiqu
e Photographique (Paul Mon)
tel, 1967), G.I. F. By Duffin
Photographic Emulsion Chem
istry (Focal Press, 1966)
Year), V. L. Mak by Zelikman et al
ing and Coating Photograph
hic Emulsion (Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a format for reacting a soluble silver salt and a soluble halogen salt, any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof may be used. You may use. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0158

[Correction method] Change

[Correction content]

The processing temperature of the color developing solution applicable to the present invention is 20 to 50 ° C, preferably 30 to 45 ° C.
It is preferable that the replenishing amount is small, but it is equivalent to 20 to 600 ml, preferably 30 to 300, per 1 m ^{2 of} the light-sensitive material.
ml. It is more preferably 40 to 200 ml, most preferably 50 to 150 ml.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0198

[Correction method] Change

[Correction content]

Further, as more preferable ones, European Patent No. 220746A2, Kokai Giho No. 87-6199, US Pat. No. 4,783,396, Japanese Patent Laid-Open No. 63-201653.
No. 63, 2016-654, etc.
A compound having an -X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, Japanese Patent Application No. 62-106885.
In one molecule described in No. 2 in the No. ₂ (X is as defined above)
And a compound having an electron-withdrawing group, JP-A-63-2713
A compound having a PO-X bond (X has the same meaning as described above) and an electron-withdrawing group in one molecule described in JP-A-44-
The compound described in No. 271341 having a C—X ′ bond (X ′ has the same meaning as X or represents —SO ₂ —) and an electron-withdrawing group in one molecule. In addition, Japanese Patent Laid-Open No. 1-
Compounds described in 1612371 and 1-161342, which release a diffusible dye by cleaving a single bond after reduction by a π bond conjugated with an electron-accepting group, can also be used.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Name of item to be corrected] 0283

[Correction method] Change

[Correction content]

[0283]

[Chemical 46]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0287

[Correction method] Change

[Correction content]

[0287]

[Chemical 48]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0324

[Correction method] Change

[Correction content]

After washing this emulsion with demineralized water, nucleic acid 0.2
g, a monodisperse silver bromide emulsion having an average grain size of 0.05 μ (containing 1.8 × 10 ⁻⁵ mol dipotassium hexachloroiridate (IV) per mol silver bromide) as silver halide. Equivalent to 5 mol%, and further chemically sensitized with about 2.5 × 10 ⁻⁶ mol / mol Ag of triethylthiourea to obtain 4.5 × 10 ⁻⁵ mol / mol of the compound (V-3) of Chemical formula 52. Ag, the compound (F-1) of Chemical formula 51 was added to 5 × 10 ⁻³
An emulsion containing mol / mol Ag was prepared and used.

[Procedure Amendment 11]

[Document name to be amended] Statement

[Name of item to be corrected] 0354

[Correction method] Change

[Correction content]

Further, with respect to Sample 202, the spectral sensitizing dye of the silver halide emulsion used in the third layer was changed to V-9 of Chemical Formula 67, and the addition amount was 6.8 × 10 ⁻⁵ mol / mol Ag. A sample was prepared which was different only in what was used, and was designated as Sample 204.

[Procedure Amendment 12]

[Document name to be amended] Statement

[Name of item to be corrected] 0369

[Correction method] Change

[Correction content]

In the above exposure with the semiconductor laser, color photographic paper (100 mm width, 148 mm width) was used under the same conditions.
When 40 sheets (mm length) are continuously exposed, the oscillation wavelength for exposing the magenta layer changes from 750 nm to 753 nm, and the mode hopping phenomenon due to the temperature change as shown in FIG. 1 occurs. Conceivable. Such a phenomenon was the same in any of Samples 201 to 204, and was observed in any of the time and intensity modulation methods.

Claims (4)

[Claims] 1. An image forming method in which at least one photosensitive layer of a photosensitive material having at least one photosensitive layer containing a photosensitive silver halide on a support is imagewise exposed using a light source that can be modulated. In the above, the exposure light source is a vertical single mode type semiconductor laser in which the emission wavelength can discontinuously change with changes in temperature or the amount of emitted light, and the emission wavelength during exposure is 1 nm per 1 nm of the photosensitive layer. The change in logarithm of spectral sensitivity of [Δlog (spectral sensitivity) / nm] is within ± 0.015, and
Moreover, the image forming method is characterized in that the photosensitive layer has a gamma (γ) of 1.5 or more. 2. An image forming method in which at least one photosensitive layer of a photosensitive material having at least one photosensitive layer containing a photosensitive silver halide on a support is imagewise exposed using a light source capable of modulation. In the above, the exposure light source is a vertical single-mode semiconductor laser in which the emission wavelength can discontinuously change with changes in temperature or the amount of emitted light, and the emission wavelength during exposure is the maximum spectral spectrum of the photosensitive layer. An image forming method characterized in that it is within a range of ± 10 nm of a sensitivity wavelength (nm), and the gamma (γ) of the photosensitive layer is 1.5 or more. 3. The emission wavelength during exposure is within a wavelength range in which the variation of the logarithm of spectral sensitivity per nm of the photosensitive layer [Δlog (spectral sensitivity) / nm] is within ± 0.015. Item 2. The image forming method according to Item 2. 4. The image forming method according to claim 1, wherein the dynamic range of the exposure amount (E) of the photosensitive layer is 2.0 or less in log E unit.