JP2881055B2 - Image forming method - Google Patents

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 photosensitive material through a light emitting element of a semiconductor laser. 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
Silver halide photosensitive materials are widely used as photosensitive materials for recording outputs such as black and white images and color images, as well as in halftone dots and continuous gradation. The reason is that a silver halide photosensitive material has high sensitivity and is excellent in gradation and sharpness, so that a high-quality system can be designed. In particular, in recent years, as the processing steps of silver halide photosensitive materials have become simpler and faster, a scanning exposure type high quality image forming system using silver halide photosensitive materials has been increasingly developed.

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 rises, the emission wavelength becomes longer and the power decreases continuously, which causes image density unevenness. It has been found that this can be improved by setting the peak wavelength of the spectral sensitivity of the photosensitive material to be longer than the wavelength of the light source (Japanese Patent Application Laid-Open No. Sho 61-52642). This method is also effective for improving image unevenness caused by droop of a semiconductor laser.

However, a semiconductor laser, particularly a vertical single mode (longitudinal single mode) type semiconductor laser, further has a so-called hopping phenomenon in which the emission wavelength fluctuates discontinuously. Was found to occur.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a scanning exposure type image forming method using a vertical single mode type semiconductor laser capable of obtaining a high quality image without exposure unevenness using a silver halide photosensitive material. To provide.

[0006]

This and other objects are achieved by the present invention which is defined below as (1) to (4). (1) In the image forming method, at least one photosensitive layer of a color photosensitive material having a photosensitive layer containing photosensitive silver halide on a support is imagewise exposed using a light source capable of modulation. The light source is a longitudinal single mode semiconductor laser whose emission wavelength can fluctuate discontinuously with a change in temperature or light emission amount, and the light emission wavelength during exposure is the spectral sensitivity per 1 nm of the photosensitive layer. An image forming method, wherein the logarithmic variation [Δlog (spectral sensitivity) / nm] is within a wavelength range within ± 0.015, and the gamma (γ) of the photosensitive layer is 1.5 or more. .

(2) An image forming method in which at least one photosensitive layer of a color photosensitive material having a photosensitive layer containing photosensitive silver halide on a support is imagewise exposed using a light source capable of modulation. The exposure light source is a vertical single mode semiconductor laser whose emission wavelength can fluctuate discontinuously with a change in temperature or light emission amount, and the emission wavelength during exposure is the maximum spectral sensitivity of the photosensitive layer. Wavelength (nm)
Wherein the gamma (γ) of the photosensitive layer is 1.5 or more.

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

(4) The image forming method according to any one of (1) to (3), wherein the dynamic range of the exposure amount (E) of the photosensitive layer is 2.0 or less in logE units.

Japanese Patent Application Laid-Open No. 2-35445 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 temperature and manufacturing variations, the spectral sensitivity distribution of the silver halide photographic light-sensitive material is within the standard value of the light source ± 25 nm. , 0.2
(Log E). Is disclosed.

On the other hand, the present invention selectively uses a vertical single mode semiconductor laser as an exposure light source, and is different from the invention disclosed in the above-mentioned publication in terms of configuration. For this reason, the above publication does not suggest a mode hopping phenomenon peculiar to the longitudinal single mode semiconductor laser. Also, there is no description about γ or dynamic range (DR) of the photosensitive layer.

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

[0013]

[Specific Configuration] Hereinafter, a specific configuration of the present invention will be described in detail. 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 which is easily modulated as an exposure light source.

Such an image forming method is effective in the color field. Therefore, the silver halide light-sensitive material that can be used in the present invention can be applied to any negative color light-sensitive material.

The exposure light source according to the present invention uses a semiconductor laser (LD) as a light emitting element. The LD, which is a semiconductor element, can control the intensity of emitted light by controlling the current supplied to the light-emitting element. Therefore, an LD can be exposed at low cost, compactly, and with high efficiency without requiring an external modulator.

Further, since the LD can collect the emitted light with high efficiency by the collimator lens, it has an advantage that a large exposure amount can be obtained.

In such an LD, since the current-light output characteristic has a high temperature dependency, control for stabilizing the light amount is indispensable for exposing a high-quality image.

In order to solve this problem, an automatic power control for controlling the current to the LD so as to make the amount of light emitted from the LD constant by using a photodiode for detecting the amount of light (PD) usually built in the LD package. (APC) is used. An externally provided photodiode may be used as the light amount detection element.

Further, the light emitting wavelength of the semiconductor light emitting device has a temperature dependency. For example, in an AlGaAs LD, 0.1.
It has a temperature coefficient of 23 to 0.27 nm / ° C.

In particular, in the present invention, in order to perform digital exposure at a single wavelength, a vertical single mode LD
Is preferably used, but the longitudinal single mode LD has a feature that a wavelength change occurs discontinuously. This is called a mode hopping phenomenon.

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

Mode hopping is easily recognized on an image when recording an image whose density continuously changes in the raster scanning direction. This is because mode hopping occurs when the light intensity of the LD continuously changes, and at this time, a change in light intensity and a change in wavelength occur. In addition, since the position where this variation occurs varies from raster to raster, it is visually recognized as a light and light stripe pattern.

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

The temperature of the LD is controlled from outside the LD package 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 fluctuations of several degrees are inevitable. The oscillation wavelength varies by about 1 nm due to the variation of several degrees Celsius.

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

As described above, in the vertical single mode LD, the emission wavelength can fluctuate discontinuously with the fluctuation of the temperature or the amount of light emission. This mode hopping phenomenon causes the fluctuation of the image density. Become.

For example, suppose 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 with} respect to the incident light λ ₁ and λ ₂ , respectively.
In this case, when the wavelength of the light source changes discontinuously, the spectral sensitivity of the photosensitive layer changes substantially by ΔS = S ₂ / S ₁ . Therefore, the image density fluctuates by γ × log ΔS (γ = gamma of the photosensitive layer).

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

From the above relationship, as the wavelength variation due to the mode hopping of the light source is larger and the wavelength variation is the same, 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 degraded.

In the present invention, at least one photosensitive layer of the silver halide photosensitive material is exposed by the LD, and such a photosensitive layer has a γ of 1.5 or more, preferably 2.0 or more. That's all. By setting the γ value to 1.5 or more, the dynamic range of the photosensitive material can be made smaller than the dynamic range of the exposure system.
The system design becomes easy, and a sufficient image density can be obtained. On the other hand, if γ is less than 1.5, the system design becomes difficult, and the ability of the photosensitive material cannot be fully utilized, and only a low-density image can be obtained. Note that 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 units, and more preferably 1.8 or less. With such a DR, L, which is an exposure light source with a narrow DR, is used.
It is suitable for D. On the other hand, if DR exceeds 2.0, it becomes impossible to utilize the entire density range of the photosensitive material. From the viewpoint of reducing the change in image density, the lower limit of DR is preferably set to about 0.3. Here, the dynamic range (DR) refers to a characteristic curve as shown in FIG. 3, which is shifted leftward by 0.2 on the logE axis from M, which is a logE point giving a density of minimum density ( _Dmin ) +0.1. Lo
The point gE (= M−0.2) is defined as A, and the maximum density (D _max ) −
The logE point that gives a concentration of 0.1 is B, which is defined as BA.

The definition of DR in such a format is as follows.
This is because the actually used density range is about _Dmin to _Dmax- 0.1. In other words, the portion before _Dmax is generally soft, and the amount of light must be largely changed in order to produce a slight difference in density in the design of the exposure apparatus, and this portion is often not used.

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

As a result, even if γ of the photosensitive layer is 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. 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.

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

In the present invention, imagewise exposure using an LD may be performed according to the configuration described in Japanese Patent Application No. 2-318351 by the present applicant. Further, in order to form an image on a light-sensitive material by LD light, the following method is used.

The laser light emitted from the LD is converted into a substantially parallel beam by the collimator lens. This beam is further linearly imaged on a polygon mirror as a deflector by using a cylindrical lens having power only in the sub-scanning direction. The beam rotates at a constant angular velocity with the rotation of the polygon mirror, but is imaged by the fθ lens so as to scan at a constant speed on the photosensitive material. In addition, 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 disclosed in
-77018 and 1-81926.

When the laser beam is deflected by the polygon mirror, jitter occurs in the rotation of the motor for rotating the polygon mirror, and there is an angular error between adjacent surfaces of the polygon mirror.
The scanning start timing on the photosensitive material of each raster will fluctuate.

For this reason, 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 influence of fluctuation and no fluctuation. The image can be exposed.

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

In order to supply the modulation signal of each pixel to the LD drive circuit in synchronization with the scanning start timing detection signal, a fixed frequency clock signal corresponding to an integral multiple of the pixel repetition period is divided in synchronization with the scanning start timing detection signal. It has a counter that starts the 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 fluctuations.

In order to modulate the LD light, the following method is used.

This modulation method includes a method of directly modulating an LD and imagewise exposing an image, a method of modulating the intensity of light for each pixel by changing a supplied current (intensity modulation),
As a method of modulating D, there is a method of controlling the light emission time for each pixel while keeping the light intensity constant (time modulation).

In the case of the former intensity modulation method, in the LD, a light-sensitive material is necessary because the light output is linear with respect to the energizing current, that is, the ratio of the maximum amount of laser oscillation to the minimum amount of light is usually as low as about 10. Cannot be covered only by laser light. Also LD
In order to widen the dynamic range, it is conceivable to use a non-linear region, that is, LED light.
Since the D light and the LED light have different imaging beam shapes on the light-sensitive material, a density variation due to the multiple exposure effect of the photosensitive material occurs, and the image quality is deteriorated.

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

Mode hopping can occur in any of the above-mentioned modulation methods, but the present invention is effective in any case. In particular, mode hopping is remarkable in the intensity modulation method, and the effect of the present invention is 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, a black and white or color photothermographic material may be used.

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

The photosensitive material that 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 properties and anti-irradiation dyes for improving sharpness can be added.

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

It is also preferable to use a photographic material which forms a color image by ordinary color development, such as a general color printing paper, as a photosensitive material used in the image forming method of the present invention. The photosensitive material used at this time contains silver halide grains as a photosensitive 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 form of an aromatic primary amine developing agent generated at the time of developing exposed silver halide grains, and a compound having an active methylene position is usually used. Used. Hereinafter, the configuration of the color photographic paper applicable to the present invention will be described.

The silver halide color photographic light-sensitive material as a color photographic 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 Also, a photosensitive material in which at least two layers are composed of emulsion layers having a spectral sensitivity maximum at 670 nm or more can be suitably used.

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

[0055]

[Table 1]

The 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 from 6 to 20 μm, more preferably from 7 to 12 μm. The method of the present invention as described above is particularly effective for a color light-sensitive material composed of multiple layers.

As the silver halide emulsion used in the present invention, an emulsion composed of silver chlorobromide or silver chloride substantially free of silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol%.
Or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the distribution of the halogen composition inside the silver halide emulsion grains, the so-called uniform type grains having the same composition in any part of the silver halide grains, and the core inside the silver halide grains and surrounding the same. A particle having a so-called laminated structure having a different halogen composition from a shell (single layer or plural layers), or a structure having a non-layered portion having a different halogen composition inside or on the surface of the particle (when the particle is on the particle surface, the edge of the particle) And particles having a structure in which portions having different compositions are joined on corners or surfaces) can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use one of the latter two particles rather than particles having a uniform structure, and this is also preferable from the viewpoint of pressure resistance. In the case where the silver halide grains have the above-described structure, even if the boundary between different portions in the halogen composition is a clear boundary, it is an unclear boundary by forming a mixed crystal due to a composition difference. Or a structure having a positive and continuous structural change.

As a photosensitive material suitable for rapid processing, a so-called high silver chloride emulsion having a high silver chloride content is preferably used. In the present invention, the silver chloride content of the high silver chloride emulsion is preferably at least 90 mol%, more preferably at least 95 mol%.

Such a high silver chloride emulsion preferably has a structure in which a silver bromide localized phase is formed in the above-mentioned layered or non-layered form inside and / or on the surface of silver halide grains. The halogen composition of the localized phase is preferably at least 10 mol% in terms of silver bromide content.
More than mol% is more preferred. These localized phases can be inside the grains, at the edges, corners, or planes of the grain surfaces. One preferred example is a phase epitaxially grown at the corners of the grains.

On the other hand, 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 the halogen composition in the grains is used for the purpose of minimizing a decrease in sensitivity when the photosensitive material is subjected to pressure. It is also preferable to use particles of

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 a circle equivalent to the projected area of the grain, and the number average thereof is calculated) is 0.1. 1μ to 2μ is preferred.

The particle size distribution is preferably a so-called monodisperse one having a coefficient of variation (the standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less. At this time, it is also preferable to use the above monodispersed emulsion by blending it in the same layer or to apply a multilayer coating in order to obtain a wide latitude.

The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, tetradecahedral or octahedral, or may have an irregular shape such as spherical or tabular. Those having an irregular crystal form or those having a complex form thereof can be used.
Further, it may be composed of a mixture of those having various crystal forms. Among them, the particles having the above-mentioned regular crystal form should be contained at 50% or more, preferably 70% or more, more preferably 90% or more.

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

The silver chlorobromide emulsion used in the present invention can be prepared according to P.I. Gl
afkides chimieet Physique
e Photographique (Paul Mon
tel, 1967); F. By Duffin
Photographic Emulsion Chem
istry (published by Focal Press, 1966)
Year), V. L. Mak by Zelikman et al
ing and Coating Photograph
hic Emulsion (Focal Press, 1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halide, any method such as a one-side mixing method, a simultaneous mixing method, and a combination thereof may be used. May be used. A method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept 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 nearly uniform grain size can be obtained.

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

The silver halide emulsion used in the present invention is
Usually, chemical sensitization and spectral sensitization are applied.

In the chemical sensitization method, sulfur sensitization typified by addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. . As the compounds used for 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 performed for the purpose of imparting spectral sensitivity to a desired light wavelength region to the emulsion of each layer in the photosensitive material. In the present invention, it is preferable to add a dye that absorbs light in a wavelength range corresponding to the target spectral sensitivity or 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 compounds and the spectral sensitization method are described in
The ones described in the upper right column of page 22 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, fluctuations in photographic performance when scanning exposure with laser light can be further reduced.

For the purpose of gold sensitization according to the present invention, compounds such as chloroauric acid or salts thereof, gold thiocyanates or gold thiosulfates can be used. The addition amount of these compounds can vary widely depending on the case, but is 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol per mol of silver halide. It is. The addition of these compounds is performed before the completion of the chemical sensitization used in the present invention.

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

The silver halide emulsion used in the present invention may contain various compounds or their precursors for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are disclosed in the above-mentioned JP-A-62-2.
No. 15272, pp. 39 to 72 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 spectrally sensitize the infrared region efficiently.

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

[0078]

Embedded image

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

In the general formula (QI), Z ₆₁ and Z ₆₂ each represent an atomic group necessary for forming a heterocyclic nucleus.

As the heterocyclic nucleus, 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 (to these rings, a condensed ring is further bonded) Or a substituent may be further bonded).

Specific examples of the heterocyclic nucleus include a thiazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a selenazole nucleus, a benzoselenazole nucleus, a naphthoselenazole nucleus, an oxazole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, and an imidazole nucleus. Nucleus, benzimidazole nucleus, naphthoimidazole nucleus, 4-quinoline nucleus, pyrroline nucleus, pyridine nucleus, tetrazole nucleus, indolenine nucleus,
Examples include a benzindolenin nucleus, an indole nucleus, a tellurazole nucleus, a benzotellurazole nucleus, and a naphthotellurazole nucleus.

R ₆₁ and R ₆₂ each represent an alkyl group,
Represents an alkenyl group, an alkynyl group or an aralkyl group. These groups and the groups described below are used in the meaning including their substituents. Taking the alkyl group as an example, it includes unsubstituted and substituted alkyl groups, 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 a halogen atom (chlorine, bromine, fluorine, etc.), a cyano group, an alkoxy group, a substituted or unsubstituted amino group, a carboxylic acid group, a sulfonic acid group, and a hydrogen atom. And the like, and one or a plurality of these may be substituted in combination.

A specific example of the alkenyl group includes 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 a lower alkyl group or an aralkyl group, it can form a 5- to 6-membered ring by linking with R _62. Also R
_{When 64} represents a hydrogen atom, R ₆₃ may be linked to another R ₆₃ to form a hydrocarbon ring or a heterocyclic ring. 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 each} represent R ₆₁ or R ₆₁ in the general formula (QI)
It has the same meaning as R _62, the same meanings as j _71, k _71, X ₇₁ and _{n 71 j 61, k 61,} X 61 and n ₆₁ each general formula (Q-I). 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 is a hydrogen atom, a lower alkyl group, in addition to an aryl group, it may form a hydrocarbon ring or a heterocyclic ring linked and the R ₇₄ and the other R _74. These rings are preferably 5- or 6-membered rings.

Q ₇₁ represents a sulfur atom, an oxygen atom, a selenium atom or ＮNR ₇₅ , wherein R ₇₅ has the same _meaning as R ₇₃ .

In formula (Q-III), Z ₈₁ represents an atomic group necessary for forming a heterocyclic ring. As this heterocyclic ring, Z
Those mentioned for 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, naphthoimidazoline and the like 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 Other synonymous with R _74, may form a hydrocarbon ring or a heterocyclic ring linked and the R ₈₃ and the other R _83. j ₈₁ has the same meaning as j _61.

In the general formula (QI), Z ₆₁ and / or
Or heterocyclic nucleus, especially a naphthothiazole nucleus of Z _62, naphthoxazole benzoselenazole nucleus, naphthoxazole nucleus, naphthoimidazole imidazole nucleus, a sensitizing dye having a 4-quinoline nucleus are preferred. Z ₇₁ and / or Z in the general formula (Q-II)
_The same applies to ₇₂ and general formula (Q-III). Further, a sensitizing dye having a methine chain forming a hydrocarbon ring or a heterocyclic ring is preferable.

Infrared sensitization uses sensitization by the M band of a sensitizing dye, so that the spectral sensitization distribution is generally broader than the sensitization by the J band. For this reason, it is preferable to correct the spectral sensitivity distribution by providing a coloring layer containing a dye in the colloid layer on the photosensitive surface side of the predetermined photosensitive layer. This colored layer is effective for preventing color mixing by a filter effect.

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

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

Measurement of the reduction potential by phase discrimination second harmonic AC voltammetry using platinum as the working electrode is described in "Journal of Imaging Science" (Jou
rnal of Imaging Science), Vol. 30, pages 27-35 (1986).

Specific examples of sensitizing dyes that can be used in the present invention are described in JP-A-2-157491, page 8, lower left column, 1st.
From the line, there is a description in the second line on the right lower column of page 13. In addition to those described here, the compounds shown in Chemical formulas 2 to 19 can also be used.

In the chemical formulas (2) to (19), Me represents a methyl group, Et represents an ethyl group, Ph represents a phenyl group,
S ^- represents a p-toluenesulfonate ion.

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In order to incorporate these spectral sensitizing dyes into a silver halide emulsion, they may be directly dispersed in the emulsion, or may be dispersed in water, methanol, ethanol, propanol, methyl cellosolve, 2,2, It may be dissolved in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent and added to the emulsion. In addition, Japanese Patent Publication No. 44-23
No. 389, JP-B-44-27555, JP-B-57-2
As described in US Pat. No. 2089 or the like, an acid or a base is co-present to form an aqueous solution, or as described in US Pat. No. 3,822,135, US Pat. May be added to the emulsion. After dissolving in a substantially water-immiscible solvent such as phenoxyethanol, a dispersion in water or a hydrophilic colloid may be added to the emulsion.
JP-A-53-102733, JP-A-58-10514
As described in No. 1, directly dispersed in a hydrophilic colloid,
The dispersion may be added to the emulsion. The timing of addition to the emulsion may be at any stage in the preparation of the emulsion which has hitherto been known to be useful. In other words, before the silver halide emulsion is formed, during the grain formation, immediately after the grain formation, before entering the washing step, before the chemical sensitization, during the chemical sensitization, and immediately after the chemical sensitization until the emulsion is cooled and solidified, during the preparation of the coating solution. , You can choose from either. Most commonly, after chemical sensitization is completed, it is performed before coating, but as described in U.S. Pat. Nos. 3,628,969 and 4,225,666, it is added simultaneously with a chemical sensitizer and spectral sensitization is performed. Sensitization can be performed simultaneously with chemical sensitization.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added before completion of silver halide grain precipitation to start spectral sensitization. Furthermore, as taught in U.S. Pat. No. 4,225,666, the spectral sensitizing dyes can be added separately, i.e., some added prior to chemical sensitization and the remainder added after chemical sensitization. It is possible at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Among them, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be 0.5 to 0.5 mol per mol of silver halide.
The range is preferably from × 10 ^-6 mol to 1.0 × 10 ^-2 mol.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10
^-3 mole range.

In the red or infrared sensitization of the present invention, the M-band sensitization is carried out, in particular, from page 13, lower right column, line 3 to page 22, lower right column, lower line 3 of JP-A-2-15749. Supersensitization with the compounds described is effective.

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

That is, the compound (F) which forms a chemically inert and substantially colorless compound by chemically bonding with the aromatic amine-based developing agent remaining after the color development and / or after the color development The compound (G) that forms a chemically inert and substantially colorless compound by chemically bonding with the oxidized form of the remaining aromatic amine-based color developing agent may be used simultaneously or alone, for example, after processing. It is preferable in order to prevent the generation of stains and other side effects due to the formation of a coloring dye due to the reaction between the color developing agent remaining in the film or the oxidized product thereof and the coupler during storage.

The light-sensitive material of the present invention is provided with a fungicide such as that described in JP-A-63-271247 to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. It is preferred to add an agent.

In the present invention, a dye may be used to improve the image quality such as sharpness, and specific examples of such a dye include the compounds shown in Chemical formulas 20 to 34.

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

The term "reflective support" used in the present invention refers to a material which enhances reflectivity to sharpen a dye image formed on a silver halide emulsion layer.
A substrate coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, calcium sulfate, etc., or a substrate 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 combined with a reflective substance, for example, a glass plate, polyethylene terephthalate, polyester film such as cellulose triacetate or cellulose nitrate, polyamide Film, polycarbonate film, polystyrene film, vinyl chloride resin and the like.

As another reflective support, a support having a mirror-reflective or second-class diffuse-reflective metal surface can be used. The metal surface preferably has a spectral reflectance of 0.5 or more in the visible wavelength range, and the metal surface is preferably roughened or made diffusely reflective using metal powder. As the metal, aluminum, tin, silver, magnesium or an alloy thereof is used, and the surface may be the surface of a metal plate, a metal foil, or a thin metal layer obtained by rolling, vapor deposition, plating, or the like. Above all, it is preferable to obtain a 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. It is preferable to provide an antistatic layer on the side of the support opposite to the side having the metal surface. For details of such a support, see, for example,
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 substance obtained by treating the surface of pigment particles with a di- to tetra-valent alcohol.

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

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(Equation 1)

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

The support used in the light-sensitive material of the present invention may be a white polyester-based support for display or a support in which a layer containing a white pigment is provided on a support having a silver halide emulsion layer. A body may be used. In order to further improve the sharpness, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.1 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 35 to 0.8.

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

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

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Further, as a cyan coupler, Japanese Patent Application Laid-Open No.
In addition to the diphenylimidazole cyan coupler described in JP-A-33144, European Patent EP 0,333,185
The 3-hydroxypyridine-based cyan couplers described in the specification of A2 (especially, couplers obtained by giving a chlorine leaving group to a 4-equivalent coupler of the coupler (42) enumerated as specific examples to give a 2-equivalent coupler, coupler (6), and the like) (9) is particularly preferable, and cyclic active methylene cyan couplers described in JP-A-64-32260 (in particular, coupler examples 3, 8, and 34 listed as specific examples) are also preferably used. .

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

In the present invention, the development time is preferably 45 seconds or less. Further, the present invention can be preferably applied to rapid processing in which the processing is substantially within 20 seconds. Here, “substantially 20 seconds” means that when the photosensitive material enters the developer tank,
It refers to the time until the photosensitive material enters the next tank, and also includes the time in the air from the developer tank to the next tank.

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

A specific preferable replenishment amount is 0.5 to 50 of the carry-in amount from the preceding bath per unit area of the light-sensitive material.
Times, preferably 2 to 15 times. Or photosensitive material 1m ²
Per volume is 300 ml or less, preferably 150 ml or less.
Replenishment may be performed continuously or intermittently.

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

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

In order to complete an image by the ultra-rapid processing of the present invention, a drying time of 20 to 40 seconds is desired. As means for shortening the drying time, means for the photosensitive material can be improved by reducing the amount of water brought into the film by reducing the amount of hydrophilic binder such as gelatin. Further, from the viewpoint of reducing the carry-in amount, it is possible to speed up drying by absorbing water with a squeeze roller or cloth immediately after leaving the washing bath. Of course, as a means for improving the dryer, it is possible to speed up drying by increasing the temperature or increasing the drying air. Further, the drying can be expedited by adjusting the angle at which the drying air is sent to the photosensitive material or by removing the exhaust air.

In the above, the color photographic paper has been described, but it is also preferable to use a heat-developable color photographic material as the photographic material used in the image forming method of the present invention. Hereinafter, the constitution of the heat developable color light-sensitive material applicable to the present invention will be described.

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

When a wide range of colors on a chromaticity diagram is obtained using 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,
There is a combination of a second infrared sensitive layer and the like. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

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

The silver halide emulsion used in the present invention may be 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 light fogging. Further, a so-called core-shell emulsion having a different phase between the inside of the grain and the grain surface layer may be used. The silver halide emulsion may be monodispersed or polydispersed, or a mixture of monodispersed emulsions may be used. The particle size is preferably from 0.1 to 2 µ, particularly preferably from 0.2 to 1.5 µ. The crystal habit of the silver halide grains may be cubic, octahedral, tetrahedral, high aspect ratio tabular, or any other.

Specifically, US Pat. No. 4,500,626, column 50, column 4628021, Research Disclosure Magazine (hereinafter abbreviated as RD) 17029 (19)
1978) and any of the silver halide emulsions described in JP-A-62-253159 can be used.

The silver halide emulsion may be used as it is after unripe, but usually it is used after chemical sensitization. Known sulfur sensitization, reduction sensitization, noble metal sensitization, and the like can be used singly or in combination for emulsions for conventional light-sensitive materials.
These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 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 a methine dye or the like. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.

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

Further, the sensitizing dyes described in the constitution of the color photographic paper described above are specific examples.

These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization.

Along with the sensitizing dye, a dye which has no spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. Patent No. 3615641, Japanese Patent Application No. 6
1-2226294).

The time when these sensitizing dyes are added to the emulsion may be before or after chemical ripening, or before or after 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 photosensitive silver halide. Particularly, in a photothermographic element, use of an organic metal salt is preferable. Among such organic metal salts, an organic silver salt is particularly preferably used.

Organic compounds which can be used to form the above-mentioned organic silver salt oxidizing agents include US Pat. No. 4,500,626.
No. 52-53, benzotriazoles, fatty acids and other compounds. Japanese Patent Application Laid-Open No. 60-1132
A silver salt of a carboxylic acid having an alkynyl group such as silver phenylpropiolate described in JP-A No. 35;
The acetylene silver described in No. 044 is also useful. Two or more 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 1 mol of the 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 suitably from 50 mg / m ² to 10 g / m ² in terms of silver.

In the present invention, various antifoggants or photographic stabilizers can be used. Examples thereof include azoles and azaindenes described in RD17643 (1978), pp. 24-25, and JP-A-59-1684.
No. 42 nitrogen-containing carboxylic acids and phosphoric acids,
Alternatively, a mercapto compound and a metal salt thereof described in JP-A-59-111636, an acetylene compound described in JP-A-62-87957, and the like are used.

As the reducing agent used in the present invention, those known in the field of diffusion transfer type color photographic materials can be used. Further, a dye-providing compound having a reducing property described later is also included (in this case, another reducing agent may be used in combination). Further, a reducing agent precursor which does not itself have a reducing property but expresses a reducing property by the action of a nucleophilic reagent, alkali or heat in 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. 83914, columns 30-31, No. 4330617,
Nos. 4590152 and pp. 17-17 of JP-A-60-140335, pp. 57-40245 and pp. 56
138736, 59-178458, 59-
Nos. 53831, 59-182449 and 59-18
No. 2450, No. 60-119555, No. 60-128
From No. 436 to No. 60-128439, No. 60-1
No. 98540, No. 60-181742, No. 61-25
No. 9253, No. 62-244444, No. 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.

Various combinations of 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, an electron transfer agent and / or an electron transfer agent may be used, if necessary, 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 mobility of the electron transfer agent or its precursor is higher than that of the diffusion-resistant reducing agent (electron donor). A particularly useful electron transfer agent is 1-phenyl-3-
Pyrazolidones or aminophenols.

The non-diffusible reducing agent (electron donor) used in combination with the electron transfer agent may be any one which does not substantially move in the layer of the photosensitive element among the reducing agents described above.
Preferred are hydroquinones, sulfonamidophenols, sulfonamidonaphthols, and JP-A-53-11.
Compounds described as electron donors in No. 0827 and dye-donating compounds having a diffusion-resistant and reducing property described later are exemplified.

In the present invention, the reducing agent is added in an amount of 0.001 to 20 mol, preferably 0.1 to 1 mol, per mol of silver.
01 to 10 mol.

Examples of the dye-donating compound used in the heat-developable color light-sensitive material that can be used in the present invention include a compound (coupler) which forms a dye by an oxidative coupling reaction. The coupler may be a 4-equivalent coupler or a 2-equivalent coupler. Further, a 2-equivalent coupler which has a diffusion-resistant group as a leaving group and forms a diffusible dye by an oxidative coupling reaction is also preferable. The diffusion resistant group may form a polymer chain. Specific examples of color developers and couplers are described in TH James "The Theory of the
Photographic Process, 4th Edition, pp. 291-334 and 354-361, JP-A-58-123533, JP-A-58-149046, JP-A-58-149047, and JP-A-58-14947.
Nos. 9-111148, 59-124399, 59
No. 174835, No. 59-231439, No. 59-
No. 231540, No. 60-2950, No. 60-295
No. 1, No. 60-14242, No. 60-23474,
No. 60-66249, and the like.

As another example of the dye donating compound,
Compounds having a function of releasing or diffusing a diffusible dye in an image form can be mentioned. 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 corresponds to a photosensitive silver salt having an image-like latent image. Alternatively, the diffusivity of the compound represented by (Dye-Y) nZ may be changed in the opposite manner, or Dye may be released and the released Dye and (Dye-Y) nZ may be separated. Represents a group having such a property as to cause a difference in diffusibility therebetween, and n represents 1 or 2, and when n is 2, two Dye-Ys may be the same or different.

Specific examples of the dye-donating compound represented by the general formula [LI] include the following compounds. The following (1) to (4) are to form a diffusible dye image (positive dye image) in reverse correspondence to the development of silver halide, and "(1)" is to form a diffusible dye image (positive dye image) in (A negative dye image).

US Pat. Nos. 3,134,764 and 336, US Pat.
No. 2819, No. 3597200, No. 3544545
No. 3,482,972, etc., a dye developing agent comprising a hydroquinone-based developing agent and a dye component linked to each other. This dye developer is diffusible in an alkaline environment, but becomes non-diffusible when reacted with silver halide.

As described in US Pat. No. 4,503,137 and the like, a nondiffusible compound which releases a diffusible dye in an alkaline environment but loses its ability when reacted with silver halide can be used. Examples of the compound include a compound capable of releasing a diffusible dye by an intramolecular nucleophilic substitution reaction described in US Pat. No. 3,980,479, US Pat.
Compounds which release a diffusible dye by an intramolecular reversal reaction of an isoxazolone ring described in JP-A No. 354 or the like.

US Pat. No. 4,559,290, European Patent No. 220746A2, US Pat. No. 4,783,396,
As described in JP-A-87-6199, a non-diffusible compound that reacts with a reducing agent remaining without being oxidized by development to release a diffusible dye can also be used.

For example, US Pat.
Nos. 9 and 4139379, JP-A-59-185333.
And compounds which release a diffusible dye by a nucleophilic substitution reaction in the molecule after reduction described in U.S. Pat. No. 4,232,107, and JP-A-59-84453.
-101649, 61-88257, RD240
No. 25 (1984) and the like, compounds which release a diffusible dye by an intramolecular electron transfer reaction after reduction, West German Patent No. 308588A, JP-A-56-14.
No. 2530, U.S. Pat. Nos. 4,434,893 and 4,619.
No. 8450, etc., compounds which release a diffusible dye by cleavage of a single bond after reduction, US Pat.
Examples include a nitro compound which releases a diffusible dye after electron acceptance described in JP-A-223 No. 223 and the like, and a compound which releases a diffusible dye after electron acceptance described in US Pat. No. 4,609,610 and the like.

More preferred are EP 220746A2, JP-A-87-6199, US Pat. No. 4,783,396, and JP-A-63-201653.
In one molecule described in JP-A-63-201654 and the like.
Compounds having an -X bond (X represents an oxygen, sulfur or nitrogen atom) and an electron-withdrawing group, Japanese Patent Application No. 62-106885.
_SO 2 -X in marked within one molecule to No. (X is as defined above)
And compounds having an electron-withdrawing group, JP-A-63-2713
No. 44, a compound having a PO-X bond (X is as defined above) and an electron-withdrawing group in one molecule.
Compounds 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 can be mentioned. Further, Japanese Patent Laid-Open No.
Nos. 162,371 and 1-161342, compounds which release a diffusible dye by cleavage of a single bond after reduction by a π bond conjugated to an electron accepting group can also be used.

Of these, compounds having an NX bond and an electron-withdrawing group in one molecule are particularly preferred. Specific examples thereof include compounds (1) described in EP-A-220746A2.
To (3), (7) to (10), (12), (13),
(15), (23) to (26), (31), (32),
(35), (40), (41), (44), (53)-
(59), (64), (70), Published Technical Report 87-619
No. 9 (11) to (23).

Compounds having a diffusible dye as a leaving group and releasing a diffusible dye upon reaction with an oxidized reducing agent (DDR coupler). Specifically, British Patent No. 1,330,524, JP-B-48-39165, U.S. Patent Nos. 3,443,940, 4,474,867, and 448
No. 3914 and the like.

Compounds (DRR compounds) that are reducible to silver halide or organic silver salts and release diffusible dyes when the partner is reduced. Since this compound does not need to use another reducing agent, it is preferable because there is no problem of image contamination due to oxidized decomposition products of the reducing agent. Representative examples are U.S. Pat. Nos. 3,923,312, 4,053,312 and 405.
Nos. 5428 and 4336322, JP-A-59-658.
No. 39, No. 59-69839, No. 53-3819,
Nos. 51-104343, RD17465, U.S. Pat. Nos. 3,725,062, 3,728,113 and 3,443.
No. 939, JP-A-58-11637 and JP-A-57-17.
No. 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, compounds (1) to (3) described in the aforementioned 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 U.S. Pat. No. 4,639,408 at columns 37 to 39 are also useful.

Other examples of the above-mentioned couplers and dye-donating compounds other than the general formula [LI] include dye silver compounds in which an organic silver salt is combined with a dye (Research Disclosure Magazine, May 1978, pp. 54-58). Azo dyes used in the heat-developed silver dye bleaching method (U.S. Pat.
957, Research Disclosure Magazine, 1976
April, pp. 30-32), leuco dyes (U.S. Pat. Nos. 3,985,565 and 4,022,617) can also be used.

A hydrophobic additive such as a dye-providing compound and a nondiffusible reducing agent can be introduced into a layer of a light-sensitive material by a known method 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
A high boiling organic solvent as described in JP-A Nos. 9-178455 and 59-178457 may be used, if necessary, with a boiling point of 50 ° C.
It can be used in combination with a low-boiling organic solvent of up to 160 ° C.

The amount of the high boiling point organic solvent is 10 g or less, preferably 5 g or less, per 1 g of the dye-providing 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-51-3985
A dispersion method using a polymer described in No. 59943 can also be used.

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

In dispersing the hydrophobic compound in the hydrophilic colloid serving as a binder, various surfactants can be used. For example, those mentioned as surfactants on pages (37) to (38) of JP-A-59-157636 can be used.

In the present invention, a compound for stabilizing an image simultaneously with activation of development can be used in the light-sensitive material. Specific compounds preferably used are described in U.S. 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 a photosensitive material. The dye-fixing material may be in the form of being separately coated on a support separate from the photosensitive material, or may be in the form of being coated on the same support as the photosensitive material. The relationship between the photosensitive 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 are also applicable 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 field of photography can be used, and specific examples thereof are described in U.S. Pat. No. 4,500,626, columns 58 to 59 and JP-A-61-88256, No. (32) to U.S. Pat.
(41) Mordant described on page 41, JP-A-62-244043
And Nos. 62-244036. Further, a dye-receiving polymer compound as described in U.S. Pat. No. 4,463,079 may be used.

[0211] The dye-fixing material may be provided with an auxiliary layer such as a protective layer, a release layer, and an anti-curl layer, if necessary. It is particularly useful to provide a protective layer.

As the binder for the constituent layers of the photosensitive material and the dye fixing material, hydrophilic binders are preferably used. Examples thereof include pages (26) to (2) of JP-A-62-253159.
8) Those described on page 8 are mentioned. Specifically, transparent or translucent hydrophilic binders are preferred, for example, gelatin, proteins or cellulose derivatives such as gelatin derivatives, starch, gum arabic, dextran, natural compounds such as polysaccharides such as pullulan, polyvinyl alcohol, Examples include polyvinylpyrrolidone, acrylamide polymers, and other synthetic polymer compounds. Further, a superabsorbent polymer described in JP-A-62-245260, that is, a homopolymer of a vinyl monomer having —COOM or —SO ₃ M (M is a hydrogen atom or an alkali metal), or those vinyl monomers or other vinyl monomers. (For example, sodium methacrylate, ammonium methacrylate, Sumikagel L-5H manufactured by Sumitomo Chemical Co., Ltd.) may also be used. These binders can be used in combination of two or more kinds.

In the case of employing a system in which a small amount of water is supplied to perform thermal development, the use of the above-described superabsorbent polymer makes it possible to rapidly absorb water.
When the superabsorbent polymer is used for the dye-fixing layer and its protective layer, it is possible to prevent the dye from being re-transferred from the dye-fixing material to another after transfer.

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

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

In the present invention, an image formation accelerator can be used in the light-sensitive material and / or the dye-fixing material.
Examples of the image formation accelerator include the promotion of a redox reaction between a silver salt oxidizing agent and a reducing agent, the promotion of a reaction such as the generation of a dye from a dye-providing substance or the decomposition or release of a diffusible dye, and the use of a photosensitive material layer. From the physicochemical function to bases or base precursors, nucleophilic compounds, high-boiling organic solvents (oils), thermal solvents, surfactants, silver Or, it is classified into a compound having an interaction with silver ions. However, these substance groups generally have a composite function and usually have some of the above-mentioned promoting effects. Details of these are described in U.S. Pat. No. 4,678,739, columns 38-40.

Examples of the base precursor include salts of an organic acid and a base which are decarboxylated by heat, compounds which release amines by an intramolecular nucleophilic substitution reaction, Lossen rearrangement or Beckmann rearrangement, and the like. An example is described in US Pat.
93 and JP-A-62-65038.

In a system in which thermal development and transfer of a dye are carried out simultaneously in the presence of a small amount of water, it is preferable to include a base and / or a base precursor in the dye-fixing material from the viewpoint of improving the storability of the photosensitive material.

In addition to the above, European Patent Publication No. 210660
No. 4,740,445, a combination of a compound which is capable of forming a complex with a metal ion constituting the hardly soluble metal compound (referred to as a complex-forming compound), and JP-A-61-232451. Compounds that generate a base by electrolysis described in the above item can also be used as the base precursor. In particular, the former method is effective. The sparingly soluble metal compound and the complex forming compound are advantageously added 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 terminators may be used for the purpose of always obtaining a constant image with respect to fluctuations in processing temperature and processing time during development. it can.

The term "development terminator" used herein means that after proper development,
It is a compound that quickly neutralizes a base or reacts with a base to reduce the base concentration in the film and stop development, or a compound that interacts with silver and a silver salt to suppress development. In particular,
Examples include an acid precursor that releases an acid when heated, an electrophilic compound that causes a substitution reaction with a coexisting base when heated, or a nitrogen-containing heterocyclic compound, a mercapto compound, and a precursor thereof. For further details, see JP-A-62-2531.
No. 59, pages (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 film physical properties such as dimensional stability, curling prevention, adhesion prevention, film crack prevention, and pressure increase / decrease sensation. Various polymer latexes can be included. Specifically, any of the polymer latexes described in JP-A Nos. 62-245258, 62-136648, and 62-110066 can be used. In particular,
When a polymer latex having a low glass transition point (40 ° C. or less) is used for the mordant layer, cracking of the mordant layer can be prevented, and when a polymer latex having a high glass transition point is used for 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 plasticizer, a sliding agent, or a high-boiling organic solvent can be used as a releasability improving agent for the light-sensitive material and the dye-fixing material. Specifically, Japanese Patent Application Laid-Open No. 62-253159 (2)
5), pages 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 dimethyl siloxane) can be used for the above purpose. As examples thereof, various modified silicone oils described in "Modified Silicone Oil" Technical Document P6-18B issued by Shin-Etsu Silicone Co., Ltd., particularly carboxy-modified silicone (trade name: X-22-3710) are effective.

Also, JP-A-62-215953, 63-63
No. 46449 is also effective.

An anti-fading agent may be used for the light-sensitive material and the dye-fixing material. Anti-fading agents include, for example, antioxidants, ultraviolet absorbers, or certain metal complexes.

Examples of the antioxidant include 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.

Examples of the ultraviolet absorber include benzotriazole compounds (US Pat. No. 3,533,794),
Thiazolidone-based compounds (US Pat. No. 3,352,681, etc.) and benzophenone-based compounds (JP-A-46-2784)
No. JP-A-54-48535 and JP-A-64-28535.
There are compounds described in JP-A-1366641, JP-A-61-88256 and the like. Further, ultraviolet absorbing polymers described in JP-A-62-260152 are also effective.

As the metal complex, US Pat.
No. 55, No. 4245018, Columns 3-36, No. 4254
195, columns 3-8, JP-A-62-174741, JP-A-61-88256, pp. 27-29, 63-1
No. 99248, Japanese Patent Application No. 62-234103 and No. 62-
There are compounds described in, for example, No. 230595.

Examples of useful discoloration inhibitors are described in JP-A-62-21.
No. 5272, pages (125) to (137).

An anti-fading agent for preventing fading of the dye transferred to the dye-fixing material may be contained in the dye-fixing material in advance, or supplied to the dye-fixing material from outside such as a photosensitive material. You may.

The above antioxidants, ultraviolet absorbers and metal complexes may be used in combination.

A fluorescent whitening agent may be used for the light-sensitive material and the dye-fixing material. In particular, it is preferable to incorporate a fluorescent whitening agent into the dye-fixing material or to supply it from outside such as a photosensitive material. For example, K. Veenkataraman ed., "The Chemis
try of Synthetic Dyes ", Volume V, Chapter 8, JP-A-61-
No. 143752 and the like. More specifically, a stilbene compound, a coumarin compound, a biphenyl compound, a benzoxazolyl compound, a naphthalimide compound, a pyrazoline compound, a carbostyril compound, and the like can be given.

The fluorescent whitening agent can be used in combination with a fading inhibitor.

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 slipperiness, antistatic, acceleration of development and the like. Specific examples of the surfactant are described in JP-A-62-173463.
And No. 62-183457.

The constituent layers of the light-sensitive material and the dye-fixing material may contain an organic fluoro compound for the purpose of improving sliding property, preventing static charge, improving releasability, and the like. Representative examples of organic fluoro compounds include JP-B-57-9053, columns 8 to 17,
JP-A-61-20944, JP-A-62-135826, etc., such as fluorine-based surfactants, or oil-like fluorine-based compounds such as fluorine oil or solid fluorine compound resins such as tetrafluoroethylene resin, etc. And hydrophobic fluorine compounds.

A matting agent can be used for the photosensitive material and the dye fixing material. Examples of the matting agent include silicon dioxide, polyolefin and polymethacrylate.
In addition to the compounds described on page 1-88256 (page 29), benzoguanamine resin beads, polycarbonate resin beads, AS resin beads and the like are disclosed in Japanese Patent Application No. 62-110064.
Nos. 62-110065.

In addition, the constituent layers of the light-sensitive material and the dye-fixing material may contain a heat solvent, an antifoaming agent, an antibacterial and antibacterial agent, colloidal silica, and the like. Specific examples of these additives are described in JP-A-61-88256, pages (26) to (32).

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

These can be used alone,
It can also be used as a support laminated on one or both sides 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,
Carbon black or another antistatic agent may be applied.

In the case of performing heat development on the heat-developable color light-sensitive material usable in the present invention, development can be carried out at a heating temperature of about 50 ° C. to about 250 ° C., particularly about 80 ° C. About 180 ° C. is useful. The dye diffusion transfer step may be performed simultaneously with the heat development, or may be performed after the heat development step. In the latter case, the heating temperature in the transfer step can be transferred within the range from the temperature in the heat development step to room temperature, but is more preferably from 50 ° C. or higher to about 10 ° C. lower than the temperature in the heat development step.

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

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

Also, JP-A-59-218443, 6
As described in detail in Japanese Patent Application Laid-Open No. 1-238056, it is also useful for a photothermographic material to perform development and transfer simultaneously or continuously by heating in the presence of a small amount of a solvent (particularly water).
In this method, the heating temperature is preferably 50 ° C. or higher and the boiling point of the solvent or lower. For example, when the solvent is water, the temperature is preferably 50 ° C. or more and 100 ° C. or less.

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). In addition, a low-boiling solvent or a mixed solution of a low-boiling solvent and water or a basic aqueous solution can also be used. Further, a surfactant, an antifoggant, a sparingly soluble metal salt and a complex-forming compound may be contained in the solvent.

These solvents can be used by a method for imparting to the dye fixing material, the photosensitive material, or both.
The amount used may be as small as not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film (especially not more than the weight of the solvent corresponding to the maximum swelling volume of the entire coating film minus the weight of the entire coating film).

As a method for applying a solvent to the photosensitive layer or the dye fixing layer, there is, for example, a method described in JP-A-61-147244, page (26). Further, the solvent may be contained in the photosensitive material or the dye-fixing material or both in advance, for example, by enclosing the solvent in microcapsules.

In order to promote the dye transfer, a method in which a hydrophilic heat solvent which is solid at normal temperature and dissolves at high temperature is incorporated in the photosensitive material or the dye fixing material can be adopted. The hydrophilic heat solvent may be incorporated in either the photosensitive 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 is preferably incorporated in the dye-fixing layer and / or an adjacent layer.

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

As a heating method in the developing and / or transferring step, a heated block or a plate is brought into contact with a heated plate, a hot presser, a heated roller, a halogen lamp heater, an infrared or far infrared lamp heater, or the like. Or passing through a high temperature atmosphere. Further, a resistive heating element layer may be provided on the photosensitive material or the dye fixing material, and the layer may be heated by being energized. 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 overlaid,
Japanese Patent Application Laid-Open No. Sho 6
The method described on page 1-127244 (27) can be applied.

For processing the light-sensitive material of the present invention, any of various developing devices can be used. For the processing of heat-developable color light-sensitive materials, see, for example, JP-A-59-75147,
Nos. 177547, 59-181353, 60-1
Nos. 8951 and 62-25944 are preferably used.

[0255]

EXAMPLES Hereinafter, the present invention will be described specifically 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 to the well-stirred aqueous solution having the composition shown in Table 7 over 15 minutes.
Solution III and Solution IV having the compositions shown in Table 1 were added over 35 minutes.
After washing with water and desalting, 25 g of gelatin was added, and 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 a 10 ^-4 second exposure.

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

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

[0259]

[Table 7]

[0260]

[Table 8]

[0261]

[Table 9]

[0262]

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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 carboxymethylcellulose as a dispersant, and 0.1 g of sodium polyacrylate were added to 100 cc of a 4% aqueous gelatin solution, and the average particle size was 0.75 mm.
Was ground for 30 minutes using glass beads. The glass beads were separated to obtain a gelatin dispersion of zinc hydroxide.

Next, a method for preparing a gelatin dispersion of a 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. The aqueous phase component heated to 60 ° C. was added thereto, and the mixture was dispersed at 5000 rpm for 30 minutes using a disperser having a diameter of 8 cm of a disperser. To this, post-water was added and stirred to obtain a uniform dispersion. This is called a gelatin dispersion of the hydrophobic additive.

[0267]

[Table 10]

With these materials, a heat-developable color light-sensitive material 101 having a multilayer structure as shown in Tables 11 and 12 was produced.

[0269]

[Table 11]

[0270]

[Table 12]

In Tables 10 to 12, the yellow dye-donating compound (1), the magenta dye-donating compound (2), and the cyan dye-donating compounds (3) and (4) are 37, 38 and 39. Further, the filter dye (5) is represented by Chemical formula 40, the auxiliary developing agent (6) is represented by Chemical formula 41, and the antifoggant (7) is represented by Chemical formula 42.
Are shown below. Further, the water-soluble polymer (8) is represented by the chemical formula (43), and the surfactants (9) and (10) are represented by the chemical formula (4).
4, the sensitizing dyes (12), (13) and (14) are
Are shown below. The antifoggant (1
5), (16), and (17) show the high boiling point solvent (1)
8), (19) and surfactants (20), (21),
(22) is shown in Chemical formula 47, respectively.

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

[0273]

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[0274]

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[0275]

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[0276]

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[0277]

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[0278]

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[0279]

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[0280]

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[0281]

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[0282]

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[0283]

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[0284]

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

In the light-sensitive material 101, the sensitizing dye (1) was used in the fifth layer instead of using 1.3 mg / m ² of the sensitizing dye (12).
2) 0.68 mg / m ² of the sensitizing dye of formula (34) 0.6
5 mg / m ² in combination, and sensitizing dye (13) 0.1 in the third layer.
Instead of using 06 mg / m ² , the sensitizing dye of formula (35)
A light-sensitive material 103 was prepared in exactly the same manner as the light-sensitive material 101 except that 0.07 mg / m ² was used.

[0287]

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

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

Emulsion (1) having an average grain size of 0.41 μm
And the yield was also substantially equal to 605 g. However, the crystal habit was potato-like with a slightly rounded cube.

Emulsion (5) Emulsion (2) except that the pH during chemical sensitization was 6.9, the pAg was 8.8, the temperature was 72 ° C., and the triethylthiourea during chemical sensitization was changed to sodium thiosulfate. Emulsion (5) was prepared in exactly the same manner as in (1).

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

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

The resulting 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 composition shown in Table 13 was used.
made.

[0296]

[Table 13]

The silicone oil (23), surfactants (24) and (25) and 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). The surfactant (9) is shown in Chemical formula 44, and includes the water-soluble polymers (26), (27),
The optical brightener (30) and the matting agent (33) are shown below.

Water-soluble polymer (26): Sumikagel L5
-H (manufactured by Sumitomo Chemical Co., Ltd.) Water-soluble polymer (27): dextran (molecular weight 70,000) Fluorescent whitening agent (30): 2,5-bis (5-tert-butylbenzoxazol (2)) thiophene Matting agent (33): benzoguanamine resin (average particle size 1
5μm)

[0299]

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[0300]

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The light-sensitive materials 101 to 104 were prepared as described in Japanese Patent Application No.
Exposure was performed using a semiconductor laser exposure device described in US Pat. The exposure conditions were as shown in Table 14.

[0302]

[Table 14]

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

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, the image-receiving material was superposed on the film surface so as to be in contact with the film surface. 25 using a heat roller so that the temperature of the water-absorbed film becomes 90 ° C.
Heated for seconds. Next, when the image receiving material was peeled off from the photosensitive material, magenta, cyan and yellow transferred images were obtained on the image receiving material.

The presence or absence of density unevenness was visually determined for the magenta and cyan transfer images.

The transferred image was measured with a self-recording densitometer, and the maximum density (Dmax) and minimum density (Dmin) at each exposure were determined.

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

The results are shown in Table 15.

The spectral sensitivities of the light-sensitive materials 101 to 104 were determined. The result is shown in FIG. As the spectral sensitivity, a relative sensitivity is used assuming that the spectral sensitivity at 755 nm of the third layer of the photosensitive material 103 is 10.

For the fifth layer (magenta) and the third layer (cyan) of the light-sensitive materials 101 to 104, respectively, the change in log (relative sensitivity) per nm in the emission wavelength region [Δlog (relative sensitivity) / nm], And the deviation of the 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 as described above, and the emission wavelength range of the third-layer exposure semiconductor laser is 755 to 758 nm.

The λmax of the photosensitive 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 understood that an image having a high Dmax and having 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 following silver halide emulsions were used for each layer.

32.0 g of lime-processed gelatin for the cyan coupler-containing layer was added to 1000 ml of distilled water, 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-dimethylimidazolidin-2-thione were added and the temperature was increased to 52.5.
° C. A solution of 62.5 g of silver nitrate in 750 ml of distilled water and 21.5 g of sodium chloride in 5 ml of distilled water
The solution dissolved in 00 ml was added at 52.5 ° C. with vigorous stirring for 40 minutes. 62.5g of silver nitrate
Dissolved in 500 ml of distilled water and sodium chloride 2
A solution of 1.5 g in 300 ml of distilled water was added to 52.5
C. with vigorous stirring over 20 minutes. In the sodium chloride aqueous solution to be added, 1 × 10 ⁻⁸ mol of potassium hexachloroiridate (IV) was added per mol of silver nitrate.

The emulsion thus obtained was observed by an electron microscope to show that the average grain size of the silver halide grains was 0.46.
μ, the particle size distribution was found to consist of monodisperse cubic particles having a coefficient of variation of 0.09.

After the emulsion was washed with desalted water, 0.2 g of nucleic acid was added.
Monodispersed bromide emulsion having an average grain size of 0.05 μm (1.2 × 10 ⁻⁵ mol of iridium hexachloride (I
V) (containing dipotassium acid) in an amount of 1.0 mol% as silver halide.
^-6 mol / mol Ag was subjected to chemical sensitization, and the compound of formula (V-6) was converted to 7 × 10 ^-6 mol / mol Ag, and the compound of formula (F-1) was converted to 5 × 10 ^-3 mol / mol. An emulsion to which mole Ag was added was prepared and used.

[0322]

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Emulsion for Magenta Coupler-Containing Layer In the preparation of the above emulsion grains, the temperature at the time of forming silver halide grains 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 the emulsion was washed with deionized water, the nucleic acid was washed with 0.2% of nucleic acid.
g, a monodispersed silver bromide emulsion having an average grain size of 0.05 μm (containing 1.8 × 10 ⁻⁵ mol of dipotassium hexachloroiridate (IV) per mol of silver bromide) was used as silver halide. 5 mol%, and further chemically sensitized with about 2.5 × 10 ⁻⁶ mol / mol Ag of triethylthiourea to give the compound of formula (V-3) 4.5 × 10 ⁻⁵ mol / mol. Ag, compound (F-1) of formula 51 was converted to 5 × 10 ^−3.
An emulsion to which mol / mol Ag was added was prepared and used.

[0325]

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Emulsion for Yellow Coupler-Containing Layer In the preparation of the above-mentioned emulsion for magenta coupler-containing layer, compound (V) was substituted for compound (V-3) instead of compound (V-3).
-7) and compound (V-8) were added at 1.2 × 10 ^-4 mol / mol Ag and 0.2 × 10 ^-4 mol / mol Ag, respectively, and compound (F-1) of formula 51 was added. Emulsions were prepared and used which differed only in that they were not added.

[0327]

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Compounds (D-1) and (D-D) shown in Chemical formulas 54 and 55 were added to the coated sample for the purpose of improving the safety against safelight and further improving the sharpness of the image.
2), (D-3), (D-4), (D-5) and (D
-6) was 16.0 mg / m ² , 6.0 mg / m ² and 8, respectively.
0 mg / m ² , 20.0 mg / m ² , 4.0 mg / m ² and 22.
0 mg / m ² was added.

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

[0330]

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[0331]

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In preparing a multilayer color photosensitive material,
After a corona discharge treatment on the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate is provided, and various photographic constituent layers are further applied to form a multi-layer color having the following layer structure. Photographic paper was produced. The coating solution was prepared as follows.

Preparation of Coating Solution for First Layer 19.1 g of yellow coupler (ExY: Chemical Formula 58), 4.4 g of color image stabilizer (Cpd-1: Chemical Formula 60) and 0 of color image stabilizer (Cpd-7: Chemical Formula 63) 0.7 g of ethyl acetate 2
4.2 cc and 4.1 g of each of the solvents (Solv-3: Chemical Formula 65) and (Solv-7: Chemical Formula 66) were added and dissolved, and this solution was dissolved in a 10% aqueous gelatin solution containing 8% of 10% sodium dodecylbenzenesulfonate. It was emulsified and dispersed in 185 cc to prepare an emulsified dispersion. This was combined with the previously prepared emulsion for a yellow coupler-containing layer, mixed and dissolved to prepare a first coating solution having the following composition.

The 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 hardener 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 in each layer was 25.0 mg / m ² and 50.50 mg / m ² , respectively.
0 mg / m ² was added.

[0336]

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In each of the yellow, magenta and cyan coloring layers, 1- (5-methylureidophenyl) -5-mercaptotetrazole was added to each of the emulsion layers at 8.0 × 10 ^-4 per mol of silver halide. It was added in moles. Further, the magenta coloring layer and the cyan coloring layer include
Compounds of formula 57 were added in an amount of 2.0 × 10 ^-3 mol each.

[0338]

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Tables 16 and 17 show the layer structure 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 a coating amount in terms of silver.

[0340]

[Table 16]

[0341]

[Table 17]

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

[0343]

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[0344]

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[0345]

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[0346]

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[0347]

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[0348]

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[0349]

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[0350]

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[0351]

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

Next, the spectral sensitizing dye of the silver halide emulsion used for the third layer of Sample 201 was changed to V-9 of Chemical Formula 67, and the addition amount was 1.4 × 10 ⁻⁵ mol / mol Ag. A sample 203 was prepared only by using the sample described above.

Further, the spectral sensitizing dye of the silver halide emulsion used for the third layer of Sample 202 was changed to V-9 of Chemical formula 67, and the added amount was 6.8 × 10 ⁻⁵ mol / mol Ag. A sample was prepared, which was different only in that the sample was used.

[0355]

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

[0358]

[Table 18]

[0359]

[Table 19]

[0360]

[Table 20]

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

For the third layer (magenta) of each of Samples 201 to 204, as in Example 1, 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

Further, the photographic characteristics of the samples 201 to 204 were determined by the same method as that used in Example 1. That is, exposure is performed for 10 ^-3 seconds using a xenon flash sensitometer manufactured by EG & G through an optical wedge and a decomposition filter that transmits light of a specific wavelength. A corresponding characteristic curve (color density-exposure curve) was created. However, the transmission wavelength of the decomposition filter was changed to 670 nm, 750 nm and 830 nm.

From the obtained characteristic curves, the γ value and the dynamic range of each layer were determined in the same manner as in Example 1. That is, as described above, for 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 0.5 larger than the corresponding exposure. The dynamic range corresponds to a value 0.2 lower than the exposure corresponding to a density 0.1 higher than the fog density and a density 0.1 lower than the maximum density (Dmax). (Δlog E) (see FIGS. 2 and 3).

Table 21 summarizes the results.

[0367]

[Table 21]

Next, a test for color density unevenness was performed using the same semiconductor laser exposure device as in Example 1. However, the semiconductor laser has an oscillation wavelength of 672 nm,
Changed to 50 nm and 830 nm. Further, the image pattern was changed so that three layers were simultaneously exposed to obtain a gradation adjusted so that the three colors of cyan, magenta and yellow were balanced with gray. For the processing of the exposed sample, the same processing steps and processing liquids as used in the sensitometry were used. Table 22 summarizes the results of evaluating the density unevenness of the obtained images.

In the above exposure with a semiconductor laser, color photographic paper (100 mm width, 148
(length) was continuously exposed for 40 sheets, the oscillation wavelength for magenta layer exposure varied from 750 nm to 753 nm, and the mode hopping phenomenon due to the temperature variation as shown in FIG. 1 occurred. Conceivable. Such a phenomenon is similar in any of the samples 201 to 204, and was observed in any of the modulation methods of time and intensity.

[0370]

[Table 22]

As is apparent from the above results, by applying the present invention, even in the laser scanning exposure method using color photographic paper, it is possible to obtain a high quality scanning image with high maximum color density and no unevenness. it can.

[0372]

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

[Brief description of the drawings]

FIG. 1 is a graph for explaining a mode hopping phenomenon due to a temperature change 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.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-35445 (JP, A) JP-A-3-121447 (JP, A) JP-A-61-231550 (JP, A) (58) Field (Int.Cl. ⁶ , DB name) G03C 5/08 G03C 1/12-1/26

Claims (4)

(57) [Claims] 1. An image forming method comprising: performing imagewise exposure on at least one photosensitive layer of a color photosensitive material having a photosensitive layer containing a photosensitive silver halide on a support using a modulatable light source; The exposure light source is a vertical single mode type semiconductor laser whose emission wavelength can fluctuate discontinuously with a change in temperature or light emission amount, and the emission wavelength during exposure is a spectral per 1 nm of the photosensitive layer. Variation of logarithm of sensitivity [Δlog
(Spectral sensitivity) / nm] is within ± 0.015 and the gamma (γ) of the photosensitive layer is 1.5.
An image forming method as described above. 2. An image forming method comprising: performing imagewise exposure on at least one photosensitive layer of a color photosensitive material having a photosensitive layer containing a photosensitive silver halide on a support using a modulatable light source; The exposure light source is a vertical single mode semiconductor laser whose emission wavelength can fluctuate discontinuously with a change in temperature or light emission amount, and the emission wavelength during exposure is the maximum spectral sensitivity wavelength of the photosensitive layer. (Nm) is within ± 10 nm, and the gamma (γ) of the photosensitive layer is 1.5 or more. 3. The light-emitting wavelength during the exposure is within a wavelength range in which the logarithmic change in spectral sensitivity per nm of the photosensitive layer [Δlog (spectral sensitivity) / nm] is within ± 0.015. Item 3. The image forming method according to Item 2. 4. The image forming method according to claim 1, wherein a dynamic range of the exposure amount (E) of the photosensitive layer is 2.0 or less in units of log E.