JPH05127324A - Silver halide photographic sensitive material and color image formation - Google Patents

Abstract

PURPOSE:To obtain a silver halide photographic sensitive material which is suitable for scanning exposure and excels resolving power and does not deteriorate much color separation by specifying the relationship of a lowering of the sensitivity of a photosensitive layer due to water soluble dyes in at least two kinds of photosensitive layers. CONSTITUTION:At least two kinds of photosensitive layers (layer A, layer B) of a photosensitive layer contain silver halide emulsion particles which are selectively and spectroscopically sensitized, suited to light beams of >=570nm (exposure of layer A: wavelength lambdaanm, exposure of layer B: lambdabnm; lambdaa>lambdab) and contain at least one kind of water soluble dyes having an absorption maximum at >=570nm. The light beam lambdaa of light beams is used and simultaneously the relationship of a lowering of the sensitivity of the photosensitive layer due to the water soluble dyes on exposure is shown by the formula I, where SQ (A:lambdaa) : sensitivity of photosensitive layer A at wavelength lambdaa without water soluble dye, SQ (B:lambdaa) : sensitivity of photosensitive layer B in the above case, SD<ye> (A:lambdaa) : sensitivity of photographic layer A at wavelength lambdaa with water soluble dye and SD<ye> (B, lambdaa) : sensitivity of photographic layer B in the above case.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material suitable for obtaining an image by scanning exposure with a high density light such as a laser or a light emitting diode, and a method for forming an image thereof. ..

[0002]

2. Description of the Related Art In recent years, techniques for transmitting and storing image information in place of electric signals and reproducing it on a CRT have been greatly developed. Along with this, the demand for obtaining a hard copy from this image information has increased, and various hard copy means have been proposed. For example, there are an electrophotographic method and a dye sublimation heat transfer method. However, many of these have poor image quality, and especially in color hard copy, they are incomparable with prints using current color paper. As a method of obtaining a hard copy from digital image information using a silver salt photograph, there is a method of obtaining a printed image by exposing using a CRT, but a satisfactory image quality can be obtained due to a thick beam of the CRT. The current situation is that it cannot be done. As a material which provides a high quality hard copy, there is a pictrography (trade name) manufactured by FUJIFILM Co., Ltd. which uses a silver halide heat development dye diffusion method and an LED scanning exposure method. Cost remains a problem.
On the other hand, due to advances in silver halide light-sensitive materials and compact and simple rapid development systems (for example, minilab system etc.), printed images of extremely high image quality can be supplied relatively easily in a short time and at low cost. Therefore, as a hard copy of image information, there is a great demand for such a hard copy material that is inexpensive, can be processed easily and quickly, and has stable performance, and that has high image quality.

As a method for obtaining a hard copy from an electric signal, a scanning exposure method is generally used in which image information is sequentially taken out and exposed, and a photosensitive material suitable for this is required. There is a so-called scanner type image forming method as a method of forming an image by scanning exposure. There are various types of recording devices that put the scanner system into practical use, and the light source for recording of these scanner type recording devices is a conventional glow lamp,
Xenon lamps, mercury lamps, tungsten lamps, light emitting diodes, etc. have been used. However, each of these light sources has a practical drawback that the output is weak and the life is short. There is a scanner that uses a coherent laser light source such as a He-Ne laser, an argon laser, a He-Cd laser, or another gas laser, or a coherent laser light source such as a semiconductor laser as a light source of a scanner system, as a means for compensating for these drawbacks. Although a high output can be obtained, the gas laser has drawbacks such as a large device, high cost, and need for a modulator. On the other hand, the semiconductor laser has advantages such as small size, low cost, easy modulation, and longer life than the gas laser. The emission wavelengths of these semiconductor lasers are mainly in the red region to the infrared region, so that a photosensitive material having high photosensitivity in the red region to the infrared region is required. However, the sensitizing dye for imparting spectral sensitivity from the red region to the infrared region is mainly a monomer band type sensitizing dye, and the wavelength dependency of the spectral sensitivity is generally broad. A full-color photosensitive material for laser (exposure wavelength λa, λb, λc) exposure is designed using these sensitizing dyes (for example, yellow is formed by exposure to a laser of λa, λ
Assuming the case where magenta is formed by exposure with the laser of b and cyan is formed by exposure with the laser of λc),
With the laser exposure of each wavelength, the photosensitive layer other than the photosensitive layer that is originally exposed to form a color also has sensitivity because the spectral sensitivity distribution of the sensitizing dye is broad, and therefore the color of the color to be formed is increased. Unwanted color is formed in the high density portion. (For example, in the case where magenta is formed by exposure with a λb laser, yellow and cyan are formed when the light amount of this exposure is large.) This means that color separation is poor.

In the conventional color light-sensitive material, it is general that yellow is formed by exposure of blue light, magenta is formed by exposure of green light, and cyan is formed by exposure of red light. In this case, spectral sensitivity is used as a sensitizing dye. This problem can be solved by using a J-band type sensitizing dye with a sharp distribution (blue photosensitive layer and green photosensitive layer) or by separating the exposed wavelength region (green photosensitive layer and red photosensitive layer). I've been around. However, in the red to infrared region, there is almost no preferable J-band type sensitizing dye at present. Further, there is a limitation on the wavelength of laser that can be used stably, and when designing a full-color light-sensitive material by laser exposure, the wavelength difference between each is about 80 nm at most. Therefore, the deterioration of the color separation becomes a big problem that the conventional photosensitive materials do not have. As a means for improving the color separation in the red to infrared region, the sensitivity difference between the photosensitive layers is sufficiently taken. Increases the gradation of the photosensitive material. Use a sensitizing dye whose spectral sensitivity distribution is as sharp as possible. A filter layer is provided between the light-sensitive layers that require color separation to reduce light that is exposed to the upper layer from reaching the lower photosensitive layer as much as possible. Etc. are possible. The method is a common method for designing a photographic light-sensitive material and is a general method. However, in this method, designing an emulsion and selecting a laser are often difficult. Although the method of 1 is advantageous in color separation, making the characteristics of the light-sensitive material in a high contrast means that a slight change in the amount of light appears as a large change in density, which causes variations in the exposure apparatus. The impact will be large and the system will be very difficult to control. In the above method, the use of a J band type sensitizing dye is also one method, but as described above, a preferable J band type sensitizing dye in the infrared region is hardly known. As the monomer type infrared sensitizing dye, JP-A-3-20,730, EP
It is known that a sensitizing dye having a sharp spectral sensitivity distribution can be obtained by selecting the structure of the infrared sensitizing dye as shown in -0,420,011 and EP-0,420,012. Has been. However, this effect is often slight, and the stability of the sensitizing dye and other photographic properties are often deteriorated. In the method of US Pat. No. 4,619,892, a non-diffusive filter layer is applied between two photosensitive layers so that the light sensitized in the upper layer reaches the lower photosensitive layer. To reduce as much as possible. And so on. However, the coating of this non-diffusive filter layer is liable to cause residual color after processing, which is a serious problem in a hard copy using a reflective support. This problem becomes more serious as the developing process time is shortened to obtain a hard copy more quickly. Therefore, it is very difficult to develop a light-sensitive material suitable for semiconductor laser exposure and excellent in color separation.

Further, when exposure is carried out using high-density light such as laser light having a long wavelength in the red to infrared region, light bleeding due to halation and irradiation is large,
It causes a large deterioration in resolution. Therefore, a water-soluble dye is used to prevent light bleeding of the light-sensitive material and to improve sharpness. The use of water-soluble dyes for preventing irradiation is generally carried out in silver halide photographic light-sensitive materials. For example, Japanese Patent Laid-Open No. 2-1577
No. 49 discloses a color light-sensitive material which has two or more light-sensitive layers spectrally sensitized in accordance with a laser light flux of 670 nm or more and which is colored with a coloring substance which can be decolorized in the development processing step. Oxonol dyes, hemioxonol dyes, merocyanine dyes, cyanine dyes and the like are generally known as these decolorizable and colorable dyes. It was believed that all of them could be used favorably. However, it has been found that these dyes deteriorate color separation when the amount of the dyes used is increased in order to sufficiently prevent irradiation. Therefore, the deterioration of the color separation due to the water-soluble dye is a very serious problem because the color separation is originally difficult especially in the color light-sensitive material of the type exposed by using at least two kinds of semiconductor lasers.

[0006]

As a semiconductor laser or a light emitting diode, it is possible to use a laser having a wavelength of about 570 nm or longer at present. Particularly, as a semiconductor laser, a laser having a wavelength of 700 nm or longer can be used. It has already been put to practical use. Therefore, the object of the present invention is to
A silver halide color photographic light-sensitive material suitable for scanning exposure using at least two monochromatic high-density light sources having a wavelength of about 570 nm or longer, particularly 700 nm or longer, excellent in resolution, and less deteriorated in color separation. Is to provide.

[0007]

The above object of the present invention is to provide a silver halide light-sensitive material having on a support at least three kinds of silver halide light-sensitive layers having different color sensitivities.
At least two types of photosensitive layers of the photosensitive layers (A layer, B layer; B layer has a spectral sensitivity maximum on the long-wave side as compared with A layer.)
Of 570 nm or more (exposure of layer A: wavelength λ a nm, B
Layer exposure: λb nm; containing silver halide emulsion grains selectively spectrally sensitized to λa <λb) and 57
The relationship between the decrease in the sensitivity of the photosensitive layer due to the water-soluble dye when exposed by using the light flux λa of the light flux, which contains at least one water-soluble dye having an absorption maximum at 0 nm or more, is represented by the formula (I). And a silver halide photographic light-sensitive material. (Formula I) S ⁰ (A; λa) -S ^Dye (A; λa) ≧ 0.4 O ≦ (S ⁰ A (λa) -S ^Dye A (λa))-(S ⁰ B (λa) -S ^Dye B (λa)) ≦ 0.2 S ⁰ (A; λa): Sensitivity of photosensitive layer A at wavelength λa in the absence of water-soluble dye S ^Dye (A; λa): Photosensitive layer in the presence of water-soluble dye Sensitivity A at wavelength λa S ⁰ (B; λa): Sensitivity at wavelength λa of photosensitive layer B without water-soluble dye S ^Dye (B; λa): Wavelength λa of photosensitive layer B when water-soluble dye is present The sensitivity of the present invention also relates to a silver halide light-sensitive material having on a support at least three kinds of silver halide light-sensitive layers having different color sensitivities, and at least two light-sensitive layers of the light-sensitive layers ( A layer, B layer; B layer has a spectral sensitivity maximum on the long-wave side as compared with A layer.
Layer exposure: wavelength λa nm, layer B exposure: λb nm; λa <λ
b)) containing at least one water-soluble dye having a silver halide emulsion grain which is selectively spectrally sensitized in accordance with (b) and having an absorption maximum at 700 nm or more, and exposed using a light flux λa of the light flux. The relationship in which the sensitivity of the photosensitive layer is lowered by the water-soluble dye at that time is more effectively achieved by the silver halide photographic light-sensitive material characterized by being represented by the formula (I).

Further, the above object of the present invention is to provide a silver halide light-sensitive material having at least three kinds of silver halide light-sensitive layers having different color sensitivities on a support, and at least two light-sensitive layers of the light-sensitive layers. (A layer, B layer; B layer has a spectral sensitivity maximum on the long-wave side as compared to A layer.) A light flux having a wavelength of 700 nm or more (A layer exposure: wavelength λ a nm, B layer exposure: λ b
nm; λa <λb) and containing at least one water-soluble dye having a silver halide emulsion grain selectively spectrally sensitized and having an absorption maximum at 700 nm or more. A silver halide photograph characterized in that the relationship between the reduction in the sensitivity of the photosensitive layer due to the dye and the maximum sensitivity of the spectral sensitivity of the A layer and the B layer when exposed using A silver halide color photographic light-sensitive material having on a reflective support at least three silver halide light-sensitive layers having different color sensitivities, each containing a light-sensitive material, especially a coupler that develops yellow, magenta, or cyan. Even more effectively achieved by the material. Formula (II) S ⁰ (A; λa) -S ^Dye (A; λa) ≧ 0.4 O ≦ (S ⁰ A (λa) -S ^Dye A (λa))-(S ⁰ B (λa) -S ^Dye B (λa)) ≦ 0.2 S _max. (A) −S _max. (B) ≦ 0.2 S ⁰ (A; λa): Sensitivity at wavelength λa of photosensitive layer A in the absence of water-soluble dye S ^Dye (A; λa): Sensitivity at wavelength λa of photosensitive layer A with water-soluble dye S ⁰ (B; λa): Sensitivity at wavelength λa of photosensitive layer B without water-soluble dye S ^Dye (B Λa): Sensitivity of photosensitive layer B at wavelength λa in the presence of water-soluble dye S _max. (A): Spectral maximum sensitivity of photosensitive layer A in the presence of water-soluble dye S _max. (B): Water-soluble dye The maximum spectral sensitivity of the light-sensitive layer B in the case where there is a further object of the present invention is to expose the above color photographic light-sensitive material by a scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds, and then perform color development processing. Color image forming method characterized by Achieved by law. Further, in the case of the color image forming method in which the color development processing time is 20 seconds or less and the total processing time including the color development processing to drying is 90 seconds or less, the effect of the present invention is more remarkably exhibited. In the present invention, the term “color sensitivity”, “spectral sensitization”, or “photosensitive layer” is used in a broad sense including not only visible light but also sensitivity to electromagnetic waves having a wavelength in the infrared region. Be done. Hereinafter, the content of the present invention will be described in detail. The light-sensitive material of the present invention needs to use a water-soluble dye. These water-soluble dyes are required to flow out or decolorize from the light-sensitive material in the development process. The water-soluble dye must contain at least one water-soluble group,
It is a dye capable of dissolving 0.2 g or more, preferably 0.5 g or more, in 100 ml of an aqueous solvent (25 ° C.). These dyes do not stay at the position of the added colloid layer, but uniformly diffuse during the coating and are distributed throughout the photosensitive material. Therefore, the purpose and characteristics are fundamentally different from the filter layer of the non-diffusible dye used in US-4,619,892. The water-soluble dye of the present invention is used for the purpose of cutting off irradiation light in a light-sensitive material to improve resolution. These water-soluble dyes are evenly distributed in the light-sensitive material film, and in a light-sensitive material having a light-sensitive layer on a reflective support like ordinary color paper, most of the amount of silver coated is small because the amount of coated silver is small. The incident light reaches the surface of the support and is reflected without being absorbed. Therefore, in such a light-sensitive material, not only the light from the surface but also the reflected light from the support greatly contributes to the sensitivity, so that it is generally the same that the sensitivity is lowered regardless of the position of the photosensitive layer. Is. Therefore, the use of the water-soluble dye does not improve the color separation as compared with the case without the dye. On the other hand, US-4,61
The filter layer of the non-diffusible dye used in No. 9,892 can prevent the light used for the exposure of the upper layer from reaching the lower layer, thereby improving the color separation as compared with the case where the filter layer is not used. Is the purpose. Therefore, it is necessary to fix between the two photosensitive layers a dye that effectively absorbs light having a wavelength used for exposure of the upper layer and does not absorb light used for exposure of the lower layer as much as possible. Moreover, from the spectral sensitivity distribution of the spectral sensitizing dye, for this purpose, a filter layer must be provided between the two photosensitive layers whose upper layer has the maximum spectral sensitivity on the shorter wave side than the lower layer. The configuration of the present invention is applied to the relationship between the spectral sensitivity of the upper layer and that of the lower layer regardless of whether the upper layer has a short wave or a long wave. As described above, the water-soluble dye does not contribute to the improvement of the color separation, but may worsen it. It is an advantage of the present invention that this deterioration can be minimized. The light-sensitive material of the present invention needs to satisfy the formula (I) by using a water-soluble dye. The respective sensitivities are measured using the scanning exposure apparatus used. The sensitivity shown here uses the common logarithm of the reciprocal of the energy of the laser beam of wavelength .lambda.a required to give a density of 1.0 for each of the photosensitive layers A and B. Furthermore, when the two types of photosensitive layers are selectively spectrally sensitized in accordance with a light flux of 700 nm or more, the difference in sensitivity between the two photosensitive layers at the maximum spectral sensitivity wavelength is 0.2 or less. It is more preferable from the viewpoint of selection of the laser of the exposure apparatus, design of the optical system, and the like. The maximum spectral sensitivity wavelength mentioned here is a wavelength that gives the maximum sensitivity of each photosensitive layer in the equienergetic spectral sensitivity distribution of the photosensitive material. Therefore, when a water-soluble dye or an antihalation layer is used, the spectral sensitivity maximum wavelength is determined from the equienergetic spectral sensitivity distribution of the photosensitive material containing the dye. The water-soluble dye preferably used in the present invention will be described in detail.

The dye used in the present invention is not particularly limited, and various known dyes conventionally known for photography can be used. In order to achieve the object of the present invention, a water-soluble dye having a small emission intensity and an absorption maximum at 570 nm or more is preferably used.

The dyes preferably used in the present invention include JP-A-64-42646 and US Pat.
Arylidene dyes described in 2,688; US 3,57
Anthraquinone dyes described in No. 5,704; Japanese Patent Publication No. 3-2
Triarylmethane dyes described in 6,813;
2-3250, JP-A-2,259,753, and 1-
Indoaniline dye described in JP-A-99040;
No. 65134, No. 2-181747, No. 2-1651.
Azomethine dye described in No. 33; JP-A-2-216140
No. 4, tetraarylpolymethine dyes; GB1,22
No. 6,562, copper phthalocyanine dye described in JP-A-1-13853; iron complex dye of 1,2-diaminonaphthalenedisulfonic acid described in US-3,177,078; US-4395544, JP-A-51- 104,3
42, J. Chem. Soc., Chem. Commun., 1639-16
40 (1986); azo dyes; JP-A 1-1218
51, No. 1-253734, metal-containing indoaniline dyes; J. Griffiths “Colourand Constitution of
Organic Molecules "Academic Press London (197
Examples thereof include the imager dyes described in 6).
The dyes described in these can be used as they are or after introducing a substituent (for example, a sulfonic acid group or a carboxyl group) as necessary. Examples of dyes preferably used in the present invention include the following general formulas (IV) to (IX)
The dyes represented by

[0011]

[Chemical 1]

In the formula, R ¹ is a hydrogen atom, a halogen atom, a sulfonic acid group, CONHR ⁷ , SO ₂ NHR ⁷ , NHCO.
R ⁷ represents a group represented by NHCONHR ⁷ or NHSO ₂ R ⁷ , wherein R ⁷ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group. R ² represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group,
R ³ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group, an ethoxy group, a 2-sulfoethoxy group, a methoxyethoxy group, etc.), NHCOR ⁷ , NHS
O ₂ R ⁷ or a group represented by NHCONHR ⁷ (R ⁷
Represents the same as the above), R ⁴ and R ⁵ may be the same or different from each other, and may be a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an acyl group (for example, an acetyl group, a propionyl group). ), A sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, etc.), and R ⁴
And R ⁵ are linked to each other to form a 5- or 6-membered ring (for example, a pyrrolidine ring,
Piperidine ring, morpholine ring, etc.) may be formed.
Further, R ⁴ and R ³ , and R ⁵ and R ³ may be connected to each other to form a 5- or 6-membered ring. R ⁶ is a hydrogen atom, sulfonic acid group, NH
COR ⁷ , NHSO ₂ R ⁷ , SO ₂ NHR ⁷ or NHC
It represents a group represented by ONHR ⁷ (R ⁷ has the same meaning as described above). n represents an integer of 1 to 4. (If n is 2 or more,
R ³ may be the same or different) provided that R ¹ , R ² ,
At least one of the groups represented by R ³ , R ⁴ , R ⁵ and R ⁶ contains a sulfonic acid group as a substituent.

Examples of the halogen atom represented by R ¹ and R ³ include F, Cl, Br and the like. R
^The alkyl group represented by ² , R ³ , R ⁴ , R ⁵ or R ⁷ is preferably a lower alkyl group having 1 to 5 carbon atoms (eg methyl group, ethyl group etc.), and a substituent (eg sulfonic acid group, carboxyl group) , A hydroxyl group, etc.).

The aryl groups represented by R ² , R ⁴ , R ⁵ or R ⁷ may be the same or different from each other, and may be a substituted or unsubstituted phenyl group (eg, a sulfonic acid group, a carboxyl group or a hydroxyl group as a substituent). , Cyano group, halogen atom (eg chlorine atom, fluorine atom, etc.), carbon number 1
To acyl groups (eg, acetyl group, propionyl group, etc.), sulfonyl groups having 1 to 5 carbon atoms (eg, methanesulfonyl group, ethanesulfonyl group, 2-sulfoethanesulfonyl group, 3-sulfopropanesulfonyl group, etc.), carbon Carbamoyl group having 1 to 5 carbon atoms (for example, unsubstituted carbamoyl group, methylaminocarbamoyl group, 2-sulfoethylcarbamoyl group, 2-carboxyethylcarbamoyl group, 2-hydroxyethylcarbamoyl group, etc.), sulfamoyl having 1 to 5 carbon atoms Group (eg, unsubstituted sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group, 2-sulfoethylsulfamoyl group, 2-carboxyethylsulfamoyl group, etc.), alkoxycarbonyl group having 1 to 5 carbon atoms (Eg methoxycarbonyl group, ethoxycarbo Group, trichloroethoxycarbonyl group, trifluoroethoxycarbonyl group, etc.), C1-C5 alkoxy group (eg, methoxy group, ethoxy group, etc.), amino group (eg, dimethylamino group, diethylamino group, etc.)} or substitution Alternatively, an unsubstituted naphthyl group (preferably the same substituent as the substituent in the case of a phenyl group) is preferable.

The substituted or unsubstituted heterocycle represented by R ⁷ represents a monocyclic heterocycle or a condensed heterocycle, for example, 1,3-thiazole ring, 1,3,4-triazole ring,
Benzothiazole ring, benzimidazole ring, benzoxazole ring, 1,3,4-thiadiazole ring, etc. (Substituents include, for example, lower alkyl groups such as methyl group and ethyl group, lower alkoxy groups such as methoxy and ethoxy groups, sulfonic acid Groups, hydroxyl groups, carboxyl groups, etc.) are preferred.

The following substituents can be mentioned as particularly preferable dyes in the formula (IV). R ¹ is CONHR
⁷ , NHCOR ⁷ or NHSO ₂ R ⁷ (R ⁷ is as defined above), R ² is hydrogen atom, R ³ is hydrogen atom, alkyl group (as defined above), alkoxy group (as defined above) , NHCOR ⁷ , or a group represented by NHCONHR ⁷ (R ⁷ is as defined above), and at least one of R ^{4 and} R ⁵ represents a sulfoalkyl group having 2 to 4 carbon atoms, and R
⁶ is a hydrogen atom, NHCOR ⁷ , NHSO ₂ R ⁷ or NH
A group represented by CONHR ⁷ (R ⁷ is as defined above), n
Represents 1 or 2. However, two or more sulfonic acid groups are contained in R ⁴ , R ⁵ or R ⁷ .

[0017]

[Chemical 2]

In the formula, R ⁸ , R ⁹ , R ^{10 and} R ¹¹ may be the same or different from each other, and are a hydrogen atom, a halogen atom (eg F, Cl, Br), a hydroxyl group, an amino group, a substituent or It represents an unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, R ¹² and R ¹³ may be the same or different from each other, and are a hydrogen atom or a halogen atom (for example, F 2
e, Cl, Br) or a sulfonic acid group. However, R
^At least one of the groups represented by ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² or R ¹³ contains a sulfonic acid group as a substituent.

The alkyl portion of the substituted or unsubstituted alkylamino group is preferably a lower alkyl group having 1 to 4 carbon atoms,
Examples of the substituent include a sulfonic acid group, a hydroxyl group, and a carboxyl group. The aryl portion of the substituted or unsubstituted arylamino group is preferably a phenyl group, and the substituent includes a lower alkyl group having 1 to 4 carbon atoms and 1 to 4 carbon atoms.
4 lower alkoxy group, sulfonic acid group, carboxyl group, hydroxyl group, halogen atom (for example, F, Cl, Br) or amino group (for example, dimethylamino group, ethylamino group).

The following substituents can be mentioned as particularly preferable dyes in the formula (V). R ⁸ , R ⁹ , R
¹⁰ or R ¹¹ may be the same or different from each other and represents a chlorine atom, a hydroxyl group, a methylamino group substituted by a sulfonic acid group or a phenylamino group substituted by a sulfonic acid group, and R ¹² and R ¹³ are They may be the same or different from each other and represent a hydrogen atom, a chlorine atom or a sulfonic acid group.
However, the dye molecule contains two or more sulfonic acid groups.

[0021]

[Chemical 3]

In the formula, R ¹⁴ represents a sulfonic acid group, and m
Represents an integer of 1 to 6 (preferably 1, 2 or 3).
More preferably, the molecule contains two sulfonic acid groups.

[0023]

[Chemical 4]

In the formula, R ¹⁵ , R ¹⁶ , R ^{17 and} R ^{18, which} may be the same or different, each represents an alkyl group, an aryl group, an acyl group or a sulfonyl group, and R ¹⁹ is an aryl group or a hetero group. Represents a cyclic group or a cyano group, R ²⁰ and R ²¹ may be the same or different from each other, Represent, n and m
Represents an integer of 1 to 4. However, R ¹⁵ , R ¹⁶ , R ¹⁷ ,
At least one of R ¹⁸ , R ¹⁹ , R ^{20 and} R ²¹ contains a sulfonic acid group as a substituent.

The alkyl group, aryl group, acyl group or sulfonyl group represented by R ¹⁵ , R ¹⁶ , R ¹⁷ or R ¹⁸ has the same meanings as those of R ⁴ of the formula (IV), and is represented by R ^19. The group has the same meaning as that of R ⁴ , and the heterocycle represented by R ¹⁹ may be substituted and may be a monocycle or a condensed ring. Examples include benzofuran and benzothiophene. Examples of the substituent have the same meaning as the substituent of the heterocycle described for R ⁷ .

The halogen atom, alkyl group and alkoxy group represented by R ²⁰ and R ²¹ have the same meanings as those of R ³ . The amino group represented by R ²⁰ and R ²¹ may be substituted, and examples thereof include an alkylamino group and an arylamino group. The alkylamino group and the arylamino group have the same meanings as those of R ⁸ . However, R ¹⁵ ,
At least one of the groups represented by R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ or R ²¹ contains a sulfonic acid group as a substituent.

More preferably in the general formula (VII), R
¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ are aryl groups or alkyl groups, R ¹⁹ is an aryl group, and R ²⁰ and R ²¹ are sulfonic acid groups. (Aryl group and alkyl group have the same meaning as above)

[0028]

[Chemical 5]

In the formula, R ²² , R ²³ , R ^{24 and} R ^{25, which} may be the same or different, each represents a hydrogen atom and a sulfonic acid group, and M represents a hydrogen atom or a metal atom. However, at least two (preferably three or more) sulfonic acid groups are included in the molecule. As the metal atom of M, Cu, N
Examples thereof include i, Cr, Al, Fe, Zn, V, Ti and Si. More preferable M is Cu.

[0030]

[Chemical 6]

In the formula, R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ may be the same or different from each other and represent a hydrogen atom and a sulfonic acid group, and M is a hydrogen atom or a metal atom (as defined above).
Represents. However, at least 2 (preferably 3) sulfonic acid groups are included in the molecule. More preferable M is Cu.

[0032]

[Chemical 7]

In the formula, R ³⁰ is a hydrogen atom, a halogen atom or C
^{ONHR 37, NHCOR 37, COR 37} , CO 2 R 37, N
The group represented by HCONHR ³⁷ or NHSO ₂ R ³⁷ (R
³⁷ represents an alkyl group, an aryl group or a heterocyclic group), and R ³¹ , R ³² or R ³³ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group,
It represents a group represented by NHCOR ³⁷ , NHCONHR ³⁷ or NHSO ₂ R ³⁷ (R ³⁷ is as defined above). R ³² and R
³³ may combine to form a 5- or 6-membered ring (eg, tetrahydropyridine ring, cyclohexene ring), R
³⁴ and R ³⁵ may be the same or different from each other and represent an alkyl group, an aryl group, an acyl group (eg, acetyl group, propionyl group) or a sulfonyl group (eg, methanesulfonyl group, ethanesulfonyl group, etc.). , R ³⁴ and R
³⁵ may be linked to form a 5- or 6-membered ring (for example, a pyrrolidine ring, a piperidine ring, etc.), and R ³⁵ and R ³⁶ or R ³⁴ and R ³⁶ may be linked to form a 5- or 6-membered ring. It may be formed. R ³⁶ is a hydrogen atom, a halogen atom, an alkyl group, a hydroxyl group, an alkoxy group (for example, a methoxy group, an ethoxy group, a 2-sulfoethoxy group, a methoxyethoxy group), NHCOR ³⁷ , NHSO ₂ R ³⁷ , NHCONHR.
Groups represented by ³⁷ (R ³⁷ is above the same meaning) it represents, n represents an integer of 1 to 4. However, R ³⁰ , R ³¹ , R ³² ,
At least one of the groups represented by R ³³ , R ³⁴ , R ^35, or R ³⁶ contains a sulfonic acid group as a substituent.

Examples of the halogen atom represented by R ³⁰ , R ³¹ , R ³² , R ³³ or R ³⁶ include F, Cl and Br. The alkyl group, aryl group or heterocyclic group represented by R ³⁷ has the same meaning as R ⁷ described above. R ³¹ ,
The alkyl group represented by R ³² , R ³³ , R ³⁴ , R ³⁵ or R ³⁶ and the aryl group represented by R ³⁴ or R ³⁵ are the same as the above R ²
Is synonymous with. More preferably, R ³⁰ is NHCOR
³⁷ or NHSO ₂ R ³⁷ (R ³⁷ is as defined above), and R
³¹ is a hydrogen atom, R ³² is a hydrogen atom, a halogen atom (for example, Cl, Br), an alkyl group (as defined above), and R ³³ is an alkyl group (as defined above), NHCOR ³⁷ or NHSO ₂ R ³⁷ (R ³⁷ is as defined above), R ³⁴ and R ³⁵ are an alkyl group or an alkyl group substituted with a sulfonic acid group (as defined above), and R ³⁶ is an alkyl group (as defined above), an alkoxy group. (Synonymous with the above) or NHCOR
³⁷ (R ³⁷ is as defined above) and n is 1. Further, the dye molecule contains at least two sulfonic acid groups.

The sulfonic acid group or carboxyl group described in the general formulas (IV) to (X) may be a salt thereof. Examples of salts include alkali metal salts such as Na and K, alkaline earth salts such as calcium, ammonium salts, organic ammonium salts such as triethylamine, tributylamine and pyridine, and intramolecular salts. Next, general formula (IV)
Specific examples represented by (X) to (X) are shown below, but the present invention is not limited thereto.

[0036]

[Chemical 8]

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

These dyes are disclosed in JP-A-62-3250.
No., "Dye Chemistry", Yutaka Hosoda (Gihodo), US 3,17
7,078, US 3,738,846 and GB
It can be easily synthesized with reference to Nos. 1,226,562 and the like.

The water-soluble dye used in the present invention can be generally dissolved in water and added to a coating solution to introduce it into a light-sensitive material.
The dye may be dissolved in a mixed liquid of water and an organic solvent (for example, methanol) and added to the coating liquid. The amount of the dye used in the present invention alone or in total is such that the reflectance of the photosensitive material containing the dye is 40% or less when measured at the exposure wavelength of the laser used for the light-sensitive material of the present invention. The amount is preferably 30% or less, more preferably 30% or less. Although the sharpness of the image is improved as the amount of the dye used is increased, the sensitivity is lowered accordingly. Therefore, the upper limit of the amount of the dye used is appropriately determined in consideration of the sensitivity. The reflectance can be calculated by measuring the reflection / absorption spectrum with a spectrophotometer equipped with an integrating sphere and determining the ratio of the reflected light to the incident light intensity.

The silver halide emulsion to be used in the present invention has the emulsion surface 0 as described in JP-A-3-84545 for the purpose of enhancing infrared spectral sensitization sensitivity and stability. High silver chloride grains containing 0.01-3 mol% of silver iodide are preferably used. Further, in order to accelerate the development processing time, a material which is substantially free of silver iodide and is made of silver chlorobromide or silver chloride can be preferably used. The phrase "substantially free of silver iodide" as used herein 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, but if an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (Shell) [a single layer or a plurality of layers] particles having a so-called laminated structure having a different halogen composition, or a structure having a portion having a different halogen composition inside or on the surface of the particle (edge of the particle when present on the particle surface, It is possible to appropriately select and use particles having a structure in which parts having different compositions are bonded to a corner or a surface. In order to obtain high sensitivity, it is advantageous to use either of the latter two particles rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

A so-called high silver chloride emulsion having a high silver chloride content is preferably used for a light-sensitive material suitable for rapid processing. In the present invention, the silver chloride content of the high silver chloride emulsion is 9
It is preferably 5 mol% or more, more preferably 97 mol% or more. In such a high silver chloride emulsion, a structure having a silver bromide localized phase in the inside and / or on the surface of the silver halide grain in a layered or non-layered manner as described above is preferable. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and preferably 20 mol%.
It is more preferable that the number exceeds. These localized phases can be present inside the particles, on the edges, corners, or on the surface of the particles, and one preferable example thereof is that epitaxially grown on the corners of the particles. 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, the silver chloride content is 9
An emulsion of substantially pure silver chloride such as 8 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 determined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1 μ to 2 μ. Is preferred. Further, the particle size distribution thereof is preferably a so-called monodispersed coefficient of variation coefficient (standard deviation of particle size distribution divided by average particle size) of 20% or less, preferably 15% or less. At this time, it is also preferable to use the above monodisperse emulsion by blending it in the same layer for the purpose of obtaining a wide latitude, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is one having a regular crystal form such as a cube, a tetradecahedron or an octahedron, an irregular shape such as a sphere or a plate.
Those having a gular) crystal form, or those having a composite form thereof can be used. It may also be a mixture of those having various crystal forms. In the present invention, it is preferable that 50% or more, preferably 70% or more, and more preferably 90% or more of the particles having the above-mentioned regular crystal form are contained in the present invention.

In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of the total grain as a projected area is also preferably used. it can. The silver chlorobromide emulsion used in the present invention is a Chimie et Phisique by P. Glafkides.
Photographique (Paul Montel, 1967), GF
Photographic Emulsion Chemistry (Focal Pre by Duffin
ss, 1966), by VL Zelikman et al Makinga
nd Coating Photographic Emulsion (Focal Press, 1964) and the like. That is, any of the acidic method, the neutral method, the ammonia method, etc. may be used, and the method of reacting the soluble silver salt with the soluble halogen salt may be any of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. A method may be used. It is also possible to use a method of forming particles in an atmosphere in which silver ions are excessive (so-called reverse mixing method). As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained. The localized phase of the silver halide grain of the present invention or its substrate includes
It is preferable to contain a different kind of metal ion or its complex ion in order to increase sensitivity, increase contrast, improve latent image stability and exposure temperature dependency. Ions or complex ions selected from iridium, rhodium, iron, etc. mainly in the localized phase, and metal ions selected mainly from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron etc. in the substrate Alternatively, it is preferable to use the complex ions in combination. Further, the type and concentration of the metal ion can be changed between the localized phase and the substrate. Plural kinds of these metals may be used. Further, metal ions such as cadmium, zinc, lead, mercury and thallium can also be used.

The silver halide emulsion used in the light-sensitive material for scanning exposure with a laser or the like is suitable for high-intensity exposure, and it is necessary to have a gradation capable of producing a required density within the laser exposure control range.
Further, when an infrared semiconductor laser is used, it is necessary to carry out infrared spectral sensitization, and especially in this case it is necessary to improve the storage stability. For these purposes, it is very useful to use iridium, rhodium, ruthenium, or iron ions or complex ions among the above metal ions. The amount of these metal ions or complex ions to be used varies greatly depending on the silver halide emulsion composition, size, dope position, etc. of the dope substrate, but each of iridium and rhodium ions is 5 × 10 ⁻⁹ mol to 1 mol of silver.
1 × 10 ⁻⁴ mol is preferable, and 1 × 10 ⁻⁷ mol to 5 × 10 ⁻³ mol of iron ion is preferably used per 1 mol of silver. These metal ion-providing compounds are used in a gelatin aqueous solution, which is a dispersion medium at the time of silver halide grain formation, in a halide aqueous solution, in a silver salt aqueous solution or in another aqueous solution,
Alternatively, it may be added to the localized phase and / or other grain portion (substrate) of the silver halide grain of the present invention by means such as adding in the form of silver halide fine grain containing metal ions in advance and dissolving the fine grain. Excuse me. The metal ion used in the present invention can be incorporated into the emulsion grains either before grain formation, during grain formation, or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, and tellurium sensitization with a tellurium compound are performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. 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. To the silver halide emulsion used in the present invention, various compounds or precursors thereof are added for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A No. 62-215272 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, a laser or L is used for exposure.
The purpose is to use monochromatic high-density light such as ED, and it is necessary to perform spectral sensitization according to the wavelength of these light fluxes. Spectral sensitization according to this luminous flux means spectral sensitization using a sensitizing dye having spectral sensitivity at the wavelength of this luminous flux, and the spectral sensitization sensitivity maximum is not necessarily the wavelength of this luminous flux. It does not mean only to match. From the viewpoint of sensitivity due to these light fluxes and color separation, it is preferable that the wavelength of this light flux coincides with the maximum spectral sensitivity wavelength. It is also preferable to design by shifting the luminous flux wavelength and the spectral sensitivity maximum wavelength. In the present invention, the addition of a dye (spectral sensitizing dye) that absorbs light in the wavelength region corresponding to the target spectral sensitivity to a photosensitive layer other than the photosensitive layer of the present invention can also be performed. preferable. Examples of spectral sensitizing dyes used for these spectral sensitizations include, for example, Heterocyclic compounds-Cyanine dye by FM Harmer.
es and relared compounds (John wiley & Sons 〔New
[York, London], 1964). As specific examples of the compound and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used.

When a semiconductor laser is used as a light source for digital exposure in the present invention, it is necessary to efficiently spectrally sensitize the red to infrared region. Particularly, in order to spectrally sensitize a region of 730 nm or more, JP-A-3-15049 1
Page 2, upper left column to Page 21, lower left column, or JP-A-3-207
No. 30, page 4, lower left column, to page 15, lower left column, EP-0, 420,
011 page 4, line 21 to page 6, line 54, EP-0,420,
012, page 4, line 12 to page 10, line 33, EP-0,44
The sensitizing dyes described in 3,466 and US-4,975,362 are preferably used. These sensitizing dyes are relatively stable chemically, are relatively strongly adsorbed on the surface of silver halide grains, and are strongly resistant to desorption by a coexisting dispersion such as a coupler. As the sensitizing dye for infrared sensitization, a compound having a reduction potential of -1.05 (VvsSCE) or a base value lower than that is preferable, and a reduction potential of-is particularly preferable.
Compounds having a value of 1.10 or less are preferred. A sensitizing dye having this characteristic is advantageous for high sensitivity, particularly for stabilizing sensitivity and latent image. The reduction potential can be measured by phase discrimination type second harmonic AC polarography. A mercury dropping electrode is used as the working electrode, and a saturated calomel electrode is used as the reference electrode.
Further, platinum is used as the counter electrode. In addition, the measurement of reduction potential by phase discrimination second harmonic AC voltammetry using platinum as the working electrode is described in "Journal of Imaging.
Sanence "(Journal of Imaging Science), No. 30
Vol. 27-35 (1986).

To incorporate these spectral sensitizing dyes in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, Japanese Patent Publication No. 44-27555, Japanese Patent Publication No. 57-
As described in US Pat. No. 22089 and the like, an aqueous solution is prepared by coexisting an acid or a base, and as described in US Pat. No. 3,822,135, US Pat. It may be added to the emulsion. Alternatively, the emulsion may be dissolved in a solvent which is substantially immiscible with water such as phenoxyethanol and then dispersed in water or a hydrophilic colloid to add to the emulsion. JP-A-53-102733, JP-A-58-105141
Alternatively, the dispersion may be directly dispersed in a hydrophilic colloid, and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, it is carried out after the completion of the chemical sensitization and before the application.
No. 6,289,139 and No. 4,225,666, the spectral sensitization can be carried out simultaneously with the chemical sensitization by adding it at the same time as the chemical sensitizer.
It can be carried out prior to chemical sensitization as described in No. 28, or it can be added before the completion of silver halide grain precipitation to initiate spectral sensitization. Furthermore, the spectral sensitizing dyes may be added separately as taught in U.S. Pat. No. 4,225,666, i.e. a portion prior to chemical sensitization and the balance after chemical sensitization. Additions are also possible and can be at any time during silver halide grain formation, including the method taught in U.S. Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the emulsion washing step or before chemical sensitization.

The amount of these spectral sensitizing dyes added is in a wide range depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ⁻³
It is in the molar range. In the present invention, when a sensitizing dye having a spectral sensitizing sensitivity from the red region to the infrared region is used, the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column, may be used. preferable. By using these compounds, it is possible to specifically enhance the storability of the light-sensitive material, the processing stability, and the supersensitizing effect. Among them, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of 0.5 × 10 ⁻⁵ mol to 5.0 mol per mol of silver halide.
× 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol to 1.0
An amount of × 10 ^-2 mol is used, and 1 is used per mol of the sensitizing dye.
The amount used is advantageously in the range of 2 times to 10,000 times, preferably 2 times to 5,000 times.

The constitution of the light-sensitive material of the present invention will be described. The light-sensitive material of the present invention has at least three silver halide emulsion layers on a support, at least two of which are 570
It is necessary to have the spectral sensitivity maximum at nm or more. The sensitive material of the present invention includes a gas laser, a light emitting diode,
It is used for digital scanning exposure using monochromatic high-density light such as a semiconductor laser. It is particularly preferred to use a semiconductor laser to make the system compact and inexpensive. In order to use this inexpensive, highly stable, and compact semiconductor laser, at least two layers are 670
It is preferable to have the spectral sensitivity maximum at nm or more.
This is because the emission wavelength range of the currently available, inexpensive and stable semiconductor lasers that can be put to practical use is currently only in the red to infrared range. However, at the laboratory level, oscillation of semiconductor lasers in the green and blue regions has been confirmed, and it is not enough that these semiconductor lasers can be used inexpensively and stably if semiconductor laser manufacturing technology is developed. Expected. In such cases, at least 2
The need for the layer to have a spectral sensitivity maximum above 670 nm is reduced.

The light-sensitive layer in the light-sensitive material of the present invention preferably contains at least one coupler capable of forming a color by a coupling reaction with an oxidation product of an aromatic amine compound. For full-color hard copy, at least three types of silver halide photosensitive layers having different color sensitivities are provided on a support, and each layer is yellow by a coupling reaction with an oxidant of an aromatic amine compound. Magenta,
Alternatively, it is preferable to contain any of the couplers that develop cyan. These three different spectral sensitivities can be arbitrarily selected according to the wavelength of the light source used for digital exposure, but it is preferable that the closest spectral sensitivity maxima be at least 30 nm apart. At least three types of photosensitive layers having different spectral sensitivity maximums (λ1, λ
The correspondence with the color forming couplers (Y, M, C) contained in 2, λ3) is not particularly limited. That is, 3 × 2 = 6 combinations are possible, but in some cases it is preferable to use the longest-wavelength photosensitive layer as the yellow coloring layer from the viewpoint of the resolution of human eyes. Also, there is no particular restriction on the coating order from the support side of the photosensitive layer having at least three different spectral sensitivity maxima, but from the viewpoint of rapid processing, the photosensitive layer containing silver halide grains having the largest average size is the uppermost layer. In some cases, it may be preferable to come to Japan. Further, from the viewpoint of sharpness, it may be preferable that the photosensitive layer having the longest wave spectral sensitivity comes to the uppermost layer. Further, in some cases, it is preferable that the lowermost layer is a magenta color-developing layer using a pyrazoloazole type magenta coupler from the viewpoint of storage stability under light irradiation of hard copy. Therefore, with these three different spectral sensitivities,
There are 36 possible combinations of the three color couplers and the layer sequence. The present invention can be effectively used for all the 36 types of light-sensitive materials. Table 1 shows the digital exposure light source
Specific examples of the coupler having a maximum spectral sensitivity and a color forming coupler are shown below, but the coupler is not limited thereto.

[0059]

[Table 1]

The exposure in the present invention will be described. The photosensitive material in the present invention is intended to be used for scanning digital exposure in which an image is exposed by moving a high-density beam light such as a laser or an LED relative to the photosensitive material. Therefore, the exposure time of the silver halide in the light-sensitive material is the time required to expose a certain minute area. As this minute area, the minimum unit for controlling the light amount from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is in a practical range of 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 1
It is 0 ^-4 seconds or less, and more preferably 10 ^-6 seconds or less.

In the light-sensitive material according to the present invention, in addition to the dye having the constitution of the present invention, a hydrophilic colloid layer is provided in order to improve safety of safelight and the like, and European Patent EP 0337490A is used.
A dye (oxonol dye, cyanine dye) which can be decolorized by the treatment described on pages 27 to 76 of No. 2 specification can be added together. Among these dyes, it is necessary to pay attention to the amount used because the color separation is deteriorated if the amount used is increased depending on the absorption wavelength range of the dye. When these dyes are used, it is preferable to select and use a dye having an absorption that overlaps the spectral sensitivity maximum of the longest-wave photosensitive layer. When these dyes and the dye of the present invention are used in combination, the optical density (logarithm of the reciprocal of transmitted light) (reflection density in the case of a reflective support) at the laser wavelength of the light-sensitive material becomes 0.5 or more. This is preferable in order to improve sharpness. To further improve the sharpness, 12% by weight or more (more preferably 14% by weight) of titanium oxide surface-treated with a dihydric or tetravalent alcohol (eg, trimethylolethane) in the water resistant resin layer of the support. Above) It is preferable to contain. Further, it is also preferable to use colloidal silver in the antihalation layer as described in JP-A-1-239544. Further, in the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent EP 0277589A2 together with a coupler.
In particular, it is preferably used in combination with a pyrazoloazole coupler. That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, the light-sensitive material according to the present invention has an anti-photosensitive property as described in JP-A-63-271247. It is preferable to add a fungicide. The support used in the light-sensitive material according to the present invention may be a white polyester-based support for a display or a support provided with a layer containing a white pigment on the support having a silver halide emulsion layer. You may use. Further, in order to further improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer coated side or the back side of the support.
In particular, the transmission density of the support is preferably set in the range of 0.35 to 0.8 so that the display can be viewed with both reflected light and transmitted light. Further, as the support used in the light-sensitive material according to the present invention, a transparent support is also preferably used. At this time, it is preferable to apply an antihalation layer on the side or surface of the support on which the silver halide emulsion layer is coated. The exposed light-sensitive material may be subjected to conventional black-and-white or color development processing, but in the case of a color light-sensitive material, it is preferable to perform bleach-fix processing after color development for the purpose of rapid processing. Especially when the high silver chloride emulsion is used,
The pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing the light-sensitive material. As additives, the following patent publications, particularly European patent EP
No. 0,355,660 A2 (JP-A-2-139544)
No.) those described in the specification are preferably used.

[0063]

[Table 2]

[0064]

[Table 3]

[0065]

[Table 4]

[0066]

[Table 5]

[0067]

[Table 6]

Further, as a cyan coupler, JP-A-2
In addition to the diphenylimidazole type cyan coupler described in JP-A-33144, European Patent EP 0333185A.
3-Hydroxypyridine cyan couplers described in No. 2 (in particular, the couplers listed as specific examples (4
(Especially preferred are couplers (6) and (9), which are obtained by adding a chlorine-leaving group to the 4-equivalent coupler of 2) to make them 2-equivalent).
It is also preferable to use a cyclic active methylene cyan coupler described in JP-A-64-32260 (specifically, coupler examples 3, 8, and 34 listed as specific examples). The method for processing the color sensitive material of the present invention includes:
The method described in JP-A-2-207250 is preferable. The processing temperature of the color developer applicable to the present invention is 20 to 5
The temperature is 0 ° C, preferably 30 to 45 ° C. The processing time is preferably substantially 20 seconds or less. The amount of replenishment is preferably as small as possible, but ^{20 to} 600 ml is appropriate per 1 m ^{2 of} the light-sensitive material, and preferably 50 to 300 ml. More preferably 60-200 ml, most preferably 60-150 ml
Is. In the present invention, it is preferable that the development time is substantially within 20 seconds. The term "substantially 20 seconds" as used herein means that the photosensitive material is stored in the next tank from the time when the photosensitive material enters the developer tank. It means the time until it enters, and it also includes the transit time in the air from the developer tank to the next tank. The pH of the washing step or the stabilizing step is preferably 4 to 10, more preferably 5 to 8. Although the temperature can be variously set depending on the use and characteristics of the light-sensitive material, it is generally 30 to 45 ° C., preferably 3
5 to 42 ° C. The time can be set arbitrarily, but a shorter time is preferable from the viewpoint of reducing the processing time. Preferably 10
~ 45 seconds, more preferably 10-40 seconds. The smaller the replenishment amount, the more preferable from the viewpoint of running cost, reduction of discharge amount, handleability and the like.

A specific preferable amount of replenishment is 0.5 to 50 times, preferably 2 to 15 times the amount carried in from the prebath per unit area of the light-sensitive material. Or 3 per 1 m ^{2 of} light-sensitive material
The amount is 00 ml or less, preferably 150 ml or less. The replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be further used in the previous step. An example of this is that the overflow of washing water reduced by the multi-stage countercurrent method is caused to flow into the bleach-fixing bath of the preceding bath, and the bleach-fixing bath is replenished with a concentrated liquid to reduce the amount of waste liquid. Next, the drying process that can be used in the present invention will be described. A drying time of 20 to 40 seconds is desired in order to complete an image by the ultra-rapid processing of the present invention. As a means for shortening the drying time, as a means on the side of the light-sensitive material, it is possible to improve by reducing the amount of water taken into the film by reducing the amount of a hydrophilic binder such as gelatin. Further, from the viewpoint of reducing the carry-in amount, it is also possible to accelerate the drying by absorbing the water with a squeeze roller or a cloth immediately after leaving the washing bath. As a means of improvement from the dryer, it goes without saying that it is possible to accelerate the drying by increasing the temperature or increasing the drying air. Further, the drying can be accelerated by adjusting the blowing angle of the drying air to the light-sensitive material or by removing the discharged air.

An embodiment of the present invention will be described below with reference to the accompanying drawings. However, the present invention is not limited to this embodiment. FIG. 1 is a schematic configuration diagram of an image forming apparatus using a silver salt photographic color paper according to an embodiment of the present invention. This image forming apparatus forms an image on a color paper by exposing the color paper, developing, bleach-fixing, washing with water and drying. The color paper (hereinafter referred to as a light-sensitive material) used in the image forming apparatus is a color photographic light-sensitive material having at least one layer of a silver halide emulsion containing 95 mol% or more of silver chloride on a support, Color development is performed with a color developing solution containing an aromatic primary amine color developing agent. Image forming apparatus main body 1
0 is an exposure device 300, a developing tank 12, a bleach-fixing tank 14,
A washing tank 16, a water draining section 17, and a drying section 18 are continuously provided, and the exposed photosensitive material 20 is developed, bleach-fixed, washed with water, dried and then carried out of the main body 10. Developing tank 12, bleach-fixing tank 14, washing tank 16, draining section 17, drying section 18
Is provided with a pair of transport rollers 24 that sandwich the photosensitive material 20 and transport each processing section. The transport roller pair 24 in the water draining section 17 also serves as a water removing roller having a function of removing water droplets on the photosensitive material 20 by squeezing, absorbing, or the like. The photosensitive material 20 is subjected to color development processing by being dipped in the processing liquid for a predetermined time while being nipped and conveyed with the emulsion surface facing down by a pair of conveying rollers 24. Development tank 1
2. The bleach-fixing tank 14 and the water washing tank 16 are provided with a treatment liquid ejecting member 30 for ejecting the treatment liquid with a strong force to generate a high-speed jet in the treatment tank at predetermined positions. Development tank 1
2. A pump 32 is provided corresponding to each of the bleach-fixing tank 14 and the washing tank 16. Each processing solution is circulated by the pump 32 and the photosensitive material 20 is discharged by the processing solution ejecting member 30.
Is jetted toward.

FIG. 2 is a block diagram of the exposure apparatus 300. The exposure device 300 emits light of three colors as one set to expose the photosensitive material 20. In the exposure apparatus 300, the drive circuits 242, 244, 246 drive the semiconductor lasers 251, 252, 253 based on the image data processed by the image processing apparatus 240 connected to a computer or the like, thereby exposing the photosensitive material 20. Expose. In the exposure apparatus 300, the light for developing magenta has a wavelength of 750 nm.
It is formed by the semiconductor laser 251 which emits the laser light of. The semiconductor laser 251 is, for example, Sharp Corporation.
It is LTO 30MF. Laser light having a wavelength of 750 nm emitted from the semiconductor laser 251 is collimator lens 2
The light is shaped through 58 and is reflected by the total reflection mirror 261 toward the polygon mirror 270. The light for developing cyan is formed by a semiconductor laser 252 that emits laser light having a wavelength of 830 nm. The laser light having a wavelength of 830 nm emitted from the semiconductor laser 252 is
The light is shaped through the collimator lens 259, and is reflected toward the polygon mirror 270 by the dichroic mirror 262 that passes the light for developing magenta and reflects the light for developing cyan. The semiconductor laser 252 is, for example, Toshiba's TOLD152R or Sharp's LTO10MF. Light for developing yellow is formed by a semiconductor laser 253 that emits laser light having a wavelength of 670 nm. The semiconductor laser 253 is, for example, TOLD9200 manufactured by Toshiba Corporation, NDL3200 manufactured by NEC Corporation, SLD1 manufactured by Sony Corporation.
It is 51U. Wavelength 67 emitted by the semiconductor laser 253
The laser light of 0 nm is shaped through the collimator lens 260, passes through the light for developing magenta and the light for developing cyan, and reflects the light for developing yellow, and the dichroic mirror 263 reflects the polygon mirror 270. Is reflected toward. The above-mentioned light for developing cyan, magenta, and yellow passes through the same optical path 264, is reflected by the polygon mirror 270, passes through the fθ lens 280, and is further reflected by the mirror 290 to reach the photosensitive material 20. Then, the polygon mirror 270 rotates about the axis 271 to scan and expose the photosensitive material 20 with the image light. Then, the photosensitive material 20
Is a direction orthogonal to the scanning direction of the laser light (indicated by arrow A)
The image is formed by sub-scanning by moving to.
Here, the moving speed of the photosensitive material 20 during the exposure is equal to the moving speed during the developing process, and the exposed portion of the photosensitive material 20 starts the developing process after the same time has elapsed. Further, although the exposure device 300 is configured to expose the photosensitive material 20 based on image information processed by a computer or the like, it is also possible to expose the photosensitive material 20 based on image information obtained by reading a document.

[0072]

【Example】

Example 1 (Preparation of Emulsion a) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (2% aqueous solution) was added. An aqueous solution containing 0.2 mol of silver nitrate, 0.2 mol of sodium chloride and 15 μg of rhodium trichloride.
And was mixed with the aqueous solution containing at 50 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride and 4.2 mg of potassium ferrocyanide were added and mixed at 56 ° C. with vigorous stirring. The addition of the aqueous silver nitrate solution and the aqueous alkali halide solution was completed. Thereafter, a copolymer of isobutene maleic acid 1-sodium salt was added, and the mixture was washed by sedimentation and desalting. Furthermore, lime-processed gelatin 90.0 g
Was added to adjust the pH and pAg of the emulsion to 6.2 and 6.5, respectively. After 5 minutes, an aqueous solution containing 0.02 mol of silver nitrate and an aqueous solution containing 0.015 mol of potassium bromide, 0.005 mol of sodium chloride and 0.8 mg of potassium hexachloroiridium (IV) ate were stirred vigorously at 40 ° C. Was added and mixed. 10 minutes later, a sulfur sensitizer (triethylthiourea) 1 × 10 ^-5 mol / molAg, chloroauric acid 1 × 10 ^-5 mol / molAg, and nucleic acid 0.2 g / molAg
Was added, and optimal chemical sensitization was performed at 50 ° C.

With respect to the obtained silver chlorobromide grains a, the grain shape, grain size and grain size distribution were determined from electron micrographs. All of these silver halide grains are cubic and have a grain size of 0.52 μm and a coefficient of variation of 0.
It was 08. The grain size is represented by the average value of the diameter of the circle equivalent to the projected area of the grain, and the coefficient of variation is the standard deviation of the grain size divided by the average grain size. Then
The halogen composition of the emulsion grains was determined by measuring the X-ray diffraction from silver halide crystals. The diffraction angle from the (200) plane was measured in detail using a monochromatic Cukα ray as a radiation source. A diffraction line from a crystal having a uniform halogen composition gives a single peak, whereas a diffraction line from a crystal having a localized phase having a different composition gives a plurality of diffraction patterns corresponding to those compositions. The halogen composition of the silver halide constituting the crystal can be determined by calculating the lattice constant from the diffraction angle of the measured peak. The measurement results of this silver chlorobromide emulsion a show that, in addition to the main peak of 100% of silver chloride, the center is at 70% of silver chloride (30% of silver bromide) and around 60% of silver chloride (40% of silver bromide). I was able to observe a broad diffraction pattern that stretched to the bottom.

(Preparation of Sensitive Material A) After corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and various photographic constituent layers were further coated. A multilayer color photographic paper having the following layer structure was prepared. The coating liquid was prepared as follows. Preparation of coating liquid for the first layer Yellow coupler (ExY) 19.1 g and color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-)
7) 0.7 g of ethyl acetate 27.2 cc and solvent (So
lv-3) and (Solv-7) 4.1 g each
The solution was added and dissolved, and the solution was dissolved in 10% sodium dodecylbenzenesulfonate (8 cc) in 10% gelatin aqueous solution 185.
cc was emulsified and dispersed to prepare an emulsified dispersion. On the other hand, the silver chlorobromide emulsion (a) has the following red-sensitive sensitizing dye (Dye-
An emulsion containing 1) was prepared. The above emulsified dispersion and this emulsion were 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 hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-
10 and Cpd-11 were added so that the total amount would be 25.0 mg / m ² and 50.0 mg / m ² , respectively. Examples of the spectral sensitizing dye of each layer include the following (Dye-1) (Dye-2)
(Dye-3) was used.

[0075]

[Chemical 18]

[0076]

[Chemical 19]

In the magenta photosensitive layer and the cyan photosensitive layer, (Cpd-12) and (Cpd-13) as supersensitizers were respectively added in an amount of 1.8 × 10 ^-3 mol per mol of silver halide and 2.
0 × 10 ⁻³ mol was added. Further, 1- (5 for the yellow color-forming emulsion layer, the magenta color-forming emulsion layer, and the cyan color-forming emulsion layer.
-Methylureidophenyl) -5-mercaptotetrazole was added to each of 8.0 x 10 per mol of silver halide.
^-4 mol was added. (Layer constitution) The composition of each layer is shown below. Numbers are coating amount (g
/ M ² ). The silver halide emulsion represents the coating amount in terms of silver. Support Polyethylene laminated paper First layer containing polyethylene containing white pigment (TiO2) and bluish dye (marine blue) First layer (red sensitive yellow color forming layer) Silver chlorobromide emulsion (a) 0.30 Gelatin 1 .22 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-3) 0.18 Solvent (Solv-7) 0.18 Color image stabilizer (Cpd-7) 0 .06

Second Layer (Color Mixing Prevention Layer) Gelatin 0.64 Color mixing inhibitor (Cpd-5) 0.10 Solvent (Solv-1) 0.16 Solvent (Solv-4) 0.08 Third layer (infrared Photosensitive magenta color-developing layer) Silver chlorobromide emulsion (a) 0.12 Gelatin 1.28 Magenta coupler (ExM) 0.23 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-3) 0.16 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-9) 0.02 Solvent (Solv-2) 0.32 Fourth layer (UV absorbing layer) Gelatin 1.41 UV absorption Agent (UV-1) 0.47 Color mixing inhibitor (Cpd-5) 0.05 Solvent (Solv-5) 0.24 Fifth layer (infrared-sensitive cyan coloring layer) Silver chlorobromide emulsion (a) 0 .23 Gelatin 1.04 Cyan coupler (ExC) 0.32 Color image stabilizer (Cpd-2) 0.03 Color image stabilizer (Cpd-4) 0.02 Color image stabilizer (Cpd-6) 0.18 Color image stabilizer (Cpd-7) 0.40 Color image Stabilizer (Cpd-8) 0.05 Solvent (Solv-6) 0.14

Sixth Layer (Ultraviolet Absorbing Layer) Gelatin 0.48 Ultraviolet Absorbing Agent (UV-1) 0.16 Color Mixing Inhibitor (Cpd-5) 0.02 Solvent (Solv-5) 0.08 Seventh Layer ( Protective layer) Gelatin 1.10 Polyvinyl alcohol acrylic modified copolymer (modification degree 17%) 0.17 Liquid paraffin 0.03

[0080]

[Chemical 20]

[0081]

[Chemical 21]

[0082]

[Chemical formula 22]

[0083]

[Chemical formula 23]

[0084]

[Chemical formula 24]

[0085]

[Chemical 25]

[0086]

[Chemical formula 26]

[0087]

[Chemical 27]

[0088]

[Chemical 28]

[0089]

[Chemical 29]

A light-sensitive material A having the same structure as that of the light-sensitive material A was prepared except that a water-soluble dye of the kind and amount shown in Table 7 was added to the fourth layer (UV absorbing layer) of the light-sensitive material A. ..

[0091]

[Table 7]

[0092]

[Chemical 30]

The dyes -4 to -8 correspond to the dyes IV-1, IV-18, IV-IV-1, X-1 and V-5 of the present invention exemplified above. The prepared light-sensitive material was exposed as follows. Semiconductor laser AlGaInP (oscillation wavelength, about 67
0 nm: Toshiba type No. TOLD9211), semiconductor laser GaAlAs (oscillation wavelength, about 750 nm: Sharp type No. LTO30MDO), GaAlAa (oscillation wavelength, about 830 nm: Sharp type No. LTO15MDO) were used. The laser light is a device capable of sequentially scanning and exposing on a color photographic paper that moves in a direction perpendicular to the scanning direction by a rotating polyhedron. Using this apparatus, the amount of light was changed to determine the relationship D-logE between the density (D) of the photosensitive material and the amount of light (E). The light intensity of the semiconductor laser is
The exposure amount was controlled by combining a pulse width modulation method that modulates the light quantity by changing the energization time to the semiconductor laser and an intensity modulation method that modifies the light quantity by changing the energization quantity. This scanning exposure is performed at 400 dpi, and the average exposure time per pixel at this time is about 10 ⁻⁷ seconds. The semiconductor laser is
A Peltier element was used to keep the temperature constant in order to suppress the fluctuation of the light quantity due to the temperature. The reciprocal of the logarithm of the light quantity required to give a density of 1.0 for each of the magenta photosensitive layer and the cyan photosensitive layer when exposed to a laser beam of 750 nm was obtained, and the respective sensitivity S _M (750) and S _C (750) were obtained. I asked. Furthermore, the sensitivities S _OM (750), S _M (750), and S _C (750) of the sample (a) not containing the dye
, S _M (750) (= S _OM (750) -S
_M (750)) and ΔS _C (750) (= S _OC (75
0) was determined -S _C (750)). Further, the density of cyan when exposed with a laser light amount of 750 nm required to give a magenta coloring density of 2.0 was taken as D _C (750) and used as a scale for color separation. (The larger D _C (750) means that the color separation is worse.) A rectangular pattern of various frequencies is obtained by using light passing through a vapor deposition interference filter 750 nm as a light source of a sensitometer (manufactured by Fuji Photo Film Co., Ltd.). The resolution of magenta color development was obtained by exposing a light-sensitive material having an optical wedge to a light-sensitive material. CTF as an index of resolution
Value (frequency 0, that is, there is no repeating rectangular pattern,
Density difference ΔD between the high density part and the low density part when continuous exposure is performed over a very wide area of the high light amount part and the low light amount part
Similar density difference in the frequency C (lines / mm) of _O and the rectangular pattern △ D _{C ratio: △ D C / △ D O} ) was determined frequency C (lines / mm) of 0.5. (The larger the value of C, the higher the resolution.) Using a spectral spectrum exposure apparatus in which an optical wedge is combined with a spectral light source obtained by combining a light source and a diffraction grating, Spectral sensitivity Spectral photographs were taken. From this photograph, the sensitivity of the photosensitive material at each wavelength was measured, and the energy distribution for each wavelength of the sensitometer, which was measured in advance, was used to obtain the equienergetic spectral sensitivity distribution of the sensitive material by sensitivity correction. The sensitivity difference ΔS between the maximum sensitivity of the magenta coloring layer and the maximum sensitivity of the cyan coloring layer of this equal energy spectral sensitivity distribution
_max. (ΔS = S _max. (Magenta) -S _max. (Cyan)) was determined. The following development processing was performed on the exposed sample. (Development treatment) The exposed sample was used after being subjected to continuous treatment (running) using a paper processor until it was replenished with twice the tank capacity for color development in the next treatment step. Processing process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 17L Bleach fixing 30-35 ℃ 45 seconds 215ml 17L Rinse 30-35 ℃ 20 seconds-10L Rinse 30-35 ℃ 20sec-10L Rinse 30 to 35 ° C 20 seconds 350ml 10 liter Dry 70 to 80 ° C 60 seconds * Replenishment amount per 1 m ² of light-sensitive material (rinse → 3 tank countercurrent method)

The composition of each processing liquid is as follows. Color developer Tank solution Replenisher Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12.0 g Sodium chloride 1.4 g-potassium carbonate 25 g 25 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 5.0 g 7.0 g N, N-bis (carboxymethyl) hydrazine 4.0g 5.0g N, N-di (sulfoethyl) hydroxylamine 1Na 4.0g 5.0g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0g 2.0g Water added 1000ml 1000ml pH ( 25 ° C) 10.05 10.45

Bleach-fixing solution (same as tank solution and replenisher) Water 400 ml Ammonium thiosulfate (700 g / l) 100 ml Sodium sulfite 17 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate disodium 5 g Ammonium bromide 40 g Water was added. 1000 ml pH (25 ° C) 6.0 Rinse solution (same as tank solution and replenisher) Ion-exchanged water (3 ppm each for calcium and magnesium)
The results of the obtained samples are shown in Table 8 below.

[0096]

[Table 8]

From the above results, it can be seen that the light-sensitive material coat using the water-soluble dye of the present invention is a light-sensitive material having good sharpness and no deterioration in color separation. Photosensitive materials using dyes other than the present invention have good sharpness, but
It can be seen that the color separation is significantly deteriorated. Further, it can be seen that the sharpness is good when ΔS _max ≦ 0.2 under the condition that the sensitivity relationship of the present invention is satisfied.

Example 2 The second layer (color mixing preventing layer) and the fourth layer (ultraviolet absorbing layer) of the light-sensitive material a of Example 1 were made of the types shown in Table 9 (absorption maximum in the film was 700 nm or less). A light-sensitive material (a) to (e) having the same structure as that of the light-sensitive material (a) was prepared except that the water-soluble dye was dividedly added so as to have the amounts shown in the table.

[0099]

[Table 9]

[0100]

[Chemical 31]

Dyes -12 and -13 correspond to the dyes V-3 and VIII-1 of the present invention exemplified above. These photosensitive materials were exposed by the same method as described in Example 1. However, the reciprocal of the logarithm of the light quantity required to give a density of 1.0 for each of the yellow photosensitive layer and the magenta photosensitive layer when exposed to a laser beam of 670 nm is obtained, and the respective sensitivities S _Y (670) and S _M ( 670). Furthermore,
Sensitivity S _OY (67) of sample (a) not using dye
0), S _OM (670) and S _Y (670), S _M (67
0), ΔS _Y (670) (= S _OY (670) −S
_Y (670)) and ΔS _M (670) (= S _OM (67
0) was determined -S _M (670). Further, the density of magenta at the time of exposure with a laser light amount of 670 nm required to give a yellow color development density of 2.0 was defined as D _M (670) and used as a scale for color separation. Also, by using light passing through a vapor deposition interference filter 670 nm as a light source of a sensitometer (manufactured by Fuji Photo Film Co., Ltd.), an optical wedge having a rectangular pattern of various frequencies is closely contacted and exposed to a photosensitive material to improve the resolution of yellow color. It was determined in the same manner as in Example 1. The exposed sample was subjected to the same development process as in Example 1. Table 10 shows the results of the obtained samples.

[0102]

[Table 10]

From the above results, it is understood that in the case of the light-sensitive materials Ha to E which satisfy the sensitivity relation of the present invention, the sharpness is good and the color separation is not deteriorated.

Example 3 (Preparation of emulsion b) 3.3 g of sodium chloride was added to a 3% aqueous solution of lime-processed gelatin, and 3.2 ml of N, N'-dimethylimidazolidine-2-thione (2% aqueous solution) was added. did. An aqueous solution containing 0.2 mol of silver nitrate, 0.2 mol of sodium chloride and 15 μg of rhodium trichloride.
Was mixed at 56 ° C. with vigorous stirring. Subsequently, an aqueous solution containing 0.78 mol of silver nitrate and an aqueous solution containing 0.78 mol of sodium chloride and 4.2 mg of potassium ferrocyanide were added and mixed at 56 ° C. with vigorous stirring. The addition of the silver nitrate aqueous solution and the alkali halide aqueous solution was completed. Then, a copolymer of isobutene maleic acid 1-sodium salt was added, and the mixture was washed by sedimentation and desalting. Furthermore, lime-processed gelatin 90.0 g
Was added to adjust the pH and pAg of the emulsion to 6.2 and 6.5, respectively. After 5 minutes at 50 ° C. (Dye-4) 2 × 10 ^-4
After 15 minutes have passed since the addition of moles, silver bromide fine particles (grain size 0.05
μm) and potassium hexachloroiridium (IV) ate 0.
An aqueous solution containing 8 mg was added and mixed with vigorous stirring. Furthermore, sulfur sensitizer (triethylthiourea) 1 × 10 ^-5
Mol / molAg, chloroauric acid 1 × 10 ⁻⁵ mol / molAg, and nucleic acid 0.2 g / molAg were added, and optimal chemical sensitization was performed at 50 ° C.

With respect to the obtained silver chlorobromide grains b, the grain shape, grain size and grain size distribution were determined from electron micrographs. All of these silver halide grains are cubic and have a grain size of 0.52 μm and a coefficient of variation of 0.
It was 08. The grain size is represented by the average value of the diameter of the circle equivalent to the projected area of the grain, and the coefficient of variation is the standard deviation of the grain size divided by the average grain size. Then
The halogen composition of the emulsion grains was determined by measuring the X-ray diffraction from silver halide crystals. The measurement results of this silver chlorobromide emulsion a show that, in addition to the main peak at 100% silver chloride, the center is at 70% silver chloride (30% silver bromide) and 60% silver chloride.
It was possible to observe a broad diffraction pattern in which the hem was stretched up to about 40% (silver bromide 40%). (Preparation of emulsions c and d) Used in emulsion b (Dye-4)
Emulsion c was obtained in the same manner as Emulsion b except that 1 × 10 ⁻⁴ mol of (Dye-1) was used instead of (Dy-1).
Emulsion d was obtained in the same manner as in emulsion b except that 5 × 10 ⁻⁵ mol of (Dye-5) was used instead of e-4).

[0106]

[Chemical 32]

(Preparation of Sensitive Material α) Instead of the emulsion a used in the first, third and fifth layers of the light-sensitive material A shown in Example 1, emulsion b was used in the first layer, Same as photosensitive material A except that emulsion c is used in the third layer and emulsion d is used in the fifth layer (however, the spectral sensitizing dyes added in the photosensitive material A are emulsions b, c,
In (d), the photosensitive material α was not used because it was already added during grain formation. This photosensitive material is 630n
Red-sensitive yellow coloring layer (first layer) having a spectral sensitivity maximum near m, red-sensitive magenta coloring layer (third layer) having a spectral sensitivity maximum near 670 nm, and infrared sensitivity having a spectral sensitivity maximum near 750 nm. It is composed of a cyan coloring layer (fifth layer). The amounts of water-soluble dyes of the kind (absorption maximum in the film is 700 nm or less) as shown in Table 11 in the second layer (color mixing prevention layer) and the fourth layer (UV absorption layer) of the light-sensitive material α are in the table. Photosensitive materials β to ι having the same structure as the photosensitive material α except that the components were added separately were prepared.

[0108]

[Table 11]

[0109]

[Chemical 33]

Dye-16 is the dye IV of the present invention exemplified above.
It corresponds to -6. The prepared light-sensitive material was exposed as follows. He-Ne gas laser (oscillation wavelength, about 633 nm),
Semiconductor laser AlGaInP (oscillation wavelength, about 670n
m: Toshiba type No.TOLD9211), semiconductor laser G
aAlAs (oscillation wavelength, about 750 nm: Sharp's type No. LTO30MDO) was used. The laser light is a device capable of sequentially scanning and exposing on a color photographic paper that moves in a direction perpendicular to the scanning direction by a rotating polyhedron. Using this apparatus, the amount of light was changed to determine the relationship D-logE between the density (D) of the photosensitive material and the amount of light (E).
The light quantity of the semiconductor laser was controlled by combining a pulse width modulation method that modulates the light quantity by changing the energization time to the semiconductor laser and an intensity modulation method that modifies the light quantity by changing the energization quantity. The gas laser was intensity modulated using an external modulating group. (A semiconductor laser has been recently developed for this 633 nm exposure, and if it becomes practicable, it is advantageous to use a semiconductor laser instead of this gas laser in terms of the compactness of the device, cost, ease of modulation, and the like. This scanning exposure is 4
The average exposure time per pixel at this time is about 10 ^-7 seconds. The semiconductor laser uses a Peltier element to keep the temperature constant in order to suppress the fluctuation of the light quantity due to the temperature. The density of each of the yellow photosensitive layer and the magenta photosensitive layer when exposed to a laser beam of 633 nm is 1.0
The reciprocal of the logarithm of the amount of light required to give _## EQU1 _## was obtained, and the respective sensitivities S _Y (633) and S _M (633) were obtained. Furthermore, the sensitivity S of the sample (α) that does not use dye
_OY (633), S _OM (633) and S _Y (633), S _M
Difference with (633), ΔS _Y (633) (= S _OY (63
3) -S _Y (633)) and ΔS _M (633) (= S _OM
(633) was determined by the -S _M (633)). Further, the density of magenta when exposed with a laser light amount of 633 nm required to give a yellow color density of 2.0 is D _M (63
3) was used as a scale for color separation. Evaporation interference filter 633 nm as the light source of the photometer (Fuji Photo Film Co., Ltd.)
The resolution of yellow color development was determined in the same manner as in Example 1 by exposing the optical material having rectangular patterns of various frequencies to the light-sensitive material in close contact with the light through. The exposed sample was subjected to the same development process as in Example 1. The results of the samples obtained are shown in Table 1.
2 shows.

[0111]

[Table 12]

From the above results, it is understood that in the case of the light-sensitive materials ζ to ι which satisfy the sensitivity relation of the present invention, the sharpness is good and the color separation is not deteriorated. On the other hand, in the light-sensitive materials β to ε which do not have the sensitivity relationship of the present invention, it is found that the color separation is deteriorated even if the sharpness is good.

Example 4 Sensitive materials prepared in Examples 1, 2 and 3, A to G, A and N
After the exposures of (e) and (a) to (i) were performed in the respective examples, the following treatments were performed. After that, the same evaluation was performed. The results also show that the constitution of the present invention can provide a light-sensitive material with less deterioration of color separation and good sharpness. Processing process Temperature Time Replenisher ^* Tank capacity (liter) Color development 35 ℃ 20 seconds 60ml 2 Bleaching fixing 30-35 ℃ 20 seconds 60ml 2 Rinse 30-35 ℃ 10 seconds -1 Rinse 30-35 ℃ 10 seconds -1 Rinse 30 ~ 35 ℃ 10 seconds 120ml 1 Dry 70 ~ 80 ℃ 20 seconds * Replenishment amount per 1m ² of light-sensitive material (Rinsing → 3 tanks countercurrent method) Composition of each processing solution is as follows. ..

Color developing solution Tank solution Replenishing solution Water 800 ml 800 ml Ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid 1.5 g 2.0 g Potassium bromide 0.015 g-Triethanolamine 8.0 g 12. 0 g Sodium chloride 4.9 g-Potassium carbonate 25 g 37 g 4-Amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline 2 · p-toluenesulfonic acid 12.8 g 19.8 g N, N- Bis (carboxymethyl) hydrazine 5.5g 7.0g Optical brightener (WHITEX 4B, Sumitomo Chemical Co., Ltd.) 1.0g 2.0g Water is added 1000ml 1000ml pH (25 ℃) 10.05 10.45 Bleach-fixer The formulations of the tank solution and the replenisher solution in the rinse solution are the same as those in Example 1. The apparatus shown in the attached drawing 1 was used for this treatment.

[0115]

According to the present invention, a color photograph having excellent image sharpness can be quickly obtained without deteriorating color separation.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of an image forming apparatus using a silver salt photographic color paper according to an embodiment of the present invention.

FIG. 2 is a configuration diagram of an exposure apparatus.

[Explanation of symbols]

 10 image forming apparatus main body 12 developing tank 14 bleach-fixing tank 16 water washing tank 17 draining section 18 drying section 18 20 photosensitive material 30 processing liquid ejecting member 32 pump 240 image signal processing apparatus 242, 244, 246 driving circuit 251, 252, 253 semiconductor Laser 258, 259, 260 Collimator lens 261 Total reflection mirror 262, 263 Dichroic mirror 270 Polygon mirror 280 fθ lens 300 Exposure device

Claims (6)

[Claims] 1. A silver halide light-sensitive material having at least three silver halide light-sensitive layers having different color sensitivities on a support, wherein at least two light-sensitive layers (A layer,
Layer B: Layer B has the maximum spectral sensitivity on the long wave side as compared with layer A. ) Contains a silver halide emulsion grain selectively spectrally sensitized in accordance with a light flux (exposure of layer A: wavelength λa nm, exposure of layer B: λb nm; λa <λb) of 570 nm or more, and 570 nm The relationship of sensitivity decrease of the photosensitive layer by the water-soluble dye when containing at least one water-soluble dye having the absorption maximum and exposed by using the light flux λa of the light flux is represented by the formula (I). A silver halide photographic light-sensitive material, characterized in that (Formula I) S ⁰ (A; λa) -S ^Dye (A; λa) ≧ 0.4 O ≦ (S ⁰ A (λa) -S ^Dye A (λa))-(S ⁰ B (λa) -S ^Dye B (λa)) ≦ 0.2 S ⁰ (A; λa): Sensitivity of photosensitive layer A at wavelength λa in the absence of water-soluble dye S ^Dye (A; λa): Photosensitive layer in the presence of water-soluble dye Sensitivity A at wavelength λa S ⁰ (B; λa): Sensitivity at wavelength λa of photosensitive layer B without water-soluble dye S ^Dye (B; λa): Wavelength λa of photosensitive layer B when water-soluble dye is present Sensitivity in 2. A silver halide light-sensitive material having at least three kinds of silver halide light-sensitive layers having different color sensitivities on a support, and at least two light-sensitive layers (A layer,
Layer B: Layer B has the maximum spectral sensitivity on the long wave side as compared with layer A. ) Is not less than 700 nm, the silver halide emulsion grains selectively spectrally sensitized according to a light flux (exposure of A layer: wavelength λa nm, exposure of B layer: λb nm; λa <λb), and 700 nm The relationship of the sensitivity decrease of the photosensitive layer by the water-soluble dye at the time of containing at least one water-soluble dye having the absorption maximum and exposing using the light flux λa of the light flux is represented by the above formula (I). A silver halide photographic light-sensitive material characterized by being processed. 3. A silver halide light-sensitive material having at least three kinds of silver halide light-sensitive layers having different color sensitivities on a support, and at least two light-sensitive layers (A layer,
Layer B: Layer B has the maximum spectral sensitivity on the long wave side as compared with layer A. ) Is not less than 700 nm, the silver halide emulsion grains selectively spectrally sensitized according to a light flux (exposure of A layer: wavelength λa nm, exposure of B layer: λb nm; λa <λb), and 700 nm Above, at least one water-soluble dye having an absorption maximum is contained, and the relationship between the decrease in the sensitivity of the photosensitive layer due to the dye when exposed using the light flux λa of the light flux and the spectral sensitivity maximum of the A layer and the B layer The sensitivity relationship of
A silver halide photographic light-sensitive material characterized by being represented by I). Formula (II) S ⁰ (A; λa) -S ^Dye (A; λa) ≧ 0.4 O ≦ (S ⁰ A (λa) -S ^Dye A (λa))-(S ⁰ B (λa) -S ^Dye B (λa)) ≦ 0.2 S _max. (A) −S _max. (B) ≦ 0.2 S ⁰ (A; λa): Sensitivity at wavelength λa of photosensitive layer A in the absence of water-soluble dye S ^Dye (A; λa): Sensitivity at wavelength λa of photosensitive layer A with water-soluble dye S ⁰ (B; λa): Sensitivity at wavelength λa of photosensitive layer B without water-soluble dye S ^Dye (B Λa): Sensitivity of photosensitive layer B at wavelength λa in the presence of water-soluble dye S _max. (A): Maximum spectral sensitivity of photosensitive layer A in the presence of water-soluble dye S _max. (B): Water-soluble dye Spectral sensitivity of photosensitive layer B when there is 4. A silver halide light-sensitive layer having at least three different color sensitivities, each of which contains a coupler which develops yellow, magenta or cyan, respectively, and is provided on a reflective support. 5. A color image forming method, which comprises subjecting the silver halide photographic light-sensitive material described in 1 above to color development processing. 5. The exposure time per pixel of the photosensitive material is 1
The color image forming method according to claim 4, wherein exposure is performed by a scanning exposure method shorter than 0 ^-4 seconds, and then color development processing is performed. 6. The color image forming method according to claim 5, wherein the color development processing time is 20 seconds or less, and the total processing time including the color development processing to drying is 90 seconds or less.