JP2000089373A - Image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-quality stable image by an inexpensive device with high productivity when a color image (color proof) for proofreading can be obtained by scanning and exposing a silver halide color photographic sensitive material based on dot picture information. SOLUTION: When an image recording material respectively mainly having at least yellow, magenta and cyan image forming units each is exposed based on the digitized dot picture information so that a dot area multilevel image is formed, it is exposed with exposure equal to or more than binary at the photosensitive area of at least one image forming unit of the image recording material in this image forming method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image recording material, preferably a silver halide color light-sensitive material (hereinafter also referred to as a color light-sensitive material), for performing color separation and halftone image conversion in a color plate making / printing process. The present invention relates to an image forming method suitable for producing a color image for calibration (color proof) from a plurality of dot image information obtained by the above method.

[0002]

2. Description of the Related Art Conventionally, as a method of obtaining a color proof from a plurality of black and white halftone images obtained by performing color separation and halftone image conversion in a color plate making and printing process, a silver halide color photosensitive material having a white support is used. Japanese Patent Application Laid-Open Nos. 56-113139 and 56-1
04335, 62-280746, 62-28
No. 0747, No. 62-280748, No. 62-280
Nos. 749 and 62-280750.

On the other hand, plate making methods for converting an image into a digital signal and editing the image on a computer without using the above-described halftone dot black-and-white film have been increasingly used. By digitizing image information, image processing, image transfer to a remote location, and editing such as image layout and color tone change can all be performed quickly.

[0004] As a method of outputting an image edited in this way as a color proof, a method of scanning and exposing a color paper with a laser is known.

[0005] However, there is a problem that the productivity is not improved because the apparatus is expensive or the scanning exposure requires a long time. In addition, a mistake caused by performing image editing on a computer is a new problem. It has been found that it is not possible to discriminate whether an overlapped portion of a black plate and another color plate overlaps only the black plate or the color plate. Was. For example, when ink characters are applied on a picture, it is impossible to recognize a mistake that a pattern is printed on the ink characters. In addition, normal yellow, magenta, cyan, and black 4
There is also a demand to cope with colors (silver, gold, pastel colors, etc.) that are difficult to reproduce with ordinary inks called special colors other than the three inks, and there is a demand for expanding the applications.

[0006]

Accordingly, an object of the present invention is to provide a color image for calibration (color proof) by scanning and exposing a silver halide color photographic material on the basis of dot image information.
It is an object of the present invention to provide an image forming method which can obtain a high-quality, stable image with high productivity using an inexpensive apparatus.

[0007]

The above object of the present invention has been attained by the following constitutions.

(1) A halftone area gradation image is formed by exposing an image recording material mainly having at least one image forming unit for each of yellow, magenta and cyan based on digitized halftone image information. In doing so,
An image forming method wherein the photosensitive area of at least one image forming unit of the image recording material is exposed at a binary or more exposure amount.

(2) The image forming method according to (1), wherein the photosensitive area of at least one image forming unit of the image recording material is exposed at an exposure amount of three or more values.

(3) Use of an image recording material in which the absolute value of the slope of a characteristic curve at an exposure amount at which the density of at least one image forming unit is close to that of a reference print is less than 0.2 to 1.0. The image forming method according to (1) or (2).

(4) Use an image recording material in which the absolute value of the slope of a characteristic curve at an exposure amount at which the density of at least one image forming unit approximates the density of a reference print is 1.0 to 2.0. The image forming method according to (1) or (2).

(5) A halftone dot area gradation image is formed by exposing an image recording material having at least one each of yellow, magenta and cyan image forming units based on digitized dot image information. In doing so,
An image forming method for exposing at least two of the yellow, magenta and cyan image forming units with the same halftone dot shape and position.

(6) A halftone dot area image is formed by exposing an image recording material having at least one each of yellow, magenta and cyan image forming units based on digitized dot image information. In doing so,
An image forming method for exposing one of the yellow, magenta and cyan image forming units and exposing another image forming unit at the same time.

(7) A halftone dot area gradation image is formed by exposing an image recording material having at least one each of yellow, magenta and cyan image forming units based on digitized dot image information. In doing so,
An image to be exposed at an exposure amount that is at least 0.15 lower than the density of the corresponding reference print over at least one of the yellow, magenta and cyan image forming units over a plurality of halftone units. Forming method.

(8) The image forming method according to any one of (1) to (7), wherein at least one semiconductor laser or light emitting diode is used as an exposure light source.

Hereinafter, the present invention will be described in detail.

In the present invention, the image recording material is preferably a color light-sensitive material, and the image forming unit refers to a silver halide emulsion layer.

In the present invention, two or more values can be taken in one photosensitive region, preferably three or more values, more preferably
The more exposure values that can be taken, the better, but the value is preferably 256 or less from the problem of complicated exposure control.

In the present invention, the density of the reference printed matter is
For example, Ja set as a standard print sample in Japan
There is pan Color (published by Japan Printing Machinery Association).

The approximation of the print density is based on the CIE
This is the point at which the distance in the LAB space is minimized. CIE
The measurement of LAB can be performed using a device such as CM2022 manufactured by Minolta.

The slope of the characteristic curve is the slope when the density is plotted on the vertical axis and the logarithm of the exposure is plotted on the horizontal axis. Normally, a negative value is used when a negative emulsion is used, and a negative value is used when a positive emulsion is used. Becomes

In the present invention, it is preferable to use a laser light source as the exposure light source.

As the laser exposure method, there are a plane scanning method using a polygon mirror, a cylinder outer surface scanning method using a rotating drum, and a cylinder inner surface scanning method. A cylindrical outer surface scanning method is preferred.

The diameter of the drum can be arbitrarily set in accordance with the size of the photosensitive material to be exposed. The number of rotations of the drum can be arbitrarily set, but an appropriate number of rotations can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern, the sensitivity of the photosensitive material, and the like. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed.
Specifically, 200 to 3000 rotations per minute is preferable.

The photosensitive material can be fixed to the drum by a mechanical means, or a number of fine holes can be provided on the surface of the drum according to the size of the photosensitive material. Can be brought into close contact with each other.
It is necessary to fix the photosensitive material as closely as possible to the drum in order to prevent troubles such as uneven image.

In the present invention, the light source unit has three light source units having different wavelengths. Here, the laser light source unit is a unit that constitutes a laser light source that outputs a laser of a specific wavelength, and there may be one laser oscillator corresponding to the laser light source of a certain wavelength, or a plurality of lasers. However, in some cases, it simultaneously functions as an image exposure light source as a laser light source of a certain wavelength.

In the present invention, the three types of laser light source units have different wavelengths, and the oscillation wavelengths are separated by 30 nm or more, preferably 50 nm or more.

In the present invention, when exposing the photosensitive material, one beam spot may be used at the same wavelength, or a plurality of beams may be irradiated simultaneously. In order to form a plurality of beam spots, the beam may be generated from a plurality of laser oscillators, or the beam of one laser light source may be split.
The plural may be two or more, and there is no particular upper limit. For example, the number is 2 to 500 or more. 2-3
Although about 0 is practically preferable, it can be appropriately selected from the viewpoint of productivity improvement and exposure control.

The laser beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. 6
Although smaller than μm is preferable in terms of image quality, adjustment is difficult or processing speed is reduced. On the other hand, 25 μm
If it is larger, the unevenness increases and the sharpness of the image also deteriorates. By narrowing the beam diameter to the above range, it is possible to produce a high-definition image without unevenness.

Japanese Patent Application Laid-Open No. Hei 4-330337 discloses a method of exposing a photosensitive material by performing a scanning exposure with a semiconductor laser. However, a problem with a rotating drum and a problem with halftone image formation are discussed. There is no description at all. According to the configuration of the present invention, for the first time, even high-definition image writing with high productivity and without unevenness can be performed at high speed.

In the present invention, the same wavelength is the same wavelength when the difference between the wavelengths of the individual laser light sources is 10 nm or less. The wavelength of the laser fluctuates depending on the environment such as the temperature and operating conditions, but the difference between the wavelengths when measured under the same environment and conditions is 10 nm or less.

As the laser for exposing the photosensitive material, various conventionally known lasers can be used.
A gas laser can provide high output, but the device is large and expensive. On the other hand, semiconductor lasers and light-emitting diodes have features such as small size, low cost, and long life.

Examples of the gas laser include a helium / cadmium laser (441.6 nm), an argon ion laser (514.4 nm), a helium neon laser (544 nm), and the like. As a semiconductor laser, AlGaInAs (650 nm), GaAlA
s (760 to 850 nm). Also, YAG
There is also a method of obtaining a light source of 532 nm by combining a laser and SHG, and a light emitting diode can also be used.
It is preferable to use at least one semiconductor laser or light emitting diode which is low cost, small, and relatively easy to control.

In the present invention, the silver halide emulsion contained in the light-sensitive material may be either a negative type or a positive type.

The exposure apparatus of the present invention is an exposure apparatus which is preferably used for large-size color printing and color proof exposure, and exposes a cartridge in which a photosensitive material wound in a roll shape can be handled in a bright room. It is loaded into the device, pulled out, cut to the length required for image formation, wound around a rotating drum, image-exposed with a laser exposure device while rotating the drum, and subsequently subjected to development processing, color It is preferably used as a means for obtaining an image. At that time, the exposure apparatus preferably has a mechanism for reading information given to the light-room cartridge and automatically identifying the type of photosensitive material and / or automatically setting exposure conditions and / or development processing conditions.

Various types of bright room cartridges have been proposed, but all known bright room cartridges can be used. In addition, by covering the outer periphery of the roll photosensitive material having a light-shielding flange with a light-shielding leader, the photosensitive material can be handled in a bright room while being shielded from light, and after loading the exposure apparatus, the leader is removed, thereby requiring a dark room. The so-called easy-loading photosensitive material, in which the roll of the photosensitive material can be easily loaded into the apparatus without being used, is also included in the light chamber cartridge of the present invention. In that case, the readable information can be given to the reader or to the flange or the like.

In the present invention, it is preferable to use a light-sensitive material having at least three silver halide emulsion layers having different spectral sensitivities. In this case, it is preferable that the silver halide emulsion contained in at least one of the emulsion layers has a spectral maximum in a wavelength region longer than the laser exposure wavelength by 2 to 10 nm. In the case of having a spectral maximum in a wavelength region smaller than 2 nm and longer than the laser exposure wavelength, there is a problem that when the laser oscillation wavelength fluctuates, the sensitivity fluctuates greatly and the image becomes unstable. On the other hand, 10 nm
In the case of having a spectral maximum in a wavelength region longer than the laser exposure wavelength, there is a problem that sensitivity is low.

The maximum spectral sensitivity can be measured by a commonly used method such as a spectral spectrograph or sensitometry using monochromatic light having different wavelengths.

It is preferable to have a maximum of spectral sensitivity in a wavelength region that is longer by at least 2 to 10 nm than at least one wavelength of at least three laser exposure units.

When the plurality of laser exposure units are composed of a plurality of oscillators, the average value of the oscillation wavelengths is used as the wavelength of the laser exposure unit.

The color light-sensitive material of the present invention has at least a yellow image forming silver halide emulsion layer, a magenta image forming silver halide emulsion layer, and a cyan image forming silver halide emulsion layer, and is contained in each emulsion layer. Silver halides have different spectral sensitivity maximum wavelengths.

In the present invention, an image is formed by exposing with a laser having a wavelength corresponding to the spectral wavelength region of each emulsion layer. At least one of the reflection densities of the raw sample measured at the wavelength of the laser exposure is formed. One is 0.8 or more, more preferably 1.0 or more.

For measuring the reflection density of the raw sample, a conventionally known method can be used. For example, the value of the spectral reflection density measured using a color analyzer 607 manufactured by Hitachi, Ltd. can be used.

As a method for adjusting the reflection density to 0.8 or more before the development processing, a method of adding a water-soluble dye having absorption to at least the spectral sensitivity region of the silver halide emulsion and / or a method of adding the lowermost layer or other It is preferable to provide an anti-halation layer in the above layer. Further, there is a method in which a dye is contained in the photosensitive material as solid fine powder to suppress diffusion of the dye in the photosensitive material.

The water-soluble dye used in the present invention includes:
Oxonol, cyanine, merocyanine, azo, anthraquinone, arylidene, etc., each of which may be mentioned.From the viewpoint of high resolution in a developing bath and non-sensitization to a silver halide emulsion, oxonol is particularly preferable. Dyes and merocyanine dyes.

Oxonol dyes are disclosed in US Pat.
7,225, JP-A-48-42826, 49-5
No. 125, No. 49-99620, No. 50-91627
No. 51-77327, No. 55-120660,
Nos. 58-24139, 58-143342, 5
9-38742, 59-11640, 59-
No. 111641, No. 59-168438, No. 60-2
No. 18641, No. 62-31916, No. 62-662
No. 75, No. 62-66276, No. 62-185755
And Nos. 62-273527 and 63-139949. Merocyanine dyes are disclosed in JP-A-50-145124, JP-A-58-120245, and JP-A-62-120245.
No. 3-35437, No. 63-35438, No. 63-3
Nos. 4539 and 63-58437.

Typical specific examples of oxonol dyes and merocyanine dyes include water-soluble yellow dyes AIY-1 to AIY-14 described in Japanese Patent Application No. 7-150291.
Similarly, water-soluble magenta dyes AIM-1 to AIM-14,
Similarly, water-soluble cyan dyes AIC-1 to AIC-14 are exemplified.

Representative examples of water-soluble dyes other than oxonol dyes and merocyanine dyes include the water-soluble yellow dye A described in Japanese Patent Application No. 7-150291.
IY-15 to AIY-18, AIM-15 to AIM-1
8, AIC-15 to AIC-18.

Further, examples of the water-soluble dye which can be used in the present invention include A-1 to A-4 described in JP-A-4-33037.
And 3 dyes.

The amount of the water-soluble dye to be used is selected and added so that the reflection density of the raw sample before development processing measured at the laser wavelength at which the photosensitive material is exposed becomes 0.8 or more.
The water-soluble dyes can be used alone or in combination of two or more.

In the present invention, an antihalation layer may be provided as the lowermost layer or another layer.

The antihalation layer contains a compound that absorbs light. Examples of the compound that absorbs light include various organic compounds and inorganic compounds having the action. As the inorganic compound, colloidal silver, colloidal manganese and the like are preferable, and colloidal silver is particularly preferable.
Since these colloidal metals have good decolorization properties, they are also effective when applied to the color light-sensitive material of the present invention.

The above colloidal silver, eg, gray colloidal silver, is reduced by keeping silver nitrate alkaline in gelatin in the presence of a reducing agent such as hydroquinone, phenidone, ascorbic acid, pyrogallol or dextrin, followed by neutralization. It is obtained by cooling and setting gelatin, and then removing the reducing agent and unnecessary salts by a noodle washing method. When the colloidal silver particles are formed in the presence of an azaindene compound or a mercapto compound during the reduction with an alkali, a colloidal silver dispersion of uniform particles can be obtained. As the amount of the colloidal silver, the reflection density of the raw sample before development measured at least at one wavelength within the exposure area for cyan image-forming silver halide was 0.8.
The amount can be selected to be as described above.

In the color light-sensitive material of the present invention, at least one of a carboxyl group, a sulfonamide group and a sulfamoyl group is contained in any silver halide emulsion layer and / or other hydrophilic colloid photographic constituent layers. The dye can be contained as a solid disperse dye by solid dispersion.

The dye having at least one of a carboxyl group, a sulfamoyl group and a sulfonamide group is more specifically a dye represented by the following general formulas [1] to [8].

[0056]

Embedded image

In the formula, R ₁ and R ₂ are each a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, -CO
_{OR 5, -COR 5, -SO 2} R 5, -SOR 5, -SO 2 N
_{(R 5) R 6, -CON} (R 5) R 6, -N (R 5) R 6, -
_{N (R 5) SO 2 R} 6, -N (R 5) COR 6, -N (R 5)
_{CON (R 6) R 7,} -N (R 5) CSN (R 6) R 7, -
OR ₅ , —SR ₅ or a cyano group, and R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a heterocyclic group. R ₅ , R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and L _{1 to} L ₅ each represent a methine chain. n ₁ represents an integer of 0 or 1, and n ₂ represents an integer of 0 to 2.

[0058]

Embedded image

Where R ₁ , R ₃ , L ₁ -L ₅ , n ₁ and n
₂ represents R ₁ , R ₃ , L _{1 to} L in the general formula [1], respectively.
It has the same meaning as ₅ , n ₁ and n _2, and E represents an acidic nucleus necessary to form an oxonol dye.

[0060]

Embedded image

Where R ₃ , R ₄ , L ₁ -L ₅ , n ₁ and n
₂ represents R ₃ , R ₄ , L _{1 to} L in the general formula [1], respectively.
₅ represents the same meaning as n ₁ and n _2, R _8, R ₉ each represent the same meaning as R _3, R _4.

X ₁ and X ₂ each represent an oxygen atom or a sulfur atom.

[0063]

Embedded image

[0064] In the formula, R _3, L ₁ and L ₂ each represent a similar meaning as R _3, L ₁ and L ₂ in formula (1), E is similar to the E in the general formula [2] Represent meaning.
Each R ₁₀ and R ₁₁ are hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen _{atom, -OR 5, -SR 5, -N} (R 5) R 6, -N
(R ₅ ) represents SO ₂ R ₆ , —N (R ₅ ) COR ₆ , —COR ₅ or —COOR ₅ . It is also possible to form a ring double bond in R ₁₀ and R _11.

X ₃ is an oxygen atom, a sulfur atom, a selenium atom,
— (R ₁₂ ) C (R ₁₃ ) — or —N (R ₃ ) —
R _3, R ₅ and R ₆ represent the same meaning as R _3, R ₅ and R ₆ in the general formula (1), respectively.

R ₁₂ and R ₁₃ each represent a hydrogen atom or an alkyl group. n ₃ represents an integer of 1 to 3.

[0067]

Embedded image

Where R ₃ , R ₄ , L ₁ , L ₂ , L ₃ and n
₁ is R ₃ , R ₄ , L ₁ , L in the general formula [1].
₂ , L ₃ and n ₁ have the same meaning, and E is a general formula [2]
Has the same meaning as E. R ₁₀ and R ₁₁ each have the same meaning as R ₁₀ and R ₁₁ in the general formula [4], and R ₁₄ has the same meaning as R ₁₀ .

[0069]

Embedded image

Where R_Three, R_Four, L₁~ L_Five, N₁And n
_TwoIs R in the general formula [1]. _Three, R_Four, L₁~ L
_Five, N₁And n_TwoHas the same meaning as_Ten, R₁₁And X_Three
Is R in the general formula [4]._Ten, R₁₁And X_Three
Represents the same meaning as X_FourIs X_ThreeAnd R_Fifteen, R₁₆Is R
_TenHave the same meaning.

[0071] X ^- represents a group having an anion. Also, R
₁₀ and R ₁₁ , and R ₁₅ and R ₁₆ can form a ring double bond.

[0072]

Embedded image

In the formula, A ₁ represents pyrrole, imidazole, pyrazole, phenol, a naphthol nucleus or a fused heterocycle.

[0074]

Embedded image

In the formula, Z ₁ , Z ₂ and Z ₃ each represent an electron-withdrawing group, and A ₂ represents an aryl group or a heterocyclic group.

Specific examples of the dyes represented by the general formulas [1] to [8] are described in Japanese Patent Application No. 7-150291.
-7.

The above carboxyl group, sulfonamide group,
The dye having at least one sulfamoyl group is a compound having a hydrophilic group which is substantially water-insoluble (with respect to water having a pH of 7 or less) and dissociates at a pH of 9 or more. Solid fine particle dispersion obtained by a method of dissolving in a solvent and dispersing in a gelatin solution (in the form of group particles having microscopic dimensions, the average particle diameter is preferably 10 μm or less, more preferably 1 μm or less;
m) or less in gelatin or a polymer binder, it can be contained in any photosensitive emulsion layer or non-photosensitive hydrophilic colloid layer in a photographic component layer.

The above carboxyl group, sulfonamide group,
The solid fine particle dispersion of a dye having at least one sulfamoyl group is insoluble in water and is stably present in the color photographic material. However, after the exposure, it is treated with a color developing solution (preferably at pH 9 or more). When the hydrophilic group in the dye compound is dissociated to become water-soluble or decolorized, most of the dye is lost from the color photographic material.

As the dye having at least one of a carboxyl group, a sulfonamide group and a sulfamoyl group, two or more dyes may be used, or a water-soluble dye may be partially used depending on the purpose of use.

The content of the dye having at least one of a carboxyl group, a sulfonamide group, and a sulfamoyl group is determined by measuring the reflectance of a raw sample before development measured at least at one wavelength within the exposure area for cyan image-forming silver halide. The amount can be selected and added so that the concentration becomes 0.8 or more. Specifically, generally 0.001 to 0.5 g / m
Preferably, it is used to be ² .

The support preferably used in the present invention has both sides of a paper substrate coated with a resin containing a polyolefin resin as a main component. When obtained by analysis, it is preferable that the integrated value (PY value) of the power spectrum in the frequency section of 1 to 12.5 mm on the surface of the support is 2.9 μm or less. The PY value is more preferably 1.8 μm or less, and still more preferably 1.15 μm or less.

When a support having a PY value larger than 2.9 μm is used, unevenness of an image becomes large and dot reproduction is deteriorated when increasing the number of rotations of the drum to improve productivity. To measure the PY value, the thickness unevenness of the polyolefin-coated support is continuously measured using a film thickness continuous measuring device (for example, manufactured by Anritsu Corporation), and the obtained measurement signal is converted to a frequency analyzer (for example, Hitachi). Electronics: V
C-2403) to obtain a frequency analysis.

The substrate (base paper) of the support can be selected from raw materials generally used for photographic printing paper. For example, in addition to natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, various raw paper materials can be mentioned. In general, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, and the like can be widely used.

Further, additives such as a sizing agent, a fixing agent, a strength enhancer, a filler, an antistatic agent and a dye which are generally used in papermaking may be blended in the support. An agent, a surface strengthening agent, an antistatic agent and the like may be appropriately applied to the surface.

The reflection support is usually 50 to 300 g / m 2.
A resin having a smooth surface having a weight of ² is used, and the resin for laminating the both surfaces is ethylene, α-olefins, for example, a homopolymer such as polypropylene, a copolymer of at least two kinds of the olefins or It can be selected from at least two kinds of mixtures of these various polymers. Particularly preferred polyolefin resins are low density polyethylene, high density polyethylene or mixtures thereof.

The molecular weight of the polyolefin resin to be laminated on the reflective support is not particularly limited, but is usually in the range of 20,000 to 200,000.

The polyolefin resin coating layer on the side of the reflection support on which the photographic emulsion is coated is preferably 25 to 50 μm, more preferably 25 to 35 μm.

As the polyolefin used for laminating the back side of the reflection support (the reflection side of the side on which the emulsion layer is provided), a mixture of low-density polyethylene and high-density polyethylene is usually melt-laminated. This layer is generally subjected to matting.

In forming the laminate on the front and back of the support,
In general, in order to increase the flatness of the developed photographic paper in a common environment, a method of slightly increasing the density of the resin layer on the front side or increasing the amount of lamination on the back side compared to the front side is used.

In general, the lamination on both the front and back surfaces of the reflection support can be formed by melt extrusion coating the polyolefin resin composition on the support. Further, it is preferable to apply a corona discharge treatment, a flame treatment, or the like to the surface of the support or, if necessary, to the front and back surfaces. Further, on the surface of the surface laminate layer, a subcoat layer for improving the adhesion to the photographic emulsion, or on the backside laminate layer, a backcoat layer for improving the printability and antistatic property may be provided. preferable.

In the polyolefin resin used for laminating the surface of the support (the surface on which the emulsion layer is provided), preferably 13 to 20% by weight, more preferably 15 to 20% by weight, of a white pigment is dispersed and mixed. As the white pigment, an inorganic and / or organic white pigment can be used, and an inorganic white pigment is preferable. Such materials include sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, finely divided silica, silicas of synthetic silicates, calcium silicate, alumina, alumina hydrate, and oxidized oxide. Examples include titanium, zinc oxide, talc, and clay.

Among these, barium sulfate is preferred.
Calcium carbonate and titanium oxide, more preferably barium sulfate and titanium oxide. The titanium oxide may be of a rutile type or an anatase type, and one whose surface is coated with a metal oxide such as hydrous alumina or hydrous ferrite is also used.

In addition, it is preferable to add an antioxidant, a color pigment for improving whiteness, and a fluorescent whitening agent.

Further, it is preferable to coat a hydrophilic colloid layer containing a white pigment on the reflective support because sharpness is improved. As the white pigment, the same white pigment as described above can be used, but titanium oxide is preferable. It is more preferable to add a hollow fine particle polymer or a high boiling point organic solvent to the hydrophilic colloid layer containing a white pigment because sharpness and / or curl resistance can be improved.

The surface shape of the reflective support may be smooth or may have an appropriate surface roughness, but it is preferable to select a reflective support having a gloss close to that of a printed matter. For example, JIS B 0601-197
6 has an average surface roughness SRa of 0.30 to 3.0.
It is preferred to use a white support that is μm.

The light-sensitive material of the present invention preferably has a surface roughness of 0.30 to 3.0 μm on the image forming surface, and can be adjusted by adding fine particle powder. This fine particle powder is often referred to in the art as a matting agent, and thus is hereinafter referred to as a matting agent unless otherwise specified.

The layer to which the matting agent is added includes a silver halide emulsion layer, a protective layer, an intermediate layer, an undercoat layer and the like, and may be added to a plurality of layers. Preferably, it is the uppermost layer of the photosensitive material.

The surface gloss on the image forming layer side of the photosensitive material preferably has a gloss close to that of a printed matter. For example, the glossiness GS of the surface of the image forming layer after processing is measured by a method specified in JIS Z8741. (60 °) of 5 to 60 is preferred.

In a preferred embodiment of the present invention, it is preferable to form a protective layer on the outermost surface of the light-sensitive material, and to add a matting agent to the protective layer.

Examples of the matting agent which can be used in the present invention include crystalline or non-crystalline silica, titanium dioxide, magnesium oxide, calcium carbonate, barium sulfate, strontium barium sulfate, alumina magnesium silicate, silver halide, silicon dioxide. , Acrylic acid-ethyl acrylate copolymer, acrylic acid-methyl methacrylate copolymer, itaconic acid-styrene copolymer, maleic acid-methyl methacrylate copolymer, maleic acid-
Examples include styrene copolymer, acrylic acid-phenyl acrylate copolymer, polymethyl methacrylate, acrylic acid-methacrylic acid-ethyl methacrylate copolymer, polystyrene, starch, and cellulose acetate propionate. Other US Patents 1,221,9
No. 80, No. 2,992, 101, etc., and these can be used alone or in combination of two or more. Colloidal silica may be used together with the matting agent.

The particle size of these matting agents is as follows.
It is preferably from 10 to 10 μm, more preferably from 3 to 10 μm.

The average particle size (referred to as rm) here means
In the case of spherical particles, it is the diameter, and in the case of cubic or non-spherical particles, it is the average value of the diameter when the projected image is converted into a circular image of the same area, and the particle size of each particle Is ri
Where the number is ni, defined by the following equation: As a specific measuring method, a method described in JP-A-59-29243 can be applied.

Rm = Σniri / Σni In the present invention, the matting agent is dispersed and contained in a layer on the side opposite to the photosensitive layer. The method may be, if necessary, a nonionic, cationic or anionic interface. In a hydrophilic binder containing an activator, if necessary, other additives are added, and dispersed by an emulsification dispersion method using a shear stress by a high-speed rotation mixer, a homogenizer, an ultrasonic dispersion, a ball mill, or the like. It can be formed by coating.

[0104] The coating amount of the matting agent layer is contained 1 m ²
50 to 500 mg is preferable, more preferably 7
0 to 300 mg. Further, the content of the matting agent is preferably 3 to 50% by weight, more preferably 5 to 20% by weight, based on the hydrophilic binder.

In the present invention, a support of a synthetic resin film such as polypropylene, the surface of which is further coated with polyolefin, can also be used.

The thickness of the reflective support is not particularly limited.
Those having a thickness of 0 to 160 μm are preferably used. Especially 9
Those having a thickness of 0 to 130 μm are more preferred.

[0107] reflective support of the photosensitive material used in the present invention is the weight per 1 m ² is 130g or less, more preferably 70~120g per 1 m ^2.

The support used for the light-sensitive material has a Taber Stiffness of 0.8.
It is preferably from 4.0 to 4.0. The Taber stiffness is a stiffness measuring instrument V-5 model 150B (Tab
er V-5 Stiffness tester: T
ABER INSTRUMENT-A TELEDYN
E Company).
The support generally has different stiffness values in the vertical and horizontal directions, but it is sufficient if at least one of the supports is within the above range.

The beam diameter of the infrared laser preferably used in the present invention is 25 μm or less, more preferably 6 to 22 μm. When scanning exposure is performed with a high-speed rotating drum, unevenness is particularly large with an infrared laser, and the sharpness of an image is also deteriorated. By narrowing the beam diameter according to the present invention, it is possible to produce a high-definition image without unevenness. Such a problem with the rotating drum is not mentioned at all in the above-mentioned Japanese Patent Application Laid-Open No. 4-330337. According to the configuration of the present invention, for the first time, it is possible to perform high-speed image writing with high productivity, uniformity, and high definition using an infrared laser.

The infrared-sensitive silver halide emulsion layer in the invention has a spectral sensitivity maximum at a wavelength longer than 700 nm. As such a method of infrared spectral sensitization, a sensitization method using an infrared sensitizing dye is particularly preferably used.

The infrared sensitizing dye to be used in the present invention is not particularly limited, but may include tricarbocyanine and / or 4-carboxysilane.
Dicarbocyanine dyes containing a quinoline nucleus are preferred, and tricarbocyanine is particularly preferred.

Among the tricarbocyanines, particularly useful ones are represented by the following general formula [Ia] or [Ib].

[0113]

Embedded image

In the formula, R ¹ and R ² may be the same or different and each represents an alkyl group (preferably having 1 to 18 carbon atoms;
Methyl, ethyl, propyl, butyl, pentyl, heptyl, etc.), substituted alkyl group ｛carboxyl group, sulfo group, cyano group, halogen atom (fluorine, chlorine,
Bromine, etc.), hydroxyl group, alkoxycarbonyl group (8 or less carbon atoms, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl, etc.), alkoxy group (7 or less carbon atoms, methoxy, ethoxy, propoxy, butoxy, benzyloxy, etc.) , Aryloxy group (phenoxy, p-tolyloxy, etc.), acyloxy group (3 carbon atoms or less, acetyloxy, propionyloxy, etc.), acyl group (8 carbon atoms, acetyl, propionyl, benzoyl, mesyl, etc.), carbamoyl Group (carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbamoyl, piberidinocarbamoyl, etc.), sulfamoyl group (sulfamoyl, N, N-dimethylsulfamoyl, morpholinosulfonyl, etc.), aryl group (phenyl, p- Hydroxyphenyl, p- carboxyphenyl, p- sulfophenyl, the alkyl group (the alkyl moiety substituted with α- naphthyl) such as -C 6
Less than). However, this substituent represents｝ which may be substituted with an alkyl group in combination of two or more.

R ³ represents a hydrogen atom, a methyl group, a methoxy group or an ethoxy group.

R ⁴ and R ⁶ each represent a hydrogen atom, a lower alkyl group (eg, methyl, ethyl, propyl), a lower alkoxy group (eg, methoxy, ethoxy, propoxy, butoxy),
Represents a phenyl group and a benzyl group.

R ⁵ is a hydrogen atom, a lower alkyl group (eg, methyl, ethyl, propyl), a lower alkoxy group (eg, methoxy, ethoxy, propoxy, butoxy), a phenyl group, a benzyl group, or —N (W ¹ ) (W ² ). Here, W ¹ and W ² each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1
~ 4, methyl, ethyl, propyl, butyl, benzyl,
Phenethyl) or an aryl group (phenyl, naphthyl,
Tol, p-chlorophenyl, etc.), and W ¹ and W ² may be linked to each other to form a 5- or 6-membered nitrogen-containing heterocyclic ring.

D represents a group of atoms necessary for completing a divalent alkylene bond, for example, ethylene or triethylene;
The alkylene linkage may be one, two or more suitable groups, for example an alkyl group having 1 to 4 carbon atoms (methyl,
Even when substituted with a halogen atom (such as chlorine or bromine) or an alkoxy group (having 1 to 4 carbon atoms, methoxy, ethoxy, propoxy, i-propoxy, butoxy, etc.), etc. Good.

D ¹ and D ² each represent a hydrogen atom.
¹ and D ² may be bonded to each other to form a divalent alkylene bond having the same meaning as D.

Z ¹ and Z ² each represent a group of nonmetal atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic ring, and include, for example, a thiazole nucleus (benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzoyl). Thiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6
-Methylbenzothiazole, 5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole,
5-ethoxybenzothiazole, 5-carboxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5,6-dimethylbenzothiazole, 5-hydroxy -6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, naphtho [2,1-d] thiazole, naphtho [1,2-d] thiazole, naphtho [2,3-d] thiazole, 5-methoxy Naphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2
3-d] thiazole, etc.); selenazole nucleus (benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-methylbenzoselenazole, 5-hydroxybenzoselenazole, naphtho [2,
1-d] selenazole, naphtho [1,2-d] selenazole and the like; an oxazole nucleus (benzoxazole, 5-
Chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole,
5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5-carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6
-Methoxybenzoxazole, 6-hydroxybenzoxazole, 4,6-dimethylbenzoxazole,
5-ethoxybenzoxazole, naphtho [2,1-
d] oxazole, naphtho [1,2-d] oxazole, naphtho [2,3-d] oxazole and the like; quinoline nucleus (2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6 -Methyl-2-quinoline, 8-
Fluoro-2-quinoline, 6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-
Quinoline, 8-fluoro-4-quinoline, etc.);
Dialkylindolenine nucleus (3,3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine, 3,3-dimethyl-5-
Methoxyindolenine, 3,3-dimethyl-5-methylindolenine, 3,3-dimethyl-5-chloroindolenine, etc.); imidazole nucleus (1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5)
-Chlorobenzimidazole, 1-ethyl-5-chlorobenzimidazole, 1-methyl-5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole, 1 -Methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-
Methyl-5-fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-
5,6-dichlorobenzimidazole, 1-allyl-
5,6-dichlorobenzimidazole, 1-allyl-5
-Chlorobenzimidazole, 1-phenylbenzimidazole, 1-phenyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho [1 , 2-d] imidazole and the like; a pyridine nucleus (pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine and the like) and the like.

Of these, thiazole nuclei and oxazole nuclei are preferably used advantageously. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus or a benzoxazole nucleus is advantageously used.

[0122] X ₁ ^- represents an acid anion, p is represents 1 or 2.

Among the 4-carboline nucleus-containing dicarbocyanine dyes used in the present invention, particularly useful ones are represented by the following general formula [II].

[0124]

Embedded image

In the formula, R ¹¹ and R ¹² each represent the above R ¹
And it represents the R ² group having the same meaning as. R ¹³ represents a group having the same meaning as R ⁴ . However, R ¹³ is preferably a lower alkyl group or a benzyl group.

V is a hydrogen atom, a lower alkyl group (methyl,
Represents an alkoxy group (e.g., methoxy, ethoxy, butoxy), a halogen atom (e.g., fluorine, chlorine), and a substituted alkyl group (e.g., trifluoromethyl, carboxymethyl).

Z ³ represents a group having the same meaning as Z ¹ and Z ² .
X ₂ ^- and p are each represented by the general formulas [Ia] and [Ib].
Has the same meaning as X ₁ ^- and p, and q and r each represent 1 or 2.

Specific examples of these infrared sensitizing dyes include those described in JP-A-2-40646, pages (6) to (9).
1 to II-21. Also, JP-A-4-33043
Compounds described in No. 7 and compounds described in JP-A-8-101486 can also be used, but are not limited thereto.

In the present invention, it is preferable that the photosensitive material wound in a roll shape is previously loaded in a cartridge that can be handled in a bright room. In a cartridge that can be handled in a bright room, a photosensitive material drawer that can be smoothly pulled out from the cartridge when installed in a device is provided with a means for blocking light so that the photosensitive material in the bright room does not receive light. Usually, when handled in a bright room, the photosensitive material inside is not exposed to light.

It is preferable that the light-sensitive material wound in a roll is loaded in the bright room cartridge in advance, and that the light-sensitive material is wound so that the emulsion surface of the light-sensitive material is disposed outside the roll.

The layer constitution of the light-sensitive material of the present invention is not particularly limited, but it is preferable that the emulsion layer having the longest spectral sensitivity wavelength be on the support side as compared with the other light-sensitive emulsion layers.
In particular, when the emulsion having the longest spectral sensitivity wavelength is an emulsion having a spectral sensitivity in the infrared, it is preferred that the emulsion layer containing the infrared emulsion is closest to the support than the other emulsion layers.

As the silver halide emulsion used in the light-sensitive material of the present invention, a surface latent image type silver halide emulsion which forms a latent image on the surface by image exposure is used, and a negative image is formed by performing development. Emulsions may be used. Further, using an internal latent image type silver halide emulsion in which the surface of the grains is not fogged in advance, fog treatment (nucleation) after image exposure and then surface development, or fog treatment after image exposure. Emulsions capable of directly obtaining a positive image by performing surface development while performing such development can also be preferably used. The emulsion containing the internal latent image type silver halide emulsion grains is a silver halide grain having a photosensitive nucleus mainly inside silver halide crystal grains and forming a latent image inside the grains upon exposure. Containing emulsion.

The fogging treatment may be performed by exposing the entire surface, may be performed chemically using a fogging agent, may use a strong developing solution, and may be performed by heat treatment or the like.

The entire surface exposure is carried out by immersing or moistening the image-exposed photosensitive material in a developing solution or other aqueous solution, and thereafter performing uniform exposure over the entire surface. The light source used here may be any light source as long as it has light in the photosensitive wavelength region of the photosensitive material,
Further, high illuminance light such as flash light can be applied for a short time, or weak light can be applied for a long time. Further, the time of the entire surface exposure can be varied over a wide range so as to finally obtain the best positive image depending on the photosensitive material, the development processing conditions, the type of the light source used, and the like. In addition, it is most preferable that the exposure amount of the entire surface exposure be given in a certain fixed range in combination with the photosensitive material. Usually, when the exposure amount is excessively increased, the minimum density increases or desensitization occurs, and the image quality tends to be reduced.

As the technique of the fogging agent that can be used in the light-sensitive material of the present invention, it is preferable to use the technique described in JP-A-6-95283, page 18, right column, line 39 to page 19, left column, line 41.

The non-pre-fogged internal latent image type silver halide grains which can be used in the light-sensitive material of the present invention include:
An emulsion having a silver halide grain that mainly forms a latent image inside the silver halide grain and has most of the photosensitive nuclei inside the grain, and includes any silver halide such as silver bromide and silver chloride. Silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like are included.

Particularly preferably, the coated silver amount is about 1 to 3.5.
A portion of the sample, coated on a transparent support in the range of g / m ² , is exposed to a light intensity scale for a defined period of time from about 0.1 seconds to about 1 second, and is substantially exposed to light. Containing no silver halide solvent, and developing at 20 ° C. for 4 minutes using the following surface developer A for developing only the surface image of the grains,
Another part of the same emulsion sample is also exposed to light and develops an image inside the grains. The maximum density not greater than 1/5 of the maximum density obtained when developed at 20 ° C. for 4 minutes with the following internal developing solution B This is an emulsion showing the density. More preferably, the maximum density obtained with the surface developer A is not greater than 1/10 of the maximum density obtained with the internal developer B.

(Surface developer A) Methol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Add water 1000 ml (Internal developer B) Methol 2 0.0g Sodium sulfite (anhydrous) 90.0g Hydroquinone 8.0g Sodium carbonate (monohydrate) 52.5g Potassium bromide 5.0g Potassium iodide 0.5g Add water 1000ml Addition of water Internal halide image type halogen preferably used Silver emulsions include those prepared by various methods. For example, conversion-type silver halide emulsions described in U.S. Pat. No. 2,592,250 and internal chemistry described in U.S. Pat. Nos. 3,206,316, 3,317,322 and 3,367,778. Silver halide emulsion having sensitized silver halide grains, having silver halide grains containing polyvalent metal ions described in US Pat. Nos. 3,271,157 and 3,447,927. Emulsions, silver halide emulsions in which the surface of silver halide grains containing a dopant described in U.S. Pat. No. 3,761,276 are weakly chemically sensitized are described in JP-A-50-8524 and JP-A-50-385.
Silver halide emulsions composed of grains having a laminated structure described in JP-A Nos. 25 and 53-2408, etc., and silver halide emulsions described in JP-A Nos. 52-156614 and 55-127549. is there.

The shape of the silver halide grains to be used may be any one of cubic, octahedral, tetrahedral composed of a mixture of (100) and (111) planes, shape having (110) plane, spherical form and flat form. You may. Average particle size is 0.05-3μm
Is preferably used. The grain size distribution may be a monodisperse emulsion having a uniform grain size and crystal habit or an emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion having a uniform grain size and crystal habit Is preferred.

In the present invention, the monodisperse silver halide emulsion means that the weight of silver halide contained within a range of ± 20% of the average particle diameter rm is 60% or more of the total weight of silver halide grains. And preferably 70% or more, more preferably 80% or more. here,
The average particle size rm is defined as the frequency ni and r of the particles having the particle size ri.
product ni × ri ³ and i ³ is defined as the particle size ri when the maximum (three significant figures, the minimum digit is ON 4 discard 5). In the case of spherical silver halide grains,
In the case of particles having a shape other than a spherical shape, the diameter is obtained by converting the projected image into a circular image having the same area. The particle size can be obtained, for example, by photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter on the print or the area at the time of projection (the number of measured particles is 1000 or more indiscriminately).

Particularly preferred highly monodisperse emulsions are those having a distribution width of not more than 20%, defined by (particle size standard deviation / average particle size) × 100 = width of distribution (%).
Here, the average particle size and the particle size standard deviation are determined from ri defined above.

A monodisperse emulsion is prepared by adding a water-soluble silver salt solution and a water-soluble halide solution to a gelatin solution containing seed particles by pAg
And controlled pH and addition by the double jet method. In determining the addition rate, JP-A-54-48521 and JP-A-58-49938 can be referred to. As a method for obtaining a more highly monodispersed emulsion, the growth method in the presence of a tetrazaindene compound disclosed in JP-A-60-122935 can be applied.

It is also preferable to add two or more monodisperse emulsions to the same color-sensitive layer.

The particle size of each emulsion layer used in the photosensitive material is as follows.
It can be determined from a wide range in consideration of its required performance, particularly various characteristics such as sensitivity, sensitivity balance, sharpness of color separation, and granularity.

In one of the preferred embodiments, the silver halide has a particle size of 0.1 to 0.6 μm for the red-sensitive layer emulsion.
The green-sensitive emulsion is 0.15 to 0.8 μm, and the blue-sensitive emulsion is 0.1 to 0.8 μm.
A range of 3 to 1.2 μm can be preferably used.

The light-sensitive material preferably contains a nitrogen-containing heterocyclic compound having a mercapto group. Preferred compounds are those represented by the general formula [XI] described in JP-A-6-95283, page 19, right column, lines 20 to 49, particularly preferably
General formula [XII] described on page 0, left column, 5 lines to page 20, right column, 2 lines
~ [XIV]. Specific examples of the compound include compounds (1) to (39) described in JP-A-64-73338, pp. 11-15.

The amount of the mercapto compound added is as follows:
It may be appropriately changed depending on the kind of the compound used and the layer to be added. In general, when it is added to the silver halide emulsion layer, it is more preferably in the range of 10 ^-8 to 10 ^-2 mol per mol of silver halide. Is 10 ^-6 to 10 ^-3 mol.

As the yellow coupler contained in the yellow image forming layer, known acylacetanilide couplers and the like can be preferably used. Specific examples of the yellow coupler include, for example, JP-A-3-24134.
Compounds represented by Y-I-1 to Y-I-55 described in No. 5, pages 5 to 9, or JP-A-3-209466 11-14.
Compounds represented by Y-1 to Y-30 on the page can also be preferably used. Furthermore, couplers represented by the general formula [Y-I] described in JP-A-6-95283, page 21, can also be mentioned.

In the present invention, λ _max of the spectral absorption of the formed yellow image is preferably ₄₂₅ nm or more, and λ _L0.2 is preferably 515 nm or less.

Λ _max and λ of spectral absorption of yellow image
_L0.2 is an exposure / processing condition that does not substantially form a color other than the yellow image forming layer, and adjusts the amount of light having photosensitivity of the yellow image forming layer. The wavelength of the maximum value when the color is developed so that
_The wavelength at which the absorbance is 0.2 at a longer wavelength than the wavelength at which the absorbance exhibits 1.0 is defined as λ _L0.2 . Substantially no color development means that the density at the maximum wavelength in each color development region is 0.0%.
The exposure condition is not more than 05.

The yellow coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 ^-3 per mol of silver halide.
To 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol.

As the magenta coupler used in the light-sensitive material of the present invention, a compound represented by the general formula [M-1] described in the right column on page 7 of JP-A-6-95283 is preferred because of its excellent spectral absorption characteristics of the coloring dye. . Preferred examples of the compound include compounds M-1 to M-19 described on pages 8 to 11 of the same publication. Still other specific examples are described in Compounds M-1 to M-61 described in EP-A-0,273,712, pp. 6-21 and 0,235,913, pp. 36-92. Compounds 1 to 223 are other than the specific examples described above.

The above magenta couplers can be used in combination with other types of magenta couplers, and usually 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-3 mol per mol of silver halide.
^-2 to 8 × 10 ^-1 mol can be used.

The spectral absorption λ _max of the magenta image formed in the light-sensitive material of the present invention is preferably ₅₃₀ to 560 _nm , and λ _L0.2 is 580 to 635 nm.
It is preferred that

Λ _max and λ of spectral absorption of magenta image
_L0.2 adjusts the amount of light having photosensitivity of the magenta image forming layer under exposure and processing conditions that do not substantially form a color other than the magenta image forming layer, and the maximum absorbance at 500 to 600 nm is 1.0 and Λ is the maximum wavelength when color is developed
_The wavelength at which the absorbance is 0.2 at a longer wavelength than the wavelength at which the absorbance exhibits 1.0 is defined as λ _L0.2 . "Substantially no color development" has the same meaning as described above.

The magenta image forming layer of the light-sensitive material of the present invention preferably contains a yellow coupler in addition to the magenta coupler. The difference in pKa between these couplers is preferably within 2 and more preferably 1.5.
Within. The preferred yellow coupler is represented by the general formula [Y-I] described in JP-A-6-95283, page 12, right column.
a). Among the couplers represented by the general formula [Y-1], particularly preferred ones are those combined with the magenta coupler represented by the general formula [M-1]. p
It is a coupler having a pKa value not lower than Ka by 3 or more.

Specific examples of the compound as the yellow coupler are described in JP-A-6-95283, pp. 12-13.
-1 and Y-2, JP-A-2-139542 13-
(Y-1) to (Y-58) described on page 17 can be preferably used, but are not limited thereto.

As the cyan coupler contained in the cyan image forming layer, known phenol couplers, naphthol couplers or imidazole couplers can be used. For example, a phenol coupler substituted with an alkyl group, an acylamino group or a ureido group, a naphthol coupler formed from a 5-aminonaphthol skeleton, and a 2-equivalent naphthol coupler having an oxygen atom introduced as a leaving group are typical examples. In the present invention, the following general formula (I)
Alternatively, it preferably contains at least one cyan coupler represented by formula (II).

[0159]

Embedded image

In the formula, R ₂₁ represents a hydrogen atom or a substituent,
R ₂₂ represents a substituent, and m represents an integer of 0 to 2. However, when m is 0, R ₂₁ represents an electron-withdrawing group, and when m is 1 or 2, at least one of R ₂₁ and R ₂₂ represents an electron-withdrawing group. When m is 2, a plurality of R ₂₂ may be the same or different.

Z ₂₁ represents a group of nonmetal atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like, and X ₂₁ represents a hydrogen atom or a reaction with an oxidized form of a color developing agent. Represents a substituent capable of leaving.

[0162]

Embedded image

In the formula, R ₃₁ and Y ₂₂ represent a hydrogen atom or a substituent, and X ₂₂ represents a hydrogen atom or a substituent which can be eliminated by reaction with an oxidized form of a color developing agent.

Z ₂₂ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring by condensing with the pyrazole ring together with —N (Y ₂₂ ) —, and the 6-membered ring has a substituent. Or a condensed ring with a benzene ring other than the pyrazole ring.

In the general formula (I), the electron-withdrawing group is
Preferably, the substituent has a substituent constant δp defined by Hammett of +0.20 or more. Specifically, sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, Examples include groups such as nitro, halogenated alkoxy, halogenated aryloxy, pyrrolyl, and tetrazolyl, and halogen atoms.

Examples of the sulfonyl group include groups such as alkylsulfonyl, arylsulfonyl, halogenated alkylsulfonyl, and halogenated arylsulfonyl.

Examples of the sulfinyl group include alkylsulfinyl, arylsulfinyl and the like.

Examples of the sulfonyloxy group include groups such as alkylsulfonyloxy and arylsulfonyloxy.

Examples of the sulfamoyl group include groups such as N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl, and N-alkyl-N-arylsulfamoyl.

Examples of the phosphoryl group include alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoryl, arylphosphoryl and the like.

Examples of the carbamoyl group include N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl,
And groups such as N-alkyl-N-arylcarbamoyl.

Examples of the acyl group include alkylcarbonyl,
And groups such as arylcarbonyl.

The acyloxy group is preferably an alkylcarbonyloxy group.

Examples of the oxycarbonyl group include groups such as alkoxycarbonyl and aryloxycarbonyl.

The halogenated alkoxy group is preferably an α-halogenated alkoxy group.

As the halogenated aryloxy group, respective groups such as tetrafluoroaryloxy and pentafluoroaryloxy are preferred.

Examples of the pyrrolyl group include groups such as 1-pyrrolyl, and examples of the tetrazolyl group include groups such as 1-tetrazolyl.

In addition to the above substituents, trifluoromethyl,
Heptafluoro-i-propyl, nonylfluoro-t-
Each group of butyl, a tetrafluoroaryl group, a pentafluoroaryl group and the like are also preferably used.

Among the substituents represented by R ₂₁ or R _22, there may be mentioned various substituents other than the electron-withdrawing group, and there is no particular limitation. Representative examples thereof include alkyl, aryl and anilino. , Acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto groups, and spiro compound residue, And a bridge hydrocarbon compound residue.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. As the aryl group, a phenyl group is preferable.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl and aryl components in the alkylthio and arylthio groups include the above-mentioned alkyl and aryl groups.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5
To 7 are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group may have 3 to 1 carbon atoms.
2, especially those having 5 to 7 are preferred.

Examples of the ureido group include an alkylureido group and an arylureido group. Examples of the sulfamoylamino group include an alkylsulfamoylamino group and an arylsulfamoylamino group. And the like. Specifically, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl and the like: As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable. , 6-tetrahydropyranyl-2-oxy, 1-phenyltetrazol-5-oxy, etc .: The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio, 2-benzothiazolylthio , 2,4-diphenoxy-1,3,5-triazole-6-thio, etc .: as siloxy groups, trimethylsiloxy, triethylsilo Shi, dimethylbutyl siloxy like: The imide group, succinimide, 3-heptadecyl succinic acid imide, phthalimide, glutarimide and the like: As the spiro compound residue, spiro [3.3] heptane -
1-yl and the like: As the bridged hydrocarbon compound residue, bicyclo [2.2.1] heptane-1-yl, tricyclo [3.1.1 ^3.7] decan-1-yl, 7,7-dimethyl - Bicyclo [2.2.1] heptan-1-yl and the like.

These groups may further contain a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

In the general formula (I), the group capable of leaving by reaction with the oxidized form of the color developing agent represented by X ₂₁ includes:
For example, halogen atoms (chlorine, bromine, fluorine, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy,
Sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Acylamino, sulfonamide, nitrogen-containing heterocycle linked by an N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0189]

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(R ₂₁ ′, R ₂₂ ′ and Z ₂₁ ′ represent the above R ₂₁ ,
R ₂₂ and Z ₂₁ have the same meanings as above, and R _g and R _h each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group), but are preferably a hydrogen atom, a halogen atom, or an alkoxy group. , An aryloxy group, an alkylthio group, an arylthio group, and a nitrogen-containing heterocyclic group linked by an N atom.

Examples of the nitrogen-containing heterocyclic ring formed by Z ₂₁ ′ include pyrazole, imidazole, benzimidazole, triazole and tetrazole.

More specifically, the compounds represented by the general formula (I) are represented by the following general formulas (a) to (g).

[0193]

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In the above general formula, (a), at least one of R ₂₁ and R ₂₃ , (b), at least one of R ₂₁ and R ₂₄ , (c), R ₂₁ , At least one of R ₂₅ and R ₂₆ , (d), at least one of R ₂₁ , R ₂₇ and R ₂₈ , (e), at least one of R ₂₁ and R ₂₉ , ( f), R ₂₁ , and (g), R ₂₁ and R
_At least one of the ₃₀ is an electron-withdrawing group.

X ₂₁ has the same meaning as X ₂₁ in formula (I), and n represents an integer of 0 to 4. Y ₂₁ represents a hydrogen atom or a substituent, and preferred substituents represented by Y ₂₁ are, for example, those which are separated from the cyan coupler before the compound of the present invention reacts with the oxidized developing agent. A group capable of leaving under alkaline conditions, such as described in JP-A-61-228444;
And substituents which are coupled off by reaction with an oxidized developing agent as described in the above publication. Preferred Y ₂₁ is a hydrogen atom.

In the general formulas (a) to (g), R ₂₁
Of to R _29, those that are not electron-withdrawing group is a hydrogen atom or a substituent, and, among R _30, those that are not electron-withdrawing group is not particularly limited as substituents, specifically the general formula ( I)
In the above, when R ₂₁ or R ₂₂ is other than an electron-withdrawing group, those described as the substituent represented by R ₂₁ or R ₂₂ can be mentioned.

The cyan coupler having an electron-withdrawing group according to the present invention is disclosed in Japanese Patent Application Nos. 62-47323 and 62-53.
No. 417, No. 62-62162, No. 62-53418
, 62-62163, 62-48895, 62-99950, and the like.

The cyan coupler represented by formula (II) has a structure in which a hetero 6-membered ring is formed by condensing with a pyrazole ring, and the substituent represented by R ₃₁ is not particularly limited, and may be a representative. Typical examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups.In addition, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Phosphonyl, acyl, carbamoyl, sulfamoyl,
Cyano, alkoxy, sulfonyloxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl , Heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto,
Nitro, sulfo and other groups, and spiro compound residues,
Bridged hydrocarbon compound residues are also included.

[0199] preferably has 1 to 32 carbon atoms as the alkyl group represented by R _31, it may be straight-chained or branched. R
_{As the} aryl group represented by ₃₁ , a phenyl group is preferable.

The acylamino group represented by R ₃₁ includes:
Examples thereof include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R ₃₁ include an alkylsulfonylamino group and an arylsulfonylamino group.

The alkyl component and the aryl component in the alkylthio group and the arylthio group represented by R ₃₁ are the same as those in the above R ₁₁
And an alkyl group and an aryl group represented by

The alkenyl group represented by R ₃₁ has 2 to ₃₂ carbon atoms, and the cycloalkyl group has 3 carbon atoms.
~ 12, particularly preferably 5 ~ 7, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R ₃₁ preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

[0205] The sulfonyl group represented by R _31, an alkylsulfonyl group, an arylsulfonyl group such as: Examples of the sulfinyl group, an alkylsulfinyl group, an arylsulfinyl group such as: Examples of the phosphonyl group, alkylphosphonyl, alkoxycarbonyl phosphonyl group , An aryloxyphosphonyl group, an arylphosphonyl group, etc .: As the acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .:
Examples of the carbamoyl group include an alkylcarbamoyl group and an arylcarbamoyl group.
Alkylsulfamoyl group, arylsulfamoyl group, etc .: as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .: as carbamoyloxy group, alkylcarbamoyloxy group, arylcarbamoyloxy group, etc .: as ureido group , An alkylureido group, an arylureido group, etc .: As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .: As the heterocyclic group, a 5- to 7-membered group is preferable. Is 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-pyrrolyl, 1-tetrazolyl, etc .: As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable. , 5,6-tetrahydropyranyl-2
-Oxy, 1-phenyltetrazole-5-oxy and the like:
The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio, 2-benzothiazolylthio, 2,4-diphenoxy-1,3,5-triazole-6-thio, etc .: siloxy Examples of the group include trimethylsiloxy, triethylsiloxy, dimethylbutylsiloxy and the like:
Examples of the imide group include succinimide, 3-heptadecylsuccinimide, phthalimide, and glutarimide. Spiro compound residues include spiro [3.3] heptane-1-yl and the like: bridged hydrocarbon compound residues. , Bicyclo [2.2.1] heptane-1-yl, tricyclo [3.
1.1 ^3.7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

The above groups may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

[0207] Examples of the group capable of splitting off upon reaction with an oxidation product of a color developing agent represented by X _22, for example, a halogen atom (chlorine, bromine, fluorine, etc.) and alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl ,

[0208]

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(R ₃₁ ′ has the same meaning as R ₃₁ , and Z ₂₂ ′
Has the same meaning as the Z _22, R _a and R _b are hydrogen atom, an aryl group, an alkyl group or a heterocyclic group), but each group such like, preferably a hydrogen atom, a halogen atom, an alkoxy group, An aryloxy group, an alkylthio group, an arylthio group, and a nitrogen-containing heterocyclic group linked by an N atom.

Preferred specific examples of the cyan coupler of the general formula (II) are represented by the following general formula (IIa).

[0211]

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In the formula, Z ₂₂ ″ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 6-membered ring containing at least one carbonyl group or at least one sulfonyl group by condensing with the pyrazole ring. The 6-membered ring may have a substituent, and may be condensed with a benzene ring in addition to the pyrazole ring.

[0213] R ₃₁ "and Y _22" represents a hydrogen atom or a substituent, X ₂₂ "has the same meaning as X ₂₂ in the general formula (II).

In formula (II), the nitrogen-containing 6-membered heterocyclic ring formed by Z ₂₂ is preferably a 6π electron system or 8π
It is an electronic system, contains 1 to 4 nitrogen atoms including at least one —N (Y ₂₂ ) —, and at least one carbonyl group contained in the 6-membered ring is —CO— or —CS −
And the like. Further, the at least one sulfonyl group the 6-membered ring contains -SO ₂ - represents a group.

[0215] Y ₂₂ each represents a hydrogen atom or a substituent, Y ₂₂
Preferred substituents represented by are, for example, those which are eliminated from the compound of the present invention after reacting with the oxidized developing agent, for example, as described in JP-A-61-228444. , or a group capable of splitting off under alkaline conditions, as described in JP-a-56-133734, etc., although substituents coupling off by reaction with oxidized developing agent can be mentioned, preferably Y ₂₂ Is a hydrogen atom.

Among the cyan couplers represented by the general formula (II), preferred specific examples are the following general formulas (A) to (A).
The compound represented by (M) is mentioned.

[0219]

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[0218]

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In the formula, R ₃₁ , R ₃₂ and R ₃₃ are represented by the formula (II)
In the same meaning as R _31, X ₂₂ has the same definition as X ₂₂ in the general formula (II). Formula (A), (F), in (K), s represents an integer of 0 to 4, when s is 2 to 4, a plurality of R ₃₂ may be the same or different.

R ₃₂ and R ₃₃ in formulas (J), (L) and (M) have the same meaning as R ₃₁ in formula (II), but R ₃₂ is not a hydroxyl group, and Z ₂₂ ″ ′
Represents an atom group necessary for forming a heterocyclic ring.

Preferred examples of the groups represented by R ₃₂ and R ₃₃ include groups such as alkyl, aryl, carboxyl, oxycarbonyl, cyano, alkoxy, aryloxy, amino, amide and sulfonamide, and hydrogen, halogen and the like. It is.

The cyan couplers of the general formula (II) are described in Japanese Patent Application Nos. 63-32488, 64-36996 and 64.
-41183, 64-52293, 64-97
Nos. 598, 64-9884 and 64-122505
No. 2, etc., and can be synthesized according to the described synthesis method and the synthesis method described in the cited reference.

The representative examples of the cyan coupler of the present invention represented by formula (I) or (II) are shown below, but are not limited thereto. For example, JP-A No. 1-144052, page (7). Upper right column-C-1 described in the upper right column of page (9)
C-35, JP-A-4-133504 (6), lower right column of page
(12) Among A-1 to M-8 described in the lower right column of the page, couplers other than representative examples can be mentioned.

[0224]

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[0225]

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[0226]

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[0227]

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[0228]

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[0229]

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[0230]

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The cyan coupler of the present invention is generally used in an amount of 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-3 mol, per mol of silver halide.
It can be used in the range of 10 ^-2 to 8 × 10 ^-1 mol.

Further, the cyan coupler of the present invention can be used in combination with another type of cyan coupler.

In order to incorporate the cyan coupler of the present invention into the color photographic material of the present invention, known techniques used for ordinary cyan couplers can be applied. It is preferable to dissolve the coupler in a high-boiling solvent and, if necessary, in combination with a low-boiling solvent, to disperse the fine particles, and to add the resulting coupler to the silver halide emulsion-containing layer. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, a wavelength adjusting agent, an anti-agglomeration agent and the like may be used in combination.

The yellow, magenta, and cyan image forming layers of the light-sensitive material of the present invention are laminated and coated on a support, but the order from the support may be any order. One preferred embodiment is, for example, a cyan image forming layer, a magenta image forming layer, and a yellow image forming layer from the side close to the support. In addition, an intermediate layer, a filter layer, a protective layer, and the like can be provided as necessary.

In each of the magenta, cyan, and yellow couplers, an anti-fading agent can be used in combination to prevent fading of the formed dye image due to light, heat, humidity, and the like. Preferable compounds include phenyl ether compounds represented by formulas I and II described in page 3 of JP-A-2-66541 and formula IIIB described in JP-A-3-174150.
A phenolic compound represented by
5, an amine compound represented by the general formula A described in JP-A-6-182741, a compound represented by the general formula XII, XIII, XIV,
The metal complex represented by XV is particularly preferred for magenta dyes. Further, the compounds represented by the general formula I 'described in JP-A-1-19649 and the compounds represented by the general formula II described in JP-A-5-11417 are particularly preferred for yellow and cyan dyes.

When an oil-in-water emulsion dispersion method is used to add a coupler or other organic compound to a light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or more, It is dissolved using a boiling point and / or a water-soluble organic solvent in combination, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant.

As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be added.

Examples of high boiling organic solvents which can be used for dissolving and dispersing the coupler and the like include phthalic acid esters such as dioctyl phthalate, di-i = decyl phthalate and dibutyl phthalate, tricresyl phosphate and trioctyl. Phosphate esters such as phosphates and phosphine oxides such as trioctylphosphine oxide are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Of course, two or more high-boiling organic solvents can be used in combination.

Particularly preferred compounds as high boiling organic solvents are those represented by the formula [H] described in JP-A-6-95283, page 22.
Compounds represented by BS-I] and [HBS-II], particularly preferably compounds represented by [HBS-II]. Specific compounds include, for example, JP-A-2-124
No. 568, pp. 53-68.
95.

Preferred compounds as a surfactant used for dispersing a photographic additive used in a light-sensitive material and adjusting the surface tension during coating are those having 8 to 3 carbon atoms in one molecule.
Those containing 0 hydrophobic groups and a sulfo group or a salt thereof are mentioned. Specific examples include A-1 to A-11 described in JP-A-64-26854. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used.
These dispersions are usually added to a coating solution containing a silver halide emulsion, but the shorter the time from dispersion to the time of addition to the coating solution, and the shorter the time from addition to the coating solution to coating. Often, both are preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

In the light-sensitive material, a compound which reacts with an oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer to prevent fog. Is preferably improved. As the compound for this, a hydroquinone derivative is preferred, and more preferably
Dialkylhydroquinones such as 5-di-t-octylhydroquinone. Particularly preferred compounds are the compounds represented by the general formula ii described in JP-A-4-133,056, and the compounds II-1 to II described on pages 13 to 14 of the same.
Compound 1 described on pages -14 and 17.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or to improve the light fastness of the dye image. Preferable examples of the ultraviolet absorber include benzotriazoles. Particularly preferable compounds are those represented by the general formula III described in JP-A-1-250944.
A compound represented by general formula III described in JP-A-64-66646;
No. 240, UV-1L to UV-27L;
Compounds represented by the general formula I described in JP-A-1633 and compounds represented by the general formulas (I) and (II) described in JP-A-5-165144.

It is preferable that the light-sensitive material contains an oil-soluble dye or pigment because the whiteness is improved. Representative specific examples of the oil-soluble dyes include compounds 1 to 27 described in pages (8) to (9) of JP-A-2-842.

Gelatin is preferably used as a binder in the light-sensitive material. In particular, gelatin extract is subjected to hydrogen peroxide treatment to remove coloring components of gelatin,
Gelatin whose transmittance has been improved by extracting from raw material ossein that has been subjected to a hydrogen peroxide treatment or using ossein manufactured from uncolored raw bone is preferable.
Gelatin may be any of alkali-treated ossein gelatin, acid-treated gelatin, gelatin derivative, and modified gelatin, and particularly preferably alkali-treated ossein gelatin.

The transmittance of gelatin was 7 when a 10% solution was prepared and the transmittance was measured at 420 nm using a spectrophotometer.
It is preferably 0% or more.

Gelatin jelly strength (by the Paggy method)
Is preferably at least 250, particularly preferably 27
0 or more.

There is no particular limitation on the ratio of gelatin to the total coating binder, but it is preferable to use a large ratio, and more specifically, a preferable effect can be obtained by using at least a ratio of 20 to 100%.

The total amount of gelatin contained on the image forming side of the light-sensitive material of the present invention is preferably less than 11 g / m ² . The lower limit is not particularly limited, but is generally preferably 3.0 g / m ² or more from the viewpoint of physical properties or photographic performance. The amount of gelatin is determined by the method of measuring water described in the Paggy Method and converting it to the weight of gelatin containing 11.0% of water.

As a hardener of a binder represented by gelatin, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination.
It is preferable to use the compounds described in JP-A-61-249054 and JP-A-61-245153. It is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of fungi and bacteria which adversely affect photographic performance and image storability.

The silver halide emulsion can be optically sensitized by a commonly used sensitizing dye. Use of a combination of sensitizing dyes used for supersensitization, such as an internal latent image type silver halide emulsion and a negative type silver halide emulsion, is also useful for the silver halide emulsion in the present invention. Sensitizing dyes are described in Research Disclosure (hereinafter referred to as R).
D) 15162 and 17643 can be referred to.

It is preferable to add a compound for adjusting the toe gradation to the light-sensitive material. Preferred compounds include
The formula [AO-] described in JP-A-6-95283, page 17
Compounds represented by II] are preferred. Specific examples of the compound include compounds II-1 to II-8 described on page 18 of the same publication. The addition amount of the compound [AO-II] is preferably 0.001 to 0.50 g / m ² , more preferably 0.005 to 0.20 g / m ² . The compounds may be used alone or in combination of two or more. Furthermore,
A quinone derivative having 5 or more carbon atoms can be used in combination with the compound [AO-II]. However, in any of these cases, the amount used is 0.001 to 0.50 g / total.
It is preferably in the range of m ² .

It is preferable to include a fluorescent whitening agent in the light-sensitive material and / or processing solution of the present invention in order to improve the whiteness.

When developing the light-sensitive material of the present invention with a color developing solution, the developing solution, the bleach-fixing solution and the stabilizing solution are respectively a replenishing developer, a replenishing bleaching solution, a replenishing fixing solution and a replenishing bleaching. The developing process can be continuously performed while replenishing the fixing solution, the replenishing stabilizing solution and the like.

In the present invention, the effect of the present invention can be more effectively exhibited when the replenishing amount of the developing solution is 700 ml or less per 1 m ^{2 of the} photosensitive material. More preferably 500 ml
It is as follows. The other processing solutions are the same as the developing solution, and the replenishment amount is 700 ml or less per m ^{2 of the} photosensitive material.
More preferably, when it is 500 ml or less, the effects of the present invention can be more effectively exhibited.

Examples of the developer which can be used in the developer used for developing the light-sensitive material of the present invention include ordinary silver halide developers such as polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, and ascorbin. It includes acids and derivatives thereof, reductones, phenylenediamines, and the like, or mixtures thereof.
Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, ascorbic acid, N, N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamidoethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline, 4-amino-N-ethyl-N- (β
-Hydroxyethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline and the like.

These developers may be incorporated in the emulsion in advance so that they act on the silver halide during immersion in a high pH aqueous solution.

The developer may further contain a specific antifoggant and development inhibitor, or these additives may be arbitrarily incorporated into the constituent layers of the photosensitive material.

In the light-sensitive material, known photographic additives can be further used. Examples of the known photographic additives include the compounds described in RD17643, page 23, section III to page 29, section XXI and RD18716, page 648 to 651.

In order to form an image using the light-sensitive material of the present invention, it is preferable to use an automatic developing machine of a light-source scanning exposure system. Specific examples of particularly preferable devices and systems for image formation include Konsensus manufactured by Konica Corporation.
L, Konsensus 570, Konsensus II
And the like.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material. In particular, a light-sensitive material having a reflective support for forming an image for direct viewing,
For example, it is suitable for a color proof photosensitive material.

[0261]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Embodiment 1 FIG. 1 is a conceptual diagram showing an example of an exposure apparatus used in the present invention.

The laser light emitted from the plurality of laser light source units (1), (2) and (3) is image-exposed to a photosensitive material set on a rotating drum via an optical unit. .

FIG. 2 is a conceptual diagram showing an example of a laser light source unit.

Laser light emitted from a plurality of laser oscillators (4), (5) and (6) for obtaining light of the same wavelength is image-exposed on a photosensitive material set on a rotating drum as a plurality of beam spots. You.

FIG. 3 is a conceptual diagram showing an example of the image forming apparatus used in the present invention.

The photosensitive material wound in a roll and stored in the light chamber cartridge is wound on a rotating drum, and then subjected to a phenomenon process to form a final image.

When an image composed of dot information was formed in the apparatus having the above configuration, a clear image without unevenness could be stably obtained.

<< Preparation of Emulsion EM-P1 >> While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KBr: NaCl = 95: 5 in molar ratio). ) Was simultaneously added by a control double jet method to obtain a cubic silver chlorobromide core emulsion having a particle size of 0.30 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added to the obtained core emulsion by a control double jet method. Thus, a shell was formed until the average particle size became 0.42 μm.
At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

After washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P1. The width of the particle size distribution of EM-P1 was 8%.

<< Preparation of Emulsion EM-P2 >> While controlling the aqueous solution containing ossein gelatin at 40 ° C., an aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (KBr: NaCl = 95: 5 by molar ratio). ) Was added simultaneously by the control double jet method to obtain a cubic silver chlorobromide core emulsion having a particle size of 0.18 μm. At this time, p is set so that a cube is obtained as the particle shape.
H and pAg were controlled.

An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in molar ratio) were simultaneously added to the obtained core emulsion by a control double jet method. Thus, a shell was formed until the average particle size became 0.25 μm.
At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

After washing with water to remove water-soluble salts, gelatin was added to obtain an emulsion EM-P2. The width of the particle size distribution of EMP-2 was 8%.

<< Preparation of Green-Sensitive Silver Halide Emulsion >> Emulsion E
After sensitizing dye GS-1 was added to M-P1 for optimal color sensitization, 600 mg per mol of silver of stabilizer T-1 was added to prepare green-sensitive emulsion Em-G1.

<< Preparation of Red-Sensitive Silver Halide Emulsion >> Emulsion E
Red-sensitive emulsion Em-R1 was prepared in the same manner as green-sensitive emulsion Em-G1, except that sensitizing dyes RS-1 and RS-2 were added to M-P2 to optimize the color sensitization.

<< Preparation of Infrared-Sensitive Silver Halide Emulsion >> A green-sensitive emulsion Em-G1 was prepared in the same manner as in the green-sensitive emulsion Em-G1 except that sensitizing dyes IRS-1 and IRS-2 were added to the emulsion EM-P2 to optimize the color. Thus, an infrared-sensitive emulsion Em-IFR1 was prepared.

<< Preparation of Pan-Sensitive Silver Halide Emulsion >> EM-
A pan-sensitive emulsion Em-H1 was prepared in the same manner as the green-sensitive emulsion Em-G1, except that the sensitizing dyes GS-1 and RS-2 were added to P1 to optimize the color sensitization.

T-1: 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene

[0280]

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[0281]

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[0282] The high density polyethylene on one side "Preparation of multi-layer color light-sensitive material", laminated with polyethylene melt containing dispersed at a content of 15 wt% of anatase type titanium oxide on the other side, the weight per 1 m ² Is 115
Em-G1, Em-R on a polyethylene-laminated paper reflective support of 125 g, 125 g, 135 g, and 150 g.
Using each emulsion of 1, Em-IFR1, each layer having the following layer constitution was applied on the side of the polyethylene layer containing titanium oxide,
Further on the back side to prepare a gelatin 6.00 g / m ^2, multi-layer color light-sensitive material samples 101 to a silica matting agent 0.65 g / m ² was coated. In addition, H-1, H-
2 was added. Surfactants SU-1, SU-2 and SU-3 were added as coating aids and dispersing aids to prepare.

SU-1: Sulfosuccinic acid di (2-ethylhexyl) ester sodium SU-2: Sulfosuccinic acid di (2,2,3,3,4,4,
5,5-octafluoropentyl) ester sodium SU-3: sodium tri-i-propylnaphthalenesulfonate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium H-2: tetrakis (vinyl) Sulfonylmethyl) methane << Layer Composition >> Each additive was shown by the coating amount (g / m ² ), and the added amount of the silver halide emulsion was shown in terms of silver.

Eighth layer (ultraviolet absorbing layer) Gelatin 1.20 Ultraviolet absorbing agent (UV-1) 0.075 Ultraviolet absorbing agent (UV-2) 0.025 Ultraviolet absorbing agent (UV-3) 0.100 Silica mat Agent 0.01 seventh layer (red-sensitive layer) gelatin 1.20 red-sensitive silver chlorobromide emulsion (Em-R1) 0.35 cyan coupler (C-1) 0.40 stain inhibitor (HQ-1) 0.02 inhibitor (T-1, T-2, T-3; molar ratio 1: 1: 1) 0.002 high boiling point organic solvent (SO-2) 0.40 sixth layer (intermediate layer) gelatin 1 0.000 Stain inhibitor (HQ-2, HQ-3; equivalent weight) 0.02 Fifth layer (green photosensitive layer) Gelatin 1.60 Green sensitive silver chlorobromide emulsion (Em-G1) 0.40 Magenta coupler (M-1) 0.25 Yellow coupler (Y-3) 0.06 Inhibitor (HQ-1) 0.035 Inhibitor (T-1, T-2, T-3; molar ratio 1: 1: 1) 0.0036 High boiling organic solvent (SO-1) 0.38 4 layers (intermediate layer) Gelatin 1.00 Anti-stain (HQ-2, HQ-3; equal weight) 0.02 Anti-irradiation dye (AI-1) 0.04 Anti-irradiation dye (AI-2) 0 .02 Third layer (infrared-sensitive layer) Gelatin 1.20 Infrared-sensitive silver chlorobromide emulsion (Em-IFR1) 0.48 Yellow coupler (Y-1) 0.20 Yellow coupler (Y-2) 0.20 Stain inhibitor (HQ-1) 0.04 Inhibitor (T-1, T-2, T-3; molar ratio 1: 1: 1) 0.0036 High boiling organic solvent (SO-1) 0 .30 Second layer (middle layer) Gelatin 0.5 Stain inhibitor (HQ-2, H 0.02 Anti-irradiation dye (AI-3) 0.15 First layer (black colloidal silver layer) Gelatin 0.70 Black colloidal silver 0.10 Support Polyethylene containing a trace amount of colorant Laminated paper SO-1: trioctylphosphine oxide SO-2: di (i-decyl) phthalate HQ-1: 2,5-di (t-butyl) hydroquinone HQ-2: 2,5-di (1,1- Dimethyl-4-hexyloxycarbonylbutyl) hydroquinone HQ-3: 2,5-di (sec-dodecyl) hydroquinone, 2,5-di (sec-tetradecyl) hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl 1: 1: 2 (weight ratio) mixture of hydroquinone T-2: 1- (3-acetamidophenyl) -5-mercaptotetrazo Le T-3: N-benzyl adenine

[0285]

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[0286]

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[0287]

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Samples 102 to 106 were prepared by adjusting the emulsion amount of each photosensitive layer of Sample 101.

Further, Sample 107 was obtained by changing the seventh layer of Sample 103 to the following structure.

Seventh layer (red-sensitive layer) Gelatin 1.20 Red-sensitive silver chlorobromide emulsion (Em-R1) 0.30 Cyan coupler (Exemplified Compound I-18) 0.25 High boiling organic solvent (SO- 3) 0.30 High boiling organic solvent (SO-4) 0.30 Stain inhibitor (HQ-1) 0.02 Inhibitor (T-1, T-2, T-3; molar ratio 1: 1: 1) ) 0.002 sO-3: tricresyl phosphate _{sO-4: p-CH 3} -C 6 H 4 -SO 2 NH-C 6 H 4 -C 12 H 25 -p samples obtained as described above Tables 101 to 107 are shown in Table 1.
Exposure was performed by changing the laser exposure output as described above. The exposure value of the laser was adjusted to take three values: solid density of each single color, black density, and density in which black and a single color overlap.

As the laser light source, a green laser is a helium-neon laser (544 nm), a red laser is a semiconductor laser (AlGaInAs: about 650 nm), and an infrared laser is a semiconductor laser (GaAlAs: about 780 n).
m) was used. The photosensitive material was brought into close contact with the rotating drum by suction and subjected to scanning exposure at 2000 revolutions / minute to record an image.
The exposure amount is 1μ for the exposure output of the green laser light source unit.
W, exposure output of infrared laser light source unit is 100μW
Met.

In this case, however, the infrared semiconductor laser was set to 1
Two of them were arranged, and the photosensitive material was simultaneously exposed to light as 12 beams of laser light via an optical means.

After the exposure, color development was performed according to the following processing steps.

The peaks in the spectral sensitivity distribution of each emulsion layer of the obtained processed sample were 548 nm for the green-sensitive emulsion, 675 nm for the red-sensitive emulsion, and 785 nm for the infrared-sensitive emulsion.

<< Processing Step >> Processing Step Temperature Time Immersion (developer) 37 ° C. for 12 seconds Fog exposure—12 seconds Developing 37 ° C. for 95 seconds Bleaching and fixing 35 ° C. for 45 seconds Stabilizing treatment 25-35 ° C. for 90 seconds Drying 50- 85 ° C. for 40 seconds The composition of each processing solution is as follows.

(Color developing solution and color developing replenishing solution) Developer replenishing solution Benzyl alcohol 15.0 ml 18.5 ml Ethylene glycol 8.0 ml 10.0 ml Diethylene glycol 15.0 ml 18.0 ml Potassium sulfite 2.5 g 2.5 g Bromide Potassium 1.0 g 0.2 g Potassium carbonate 25.0 g 25.0 g T-1 0.1 g 0.1 g Hydroxylamine sulfate 5.0 g 5.0 g Sodium diethylenetriaminepentaacetate 2.0 g 2.0 g 4-amino-N- Ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g 5.4 g Optical brightener (4,4′-diaminostilbene disulfonic acid derivative) 1.0 g 1.0 g Potassium hydroxide 2.0 g 2.0 g Water was added to make up the total volume to 1 liter, developer to pH 10.15, replenisher Adjusted to pH 10.35.

(Bleach-fixing solution and bleach-fixing replenisher) Ferric ammonium diethylenetriaminepentaacetate 90.0 g Ammonium thiosulfate (70% aqueous solution) 180.0 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-mercapto-1, 2 , 4-triazole 0.15 g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to make the total volume 1 liter.

(Stabilizing Solution and Stabilizing Replenishing Solution) o-phenylphenol 0.1 g 1-hydroxyethylidene-1,1-diphosphonic acid 4.0 g diethylenetriaminepentaacetic acid 2.0 g ammonium hydroxide (28% aqueous solution) 7 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Water is added to make up to 1 liter, and the pH is adjusted to 7.5 with ammonium hydroxide or sulfuric acid.

Incidentally, the stabilizing treatment was of a countercurrent type having a three-tank configuration. Further, the replenishment amount, a developing solution, the bleach-fixing solution, stabilizing solution both were with the photosensitive material 1 m ² per 320 ml.

Using Konsensus 570 manufactured by Konica Corporation, a color proof composed of halftone images was prepared, and the following evaluation was performed.

Both ink reproducibility and color reproducibility, Japan Co.
The evaluation was made based on the color difference from the color sample of lor (distance ΔE in the CIELAB color space). The measurement was made by Minolta Colorimeter C.
M-2002 was used.

<Black Reproducibility> The color difference was evaluated on a four-point scale.

A: 0 ≦ color difference ≦ 2 ○: 2 <color difference ≦ 3 Δ: 3 <color difference ≦ 5 ×: 5 <color difference <color reproducibility> The color difference was evaluated on a four-point scale.

A: 0 ≦ color difference ≦ 5 ○: 5 <color difference ≦ 7 Δ: 7 <color difference ≦ 9 ×: 9 <color difference <overprint detectability> Black and color (Y, M, C) overlap It was visually evaluated whether or not could be detected.

<Unevenness> Image unevenness was visually observed with a loupe and evaluated on a three-point scale.

：: No unevenness is observed at all Δ: Slight unevenness is observed X: Clearly unevenness is observed <Dot gain (D / G)> D / G at the time of preparation exposure
The magnitude (absolute value) of the variation of n = 10 at 50% is 4
It was rated on a scale.

A: 0 ≦ D / G ≦ 0.5 O: 0.5 <D / G ≦ 1.0 Δ: 1.0 <D / G ≦ 1.5 ×: 1.5 <D / G Result Are also shown in Table 1.

[0308]

[Table 1]

As shown in Table 1, overprinting could be detected by adjusting the exposure amount to three values (white background, single color density, black density) for the yellow, magenta and cyan color forming layers.

Those having a shoulder gradation smaller than the range of the present invention are as follows.
Even if overprinting can be detected, color reproducibility deteriorates. In addition, density unevenness of other layers occurred. On the other hand, when the shoulder gradation is larger than the range of the present invention, the layer has large unevenness and the image quality deteriorates.

Further, by using a cyan coupler as an exemplified compound, color reproducibility is improved.

Example 2 A proof in which the monochromatic color reproducibility and the black color reproducibility were close to those of a printed matter was obtained by adjusting and exposing the laser exposure value to two values (white background, single color density).

Example 3 A proof of a printed matter including a spot color was obtained by adjusting the laser exposure value so as to take 256 values, and a proof approximating the printed matter including the spot color was obtained.

[0314]

According to the image forming method of the present invention, a high-quality calibration color image (color proof) can be stably obtained from a plurality of dot information.

[Brief description of the drawings]

FIG. 1 is a conceptual diagram illustrating an example of an exposure apparatus used in the present invention.

FIG. 2 is a conceptual diagram illustrating an example of a plurality of laser light source units.

FIG. 3 is a conceptual diagram illustrating an example of an image forming apparatus used in the present invention.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H016 AA01 AC01 BB02 BC01 BK02 BK03 BK04 BK05 BK06 BL02 BL07 BL08 2H106 AA02 AA12 AA47 AA80 AA82 AB04 AB46 AB53 AB64 AB88 BA91

Claims (8)

[Claims] 1. An area gradation image of halftone dots is formed by exposing an image recording material having at least one each of yellow, magenta and cyan image forming units based on digitized halftone image information. An image forming method, wherein the image recording material is exposed at a binary or more exposure amount in a photosensitive region of at least one image forming unit. 2. The image forming method according to claim 1, wherein the image forming material is exposed to a light-sensitive area of at least one image forming unit with an exposure amount of three or more values. 3. An image recording material in which the absolute value of the slope of a characteristic curve at an exposure amount at which the density of at least one image forming unit is close to that of a reference print is less than 0.2 to 1.0. The image forming method according to claim 1 or 2, wherein: 4. An image recording material in which the absolute value of the slope of a characteristic curve at an exposure amount at which the density of at least one image forming unit approximates the density of a reference print is 1.0 to 2.0. The image forming method according to claim 1, wherein: 5. A halftone dot area gradation image is formed by exposing an image recording material mainly having at least one each of yellow, magenta and cyan image forming units based on digitized dot image information. An exposing step of exposing at least two of the yellow, magenta and cyan image forming units to the same halftone dot shape and position. 6. A halftone dot area gradation image is formed by exposing an image recording material having at least one each of yellow, magenta and cyan image forming units based on digitized dot image information. Image forming, wherein one of the yellow, magenta, and cyan image forming units is exposed and another is simultaneously exposed to another image forming unit. Method. 7. An area gradation image of halftone dots is formed by exposing an image recording material mainly having at least one image forming unit for each of yellow, magenta and cyan based on digitized halftone image information. At this time, at least one of the yellow, magenta and cyan image forming units is straddled over a plurality of halftone units, and is exposed at an exposure amount that is 0.15 or more lower than the density of the corresponding reference print. An image forming method. 8. The image forming method according to claim 1, wherein at least one semiconductor laser or light emitting diode is used as an exposure light source.