JPH10142752A - Methods for forming color image and color proof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the method for forming the color image high in productivity and free from uneven exposure and superior in stability by scanning exposure and to provide the method for forming the color proof capable of stably obtaining dot images free from uneven exposure by the scanning exposure from dot image information obtained by color separation and dot image conversion in the manufacturing process of a color printing plate and a printing process. SOLUTION: A color image is formed by winding a silver halide photographic sensitive material on a rotary drum and imagewise exposing the rotating material to laser beams and this silver halide color photographic sensitive material has a reflective support in a weight of <=130g/m<2> and the raw unexposed material has a reflection density of >=0.8 in the laser beam wavelength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic material (hereinafter, also referred to as "color photographic material").
More specifically, the present invention relates to a color image forming method for performing scanning exposure using a rotating drum.

[0002] The present invention also relates to a method for producing a color image for calibration (color proof) by scanning exposure from halftone image information obtained by color separation and halftone image conversion in a plate making and printing process.

[0003]

2. Description of the Related Art Conventionally, in color plate making and printing processes,
As a method of obtaining a color proof from a plurality of black and white halftone images obtained by color separation and halftone image conversion, there is a method of producing a color proof using a silver halide color photographic light-sensitive material having a white support. 56-113139, 5
6-104335, 62-280746, 62
-280747, 62-280748, 62-
No. 2,807,492 and No. 62-280750.

[0004] 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 come into wide use. By digitizing the image information, the image processing, the image can be quickly sent to a remote place, or the image in which the layout, the color tone, etc. of the image are changed can be quickly edited.

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, but has various problems in practical use.

For example, in order to output as a printing proof, it is necessary to output to a relatively large area, and it takes a long time to scan and expose it, and productivity is remarkably high. Will be inferior.

Further, when an apparatus capable of performing scanning exposure for a large-format color proof is constructed, the apparatus becomes very large, and cannot be used in a place where the installation area is limited. Has been proposed, and the scanning exposure is performed by laser. However, even in the method of rotating the photosensitive material with the drum, it is necessary to expose a high-definition image, or to increase the number of rotations of the drum in order to further improve productivity. There is. In particular, when a halftone image is to be output by exposure, a non-uniform image is a fatal defect.
In addition, there is a problem in that when a plurality of identical images are output, a different finish is obtained.

Japanese Patent Application Laid-Open No. Hei 4-330337 discloses an exposure method in which scanning exposure is performed using a semiconductor laser.
There is no description about the problem with the rotating drum or the problem with the dot image formation.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to form a color image with high productivity, no exposure unevenness and excellent stability in obtaining a color image by scanning and exposing a silver halide photographic material. It is to provide a method.

Further, in the color plate making / printing process, halftone image information obtained by color separation and halftone image conversion is
It is an object of the present invention to provide a method for producing a color proof capable of stably obtaining a halftone image without exposure unevenness by scanning exposure.

[0011]

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

(1) In a color image forming method in which a silver halide photographic light-sensitive material is wound around a rotating drum and an image is exposed with a laser while rotating the photosensitive material, the silver halide photographic light-sensitive material has a weight per 1 m ^2. A color image forming method having a reflective support of 130 g or less and a reflection density of a raw sample at a wavelength of the laser of 0.8 or more.

(2) The power spectrum for each spatial frequency obtained by continuously measuring the thickness of the reflective support and analyzing the fluctuation of the thickness by the fast Fourier transform is 1 to 1
The square root (PY) of the one integrated over the frequency interval of 2.5 mm
(1) is 2.9 μm or less.

(3) The silver halide photographic material has at least one infrared-sensitive silver halide emulsion layer, and at least one of the laser exposures has a beam diameter of 25 μm.
The color image forming method according to (1) or (2), which is the following infrared laser.

(4) Color-separated yellow, magenta,
In a method for producing a color proof that exposes a silver halide color photographic light-sensitive material based on halftone image information consisting of cyan and black image information, the exposure wraps the silver halide photographic light-sensitive material around a rotating drum, Image exposure is performed with a laser while rotating, and at least a part of the dot image information has a dot area ratio of 40%.
And the number of dot elements per inch ² is 20
Production of a color proof in which the halftone dot image is converted so as to be 0 × 10 ³ or more, and the silver halide photographic material has a reflective support having a weight per 130 m ² or less per 1 m ^2. Method.

Hereinafter, the present invention will be described in more detail.

In the present invention, when performing scanning exposure on a photosensitive material, the photosensitive material is set so as to be wound around a rotating drum, and laser exposure is performed in accordance with image information in synchronization with the rotation of the rotating drum. 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 set arbitrarily, but an appropriate number of rotations can be selected according to the beam diameter of the laser light, the energy intensity of the laser light, the writing pattern of the laser light, 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.
00 to 3000 rotations are preferred.

The photosensitive material can be fixed to the drum by 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.

As the laser for exposing the photosensitive material, various conventionally known lasers can be used.
Although a gas laser can provide high output, the device is large and expensive, and requires a modulator. On the other hand, semiconductor lasers have features such as small size, low cost, and long life. Some semiconductor lasers have an oscillation wavelength from the visible part to the infrared.

As an example of a gas laser that emits visible light, a helium-cadmium laser (oscillation wavelength 441.
6 nm, the same applies hereinafter), argon ion laser (51
4.4 nm), helium neon laser (632.8 n)
m) and the like. As a semiconductor laser, A
lGaInAs (670 nm), GaAlAs (750
nm), GaAlAs (760-850 nm) and the like, but are not limited thereto.

The reflective support of the light-sensitive material of the present invention is the weight per 1 m ² is 130g or less, more preferably is the weight per 1 m ² is 70～120G.

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, and at least one of the reflection densities of the raw sample measured at the wavelength of the laser exposure. 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 antihalation in the 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, and other dyes.Examples include oxonol from the viewpoint of high resolution in a development processing bath and non-sensitization to a silver halide emulsion. Dyes and merocyanine dyes.

As the oxonol dye, US Pat.
187, 225, JP-A-48-42826, and 49
No.-5125, No.49-99620, No.50-916
No. 27, No. 51-77327, No. 55-120660
No. 58-24139, No. 58-143342,
No. 59-38742, No. 59-111640, No. 5
Nos. 9-111641, 59-168438 and 60
-218641, 62-31916, 62-6
No. 6275, No. 62-66276, No. 62-1857
No. 55, No. 62-273527, No. 63-13994
No. 9, etc. Also, as merocyanine dyes, JP-A-50-145124 and JP-A-58-12012
No. 5, 63-35437 and 63-35438,
Nos. 63-34539 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 can be mentioned.

Typical examples of water-soluble dyes other than oxonol dyes and merocyanine dyes include water-soluble yellow dyes AIY-15 to AIY-18 and AIM- described in Japanese Patent Application No. 7-150291. 15-AIM-
18, AIC-15 to AIC-18.

The water-soluble dyes usable 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 on 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 reducing agents 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.

The coating weight of the colloidal silver is such that 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 is 0.8.
The amount can be selected so as 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 may be contained as a 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].

[0038]

Embedded image

In the formula, R ₁ and R ₂ each represent 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.

[0040]

Embedded image

Where R ₁ , R ₃ , L ₁ -L ₅ , n ₁ and n
₂ represents the same meaning as in the general formula [1], and E represents an acidic nucleus necessary for forming an oxonol dye.

[0042]

Embedded image

Where R ₃ , R ₄ , L ₁ -L ₅ , n ₁ and n
₂ represents the same meaning as in the general formula [1], and R ₈ ,
R ₉ has the same meaning as R ₃ and R ₄ .

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

[0045]

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In the formula, R ₃ , L ₁ and L ₂ have the same meanings as in the general formula [1], and E has the same meaning as in the general formula [2]. 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) SO} 2 R 6, -N (R 5) COR 6, -C
It represents an OR 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 have the same meaning as in the general formula [1].

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

[0049]

Embedded image

In the formula, R ₃ , R ₄ , L ₁ , L ₂ , L ₃ and n ₁ have the same meaning as in the general formula [1], and E has the same meaning as in the general formula [2]. R ₁₀ and R ₁₁ have the same meanings as in formula (4), and R ₁₄ has the same meanings as R ₁₀ .

[0051]

Embedded image

Where R ₃ , R ₄ , R ₁₀ , R ₁₁ , L ₁ -L ₅ ,
X ₃ , n ₁ and n ₂ represent the same meaning as in the general formula [1],
X ₄ has the same meaning as X ₃ , and R ₁₅ and R ₁₆ have the same meanings as R ₁₀ .

[0053] 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.

[0054]

Embedded image

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

[0056]

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 JP-A-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 used in combination 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 at least 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
^It is preferably 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 the productivity is improved by increasing the number of rotations of the drum.

In order to measure the PY value, the thickness unevenness of the polyolefin-coated support is continuously measured using a film thickness continuous measuring machine (for example, manufactured by Anritsu Corporation), and the obtained measurement signal is analyzed by a frequency analyzer. (For example, Hitachi Electronics:
VC-2403).

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 generally used in papermaking may be incorporated 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 often matted.

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 sides of the reflective 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. It is also preferable to provide a sub-coat layer on the surface of the surface laminate layer for improving the adhesion to the photographic emulsion, or a back coat layer on the back surface of the laminate layer for improving the printability and antistatic properties.

The polyolefin resin used for laminating the surface of the support (the surface on which the emulsion layer is provided) preferably contains 13 to 20% by weight, more preferably 15 to 20% by weight, of a white pigment dispersed and mixed therein. As the white pigment, an inorganic and / or organic white pigment can be used, and preferably an inorganic white pigment, such as a sulfate of an alkaline earth metal such as barium sulfate, calcium carbonate, or the like. Alkaline earth metal carbonates, finely divided silica, synthetic silicate silica, calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, clay and the like.

Of 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 colored pigment for improving whiteness, and a fluorescent whitening agent.

Further, it is preferable to form a hydrophilic colloid layer containing a white pigment on the reflective support, because the 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 0601-1976
Has an average surface roughness SRa of 0.30 to 3.0 μm
It is preferred to use a white support having a m.

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. An agent can be contained. The layers to which the matting agent is added include a silver halide emulsion layer, a protective film, an intermediate layer,
There is an undercoat layer and the like, which may be added to a plurality of layers, and is preferably 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 material. 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 fine particle powder to the protective layer. Japanese Patent Application Laid-Open No. 6-95283 describes a fine particle powder (matting agent) and a method of using the same.
It is preferable to use the technique described in page 4, left column, line 42 to page 4, right column, line 33.

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

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.

In the present invention, scanning exposure is performed on a color photosensitive material based on halftone image information composed of color-separated yellow, magenta, cyan, and black image information.
In the step of producing a color proof, at least a part of the halftone dot image information is such that the number of halftone dots per inch ² is 200 × 10 ³ or more when the halftone dot area ratio is 40%. It has a particularly remarkable effect when using the converted one. Preferably 300 × 10
³ or more, more preferably 400 × 10 ³ or more, especially 400
× 10 ^{3 to} 2000 × 10 ³ is preferred. The number of the halftone dots can be measured by counting halftone images captured by an optical microscope or the like.

The infrared-sensitive silver halide emulsion layer in the present 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 used in the present invention is not particularly limited, but may be tricarbocyanine and / or 4-carboxynin.
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].

[0089]

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 carbon atom).
-18, 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 as a substituent) (C 8 or less, methoxycarbonyl,
Ethoxycarbonyl, benzyloxycarbonyl, etc.),
Alkoxy group (C7 or less, methoxy, ethoxy, propoxy, butoxy, benzyloxy, etc.), aryloxy group (phenoxy, p-tolyloxy, etc.), acyloxy group (C3 or less, acetyloxy, propionyloxy, etc.) An acyl group (having 8 or less 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, α
-Naphthyl or the like) or the like (an alkyl moiety having 6 or less carbon atoms). However, this substituent 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 to complete 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 for completing 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-methylbezothiazole, 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; pyridine nucleus (pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine and the like).

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

[0098] X ₁ ^- represents an acid anion, p is represents 1 or 2.

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

[0100]

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 the same group 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.

The light-sensitive material of the present invention may have a hydrophilic colloid layer containing fine powder and having a dry film thickness of 3 to 15 μm on the surface of the reflection support opposite to the side having the silver halide emulsion layer. preferable. This fine particle powder is often referred to in the art as a matting agent, and hence is hereinafter referred to as a matting agent unless otherwise specified.

Examples of the matting agent usable 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, and 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 preferably 1 to 10 μm, more preferably 3 to 10 μm.
It is.

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 the 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.

The amount of the matting agent to be applied was 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.

As the silver halide emulsion used for 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 performed by dipping 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 depending on the photosensitive material, the development processing conditions, the type of the light source used, and the like so that the best positive image is finally obtained. 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 a technique for fogging agents 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 Internal latent image preferably used in the present invention Silver halide emulsions include those prepared by various methods. For example, a conversion-type silver halide emulsion described in U.S. Pat. No. 2,592,250, U.S. Pat. No. 3,206,316.
Nos. 3,317,322 and 3,367,778
No. 3,271,157 having internally chemically sensitized silver halide grains.
No. 3,447,927, emulsions having silver halide grains containing polyvalent metal ions, and silver halide containing a dopant described in U.S. Pat. No. 3,761,276. Silver halide emulsions in which the grain surfaces of the grains are weakly chemically sensitized, JP-A-50-8524, JP-A-50-8524;
And silver halide emulsions having a laminated structure described in JP-A Nos. 38525 / 535-2408 and others, and JP-A Nos. 52-156614 and 55-1275.
No. 49, for example.

The silver halide grains used in the present invention may be in the form of a cube, an octahedron, a tetrahedron composed of a mixture of (100) and (111) planes, a shape having a (110) plane, a sphere, a flat plate, or the like. Any one may be used. Average particle size is 0.0
Those having a size of 5 to 3 μm can be 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, a monodisperse silver halide emulsion is defined as a silver halide emulsion having a grain size within ± 20% of the center of the average grain size rm is 60% or more of the total silver halide grain weight. 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 by, for example, photographing the particle with an electron microscope at a magnification of 10,000 to 50,000 times and actually measuring the particle diameter or the area at the time of projection on the print (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 mixing a water-soluble silver salt solution and a water-soluble halide solution in 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 light-sensitive material of the present invention is within a wide range in consideration of the required properties, especially various characteristics such as sensitivity, sensitivity balance, color separation sharpness, and graininess. Can be determined from

In one preferred embodiment, the silver halide has a particle size of 0.1 to 0.6 μm for the red-sensitive layer emulsion.
The green-sensitive layer emulsion is O.D. 15-0.8 μm, blue-sensitive emulsion is 0.1 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 general formula [XI] described in JP-A-6-95283, page 19, right column, lines 20 to 49, and particularly preferably described in JP-A-6-95283, page 20, left column, lines 5 to page 20, right column, line 2. Of the general formula [XI
I] to [XIV]. In addition, as a specific example of the compound,
For example, compounds (1) to (39) described on pages 11 to 15 of JP-A-64-73338 can be exemplified.

[0126] The above mercapto compound may vary appropriately depending on the kind and layer the addition of compounds to be used as an additive amount, in general, when added to a silver halide emulsion layer, per mol of silver halide 10 ^{- It is in} the range of ⁸ to 10 ^-2 mol, more preferably 10 ^-6 to 10 ^-3 mol.

The yellow image-forming, magenta image-forming and cyan image-forming silver halide emulsion layers of the color light-sensitive material of the present invention each contain a silver halide emulsion having a spectral sensitivity wavelength region different from each other. In at least one of the yellow, magenta, and cyan image-forming silver halide emulsion layers, an emulsion having a spectral sensitivity wavelength region different from each other contained in the yellow, magenta, and cyan image-forming silver halide emulsion layers. Both of them preferably contain a silver halide emulsion having a spectral sensitivity having a common portion.

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 preferable because the colorant has good spectral absorption characteristics. . 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 include compounds M-1 to M-61 and EP 0235913 36 to 9 described in EP-A-0273712, pp. 6-21.
Among the compounds 1 to 223 described on page 2, there are compounds other than the specific examples described above.

The above magenta couplers can be used in combination with other types of magenta couplers, and are 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 λ _max of the spectral absorption of the magenta image formed in the light-sensitive material according to the present invention is 530 to 560 nm.
Λ _L0.2 is preferably ₅₈₀ to 635.
It is preferably nm.

Here, λ _L0.2 of the spectral absorption of the magenta image
And λ _max are quantities measured in the following manner.

(Measurement Method of λ _L0.2 and λ _max ) When a positive emulsion is used as a light-sensitive material, a color light-sensitive material is uniformly exposed to a minimum amount of red light capable of obtaining a minimum density of a cyan image. After uniformly exposing with a minimum amount of blue light to obtain the minimum density of a yellow image, irradiating white light through an ND filter, and developing, an integrating sphere was attached to a spectrophotometer, and magnesium oxide was used. A magenta image is prepared by adjusting the density of the ND filter so that the maximum value of absorbance when measuring spectral absorption at 500 to 700 nm with a zero correction using a standard white plate of No. 1 is 1.0. When a negative type emulsion is used for a magenta coupler or a photosensitive material, ND
The density of the ND filter is adjusted so that when the magenta image is formed by applying green light through the filter and developing the magenta image, the same maximum absorbance as that of the positive is obtained. λ _L0.2 refers to a wavelength at which this magenta image has a longer absorbance than the wavelength at which the maximum absorbance shows 1.0 and the absorbance shows 0.2 on the spectral absorbance curve.

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. This preferred yellow coupler is represented by the general formula [Y-I] described in JP-A-6-95283, page 12, right column.
a). Particularly preferred among the couplers represented by the general formula [Y-1] are, when combined with the magenta coupler represented by the general formula [M-1], the p-value of the coupler represented by the combination [M-1].
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-
To (Y-1) to (Y-58) described on pages 17 to 17 can be preferably used, but are not of course limited thereto.

As the cyan coupler contained in the cyan image forming layer, known phenol, naphthol 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, a bi-equivalent naphthol coupler having an oxygen atom introduced as a leaving group, and the like are typical examples. It is. Of these, preferred compounds are those represented by the general formula [C] described in JP-A-6-95283, page 13.
-I] and [C-II].

The cyan coupler is usually used in the silver halide emulsion layer in an amount of 1 × 10 ⁻³ to 1 × 10 ⁻³ per mol of silver halide.
It can be used in an amount of 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ 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, the 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.

The λ _L0.2 of the spectral absorption of the yellow image is
This is a value defined by the contents described in JP-A-6-95283, page 21, right column, lines 1 to 24, and is a spectral absorption characteristic representing the magnitude of unnecessary absorption on the long wavelength side of a yellow dye image.

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.

In order to adjust the spectral absorption characteristics of the magenta, cyan and yellow images, it is preferable to add a compound having a color tone adjusting effect. As the compound for this, compounds represented by the general formulas [HBS-I] and [HBS-II] described in JP-A-6-95283, page 22, are preferred, and more preferably the compounds represented by the general formula described on page 22 of the same. It is a compound represented by [HBS-II].

The yellow, magenta and cyan image forming layers in 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.

An anti-fading agent can be used in combination with each of the magenta, cyan, and yellow couplers 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 the formula:
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 the oil-in-water emulsion dispersion method is used to add the coupler or other organic compound used in the light-sensitive material, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher, if necessary. To dissolve in combination with a low boiling point and / or water-soluble organic solvent, and emulsify and disperse 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 the high boiling point organic solvent 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 general 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.

As a compound preferable as a surfactant used for dispersing a photographic additive used in a light-sensitive material or adjusting a surface tension at the time of coating, a compound 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 the 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 those represented by the general formula ii described in JP-A-4-133,056, and the compounds II-1 to II-14 described on pages 13 to 14 of the publication.
Compounds 1 described on pages II-14 and 17 are mentioned.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog and 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.

In the light-sensitive material, gelatin is preferably used as a binder. 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.

Jelly strength of gelatin (based on the Paggy method)
Is preferably at least 250, particularly preferably 27
0 or more.

The ratio of gelatin to total coated gelatin is not particularly limited, but it is preferable to use a large ratio, and specifically, to use a ratio of at least 20 to 100% to obtain a favorable effect.

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 vinylsulfone 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.

In the light-sensitive material of the present invention, the reflection density of the raw sample at the maximum wavelength of the spectral sensitivity of the cyan image-forming silver halide emulsion layer is preferably 0.7 or more. The above-mentioned light-sensitive material can be obtained by including a dye having an absorption at the above-mentioned wavelength and a coloring material such as black colloidal silver in any of the photographic constituent layers.

The color light-sensitive material of the present invention may contain a water-soluble dye in any silver halide emulsion layer and / or other hydrophilic colloid photographic constituent layers. A dye having at least one of a carboxyl group, a sulfonamide group and a sulfamoyl group may be contained as a solid fine particle dispersion in an arbitrary silver halide emulsion layer and / or another hydrophilic colloid photographic component layer. it can. Examples of the dye having at least one of a carboxyl group, a sulfamoyl group and a sulfonamide group include JP-A-6-952.
No. 83, pp. 14-16, compounds represented by formulas [I]-[IX].

Of the above general formulas [I] to [IX], [I] to [I]
Specific examples of the dye represented by [VIII] include, for example, I-1 to VIII described in JP-A-4-18545, pages 13 to 35.
-7, but is not limited thereto.

The layer containing the dye or colloidal silver is not particularly limited, but is preferably contained in a non-photosensitive hydrophilic colloid layer between the support and the emulsion layer closest to the support.

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 foot tone 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 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. Further, a quinone derivative having 5 or more carbon atoms can be used in combination with the compound of [AO-II]. However, in any of these cases, the amount used is 0.001 to 0.50 g as a whole.
/ M ² .

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

When the light-sensitive material of the present invention is developed 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 solution. The developing process can be continuously performed while replenishing the fixing solution, the replenishing stabilizing solution and the like.

In the present invention, the replenishment amount of the developer is
Material 1m^TwoMore effective if less than 700ml per
The effects of the present invention can be exhibited. More preferably 500 ml
It is as follows. The other processing solutions are the same as the developing solutions.
Yes, replenishment amount is 1m of photosensitive material ^Two700ml or less per
More preferably, the effect of the present invention is less than 500 ml.
Can be exhibited more effectively.

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. Acids and derivatives thereof, reductones, phenylenediamines and the like, or mixtures thereof are included. 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 previously contained in an emulsion and act on silver halide during immersion in a high pH aqueous solution.

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

In the photographic 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 photosensitive material of the present invention, it is preferable to use an automatic developing machine of a light source section scanning exposure system. Specific examples of particularly preferable apparatuses 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, and is particularly preferably applied to a light-sensitive material having a reflective support for forming an image for direct viewing. For example, a light-sensitive material for color proof can be used.

[0173]

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

Example 1 (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) at the same time by a control double jet method, and a particle size of 0.3
A 0 μm cubic silver chlorobromide core emulsion was obtained. At that time, the pH and pAg were controlled so that a cube was obtained as the particle shape.

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. The 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 simultaneously added by a 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.

To the obtained core emulsion, an aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (KBr: NaCl = 40: 60 in a molar ratio) were simultaneously added by a control double jet method. 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 emulsion EM-P2. The width of the particle size distribution of EM-P2 was 8%.

(Preparation of Blue-Sensitive Silver Halide Emulsion) Emulsion E
After sensitizing dye BS-1 was added to M-P1 for optimal color sensitization, stabilizer T-1 was added in an amount of 600 mg per mol of silver to prepare blue-sensitive emulsion Em-B1.

(Preparation of Green-Sensitive Silver Halide Emulsion) Emulsion E
A green-sensitive emulsion Em was prepared in the same manner as the blue-sensitive emulsion Em-B1, except that the sensitizing dye GS-1 was added to M-P2 to optimize the color sensitization.
-G1 was produced.

(Preparation of Red-Sensitive Silver Halide Emulsion) Emulsion E
A red-sensitive emulsion Em-R1 was prepared in the same manner as the blue-sensitive emulsion Em-B1, except that sensitizing dyes RS-1 and RS-2 were added to M-P2 for optimal color sensitization.

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

[0184]

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[0185] The high density polyethylene on one side was laminated a polyethylene melt containing dispersed at a content of 15 wt% of anatase type titanium oxide on the other side, 1 m ²
Weight per unit 115g, 125g, 135g, 150
g on a polyethylene-laminated paper reflective support.
Using each emulsion of m-B1, Em-G1, and Em-R1, each layer having the following constitution was coated on the side of the polyethylene layer containing titanium oxide, and further, 6.00 g / g of gelatin was formed on the back side.
Multilayer color photosensitive material samples 1-1 to 1-9 coated with m ² and 0.65 g / m ^{2 of} a silica matting agent were prepared.

H-1 and H-2 were added as hardening agents. Surfactant SU is used as a coating aid and a dispersing aid.
-1, SU-2 and SU-3 were added.

SU-1: di (2-ethylhexyl) sulfosuccinate sodium sodium SU-2: di (2,2,3,3,4,4, sulfosuccinate)
5,5-octafluoropentyl) ester sodium SU-3: sodium tri-i-propylnaphthalenesulfonate H-1: 2,4-dichloro-6-hydroxy-s-triazine sodium H-2: tetrakis (vinylsulfonyl) Methyl) methane The amount of each additive is shown by the coating amount (g / m ² ), and the amount of the silver halide emulsion added is shown in terms of silver.

Ninth layer (ultraviolet absorbing layer) Gelatin 1.60 Ultraviolet absorbing agent (UV-1) 0.070 Ultraviolet absorbing agent (UV-2) 0.025 Ultraviolet absorbing agent (UV-3) 0.120 Silica mat Agent 0.01 8th layer (blue-sensitive layer) gelatin 1.10 blue-sensitive emulsion (Em-B1) 0.34 yellow coupler (Y-1) 0.19 yellow coupler (Y-2) 0.19 inhibitor (T-1, T-2, T-3; molar ratio 1: 1: 1) 0.004 Stain inhibitor (HQ-1) 0.004 High boiling point organic solvent (SO-1) 0.30 7th layer (Intermediate layer) Gelatin 0.94 Stain inhibitor (HQ-2, HQ-3; equivalent weight) 0.02 Exemplary compound (SO-2) 0.05 Anti-irradiation dye (AI-3) Table 2 Sixth layer (Yellow colloid silver layer) Gelatin 0.45 Yellow colloid silver 0.05 Stain inhibitor (HQ-1) 0.03 High boiling organic solvent (SO-2) 008 Polyvinyl pyrrolidone 0.04 Fifth layer (intermediate layer) Gelatin 0.45 Stain inhibitor (HQ-2) ) 0.014 Antistain agent (HQ-3) 0.014 High boiling organic solvent (SO-2) 0.006 Fourth layer (green photosensitive layer) Gelatin 1.25 Green sensitive silver chlorobromide emulsion (Em- G1) 0.37 Magenta coupler (M-1) 0.25 Stain 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 Third layer (intermediate layer) Gelatin 0.80 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.01 Irradiation prevention Dye (AI-1) Table 2 Second layer (red-sensitive layer) Gelatin 0.90 Red-sensitive silver chlorobromide emulsion (Em-R1) 0.35 Cyan coupler (C-1) 0.35 Stain inhibitor (HQ-1) 0.02 Suppression Agent (T-1, T-2, T-3; molar ratio 1: 1: 1) 0.002 High boiling organic solvent (SO-1) 0.18 First layer (white pigment-containing layer) Gelatin 1.20 Liquid paraffin 0.55 Anti-irradiation dye (AI-2) Table 2 Titanium oxide 0.50 Support Polyethylene laminated paper containing a trace amount of colorant 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-hexyloxycarbonyl) butyl} hydroquinone HQ-3: 2.5 − A mixture of -sec-dodecylhydroquinone, 2,5-di-sec-tetradecylhydroquinone, and 2-sec-dodecyl-5-sec-tetradecylhydroquinone at a weight ratio of 1: 1: 2 T-2: 1- (3- (Acetamidophenyl) -5-mercaptotetrazole T-3: N-benzyladenine

[0189]

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[0190]

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[0191]

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Table 1 shows the color photographic material samples 1-1 to 1-9 obtained as described above. The amounts of the irradiation dyes of the first, third and seventh layers were adjusted so as to be the values shown in Table 1 when measured at the laser wavelength for exposure.

Further, Sample 1-10 was prepared in which an antihalation colloid silver layer having the following constitution was provided between the paper support and the first layer.

<Antihalation Layer of Sample 1-10> Gelatin 1.0 g / m ² Gray colloidal silver 0.05 g / m ²

[0195]

[Table 1]

The obtained samples 1-1 to 1-10 were exposed to a blue laser beam corresponding to a yellow dot test chart image, a green laser beam corresponding to a magenta dot test chart image, and a cyan dot using the following laser scanning exposure apparatus. Exposure was performed by combining red laser exposure corresponding to the dot test chart image and blue, green, and red exposure corresponding to the black dot test chart image, and development was performed in the following processing step-1.

As the laser exposure light source, a blue laser
・ Cd laser (441.6nm), green laser is H
The semiconductor laser (AlGaInAs: about 670 nm) was used for the e-Ne laser (544 nm) and the red laser.

The photosensitive material was brought into close contact with the rotating drum by suction, and the number of rotations was set to 800 rotations / minute and 2,000 rotations / minute, and an image was recorded by main scanning and sub scanning. Exposure is on a white background,
The exposure was performed at an optimum exposure in consideration of the maximum density and the reproducibility of halftone dots of 3%.

With respect to each of the images obtained as described above, the image unevenness and the visual reproducibility of 2% dot reproduction were visually determined, and the gray color composed of 10% and 50% halftone dots of the three colors Y, M, and C, respectively. The color tone fluctuation of the image was evaluated and summarized in Table 2.

[0200] Incidentally, Y, image portions tone variation consisting M, C3-color halftone is to Y, M, and the concentration D _B50, D _G50, D _R50 to the image portion was densitometry at C each 50%, Y , M, C
When the density of the image portion at each 10% is measured as density D _B10 , D _G10 , and D _R10 , D _Y = {(D _B10 / D _G10 ) / (D _B50 / D _G50 ) −1} ² D _C = {( _DR10 / _DG10 ) / ( _DR50 / _DG50 ) -1} ² was evaluated. What is the difference between this value and the image tone (gray approximation) consisting of 50% halftone dots of Y, M and C each of the image tone (gray approximation) consisting of 10% halftone dots of Y, M and C? The smaller the value, the smaller the color tone variation in the halftone dot area, and is more preferable.

Processing Step-1 Temperature Time Immersion (Developer) 37 ° C. for 12 seconds Fog Exposure—12 seconds Development 37 ° C. 95 seconds Bleaching and Fixing 35 ° C. 45 seconds Stabilization Treatment 25-30 ° C. 90 seconds Drying 60-85 ° C. 40 second color developer composition Benzyl alcohol 15.0 ml Ceric sulfate 0.015 g Ethylene glycol 8.0 ml Potassium sulfite 2.5 g Potassium bromide 0.6 g Sodium chloride 0.2 g Potassium carbonate 25.0 g T-1 0.1 g Hydroxylamine sulfate 5.0 g sodium diethylenetriaminepentaacetate 2.0 g 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5 g fluorescent brightener (4,4′-diaminostilbene disulfonic acid) Derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 15.0 ml Add water to make the total volume 1000 ml and adjust to pH 10.15.

Composition of bleach-fixing solution Ferric ammonium diethylenetriaminepentaacetate 90.0 g Diethylenetriaminepentaacetic acid 3.0 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 1000 ml.

Stabilizing solution composition o-phenylphenol 0.3 g potassium sulfite (50% aqueous solution) 12.0 ml ethylene glycol 10.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.5 g bismuth chloride 0.2 g zinc sulfate 7-hydrate 0.7 g Ammonium hydroxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g Add water The total volume is made up to 1000 ml and the pH is adjusted to 7.5 with ammonium hydroxide or sulfuric acid.

Incidentally, the stabilization treatment was of a countercurrent type having a two-tank configuration.

Next, the formulation of the replenisher for performing the running process will be described.

Color developing replenisher benzyl alcohol 18.5 ml ceric sulfate 0.015 g ethylene glycol 10.0 ml potassium sulfite 2.5 g potassium bromide 0.3 g sodium chloride 0.2 g potassium carbonate 25.0 g T-1 1 g hydroxylamine sulfate 5.0 g sodium diethylenetriaminepentaacetate 2.0 g 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 5.4 g fluorescent brightener (4,4′-diaminostilbene disulfonic acid) Derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Water is added to bring the total volume to 1 liter, and the pH is adjusted to 10.35.

Bleach-fix solution replenisher Same as the above-mentioned bleach-fix solution.

Stabilizing solution replenisher Same as the above stabilizing solution.

[0209] The replenishment amounts are the development replenisher, the bleach-fixer,
Stabilizing solution together, and the photosensitive material 1 m ² per 320 ml.

A color proof consisting of halftone images was prepared using Konsensus 570 manufactured by Konica Corporation.
Processing was continued until the total amount of the replenished color developing replenisher was three times the amount of the color developing tank.

Incidentally, the ranking of the evaluation by visual judgment is as follows.
1: markedly inferior, 2: inferior, 3: good.

[0212]

[Table 2]

From the results shown in Table 2, the sample of the present invention has a small image unevenness, is excellent in the reproducibility of 2% of each of Y, M and C, and is formed from Y, M and C halftone dots. It can be seen that the gray tone is small and good even if the dot area varies.

Example 2 (Preparation of infrared-sensitive silver halide emulsion) Emulsion EM-P2
Infrared-sensitive emulsion Em-IFR1 was prepared in the same manner as in the blue-sensitive emulsion Em-B1, except that the sensitizing dyes IRS-1 and IRS-2 were added to the emulsion to optimize the color sensitization.

[0215] The high density polyethylene on one side was laminated a polyethylene melt containing dispersed at a content of 15 wt% of anatase type titanium oxide on the other side, 1 m ²
Each of the emulsions Em-G1 and Em-R1 and Em-G1 were placed on a paper pulp reflective support having a weight of
Using IFR1, each layer having the following constitution was applied on the side of the polyethylene layer containing titanium oxide, and further on the back side, gelatin 6.00 g / m ² , silica matting agent 0.6
Multilayer color photographic material sample 2-1 coated with 5 g / m ²
2-10 were produced. In addition, H-1 and H-2 are used as hardeners.
Was added. Surfactants SU-1, SU-2 and SU-3 were added as coating aids and dispersing aids. Table 3 shows the PY value of the base paper used and the weight per 1 m ² .

[0216]

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[0219]

[Table 3]

8th layer (ultraviolet absorbing layer) (g / m ² ) Gelatin 1.60 Ultraviolet absorbing agent (UV-1) 0.070 Ultraviolet absorbing agent (UV-2) 0.025 Ultraviolet absorbing agent (UV-3) 0.120 Silica matting agent 0.01 Seventh layer (green-sensitive layer) Gelatin 1.25 Green-sensitive silver chlorobromide emulsion (Em-G1) 0.37 Magenta coupler (M-1) 0.25 Stain prevention Agent (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 6th layer (Intermediate layer) Gelatin 0.80 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.01 Anti-irradiation dye (AI-1) 0.04 Fifth layer (red-sensitive layer) ) Gelatin 0.90 Red-sensitive silver chlorobromide emulsion (Em-R1) 0.35 cyan coupler (C-1) 0.35 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-1) 0.18 Fourth layer (intermediate layer) Gelatin 0.80 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.01 Anti-irradiation dye (AI) -2) 0.05 Third layer (infrared-sensitive layer) Gelatin 1.10 Infrared-sensitive emulsion (Em-IFR1) 0.34 Yellow coupler (Y-1) 0.19 Inhibitor (T-1, T-2, T-3; molar ratio 1: 1: 1) 0.004 Stain inhibitor (HQ-1) 0.004 High boiling organic solvent (SO-1) 0.30 Second layer (intermediate layer) Gelatin 1.20 Anti-irradiation dye (AI-4) 0.05 First layer (gray Lloyd silver layer) polyethylene-laminated paper containing a colorant gelatin 2.20 gray colloidal silver 0.12 support trace

[0219]

Embedded image

The obtained samples 2-1 to 2-10 were exposed to an infrared laser corresponding to a yellow dot test chart image using a laser scanning exposure apparatus described below, and a green color corresponding to a magenta dot test chart image. Laser exposure, red laser exposure corresponding to the cyan halftone test chart image, and green, red, and infrared exposure corresponding to the black halftone test chart image were performed. The exposed sample was processed in the same manner as in the processing step-1 to obtain an image.

As the laser exposure light source, the green laser is He.
Ne laser (544 nm), red laser is a semiconductor laser (AlGaInAs: about 670 nm), and 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 the rotation was performed at 2000 revolutions / minute, and an image was recorded by main scanning and sub scanning. The exposure was set at an optimal exposure in consideration of white background, maximum density, and halftone dot reproducibility of 3%.

With respect to the obtained image, the image unevenness was visually observed, the visual reproducibility of 2% halftone dot was visually determined, and the color tone fluctuation of a gray image composed of 10% and 50% halftone dots of each of the three colors YMC was evaluated. Summarized in 4. The content of the evaluation was performed according to Example 1.

[0223]

[Table 4]

From the results in Table 4, it can be seen that the sample of the present invention has a small image unevenness, is excellent in the reproducibility of 2% of each of Y, M and C, and has a gray color formed from the Y, M and C halftone dots. It can be seen that the color tone is small and good even if the dot area fluctuates.

Example 3 Each layer having the following constitution was coated on a support obtained by laminating polyethylene on one side of a paper support and polyethylene containing polyethylene containing titanium oxide on the other side of the first layer. Thus, a multilayer color photosensitive material was produced. The weight is 1m
A sample manufactured using 115 g of support per ² was designated as Sample 3-1 and a sample manufactured using 135 g of support was designated as Sample 3-2.

Eighth layer (ultraviolet absorbing layer) (g / m ² ) Gelatin 1.60 Ultraviolet absorbing agent (UV-1) 0.070 Ultraviolet absorbing agent (UV-2) 0.025 Ultraviolet absorbing agent (UV-3) ) 0.120 Silica matting agent 0.01 Seventh layer (green-sensitive layer) Gelatin 1.25 Green-sensitive silver chlorobromide emulsion (Em-G2) 0.37 Magenta coupler (M-1) 0.25 Yellow coupler (Y-3) 0.06 Stain 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 Sixth layer (intermediate layer) Gelatin 0.80 Stain inhibitor (HQ-2) 0.03 Stain inhibitor (HQ-3) 0.01 Anti-irradiation dye (AI-1) 0 .02 5th layer (red-sensitive layer) Gelatin 0.9 Red-sensitive silver chlorobromide emulsion (Em-R2) 0.35 Cyan coupler (C-1) 0.35 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-1) 0.18 fourth layer (intermediate layer) gelatin 0.80 stain inhibitor (HQ-2) 0.03 stain inhibitor ( HQ-3) 0.01 Anti-irradiation dye (AI-2) 0.02 Third layer (infrared-sensitive layer) Gelatin 1.10 Infrared-sensitive emulsion (Em-IFR2) 0.34 Yellow coupler (Y -1) 0.19 Inhibitor (T-1, T-2, T-3; molar ratio 1: 1: 1) 0.004 Stain inhibitor (HQ-1) 0.004 High boiling organic solvent (SO- 1) 0.30 Second layer (middle layer) Gelatin 1.20 Anti-irradiation dye (AI-4) 0.02 First layer (gray colloidal silver layer) Gelatin 2.20 Gray colloidal silver 0.10 Support Polyethylene laminated paper containing a trace amount of colorant (Preparation of green-sensitive silver halide emulsion) 40 2 kept at ℃
% Solution of gelatin, the following (Solution A) and (Solution B) were added simultaneously while controlling pAg = 7.3 and pH = 3.0, and the following (Solution C) and (Solution D) were further added. pAg =
It was added simultaneously while controlling to 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.

(Solution A) 3.42 g of sodium chloride 0.03 g of potassium bromide 200 ml with addition of water (Solution B) 10 g of silver nitrate 200 ml with addition of water (Solution C) K ₂ IrCl ₆ 2 × 10 ⁻⁸ mol / mol Ag Sodium chloride 102.7 g K ₄ Fe (CN) ₆ 1 × 10 ⁻⁵ mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml After completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to obtain an average particle size of 0.43 μm.
m, coefficient of variation of particle size distribution 0.08, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMN-1 was obtained.

The emulsion EMN-1 obtained above was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to obtain a green sensitive emulsion EM-G2.

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol AgX Sensitizing dye GS- 14 × 10 ⁻⁴ mol AgX (Preparation of red-sensitive silver halide) EMN-1 except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. In the same manner as in the above, a monodispersed cubic emulsion EMN-2 having an average particle size of 0.5 μm, a variation coefficient of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds to obtain a red-sensitive emulsion EM
-R2 was obtained.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol AgX sensitizing dye RS- 12 × 10 ⁻⁴ mol AgX sensitizing dye RS-2 2 × 10 ⁻⁴ mol AgX (Preparation of infrared-sensitive silver halide) Optimum at 60 ° C. with respect to the above EMP-2 using the following compound Chemical sensitization was performed to obtain an infrared-sensitive emulsion EM-IFR2.

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol AgX sensitizing dye IRS- 11 × 10 ⁻⁴ mol AgX sensitizing dye IRS-2 1 × 10 ⁻⁴ mol AgX STAB-1: 1- (3-acetamidophenyl) -5
-Mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole The obtained samples 3-1 and 3-2 were subjected to laser scanning described below. Exposure with infrared laser corresponding to yellow dot test chart image, green laser exposure corresponding to magenta dot test chart image, red laser exposure corresponding to cyan dot test chart image, black dot test chart with exposure equipment Green, red, and infrared exposures corresponding to the images were prepared.

As the laser exposure light source, the green laser is He.
Ne laser (544 nm), red laser is a semiconductor laser (AlGaInAs: about 670 nm), and 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 the rotation was performed at 2000 revolutions / minute, and an image was recorded by main scanning and sub-scanning. The laser beam diameter was changed to 20 μm, 23 μm, 26 μm, and 29 μm, respectively. The exposure amount was set to an optimum exposure amount in consideration of white background, maximum density, and halftone dot reproducibility of 3% under each condition.

Each sample exposed was subjected to the following processing step-2.
And an image was obtained.

Processing Step-2 Processing Step Temperature Time Replenishment Color Development 37.0 ± 0.3 ° C. 120 seconds 300 ml Bleaching and Fixing 35.0 ± 0.5 ° C. 45 seconds 300 ml Stabilization 30-35 ° C. 90 seconds 600 ml Drying 50 to 80 ° C for 40 seconds The composition of the developing solution is shown below.

Color developing tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.2 g 0.2 g potassium chloride 3.5 g potassium sulfite 0.25 g 0.5 g N- Ethyl-N- (β-hydroxyethyl) -4-aminoaniline sulfate 3.0 g 4.0 g N, N-diethylhydroxyamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g sodium diethylenetriaminepentaacetate 2. 0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the total volume 1 liter, and the tank solution was pH = 1.
At 0.10, the replenisher is adjusted to pH = 10.42.

Bleach-fixing solution and replenisher solution Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 2.0 g ammonium sulfite (40% aqueous solution) 27.5 ml Water was added to make up to 1 liter, and the pH was adjusted to 6.5 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinowar SFP) 2.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8 g Ethylenediaminetetraacetic acid / sodium 1.5 g Potassium sulfite 5.0 g The pH is adjusted to 8.0 with sulfuric acid or aqueous ammonia.

With respect to the image obtained as described above,
Visually determine the image unevenness and 2% halftone dot reproducibility,
The color tone fluctuation of a gray image in which black dots consisted of 10% and 50%, respectively, was evaluated and summarized in Table 5.

[0240]

[Table 5]

From the results shown in Table 5, the sample of the present invention has a small image unevenness, is excellent in the reproducibility of 2% of each of Y, M and C, and is formed from Y, M and C halftone dots. It can be seen that the gray tone is small and good even if the dot area varies.

Example 4 (Preparation of Blue-Sensitive Silver Halide) Same as EMN-1 except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed. To have an average particle size of 0.85 μm,
A monodisperse cubic emulsion EMN-3 having a coefficient of variation of 0.07 and a silver chloride content of 99.5% was obtained.

The following compound was used for EMN-3 to give 6
Optimum chemical sensitization at 0 ° C. and red-sensitive emulsion EM-B2
I got

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-3 8 × 10 ⁻⁴ mol AgX Sensitizing dye BS-1 2 × 10 ⁻⁴ mol AgX Example 3 Photosensitive material sample 4-1 (support weight: 110 g) and sample 4-2 in the same manner as samples 3-1 and 3-2.
(Support weight: 130 g). However, sample 3
The second layer and the third layer of Nos. -1 and 3-2 were manufactured by substituting the following configuration.

Third layer (blue-sensitive layer) (g / m ² ) Gelatin 1.10 Blue-sensitive emulsion (Em-B2) 0.34 Yellow coupler (Y-1) 0.19 Inhibitor (T-1, T-2, T-3; molar ratio 1: 1: 1) 0.004 Stain inhibitor (HQ-1) 0.004 High boiling organic solvent (SO-1) 0.30 Second layer (intermediate layer) Gelatin 1.20 Anti-irradiation dye (AI-3) 0.02 The obtained samples 4-1 and 4-2 were exposed to a blue laser corresponding to a yellow dot test chart image using a laser scanning exposure apparatus described below. , Green laser exposure corresponding to magenta halftone test chart image, red laser exposure corresponding to cyan halftone test chart image, green laser light, red laser light, blue laser corresponding to black halftone test chart image It was carried out to prepare a light.

The exposed sample was processed in the same manner as in the processing step-2 to obtain an image. As the laser exposure light source, the blue laser is a Be / Cd laser (441.6 nm),
A green laser is a He / Ne laser (544 nm), and a red laser is a semiconductor laser (AlGaInAs: about 6).
70 nm). The photosensitive material was brought into close contact with the rotating drum by suction, and the rotation was performed at 2000 revolutions / minute, and an image was recorded by main scanning and sub-scanning. Exposure amount is white background, maximum density, 3
%, Taking into account the halftone dot reproducibility.

The dot image information used for this exposure is 1
Exposure was performed based on image information created by the AM screen method at 300 lines per inch. Exposure was also performed based on image information created by the so-called FM screen method, in which the size of one halftone dot was approximately 20 μm. When printed properly using each document, sharpness appears to be higher when using a 20 μm FM screen document than when using the 300-line AM screen document.

It should be noted that 1i when the dot area ratio is 40%
The number of halftone elements per nch ² was 90 × 10 ³ in the former document information, and 645 × 10 ³ in the latter.

With respect to the image obtained as described above,
Visually determine the image unevenness and 2% halftone dot reproducibility,
The color tone fluctuation of a gray image composed of 10% and 50% halftone dots of each of the three colors Y, M, and C was evaluated, and is shown in Table 6.

[0250]

[Table 6]

From the results in Table 6, it can be seen that the sample of the present invention has a small image unevenness,
It can be seen that 2% is excellent in dot reproducibility, and that the gray tone formed from the Y, M, and C dots is small and good even if the dot area varies.

[0252]

According to the present invention, a silver halide photographic material can be scanned and exposed to obtain a color image with high productivity, no exposure unevenness, and excellent stability. This makes it possible to stably produce a color proof having a halftone image with no exposure unevenness by scanning exposure from halftone image information obtained by color separation and halftone image conversion in the color plate making and printing process.

Claims (4)

[Claims] 1. A color image forming method in which a silver halide photographic light-sensitive material is wound around a rotating drum and an image is exposed by a laser while rotating the silver halide photographic light-sensitive material, wherein the silver halide photographic light-sensitive material weighs 130 g per 1 m ^2. A color image forming method comprising the following reflective support, and wherein the reflection density of the raw sample at the wavelength of the laser is 0.8 or more. 2. The power spectrum for each spatial frequency obtained by continuously measuring the thickness of the reflective support and analyzing the fluctuation of the thickness by a fast Fourier transform is 1 to 12.5.
2. The color image forming method according to claim 1, wherein the square root (PY value) of the integral in the frequency section of mm is 2.9 [mu] m or less. 3. The silver halide photographic material has at least one infrared-sensitive silver halide emulsion layer, and at least one of the laser exposures is an infrared laser having a beam diameter of 25 μm or less. Claim 1 or 2
The color image forming method as described above. 4. Based on halftone image information composed of color-separated yellow, magenta, cyan and black image information,
In a method for producing a color proof for exposing a silver halide color photographic light-sensitive material, the exposure is to wind a silver halide photographic light-sensitive material around a rotating drum, and perform image exposure with a laser while rotating the material, and When at least a part of the halftone image information has a halftone area ratio of 40%, the number of halftone elements per inch ² is 200 ×
A color having a halftone image converted to 10 ³ or more, and wherein the silver halide photographic light-sensitive material has a reflective support having a weight per 1 m ² of 130 g or less. How to make proofs.