JP3362287B2 - Method for preparing silver halide color photographic light-sensitive material and color proof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention is suitable for producing a proof color image (color proof) from a plurality of black and white halftone images obtained by color separation and halftone image conversion in a color plate making / printing process. The present invention relates to a silver halide color photographic light-sensitive material and a method for producing a color proof using the same.

[0002]

BACKGROUND OF THE INVENTION Conventionally, in the process of color plate making / printing, as a method for obtaining a color proof from a plurality of black and white halftone images obtained by color separation and halftone image conversion, a photopolymer or a diazo compound is used. An overlay method for forming a color image and a surprint method are known.

The overlay method is very simple and inexpensive to produce, and has the advantage that it can be used for proofreading by simply stacking four color (subtractive primary colors and black) film sheets. There is a drawback in that the overlapping produces gloss, which results in a texture different from that of the printed matter.

In the surprint method, a colored image is superposed on one support, and a method of obtaining a colored image by toner development utilizing the adhesiveness of a photopolymerizable material is disclosed in US Pat. No. 3,582,327. Nos. 3,607,264 and 3,620,726.

Further, a color proof is formed by transferring a photosensitive coloring sheet to a support, forming an image by exposure and development, laminating another coloring sheet thereon, and repeating the same process. The method of creating is 47
-27441 and JP-A-56-501217.

Further, a method is known in which a photosensitive colored sheet is used and each colored image obtained by exposing and developing the corresponding color separation film is transferred and formed on one support.
-Known as No. 97140. As the colorant of the toner and the color sheet for forming these images, the same coloring material as the printing ink can be used, and thus the color tone of the obtained color proof becomes similar to that of the printed matter.

However, these methods have the drawbacks that images must be superposed or transferred in the process of producing a color proof, which requires a long operation time and a high manufacturing cost.

As a solution to these drawbacks, a method for producing a color proof using a silver salt color photographic light-sensitive material having a white support is disclosed in JP-A-56-113139 and JP-A-5-113139.
6-104335, 62-280746, 62-280747, 62-280
No. 748, No. 62-280749, No. 62-280750, No. 62-280849, etc.

In this method, a color-separated black-and-white halftone image composed of a plurality of sheets converted from a color original into a halftone image which has been color-separated is sequentially printed on one sheet of color paper by a method such as contact printing to develop color. A color image formed by a dye formed from a coupler imagewise by color development is used as a proof image.

However, in this technique, a region having a small halftone dot area (small dot), a region having a medium halftone dot area (middle dot),
When attempting to reproduce neutral gray over a large dot area (large dot), a slight shift in the dot reproducibility of yellow, magenta, and cyan occurs, or if the exposure amount fluctuates, the gray It causes a problem in reproducibility. That is, if a slight change in image exposure or a change in processing conditions occurs, neutral gray reproduced from halftone dots of yellow, magenta, and cyan is difficult to be reproduced in gray.

In order to improve this defect, there is merely a problem in the reproducibility of halftone dots, and if the halftone dots are reproduced well, the problem is not always solved, and a cyan image, a magenta image,
It is also said that the color tone of the yellow image and the degree of approximation of the printing ink are related.

[0012]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to prepare a color proof from halftone image information obtained by color separation and halftone image conversion using a silver halide color photographic light-sensitive material. The present invention provides a photosensitive material for a color proof that stably obtains a color proof in which reproduction of neutral gray from small dots to large dots is improved, and a method of producing a color proof using the same.

[0013]

The above object of the present invention has been achieved by the following constitution.

(1) At least one yellow image-forming silver halide emulsion layer, at least one magenta image-forming silver halide emulsion layer, and at least one cyan image-forming silver halide emulsion on a support. In a silver halide color photographic light-sensitive material having a layer, at least one coupler represented by the general formula (I) [Chemical formula 1] or (II) [Chemical formula 2] in the cyan image forming silver halide emulsion layer. And a raw silver halide color photographic light-sensitive material having a raw reflection density of 0.8 or more as measured at at least one wavelength in the exposed area with respect to cyan image-forming silver halide.

(2) At least 1 on the image forming layer side of the support.
Layer having a light-reflecting layer containing a white pigment, and the amount of the white pigment contained in the light-reflecting layer is 20% by weight or more based on the amount of the binder in the light-reflecting layer. Photosensitive material.

(3) A yellow image forming layer, a magenta image forming layer, and a cyan image forming layer are formed on a support based on halftone dot image information composed of color-separated yellow image information, magenta image information, cyan image information and black image information. In the process of exposing and processing a silver halide color photographic light-sensitive material having an image forming layer to form a yellow image, a magenta image and a cyan image to form a color proof, the silver halide color photographic light-sensitive material is ) Or (2), a method for producing a color proof which is a silver halide color photographic light-sensitive material.

The present invention will be described in more detail below.

First, the cyan coupler represented by the general formula (I) or (II) will be described.

[0019]

[Chemical 3]

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

Z ₁ represents a group of non-metal atoms necessary for forming a nitrogen-containing 5-membered heterocycle which may be condensed with a benzene ring and the like, and X ₁ represents a reaction with a hydrogen atom or an oxidant of a color developing agent. Represents a substituent capable of splitting off.

[0022]

[Chemical 4]

In the formula, R ₁₁ and Y ₂ represent a hydrogen atom or a substituent, and X ₂ represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidation product of a color developing agent.

Z ₂ represents a group of non-metal atoms necessary for forming a nitrogen-containing 6-membered heterocycle by condensing with the pyrazole ring together with -N (Y ₂ )-, and the 6-membered ring has a substituent. Alternatively, it may be condensed with a benzene ring in addition to the pyrazole ring.

The electron-withdrawing group in the general formula (I) is
Substituent constant δp preferably defined by Hammett
Is +0.20 or more, specifically, sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, acyl, acyloxy, oxycarbonyl, carboxyl, cyano, nitro, halogenated alkoxy, halogenated aryl. Each group such as oxy, pyrrolyl, and tetrazolyl, a halogen atom and the like can be mentioned.

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

Examples of the sulfinyl group include groups such as alkylsulfinyl and arylsulfinyl.

Examples of the sulfonyloxy group include alkylsulfonyloxy and arylsulfonyloxy groups.

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

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

Examples of the carbamoyl group include N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl and N-alkyl-N-arylcarbamoyl groups.

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

The acyloxy group is preferably an alkylcarbonyloxy group.

Examples of the oxycarbonyl group include alkoxycarbonyl and aryloxycarbonyl groups.

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

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

Examples of the pyrrolyl group include groups such as 1-pyrrolyl.

Examples of the tetrazolyl group include groups such as 1-tetrazolyl.

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

Of the substituents represented by R ₁ or R ₂ , various substituents other than the electron-withdrawing group can be mentioned, and there is no particular limitation, but typical ones are alkyl,
Aryl, anilino, acylamino, sulfonamide,
Alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino , Alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto groups, spiro compound residues, bridged hydrocarbon compound residues and the like.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group is preferably a phenyl group.

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

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

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the above alkyl groups and aryl groups.

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

The cycloalkenyl group has 3 to 1 carbon atoms.
2, especially 5 to 7 are preferred.

Examples of the ureido group include an alkylureido group and an arylureido group: a sulfamoylamino group such as an alkylsulfamoylamino group and an arylsulfamoylamino group: a heterocyclic group having 5 to 7 members 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc .: Heterocycle An oxy group having 5- to 7-membered heterocycle is preferable, for example, 3 , 4,5,6-Tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5-oxy group, etc .: The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group. , 2-benzothiazolylthio group, 2,
4-diphenoxy-1,3,5-triazole-6-thio group etc .: trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group etc. as siloxy group: imide group as succinimide group, 3-heptadecyl amber Acid imide group,
Phthalimide group, glutarimide group, etc .: Spiro compound residue as spiro [3.3] heptan-1-yl, etc .: Bridged hydrocarbon compound residue as bicyclo [2.2.1] heptane-1-yl
And tricyclo [3.1.1 ^3.7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

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

In the general formula (I), examples of the group represented by X which can be removed by the reaction with the oxidation product of the color developing agent include, for example, a halogen atom (chlorine, bromine, fluorine, etc.), alkoxy, aryloxy, and heterocyclic oxy. , Acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio,
Acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0051]

[Chemical 5]

(R ₁ ′, R ₂ ′ and Z ₁ ′ are the above R ₁ and R ₂
And R ₁ have the same meanings, and R _g and R _h each represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group) and the like, but are preferably a hydrogen atom, a halogen atom, an alkoxy group, aryl. It is an oxy group, an alkylthio group, an arylthio group, or a nitrogen-containing heterocyclic group bonded at the N atom.

Examples of the nitrogen-containing heterocycle formed by Z include a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring and a tetrazole ring.

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

[0055]

[Chemical 6]

[0056] In the above general formula, in (a), at least one of the at least one of R ₁ and R _3, in (b), R ₁ and R _4, in (c), R _1, At least one of R ₅ and R ₆ , (d) at least one of R ₁ , R ₇ and R ₈ ; (e) at least one of R ₁ and R ₉ ; In f), R ₁ and in (g), R ₁ and R
_At least one of the _ten is an electron-withdrawing group.

X ₁ has the same meaning as X ₁ in formula (I), and n represents an integer of 0-4. Y ₁ represents a hydrogen atom or a substituent, and a preferable substituent represented by Y ₁ is, for example, a compound which leaves the cyan coupler before the compound of the present invention reacts with an oxidized product of a developing agent, and is, for example, Kaisho
61-228444, etc., a group capable of splitting off under alkaline conditions, or a reaction with an oxidized product of a developing agent, as described in JP-A-56-133734, etc. The substituent which turns off can be mentioned. Preferred Y ₁ is a hydrogen atom.

In the general formulas (a) to (g), R ₁
Among R ₁₀ to R ₁₀ , those that are not electron-withdrawing groups represent hydrogen atoms or substituents, and those of R ₁₀ that are not electron-withdrawing groups are not particularly limited as substituents. ), When R ₁ or R ₂ is other than an electron-withdrawing group, those mentioned as the substituent represented by R ₁ or R ₂ can be mentioned.

Cyan couplers having an electron-withdrawing group according to the present invention are disclosed in Japanese Patent Application Nos. 62-47323, 62-53417 and 62-6.
No. 2162, No. 62-53418, No. 62-62163, No. 62-48895,
It can be easily synthesized according to the method described in No. 62-99950.

The cyan coupler represented by the general formula (II) has a structure in which it is condensed with a pyrazole ring to form a hetero 6-membered ring, and the substituent represented by R ₁₁ is not particularly limited, and is a typical one. Specific examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio,
Examples thereof include arylthio, alkenyl, and cycloalkyl groups. In addition to these, a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy. , Heterocyclic oxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio,
Examples also include groups such as thioureido, carboxyl, hydroxyl, mercapto, nitro and sulfo, as well as spiro compound residues and bridged hydrocarbon compound residues.

The alkyl group represented by R ₁₁ preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group represented by R ₁₁ is preferably a phenyl group.

The acylamino group represented by R ₁₁ is
Examples thereof include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R ₁₁ include an alkylsulfonylamino group and an arylsulfonylamino group.

[0065] alkylthio group represented by R _11, the alkyl moiety in the arylthio group, the aryl moiety the R ₁₁
And an alkyl group and an aryl group represented by.

The alkenyl group represented by R ₁₁ has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 3 carbon atoms.
12, particularly 5 to 7, are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R ₁₁ preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R ₁₁ is an alkylsulfonyl group, an arylsulfonyl group, etc .: The sulfinyl group is an alkylsulfinyl group, the arylsulfinyl group, etc .: A phosphonyl group is an alkylphosphonyl, an alkoxyphosphonyl group. , An aryloxyphosphonyl group, an arylphosphonyl group, etc .: As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc .:
As the carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc .: As the sulfamoyl group,
Alkylsulfamoyl group, arylsulfamoyl group, etc .: As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc .: As a carbamoyloxy group, an alkylcarbamoyloxy group, an arylcarbamoyloxy group, etc .: As an ureido group , An alkylureido group, an arylureido group, etc .: As a sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .: As a heterocyclic group, a 5- to 7-membered one is preferable. Is a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group, a 1-pyrrolyl group, a 1-tetrazolyl group: a heterocyclic oxy group having a 5- to 7-membered heterocycle Preferably, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyltetrazole-5- Oxy group, etc .: The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-
Diphenoxy-1,3,5-triazole-6-thio group, etc .: As siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .: As imide group, succinimide group, 3-heptadecyl succinimide group Group, phthalimido group, glutarimido group, etc .: Spiro compound residue as spiro [3.3] heptan-1-yl, etc .: Bridged hydrocarbon compound residue as bicyclo [2.2.1] heptan-1-yl, tricyclo [3.1.1 ^3.7 ] decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

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

Examples of the group represented by X ₂ which can be removed by the reaction with the oxidation product of the color developing agent include, for example, a halogen atom (chlorine, bromine, fluorine, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl ,

[0071]

[Chemical 7]

(R ₁₁ ′ has the same meaning as R ₁₁ and Z ₂ ′
Has the same meaning as the above Z ₂ , and R _a and R _b each represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group) and the like, but are preferably a hydrogen atom, a halogen atom, an alkoxy group, It is an aryloxy group, an alkylthio group, an arylthio group, or a nitrogen-containing heterocyclic group bonded at the N atom.

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

[0074]

[Chemical 8]

In the formula, Z ₂ ″ represents a group of non-metal atoms necessary for forming a nitrogen-containing 6-membered ring containing at least one carbonyl group or at least one sulfonyl group by being condensed with the pyrazole ring. The 6-membered ring may have a substituent and may be condensed with a benzene ring in addition to the pyrazole ring.

[0076] R ₁₁ "and Y _2" represents a hydrogen atom or a substituent, X ₂ "has the same meaning as X ₂ in the general formula (II).

In the general formula (II), the nitrogen-containing 6-membered heterocycle formed by Z is preferably a 6π electron system or an 8π electron system, and contains 1 to 4 containing at least one —N (Y ₂ ) —.
At least one carbonyl group containing 6 nitrogen atoms and contained in the 6-membered ring represents a group such as -CO- or -CS-. Further, the at least one sulfonyl group contained in the 6-membered ring represents a —SO ₂ — group.

Y ₂ represents a hydrogen atom or a substituent, and a preferred substituent represented by Y ₂ is, for example, one which is eliminated from the compound of the present invention after reacting with an oxidized product of a developing agent. However, for example, the substituent represented by Y ₂ is disclosed in JP-A-61-22
Under alkaline conditions, as described in No. 8444,
Examples thereof include a group capable of splitting off and a substituent described in JP-A-56-133734, which is coupled off by reaction with an oxidized product of a developing agent. Preferably, Y ₂ is a hydrogen atom. is there.

Among the cyan couplers represented by the general formula (II), preferred specific examples include the following general formulas (A) to (A).
Examples thereof include compounds represented by (M).

[0080]

[Chemical 9]

[0081]

[Chemical 10]

In the formula, R ₁₁ , R ₁₂ and R ₁₃ are represented by the general formula (II)
In the same meaning as R _11, X ₂ has the same definition as X ₂ in the general formula (II). In the general formulas (A), (F), and (K), p represents an integer of 0 to 4, and when p is 2 to 4, a plurality of R ₁₂ may be the same or different.

R ₁₂ and R ₁₃ in the general formulas (J), (L) and (M) have the same meaning as R ₁₁ in the general formula (II), but R ₁₂ is not a hydroxyl group.
Z ₂ ″ ″ represents an atomic group necessary for forming a heterocycle.

Preferred as the groups represented by R ₁₂ and R ₁₃ are, for example, alkyl, aryl, carboxyl, oxycarbonyl, cyano, alkoxy, aryloxy, amino, amide and sulfonamide groups, hydrogen atom, halogen atom and the like. Is.

The cyan coupler of the general formula (II) is disclosed in Japanese Patent Application No.
63-321488, 64-36996, 64-41183, 64-5229
3, including the couplers described in 64-97598, 64-9884 and 64-125052, and according to the synthetic method described and the synthetic method described in the cited document Can be synthesized.

The representative examples of the cyan coupler of the present invention represented by the general formula (I) or (II) are shown below, but the present invention is not limited thereto and, for example, JP-A 1-144052, page (7). C-1 to C-35 described in the upper right column to the upper right column on page 9, A-1 to M- described in the lower right column on page (6) to page (12) of JP-A No. 4-133054 Among them, couplers other than the representative examples can be mentioned.

[0087]

[Chemical 11]

[0088]

[Chemical 12]

[0089]

[Chemical 13]

[0090]

[Chemical 14]

[0091]

[Chemical 15]

[0092]

[Chemical 16]

[0093]

[Chemical 17]

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

The cyan coupler of the present invention can be used in combination with other types of cyan couplers.

To incorporate the cyan coupler of the present invention into the color light-sensitive material of the present invention, known techniques used in ordinary cyan couplers can be applied. It is preferable that the coupler is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, dispersed in the form of fine particles and added to the silver halide emulsion. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination.

In the present invention, the raw reflection density measured at at least one wavelength in the exposed region for cyan image-forming silver halide is 0.8 or more, which is the spectral sensitivity distribution of cyan image-forming silver halide. When I took
It means that the reflection density of a raw sample measured at any wavelength in the wavelength region having a sensitivity higher than 30% of the maximum density is 0.8 or more. A conventionally known method can be used to measure the reflection density of the raw sample. For example, the value of the spectral reflection density measured by using a color analyzer 607 manufactured by Hitachi, Ltd. can be used.

As a method for increasing the reflection density before the development treatment to 0.8 or more, a water-soluble dye having absorption in at least the spectral sensitivity region of a cyan image-forming silver halide emulsion and / or a lowermost layer may be used. A method of providing anti-halation on layers other than is preferable. Further, there is a method of suppressing the diffusion of the dye in the light-sensitive material by incorporating the dye in the light-sensitive material as a solid fine powder.

As the water-soluble dye used in the present invention,
Oxonol dye, cyanine dye, merocyanine dye,
Azo dyes, anthraquinone dyes, allylidene dyes and the like can be mentioned. Particularly preferred dyes are oxonol dyes and merocyanine dyes from the viewpoints of high decomposability in a developing solution and non-sensitization to a silver halide emulsion.

Examples of oxonol dyes include US Pat.
7,225, JP-A-48-42826, 49-5125, 49-99620
No. 50, No. 50-91627, No. 51-77327, No. 55-120660, No. 5
8-24139, 58-143342, 59-38742, 59-11164
0, 59-111641, 59-168438, 60-218641,
62-31916, 62-66275, 62-66276, 62-185
No. 755, No. 62-273527, No. 63-139949, etc.

As the merocyanine dye, there is disclosed in JP-A-50-145.
No. 124, No. 58-120245, No. 63-35437, No. 63-35438,
63-34539, 63-58437, etc.

Typical specific examples of the oxonol dye and the merocyanine dye are shown below, but the invention is not limited thereto.

(Water-soluble yellow dye)

[0104]

[Chemical 18]

[0105]

[Chemical 19]

[0106]

[Chemical 20]

[0107]

[Chemical 21]

[0108]

[Chemical formula 22]

(Water-soluble magenta dye)

[0110]

[Chemical formula 23]

[0111]

[Chemical formula 24]

[0112]

[Chemical 25]

[0113]

[Chemical formula 26]

[0114]

[Chemical 27]

(Water-soluble cyan dye)

[0116]

[Chemical 28]

[0117]

[Chemical 29]

[0118]

[Chemical 30]

[0119]

[Chemical 31]

[0120]

[Chemical 32]

Typical specific examples of water-soluble dyes other than oxonol dyes and merocyanine dyes are shown below, but the invention is not limited thereto.

[0122]

[Chemical 33]

[0123]

[Chemical 34]

[0124]

[Chemical 35]

[0125]

[Chemical 36]

The amount of the water-soluble dye used is such that the reflection density of the raw sample before development, measured at at least one wavelength in the exposed area of the cyan image forming silver halide of the color light-sensitive material, is 0.8 or more. Can be selected and added.

The water-soluble dyes of the present invention can be used alone or in combination of two or more.

In the present invention, an antihalation layer may be provided on the bottom layer or other layers.

The antihalation layer contains a compound that absorbs light. As the compound that absorbs light, various organic compounds and inorganic compounds having the action are used.

As the inorganic compound, colloidal silver, colloidal manganese and the like are preferable, but colloidal silver is particularly preferable. Since these colloidal metals have good decolorizing properties,
It is also effective when applied to the color light-sensitive material of the present invention.

The above colloidal silver, for example, gray colloidal silver, is obtained by reducing silver nitrate in gelatin in a gelatin in the presence of a reducing agent such as hydroquinone, phenidone, ascorbic acid, pyrogallol or dextrin, and then neutralizing, It is obtained by cooling and setting gelatin, and then removing the reducing agent and unnecessary salts by a noodle washing method. When reducing with alkaline,
When colloidal silver particles are produced in the presence of an azaindene compound or a mercapto compound, a colloidal silver dispersion liquid having uniform particles can be obtained.

As the amount of colloidal silver, the amount was selected so that the reflection density of the raw sample before development treatment measured at at least one wavelength in the exposure area for cyan image-forming silver halide was 0.8 or more. Can be added.

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 is 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].

[0135]

[Chemical 37]

In the formula, R ₁ and R ₂ are hydrogen atoms, alkyl groups,
Alkenyl group, aryl group, heterocyclic group, -COOR ₅ , -COR
₅ , -SO ₂ R ₅ , -SOR ₅ , -SO ₂ NR ₅ R ₆ , -CONR ₅ R ₆ , -NR ₅ R ₆ , -NR
₅ SO ₂ R ₆ , -NR ₅ COR ₆ , -NR ₅ CONR ₆ R ₇ , -NR ₅ CSNR ₆ R ₇ , -OR ₅ ,-
SR ₅ or a cyano group is represented, and R ₃ and R ₄ 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 represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and L
_{1 to} L ₅ represent a methine chain. n ₁ represents an integer of 0 or 1, and n ₂ represents an integer of 0-2.

[0137]

[Chemical 38]

In the formula, R ₁ , R ₃ , L _{1 to} L ₅ , n ₁ and n ₂ are
Each has the same meaning as in the general formula [1].

E represents the acidic nucleus necessary to form the oxonol dye.

[0140]

[Chemical Formula 39]

In the formula, R ₃ , R ₄ , L _{1 to} L ₅ , n ₁ and n ₂ are
Each has the same meaning as in the general formula [1], and R ₈ and R ₉ are R
It has the same meaning as ₃ and R ₄ .

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

[0143]

[Chemical 40]

In the formula, R ₃ , L ₁ and L ₂ have the same meaning as in the general formula [1], and E has the same meaning as in the general formula [2]. R _10, R ₁₁ is a 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, -NR} 5 R 6, -NR 5 SO 2 R ₆ , -NR ₅ COR
Represents ₆ , -COR ₅ or -COOR ₅ . Alternatively, R ₁₀ and R ₁₁ may form a ring double bond. X ₃ represents an oxygen atom, a sulfur atom, a selenium atom,-(R ₁₂ ) C (R ₁₃ )-or -N (R ₃ )-, and R
₃ , R ₅ and R ₆ have the same meanings as in the general formula [1].

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

[0146]

[Chemical 41]

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 .

[0148]

[Chemical 42]

In the formula, R ₃ , R ₄ , R ₁₀ , R ₁₁ , L _{1 to} L ₅ , X ₃ ,
n ₁ and n ₂ have the same meanings 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 .

X ⁻ represents a group having an anion. Also, R
_A ring bilayer bond can be formed by ₁₀ and R ₁₁ , and R ₁₅ and R ₁₆ .

[0151]

[Chemical 43]

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

[0153]

[Chemical 44]

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

Specific examples of the dyes represented by the general formulas are shown below, but the invention is not limited thereto.

[0156]

[Chemical formula 45]

[0157]

[Chemical formula 46]

[0158]

[Chemical 47]

[0159]

[Chemical 48]

[0160]

[Chemical 49]

[0161]

[Chemical 50]

[0162]

[Chemical 51]

[0163]

[Chemical 52]

[0164]

[Chemical 53]

[0165]

[Chemical 54]

[0166]

[Chemical 55]

[0167]

[Chemical 56]

[0168]

[Chemical 57]

[0169]

[Chemical 58]

[0170]

[Chemical 59]

[0171]

[Chemical 60]

[0172]

[Chemical formula 61]

[0173]

[Chemical formula 62]

[0174]

[Chemical formula 63]

[0175]

[Chemical 64]

[0176]

[Chemical 65]

The dye compound of the present invention is a compound having a hydrophilic group which is substantially insoluble in water (with respect to water having a pH of 7 or less) and dissociates at a pH of 9 or more. A solid fine particle dispersion (in the form of collective particles of microscopic size, the average particle size of which is preferably
10 μm or less, more preferably 1 μm or less), by being present in a gelatin or polymer binder,
It can be contained in any light-sensitive emulsion layer or non-light-sensitive hydrophilic colloid layer in the photographic constituent layers.

The solid solid fine particle dispersion of the present invention is water-insoluble and stably present in the color photographic light-sensitive material, but after exposure, it is treated with a color developing solution (preferably pH 9 or more) to give a dye. Most of the compound disappears from the color photographic light-sensitive material due to the hydrophilic group in the compound dissociating to become water-soluble or decolorizing.

Two or more kinds of the dyes of the present invention may be used,
Depending on the purpose of use, part of the water-soluble dye may be used in combination.

The content of the dye of the present invention is selected so that the reflection density of the raw sample before the development treatment is 0.8 or more, which is measured at at least one wavelength in the exposed area with respect to the cyan image forming silver halide. Can be added. Specifically, it is generally preferable to use it in an amount of 0.001 to 0.5 g / m ² .

In the present invention, at least one layer of a light reflecting layer containing a white pigment is provided on the image forming side of the support, and the amount of the white pigment contained in the light reflecting layer is the binder amount of the light reflecting layer. Is preferably 20% by weight or more.

The light-reflecting layer according to the invention may be one in which the polyolefin resin coating layer provided on the surface of the support contains a white pigment, or a hydrophilic colloid containing a white pigment provided on the support. It may be a layer.

The polyolefin resin coating layer as the light reflecting layer can contain a white pigment in a weight ratio of preferably 20 to 40% or more with respect to the coating amount of the binder of the light reflecting layer. When a resin that cures with actinic rays such as ultraviolet rays and electron beams is used as a binder, a white pigment having a relatively high content can be contained.

In the present invention, a hydrophilic colloid layer containing a white pigment can be preferably used as the light reflecting layer.
In that case, the white pigment may preferably contain 20 to 80% by weight or more of the white pigment with respect to the coating amount of the binder of the light reflecting layer. More preferably 30% to 70%
Is.

As the white pigment, inorganic and / or organic white pigments can be used, preferably inorganic white pigments. Examples of such white pigments include alkaline earth metal sulfates such as barium sulfate and carbonates. Carbonate of alkaline earth metal such as calcium, fine powder silicic acid, silica of synthetic silicate, calcium silicate, alumina, hydrated alumina, titanium oxide,
Examples thereof include zinc oxide, talc and clay.

Of these, preferably barium sulfate,
Calcium carbonate and titanium oxide, more preferably barium sulfate and titanium oxide.

Titanium oxide may be of rutile type or anatase type, and the one whose surface is coated with a metal oxide such as hydrous alumina oxide or hydrous ferrite is also used.

In addition, various additives such as colored pigments, fluorescent whitening agents and antioxidants may be added.

The coating amount of the white pigment is preferably 1 to 50.
in the range of g / m ^2, more preferably in the range of 2 to 20 g / m ^2.

The color light-sensitive material of the present invention may be either negative type or positive type.

As the silver halide emulsion used in the present invention, a surface latent image type silver halide emulsion which forms a latent image on the surface by imagewise exposure is used, and silver halide which forms a negative image by development. An emulsion may be used. or,
Using an internal latent image type silver halide emulsion in which the grain surface is not fogged in advance, image exposure is subjected to fog treatment (nucleation treatment) and then surface development, or after image exposure, while performing fog treatment, the surface The thing which can obtain a positive directly by developing is also used preferably.

The above-mentioned fog treatment may be carried out by exposing the entire surface, chemically using a fog agent, using a strong developing solution, or by heat treatment. The emulsion containing the internal latent image type silver halide emulsion grains is a silver halide grain having a photosensitive nucleus mainly inside the silver halide crystal grains and forming a latent image inside the grains by exposure. The emulsion contained.

Various techniques have been known so far in the technical field of the internal latent image type direct positive. For example, U.S. Patents 2,592,250, 2,466,957, 2,497,875,
2,588,982, 3,761,266, 3,761,276, 3,7
The methods described in 96,577 and British Patent 1,151,363 are known.

Although the mechanism of forming a positive image is not always clear, for example, Photographic Science and Engineering (Photographic Science and Engineering)
andEngineering), Vol. 20, p. 158 (1976), describes as follows.

Photoelectrons generated in the silver halide crystal grains by imagewise exposure are selectively captured inside the grains to form an internal latent image. Since this internal latent image acts as an effective trap center for electrons in the conduction band, in the exposed particles, the electrons injected in the subsequent fog development process are trapped inside and assist the latent image. Become. In this case, the latent image is inside and therefore not developed by surface development. On the other hand, in particles that have not been subjected to image exposure, at least some of the injected electrons are captured on the surface of the particle and a latent image is formed there, so that the particle is developed by surface development.

The non-pre-fogged internal latent image type silver halide grains which can be used in the present invention form a latent image mainly inside the silver halide grains and have most of the photosensitive nuclei inside the grains. An emulsion having silver halide grains, comprising any silver halide such as silver bromide, silver chloride,
It includes silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like.

Particularly preferably, the coated silver amount is about 1 to 3.5 g.
A portion of the sample coated on the transparent support so as to be in the range of 1 / m ² is exposed to the light intensity scale for a predetermined time from about 0.1 second to about 1 second, and is substantially halogenated. When only the surface image of a grain not containing a silver solvent is developed using the following surface developer A at 4 ° C. for 4 minutes, another part of the same emulsion sample is similarly exposed and It is an emulsion showing a maximum density which is not larger than 1/5 of the maximum density obtained when the image is developed with the following internal developer B at 20 ° C. for 4 minutes. More preferably, the maximum density obtained with surface developer A is less than the maximum density obtained with internal developer B.
It is not larger than 1/10.

(Surface developer A) Metol 2.5 g L-ascorbic acid 10.0 g Sodium metaborate (tetrahydrate) 35.0 g Potassium bromide 1.0 g Water was added to 1000 ml (internal developer) Metol 2.0 g Sodium sulfite (anhydrous) ) 90.0 g Hydroquinone 8.0 g Sodium carbonate (monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Water was added to 1000 ml Further, the internal latent image type silver halide emulsions preferably used in the present invention are various. Those prepared by the method are included. For example, conversion type silver halide emulsions described in U.S. Pat.No. 2,592,250, or U.S. Pat.
Nos. 6,3,317,322 and 3,367,778, and silver halide emulsions having internally chemically sensitized silver halide grains, or U.S. Patents 3,271,157 and 3,447,927.
Emulsion having silver halide grains containing a polyvalent metal ion described in U.S. Pat. Or a silver halide emulsion comprising grains having a laminated structure described in JP-A Nos. 50-8524, 50-38525 and 53-2408, and others. Examples thereof include silver halide emulsions described in JP-A-156614 and JP-A-55-127549.

The internal latent image type silver halide grains preferably used in the present invention are silver halides having any halogen composition, for example, silver bromide, silver chloride, silver chlorobromide, silver chloroiodide, silver iodobromide. Any silver chloroiodobromide may be used. The grains containing silver chloride have excellent developability and are suitable for rapid processing.

The shape of the silver halide grains used in the present invention is cubic, octahedral, or a mixture of (100) and (111) faces.
It may be a tetrahedron, a shape having a (110) plane, a spherical shape, a flat shape, or the like. An average particle size of 0.05 to 3 μm can be preferably used. The grain size distribution may be a monodisperse emulsion having uniform grain size and crystal habit, or an emulsion having no uniform grain size or crystal habit, but a monodisperse silver halide emulsion having uniform grain size and crystal habit. Is preferred. In the present invention, the monodisperse silver halide emulsion means that the weight of silver halide contained within a grain size range of ± 20% centered on the average grain size r is
It means 60% or more of the total weight of silver halide grains,
It is preferably 70% or more, more preferably
80% or more. Here, the average particle diameter r is defined as the particle diameter r _i of when the product n _i × r _i ³ of the frequency n _i and r _i ³ of particles having a particle size r _i becomes maximum. (Three significant digits and the least significant digit are rounded up to the nearest four.) The grain size referred to here is the diameter of a spherical silver halide grain, or the grain diameter of a grain other than a spherical grain. It is the diameter when the projected image is converted into a circular image of the same area. The particle size is, for example, 1 with an electron microscope.
It can be obtained by enlarging the image by 10,000 to 50,000 times and measuring the particle diameter on the print or the area at the time of projection. (The number of measured grains shall be 1000 or more indiscriminately.) Particularly preferred highly monodisperse emulsion is (grain size standard deviation / mean grain size) × 100 = distribution defined by breadth (%) of distribution Is less than 20% wide. Here, the average particle size and the particle size standard deviation are obtained from r _i defined above.

A monodisperse emulsion is prepared by adding a water-soluble silver salt solution and a water-soluble halide solution in a gelatin solution containing seed grains to pAg and pH.
Under the control of the double jet method. In determining the addition rate, reference can be made to JP-A-54-48521 and JP-A-58-49938.

As a method for obtaining a more advanced monodisperse emulsion, a growth method in the presence of a tetrazaindene compound disclosed in JP-A-60-122935 can be applied.

The fog processing in the internal latent image type direct positive image formation preferably used in the present invention can be carried out by exposing the whole surface or by using a compound which generates fog nuclei, that is, a fog agent.

The whole surface exposure is carried out by immersing the imagewise exposed light-sensitive material in a developing solution or other aqueous solution or moistening it and then uniformly exposing the whole surface. The light source used here may be any light source as long as it has light in the photosensitive wavelength region of the photographic light-sensitive material,
Further, high illuminance light such as flash light may be applied for a short time, or weak light may be applied for a long time. Further, the time of the whole surface exposure can be varied over a wide range so that the best positive image can be finally obtained depending on the photographic light-sensitive material, the development processing conditions, the kind of the light source used and the like. Further, it is most preferable that the exposure amount of the whole surface exposure gives a certain range of exposure amount in combination with the photosensitive material. Usually, when the exposure amount is excessively increased, the minimum density is increased or desensitized, and the image quality tends to be deteriorated.

Next, the fog agent preferably used in the present invention will be described.

A wide variety of compounds can be used as the fog agent used in the present invention, and the fog agent only needs to be present at the time of development processing. For example, in the constituent layers other than the support of the photographic light-sensitive material (among them). In particular, it is preferably in a silver halide emulsion layer), or in a developing solution or a processing solution prior to the development processing. The amount used can be varied over a wide range depending on the purpose, and the preferable amount added is that when it is added to the silver halide emulsion layer,
1-1,500 mg, preferably 10 per mol of silver halide
~ 1,000 mg. When it is added to a processing solution such as a developing solution, the addition amount is preferably 0.01 to 5 g / liter, particularly preferably 0.05 to 1 g / liter.

Examples of the fogging agent used in the present invention include hydrazines described in US Pat. Nos. 2,563,785 and 2,588,982, or hydrazides or hydrazine compounds described in US Pat. No. 3,227,552; US Pat.
No. 615, No. 3,718,479, No. 3,719,494, No. 3,734,738 and No. 3,759,901, heterocyclic quaternary nitrogen salt compounds; further silver halides such as acylhydrazinophenylthioureas described in U.S. Pat. No. 4,030,925. Examples thereof include compounds having an adsorption group on the surface. Further, these fogging agents can be used in combination. For example, RD mentioned above
15162 describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent, and this combination technique is also effective in the present invention. As the fogging agent used in the present invention, either an adsorption type or a non-adsorption type can be used, or they can be used in combination.

Specific examples of useful fogging agents include hydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-acetyl-2-phenylhydrazine, 1-formyl-2- (4-methylphenyl) hydrazine, 1 Hydrazine compounds such as -methylsulfonyl-2-phenylhydrazine, 1-methylsulfonyl-2- (3-phenylsulfonamidophenyl) hydrazine, 1-benzoyl-2-phenylhydrazine, and formaldehydephenylhydrazine; 3- (2-formylethyl ) -2-Methylbenzothiazolium bromide, 3- (2-acetylethyl) -2-benzyl-5-phenylbenzoxazolium bromide, 3- (2-acetylethyl) -2-benzylbenzoselenazolium bromide , 2-methyl-3- [3- (phenylhydrazino) propyl] benzothiazolium bromide, 1,2
-Dihydro-3-methyl-4-phenylpyrido [2,1-b] benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phenylpyrido [2,1-b] benzoselenazolium bromide,
4,4'-Ethylenebis (1,2-dihydro-3-methylpyrido [2,1
-b] N-substituted quaternary cycloammonium salts such as benzothiazolium bromide; 5- (3-ethyl-2-benzothiazolinylidene) -3- [4- (2-formylhydrazino) phenyl] Rhodanine, 1,3-bis [4- (2-formylhydrazino) phenyl] thiourea, 7- (3-ethoxythiocarbonylaminobenzamide) -9-methyl-10-propargyl-1,2,3,4- Examples thereof include tetrahydroacridinium trifluoromethanesulfonate, 1-formyl-2- [4- {3- (2-methoxyphenyl) ureido} phenyl] hydrazine and the like.

The photographic light-sensitive material having a silver halide emulsion layer according to the present invention forms a positive image directly by subjecting it to imagewise exposure and then developing it in the presence of a fogging agent.

The developer which can be used in the developer used for developing the photographic light-sensitive material according to the present invention is:
Conventional silver halide developers, for example, polyhydroxybenzenes such as hydroquinone, aminophenols, 3-
Pyrazolidones, ascorbic acid and its derivatives, reductones, phenylenediamines, etc., 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 Etc. It is also possible to incorporate these developers in the emulsion in advance so that they act on the silver halide during the immersion in the high pH aqueous solution.

The developer used in the present invention may further contain a specific antifoggant and development inhibitor, or these developer additives may be optionally incorporated in the constituent layers of the photographic light-sensitive material. Is also possible.

Known photographic additives can be used in the silver halide photographic light-sensitive material of the present invention.

Examples of known photographic additives include the compounds described in RD17643 and RD18716 shown below.

Additive RD17643 RD18716 Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right sensitizing dye 23 IV 648 Upper right development accelerator 29 XXI 648 Upper right antifoggant 24 VI 649 Lower right stabilizer Stabilization 〃 Color staining prevention Agent 25 VII 650 Left-right Image stabilizer 25 VII UV absorber 25-26 VII 649 Right-650 left Filter dye 〃 〃 Whitening agent 24 V Hardening agent 26 X 651 Right Coating aid 26-27 XI 650 Right interface Activator 26-27 XI 650 Right Plasticizer 27 XII 650 Right Sliding agent 〃 〃 Static inhibitor 〃 〃 Matting agent 28 XVI 650 Right binder 29 IX 651 Right In the emulsion layer of the light-sensitive material of the present invention, a color developing agent is used. It is possible to use a dye-forming coupler which forms a dye by a coupling reaction with the oxidant. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, the silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

[0215]

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

Example 1 Corona discharge was applied to both front and back sides of a base paper having a basis weight of 80 g / m ² .
A 27 μm thick resin coating layer consisting of high-density polyethylene containing anatase-type titanium dioxide at a concentration of 15% was formed on the surface by an extrusion coating method, and the back surface was coated with a co-extrusion coating method to form two layers up and down. A polyethylene resin coating layer having a layer structure was formed to obtain a support.

On the obtained support, each layer having the constitution shown below was coated on the side of the polyethylene layer containing titanium oxide, and the back side was coated on the back side thereof to obtain a multilayer silver halide color photograph. A light-sensitive material was prepared.

(Preparation of Emulsion EM-1) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate, potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to obtain a particle size of 0.30
A μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method. , Average particle size
The shell was formed to 0.42 μm. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. In the shell forming step, 1 × 10 ^-8 mol of K ₃ RhBr ₆ was added to 1 mol of the final silver halide in an aqueous solution containing potassium bromide and sodium chloride.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-1. The breadth of distribution of this emulsion EM-1 was 8%.

(Preparation of Emulsion EM-2) While controlling the aqueous solution containing ossein gelatin at 40 ° C., the aqueous solution containing ammonia and silver nitrate and potassium bromide and sodium chloride (molar ratio KBr: NaCl = 95: 5). ) Is added at the same time by the control double jet method to give a particle size of 0.26
A μm cubic silver chlorobromide core emulsion was obtained. At that time, pH and pAg were controlled so as to obtain a cubic particle shape.

An aqueous solution containing ammonia and silver nitrate and an aqueous solution containing potassium bromide and sodium chloride (molar ratio KBr: NaCl = 40: 60) were simultaneously added to the obtained core emulsion by the control double jet method. , Average particle size
The shell was formed to 0.36 μm. At that time, pH and pAg were controlled so as to obtain a cubic particle shape. Further, in the shell forming step, K ₃ RhBr ₆ having a final finish of 1 × 10 ^-8 mol was added to an aqueous solution containing potassium bromide and sodium chloride, based on 1 mol of silver halide.

After washing with water to remove the water-soluble salt, gelatin was added to obtain an emulsion EM-2. The breadth of distribution of this emulsion EM-2 was 8%.

(Preparation of Blue Sensitive Emulsion EM-1B) EM-1
A sensitizing dye D-1 was added thereto for color sensitization, and then 600 mg of T-1 was added per mol of silver to prepare a blue-sensitive emulsion EM-1B.

(Preparation of Green Sensitive Emulsion EM-2G) EM-2
A green-sensitive emulsion EM-2G was prepared in the same manner as the blue-sensitive emulsion except that the sensitizing dye D-2 was added thereto for color sensitization.

(Preparation of Red Sensitive Emulsion EM-2R) EM-2
A red-sensitive emulsion EM-2R was prepared in the same manner as the blue-sensitive emulsion except that the sensitizing dyes D-3 and D-4 were added thereto for color sensitization.

(Preparation of pan-sensitive emulsion EM-1P) EM-1
A general-purpose emulsion EM was prepared in the same manner as the blue-sensitive emulsion except that the sensitizing dyes D-1, D-2, D-3 and D-4 were added to the emulsion to perform color sensitization.
-1P was prepared.

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

[0229]

[Chemical formula 66]

EM-1B, EM-2G, EM-2
Using R and EM-1P, the first to eighth layers were coated on the front surface of the support and the ninth layer was coated on the back surface of the support in the following constitution to prepare a color photographic light-sensitive material. SA-1 as a coating aid
And SA-2 are used, and H-1 and H-2 are used as hardeners.
Was used to prepare Sample 1.

SA-1: sulfosuccinic acid di (2-ethylhexyl) ester / sodium SA-2: sulfosuccinic acid di (2,2,3,3,4,4,5,5-octafluoropentyl) ester Sodium H-1: 2,4-dichloro-6-hydroxy-s-triazine
Sodium H-2: Tetrakis (vinylsulfonylmethyl) methane layer composition Coating amount (g / m ² ) Eighth layer gelatin 0.78 (UV-UV absorber (UV-1) 0.065 absorber layer) UV-absorber (UV-2 ) 0.120 UV absorber (UV-3) 0.160 Oil-soluble dye 1 0.5 × 10 ^-3 Oil-soluble dye 2 0.5 × 10 ^-3 Solvent (SO-2) 0.1 Silica matting agent 0.03 7th layer Gelatin 1.43 (blue sensitive layer) Blue-sensitive emulsion EM-1B (coating silver amount) 0.5 Yellow coupler (YC-1) 0.82 Antistain agent (AS-2) 0.025 Solvent (SO-1) 0.82 Inhibitor (ST-1, ST-2, T-1) ) Sixth layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1, AS-3, AS-4 equivalent) 0.055 Solvent (SO-2) 0.072 Anti-irradiation dye (AI-3) 0.03 Fifth layer gelatin 0.42 (Colloy Yellow colloidal silver 0.03 De silver layer Anti-color mixture (AS -1, 1, AS-3, AS-4 equivalent) 0.04 Solvent (SO-2) 0.049 Polyvinylpyrrolidone (PVP) 0.047 Fourth layer Gelatin 0.54 (Intermediate layer) Anti-color mixing agent (AS-1, AS-3, AS) -4 equivalent) 0.055 Solvent (SO-2) 0.072 Third layer Gelatin 1.43 (Green-sensitive layer) Green-sensitive emulsion EM-2G (Coated silver amount) 0.50 Magenta coupler (MC-1) 0.25 Yellow coupler (YC- 2) 0.06 Anti-stain agent (AS-2) 0.019 Solvent (SO-1) 0.31 Inhibitor (ST-1, ST-2, T-1) Second layer Gelatin 0.75 (Intermediate layer) Anti-color mixing agent (AS-1) , AS-3, AS-4 equivalent) 0.055 Solvent (SO-2) 0.072 Irradiation prevention dye (AI-1) Table Irradiation prevention dye (AI-2) 0.03 1st layer Gelatin 1.38 (red sensitive layer) Red Sensitive emulsion EM-2R (Amount of coated silver) 0.30 Cyan coupler ( ) 0.44 Solvent (SO-1) 0.31 Anti-staining agent (AS-2) 0.015 Inhibitor (ST-1, ST-2, T-1) 9th layer Gelatin 6.00 (Back layer) Silica matting agent 0.65 Based on silver conversion.

SO-1: trioctyl phosphate SO-2: dioctyl phthalate AS-1: 2,4-di-t-octylhydroquinone AS-2: 2,4-di-t-butylhydroquinone ST-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole ST-2: N-benzyladenine

[0233]

[Chemical formula 67]

[0234]

[Chemical 68]

[0235]

[Chemical 69]

[0236]

[Chemical 70]

[0237]

[Chemical 71]

(Evaluation of halftone dot image: standard exposure amount) With respect to the sample obtained as described above, the black plate and the cyan plate of the halftone dot original document were brought into close contact with each other and the exposure conditions shown below-1
Exposed. Next, the black plate and the magenta plate were brought into close contact with the sample and exposed under the exposure condition-2 shown below. Further, the black plate and the yellow plate were brought into close contact with the sample and exposed under the exposure condition-3 shown below.

(Evaluation of halftone image: fluctuation of exposure amount of red light)
A black plate and a cyan plate of a halftone original document were brought into close contact with the sample obtained as described above, and the sample was exposed at an exposure amount 1.2 times the exposure condition-1 shown below. Next, the black plate and the magenta plate were brought into close contact with the sample and exposed under the exposure condition-2 shown below. Further, the black plate and the yellow plate were brought into close contact with the sample and exposed under the exposure condition-3 shown below.

Each of the light-sensitive materials exposed by the halftone dot image as described above was processed by the following development processing steps to obtain a dye image consisting of halftone dots.

Of the obtained image, the neutral image portion composed of halftone dots of each of the yellow plate, the magenta plate, and the cyan plate was obtained by measuring the densities of the portions having halftone dot areas of 10% and 50%, respectively. The evaluation results are shown in Table 1.

Here, by evaluating how the ratio (D _R / D _G ) of the red density to the green density of the neutral portion changes with the halftone dot area of 10% with respect to the value when the halftone dot area of 50% is evaluated. The variation in color balance was evaluated as an index of neutral reproducibility. That is, the value of D _R / D _G at dot 50 percent is 100, the value of D _R / D _G at dot 10% approximate the color balance in the middle and small point the closer to 100 And has excellent neutral reproducibility. The concentration was measured using PDA-65.

That is, the following numerical values were evaluated.

(D _R / D _G ) ₁₀ / (D _R / D _G ) ₅₀ × 100 = D _R / D _G (exposure condition-1) Each photosensitive material was treated with a red filter (Ratten No. 26) and an ND filter. When the white light is exposed through the ND filter, the density of the ND filter is adjusted, and the exposure is performed for 0.5 seconds with the minimum exposure amount that minimizes the red light density after the development processing.

(Exposure condition-2) When exposing each light-sensitive material to white light through a green filter (Ratten No. 58) and an ND filter, the ND filter density was adjusted to minimize the green light density after development processing. The minimum exposure dose is 0.5 seconds.

(Exposure condition-3) When exposing each light-sensitive material to a white light through a blue filter (Ratten No. 47B) and an ND filter, the ND filter density is adjusted to minimize the blue light density after the development processing. The minimum exposure dose is 0.5 seconds.

A daylight fluorescent lamp was used as the light source under the exposure conditions 1 to 3.

[0248]   Treatment process-1 Temperature time   Immersion (Developer) 37 ℃ 12 seconds   Fog exposure-12 seconds (1 lux)   Image 37 ℃ 95 seconds   Bleach fixing 35 ℃ 45 seconds   Stabilization treatment 25-30 ℃ 90 seconds   Dry 60-85 ℃ 40 seconds The composition of the treatment liquid is as follows.

(Color developer) Benzyl alcohol 15.0 ml Cerium 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 Diethylenetriamine pentasodium acetate 2.0g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 4.5g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Diethylene glycol 15.0 ml Add water to bring the total volume to 1 liter and adjust the pH to 10.15.

(Bleach-fixing solution) Diethylenetriamine pentaacetic acid ferric ammonium 90.0 g Diethylenetriamine pentaacetic acid 3.0 g Ammonium thiosulfate (70% aqueous solution) 180 ml Ammonium sulfite (40% aqueous solution) 27.5 ml 3-Mercapto-1,2,4-triazole Adjust the pH to 7.1 with 0.15 g potassium carbonate or glacial acetic acid and add water to bring the total volume to 1 liter.

(Stabilizing Solution) o-Phenylphenol 0.3 g Potassium sulfite (50% aqueous solution) 12 ml Ethylene glycol 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Zinc sulfate heptahydrate 0.7 g Ammonium hydroxide (28% aqueous solution) 2.0 g Polyvinylpyrrolidone (K-17) 0.2 g Fluorescent brightener (4,4'-diaminostilbenedisulfonic acid derivative) 2.0 g Add water to bring the total volume to 1 liter and add ammonium hydroxide. Alternatively, adjust the pH to 7.5 with sulfuric acid. The stabilization treatment was a countercurrent system with a two tank structure.

The formulation of the replenisher for running is shown below.

(Color developer replenisher) benzyl alcohol 18.5 ml cerium sulphate 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 0.1 g hydroxylamine sulfate 5.0 g Sodium diethylenetriamine pentaacetate 2.0 g 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline sulfate 5.4 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Diethylene glycol 18.0 ml Add water to make the total volume 1 liter and adjust the pH to 10.35.

(Replenisher for bleach-fixing solution) Same as the above-mentioned bleach-fixing solution.

(Stabilizer Replenisher) The same as the above stabilizer.

The replenishing amount is the developer replenishing solution, the bleach-fixing solution,
The stabilizing solution was 320 ml per 1 m ^{2 of the} light-sensitive material.

[0257]

[Table 1]

As is clear from the results in the table, the samples of the present invention show small collapse of the color balance D _R / D _G even when the exposure amount changes, and are excellent in neutral reproducibility.

On the other hand, in the samples other than the present invention, it is understood that the color balance is lost due to the variation of the exposure amount, that is, the neutral reproducibility is poor.

Example 2 Sample 50 was prepared in the same manner as sample 8 prepared in Example 1. In Sample 50, EM-1P was added to the red-sensitive emulsion EM-2R of the first layer (red-sensitive layer) of Sample 8 and EM-1P was added to the green-sensitive emulsion EM-2G of the third layer (green-sensitive layer). Sensitive emulsion EM
-1P, and the blue-sensitive emulsion EM-1B of the seventh blue-sensitive layer
In addition to the above, a pan-sensitive emulsion EM-1P was added, and coating was performed with the following constitution to prepare a sample. In the preparation of the coating solution, the pan-sensitive emulsion was mixed with the coating solution prepared by removing the pan-sensitive emulsion contained in the first layer, the third layer and the seventh layer, and coating was performed immediately after that. .

Layer composition Coating amount (g / m ² ) Seventh layer Blue-sensitive emulsion EM-1B (coating silver amount) 0.4 (blue-sensitive layer) Pan-sensitive emulsion EM-1P (coating silver amount) 0.1 Third layer Green-sensitive emulsion EM-2G (coated silver amount) 0.40 (green-sensitive layer) Pan-sensitive emulsion EM-1P (coated silver amount) 0.1 First layer Red-sensitive emulsion EM-2R (coated silver amount) 0.24 (red-sensitive layer) Pan Sensitive Emulsion EM-1P (Amount of coated silver) 0.06 The sample 50 obtained as described above was exposed and processed in the same manner as in Example 1, and the neutral reproducibility was evaluated according to Example 1.

The results are shown below. It can be seen that the samples of the present invention maintain a good color balance even when the exposure amount changes and are excellent in neutral reproducibility.

Sample No. Coupler Raw Sample Concentration Standard Exposure Red Exposure Change 50 I-1 0.97 95 93 Example 3 A sample was prepared in the same manner as Sample 8 of Example 1, except that a support and a first red-sensitive layer were used. Between the substrate and the side closer to the support, an A1 layer (white pigment layer) and an A2 layer (intermediate layer) having the following constitution are provided to provide a sample.
Got 51-54.

Layer composition Coating amount (g / m ² ) A2 layer Gelatin 0.54 (intermediate layer) Color mixture inhibitor (AS-1, AS-3, AS-4 equivalent) 0.055 Solvent (SO-2) 0.072 A1 Layer Gelatin 1.00 (white pigment layer) Titanium oxide The following amount Sample No. Titanium oxide coating amount Sample No. Titanium oxide coating amount 51 0.15 53 1.50 52 0.30 54 3.00 Furthermore, instead of the A1 layer white pigment layer of Sample 51 above, Sample 55 was prepared by providing a B1 layer antihalation layer.

Layer composition Coating amount (g / m ² ) B1 layer Gelatin 0.54 (halation black colloidal silver 0.06 prevention layer) Polyvinylpyrrolidone (PVP) 0.03 Samples 51 to 55 obtained as described above Exposure and treatment were carried out in the same manner as in 1, and the neutral reproducibility was evaluated according to Example 1.

As a result, it was shown that the samples 51 to 55 of the present invention maintained good color balance even when the exposure amount varied, that is, they were excellent in neutral reproducibility.

[0267]   Sample No. Coupler Raw sample concentration Standard exposure Red exposure change     51 I-1 0.90 93 91     52 〃 0.92 95 93     53 〃 0.92 95 93     54 〃 0.92 96 94     55 〃 1.10 96 94

[0268]

By using the silver halide color photographic light-sensitive material according to the present invention, a color proof excellent in reproduction of neutral gray can be stably prepared from halftone image information.

Continuation of the front page (56) Reference JP-A-4-37744 (JP, A) JP-A-3-156453 (JP, A) JP-A-3-230151 (JP, A) JP-A 64-557 (JP , A) JP 3-289649 (JP, A) JP 5-134372 (JP, A) JP 2-64630 (JP, A) JP 3-156451 (JP, A) JP 5-80473 (JP, A) JP-A-3-229239 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03C 7 / 38,1 / 91,7 / 00

Claims (3)

(57) [Claims] 1. A support having at least one yellow image-forming silver halide emulsion layer, at least one magenta image-forming silver halide emulsion layer, and at least one cyan image-forming silver halide emulsion layer. And a cyan image forming silver halide emulsion layer containing at least one coupler represented by the following general formula (I) or (II), and having a cyan image forming property. A silver halide color photographic light-sensitive material having a raw reflection density of 0.8 or more measured at at least one wavelength in an exposed region of silver halide. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom or a substituent, R ₂ represents a substituent, and m represents an integer of 0 to 2. However, when m is 0, R ₁ represents an electron-withdrawing group, and when m is 1 or 2, at least one of R ₁ and R ₂ represents an electron-withdrawing group. m
When is 2, a plurality of R ₂ may be the same or different. Z ₁ represents a non-metal atom group necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring and the like, and X ₁ is released by reaction with a hydrogen atom or an oxidant of a color developing agent. It represents a substituent to be obtained. ] [Chemical 2] [In the formula, R ₁₁ and Y ₂ represent a hydrogen atom or a substituent, and X ₂
Represents a hydrogen atom or a substituent capable of splitting off upon reaction with an oxidized product of a color developing agent. Z ₂ represents a non-metal atom group necessary for forming a nitrogen-containing 6-membered heterocycle by condensing with the pyrazole ring together with -N (Y ₂ )-, and the 6-membered ring may have a substituent. Well, other than the pyrazole ring, it may be condensed with a benzene ring. ] 2. The support has a light reflecting layer containing at least one layer of a white pigment on the image forming layer side of the support, and the amount of the white pigment contained in the light reflecting layer is 20% by weight of the amount of the binder in the light reflecting layer. %
The silver halide color photographic light-sensitive material according to claim 1, which is above. 3. A yellow image forming layer, a magenta image forming layer, and a cyan image on a support based on halftone dot image information consisting of color-separated yellow image information, magenta image information, cyan image information and black image information. Exposing and processing a silver halide color photographic light-sensitive material having a forming layer,
In the step of forming a yellow proof, a magenta image, and a cyan image to form a color proof, the silver halide color photographic light-sensitive material is the silver halide color photographic light-sensitive material according to claim 1 or 2. How to create a color proof.