JP2002023324A - Photographic coupler and silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a yellow colored magenta coupler excellent in solubility and producible at a low cost and to provide a yellow colored magenta coupler having high development activity, ensuring low fog even when used in combination with a high sensitivity silver halide emulsion and a high color forming coupler and also having stability even to light, heat and moisture. SOLUTION: The photographic coupler of formula (I) (where R1 and R2 are each a substituent; R3 is alkyl, alkenyl, alkynyl or aryl; L is -CO-; Q is H, halogen or alkoxy; (k) is an integer of 1-5; (m) is an integer of 0-5; (n) is an integer of 0 or 1; in the case of k>=2, plural symbols R1 may be the same or different; and m>=2, plural symbols R2 may be the same or different) is provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a photographic coupler and a silver halide color photographic light-sensitive material, and more particularly to a yellow colored magenta coupler and a silver halide light-sensitive material containing the same.

[0002]

2. Description of the Related Art In color photographic light-sensitive materials, yellow, magenta and cyan dyes formed from couplers do not always have ideal absorption characteristics. For example, a magenta dye image absorbs a small amount of blue light in addition to the necessary green light absorption, causing distortion in color reproducibility.
To remove this distortion, a yellow colored magenta coupler is used. A masking method using such a colored coupler is described in, for example, J. Mol. Photo. Soc. A
m. , 13, 94 (1947); Photo. Soc. Am. , 40,166 (1
950); Am. Chem. Soc. , 72, 1533 (1950). For a colored magenta coupler having a main absorption in the blue light region, U.S. Pat.
Nos. 054, 2,449,966, 2,763,552 and 2,983,608. Also, as patents defining the azo moiety, U.S. Pat.Nos. 3,519,429, 3,615,506, 1,044,
Nos. 778, 3,476,564, JP-A-49-123625, and 49-13
No. 1448 and No. 54-52532, No. 52-42121, No. 52-1027
No. 23 and No. 53-63016 are known. In these colored magenta couplers, it is difficult to adjust the main absorption to a preferable wavelength, or the developing activity is low, so that the masking effect is reduced, and further, the light of the coupler itself,
There are problems such as low stability to heat and humidity, and the present situation is that the coloring properties are adjusted and used by combining several kinds of colored couplers. In addition, the skeleton used for the yellow colored magenta coupler generally has low solubility, and a device for improving the solubility is required. As a coupler which has solved these problems, Japanese Patent Application Laid-Open No. 62-5083
The coupler described in No. 0 is known. The coupler is
A coupler having a characteristic azo moiety and having a branched alkoxy group. Certainly, the solubility is improved, but as a result, the molecular structure becomes complicated, which is not preferable in terms of cost.

On the other hand, in recent years, color negative films have been more and more demanded for color reproducibility, high sensitivity and thin layer. In particular, in order to achieve color reproducibility, the use ratio of yellow colored magenta couplers is higher than ever. Further, the cost of color negative films has been reduced more than before. Under these circumstances, yellow colored couplers currently in practical use are not always satisfactory in terms of solubility and cost, and there is a real need for improvement.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a yellow colored magenta coupler which is excellent in solubility and can be produced at low cost. The second object of the present invention is to have a high developing activity, low fog even when used in combination with a high-sensitivity halogenated emulsion or a high-color-forming coupler,
An object of the present invention is to provide a yellow colored magenta coupler that is stable to heat and humidity.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that yellow colored magenta couplers represented by the following general formula (I) have good characteristics, and contain the couplers. It has been found that the above objects can be achieved by a silver halide color photographic light-sensitive material.

[0006]

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In the formula, R ₁ and R ₂ represent a substituent, and R ₃
Represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group. L represents -CO-, Q is a hydrogen atom,
Represents a halogen or an alkoxy group. Here, k represents an integer of 1 to 5, m represents an integer of 0 to 5, and n represents an integer of 0 or 1. k
When R is 2 or more, R ₁ may be the same or different;
Is 2 or more, R ₂ may be the same or different.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The present invention relates to a novel photographic coupler represented by the above general formula (I) (hereinafter, also referred to as “photographic coupler of the present invention”).

In the formula, R ₁ and R ₂ represent a substituent, and examples of the substituent include a halogen atom (eg, a chlorine atom,
Bromine atom, fluorine atom, alkyl group (preferably having 1 to 60 carbon atoms, for example, methyl, ethyl, propyl, is
o-butyl, t-butyl, t-octyl, 1-ethylhexyl, nonyl, cyclohexyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl), alkenyl group (preferably having 2 to 60 carbon atoms, for example, vinyl, Allyl, oleyl), cycloalkyl group (preferably having 5 to 60 carbon atoms, for example, cyclopentyl, cyclohexyl, 4-t-butylcyclohexyl,
1-indanyl, cyclododecyl), an aryl group (preferably having 6 to 60 carbon atoms, for example, phenyl, p-tolyl, naphthyl), an acylamino group (preferably having 2 carbon atoms)
~ 60. For example, acetylamino, pivaloylamino,
n-butanamide, octanoylamino, 2-hexyldecaneamide, 2- (2 ', 4'-di-t-amylphenoxy) butanamide, benzoylamino, nicotinamide), a sulfonamide group (preferably having 1 to 6 carbon atoms)
0. For example, methanesulfonamide, octanesulfonamide, benzenesulfonamide), ureido group (preferably having 2 to 60 carbon atoms, for example, decylaminocarbonylamino, di-n-octylaminocarbonylamino), urethane group (preferably having carbon number 2 to 60. For example, dodecyloxycarbonylamino, phenoxycarbonylamino, 2-ethylhexyloxycarbonylamino), an alkoxy group (preferably having 1 to 60 carbon atoms, for example, methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, Methoxyethoxy), an aryloxy group (preferably having 6 to 60 carbon atoms, for example, phenoxy, 2,4-di-t-amylphenoxy, 4-t-octylphenoxy, naphthoxy), an alkylthio group (preferably having 1 to 60 carbon atoms) 60. Example For example, methylthio, ethylthio, butylthio, hexadecylthio), an arylthio group (preferably having 6 to 60 carbon atoms, for example, phenylthio, 4-todecyloxyphenylthio), an acyl group (preferably having 1 to 60 carbon atoms, for example, acetyl, Benzoyl, butanoyl, dodecanoyl), a sulfonyl group (preferably having 1 to 60 carbon atoms; for example, methanesulfonyl, butanesulfonyl, toluenesulfonyl), a cyano group, and a carbamoyl group (preferably having 1 to 60 carbon atoms)
N, N-dicyclohexylcarbamoyl), a sulfamoyl group (preferably having 0 to 60 carbon atoms, for example, N, N-
Dimethylsulfamoyl), hydroxy group, sulfo group,
Carboxyl group, nitro group, alkylamino group (preferably having 1 to 60 carbon atoms; for example, methylamino, diethylamino, octylamino, octadecylamino), and arylamino group (preferably having 6 to 60 carbon atoms; for example, phenylamino, naphthyl) Amino, N-methyl-N-phenylamino), heterocyclic group (preferably having 0 to 60 carbon atoms).
Preferably, the heteroatoms in the ring include those selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and those containing a carbon atom as a ring-constituting atom in addition to a heteroatom are more preferable, and the number of ring members is 3 to 8, Preferably it is 5-6, for example, morpholino, piperidino, pyrrolidino),
An acyloxy group (preferably having 1 to 60 carbon atoms; for example,
Formyloxy, acetyloxy, myristoyloxy, benzoyloxy), alkoxycarbonyl group (preferably having 1 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl)
And the like.

Among the above, alkyl, cycloalkyl, aryl, acylamino, ureido, urethane, alkoxy, aryloxy, alkylthio, arylthio, acyl, sulfonyl, cyano, carbamoyl , A sulfamoyl group includes those having a substituent, such as an alkyl group, a cycloalkyl group, an aryl group, an acylamino group,
Examples include a ureido group, a urethane group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acyl group, a sulfonyl group, a cyano group, a carbamoyl group, and a sulfamoyl group.

Of the above substituents, R ₁ is preferably an alkoxy group, an alkyl group, an aryl group, or an acylamino group. More preferably, an alkoxy group,
Among the acylamino groups, the most preferred is an acylamino group.

Of the above substituents, those preferred as R ₂ are a halogen atom, an alkoxycarbonyl group, a nitro group, a cyano group and a sulfonyl group. More preferred are a halogen atom and an alkoxycarbonyl group, and most preferred is a halogen atom. Among the halogen atoms, a chlorine atom is most preferred. k represents an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. When k is 2 or more, R ₁ may be the same or different. m is from 0 to 5
, Preferably an integer of 3 to 5, more preferably an integer of 3. When m is 2 or more, R ₂ may be the same or different. L is -CO-. n is 0
Or represents an integer of 1. Q represents a hydrogen atom, an alkoxy group or a halogen atom, and preferably represents a halogen atom. Among the halogen atoms, a chlorine atom is preferred.

R ₃ represents an alkyl group, an alkenyl group, an alkynyl group or an aryl group. The alkyl group, alkenyl group, and alkynyl group referred to herein include linear, branched, and cyclic substituted or unsubstituted. The aryl group also includes a substituted or unsubstituted aryl group. The alkyl group preferably has 1 to 30 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl,
-Cyanoethyl, 2-ethylhexyl, 2-hexyloctyl, 2-octyldecyl, 2-octyldecyl),
The cycloalkyl group preferably has 3 to 30 carbon atoms.
Or a substituted or unsubstituted cycloalkyl group (for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl) or a bicycloalkyl group, preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, A monovalent group obtained by removing one hydrogen atom from 5 to 30 bicycloalkanes (for example,
Bicyclo [1,2,2] heptane-2-yl, bicyclo [2,2,2] octan-3-yl).

The alkenyl group is preferably a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms (eg, vinyl, allyl, prenyl, geranyl, oleyl), and the cycloalkenyl group is preferably a substituted or unsubstituted alkenyl group having 3 to 30 carbon atoms. An unsubstituted cycloalkenyl group, that is, a monovalent group obtained by removing one hydrogen atom from a cycloalkene having 3 to 30 carbon atoms (for example, 2-cyclopentene-
1-yl, 2-cyclohexen-1-yl). The bicycloalkenyl group is preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one double bond (for example, bicyclo [2 , 2,
1] Hept-2-en-1-yl, bicyclo [2,2,
2] Oct-2-en-4-yl). The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms (eg, ethynyl, propargyl, trimethylsilylethynyl group). As the aryl group, a substituted or unsubstituted aryl group having preferably 6 to 30 carbon atoms (for example, phenyl, p-tolyl, naphthyl, m-
Chlorophenyl, o-hexadecanoylaminophenyl).

R ₃ is preferably an unsubstituted alkyl group, and preferably has 5 to 30 carbon atoms. More preferably, it is a branched alkyl group having 6 to 30 carbon atoms, and most preferably, R ₃ is a branched alkyl group represented by the following formula.

[0017]

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In the formula, p and q represent integer values of 2 to 20. Hereinafter, specific examples of the photographic coupler represented by formula (I) of the present invention are listed, but the present invention is not limited thereto.

[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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(Synthesis Examples) Specific synthesis examples of the photographic coupler of the present invention will be described below, but the present invention is not limited thereto.

Synthesis Example 1 Synthesis of Yellow Colored Magenta Coupler (1) A yellow colored magenta coupler (1), which is an exemplary compound of the present invention, was synthesized by the following method.

[0028]

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Synthesis of Compound C Thionyl chloride (42 mL) was added dropwise to a solution of Compound B (176 g) in ethyl acetate (500 mL) at 60 ° C., stirred for 1 hour under reflux and then cooled to 25 ° C. This solution was added dropwise to a solution of compound A (205.7 g) in dimethylacetamide (800 mL) / ethyl acetate (200 mL) at 10 ° C., and the mixture was stirred at 25 ° C. for 2 hours. Ethyl acetate (500 mL) and 1 mol / m3 aqueous hydrochloric acid (500 mL) were added to the solution, and the mixture was separated. The organic layer was washed twice with water, washed with saturated saline, and concentrated under reduced pressure. Compound C (265) was recrystallized from the concentrated residue from ethyl acetate (400 mL) / acetonitrile (1000 mL).
g) was obtained.

Synthesis of Exemplified Compound (1) p-Pivaloylaminoaniline (12.8 g) in methanol (100 m
L) / water (20 mL) solution at 0 ° C at 11.2 mol / m3 aqueous hydrochloric acid (16.9 mL)
And sodium nitrite aqueous solution (4.3 g of sodium nitrite
/ 19 mL of water) was added dropwise, and the mixture was stirred at 0 ° C for 30 minutes to prepare a diazonium salt. Compound C (15 g), sodium acetate (15
g), 30 mL of methanol and 150 mL of ethyl acetate were added dropwise with the above diazonium salt (65 g) at 15 ° C, and the mixture was stirred at 25 ° C for 30 minutes. Water (150 mL) was added to the reaction solution to separate it. The organic layer was dried over magnesium sulfate and concentrated under reduced pressure. The concentrated residue was purified by column (developing solvent: dichloromethane / ethyl acetate = 10/1) to obtain Exemplified Compound (1) (17.2 g).

Synthesis Example 2 Synthesis of Yellow Colored Magenta Coupler (10) In the same manner as in Synthesis Example 1, synthesis was performed by the following method.

[0032]

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Except that the diazo component of Synthesis Example 1 was changed,
The same reaction as in Synthesis Example 1 was carried out to obtain a yellow colored magenta coupler (10) as a target exemplified compound.

The present invention also relates to a light-sensitive material having on a support at least one light-sensitive layer containing a photographic coupler represented by the above general formula (I). The coupler of the present invention may be used in any layer of a light-sensitive material, but is preferably used in a silver halide light-sensitive layer, and particularly preferably in a green light-sensitive layer. When the green-sensitive layer is divided into two or more layers having different sensitivities, for example, when the green-sensitive layer is divided into a high-sensitive green-sensitive layer, a medium-sensitive green-sensitive layer, and a low-sensitive green-sensitive layer, the green-sensitive layer has at least one of these layers. It is preferably used, more preferably used for two or more layers, and particularly preferably used for all three layers. A preferred coating amount of the coupler of the present invention is 0.01 to 1.00 g / m ² ,
0.5 g / m ² , more preferably 0.075 to 0.2 g / m ^2.
0 g / m ² is particularly preferred.

Various additives can be used in the silver halide color photographic light-sensitive material containing a photographic coupler of the present invention depending on the purpose. These additives are described in more detail in Research Disclosure (hereinafter abbreviated as RD), Item 17643 (December 1978), and I.
tem18716 (November 1979) and Item
308119 (December 1989),
The relevant locations are summarized below.

Additive type RD17643 RD18716 RD308119 Chemical sensitizer page 23 page 648 right column page 996 2. Sensitivity increasing agent Same as above 3. 3. Spectral sensitizer, page 23-24 page 648 right column-page 996 right column-supersensitizer 649 page right column 998 page right column Brightener page 24 page 998 right column 5. 5. Antifoggant page 24 to 25 page 49 right column page 998 right column and stabilizer 1000 page right column 6. Light absorber, page 25-26, page 649, right column-page 1003, left column-filter dye, page 650, left column, page 1003, right column UV absorber 7. Stain inhibitor 25 pages right column 650 left to right column 1002 right Dye image stabilizer page 25 1002 right 9. Hardening agent Page 26 Page 651 Left column 1004 right to 1005 left 10. Binder page 26 Same as above 1003 right to 1004 right 11. Plasticizers, lubricants 27 pages 650 pages right column 1006 left to 1006 right 12. Coating aid, pages 26 to 27 Same as above 1005 left to 1006 left Surfactant 13. Static page 27 Same as above 1006 right to 1007 left Inhibitor 14. Matting agent 1008 left to 1009 left Techniques such as layer arrangement that can be used in the silver halide photographic light-sensitive material containing a photographic coupler of the present invention, and functional couplers such as silver halide emulsions, dye-forming couplers, and DIR couplers , Various additives, and development processing are described in European Patent No. 056596A1 (October 1993).
And published patents cited therein. The following is a list of each item and the corresponding locations.

1. 1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to page 62, line 14 2. Intermediate layer: page 61, lines 36-40, 3. Multilayer effect imparting layer: page 62, lines 15-18, 4. Silver halide composition: page 62, lines 21-25, 5. Silver halide crystal habit: page 62, line 26-30, 6. Silver halide grain size: page 62, lines 31-34, 7. Emulsion manufacturing method: page 62, line 35-40, Silver halide grain size distribution: page 62, 41-42
Row, 9. 9. Tabular grains: page 62, lines 43-46, 10. Internal structure of particle: page 62, line 47 to line 53, Emulsion latent image formation type: page 62, line 54-page 63, 5
Line, 12. 12. Physical ripening and chemical ripening of emulsion: page 63, line 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogged emulsion: p. 63, lines 14-31, Non-light-sensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49-50, Photographic additive: RD Item 17643 (197
December 18), Item 18716 (November 1979)
Monday) and Item 307105 (November 1989)
The following shows each item and its related places.

Types of Additives RD17643 RD18716 RD307105 (1) Chemical sensitizer page 23, page 648, right column, page 866 (2) Sensitivity enhancer, page 648, right column (3) Spectral sensitizer, pages 23-24, page 648, right Columns to 866 to 868 Super sensitizer page 649 right column (4) Brightener 24 page 647 page right column 868 (5) Antifoggant, page 24 to 25 page 649 right column 868 to 870 Stabilizer (6) Light absorber, pages 25 to 26, page 649, right column to page 873, filter dye, page 650, left column, UV absorber (7) Stain inhibitor, page 25, right column, 650 left column to right column, page 872 (8) Image stabilizer page 25 page 650 left column page 872 (9) hardener 26 page 651 left column 874-875 (10) binder 26 page 651 left column 873-874 (11) plasticizer, lubricant 27 Page 650 Right column Page 876 (12) Coating aid, 26 to 27 Page 650 Right column 875 to 876 Surfactant (13) Static 27 Page 650 Right column 876 to 877 Inhibitor (14) Matting agent 878-879.

18. Formaldehyde scavenger: 6
Page 4, lines 54-57; Mercapto antifoggant: page 65, line 1-2, 20. Release agent such as fogging agent: page 65, lines 3-7, 21. Dye: page 65, line 7-10, 22. General color couplers: p. 65, lines 11-13, 23. Yellow, magenta and cyan couplers: page 65, 1
Lines 4-25, 24. Polymer coupler: page 65, lines 26-28, 25. Diffusible dye-forming coupler: page 65, lines 29-31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39-44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49-53, 30. Other DIR couplers: page 65, line 54-page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40-page 67, 1
Row, 35. Back layer: page 67, line 3-8, 36. General processing: page 67, lines 9-11, 37. Developer and developer: page 67, lines 12-30, 38. Developer additives: page 67, lines 31-44, 39. Inversion processing: page 67, lines 45 to 56, 40. Processing solution opening ratio: page 67, line 57-page 68, line 12, 41. Developing time: page 68, lines 13-15, 42. Bleaching-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic developing machine: page 69, lines 32-40, 44. Rinsing, rinsing, stabilization: page 69, line 41-page 70, line 18
Row, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70, lines 34-38, 48. Use for film with lens: page 70, lines 39-41.

Example 1 Em-O was prepared from a silver halide emulsion Em-A by the following production method. (Preparation of Em-A) An aqueous solution 1 containing 1.0 g of low molecular weight gelatin having a weight average molecular weight of 15,000 and 1.0 g of KBr.
200 mL was kept at 35 ° C. and stirred vigorously. AgNO
30 mL of an aqueous solution containing 1.9 g of ₃ and 1.5 g of KBr and 0.7 g of low molecular weight gelatin having a weight average molecular weight of 15,000.
g of an aqueous solution containing 30 g was added by a double jet method over 30 seconds to form nuclei. At this time, the excess concentration of KBr was kept constant. 6 g of KBr was added, and the mixture was heated to 75 ° C. and aged. After ripening, add succinated gelatin to 35
g was added. The pH was adjusted to 5.5. ₃ AgNO 3
An aqueous solution of KBr and 150 mL of an aqueous solution containing 0 g were added over 16 minutes by a double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. further,
An aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 15 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at -25 mV.

132 mL of an aqueous solution containing 35 g of AgNO ₃
And an aqueous KBr solution were added over 7 minutes by the double jet method. KB so that the potential at the end of the addition becomes -20 mV.
The addition of the r aqueous solution was adjusted. After the temperature was adjusted to 40 ° C., 5.6 g of Compound 1 in terms of KI was added, and 64 mL of a 0.8 M aqueous sodium sulfite solution was further added. Further N
The pH was raised to 9.0 by adding an aqueous solution of aOH and held for 4 minutes to rapidly generate iodide ions.
Returned to 5. After the temperature was returned to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After completion of the addition, an aqueous solution 250 containing 70 g of AgNO ₃
mL and KBr aqueous solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, 80 g of lime-treated gelatin having a calcium concentration of 1 ppm was added, and the pH was adjusted to 5.8 and the pAg was adjusted to 8.7 at 40 ° C.

[0042]

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The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively. The above emulsion was heated to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm was added in terms of Ag, and shelled. Next, sensitizing dyes 1, 2, and 3 were added in the form of solid fine dispersion in the form of 5.85 × 10 ^-4 mol, 3.06 × 10 ^-4 mol, and 9.00 × 10 ^-6 mol, respectively, per mol of silver. did. Sensitizing dyes 1, 2,
The solid fine dispersion of No. 3 was prepared as follows. As shown in the preparation conditions in Table 1, after dissolving the inorganic salt in ion-exchanged water, adding a sensitizing dye, and dispersing the mixture at 2,000 rpm for 20 minutes using a dissolver blade at 60 ° C. Solid fine dispersions of dyes 1, 2, and 3 were obtained.

When the sensitizing dye was added and the adsorption of the sensitizing dye reached 90% of the amount adsorbed in the equilibrium state, calcium nitrate was added so that the calcium concentration became 250 ppm. The amount of sensitizing dye adsorbed is determined by separating the solid layer and the liquid layer by centrifugal sedimentation, measuring the difference between the amount of sensitizing dye added first and the amount of sensitizing dye in the supernatant, and adsorbing the sensitizing dye. The amount of dye was determined. After addition of calcium nitrate, potassium thiocyanate,
Chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea and compound 4 were added to optimize chemical sensitization.
N, N-dimethylselenourea is used in an amount of 3.
40 × 10 ^-6 mol was added. Compound 2 at the end of chemical sensitization
And Compound 3 were added to prepare Em-A.

[0045]

[Table 1]

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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(Preparation of Em-B) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 5 g, and the succinated gelatin was trimmed to give a trimellit with a weight average molecular weight of 100,000 containing 35 μmol methionine per gram. The compound 1 was replaced with 8.0 g of the compound 5 in terms of KI, and the amount of the sensitizing dye added before the chemical sensitization was changed with respect to the sensitizing dyes 1, 2, and 3. 6.50 × 10 ^-4 mol, 3.40 × 10 ^{-4 respectively}
Mol, 1.00 × 10 ⁻⁵ mol, and the amount of N, N-dimethylselenourea added during chemical sensitization is 4.
Em-B was prepared in the same manner as Em-A except that the amount was changed to 00 × 10 ⁻⁶ mol.

[0053]

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(Preparation of Em-C) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 1.5 g,
The succinated gelatin was replaced with phthalated gelatin having a weight average molecular weight of 100,000 and a phthalation rate of 97% containing 35 μmol / g of methionine, and Compound 1 was replaced by KI.
The amount of the sensitizing dye added before the chemical sensitization was 7.80 × 10 ⁻⁴ mol, 4.08 × 10 ^{4 with} respect to the sensitizing dyes 1, 2, and 3, respectively. ^-4 mol,
The amount was changed to 1.20 × 10 ⁻⁵ mol, and the amount of N, N-dimethylselenourea added during chemical sensitization was 5.00 × 1.
Except for changing the 0 ^-6 mol in the same manner as Em-A Em
C was prepared.

[0055]

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(Adjustment of Em-E) Weight average molecular weight 150
1.0 g of low molecular weight gelatin and 1.0 g of KBr
The aqueous solution containing 1200 mL was kept at 35 ° C. and stirred vigorously. 30 mL of an aqueous solution containing 1.9 g of AgNO ₃ , KBr
30 mL of an aqueous solution containing 1.5 g and 0.7 g of low molecular weight gelatin having a weight average molecular weight of 15,000 was added over 30 seconds by a double jet method to form nuclei. At this time, KB
The excess concentration of r was kept constant. Add 6 g of KBr and add 7 g
The temperature was raised to 5 ° C. and ripened. After ripening, 15 g of succinated gelatin and 20 g of the aforementioned trimellitated gelatin were used.
g was added. The pH was adjusted to 5.5. ₃ AgNO 3
An aqueous solution of KBr and 150 mL of an aqueous solution containing 0 g were added over 16 minutes by a double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. further,
An aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added by a double jet method over 15 minutes while accelerating the flow rate so that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was kept at −25 mV.

132 mL of an aqueous solution containing 35 g of AgNO ₃
And an aqueous KBr solution were added over 7 minutes by the double jet method. KB so that the potential at the end of the addition becomes -20 mV.
The addition of the r aqueous solution was adjusted. KBr was added and the potential was-
After the voltage was adjusted to 60 mV, 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was added. After the addition, an aqueous solution of low molecular weight gelatin having a weight average molecular weight of 15,000 and AgN
AgI fine particles having a sphere equivalent diameter of 0.008 μm prepared by mixing an O ₃ aqueous solution and a KI aqueous solution in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570 and immediately before addition thereof. 7. Emulsion was converted to KI.
While continuously adding 0 g, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes while keeping the potential at −60 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, 80 g of lime-treated gelatin having a calcium concentration of 1 ppm was added, and the pH and pAg were adjusted to 5.8 and 8.7 at 40 ° C., respectively.
Was adjusted.

The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively. Sensitizing dyes 1, 2, and 3 were changed to sensitizing dyes 4, 5, and 6, and the added amount was 7.73 ×
10 ^-4 mol, 1.65 × 10 ^-4 mol, 6.20 × 10 ^-5
Em-E was prepared in the same manner as in Em-A except that the moles were used.

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[0060]

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[0061]

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(Preparation of Em-F) Weight average molecular weight 150
1.0 g of low molecular weight gelatin and KBr of 1.00.
Keep 1200 mL of an aqueous solution containing 0 g at 35 ° C,
Stirred. AgNO_Three30 mL of an aqueous solution containing 1.9 g of
Low molecular weight of 1.5 g Br and weight average molecular weight of 15,000
Double-jet 30 mL of an aqueous solution containing 0.7 g of gelatin.
Nucleation was carried out by adding over a period of 30 seconds. this
At that time, the excess concentration of KBr was kept constant. Add 5g of KBr
The mixture was heated to 75 ° C. and aged. After aging, succulent
Add 20 g of gelatin and 15 g of phthalated gelatin
Was. The pH was adjusted to 5.5. AgNO _ThreeContains 30g
150mL of aqueous solution and KBr aqueous solution by double jet method
Added over 16 minutes. At this time, the silver potential is
-25 mV with respect to the metal electrode. Furthermore, AgNO
_ThreeAqueous solution containing 110 g and KBr aqueous solution
Flow rate so that the final flow rate is 1.2 times the initial flow rate by the
Accelerated and added over 15 minutes. At this time, the size
A 0.03 μm AgI fine grain emulsion having a silver iodide content of 3.
At the same time, accelerate the flow rate to 8% and add
The potential was kept at -25 mV.

132 mL of an aqueous solution containing 35 g of AgNO ₃
And an aqueous KBr solution were added over 7 minutes by the double jet method. After adjusting the potential to −60 mV by adding an aqueous KBr solution, 9.2 g of an AgI fine grain emulsion having a size of 0.03 μm in terms of KI was added. 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After completion of the addition, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and K
An aqueous Br solution was added over a period of 20 minutes while maintaining the potential at 60 mV. At this time, the yellow blood salt was added in an amount of 1. mol per mol of silver.
0 × 10 ^-5 mol was added. After washing with water, 80 g of lime-treated gelatin having a calcium concentration of 1 ppm was added, and the pH was adjusted to 5.8 and the pAg was adjusted to 8.7 at 40 ° C.

The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively. Sensitizing dyes 1, 2, and 3 were replaced with sensitizing dyes 4, 5, and 6, and the added amount was 8.50 × 1 each.
0 ^-4 mol, 1.82 × 10 ^-4 mol, subjected to chemical sensitization in the same manner as Em-B except that the 6.82 × 10 ^-5 mol,
Em-F was prepared.

(Preparation of Em-G) Weight average molecular weight 150
1.0 g of low molecular weight gelatin of 00 and 1.0 g of KBr
Was kept at 35 ° C. and stirred vigorously. AgNO ₃ chemical sensitization is an aqueous solution 3 containing 1.9 g
0 mL, KBr 1.5 g and weight average molecular weight 15,000
30 g of an aqueous solution containing 0.7 g of low-molecular-weight gelatin was added by a double jet method over 30 seconds to form nuclei. At this time, the excess concentration of KBr was kept constant. KB
r was added, and the temperature was raised to 75 ° C. to ripen. After the ripening, 15 g of the above-mentioned trimellitized gelatin and 20 g of the above-mentioned phthalated gelatin were added. The pH was adjusted to 5.5. 150 mL of aqueous solution containing 30 g of AgNO3 and K
An aqueous Br solution was added by the double jet method over 16 minutes. At this time, the silver potential is set to −25 with respect to the saturated calomel electrode.
mV.

Further, AgNO₃Containing 110 g of
And the aqueous solution of KBr, the final flow rate is the initial flow rate by the double jet method.
Over 15 minutes by accelerating the flow rate to 1.2 times the volume
Was added. At this time, AgI fine particles with a size of 0.03 μm
The emulsion was simultaneously run so that the silver iodide content was 3.8%.
And accelerate the addition, and keep the silver potential at -25 mV.
Was. AgNO₃132 mL of an aqueous solution containing 35 g of
The aqueous solution was added by the double jet method over 7 minutes. Electric
Adjust the addition of KBr aqueous solution so that the potential becomes -60 mV
did. AgI fine grain emulsion having a size of 0.03 μm
7.1 g was added in conversion. Benzothiosulfonic acid nato
1 mg of lithium was added, and the calcium concentration was 1 pp.
13 g of lime-processed gelatin were added. After the addition,
AgNO₃250 mL of an aqueous solution containing 70 g of
Apply the aqueous solution for 20 minutes while maintaining the potential at 60 mV.
Added. At this time, the yellow blood salt was added 1.0 × to 1 mol of silver.
10 ^-5Mole was added. After washing with water, calcium concentration 1
80 g of lime-treated gelatin at 40 ° C.
H was adjusted to 5.8 and pAg to 8.7.

The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively. Sensitizing dyes 1, 2, and 3 were changed to sensitizing dyes 4, 5, and 6, and the amount of each added was 1.00 × 1
0 ^-3 mol, 2.15 × 10 ^-4 mol, 8.06 × 10
Em-G was prepared by performing chemical sensitization in the same manner as in Em-C except that ^-5 mol was used.

(Preparation of Em-J) In the preparation of Em-B, sensitizing dyes added before chemical sensitization were changed to sensitizing dyes 7 and 8, and the added amount of each was 7.65 × 10 ^-4. Mole,
Em-J was prepared in the same manner as Em-B except that the amount was 2.74 × 10 ⁻⁴ mol.

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(Preparation of Em-L) (Preparation of silver bromide seed emulsion) Average sphere equivalent diameter: 0.6 μm, average aspect ratio: 9.0, 1.16 silver / kg emulsion
A silver bromide tabular emulsion containing 66 g of mol and gelatin was prepared. (Growth Step 1) 0.3 g of modified silicone oil was added to 1250 g of an aqueous solution containing 1.2 g of potassium bromide and succinated gelatin having a succination ratio of 98%. After the silver bromide tabular emulsion containing 0.086 mol of silver was added, the mixture was stirred at 78 ° C. An aqueous solution containing 18.1 g of silver nitrate and 5.4 mol of silver to which silver iodide fine particles having an equivalent sphere diameter of 0.037 μm were added were added. Further, at this time, an aqueous potassium bromide solution was added by a double jet while adjusting the pAg to 8.1. (Growth Process 2) After adding 2 mg of sodium benzenethiosulfonate, 0.45 g of 3,5-disulfocatechol disodium salt and 2.5 mg of thiourea dioxide were added.

Further, an aqueous solution containing 95.7 g of silver nitrate and an aqueous solution of potassium bromide were accelerated by a double jet to obtain an aqueous solution.
Added over minutes. At this time, the sphere equivalent diameter is 0.03
7 μm silver iodide fine grains were added in an amount of 7.0 mol with respect to the added silver. At this time, the amount of potassium bromide in the double jet was adjusted so that the pAg became 8.1. After the addition was completed, 2 mg of sodium benzenethiosulfonate was added.

(Growth Process 3) An aqueous solution containing 19.5 g of silver nitrate and an aqueous solution of potassium bromide were added by a double jet over 16 minutes. At this time, the amount of the aqueous potassium bromide solution was adjusted so that the pAg became 7.9. (Addition of poorly soluble silver halide emulsion 4) After adjusting the above host grains to 9.3 with an aqueous potassium bromide solution, 25 g of the above silver iodide fine grain emulsion having an equivalent sphere diameter of 0.037 μm was added within 20 seconds. Was added rapidly. (Formation 5 of outermost shell layer) An aqueous solution containing 34.9 g of silver nitrate was further added over 22 minutes.

This emulsion was tabular grains having an average aspect ratio of 9.8 and an average equivalent sphere diameter of 1.4 μm, and the average silver iodide content was 5.5 mol%.

(Chemical sensitization) After rinsing with water, the succination ratio was 98.
% Succinated gelatin and calcium nitrate at 40 ° C
And adjusted to pH 5.8 and pAg 8.7. The temperature was raised to 60 ° C., and a silver bromide fine grain emulsion of 0.07 μm was added to 5 × 10 ^−3.
After 20 minutes, sensitizing dyes 9, 10 and 11 were added. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea and compound 4 were added, and the mixture was optimally chemically sensitized. Compound 3 was added 20 minutes before the end of chemical sensitization, and Compound 7 was added at the end of chemical sensitization. Here, the optimal chemical sensitization is 1/100.
The sensitizing dye and each compound were added in an amount of 10 ^-1 to 1 per mol of silver halide so that the sensitivity at the time of exposure was the highest.
It means that it was selected from the added amount range of 0 ^-8 mol.

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[0077]

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(Preparation of Em-O) An aqueous gelatin solution (1250 mL of distilled water, 48 g of deionized gelatin, 0.75 g of KBr) was charged into a reaction vessel equipped with a stirrer, and the temperature of the solution was maintained at 70 ° C.

276 mL of an AgNO ₃ aqueous solution was added to this solution.
(Containing 12.0 g of AgNO ₃ ) in equimolar concentration with KBr
The aqueous solution was prepared by the controlled double jet addition method.
It was added over a period of minutes while maintaining the pAg at 7.26. Then, the temperature was lowered to 68 ° C., and 7.6 mL of 0.05% by mass thiourea dioxide was added.

Subsequently, 592.9 mL of an aqueous AgNO ₃ solution was added.
(Including 108.0 g of AgNO ₃ ) in equimolar KB
A mixed aqueous solution of r and KI (KI was 2.0 mol%) was added over 18 minutes and 30 seconds by a controlled double jet addition method while maintaining the pAg at 7.30. 5 minutes before the completion of the addition, 0.1% by mass of thiosulfonic acid was added to 18.
0 mL was added.

The obtained particles had an average sphere equivalent diameter of 0.19 μm.
m, cubic grains having an average silver iodide content of 1.8 mol%.
Was. Em-O is desalted by ordinary flocculation method
-After re-dispersing by washing with water, the pH is adjusted to 6.degree.
2. The pAg was adjusted to 7.6. Next, on Em-O
Then, the following spectral sensitization and chemical sensitization were performed. Destination
Sensitizing dyes 10, 11 and 12 per mole of silver
3.37 × 10 each ^-FourMol / mol, KBr 8.82 ×
10^-FourMol / mol, sodium thiosulfate 8.83 × 1
0^-FiveMol / mol, potassium thiocyanate is 5.95 × 1
0^-FourMol / mol and potassium chloroaurate 3.07 × 1
0^-FiveAging was performed at 68 ° C. by adding mol / mol. In addition,
The aging time is such that the sensitivity of 1/100 second exposure is the highest.
Was adjusted to

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For the preparation of (Em-D, H, I, K, M, N) tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. Further, according to the examples of JP-A-3-237450, gold sensitization was carried out in the presence of the spectral sensitizing dyes shown in Table 2 and sodium thiocyanate.
Sulfur sensitization and selenium sensitization are applied. Emulsions D, H,
I and K contain optimum amounts of Ir and Fe. Emulsion M, N
Is subjected to reduction sensitization during grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

[0086]

[Table 2]

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[0088]

[Table 3]

In Table 3, dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

1) Support The support used in this example was prepared by the following method. 1) First layer and undercoat layer For a polyethylene naphthalate (PEN) support having a thickness of 90 μm, the processing atmosphere pressure was applied to both surfaces of each support.
66 × 10 Pa, H ₂ O partial pressure in atmosphere gas 75%, discharge frequency 30 kHz, output 2500 W, processing intensity 0.5
Glow discharge treatment was performed at kV · A · min / m ² . On this support, a coating solution having the following composition was applied as a first layer for forming a back layer at a coating amount of 5 mL / m ² by using a bar coating method described in JP-B-58-4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0.5 parts by mass Water 49 parts by mass Polyglycerol polyglycidyl ether 0.16 parts by mass 0.1 parts by mass of poly (polymerization degree 20) oxyethylene 0.1 parts by mass Sorbitan monolaurate Wound around a stainless steel core, 110 ° C (Tg of PEN support: 119)
C) for 48 hours, heat-histored and annealed, followed by a bar coating method using a coating solution of the following composition as an undercoat layer for emulsion on the side opposite to the first layer side with the support interposed therebetween.
Coating was performed at a coating amount of 10 mL / m ² .

Gelatin 1.01 part by mass Salicylic acid 0.30 part by mass Resorcin 0.40 part by mass Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 part by mass Water 3.53 parts by mass Methanol 84.57 parts by mass n -Propanol 10.08 parts by mass Further, a second layer and a third layer described later are sequentially applied on the first layer, and finally, a color negative photosensitive material having a composition described later is overlaid on the opposite side across the support. Thus, a transparent magnetic recording medium having a silver halide emulsion layer was prepared.

2) Second layer (transparent magnetic recording layer) (i) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, S _BET : 39 m ² / g, Hc: 6.56 × 10 ⁴ A /
^{m, σs: 77.1Am 2 /kg,σr:37.4Am 2} /
kg) 1100 parts by mass, water 220 parts by mass, and 165 parts by mass of a silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] were added and kneaded well with an open kneader for 3 hours. . The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles. Furthermore, with the following prescription,
The mixture was kneaded again in an open kneader for 4 hours.

The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the following formulation was finely dispersed in a sand mill (1/4 G sand mill) at 2000 rpm for 4 hours. did. As the medium, glass beads having a diameter of 1 mm were used.

The above kneading liquid 45 g diacetyl cellulose 23.7 g methyl ethyl ketone 127.7 g cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation.

(Ii) Preparation of Intermediate Solution Containing Magnetic Substance 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After that, the mixture was stirred with a disper to prepare a "magnetic substance-containing intermediate liquid". An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation.

(A) Sumicorundum AA-1.5 (average primary particle size 1.5 μm, specific surface area 1.3 m ² / g) Preparation of particle dispersion Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone Co., Ltd.) 0.48 g Diacetyl cellulose solution 227.52 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) A ceramic-coated sand mill (1/1) 4G sand mill)
Finely dispersed at 0 rpm for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used. (B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used. This is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium,
The solids content is 30%.

(Iii) Preparation of Second Layer Coating Solution The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK -ST "[dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Co., Ltd.) diluent 203 g (solid content 20) %, Diluting solvent: methyl ethyl ketone / cyclohexanone = 1/1) methyl ethyl ketone 170 g cyclohexanone 170 g The coating solution obtained by mixing and stirring the above was applied with a wire bar so as to have an application amount of 29.3 mL / m ² . Drying is 1
Performed at 10 ° C. The thickness as a magnetic layer after drying is 1.0
μm.

3) Third layer (layer containing higher fatty acid ester slip agent) (i) Preparation of stock solution of slip agent The following solution A was heated and dissolved at 100 ° C, added to Solution A, and then dispersed with a high-pressure homogenizer. To prepare a stock solution of a slip agent.

[0100] A solution following compound 399 parts by weight _{C 6 H 13 CH (OH)} (CH 2) 10 COOC 50 H 101 The following compound 171 parts by weight _{n-C 50 H 101 O (} CH 2 CH 2 O) 16 H Cyclohexanone 830 Parts by mass A Liquid Cyclohexanone 8600 parts by mass.

(Ii) Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation. Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by mass Compound 8 2 .93 parts by mass

Embedded image 88.00 parts by mass of Sea Hosta KEP50 (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.) After stirring for 10 minutes in the above-mentioned formulation, the following is further added. Diacetone alcohol 252.93 parts by mass. While the above solution is ice-cooled and stirred, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
)) For 3 hours to obtain a spherical inorganic particle dispersion c1.
Was completed.

(Iii) Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation. XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass methyl ethyl ketone 120 parts by mass cyclohexanone 120 parts by mass (solid content: 20%, solvent: methyl ethyl ketone / cyclohexanone = 1 / 1). While cooling with ice and stirring, the ultrasonic homogenizer “SONIFIER450 (BRANSON
The mixture was dispersed for 2 hours by using the above method (manufactured by Co., Ltd.) to complete a spherical organic polymer particle dispersion c2.

(Iv) Preparation of Third Layer Coating Solution The following was added to 542 g of the above-mentioned slip agent dispersion stock solution to prepare a third layer coating solution.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g Dispersion [c1] of the Seahosta KEP5 53.1 g Dispersion [c2] of the spherical organic polymer particles 300 g FC431 2.65 g (3M Co., Ltd.) BYK310 5.3 g (manufactured by BYK Chemi Japan, solid content 25%).

The above third layer coating solution was applied on the second layer by 10.3
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of Photosensitive Layer Next, on the side opposite to the back layer obtained above, each layer having the following composition was applied in multiple layers to prepare a color negative film. (Composition of photosensitive layer) The main materials used in each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow coupler H: Gelatin hardener (specific compounds are listed below, followed by a number followed by a number, followed by a chemical formula).

The number corresponding to each component indicates the coating amount in g / m ² , and for silver halide, it indicates the coating amount in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.102 0.07 μm Silver Iodobromide Emulsion Silver 0.01 Gelatin 0.905 ExM-1 0.060 ExC-1 0.002 ExC -3 0.002 Cpd-2 0.001 F-8 0.010 HBS-1 0.005 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.060 Gelatin 0.445 ExF-1 0.002 F-8 0.012 Solid disperse dye ExF-7 0.130 HBS-1 0.074.

Third layer (intermediate layer) ExC-2 0.055 Cpd-1 0.093 Polyethyl acrylate latex 0.200 HBS-1 0.100 Gelatin 0.730 Fourth layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.582 Em-C silver 0.312 ExC-1 0.168 ExC-2 0.021 ExC-3 0.074 ExC-4 0.131 ExC-5 0.010 ExC-6 0.007 ExC-8 0.050 ExC-9 0.020 Cpd-2 0.025 Cpd-4 0.025 HBS-1 0.114 HBS-5 0.038 Gelatin 1.464.

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.440 Em-C Silver 0.415 ExC-1 0.144 ExC-2 0.078 ExC-3 0.020 ExC-40 .113 ExC-5 0.023 ExC-6 0.010 ExC-8 0.016 ExC-9 0.005 Cpd-2 0.036 Cpd-4 0.028 HBS-1 0.129 Gelatin 1.186 6th Layer (high-sensitivity red-sensitive emulsion layer) Em-A Silver 1.100 ExC-1 0.170 ExC-3 0.045 ExC-6 0.025 ExC-8 0.112 ExC-9 0.020 Cpd-20 0.064 Cpd-4 0.077 HBS-1 0.339 HBS-2 0.120 Gelatin 1.255.

Seventh layer (intermediate layer) Cpd-1 0.094 Cpd-6 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886 Eighth Layer (layer giving a multilayer effect to the red-sensitive layer) Em-J silver 0.283 Em-K silver 0.303 Cpd-4 0.028 ExM-2 0.115 ExM-3 0.018 ExM-4 0.029 ExY-1 0.020 ExY-4 0.026 ExC-7 0.022 HBS-1 0.094 HBS-3 0.003 HBS-5 0.030 Gelatin 0.600.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.339 Em-G silver 0.324 Em-I silver 0.077 ExM-2 0.358 ExM-3 0.050 ExY-1 0.024 ExC-7 0.010 HBS-1 0.098 HBS-3 0.010 HBS-4 0.077 HBS-5 0.548 Cpd-5 0.010 Gelatin 1.490 10th layer (medium sensitivity green) (Emulsion-sensitive layer) Em-F silver 0.448 ExM-2 0.032 ExM-3 0.029 ExM-4 0.034 ExY-3 0.007 ExC-6 0.010 ExC-7 0.016 ExC-8 0.010 HBS-1 0.060 HBS-3 0.002 HBS-4 0.030 HBS-5 0.016 Cpd-5 0.004 Gelatin 0.450.

Eleventh layer (high-sensitivity green-sensitive emulsion layer) Em-E silver 0.804 ExC-6 0.003 ExC-8 0.012 ExM-1 0.014 ExM-2 0.010 ExM-30 026 ExM-4 0.019 ExY-3 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 HBS-1 0.150 HBS-5 0.034 Polyethyl acrylate latex 0.095 Gelatin 0.949 12th layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.160 Solid disperse dye ExF-5 0.015 Oil-soluble dye ExF-6 0.012 HBS-1 049 gelatin 0.650.

Thirteenth layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.110 Em-M silver 0.324 Em-N silver 0.245 ExC-1 0.024 ExC-7 0.010 ExY-1 0.002 ExY-2 0.850 ExY-4 0.054 Cpd-2 0.104 Cpd-3 0.004 HBS-1 0.225 HBS-5 0.078 Gelatin 2.038 14th layer (high sensitivity blue Sensitive emulsion layer) Em-L silver 0.720 ExY-2 0.221 ExY-4 0.065 Cpd-2 0.073 Cpd-3 0.001 HBS-1 0.071 Gelatin 0.678.

Fifteenth layer (first protective layer) 0.07 μm silver iodobromide emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F -18 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 Gelatin 1.984 16th layer (second protective layer) H-1 0.400 B-1 (1.7 μm in diameter) ) 0.050 B-2 (1.7 μm in diameter) 0.150 B-3 0.050 S-1 0.200 Gelatin 0.750 Further, each layer may have a preservability, a processing property, a pressure resistance, and an antifungal property.
In order to improve antibacterial properties, antistatic properties and coatability, W-
1 to W-6, B-4 to B-6, F-1 to F
-19 and lead salts, platinum salts, iridium salts, and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the twelfth layer was dispersed by the following method. ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight aqueous solution) 0.376 kg F-15 (7% aqueous solution) 0.011 kg Water 4 0.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH) After the slurry having the above composition was coarsely dispersed by stirring with a dissolver, the peripheral speed was 10 m / min using an agitator mill LMK-4.
s, a discharge rate of 0.6 kg / min, a filling rate of zirconia beads having a diameter of 0.3 mm of 80%, and an absorbance ratio of the dispersion of 0.29.
To obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

Similarly, ExF-4 and ExF-7
Was obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by a microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

The compounds used for each layer are shown below.

[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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The above silver halide color photographic light-sensitive material is referred to as Sample 001.

In preparing the coating solution for the tenth layer of Sample 001, the following emulsion A was prepared and used. ExM-2 20.0
g, ExM-3 18.1g, ExM-4 21.3g, ExY-3 4.4g, ExC-6 6.3
g, ExC-7 10.0g, ExC-8 6.3g, HBS-1 37.5g, HBS-3 1.3
g, HBS-4 18.8g, HBS-5 10.0g, Cpd-5 2.5g, W-5 20.0g
Was dissolved in 200 cc of ethyl acetate at 68 ° C., mixed with a 10% aqueous gelatin solution and emulsified with a homogenizer, and then ethyl acetate was removed under reduced pressure to obtain an emulsion A. Emulsion A ExM-3 was used as the yellow colored magenta coupler of the present invention (1), (2),
Emulsions B, C, D, and E were prepared in the same manner except that (5) and (10) were replaced by equimolar amounts.

These emulsions were aged at 40 ° C. for 48 hours and those not aged. Emulsions BE instead of Emulsions A used in preparing the tenth layer of Sample 001
And the samples 002 to 005 were obtained in the same manner as in Sample 001, except that the tenth layer was formed by using.

The sample was exposed for 1/100 second through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge. Developed by Fuji Photo Film Co., Ltd. automatic developing machine F
Performed as follows using P-360B. Remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in Publication Technique No. 94-4992 (issued by the Invention Association).

The processing steps and the composition of the processing solution are shown below. (Processing process) Process Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C ─ 5L fixing (2) 50 38.0 ℃ 8mL 5L Washing with water 30sec 38.0 ℃ 17mL 3L stable (1) 20sec 38.0 ℃ ─ 3L stable (2) 20sec 38.0 ℃ 15mL 3L Drying 1min 30sec 60.0 ℃ The stabilizing solution and the fixing solution are counter-current systems from (2) to (1) per 1.1 m of 35 mm width (corresponding to one shot every 24), and the overflow solution of the washing water is all introduced into the fixing bath (2). . The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 2.5 mL, 2.0 mL, and 1.1 mm, respectively, of the photosensitive material having a width of 35 mm. 2.0 mL. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The opening area of the above processor is 10 to 10 with the color developing solution.
0cm ² , 120cm ^{2 for} bleaching solution, about 1 other processing solution
00 cm ² . The composition of the treatment liquid is shown below.

(Color developing solution) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy -6-methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino Aniline sulfate 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenishing solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Add water 1.0L 1.0L pH [adjusted with aqueous ammonia] 4.6 4.0 (Fixing (1) tank liquid) 5:95 (volume ratio) mixture of the above bleaching tank liquid and the following fixing tank liquid .

(PH 6.8) (Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 721 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 1339 Water was added to 1.0 L 1.0 L pH [adjusted with aqueous ammonia and acetic acid] 7.4.45.

(Washing water) Tap water was converted to H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L
Was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Measuring the magenta concentration of the sample after adding 1.0 L pH 8.5 with water,
The magenta densities of the respective samples were compared at an exposure amount where the magenta density of No. 1 indicated a density of fog + 1.0. Table 4 shows the decrease in color density due to the aging of the emulsion at 40 ° C. as a relative value to the case where the aging did not proceed. The larger the value, the better.

[0140]

[Table 4]

From Table 4, it can be seen that the sample using the compound of the present invention has a small change in photographic properties when the emulsion is aged, and is thus preferable. The photographic coupler of the present invention was applied to the eighth layer and the ninth layer.
A sample used for the layer and the eleventh layer was prepared, and an experiment similar to the experiment performed for the above-described tenth layer was performed. The change in photographic properties caused by the above was small and a favorable result was obtained.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masaaki Tsukase 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Photo Film Co., Ltd. (Reference) 2H016 BF04 BG01 BG02 BH01

Claims (2)

[Claims] 1. A photographic coupler represented by the following general formula (I). Embedded image In the formula, R ₁ and R ₂ represent a substituent, R ₃ is an alkyl group,
Represents an alkenyl group, an alkynyl group or an aryl group. L represents -CO-, and Q represents a hydrogen atom, a halogen or an alkoxy group. Here, k represents an integer of 1 to 5, m represents an integer of 0 to 5, and n represents an integer of 0 or 1. R when k is 2 or more
₁ may be the same or different, and when m is 2 or more, R
₂ may be the same or different. 2. A silver halide color photographic light-sensitive material comprising, on a support, at least one light-sensitive layer containing the photographic coupler according to claim 1.