JPH0713281A - Silver halide emulsion - Google Patents

Abstract

PURPOSE:To enhance sensitivity and stability of a latent image by allowing a specified compound to be adsorbed to the surfaces of flat silver halide grains. CONSTITUTION:The <=90% areas of the, edge parts and all opposite parallel principal faces to the surfaces of flat silver halied grains are crystal faces (111) and the surfaces adsorbs the compound represented by formulae I and II in which each of R1-R4 is H, alkyl, alkenyl, alkynyl, aryl, or a heterocyclic group; each of R5-R8 is a substituent; each of L1 and L2 is a methine group; Z is an 0, S, or Se atom, or the like; each of R9 and R10 is H, alkyl, or the like; Z2 is an atomic group necessary to form an imidazole ring; R12 is alkyl; R13 is H or alkylene necessary to combine with R12 to form a ring; and R11 is a monocyclic or bicyclic aryl group.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide emulsion, and more particularly to a silver halide emulsion having high sensitivity and excellent latent image stability.

[0002]

BACKGROUND OF THE INVENTION In recent years, the demand for higher sensitivity in photographic light-sensitive materials has become stronger and stronger, and the demand for improved storage stability for maintaining these performances for a long time has also increased.

Heretofore, in the art, prevention of electron-hole recombination using an internal high iodine type core-shell emulsion, improvement of latent image forming efficiency by selective chemical sensitized nucleus growth, and use of a supersensitizer have been used. Various sensitizing technologies have been studied such as improving the electron transfer efficiency from the sensitizing dye to the silver halide crystal, but in order to satisfy the demand for higher sensitivity in the future, more comprehensive multi-technology Will be required. Moreover, the stability of the formed latent image was not sufficient in the above examination.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide means for obtaining a silver halide emulsion having high sensitivity and excellent latent image stability.

[0005]

In the silver halide emulsion of the present invention which achieves the above object, at least 70% of the total projected area of the silver halide grains contained in the emulsion is tabular silver halide, and 90% or less of all the parallel main planes of the silver halide grains facing each other and the faces of the edge portions are (111) crystal faces, and the surface of the tabular silver halide grains has the following general formula [I] and / or The compound represented by [II] is adsorbed.

[0006]

[Chemical 3]

[In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ and R 4
₇ and R ₈ each represent a substituent. L ₁ and L ₂ each represent a methine group, Z is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —C (R ₉ ) (R ₁₀ ) — or —N.
Represents (R ₉ )-. R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Also, R ₁ and R ₂ , R ₃ and R
₄ , R ₅ and R ₆ , R ₇ and R ₈ , and R ₉ and R ₁₀ may be bonded to each other to form a ring. ]

[0008]

[Chemical 4]

Z ₂ represents an atomic group necessary for forming an imidazole nucleus. R ₁₂ is an alkyl group (the carbon chain is S,
It may be replaced by a hetero atom such as N or O). R ₁₃ represents a hydrogen atom or an alkylene group necessary for forming a ring by bonding with R ₁₂ . R ₁₁ represents up to a bicyclic aryl group.

The present invention will be described below. (Silver Halide Grains) The silver halide grains constituting the silver halide emulsion according to the present invention mainly have two or more parallel planes, preferably an even number, and particularly preferably two parallel planes. It has a plane.

In the present invention, it is especially important that 90% or less of all the parallel main planes of the tabular silver halide grains facing each other and the planes of the edge portions are (111) crystal planes. Usually, the main plane of tabular silver halide grains is (11
1) surface. It is well known that the crystal plane of the edge portion other than the main plane is usually only the (111) plane. That 90% or less of the face of the edge portion is the (111) crystal face means that the edge portion has more than 10% of crystal faces other than the (111) face. In the present invention, the (100) plane is preferable as a crystal plane other than the (111) plane. In the present invention, the (111) crystal plane of the edge portion surface is preferably 75% or less. That is, it is particularly preferable that more than 25% of crystal planes other than the (111) plane exist. And this is (10
It is preferably 0) plane.

In the present invention, the method for measuring the crystal plane of the edge portion of the tabular silver halide grain is described in Journal.
al of Imaging Science, vo
l. 29, No 5, Sept. 1985, SPRIN
GFIELD US P.I. The method reported by Tani et al. In 165-171 can be used. In the present invention, the (111) crystal plane of the edge portion of the tabular silver halide grain is 90% or less, preferably 75%.
In the following, various known methods can be used in combination. Particularly, by setting the pH during tabular silver halide grain formation to near neutral, preferably pH 4 or more and 9 or less, or crystal This can be achieved by forming tabular silver halide grains in the presence of a face-selective adsorption type compound. As the compound, a sensitizing dye for photography or a nitrogen-containing heterocyclic compound is useful.

The silver halide grains of the present invention have any silver halide composition except that they contain silver iodide. For example, each of the above embodiments is composed of any composition such as silver iodobromide, silver chloroiodobromide, silver chloroiodobromide and a mixture thereof, and silver iodobromide is particularly preferably used.

The silver halide emulsion of the present invention preferably comprises silver iodobromide having an average silver iodide content of 4 to 20 mol%, particularly preferably 5 to 15 mol%. .

To form the light-sensitive material of the present invention, an emulsion other than the emulsion of the present invention can be used in combination, if necessary. In this case, the silver halide composition of the emulsion used in combination is arbitrary, and for example, silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, silver chloride, or the like, or a mixture thereof is used. Good. Silver halide grains are generally prepared and used in the form of silver halide emulsions containing the grains. At least 70% of the total projected area of the silver halide grains used in the present invention are tabular grains.

In the present invention, the projected area of a grain can be calculated from the sum of the grain areas. The projected area for obtaining the total projected area is, in each case, obtained by magnifying a silver halide crystal sample distributed on the sample stage to an extent of 10,000 to 50,000 times with an electron microscope so that the grains do not overlap each other. Shoot,
It can be obtained by actually measuring the projected area on the print (the number of measurement is 1000 or more indiscriminately).

Particularly preferred highly monodisperse emulsions of the present invention are those in which the breadth of distribution defined by (grain size standard deviation) / (mean grain diameter) × 100 = (breadth of distribution)% is 20% or less. Is. The particle size is a diameter when a projected image of the particle is converted into a circular image having the same area.

Here, the particle size measuring method is based on the above-mentioned measuring method. The average particle size is a simple average. (Average grain size) = Σd ₁ n ₁ / Σn ₁ The average grain size of the silver halide emulsion grains used in the present invention is
The thickness is preferably 0.1 to 5.0 μm, more preferably 0.15 to 3.0 μm, and particularly preferably 0.2 to
It is 2.0 μm.

Monodisperse emulsions are preferable because they have good graininess and, at the same time, have excellent image sharpness in the size range where light scattering is small. Regarding the monodisperse emulsion, for example, JP-A-54-48521, JP-A-54-99419,
56-16124, 56-78831, U.S. Pat. No. 4,444,877, JP-A-57-182730.
No. 58-49938, No. 58-37635, U.S. Pat. No. 4,446,228, JP-A-58-1065.
No. 32, No. 58-107530, No. 58-12653
No. 1, 58-149037, 59-10947.
No. 59, No. 29-29243, No. 59-72440, No. 59-140443, No. 59-148049, No. 5
No. 9-177535, No. 59-152438 and the like. (Compound represented by the general formula [I]) The compound represented by the general formula [I] of the present invention (hereinafter, also referred to as the compound of the present invention) is

[0020]

[Chemical 5]

[Wherein R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ and R 4
₇ and R ₈ each represent a substituent. L ₁ and L ₂ each represent a methine group, Z is an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —C (R ₉ ) (R ₁₀ ) — or —N.
Represents (R ₉ )-. R ₉ and R ₁₀ each represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. Also, R ₁ and R ₂ , R ₃ and R
₄ , R ₅ and R ₆ , R ₇ and R ₈ , and R ₉ and R ₁₀ may be bonded to each other to form a ring. In the general formula [I], the alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ includes methyl, ethyl, propyl, i-propyl, butyl, t-butyl, pentyl, cyclopentyl, hexyl, Cyclohexyl, octyl, dodecyl and the like can be mentioned. These alkyl groups further include halogen atoms (eg chlorine, bromine, fluorine etc.), alkoxy groups (eg methoxy, ethoxy, 1,1-dimethylethoxy, hexyloxy, dodecyloxy etc.), aryloxy groups (eg phenoxy, naphthyl). Oxy, etc.), aryl groups (eg phenyl, naphthyl etc.), alkoxycarbonyl groups (eg methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, 2-ethylhexylcarbonyl etc.), aryloxycarbonyl groups (eg phenoxycarbonyl, naphthyloxycarbonyl etc.), Alkenyl groups (eg vinyl, allyl etc.), heterocyclic groups (eg 2-pyridyl, 3-pyridyl, 4-pyridyl, morpholyl, piperidyl, piperazyl, pyrimidyl, pyrazolyl, furyl etc.), alkynyl groups (eg Propagyl), amino group (eg, amino, N, N-dimethylamino, anilino, etc.), hydroxyl group, cyano group, sulfo group, carboxyl group, sulfonamide group (eg, methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, octyl) Sulfonylamino, phenylsulfonylamino, etc.) and the like.

Examples of the alkenyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include vinyl and allyl. Examples of the alkynyl group represented by R ₁ , R ₂ , R ₃ and R ₄ include propargyl. R ₁ , R ₂ ,
Examples of the aryl group represented by R ₃ and R ₄ include phenyl and naphthyl. R ₁ , R ₂ , R ₃ , R
Examples of the heterocyclic group represented by ₄ include a pyridyl group (eg, 2-pyridyl, 3-pyridyl, 4-pyridyl, etc.),
Examples thereof include thiazolyl group, oxazolyl group, imidazolyl group, furyl group, thienyl group, pyrrolyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, selenazolyl group, sulforanyl group, piperidinyl group, pyrazolyl group and tetrazolyl group.

The above alkenyl group, alkynyl group, aryl group and heterocyclic group are all the same as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups shown as the substituents of the alkyl groups. It can be replaced by a group.

The substituent represented by R ₅ , R ₆ , R ₇ and R ₈ is an alkyl group, an alkenyl group, an alkynyl group,
Aryl group, heterocyclic group, halogen atom, alkoxy group,
Aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, sulfonamide group, sulfamoyl group, ureido group, acyl group, carbamoyl group, amide group, sulfonyl group, amino group, cyano group, nitro group, carboxyl group, hydroxyl group, Represents a hydrogen atom and the like. These groups can be substituted with the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups shown as the substituents of the alkyl groups.

The ring formed by R ₁ and R ₂ is, for example, benzene, naphthalene, thiophene, pyridine, furan, pyrimidine, cyclohexene, pyran, pyrrole,
Examples include rings such as pyrazine and indole.

Examples of the ring which can be formed by R ₃ and R ₄ include rings such as piperidine, pyrrolidine, morpholine, pyrrole, pyrazole, piperazine and the like.

Examples of the ring formed by R ₉ and R ₁₀ include rings such as cyclopentane and cyclohexane.

The above rings can be substituted with the same groups as the alkyl groups represented by R ₁ , R ₂ , R ₃ and R ₄ and the groups mentioned as the substituents of the alkyl groups.

The methine group represented by L ₁ and L ₂ may have a substituent, and examples of the substituent include an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group and an aryloxy group. A carbonyl group and the like can be mentioned. These groups further include R ₁ , R ₂ ,
The alkyl group represented by R ₃ and R ₄ and a group similar to the group shown as the substituent of the alkyl group can be substituted.

Specific examples of the compound represented by the general formula [I] used in the present invention are shown below, but the present invention is not limited thereto.

[0031]

[Chemical 6]

[0032]

[Chemical 7]

[0033]

[Chemical 8]

[0034]

[Chemical 9]

[0035]

[Chemical 10]

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

Specific synthesis examples of the compound of the present invention are shown below, but other compounds can be easily synthesized by the same method.

Synthesis Example (Synthesis of Exemplified Compound 4) To 14.9 g of 2-methylbenzothiazole were added 17.7 g of p-diethylaminobenzaldehyde, 6 g of sodium hydride (60% hard oil) and 60 cc of dimethylformamide, and the mixture was stirred at room temperature. The reaction was carried out for 30 minutes. The reaction solution was poured into water and the precipitated solid was filtered. The solid was dried and then recrystallized from methanol to obtain the desired product. Yield 19.4
g (63%).

Next, the compound represented by the general formula [II] will be described.

[0042]

[Chemical 14]

Z ₂ represents an atomic group necessary for forming an imidazole nucleus. R ₁₂ is an alkyl group (the carbon chain is S,
It may be replaced by a hetero atom such as N or O). R ₁₃ represents a hydrogen atom or an alkylene group necessary for forming a ring by bonding with R ₁₂ . R ₁₁ represents up to a bicyclic aryl group.

Specific examples of the imidazole nucleus formed by Z ₂ in the general formula [II] are as follows. Imidazole; 1-Alkylimidazole; 1-Alkyl-4-phenylimidazole; 1-Alkyl-
Imidazoles such as 4,5-dimethylimidazole. Benzimidazole; 1-alkylbenzimidazole;
1-alkyl-5,6-dichlorobenzimidazole;
1-tolyl-5-chlorobenzimidazole; 1-alkyl-5-bromobenzimidazole; 1-alkyl-
5-chlorobenzimidazole; 1-alkyl-5-fluorobenzimidazole; 1-alkyl-5-thiocyanite benzimidazole; 1-alkyl-5-acetyl-6-chlorobenzimidazole; 1-phenyl-
5,6-Dichlorobenzimidazole; 1-alkyl-
5-trifluoromethylbenzimidazole; 1-alkyl-5-methylsulfonylbenzimidazole; 1-
Alkyl-5-methoxycarbonylbenzimidazole; 1-alkyl-5-ethoxycarbonylbenzimidazole; 1-alkyl-5-carboxybenzimidazole; 1-alkyl-5-benzoylbenzimidazole; 1-alkyl-5-acetylbenzimidazole, etc. Benzimidazole. 1-alkylnaphtho [1,
2-d] imidazole; 1-alkylnaphtho [2,1-
d] imidazole; 1-alkylnaphtho [2,3-d]
The carbon chain of the 1-alkyl group such as naphthimidazole such as imidazole may be replaced by a hetero atom such as S, N, O.

The alkyl group represented by R ₁₂ may have a carbon chain substituted with a hetero atom such as O, N, S or may be branched and has an unsaturated bond in the alkyl chain. May be. More preferably, it has 10 or less carbon atoms, and has an atom or a substituent such as sulfo, aryl, carboxy, amino (primary, secondary, tertiary), alkoxy, aryloxy, hydroxy, alkoxycarbonyl, or cyano. May be. (For example, methyl group, ethyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, benzyl group, phenethyl group, carboxyethyl group, carboxymethyl group, dimethylaminopropyl group, methoxyethyl group, phenoxypropyl group, methylsulfonylethyl group. , Pt-butylphenoxyethyl group, cyclohexyl group, octyl group, decyl group, carbamoylethyl group, sulfophenethyl group, sulfobenzyl group, 2-hydroxy-3-sulfopropyl group, ethoxycarbonylethyl group, 2,3- Disulfopropoxypropyl group, sulfopropoxyethoxyethyl group, trifluoroethyl group, carboxybenzyl group, cyanopropyl group, p-carboxyphenethyl group, ethoxycarbonylmethyl group, pivaloylpropyl group, propionylethyl group Group, anisyl group, acetoxyethyl group, benzoyloxypropyl group, chloroethyl group, morpholinoethyl group, acetylaminoethyl group, N-ethylaminocarbonylpropyl group, allyl group, 2-butenyl group, 2-propynyl group, cyanoethyl group, etc. ).

The aryl group represented by R ₁₁ is preferably a bicyclic aryl group, and specific examples thereof include a phenyl group, a naphthyl group, a tolyl group, an anisyl group,
Examples thereof include carboxyphenyl group, methoxycarbonylphenyl group, chlorophenyl group, xylyl group, thienyl group and furyl group. When R ₁₃ is combined with R ₁₂ to form a ring, it is particularly preferable to form a 5-, 6- or 7-membered ring.

Specific examples of the compound represented by the general formula [II] are shown below, but the present invention is not limited thereto.

[0048]

[Chemical 15]

[0049]

[Chemical 16]

[0050]

[Chemical 17]

The compound of the present invention (the compound represented by the general formula [I] and / or [II]) is added in an amount of 2 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide. Is preferable, and 2 × 10 ^{−7 to} 5 × 10 ⁻³ is more preferable.

As a method for adding the compound of the present invention to a silver halide emulsion, a method well known in the art can be used. For example, the compound can be dispersed directly in the emulsion, or dissolved in a water-soluble solvent such as pyridine, methanol, ethanol, methyl cellosolve, acetone, fluorinated alcohol, dimethylformamide, or a mixture thereof, or diluted with water. Alternatively, it can be dissolved in water and added to the emulsion in the form of a solution. Ultrasonic vibration can also be used in the melting home.

Further, the compound of the present invention is prepared according to US Pat.
As disclosed in JP-B-46-24185, a method of dissolving in a volatile organic solvent as described in JP-A-9-987, and adding a dispersion prepared by dispersing this solution in a hydrophilic colloid to an emulsion. Alternatively, a method in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved and the dispersion is added to the emulsion is also used.

Further, the compound of the present invention can be added to the emulsion in the form of a dispersion prepared by an acid solution dispersion method.

Of the compounds represented by the general formula [I] according to the present invention, those in which Z is an oxygen atom are preferably used. Further, those in which R ₃ and R ₄ form a morpholine ring are more preferably used. That is, a compound in which Z is an oxygen atom and R ₃ and R ₄ form a morpholine ring is most preferably used.

(Sensitizing dye, etc.) In the silver halide, an appropriate sensitizing dye is added in an amount of 5 × 10 ^{−5 to} 3 with respect to 1 mol of the silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. × 10
^-3 mol may be added for optical sensitization. Various kinds of sensitizing dyes can be used, and one kind or a combination of two or more kinds of sensitizing dyes can be used.

Examples of the sensitizing dye that can be advantageously used in the present invention include the followings.

That is, as the sensitizing dye used in the blue-sensitive silver halide emulsion, for example, West German Patent 929,080.
U.S. Pat. Nos. 2,231,658 and 2,493,7
No. 48, No. 2,503,776, No. 2,519,00
No. 1, No. 2,912,329, No. 3,656,959
Issue No. 3,672,897 Issue No. 3,694,217
No. 4,025,349, No. 4,046,572
U.S. Pat. No. 1,242,588, Japanese Patent Publication No.44-14
Examples thereof include those described in No. 030 and No. 52-24844. In particular, the dye disclosed in Japanese Patent Application No. 3-343348 is preferably used.

The sensitizing dye used in the green-sensitive silver halide emulsion is, for example, US Pat. No. 1,939,201.
No. 2,072,908, No. 2,739,149
No. 2,945,763, British Patent 505,979.
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanines as described in JP-A No. 1994-242242.

Further, as the sensitizing dye used in the red-sensitive silver halide emulsion, for example, US Pat. No. 2,269,23 is used.
No. 4, No. 2,270,378, No. 2,442,710
Representative examples thereof include cyanine dyes, merocyanine dyes, and complex cyanine dyes described in JP-A Nos. 2,454,629 and 2,776,280. Furthermore, US Pat. No. 2,213,99
No. 5, No. 2,493,748, No. 2,519,001
Cyanine dyes, merocyanine dyes or complex cyanine dyes such as those described in U.S. Pat. No. 5,839,095 and West German Patent 929,080 can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone,
Also, these may be used in combination. If necessary, optical sensitization may be performed in a desired wavelength range by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination.

A typical example of a particularly preferable spectral sensitization method is, for example, JP-B-4 relating to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine.
No. 3-4936, No. 43-22884, No. 45-18
No. 433, No. 47-37443, No. 48-28293.
No. 49-6209, No. 53-12375, JP-A Nos. 52-23931, 52-51932, 54.
-80118, 58-153926, 59-1
16646, the same 59-116647, etc. are mentioned.

The combination of carbocyanine having a benzimidazole nucleus with another cyanine or merocyanine is described in, for example, Japanese Patent Publication No. 45-25831.
No. 47, No. 47-11114, No. 47-25379, No. 48-38406, No. 48-38407, No. 54-.
34535, 55-1569, JP-A-50-33.
No. 220, No. 50-38526, No. 51-10712
No. 7, No. 51-115820, No. 51-135528
No. 52-104916, No. 52-104917, and the like.

Further, as a combination of benzoxazolocarbocyanine (oxacarbocyanine) and other carbocyanine, for example, Japanese Patent Publication No. 4-3275.
3, No. 46-11627, and JP-A No. 57-1483.
And those relating to merocyanine include, for example, Japanese Examined Patent Publication Nos. 48-38408, 48-41204 and 50-
40662, JP-A-56-25728, 58-1
0753, 58-91445, 59-1166.
No. 45, No. 50-33828 and the like.

The combination of thiacarbocyanine with other carbocyanines includes, for example, Japanese Patent Publication Nos. 43-4932, 43-4933, and 45-26.
470, 46-18107, 47-8741
JP-A-59-114533 and the like, and JP-B-4 using a zeromethine or dimethine merocyanine, monomethine or trimethine cyanine and styryl dye.
The method described in 9-6207 can be advantageously used.

To add these sensitizing dyes, a dye solution is previously dissolved in a hydrophilic organic solvent such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659. Used. The silver halide emulsion may be added at any time from the start of chemical ripening, during ripening, and at the end of ripening, and in some cases, it may be added immediately before the emulsion coating.

In the present invention, a particularly preferred combination of sensitizing dyes is the combination disclosed in Japanese Patent Application No. 3-109171. That is, a combination of at least one of the asymmetric cyanine dyes and a symmetric cyanine dye having each of the heterocyclic nuclei constituting the dye is preferable.

In the case where a silver halide emulsion of the present invention is used to form a light-sensitive material, silver halide emulsions other than the emulsion of the present invention which are used as necessary are generally preferably used after physical ripening and chemical ripening. In general, spectral sensitization is used depending on the photosensitive layer of each color. Additives that can be used in such a process are Research Disclosure No. 17643, No. 18716 and No. Thirty
8119 (hereinafter, RD17643 and RD187, respectively)
16 and RD308119).
The table below shows the locations.

Item RD308119 RD17643 RD18716 Page / Item page Page Chemical sensitizer 996 III-A 22 648 Antifoggant 998 VI 24-25 649 Stabilizer 998 VI 24-25 649 In the practice of the present invention Known photographic additives that can be used are also exemplified in the above-mentioned Research Disclosure. Shown below are the relevant locations.

Item RD308119 RD17643 RD18716 Page / Item page Page Color turbidity inhibitor 1002 VII-I Item 25 650 Dye image stabilizer 1002 VII-J Item 25 Whitening agent 998 V 24 Ultraviolet absorber 1003 VIIIC, 25 -26 XIIIC paragraph Light absorber 1003 VIII 25-26 Light-scattering agent 1003 VIII Filter dye 1003 VIII 25-26 Binder 1003 IX 26 651 Static inhibitor 1006 XIII 27 650 Hardener 1004 X 26 651 Plasticizer 1006 XII 27 6 Agent 1006 XII 27 650 Activator / Coating aid 1005 XI 26-27 650 Matting agent 1007 XVI Developer 1011 XXB (Contained in light-sensitive material) Silver halide milk of the present invention As the agent, various couplers can be used depending on the color to be developed in the photosensitive layer of each color, and specific examples thereof are described in the above-mentioned Research Disclosure. Shown below are the relevant locations.

Item RD308119 RD17643 page / item item Yellow coupler 1001 VII-D item VII C to G item Magenta coupler 1001 VII-D item VII C to G item Cyan coupler 1001 VII-D item VII C to G colored item Coupler 1002 VII-G term VII G term DIR coupler 1001 VII-F term VII F term BAR coupler 1002 VII-F term Other useful residue releasing coupler 1001 VII-F term Alkali-soluble coupler 1001 VII-E term of the present invention When various additives are used in a light-sensitive material using a silver halide emulsion, these can be added by the dispersion method described in RD308119XIV.

In the present invention, the above-mentioned RD17643 is used.
28, RD 18716, pages 647-8 and RD30.
The supports described in XVII of 8119 can be used.

The light-sensitive material using the silver halide emulsion of the present invention can be provided with auxiliary layers such as the filter layer and the intermediate layer described in the above-mentioned item RD308119VII-K.

The light-sensitive material using the silver halide emulsion of the present invention can have various layer constitutions such as the forward layer, the reverse layer and the unit constitution described in the above-mentioned item RD308119VII-K.

The present invention is represented by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. It can be applied to various color light-sensitive materials.

The light-sensitive material using the silver halide emulsion of the present invention is described in RD17643, pages 28 to 29, RD18716.
And the conventional method described in XIX of RD308119.

[0077]

EXAMPLES The present invention will be specifically described below with reference to examples. The present invention is not limited to these examples.

(Preparation of Seed Emulsion) A hexagonal tabular seed emulsion was prepared by the following method. <Solution A> ossein gelatin 4.26g Distilled water 1700ml polyisopropylene - polyethyleneoxy - disuccinic 10% ester sodium salt aqueous ethanol _{0.4ml KBr 1.9g 10% H 2 SO} 4 10.2ml < solution B> 1 255 N AgNO ₃ aqueous solution 497 ml <Solution C> KBr 84.6 g KI 7.5 g Distilled water to 604 ml <Solution D> 1.75 N KBr aqueous solution The following silver potential control amount at 35 ° C, Japanese Patent Publication No. 58-58288. 58-
Using the mixing stirrer described in the specification of No. 58289, 9.08 ml of each of solution B and solution C was added to solution A by the simultaneous mixing method over a period of 2 minutes to perform nucleation.

After stopping the addition of solution B and solution C, 3
Take 0 minutes to raise the temperature of solution A to 60 ° C.,
The solutions B and C were again mixed by the simultaneous mixing method at 19.5 m each.
It was added at a flow rate of 1 / min for 25 minutes. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mV using the solution D. After the addition was completed, the pH was adjusted to 6 with 3% KOH, an aqueous solution containing 21.3 g of ossein gelatin was added, and seed emulsion E was added.
It was set to M-0. The seed emulsion EM-0 thus prepared was
90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular plate has an average thickness of 0.07 μm and an average diameter (converted to a circle diameter). It was found to be 0.5 μm by electron microscope observation. Seed emulsion EM-0 contained 0.6215 mol of silver halide in 4612 ml of emulsion.

(Preparation of tabular emulsion EM-1) 4 shown below
A tabular silver iodobromide emulsion EM-1 containing 2.46 mol% AgI was prepared by using the various solutions. <Solution A> Seed emulsion EM-0 .6215 mol (4612ml) <solution B> 3.50N to 1467Ml with AgNO ₃ aqueous 1467Ml <solution C> KBr 599g KI 17.0g distilled water <solution D> 1.75 N KBr aqueous solution The following silver potential control amount

At 60 ° C, Japanese Patent Publication No. 58-58288
No. 58-58289, the total amount of Solution B and Solution C in Solution A is required to be 95.14 minutes at a rate of 15.45 ml / min by the simultaneous mixing method. Additive growth was performed. During this period, the silver potential was controlled to be +28.0 mV by using the solution D. After the completion of the addition, water was washed by a precipitation method (using phenylcarbamoylated gelatin) according to a conventional method to remove excess salts, and an aqueous gelatin solution containing 47.57 g of ossein gelatin was added, followed by redispersion with stirring.

This emulsion EM-1 contained 5.756 mol of silver halide in 2445 ml of emulsion, and the pH of the emulsion solution at 40 ° C. was adjusted to 5.8 and pAg was adjusted to 8.06. About 3000 particles of EM-1 were observed and measured by an electron microscope to analyze the shape. The results are shown in Table 1.

(Preparation of tabular emulsion EM-2) A tabular silver iodobromide emulsion EM-2 containing 2.0 mol% AgI was prepared using the following four kinds of solutions. <Solution A> Ocein gelatin 7.7 g Seed emulsion (EM-0) 0.02875 mol Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% aqueous ethanol solution 2.0 ml Distilled water is added to make 800 ml <. Solution B> 1.5 N AgNO ₃ aqueous solution 183 ml <Solution C> NBr 91 g KI 2.60 g Ocein gelatin 10.98 g Distilled water is added to make 548.4 ml <Solution D> 3.5 N KBr aqueous solution Silver potential control amount below <Solution E> 1. ON HNO ₃ aqueous solution pH control amount below

At 65 ° C, Japanese Patent Publication No. 58-58288
No. 58-58289, a mixture stirrer was used to add and grow all the amounts of solution B and solution C in solution A by the simultaneous mixing method in the following pattern. During this period, the silver potential was controlled to be -1 mV and pH was 2.0.

[Min] Solution B Solution C Addition time Flow rate [ml / min] 10 2.23 6.69 20 4.39 13.17 40 6.54 19.62 41.15 6.67 20.01 It went for 41.15 minutes.

The flow rate of addition was linearly increased from the start to the end. The above shows 0, 20, 40 and the flow rate at the end. After the completion of the addition, water was washed by a precipitation method (using phenylcarbamoylated gelatin) according to a conventional method to remove excess salts, and an aqueous gelatin solution containing 47.57 g of ossein gelatin was added, followed by redispersion with stirring.

This emulsion EM-2 contained 5.756 mol of silver halide in 2445 ml of emulsion, and the pH of the emulsion solution at 40 ° C. was adjusted to 5.8 and pAg was adjusted to 8.06. About 3000 particles of EM-2 were observed and measured with an electron microscope to analyze the shape. The results are shown in Table 1.
Shown in.

[0088]

[Table 1]

Then, for each emulsion, the following pattern 1,
Color sensitization and chemical sensitization of 2 were performed.

(Pattern 1) pAg 8.0, pH 5.8
Was prepared, and at the temperature of 55 ° C., a sensitizing dye described later was also used for 30 minutes for adsorption to perform spectral sensitization. After that, 2.0 × 10 ⁻⁶ mol / mol AgX of sodium thiosulfate was added and aged for 60 minutes, and then chloroauric acid 4.4 × 10
A mixture of ^-7 mol / mol AgX and ammonium thiocyanate was added, and the mixture was aged for 30 minutes.

(Pattern 2) Color sensitization and chemical sensitization were performed in the same manner as in Pattern 1 except that the compound [I] was added at the same time when the sensitizing dye was added in Pattern 1.
Emulsion No. subjected to color sensitization and chemical sensitization Is as follows.

[0092]

[Table 2]

Samples were prepared as shown in Table 3 by using the emulsion prepared as described above in the fourth, seventh and tenth layers of the light-sensitive material having the following constitution.

The following back layer is coated on the surface of a polyethylene terephthalate film support, and the following emulsion layer is coated on the surface to prepare a light-sensitive material sample.

<Back Layer> First Layer: Gelatin 4.5 g Sodium-di- (2-ethylhexyl) -sulfosuccinate 1.0 g Sodium tripolyphosphate 76 mg Citric acid 16 mg Carboxyalkyl dextran sulfate 49 mg Vinyl sulfone type hardener 23 mg

Second layer (outermost layer): gelatin 1.5 g Polymer beads (average particle size: 3 μm, polymethylmethacrylate) 24 mg Sodium-di- (2-ethylhexyl) -sulfosuccinate 15 mg Carboxyalkyl dextran sulfate 12 mg Vinyl Sulfone type hardener 30 mg Mixture of compound SB-1 and compound SB-2 30 mg Compound SB-3 100 mg <Emulsion layer> First layer: antihalation layer (HC) black colloidal silver 0.15 g UV absorber (UV-1 ) 0.20 g Compound (CC-1) 0.02 g High boiling point solvent (Oil-1) 0.20 g High boiling point solvent (Oil-2) 0.20 g Gelatin 1.6 g

Second layer: intermediate layer (IL-1) gelatin 1.3 g

Third layer: low-sensitivity red-sensitive emulsion layer (RL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.4 g Silver iodobromide emulsion (average grain Diameter 0.4 μm, average iodine content 8.0 mol%) 0.3 g Sensitizing dye (S-1) 3.2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-2) 3. 2 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.2 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C-1) 0.50 g Cyan coupler (C-2) ) 0.13 g Colored cyan coupler (CC-1) 0.07 g DIR compound (D-1) 0.006 g DIR compound (D-2) 0.01 g High boiling point solvent (Oil-1) 0.55 g Gelatin 1.0 g

Fourth layer: High-sensitivity red-sensitive emulsion layer (RH) Silver iodobromide emulsion (EM-A) 0.9 g Sensitizing dye (S-1) 1.7 × 10 ⁻⁴ (mol / silver 1 mol) ) Sensitizing dye (S-2) 1.6 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-3) 0.1 × 10 ⁻⁴ (mol / silver 1 mol) Cyan coupler (C- 2) 0.23 g Colored cyan coupler (CC-1) 0.03 g DIR compound (D-2) 0.02 g High boiling point solvent (Oil-1) 0.25 g Gelatin 1.0 g

Fifth layer: Intermediate layer (IL-2) gelatin 0.8 g

Sixth layer: low-sensitivity green-sensitive emulsion layer (GL) Silver iodobromide emulsion (average grain size 0.4 μm, average iodine content 8.0 mol%) 0.6 g Silver iodobromide emulsion (average grain Diameter 0.3 μm, average iodine content 2.0 mol%) 0.2 g Sensitizing dye (S-4) 6.7 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-5) 0. 8 × 10 ⁻⁴ (mol / silver 1 mol) Magenta coupler (M-1) 0.17 g Magenta coupler (M-2) 0.43 g Colored magenta coupler (CM-1) 0.10 g DIR compound (D-3) 0.02g High boiling point solvent (Oil-2) 0.7g Gelatin 1.0g

Seventh layer: High-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (EM-A) 0.9 g Sensitizing dye (S-6) 1.1 × 10 ⁻⁴ (mol / silver 1 mol) ) Sensitizing dye (S-7) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (S-8) 0.3 × 10 ⁻⁴ (mol / silver 1 mol) Magenta coupler (M- 1) 0.30 g Magenta coupler (M-2) 0.13 g Colored magenta coupler (CM-1) 0.04 g DIR compound (D-3) 0.004 g High boiling point solvent (Oil-2) 0.35 g Gelatin 1. 0 g

Eighth layer: Yellow filter layer (YC) Yellow colloidal silver 0.1 g Additive (HS-1) 0.07 g Additive (HS-2) 0.07 g Additive (SC-1) 0.12 g High boiling point solvent (Oil-2) 0.15 g Gelatin 1.0 g

Ninth layer: low-sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (average grain size 0.3 μm, average iodine content 2.0 mol%) 0.25 g Silver iodobromide emulsion (average grain Diameter 0.4 μm, average iodine content 8.0 mol%) 0.25 g Sensitizing dye (S-9) 5.8 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.6 g Yellow coupler (Y-2) 0.32 g DIR compound (D-1) 0.003 g DIR compound (D-2) 0.006 g High boiling point solvent (Oil-2) 0.18 g Gelatin 1.3 g

Layer 10: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (EM-A) 0.5 g Sensitizing dye (S-10) 3.0 × 10 ⁻⁴ (mol / silver 1 mol) ) Sensitizing dye (S-11) 1.2 × 10 ⁻⁴ (mol / silver 1 mol) Yellow coupler (Y-1) 0.18 g Yellow coupler (Y-2) 0.10 g High boiling point solvent (Oil-2) ) 0.05g gelatin 2.0g

Eleventh layer: First protective layer (PRO-1) Silver iodobromide emulsion (average particle size: 0.08 μm) 0.3 g UV absorber (UV-1) 0.07 g UV absorber (UV-2) ) 0.10 g Additive (HS-1) 0.2 g Additive (HS-2) 0.1 g High boiling point solvent (Oil-1) 0.07 g High boiling point solvent (Oil-3) 0.07 g Gelatin 0.8 g

Twelfth layer: Second protective layer (PRO-2) Compound (Compound A) 0.04 g Compound (Compound B) 0.004 g Polymethyl methacrylate (average particle size 3 μm) 0.02 g Methyl methacrylate: Ethyl methacrylate: Methacrylic acid = 3: 3: 4 (weight ratio) copolymer (average particle size: 3 μm) 0.13 g Gelatin 0.7 g

Regarding the silver iodobromide emulsions used in the emulsion layers other than the fourth, seventh and tenth layers, the average grain size of the seed crystals, the humidity,
The emulsions having different average grain sizes and silver iodide contents were adjusted by changing pAg, pH, flow rate, addition time and halide composition. All were core / shell type monodisperse emulsions having a distribution of 20% or less. Each emulsion was subjected to optimum chemical ripening in the presence of sodium thiosulfate, chloroauric acid and ammonium thiocyanate to obtain a sensitizing dye, 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene, 1
-Phenyl-5-mercaptotetrazole was added.
In addition, the above-mentioned photosensitive materials further include compounds Su-1 and Su-.
2, viscosity modifier, hardener H-1, H-2, stabilizer ST-
1, antifoggants AF-1 and AF-2 (weight-average molecular weights of 10,000 and 1,100,000),
Dyes AI-1, AI-2 and Compound DI-1 (9.4 m
g / m ² ).

[0109]

[Chemical 18]

[0110]

[Chemical 19]

[0111]

[Chemical 20]

[0112]

[Chemical 21]

[0113]

[Chemical formula 22]

[0114]

[Chemical formula 23]

[0115]

[Chemical formula 24]

[0116]

[Chemical 25]

[0117]

[Chemical formula 26]

[0118]

[Chemical 27]

The latent image stability of the samples 1 to 10 prepared as described above was evaluated. However, each sample was divided into 2 parts, and 1 part was stored at 23 ° C. and 55% RH for 1 day, then subjected to ordinary white wedge exposure, and developed and post-treated as shown in the following processing steps. , Sensitometry was obtained using the sample. The other part was the same as above until the exposure, and then stored at 23 ° C. and 55% RH for 7 days, and sensitometry was obtained by the same procedure.

[Treatment process] Treatment process Treatment time Treatment temperature Complementary amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 cc Bleach 45 seconds 38 ± 2.0 ° C. 150 cc fixed 1 Minutes 30 seconds 38 ± 2.0 ° C. 830 cc stability 60 seconds 38 ± 5.0 ° C. 830 cc dry 1 minute 55 ± 5.0 ° C .- * Replenishment amount is a value per 1 m ² of the light-sensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and their replenishers were used. Color developer Water 800 cc Potassium carbonate 30 g Sodium hydrogen carbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-Amino-3-methyl -N-Ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Water was added to make 1 liter and potassium hydroxide or 20
Adjust to pH 10.06 with% sulfuric acid.

Color developing replenisher liquid 800 cc Potassium carbonate 35 g Sodium hydrogen carbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-methyl-N-ethyl-N-aniline sulfate (β- Hydroxylethyl) 6.3 g Potassium hydroxide 2 g Diethylenetriaminepentaacetic acid 3.0 g Water is added to make 1 liter and potassium hydroxide or 20
Adjust to pH 10.18 with% sulfuric acid.

Bleaching solution Water 700 cc 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 40 g Ammonium bromide 150 g Glacial acetic acid 40 g Water was added to make 1 liter, and aqueous ammonia or glacial acetic acid was used. PH to 4.4.

Bleaching Replenisher Water 700 cc 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 175 g Ethylenediaminetetraacetic acid 2 g Sodium nitrate 50 g Ammonium bromide 200 g Glacial acetic acid 56 g After adjusting to pH 4.4 with aqueous ammonia or glacial acetic acid , And add water to make 1 liter.

Fixing solution Water 800 cc Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting to pH 6.2 with aqueous ammonia or glacial acetic acid, water is added to make 1 liter.

Fixing replenisher water 800 cc ammonium thiocyanate 150 g ammonium thiosulfate 180 g sodium sulfite 20 g ethylenediaminetetraacetic acid 2 g After adjusting to pH 6.5 with aqueous ammonia or glacial acetic acid, water is added to make 1 liter.

Stabilizer and Stable Replenisher Water 900 cc Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UC-L-77) 0.1 g Ammonia water 0.5 cc After adding water to make 1 liter, ammonia water or 5
Adjust to pH 8.5 with 0% sulfuric acid. The evaluation results are summarized in Table 3.

[0128]

[Table 3]

[0129]

As is clear from Table 3, according to the present invention, the sensitivity is high and the latent image stability is excellent.

Claims (1)

[Claims] 1. At least 70% of the total projected area of the silver halide grains contained in the emulsion is tabular silver halide, and all of the parallel main planes of the tabular silver halide grains facing each other are parallel to each other. 90% or less of the edge surface is (111)
A silver halide emulsion having a crystal plane and a compound represented by the following general formula [I] and / or [II] adsorbed on the surface of the flat silver halide grains. [Chemical 1] [Wherein R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom,
It represents an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group, and R ₅ , R ₆ , R ₇ and R ₈ each represent a substituent. L ₁ and L ₂ each represent a methine group, and Z represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom, —C (R ₉ ) (R ₁₀ ) — or —N (R ₉ ) —. R ₉ and R ₁₀ are each a hydrogen atom, an alkyl group,
It represents an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. In addition, R ₁ and R ₂ , R ₃ and R ₄ , R ₅ and R ₆ ,
R ₇ and R ₈ , and R ₉ and R ₁₀ may be bonded to each other to form a ring. ] [Chemical 2] Z ₂ represents an atomic group necessary for forming an imidazole nucleus. R ₁₂ represents an alkyl group (the carbon chain may be replaced by a hetero atom such as S, N, O). R ₁₃ represents a hydrogen atom or an alkylene group necessary for forming a ring by bonding with R ₁₂ . R ₁₁ represents up to a bicyclic aryl group.