JP2003233146A - Silver halide emulsion - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide emulsion having high sensitivity and high contrast, ensuring a small variation of sensitivity due to difference in humidity condition in exposure and excellent in the reciprocity law characteristics under high illuminance. <P>SOLUTION: The silver halide emulsion has been chemically sensitized with a compound which releases a compound having a chalcogen atom-metal atom bond. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide emulsion, and more specifically, low fog, high sensitivity, high contrast, excellent reciprocity property under high illuminance, and sensitivity fluctuation due to difference in conditions during exposure and development. The present invention relates to a silver halide emulsion having a small size and excellent wet abrasion resistance, a stable production method thereof, and a silver halide color photographic light-sensitive material using the same.

[0002]

2. Description of the Related Art In recent years, with respect to color photographic paper, demands for performance such as high sensitivity, high image quality, toughness during processing, etc. are increasing. There is a demand for an emulsion having a small amount of photographic properties, an emulsion having a small variation in photographic properties due to differences in temperature and humidity conditions during exposure, and an emulsion having excellent wet abrasion resistance. On the other hand, recently, with the widespread use of laser scanning exposure apparatuses, suitability for exposure with high illuminance in a short time is also one of the important performances. The major features of laser scanning exposure are that exposure can be speeded up and resolution can be improved. However, if this is used for color photographic paper, it will be used for a very short time (specifically 10 ⁻⁶
Second) and exposure suitability at high illuminance are required.

The chemical sensitization method is considered to play a large role in responding to such demands, and various noble metal sensitization methods and chalcogen sensitization methods have been proposed. However, most of them use a noble metal sensitizer and a chalcogen sensitizer together. Improvements in noble metal sensitizers have been made until very recently, as shown below by examples of gold sensitizers. (Regarding Gold Sensitizer) The gold sensitization method is an effective means for achieving high sensitivity and suitability for exposure to high illuminance. It has long been known to use Au (III) compounds such as chloroauric acid. Although chloroauric acid is sufficiently stable in an aqueous solution, it is insufficient in terms of sensitivity, gradation, suitability for exposure to high illuminance, sensitivity fluctuation during storage, wet abrasion resistance, toughness against temperature and humidity environment during exposure, etc. It is photographic and needs improvement. As a gold compound used for gold sensitization, a gold (I) compound containing a mesoionic ligand (hereinafter referred to as a mesoionic gold (I) compound) is known. JP-A-4-267249 discloses a highly sensitive and hard emulsion. It is disclosed to be useful in manufacturing. However, as disclosed in JP-A No. 11-218870, the mesoionic gold (I) compound is known to have a problem in stability in a solution. The stability in a solution is a condition essential for stable production of an emulsion having a constant quality, and therefore, improvement has been desired. As one of the solutions to this problem, Japanese Patent Application Laid-Open No. 11-218870 proposes a method using a gold (I) complex of a mercapto compound. Although this gold sensitizer has been improved in terms of solution stability, it is still a compound that decomposes and is not a sufficient solution. In addition, it is not a sufficient solution because it has wet abrasion resistance and is in a temperature and humidity environment during exposure. Further, since it gives insufficient photographic properties in terms of wet abrasion resistance and toughness against a temperature and humidity environment at the time of exposure, improvements have been desired.

(Regarding chalcogen sensitizers) Further, chalcogen sensitizers are not limited to sulfur sensitizers, and selenium sensitizers (for example, JP-A-5-40324 and JP-A-4-258).
32, same 4-271341, same 4-109240, same 5
-224332, 6-43576, 6-17525
8), tellurium sensitizer (for example, JP-A-4-33304).
3, 5, 5-303157, 4-204640).

However, many of these are noble metal sensitizers,
It was an improvement of a chalcogen sensitizer, and an attempt was made to achieve a noble metal chalcogen sensitization (for example, gold sulfur sensitization, gold selenium sensitization) by using both in combination. That is, a noble metal sensitizer is used to introduce a noble metal atom into a silver halide emulsion, and a chalcogen sensitizer is used to introduce a chalcogen atom into a silver halide emulsion. Was achieved. So far,
A method of chemically sensitizing a molecule that releases a compound having a chalcogen atom-metal atom bond has not been known.

Various examples are known as the chemical sensitization method using a compound containing a chalcogen atom and a metal atom, and a gold complex and a gold salt coordinated with a sulfur atom have been proposed as a gold sensitizer. There is. However, in many of the gold compounds proposed in this manner, the gold compound alone functions only as a gold sensitizer and does not substantially function as a gold sulfur sensitizer. One example thereof is a gold (I) compound containing a mesoionic ligand (hereinafter referred to as a mesoionic gold (I) compound), which is disclosed in JP-A-4-267.
No. 249. Another example of a single compound which cannot be sensitized with gold sulfur is a gold (I) complex of a mercapto compound described in JP-A No. 11-218870. Similarly,
The gold salt of the mercapto compound described in JP-A-8-69075 was also found to be substantially unsensitized to gold-sulfur with a single compound based on the results shown in the examples below. Gold (I) trisodium dithiosulfate (hypo gold) has long been known as an example of gold-sulfur sensitization with a single compound. But,
The following description of JP-A-4-267249, "This gold (I) compound contains two thiosulfate ions bound to gold. Also, in addition to gold in a photographic silver halide emulsion, these ions May participate in the sensitization reaction. Therefore, this gold (I) compound is not suitable for chemically sensitized silver halide compositions in which a sulfur amount of less than 2: 1 molar ratio with gold is desirable. . ", Gold dithiosulfate (I) 3
It is clear that sodium (hypo gold) has problems. In fact, the sensitization method with this is
It gives almost the same results as the sensitization method with 2 times the molar amount of thiosulfate with respect to Au (I). Also, there is no mention of the release of chalcogen-gold pairs. As an example similar to trisodium dithiosulfate (I), Japanese Patent Application Laid-Open No. 2001-2001
-75215 discloses an Au (I) complex having two molecules of thiourea compound as a ligand. However, since two molecules of thiourea compound function as a sulfur sensitizer, gold dithiosulfate (I ) It has the same problem as trisodium. As another example of gold-sulfur sensitization with a single compound, Japanese Patent Publication No. 45-
29274 describes a gold sensitization method with mercaptoglucoside gold (I). This is 1: 1 Au and sulfur atom
Therefore, the above problem does not occur. However, mercaptoglucoside gold (I) is a general term for four types of isomers, and although the patent has a structural formula, it does not clearly specify the three-dimensional structure, and thus does not refer to a specific compound. Also, there is no mention of the release of chalcogen-gold pairs.

Therefore, hitherto, no method has been known to carry out chemical sensitization with a molecule releasing a compound having a chalcogen atom-metal atom bond. Further, a specific solution that satisfies the above-mentioned various photographic properties and does not have the above-mentioned problems has been desired.

[0008]

The object of the present invention is low fog, high sensitivity, high contrast, and different conditions during exposure and development (exposure humidity, exposure temperature, time interval from exposure to development).
To provide a silver halide emulsion excellent in reciprocity property at high illuminance, a method for producing the same, a silver halide color photographic light-sensitive material using the same, and an image forming method. It is in.

[0009]

As a result of intensive studies by the present inventors, the above object was effectively achieved by the means described below. That is, (1) a silver halide emulsion characterized in that a compound releasing a compound having a chalcogen atom-metal atom bond is added and reacted. (2) A silver halide emulsion characterized by being chemically sensitized by a compound releasing a compound having a chalcogen atom-metal atom bond. (3) The silver halide emulsion according to (1) or (2), wherein the compound releasing a compound having a chalcogen atom-metal atom bond is a compound releasing a compound having an MCh structure. However, Ch represents an S atom, a Se atom, or a Te atom. M represents a metal element of Groups 3 to 12 of Period 4 to Period 6 of the Periodic Table. (4) The silver halide emulsion according to (3), wherein the compound that releases the compound having the MCh structure is a compound that releases Au ^I S ⁻ ions. However, as a compound that releases the compound having the MCh structure, β
Exclude gold (I) thioglucose based molds. (5) The silver halide emulsion according to (3), wherein the compound that releases the compound having the MCh structure is a compound that releases Au ^I S ⁻ ions. However, as a compound that releases the compound having the MCh structure,
Exclude gold (I) thioglucose. (6) The silver halide emulsion according to (3), wherein the compound that releases the compound having the MCh structure is a compound that releases Au ^I Se ⁻ ions. (7) The silver halide emulsion according to (3), wherein the compound that releases the compound having the MCh structure is a compound that releases Au ^I Te ⁻ ions. (8) The compound releasing the compound having the MCh structure in (3) above is a compound represented by the following general formula (AUS1) or general formula (AUS1)
2) The silver halide emulsion according to (3), which is selected from the compounds represented by formula (AUS3).

[0010]

[Chemical 1]

In the formula, Ch represents an S atom, a Se atom or a Te atom. In the general formula (AUS1), W1, W2, and W3 each represent a hydrogen atom or a substituent, and the sum of Hammett's substituent constant σp values of W1, W2, and W3 is 0.5 or more. However, W1,
W2 and W3 are oxygen atom, sulfur atom, or nitrogen atom, and are C-ChAu.
It is not connected to. In the general formula (AUS2), M represents a methylene group, R2 represents an alkyl group, and R1 and R3 represent a hydrogen atom or a substituent. In formula (AUS3), Q1 represents a hydrogen atom or a substituent, Q2 and Q3 each represent an alkyl group, and E represents a methylene group. (9) The silver halide emulsion as described in (3) or (4), wherein the compound releasing the compound having the MCh structure is a thioglucose gold (I) compound mainly containing α-type. . (10) The silver halide emulsion as described in (3) or (5), wherein the compound releasing the compound having the MCh structure is a selenoglucose gold (I) compound containing α-type as a main component. . (11) The silver halide emulsion as described in (9) or (10), which is a thioglucose gold (I) compound or a selenoglucose gold (I) compound having an α type ratio of 60% or more. . (12) The silver halide emulsion as described in (1) to (11), which has a silver chloride content of 90 mol% or more. (13) The silver halide emulsion according to (12), which contains an iridium complex having a thiazole compound as a ligand. (14) The silver halide emulsion according to (13), which contains [IrCl ₅ (5-CH ₃ -thiazole)] ^2- complex ion. (15) The silver halide emulsion according to (14), which has a silver iodide-containing phase of 0.01 to 0.50 mol% per mol of total silver in the shell portion of the silver halide grain. (16) A silver halide color photographic light-sensitive material having at least one layer of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. At least one of the silver halide emulsion layer, the green-sensitive silver halide emulsion layer, and the red-sensitive silver halide emulsion layer is a silver halide color photographic light-sensitive material containing the emulsion described in (1) to (15) above. An image forming method, comprising: performing a scanning exposure with a laser light beam modulated based on image information, the exposure time per pixel being shorter than 10 ⁻⁴ seconds, and then performing development processing.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The principle of the present invention is to chemically sensitize a silver halide emulsion by releasing a compound having a chalcogen-metal atom bond. In the present invention, the compound having a chalcogen-metal atom bond is a molecule releasing a compound having an MCh structure, and the molecule releasing a compound having an MCh structure is a metal element represented by M and Ch. It is a compound that releases ions composed of chalcogen elements. Here, M is a metal element of groups 3 to 12 (for example, Au, Pt, Ir, etc.) in the 4th to 6th periods of the periodic table, and Ch is an S atom, Se atom, or Te atom, and Ch Has a negative charge of 2, but the transition elements can have various valences. Therefore, when M is Au (I) and Ch is S, MCh represents an [Au ^I S] ⁻ ion. In the present invention, M is preferably 9 to 11
It is a metal element of the group, more preferably Pt and Au, most preferably Au.

[0013] In the present invention, AuCh ^- the compounds which release ions having a structure, the compound 70 ° C., 2 hours, upon heating in a suitable solvent, AuCh ^- compounds which release ions having the structure means. More specifically, a method for determining whether a certain compound is a compound that releases an ion having an AuCh ⁻ structure will be described.

(A) A method of judging whether or not the compound releases an ion having an AuS ^- structure. The compound sample is dissolved or dispersed in a suitable solvent, and then a large excess of a silver nitrate solution of the compound to be determined is added, followed by heating to 70 ° C.
React for hours. Many of the compounds that release ions having the AuCh ⁻ structure generate a precipitate, and the formed precipitate is filtered out. This precipitate was analyzed by powder X-ray diffraction, and A
Confirm that it is gAuS. Or X-ray fluorescence or I
Elemental analysis is carried out using a method such as CP to confirm that it is AgAuS. Then, the yield of the obtained precipitate and the yield are obtained, and the yield is 5 based on the reactive Ch in the substrate.
A compound to which AgAuS is given at 0% or more is determined as "a compound that releases an ion having an AuS ^- structure". still,
In some cases, the silver complex of the compound sample may precipitate without AgAuS precipitation exceeding 50% yield. Also in this case,
It is not a compound that releases an ion having an AuS ⁻ structure used in the present invention. AgAuS precipitates in a yield of more than 50%, and another compound may precipitate in some cases. In this case, the compound releases ions having an AuS ^- structure used in the present invention. Incidentally, general gelatin which is added to the emulsion may be added to this reaction system. The pH of this reaction system is 12 or less, preferably 10 or less,
The following is more preferable, and 3 to 7 is most preferable.

(B) The determination as to whether the compound releases the ion having the AuSe ^- structure or the compound releasing the ion having the AuTe ^- structure is performed in the same manner as in the above (A).

[0016] The suitable solvent here is an ordinary solvent capable of dissolving both the sample compound and silver nitrate,
Specifically, it is water, acetonitrile, methanol, ethanol, 1,4-dioxane, or a mixed solvent thereof.

Other molecules that release a compound having an MCh structure can be determined in the same manner as above. In addition, AuS from the compound AUS1-8 of the present invention described later
^- the ion emission, actually punished examined by treating the above method, to obtain a black powder AgAuS in 95% yield, this compound AuS ^- it is confirmed is ion releasing compounds having the structure It was

The following uses the above-mentioned determination method,
Describe our way of thinking. In the first place AuS^-Ion is A
u⁺And S^2-Reaction to dissociate with and another molecule of S ^2-Io
And HS^-Reaction to bind with, and further Au₂Forming S
May cause reactions such as forming a colloidal dispersion,
It is a chemical species. Therefore, AuS^-Ion is taken out purely
It's difficult. However, AuS^-Another stable ion
Indirectly converting to AuS^-The release of
It is possible to do so. AuS^-Capture ions with silver ions
By capturing and converting to stable AgAuS, AuS^-Structure
To see if the release of ions with
It will be possible.

Next, in order to specifically describe the Au ^I Ch ⁻ ion-releasing compound used in the present invention, the general formula of the compound will be described. However, the compounds that release Au ^I Ch ⁻ ions are not limited to these.
The compound releasing the Au ^I Ch ⁻ ion in the present invention is
The following general (AUS1), general formula (AUS2), general formula (AUS3)
Can be selected from the compounds represented by.

[0020]

[Chemical 2]

In the formula, Ch represents an S atom, a Se atom or a Te atom. In the general formula (AUS1), W1, W2, and W3 each represent a hydrogen atom or a substituent, and the total Hammett's substituent constant σp value of W1, W2, and W3 is 0.5 or more. However, W1, W2,
W3 is an oxygen atom, a sulfur atom, or a nitrogen atom and is not linked to C-ChAu. In the general formula (AUS2), M represents a methylene group, R2 represents an alkyl group, and R1 and R3 each represent a hydrogen atom or a substituent. In formula (AUS3), Q1 represents a hydrogen atom or a substituent, Q2 and Q3 each represent an alkyl group, and E represents a methylene group.

In the formulas (AUS1) to (AUS3), Ch represents an S atom, a Se atom or a Te atom, but in the present invention, an S atom or a Se atom is preferable, and a Se atom is more preferable.

In the general formula (AUS1), W1, W2 and W3 each represent a hydrogen atom or a substituent, and the sum of Hammett's substituent constant σp values of W1, W2 and W3 is 0.5 or more. However W
1, W2 and W3 are oxygen atom, sulfur atom and nitrogen atom and are not linked to C-ChAu. Here, the σp values of various substituents are shown in Journal of Medicinal Chemistry, Volume 16, 1207.
Page, 1973, etc. Since the sum of Hammett's substituent constant σp values of W1, W2, and W3 is 0.5 or more, the σp value of at least one group of W1, W2, and W3 is preferably 0.2 or more. , As such a group,
Acyl group, formyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, cyano group,
Examples thereof include a nitro group, an alkylsulfonyl group, an arylsulfonyl group and a sulfamoyl group.

In the general formula (AUS2), M represents a methylene group, R2 represents an alkyl group, and R1 and R3 represent a hydrogen atom or a substituent. The methylene group represented by M may have a substituent.

In the general formula (AUS3), Q1 represents a hydrogen atom or a substituent, Q2 and Q3 represent an alkyl group, E represents a methylene group, and an oxygen atom, which may have a substituent,
It does not have a substituent bonded by a nitrogen atom or a sulfur atom.

In the explanation of each group of the formulas (AUS1) to (AUS3), the substituent is, for example, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), an alkyl group (linear, branched or cyclic substitution). Or an unsubstituted alkyl group, including a bicycloalkyl group, a tricyclo structure, an active methine group, etc.), an alkenyl group, an alkynyl group, an aryl group,
Heterocyclic group (5- to 7-membered, substituted or unsubstituted, saturated or unsaturated heterocycle containing at least one of N atom, O atom, and S atom, and may be a monocycle Further, it may form a condensed ring together with other aryl ring or hetero ring, for example, pyrrolyl group, pyrrolidinyl group, pyridyl group, piperidyl group, piperazinyl group, imidazolyl group, pyrazolyl group, pyrazinyl group, pyrimidinyl group, triazinyl group, Triazolyl group, tetrazolyl group, quinolyl group, isoquinolyl group, indolyl group, indazolyl group, benzimidazolyl group, pyranyl group, chromeenyl group, thienyl group, oxazolyl group, oxadiazolyl group, thiazolyl group, thiadiazolyl group, benzoxazolyl group, benzothiazolyl group , Morpholino group, morpholinyl group, etc. Position does not matter), an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic oxycarbonyl group, a carbamoyl group,
N-hydroxycarbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamoyl group, thiocarbamoyl group, N-sulfamoylcarbamoyl group, carbazoyl group, carboxy group (including salts thereof), oxalyl Group, oxamoyl group, cyano group, formyl group, hydroxy group, alkoxy group (including groups containing repeating ethyleneoxy group or propyleneoxy group unit), aryloxy group, heterocyclic oxy group, acyloxy group, alkoxycarbonyloxy group, Aryloxycarbonyloxy group, carbamoyloxy group, sulfonyloxy group, silyloxy group,
Nitro group, amino group, (alkyl, aryl, or heterocycle) amino group, acylamino group, sulfonamide group, ureido group, thioureido group, N-hydroxyureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group , Sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, ammonio group, oxamoylamino group, N-
(Alkyl or aryl) sulfonylureido group, N
-Acylureido group, N-acylsulfamoylamino group, hydroxyamino group, heterocyclic group containing a quaternized nitrogen atom (for example, pyridinio group, imidazolio group, quinolinio group, isoquinolinio group), isocyano group, imino group, Mercapto group (and salt thereof), alkylthio group, arylthio group, heterocyclic thio group, (alkyl,
Aryl or heterocycle) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group (and salts thereof),
Sulfamoyl group, N-acyl sulfamoyl group, N-
A sulfonylsulfamoyl group (and a salt thereof), a phosphino group, a phosphinyl group, a phosphinyloxy group,
It means a phosphinylamino group, a silyl group or the like. Here, the salt means a salt with a cation such as an alkali metal, an alkaline earth metal or a heavy metal, or an organic cation such as an ammonium ion or a phosphonium ion. R2, Q2,
The alkyl group of Q3 is the same as the "alkyl group" in the above substituents, and among the alkyl groups, a methyl group or an ethyl group is preferable.

These substituents may be further substituted with these substituents.

In the formulas (AUS1) to (AUS3), the Au atom may be bonded to another ligand, but a ligand coordinated with a phosphorus atom is not preferred, and a trialkylphosphine coordination is particularly preferred. Child is not good. (The P ligand is presumed to have too strong a bond with Au and affect the formation of sensitized nuclei.)

In the general formula (AUS1), preferably W
1, W2 has a total Hammett's substituent constant σp value of W1, W2 and W3 of 0.5 or more, and W1 and W2 are acyl group, formyl group, carbamoyl group, alkoxycarbonyl group and aryloxycarbonyl group. , A cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group. More preferably, the sum of σp values is 0.7 or more, and W1 and W2 are an acyl group, a carbamoyl group, an alkoxycarbonyl group, a cyano group, a nitro group,
It is an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and W3 is a hydrogen atom or an alkyl group. Most preferably, the sum of σp values is 0.9 or more, and W1 and W2 are an acyl group, a carbamoyl group, an alkoxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, and a sulfamoyl group, W3 is a hydrogen atom or an alkyl group.

In the general formula (AUS2), preferably M
Is a methylene group, R2 represents an alkyl group, and R1 and R3 represent a hydrogen atom or an alkyl group.

In the general formula (AUS3), Q1 represents a hydrogen atom, an alkyl group, an aryl group or an alkoxy group, and Q1
2, Q3 represents an alkyl group, and E represents a methylene group.

Of the compounds represented by the general formulas (AUS1) to (AUS3), the compounds represented by the general formulas (AUS1) and (AUS2) are preferable, and the compounds represented by the general formula (AUS1) are most preferable. Compound.

Next, specific examples of the compound that releases an ion having an AuCh ^- structure will be shown below. However, the present invention is not limited to these.

[0034]

[Chemical 3]

Next, a method for synthesizing the compound for releasing the compound having the MCh structure used in the present invention will be described. AUS1-8: A method for synthesizing (D) -α-thioglucose gold (I). According to the following literature, 1-Thio-α-D-glucose was synthesized, and then mercapto compound was converted into Au of mercapto compound.
Α-Thioglucose gold (I) can be synthesized by a conventional method for synthesizing (I) salt. Organic Letter, Vol.3, No.3, p405, 2001, Carbohydrate Reserch, Vol.200, p497, 1990. Other compounds can also be synthesized according to a conventional method for synthesizing an Au (I) salt of a mercapto compound. That is, in order to obtain the Au (I) salt, first, the corresponding mercapto compound is synthesized. Then, a readily available Au (III) compound (eg, AuBr3, NaAuCl3, etc.) can be synthesized by reducing it to Au (I) with 2,2'-thiodiethanol and reacting with the above mercapto compound. it can. Corresponding Se homologues and Te homologues can be obtained by using Se compounds and Te compounds instead of mercapto compounds. However, as is well known as the property of Se and Te compounds, since selenols and tellurols are easily oxidized and converted to diselenide and ditelluride, once diselenide and diteluride are obtained, they are immediately reduced and then immediately converted. A method of reacting with Au (I) can also be used.

We have found the surprising fact that the α-thioglucose gold (I) used in the present invention provides favorable photographic properties such as high sensitivity. Furthermore, it was found that α-thioglucose gold (I) is an AuS ^- releasing compound. That is, when thioglucose gold (I) is used as the chemical sensitizer, it is preferable that the α-form is the main component (the main component is the largest proportion of all isomers of thioglucose gold (I) ( A larger proportion than other ingredients) is said to account for). More preferably, α type is 60%
It is above, and particularly preferably 80% or more. In addition,
α-Thioglucose gold (I) is available in Japanese Examined Patent Publication No. 45-2927.
It is one of the compounds included in the mercaptoglucoside gold (I) described in 4 above. However, Japanese Examined Sho 45-2927
The mercaptoglucoside gold (I) salt of the general formula described in 4 is 4
It does not disclose any specific compound because it refers to a group of compounds including isomers of different types. D and L among four isomers
The difference between the types is less important because they have the same chemical properties, except that the cheap type D is advantageous for industrial use. on the other hand,
Chemically depending on whether the anomeric position is α-type or β-type
The physical properties are likely to be different and this difference is significant. About β type so far, Collection Czechoslov.
Chem. Commun. Vol. 26, p. 2084, 1961, but other reports on mercaptoglucoside gold (I) are unclear whether it is the α-type or β-type other than the above-mentioned report. It was also uncertain about 29294. To clarify this, the stereoisomer at the anomeric position is the NM of the anomeric proton.
By applying the fact that it is possible to distinguish by observing R,
Successful separation and quantification of molds. As a result,
It was found that β-type was the main component in the synthesis method described in 9274.

[0037] In the present invention, preferably, AuCh ^-
In determining whether or not the compound releases a structured ion, 100 times mol of silver nitrate as compared with the evaluation sample was used, and
It is a compound having a yield of AgAuS precipitate of 50% or more, which is obtained by heating at 0 ° C. for 30 minutes. More preferably, using 10000 times the molar amount of silver nitrate as the evaluation sample,
AgAuS obtained by heating to 50 ° C. and heating for 30 minutes
Is a compound having a yield of precipitation of more than 50%. Even more preferably, it is a compound in which the yield of AgAuS precipitation obtained by heating to 50 ° C. for 30 minutes using silver nitrate of 1,000,000 times the molar amount of the evaluation sample exceeds 50%. Most preferably, it is a compound in which the yield of AgAuS precipitation obtained by heating to 50 ° C. for 30 minutes using silver nitrate of 100,000,000 times the molar amount of the evaluation sample exceeds 50%. Further, in the present invention, preferably A
uS ^- compounds to release ions having a structure, and / or, AuSe ^- it is preferable to use a compound capable of releasing ions having the structure. In particular, it is preferable to use a compound that releases ions having an AuSe ⁻ structure.

The addition amount of the gold compound used in the present invention can be varied over a wide range depending on the case, but it is 1 × 10 ^-6 to 1 × 10 ^-3 mol, preferably 5 × 10 ^-6 mol per mol of silver halide.
˜1 × 10 ⁻⁴ mol. More preferably 1 × 10 ⁻⁵ or more
It is 5 × 10 ⁻⁵ mol.

The gold compound of the present invention is
It can be added at any stage until just before the end of chemical sensitization. The preferred addition timing is after desalting and during the chemical sensitization step.

The sensitization method using the gold compound of the present invention may be applied to other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization or other gold sensitization methods or other than gold compounds. You may combine it with the precious metal sensitization. In the present invention,
Preferably, the sensitizing method using the gold compound of the present invention alone, the sensitizing method using sulfur, the combined use of sulfur sensitization, and the combined use of selenium sensitization.

The silver halide grains in the silver halide emulsion used in the present invention are preferably cubic or tetradecahedral crystal grains having substantially {100} faces (these grains have rounded vertexes and higher grains). May have the following planes) or octahedral crystal grains, or 50 of the total projected area
A tabular grain having an aspect ratio of 2 or more and having at least 100% of {100} planes or {111} planes is preferable. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of particles. In the present invention, cubic grains or tabular grains having {100} faces as main planes or tabular grains having {111} faces as main planes are preferably applied.

As the silver halide emulsion used in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsion and the like can be used. From the viewpoint of rapid processability, silver chloride is used. A silver chloride, silver chlorobromide, silver chloroiodide or silver chlorobromoiodide emulsion having a content of 90 mol% or more is preferable, more preferably a silver chloride content of 95 mol% or more, further preferably 98 mol%. The above silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsions are preferred. Among such silver halide emulsions,
In the present invention, the shell portion of the silver halide grain,
High sensitivity can be obtained with a silver iodide-containing phase (particularly preferably silver iodochloride phase) having a silver iodide content of 0.01 to 0.50 mol%, more preferably 0.05 to 0.40 mol% based on the total silver mol. ,
It is preferable because it is excellent in high-illuminance exposure suitability. Further, those having a silver bromide localized phase of 0.2 to 5 mol%, more preferably 0.5 to 3 mol% based on the total silver mol on the surface of the silver halide grain can obtain high sensitivity and It is particularly preferable because the photographic performance can be stabilized.

When the emulsion of the present invention contains silver iodide, the iodide ion is introduced by adding a solution of iodide salt alone or in combination with addition of a silver salt solution and a high chloride salt solution. An iodide salt solution may be added. In the latter case, the iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the iodide salt and the high chloride salt. The iodide salt is added in the form of a soluble salt such as an alkali or alkaline earth iodide salt. Alternatively, US Pat. No. 5,389,
Iodide can also be introduced by cleaving the iodide ion from the organic molecule described in US Pat. No. 508. Further, fine silver iodide grains can be used as another iodide ion source.

The addition of the iodide salt solution may be concentrated at one stage of grain formation, or may be performed over a certain period. The position of introduction of iodide ions into the high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fog. When the iodide ion is introduced inside the emulsion grains, the increase in sensitivity is small. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the grain volume, more preferably outside 70%, and most preferably outside 80%. The addition of the iodide salt solution is preferably completed within 98% of the grain volume, and most preferably within 96%. When the addition of the iodide salt solution is completed slightly inside the grain surface, an emulsion having higher sensitivity and lower fog can be obtained.

The distribution of the iodide ion concentration in the grain in the depth direction is determined by etching / TOF-SIMS (Time of Flight).
-Secondary Ion Mass Spectrometry) method, for example, TRIFTII type TOF-SIMS manufactured by Phi Evans. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Manual, Secondary Ion Mass Spectrometry” edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (issued in 1999). When the emulsion grains are analyzed by the etching / TOF-SIMS method, it can be analyzed that the iodide ions are exuded toward the grain surface even after the addition of the iodide salt solution is completed inside the grains. When the emulsion of the present invention contains silver iodide, the iodide ion has a maximum concentration on the surface of the grain and the iodide ion concentration decreases toward the inside, as analyzed by an etching / TOF-SIMS method. Is preferred.

When the emulsion of the present invention contains a silver bromide localized phase, it is preferred that the silver bromide localized phase having a silver bromide content of at least 10 mol% is epitaxially grown on the grain surface. The silver bromide content of the silver bromide localized phase is 10 to 10.
The range of 60 mol% is preferable, and the range of 20 to 50 mol% is the most preferable. The silver bromide localized phase is preferably composed of 0.1 to 5 mol% of silver based on the total amount of silver constituting the silver halide grains in the present invention, and 0.3 to 4 mol%.
More preferably, it is composed of silver. In the silver bromide localized phase, iridium (III) chloride, iridium (III) bromide, iridium (II) chloride, hexachloroiridium (III) sodium salt, hexachloroiridium (IV) potassium salt are contained. , Hexaammineiridium (I
It is preferable to include a Group VIII metal complex ion such as V) salt, trioxalatoiridium (III) salt, or trioxalatoiridium (IV) salt. The addition amount of these compounds is wide depending on the purpose, but is preferably 10 ^-9 to 10 ^-2 mol per mol of silver halide.

In the present invention, transition metal ions may be added in the process of forming and / or growing silver halide grains to incorporate the metal ions into the inside and / or the surface of the silver halide grains. The metal ion used is preferably a transition metal ion, among which iron, ruthenium, iridium, osmium, lead, cadmium,
Alternatively, it is preferably zinc. Further, these metal ions are more preferably used as a hexacoordinate octahedral complex with a ligand. When an inorganic compound is used as a ligand, cyanide ion, halide ion,
It is preferable to use thiocyan, hydroxide ion, peroxide ion, azide ion, nitrite ion, water, ammonia, nitrosyl ion, or thionitrosyl ion, and the above iron, ruthenium, iridium, osmium, lead, It is also preferable to use it by coordinating with any metal ion of cadmium or zinc, and it is also preferable to use plural kinds of ligands in one complex molecule. Also,
An organic compound can be used as the ligand, and preferred organic compounds include a chain compound having a main chain having 5 or less carbon atoms and / or a 5-membered or 6-membered heterocyclic compound. More preferable organic compound is a compound having a nitrogen atom, a phosphorus atom, an oxygen atom, or a sulfur atom in the molecule as a coordination atom to a metal, and most preferably furan, thiophene, oxazole, isoxazole, thiazole, isothiazole. , Imidazole, pyrazole, triazole, furazan, pyran, pyridine, pyridazine, pyrimidine, and pyrazine, and compounds having these compounds as a basic skeleton and substituents introduced into them are also preferable.

Suitable as a combination of a metal ion and a ligand
More preferably, iron and ruthenium ions and cyanide
It is a combination of ions. In these compounds
Anion ions to the central metal iron or ruthenium
It is preferable that the majority of the coordination numbers of
Coordination sites are thiocyan, ammonia, water and nitrosyl.
On, dimethyl sulfoxide, pyridine, pyrazine, or
Or, it is preferable that it is occupied by 4,4'-bipyridine.
Yes. Most preferably, all six coordination sites of the central metal are si
Occupied with an anide ion, a hexacyanoiron complex or
Forming a hexacyanoruthenium complex. This
Complexes with these cyanide ions as ligands are forming particles
1 x 10 per mole of silver^-81 x 10 from mole^-2Add mol
1 × 10^-65 x 10 from mole^-FourMolar addition
Most preferably. Iridium as the central metal
When used as a ligand, it is preferably a fluoride ion.
And chloride, bromide, and iodide
In particular, use chloride ion or bromide ion.
And are preferred. Specifically preferred as an iridium complex
Is [IrCl₆]^3-, [IrCl₆]^2-, [IrCl_Five(thiazole)]^2-, [Ir
Cl_Five(5-CH₃-thiazole)]^2-, [IrCl_Five(H₂O)]^2-, [IrCl_Five(H
₂O)]^-, [IrCl_Four(H₂O)₂]^-, [IrCl_Four(H₂O)₂]⁰, [IrCl₃(H
₂O)₃]⁰, [IrCl₃(H₂O)₃]⁺, [IrBr₆]^3-, [IrBr₆]^2-, [Ir
Br_Five(H₂O)]^2-, [IrBr_Five(H₂O)]^-, [IrBr_Four(H₂O)₂]^-, [IrB
r_Four(H₂O)₂]⁰, [IrBr₃(H₂O)₃]⁰, And [IrBr₃(H ₂O)₃]⁺
Is. These iridium complexes are used for the silver molybdenum during grain formation.
1 × 10 per le^{- Ten}1 x 10 from mole^-3Adding moles
Is preferred, 1 × 10^-81 x 10 from mole^-FiveMole addition
And are most preferred. Centered around ruthenium and osmium
When used as a metal, nitrosyl ion, thionitrosyl
Ions, or water molecules and chloride ions as ligands
It is also preferable to use. More preferably pentachloro
Nitrosyl complex, pentachlorothionitrosyl complex,
Is to form a pentachloroaqua complex,
It is also preferred to form a hexachloro complex. these
Complex is 1 × 10 per mol of silver during grain formation^-TenFrom mole
1 x 10^-6It is preferable to add a mole, and more preferably
1 x 10^-91 x 10 from mole^-6It is to add a mole.

In the present invention, the above complex is added directly to the reaction solution at the time of forming silver halide grains, or to an aqueous halide solution for forming silver halide grains, or to a solution other than that. It is preferably incorporated into the silver halide grain by adding it to the grain forming reaction solution. Further, it is also preferable to combine these methods to incorporate them in the silver halide grains.

When these complexes are incorporated into silver halide grains, it is preferable that they are uniformly present inside the grains, but JP-A-4-208936 and JP-A-2-12524.
5, as disclosed in JP-A-3-188437, it is also preferable that the particles are present only in the particle surface layer,
It is also preferable that the complex is present only inside the particles and a layer not containing the complex is added to the surface of the particles. Also, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, it is possible to modify the surface phase of particles by physically aging them with fine particles in which a complex is incorporated. preferable. Further, these methods can be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the complex is contained, and the complex may be contained in any of the silver chloride layer, the silver chlorobromide layer, the silver bromide layer, the silver iodochloride layer and the silver iodobromide layer. Is also preferable.

The average grain size of silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. It is preferably 1 μm or more and 2 μm or less. In addition, their particle size distributions are coefficient of variation (standard deviation of particle size distribution divided by average particle size) 2
0% or less, preferably 15% or less, more preferably 10%
% Or less, so-called monodisperse particles are preferable. At this time, for the purpose of obtaining a wide latitude, it is also preferable to use two or more kinds of the above monodisperse emulsions having different average grain sizes by blending them in the same layer, or to perform multilayer coating.

The silver halide emulsion used in the present invention includes various compounds or precursors thereof for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. Can be added. Specific examples of these compounds are described in JP-A-62-2.
Those described on pages 39 to 72 of the specification of Japanese Patent No. 15272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compounds described in EP 0447647 (wherein the aryl residue has at least one electron-withdrawing group) are also preferably used.

In the present invention, in order to improve the storage stability of the silver halide emulsion, the hydroxamic acid derivative described in JP-A-11-109576 and JP-A-11-32709.
A cyclic ketone having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group described in No. 4 (particularly represented by the general formula (S1), paragraphs 0036 to 0071) Can be incorporated into the specification of the present application), and sulfo-substituted catechols and hydroquinones described in JP-A No. 11-143011 (for example,
4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,
3-dihydroxybenzene sulfonic acid, 2,5-dihydroxybenzene sulfonic acid, 3,4,5-trihydroxybenzene sulfonic acid and salts thereof, etc., in the general formula (A) of US Pat. No. 5,556,741. Hydroxylamines represented (The description of U.S. Pat. No. 5,556,741 from column 4, line 56 to column 11, line 22 is preferably applied also in the present application, and is included as part of the specification of the present application. The water-soluble reducing agents represented by formulas (I) to (III) of JP-A No. 11-102045 are preferably used in the present invention.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, Heterocyclic compounds-Cyanine by FM Harmer.
dyes andrelated compounds (John Wiley & Sons [New
York, London] 1964). As specific examples of compounds and the spectral sensitization method, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A-3-123 is known.
The spectral sensitizing dye described in JP-A No. 340 is very preferable from the viewpoint of stability, strength of adsorption, temperature dependence of exposure and the like.

The amount of these spectral sensitizing dyes added is in a wide range depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range.

The silver halide emulsion used in the present invention can be subjected to a conventional chemical sensitization method or can be used in combination with it, in addition to the treatment with the compound according to the present invention. In the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, reduction sensitization, or the like can be used alone or in combination. Compounds used for chemical sensitization are described in JP-A-62-215.
Nos. 272, page 18, lower right column to page 22, upper right column are preferably used.

The silver halide emulsion used in the present invention is
Gold sensitization with a compound other than the compound according to the present invention can also be used in combination. This is because the gold sensitization can increase the sensitivity of the emulsion and reduce fluctuations in photographic performance when scanning exposure is performed with a laser beam or the like.
The sensitization with the gold compound disclosed in the present invention is also one of the gold sensitization methods. In addition, gold sensitization with various inorganic gold compounds or inorganic ligands ( I (I) compounds having an I) complex and an organic ligand can be used. As the inorganic gold compound, for example, chloroauric acid or a salt thereof, and as the gold (I) complex having an inorganic ligand, for example, a gold dithiocyanate compound such as potassium gold (I) dithiocyanate or gold (I) 3 dithiosulfate is used. Compounds such as sodium dithiosulfate compounds such as sodium can be used.

As the gold (I) compound having an organic ligand, bis gold (I) mesoionic heterocycles described in JP-A-4-267249, for example, gold (I) tetrafluoroborate bis (1,4) , 5-Trimethyl-1,2,4-triazolium-3-thiolate), an organic mercapto gold (I) complex described in JP-A-11-218870, such as potassium bis (1- [3- (2-sulfonate benzamide) ) Phenyl] -5-mercaptotetrazole potassium salt) Aurate (I) pentahydrate, a gold (I) compound coordinated with a nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydan) Toinato) gold (I) sodium salt tetrahydrate can be used. Further, a gold (I) thiolate compound described in US Pat.
-69074, JP-A-8-69075, JP-A-9-2
69554 gold compounds, US Pat. No. 56208
The compounds described in No. 41, No. 5912112, No. 5620841, No. 5939245, and No. 5912111 can also be used. The addition amount of these compounds may be varied over a wide range depending on the case, but 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 5 × 10 ⁻⁶ mol, per mol of silver halide.
Is about 5 × 10 ⁻⁴ mol.

The silver halide photographic light-sensitive material of the present invention comprises
Conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as the photographic support. As the transmissive support, a transparent film such as a cellulose nitrate film or polyethylene terephthalate, a polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG), or a polyester of NDCA, terephthalic acid and EG is used. Those provided with an information recording layer such as a magnetic layer are preferably used. As the reflection type support, a reflection support which is laminated with a plurality of polyethylene layers or polyester layers and which contains a white pigment such as titanium oxide in at least one layer of such a water resistant resin layer (laminate layer) is preferable.

In the present invention, a more preferable reflective support is one having a polyolefin layer having fine pores on the paper base on which the silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer on the silver halide emulsion layer side preferably has no microvoids (eg polypropylene, polyethylene) and is close to the paper substrate. More preferably, it is made of a polyolefin (for example, polypropylene, polyethylene) having micropores on its side. The density of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is 0.40 to 0.40.
It is preferably 1.0 g / ml, and 0.50 to 0.
70 g / ml is more preferred. The thickness of these multi-layer or one-layer polyolefin layers located between the paper substrate and the photographic constituent layers is preferably 10 to 100 μm, and 15
˜70 μm is more preferable. Further, the thickness ratio of the polyolefin layer and the paper substrate is preferably 0.05 to 0.2,
0.1 to 0.5 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (rear surface) of the above-mentioned paper base from the photographic constituent layers from the viewpoint of increasing the rigidity of the reflection support. In this case, the polyolefin layer on the back surface has a matte surface. Preferred are polyethylene or polypropylene, and more preferred is polypropylene. The polyolefin layer on the back surface is preferably 5 to 50 μm, more preferably 10 to 30 μm, and further preferably the density is 0.7 to 1.1 g / ml. In the reflective support of the present invention, a preferred embodiment regarding the polyolefin layer provided on the paper substrate is described in JP-A-10-3.
33277, 10-333278, 11-52.
No. 513, No. 11-65024, EP0880065.
And the examples described in EP 0880066.

Further, it is preferable that the waterproof resin layer contains a fluorescent whitening agent. Further, the fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, benzoxazole-based, coumarin-based, and pyrazoline-based fluorescent whitening agents can be preferably used, and benzoxazolylnaphthalene-based and benzoxazolyl stilbene-based fluorescent whitening agents are more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . When mixed with the water resistant resin, the mixing ratio is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass based on the resin. The reflective support may be a transmissive support or a reflective support such as the one described above coated with a hydrophilic colloid layer containing a white pigment. Further, the reflection type support may be a support having a metal surface of specular reflection or type II diffuse reflection.

As the support used in the light-sensitive material according to the present invention, a white polyester support or a layer containing a white pigment for a display is provided on the support having a silver halide emulsion layer. A support may be used. Further, in order to improve the sharpness, it is preferable to apply an antihalation layer on the silver halide emulsion layer-coated side or the back side of the support. Especially, the transmission density of the support is 0.35 so that the display can be viewed with both reflected light and transmitted light.
It is preferable to set in the range of 0.8.

In the light-sensitive material according to the present invention, a hydrophilic colloid layer for the purpose of improving the sharpness of an image can be decolorized by a treatment described in European Patent EP 0,337,490A2, pages 27 to 76. A dye (among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the light-sensitive material becomes 0.70 or more, or a divalent to tetravalent alcohol (eg, an alcohol) is added to the water-resistant resin layer of the support. 1 part of titanium oxide surface-treated with trimethylolethane)
It is preferable to contain 2 mass% or more (more preferably 14 mass% or more).

In the light-sensitive material of the present invention, a hydrophilic colloid layer is used for the purpose of preventing irradiation and halation and improving safety of safelight. It is preferable to add the dyes described above, which can be decolorized by the treatment (in particular, oxonol dyes and cyanine dyes). Furthermore, the dyes described in European Patent EP0819977 are also preferably added to the present invention. Some of these water-soluble dyes may deteriorate color separation and safelight safety when the amount used is increased. Examples of dyes that can be used without deteriorating color separation include JP-A-5-127324 and 5-1.
The water-soluble dyes described in No. 27325 and No. 5-216185 are preferable.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by treatment with a water-soluble dye is used. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a processing color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to install a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is in the wavelength range used for exposure (400 nm for ordinary printer exposure).
It is preferable that the optical density value is 0.2 or more and 3.0 or less at a wavelength having the highest optical density in the visible light region of up to 700 nm, the wavelength of the scanning exposure light source used in the case of scanning exposure). It is more preferably 0.5 or more and 2.5 or less, and particularly preferably 0.8 or more and 2.0 or less.

A conventionally known method can be applied to form the colored layer. For example, Japanese Patent Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page, and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method of incorporating a solid fine particle dispersion in a hydrophilic colloid layer, a method of mordanting an anionic dye with a cationic polymer, a method of halogenating the dye Examples thereof include a method of adsorbing to fine particles such as silver and fixing in a layer, a method of using colloidal silver as described in JP-A-1-239544, and the like. As a method for dispersing a fine powder of a pigment in a solid state, for example, a method of containing a fine powder dye that is substantially water-insoluble at a pH of 6 or less but is substantially water-soluble at a pH of 8 or more is disclosed. 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye on a cationic polymer is described in JP-A-2-84637, pages 18 to 26. For the preparation method of colloidal silver as a light absorber, see US Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, the method of incorporating a fine powder dye and the method of using colloidal silver are preferable.

Silver halide photographic light-sensitive materials include color negative films, color positive films, color reversal films,
It is used as a color reversal photographic paper, a color photographic paper, and the like. Among them, it is preferable to use it as a color photographic paper. The color photographic paper preferably has at least one yellow color forming silver halide emulsion layer, at least one magenta color forming silver halide emulsion layer, and at least one cyan color forming silver halide emulsion layer. The silver halide emulsion layers are a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer in order from the support.

However, a layer structure different from this may be adopted. The silver halide emulsion layer containing a yellow coupler may be arranged at any position on the support, but when the yellow coupler containing layer contains silver halide tabular grains, a magenta coupler containing halogenated It is preferably coated at a position farther from the support than at least one of the silver emulsion layer or the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by a sensitizing dye, the yellow-coupler-containing silver halide emulsion layer is located farthest from the support than other silver halide emulsion layers. It is preferably coated. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a central layer of the other silver halide emulsion layers, and from the viewpoint of reducing photofading, the cyan coupler-containing silver halide emulsion layer is The bottom layer is preferred. Further, each of the yellow, magenta and cyan color forming layers may be composed of two layers or three layers. For example, as described in JP-A-4-75055, JP-A-9-114035, JP-A-10-246940, U.S. Pat. No. 5,576,159, etc., a coupler layer containing no silver halide emulsion is used as a silver halide emulsion. It is also preferable to provide it adjacent to the emulsion layer to form a color forming layer.

The silver halide emulsion and other materials (additives and the like) and photographic constituent layers (layer arrangement and the like) applied in the present invention, and the processing method and processing addition applied for processing the light-sensitive material. As the agent, JP-A-62-2
15272, JP-A-2-33144, European Patent EP
Those described in 0,355,660A2, particularly those described in European Patent EP0,355,660A2 are preferably used. Furthermore, JP-A-5-34
No. 889, No. 4-359249, No. 4-313753
No. 4, No. 4-270344, No. 5-66527, No. 4
-34548, 4-145433, 2-854.
Issue 1, 1-158431, 2-90145, 3
The silver halide color photographic light-sensitive materials and their processing methods described in JP-A-194539, JP-A-2-93641, European Patent Publication No. 0520457A2 and the like are also preferable.

Particularly, in the present invention, the above-mentioned reflection type support, silver halide emulsion, further different metal ion species doped in silver halide grains, storage stabilizer for silver halide emulsion or antifoggant. , Chemical sensitization method (sensitizer),
Spectral sensitization method (spectral sensitizer), cyan, magenta, and yellow couplers and their emulsion dispersion method, color image storability improving agent (anti-staining agent and anti-fading agent), dye (coloring layer), gelatin species, photosensitive material With respect to the layer structure of the above-mentioned and the pH of the coating film of the light-sensitive material, those described in each part of the patent shown in Table 1 below are particularly preferably applicable.

[0072]

[Table 1]

Other cyan, magenta and yellow couplers are described in JP-A-62-215272, No. 9
Page 1, upper right column, line 4 to page 121, upper left column, line 6;
No. 33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right column, line 6 to page 35, lower right column, line 11 and EP0355,660A2, page 4, line 15 to 27th line, 5th page, 30th line to 28th page, last line, 45th page, 29th line to 3rd line
The couplers described on line 1, page 47, line 23 to page 63, line 50 are also useful. The present invention also relates to WO-98 / 33.
General formulas (II) and (III) of 760, JP-A-10-22
A compound represented by General Formula (D) of 1825 may be added, which is preferable.

A more specific description will be given below. As the cyan coupler that can be used, a pyrrolotriazole-based coupler is preferably used, and the coupler represented by the general formula (I) or (II) of JP-A-5-313324 and the general formula (I of JP-A-6-347960) can be used. ), As well as the exemplary couplers described in these patents. Phenol-based and naphthol-based cyan couplers are also preferable, for example, JP-A-10-3332.
A cyan coupler represented by formula (ADF) described in No. 97 is preferable. As cyan couplers other than the above,
European Patent EP 0488248 and EP 0491
Pyrroloazole-type cyan couplers described in 197A1 and 2,2, described in US Pat. No. 5,888,716.
5-diacylaminophenol couplers, pyrazoloazole type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position described in U.S. Pat. Nos. 4,873,183 and 4,916,051, particularly, JP-A-8-1711
Pyrazoloazole type cyan couplers having a carbamoyl group at the 6-position described in JP-A-85, JP-A-8-31360 and JP-A-8-339060 are also preferable.

In addition to the diphenylimidazole type cyan couplers described in JP-A-2-33144, 3-hydroxypyridine type cyan couplers (in particular, the couplers listed as specific examples) described in European Patent EP 0333185A2. (42) 4-equivalent coupler having a chlorine-releasing group to make it 2-equivalent, couplers (6) and (9) are particularly preferable) and JP-A-64-322.
Cyclic active methylene-based cyan couplers described in JP-A No. 60 (specifically, coupler example 3 listed as a specific example,
8, 34 are particularly preferred), European Patent EP 0456622.
It is also possible to use the pyrrolopyrazole type cyan couplers described in 6A1 and the pyrroloimidazole type cyan couplers described in European Patent EP0484909.

Among these cyan couplers, the pyrroloazole type cyan coupler represented by the general formula (I) described in JP-A No. 11-228138 is particularly preferable,
The description of paragraph numbers 0012 to 0059 of the patent, including the exemplary cyan couplers (1) to (47), is directly applied to the present application and is preferably incorporated as a part of the specification of the present application.

As the magenta couplers to be used, 5-pyrazolone type magenta couplers and pyrazoloazole type magenta couplers as described in the publicly known documents of the above table are used, and among them, hue, image stability, color developability, etc. 2 as described in JP-A-61-65245.
A secondary or tertiary alkyl group having a pyrazolotriazole ring 2,
A pyrazolotriazole coupler directly connected to the 3 or 6 position,
A pyrazoloazole coupler containing a sulfonamide group in the molecule as described in JP-A-61-65246,
Pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group as described in JP-A-61-147254 and alkoxy at the 6-position as described in European Patent Nos. 226,849A and 294,785A. The use of pyrazoloazole couplers having groups or aryloxy groups is preferred. In particular, as the magenta coupler, the general formula (MI) described in JP-A-8-122984 is used.
Pyrazoloazole couplers represented by are preferable, and paragraph numbers 0009 to 0026 of the patent are directly applied to the present application and are incorporated as a part of the specification of the present application. In addition to this, European Patent Nos. 854384 and 884640
The pyrazoloazole couplers having steric hindrance groups at both the 3- and 6-positions described in JP-A No. 10-29750 are also preferably used.

Further, as the yellow coupler, in addition to the compounds described in the above table, European Patent EP0447969
Acylacetamide type yellow couplers having a 3- to 5-membered cyclic structure in the acyl group described in A1 specification, malondianilide type yellow couplers having a cyclic structure described in European Patent EP 0482552A1, European Published Patent No. 953870A1. No., No. 953871A1,
No. 953872A1, No. 953873A1, No. 953874A1, No. 953875A1 and the like, pyrrole-2 or 3-yl or indole.
2 or 3-ylcarbonylacetic acid anilide type coupler,
The acylacetamide type yellow coupler having a dioxane structure described in US Pat. No. 5,118,599 is preferably used. Among them, it is particularly preferable to use an acylacetamide type yellow coupler whose acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide type yellow coupler in which one of the anilide constitutes an indoline ring. These couplers can be used alone or in combination.

The coupler is a loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents described in the table above.
It is preferable that the polymer is impregnated with or dissolved in a water-insoluble and organic solvent-soluble polymer and then emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449 at columns 7 to 15 and International Publication WO88 / 00723 at pages 12 to 30. The homopolymers or copolymers mentioned may be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high molecular weight redox compounds described in JP-A-5-333501, WO98 / 33
760, phenidone and hydrazine compounds described in U.S. Pat. No. 4,923,787 and the like, JP-A-5-2496.
The white couplers described in JP-A No. 37, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In addition, especially raising the pH of the developer,
In the case of accelerating development, German Patent No. 1961878
It is also preferable to use the redox compounds described in 6A1, European Patent 839623A1, European Patent 842975A1, German Patent 1980846A1 and French Patent 2760460A1.

In the present invention, a compound having a triazine skeleton having a high molar extinction coefficient is preferably used as the ultraviolet absorber, and for example, the compounds described in the following patents can be used. These are preferably added to the photosensitive layer and / or the non-photosensitive layer. JP-A-46-333
5, No. 55-152776, JP-A-5-19707.
No. 4, No. 5-232630, No. 5-307232,
6-211813, 8-53427, 8-2
No. 34364, No. 8-239368, No. 9-3106.
No. 7, No. 10-15898, No. 10-147577.
No. 10-182621, German Patent No. 197397.
97A, European Patent No. 711804A and Japanese Patent Publication No.
Compounds described in, for example, No. 501291.

As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As preferable gelatin, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably 5 ppm.
Or less, and more preferably 3 ppm or less. The amount of calcium contained in the light-sensitive material is preferably 20 mg.
/ M ² or less, more preferably 10 mg / m ² or less, most preferably 5 mg / m ² or less. In the present invention, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, JP-A-63-271247 is used.
It is preferable to add an antibacterial / antifungal agent as described in JP-A No. Further, the film pH of the light-sensitive material is preferably 4.0 to 7.0, and more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the light-sensitive material from the viewpoints of improving the coating stability of the light-sensitive material, preventing the generation of static electricity, adjusting the charge amount, and the like. Examples of the surfactant include anionic surfactants, cationic surfactants, betaine surfactants and nonionic surfactants, and examples thereof include those described in JP-A-5-333492. The surfactant used in the present invention is preferably a fluorine atom-containing surfactant. Particularly, a fluorine atom-containing surfactant can be preferably used.

The amount of these surfactants added to the light-sensitive material is not particularly limited, but is generally 1 × 10.
^-5 to ¹ g / m ² , preferably 1 x 10 ^-4 to 1 x 10 ^-1 g
/ M ² , more preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ^2.
Is. These fluorine atom-containing surfactants may be used alone or in combination with other conventionally known surfactants, but preferably in combination with other conventionally known surfactants.

The photosensitive material is used in a cathode ray (CR
It is also suitable for the scanning exposure method using T). A cathode ray tube exposure apparatus is simpler and more compact than an apparatus using a laser, and is low in cost. Moreover, the optical axis and color can be easily adjusted. For the cathode ray tube used for image exposure, various light-emitting bodies that emit light in the spectral region are used as necessary. For example, any one of a red light emitting body, a green light emitting body, and a blue light emitting body, or a mixture of two or more thereof is used. The spectral region is not limited to the above red, green, and blue, and a fluorescent substance that emits light in a yellow, orange, violet, or infrared region is also used. In particular, a cathode ray tube that emits white light by mixing these light emitters is often used.

When the light-sensitive material has a plurality of light-sensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at once, that is, the cathode ray. Image signals of a plurality of colors may be input to the tube so that the tube emits light. A method of sequentially inputting image signals for each color to sequentially emit light of each color and exposing through a film that cuts colors other than that color (field sequential exposure)
In general, frame sequential exposure is preferable for high image quality because a high resolution cathode ray tube can be used.

The photosensitive material is a monochromatic laser such as a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser, or a second harmonic emission light source (SHG) in which a solid-state laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal are combined. A digital scanning exposure method using density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) which is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, it is preferable to use a semiconductor laser in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

Further, as the laser light source, specifically,
A blue semiconductor laser with a length of 430 to 450 nm (2001 March)
Mon Nichia started at the 48th Joint Lecture on Applied Physics
Table), semiconductor laser (oscillation wavelength about 940 nm)
LiNbO having a waveguide-like inverted domain structure₃SH
Approximately 470nm blue extracted after wavelength conversion by G crystal
Color laser, semiconductor laser (oscillation wavelength about 1060n
m) LiNbO having a waveguide-like inverted domain structure
₃530 wavelength converted by SHG crystal of
nm green laser, wavelength 685 nm red semiconductor laser
Laser (Hitachi type No. HL6738MG), wavelength approx.
650nm red semiconductor laser (Hitachi type No. H
L6501MG) and the like are preferably used. like this
When using a different scanning exposure light source, the spectral sensitivity pole of the photosensitive material
Large wavelength can be arbitrarily set according to the wavelength of the scanning exposure light source used.
Can be set. Use a semiconductor laser as an excitation light source
Solid-state laser or semiconductor laser and nonlinear optics
In the SHG light source obtained by combining crystals,
Since the oscillation wavelength can be halved, blue light and green light can be obtained.
It Therefore, the maximum spectral sensitivity of the photosensitive material is normal blue, green,
It is possible to have three wavelength regions of red. this
The exposure time in such scanning exposure is the pixel density of 400
The pixel size is defined as the exposure time when dpi is set.
In other words, the preferable exposure time is 10 ^-FourLess than a second
Preferably 10^-6It is less than a second.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. To process the light-sensitive material of the present invention, page 26, lower right column, line 1 to page 34, upper right column, line 9 of JP-A-2-207250, and page 5, upper left column of JP-A-4-97355. The processing materials and processing methods described in the 17th line to the 18th lower right column, 20th line can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

The present invention is preferably applied to a light-sensitive material having rapid processing suitability. The color development time means the time from when the light-sensitive material enters the color developing solution to when it enters the bleach-fixing solution in the next processing step. For example, in the case of processing with an automatic developing machine, etc., the time during which the photosensitive material is immersed in the color developing solution (so-called in-liquid time), and the photosensitive material leaves the color developing solution to bleach-fix in the next processing step. The total of the time during which the film is transported in the air toward the bath (so-called air time) is called the color development time. Similarly, the bleach-fixing time refers to the time from when the light-sensitive material enters the bleach-fixing solution until it enters the next washing or stabilizing bath. Further, the washing or stabilizing time means a time (so-called in-liquid time) during which the light-sensitive material enters the washing or stabilizing solution and then remains in the solution for the drying step.

When rapid processing is performed in the present invention,
The color development time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and more preferably 30 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and further preferably 30 seconds or less and 6 seconds or more. The washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds.
Seconds or less and 6 seconds or more.

As a method of developing a photosensitive material after exposure, a method of developing with a conventional developing solution containing an alkali agent and a developing agent, an activator such as an alkaline solution containing a developing agent in a photosensitive material and containing no developing agent is used. In addition to a wet method such as a method of developing with a beta solution, a heat developing method without using a processing solution can be used. In particular, the activator method is a preferable method because the processing solution does not contain a developing agent, so that the processing solution can be easily managed and handled, and that the load at the time of processing the waste solution is small and the environment can be preserved. In the activator method, the developing agent or its precursor incorporated in the light-sensitive material is, for example, JP-A-8-2343.
88, 9-152686, 9-152693
Nos. 9-212814 and 9-160193 are preferred.

A developing method in which the amount of silver coated on the light-sensitive material is reduced and an image amplification process (intensification process) using hydrogen peroxide is also preferably used. In particular, it is preferable to use this method as an activator method. Specifically, JP-A-8
The image forming method using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152695 is preferably used. In the activator method, after processing with an activator solution, desilvering processing is usually performed, but in the image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted and a simple method such as washing with water or stabilization can be performed. Further, in the method of reading image information from a light-sensitive material with a scanner or the like, it is possible to adopt a processing form which does not require desilvering processing even when a light-sensitive material having a high silver content such as a light-sensitive material for photographing is used.

The activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention may be of known materials and methods. Preferably Research Disclosure Item 36544
(September 1994) pp. 536-541, JP-A-8
What was described in No. 234388 can be used.

When exposing the photosensitive material to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. In the present invention, European patent EP 0789270A1 and EP 078
As described in No. 9480A1, before giving image information, pre-exposure a yellow microdot pattern,
Copying restrictions may be applied.

The light-sensitive material can be preferably used in combination with the exposure and development system described in the following known materials. -Automatic printing and developing system described in JP-A-10-333253-Photosensitive material conveying device described in JP-A-2000-10206-Recording system including an image reading device described in JP-A-11-215312-JP-A-11-88619 Japanese Patent Laid-Open No. 10-2029
An exposure system comprising a color image recording system described in 50. A digital photo printing system including a remote diagnosis system described in Japanese Patent Laid-Open No. 10-210206.

[0097]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Example 1 (Preparation of Emulsion A Used for Blue Sensitive Emulsion Layer) A 1: 1 mixture (silver mol ratio) of a cubic large size emulsion A1 having an average grain size of 0.70 μm and a small size emulsion A2 having an average grain size of 0.50 μm was prepared. Then
This is Emulsion A. The coefficients of variation of the grain size distributions of Emulsions A1 and A2 were 0.09 and 0.11. In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the surface of the grain based on silver chloride. The volume from the outermost layer of this particle is 1
In the portion corresponding to 0%, 0.1 mol% of iodine ions are present with respect to the total halogen, and 1 × 10 ^-6 mol of K ₄ Ru (CN) _{6 is} contained per 1 mol of silver halide. 1 × 10 ⁻⁷ mol of yellow blood salt was present per 1 mol, and 1 × 10 ⁻⁸ mol of K ₂ IrCl ₅ (H ₂ O) was present per 1 mol of silver halide. The following blue-sensitive sensitizing dyes A and B were added to this emulsion in an amount of 3.2 × 10 ^-4 mol per mol of silver with respect to Emulsion A1 and 4.4 × 10 ^-4 mol with ^respect to Emulsion A2, respectively, for spectral sensitization. .

[0098]

[Chemical 4]

(Preparation of emulsion B used in the green-sensitive emulsion layer)
A cubic, emulsion B having an average grain size of 0.40 μm was prepared. Coefficient of variation of particle size distribution is 0.0
9. 0.4 mol% of silver bromide was locally contained on the grain surface.
0.1 mol% of silver iodide was contained near the grain surface. Similarly to Emulsion A, K ₄ Ru (CN) ₆ , yellow blood salt, K ₂
IrCl ₅ (H ₂ O) was present. Emulsion B was prepared as described above. Sensitizing dye D was 3.3 x 1 per mol of silver halide.
0 ^-4 mol, sensitizing dye E was added in an amount of 5 x 10 ^-5 mol per mol of silver halide, and sensitizing dye F was added in an amount of 2.3 x 10 ^-4 mol per mol of silver halide.

[0100]

[Chemical 5]

(Preparation of emulsion C used in the red-sensitive emulsion layer)
Cubic, large size emulsion C with average grain size 0.40 μm
A 1: 1 mixture (silver molar ratio) of 1 and 0.30 μm small size emulsion C2 was prepared. Coefficients of variation of particle size distribution are 0.09 and 0.11. Each size emulsion contained 0.1 mol% silver iodide near the grain surface and 0.8 mol% silver bromide locally contained in the grain surface.
Similarly to Emulsion A, K ₄ Ru (CN) ₆ , yellow blood salt and K ₂ IrCl ₅ (H ₂ O) were present in the emulsion grains. Sensitizing dyes G and H, respectively, per mol of silver halide are 8.0 × 10 ⁻⁵ mol for a large size emulsion and 1 for a small size emulsion.
0.7 × 10 ⁻⁵ mol was added. Further, the following compound I
In the red-sensitive emulsion layer 3.0 × 1 per mol of silver halide
0 ^-3 mol was added.

[0102]

[Chemical 6]

[0103]

[Chemical 7]

(Preparation of color photographic light-sensitive material and coating sample) The surface of a support having both sides of paper coated with polyethylene resin was subjected to corona discharge treatment, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate. Is provided
Further, the photographic constituent layers of the first layer to the seventh layer were sequentially coated to prepare a sample (101) of a silver halide color photographic light-sensitive material having the layer structure shown below. The coating liquid for each photographic constituent layer is
It was prepared as follows.

Preparation of coating liquid for first layer Yellow coupler (ExY) 57 g, color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
21 g of solvent (Solv-1) and 80 m of ethyl acetate
22 g of a 23.5% by mass gelatin aqueous solution containing 4 g of sodium dodecylbenzenesulfonate.
Emulsified and dispersed in 0 g by a high-speed stirring emulsifying machine (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion A were mixed and dissolved to prepare a coating solution for the first layer having the composition described below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Examples of the gelatin hardening agent for each layer include sodium (2,4-dichloro-6-oxide-1,
3,5-triazine) (H-1), (H-2), (H-
3) was used. In addition, Ab-1, Ab-2, Ab in each layer
-3 and Ab-4 are each 15.0 mg / m in total amount.
^{2, 60.0mg / m 2, 5.0mg} / m 2 and 10.0
It was added so as to be mg / m ² .

[0107]

[Chemical 8]

[0108]

[Chemical 9]

Next, the chemical sensitization step will be described. The above emulsion was heated to 40 ° C., chloroauric acid and the optimum amount of sodium thiosulfate pentahydrate were added, then heated at 60 ° C. for 40 minutes, then heated to 60 ° C. or higher, After adding a sensitizing dye and cooling to 40 ° C., 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the silver halide in an amount of 3.3 × 10 ⁻⁴ mol and 1.0 × 10 ⁻ mol, respectively. ³
Mol and 5.9 x 10 ^-4 mol. The emulsion of the present invention was prepared by chemical sensitization by changing chloroauric acid and sodium thiosulfate pentahydrate to the compound of the present invention as shown in Table 2 later.

Further, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to each of the second layer, the fourth layer, the sixth layer and the seventh layer at 0.2 mg / m 2.
² , 0.2 mg / m ² , 0.6 mg / m ² , 0.1 mg
/ M ² was added.

For the blue-sensitive emulsion layer and the green-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a, 7 was used.
-Tetrazaindene was added in an amount of 1 x 10 ^-4 mol and 2 x 10 ^-4 mol per mol of silver halide, respectively. Further, a copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200
000-400000) in an amount of 0.05 g / m ² . In addition, catechol-in the second layer, the fourth layer and the sixth layer
Disodium 3,5-disulfonate 6 mg / each
m ² , 6 mg / m ² , and 18 mg / m ² were added. In addition, the following dyes (the amount in parentheses represents the coating amount) were added to prevent irradiation.

[0112]

[Chemical 10]

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). Silver halide emulsion,
Indicates the coating amount in terms of silver. Support Polyethylene resin laminated paper [White pigment (TiO ₂ ; content 16% by mass, ZnO; content 4% by mass) and a fluorescent whitening agent (4,4′-bis (5 -Methylbenzoxazolyl) stilbene, content 0.03% by mass, including bluing dye (ultimate blue)] First layer (blue sensitive emulsion layer) Emulsion A 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 color image stabilizer (Cpd-1) 0.07 color image stabilizer (Cpd-2) 0.04 color image stabilizer (Cpd-3) 0.07 color image stabilizer (Cpd-8) 02 Solvent (Solv-1) 0.21

[0114]   Second layer (color mixing prevention layer)     Gelatin 0.99     Color mixing inhibitor (Cpd-4) 0.09     Color image stabilizer (Cpd-5) 0.018     Color image stabilizer (Cpd-6) 0.13     Color image stabilizer (Cpd-7) 0.01     Solvent (Solv-1) 0.06     Solvent (Solv-2) 0.22

[0115]   Third layer (green sensitive emulsion layer)     Emulsion B 0.14     Gelatin 1.36     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.14     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-4) 0.002     Color image stabilizer (Cpd-6) 0.09     Color image stabilizer (Cpd-8) 0.02     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.11     Solvent (Solv-4) 0.22     Solvent (Solv-5) 0.20

[0116]   Fourth layer (color mixing prevention layer)     Gelatin 0.71     Color mixing prevention layer (Cpd-4) 0.06     Color image stabilizer (Cpd-5) 0.013     Color image stabilizer (Cpd-6) 0.10     Color image stabilizer (Cpd-7) 0.007     Solvent (Solv-1) 0.04     Solvent (Solv-2) 0.16

[0117]   Fifth layer (red sensitive emulsion layer)     Emulsion C 0.12     Gelatin 1.11.     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-1) 0.05     Color image stabilizer (Cpd-6) 0.06     Color image stabilizer (Cpd-7) 0.02     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-10) 0.01     Color image stabilizer (Cpd-14) 0.01     Color image stabilizer (Cpd-15) 0.12     Color image stabilizer (Cpd-16) 0.03     Color image stabilizer (Cpd-17) 0.09     Color image stabilizer (Cpd-18) 0.07     Solvent (Solv-5) 0.15     Solvent (Solv-8) 0.05

[0118]   Sixth layer (UV absorption layer)     Gelatin 0.46     UV absorber (UV-B) 0.45     Compound (S1-4) 0.0015     Solvent (Solv-7) 0.25   Seventh layer (protective layer)     Gelatin 1.00     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.02     Surfactant (Cpd-13) 0.01

[0119]

[Chemical 11]

[0120]

[Chemical 12]

[0121]

[Chemical 13]

[0122]

[Chemical 14]

[0123]

[Chemical 15]

[0124]

[Chemical 16]

[0125]

[Chemical 17]

[0126]

[Chemical 18]

[0127]

[Chemical 19]

[0128]

[Chemical 20]

Using the chemical sensitizers shown in Table 2 below, instead of the chemical sensitizers in the chemical sensitization step, the remaining emulsions were prepared in the same manner as the emulsion B of the sample (101), and the sample (101 The remaining samples were prepared in the same manner as in (1).

The following experiments were conducted to examine the photographic characteristics of these samples. Experiment 1 Sensitometry (low illuminance and high illuminance) Each coated sample was subjected to gradation exposure for sensitometry using a sensitometer (FWH type manufactured by Fuji Photo Film Co., Ltd.). Equipped with SP-2 filter, exposure amount 200l
Exposure was performed for 10 seconds at low illuminance at x · sec (lux · sec). In addition, a high-intensity exposure sensitometer (HIshita Denso Co., Ltd. HI
E type) was used to provide gradation exposure for sensitometry. An SP-2 filter was attached and exposed to high illuminance for 10 ^-4 seconds. After the exposure, color development processing A described later was performed.

The magenta color density of each sample after the treatment was measured, and the 10-second exposure low illuminance sensitivity and the 10 ^-4 second exposure high illuminance sensitivity were obtained, respectively. The sensitivity was defined by the reciprocal of the exposure amount that gives a color density 1.5 higher than the minimum color density, and the relative value was defined as the relative value with the developed sensitivity of Sample (101) being 100. Further, the gradation was obtained from the slope of the line between the sensitivity point and the sensitivity point at the density of 1.5.

Experiment 2 Dependence of Sensitivity on Exposure Humidity 55% and 80% relative humidity when exposing each sample
Set to. After the exposure for 1/10 seconds, the process A was performed, and the magenta color density of each sample was measured. The sensitivity was defined by the reciprocal of the exposure amount that gives a color density 0.5 higher than the minimum color density, and the relative value when the sensitivity of the sample (101) was 100 was defined as the relative sensitivity. The difference (hereinafter referred to as dS (humidity)) obtained by subtracting the relative sensitivity when exposed at 80% humidity from the relative sensitivity when exposed at 55% humidity was obtained.

The results of Experiment 1 and Experiment 2 are summarized in Table 2.
It was shown to.

[0134]

[Table 2]

The following can be seen from Table 2 and this example. The emulsion using the compound that releases the ion having the AuS ^- structure of the present invention includes a conventional gold sulfur sensitized emulsion using chloroauric acid (Sample 101) and a gold sulfur sensitized emulsion using mesoionic gold (Sample Higher sensitivity than that of 102). Particularly high sensitivity at 10 ⁻⁴ second exposure (high illuminance exposure) and excellent reciprocity law characteristics. Moreover, while the conventional gold-sulfur sensitized emulsion had a problem that the sensitivity was likely to change due to humidity fluctuation during exposure,
It has been found that the emulsion of the present invention has the advantage that sensitivity fluctuation is extremely small. AuS ^- Structure comparison and compound B that does not release ions having the same AuS ^- the meso-ionic gold does not release ions having the structure (comparative compound A), the above effects were obtained. Further, when Comparative Compound A, Comparative Compound B, and Comparative Compound C were used without the combined use of the sulfur sensitizer, the sensitivity was remarkably low. Therefore, in the method using these gold sensitizers, sufficient sensitivity cannot be obtained without the combined use of sulfur sensitizers. It is believed that Comparative Compounds A 1, B 2, and C function only as gold sensitizers and substantially do not function as gold sulfur sensitizers. On the other hand, when Na ₃ Au (S ₂ O ₃ ) ₂ or the comparative compound D was used, without using the sulfur sensitizer, the sample 10
High sensitivity (10 sec exposure) exceeding gold sulfur sensitized emulsions such as 1
However, there was a problem that the sensitivity at the time of 10 ⁻⁴ second exposure was low. Further, the same experiment was conducted by mercaptoglucoside gold (I) (gold (I) thioglucose) described in JP-B-45-29274 was synthesized according to JP-B-45-29274 and used as a gold sensitizer. It was possible to obtain a slightly preferable result, which was equal to or higher than that of the conventional gold sensitization method. In addition, Japanese Examined Sho
The mercaptoglucoside gold (I) described in 5-29274 is
No distinction is made between α and β types. This time, we examined the three-dimensional structure and sensitizing function in more detail. That is, β
The use of mercaptoglucoside gold (I) containing only the type results in low sensitivity, and α-thioglucose gold (I) containing α type as the main component
Was found to be particularly excellent. In addition, gold (I) of the present invention
Even better results were obtained when thiomannose or the like was used. In particular, it showed remarkable effects in terms of sensitivity during exposure to high illuminance and resistance to humidity fluctuation during exposure.

The processing steps are shown below. [Processing A] The light-sensitive material 101 was processed into a roll having a width of 127 mm, imagewise exposed using a mini-lab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., and then double the color developing tank capacity in the following processing step. Until then, continuous treatment (running test) was performed. The treatment using this running liquid was designated as treatment A. Treatment process Temperature Time Replenishment amount * Color development 38.5 ° C. 45 seconds 45 ml Bleach fixing 38.0 ° C. 45 seconds 35 ml Rinse (1) 38.0 ° C. 20 seconds-Rinse (2) 38.0 ° C. 20 seconds -Rinse (3) ** 38.0 ° C 20 seconds-Rinse (4) ** 38.0 ° C 30 seconds 121 ml * Replenishment amount per 1 m ^{2 of} photosensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. The rinsing liquid is taken out from the rinsing device (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the same tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was performed from the tank countercurrent system from (1) to (4).)

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher] 800 ml water 800 ml Dimethylpolysiloxane-based surfactant 0.1g 0.1g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8g 8.8g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0g 10.0g 4,5-dihydroxybenzene-1,3- Sodium disulfonate 0.5g 0.5g Potassium chloride 10.0g- Potassium bromide 0.040g 0.010g Triazinylaminostilbene fluorescent 2.5g 5.0g Whitening agent (Hakkor FWA-SF / Showa Kagaku) Sodium sulfite 0.1g 0.1g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine                                     8.5g 11.1g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4 -Amino-4-aminoaniline / 3/2 sulfuric acid monohydrate                                     5.0 g 15.7 g Potassium carbonate 26.3g 26.3g Add water 1000 ml 1000 ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid)                                   10.15 12.50

[0138] [Bleach fixer] [Tank solution] [Replenisher] Water 700 ml 600 ml Ethylenediaminetetraacetate Iron (III) ammonium                                   47.0 g 94.0 g Ethylenediaminetetraacetic acid 1.4g 2.8g m-carboxybenzene fulphinic acid                                       8.3g 16.5g Nitric acid (67%) 16.5g 33.0g Imidazole 14.6g 29.2g Ammonium thiosulfate (750 g / l)                         107.0 ml 214.0 ml Ammonium sulfite 16.0 g 32.0 g Ammonium bisulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted with 25 ° C / acetic acid and ammonia)                                     6.0 6.0

[0139] [Rinse solution] [Tank solution] [Replenisher] Chlorinated sodium isocyanurate 0.02g 0.02g Deionized water (conductivity 5μS / cm or less)                             1000 ml 1000 ml pH 6.5 6.5

Example 2 Using the emulsion prepared in Example 1, a thin-layered sample was prepared by changing the layer structure from (101) as follows. A sample was prepared in which the emulsion B of the third layer was changed to the emulsion prepared in Example 1. Experiments 1 and 2 of Example 1 were performed on these samples. The layer structure is shown in Sample (201). The results are similar to the results of Example 1, and the effect of the present invention was confirmed even in the ultra-rapid treatment of the thinned sample.

[0141]   Preparation of sample 201   First layer (blue sensitive emulsion layer)     Emulsion A 0.24     Gelatin 1.25     Yellow coupler (ExY) 0.57     Color image stabilizer (Cpd-1) 0.07     Color image stabilizer (Cpd-2) 0.04     Color image stabilizer (Cpd-3) 0.07     Color image stabilizer (Cpd-8) 0.02     Solvent (Solv-1) 0.21

[0142]   Second layer (color mixing prevention layer)     Gelatin 0.60     Color mixing inhibitor (Cpd-19) 0.09     Color image stabilizer (Cpd-5) 0.007     Color image stabilizer (Cpd-7) 0.007     UV absorber (UV-C) 0.05     Solvent (Solv-5) 0.11

[0143]   Third layer (green sensitive emulsion layer)     Emulsion B 0.14     Gelatin 0.73     Magenta coupler (ExM) 0.15     Ultraviolet absorber (UV-A) 0.05     Color image stabilizer (Cpd-2) 0.02     Color image stabilizer (Cpd-7) 0.008     Color image stabilizer (Cpd-8) 0.07     Color image stabilizer (Cpd-9) 0.03     Color image stabilizer (Cpd-10) 0.009     Color image stabilizer (Cpd-11) 0.0001     Solvent (Solv-3) 0.06     Solvent (Solv-4) 0.11     Solvent (Solv-5) 0.06

[0144]   Fourth layer (color mixing prevention layer)     Gelatin 0.48     Color mixing prevention layer (Cpd-4) 0.07     Color image stabilizer (Cpd-5) 0.006     Color image stabilizer (Cpd-7) 0.006     Ultraviolet absorber (UV-C) 0.04     Solvent (Solv-5) 0.09

[0145]   Fifth layer (red sensitive emulsion layer)     Emulsion C 0.12     Gelatin 0.59     Cyan coupler (ExC-2) 0.13     Cyan coupler (ExC-3) 0.03     Color image stabilizer (Cpd-7) 0.01     Color image stabilizer (Cpd-9) 0.04     Color image stabilizer (Cpd-15) 0.19     Color image stabilizer (Cpd-18) 0.04     Ultraviolet absorber (UV-7) 0.02     Solvent (Solv-5) 0.09

[0146]   Sixth layer (UV absorption layer)     Gelatin 0.32     Ultraviolet absorber (UV-C) 0.42     Solvent (Solv-7) 0.08   Seventh layer (protective layer)     Gelatin 0.70     Acrylic modified copolymer of polyvinyl alcohol     (Modification degree 17%) 0.04     Liquid paraffin 0.01     Surfactant (Cpd-13) 0.01     Polydimethylsiloxane 0.01     Silicon dioxide 0.003

Each of the prepared samples was exposed in the same manner as in Experiments 1 and 2 of Example 1, and the color development processing was carried out according to the development processing B shown below and an ultra-rapid processing.

[Processing B] The above-mentioned photosensitive material was processed into a roll having a width of 127 mm, and the processing time and the processing temperature were changed by using an experimental processor which was modified from Fuji Photo Film Co., Ltd. minilab printer processor PP350. Imagewise exposure is performed on a photosensitive material sample from a negative film having an average density, and continuous processing (running test) is carried out until the capacity of the color developing replenisher used in the following processing steps becomes 0.5 times the capacity of the color developing tank. It was

Processing step Temperature Time Replenishment amount * Color development 45.0 ° C. 15 seconds 45 mL Bleach fixing 40.0 ° C. 15 seconds 35 mL Rinse 1 40.0 ° C. 8 seconds − Rinse 2 40.0 ° C. 8 seconds − Rinse 3 ** 40.0 ° C. 8 sec-Rinse 4 ** 38.0 ° C. 8 sec 121 mL Dry 80 ° C. 15 sec (Note) * Replenishment amount per 1 m ^{2 of} light-sensitive material ** Rinse screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Attach to (3) and rinse (3)
The rinse liquid is taken out from the pump and sent to a reverse osmosis module (RC50D) by a pump. The permeated water sent in the same tank is supplied to the rinse (4), and the concentrated liquid is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 mL / min, and the temperature was circulated for 10 hours a day. The rinse was a 4-tank countercurrent system from (1) to (4).

The composition of each processing liquid is as follows. [Color developer] [Tank liquid] [Replenisher]   Water 800mL 600mL   Optical brightener (FL-1) 5.0 g 8.5 g   Triisopropanolamine 8.8g 8.8g   Sodium p-toluenesulfonate 20.0 g 20.0 g   Ethylenediaminetetraacetic acid 4.0 g 4.0 g   Sodium sulfite 0.10g 0.50g   Potassium chloride 10.0g-   4,5-dihydroxybenzene-1,3-     Sodium disulfonate 0.50g 0.50g   Disodium-N, N-bis (sulfonate     Ethyl) hydroxylamine 8.5 g 14.5 g   4-Amino-3-methyl-N-ethyl-N- (β-     Methanesulfonamidoethyl) aniline / 3/2     Sulfate / monohydrate 10.0g 22.0g   Potassium carbonate 26.3g 26.3g   Add water to the total volume 1000 mL 1000 mL   pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6

[0151] [Bleach fixer] [Tank solution] [Replenisher]   Water 800mL 800mL   Ammonium thiosulfate (750 g / mL) 107 mL 214 mL   Succinic acid 29.5g 59.0g   Ethylenediaminetetrairon acetate (III)     Ammonium 47.0 g 94.0 g   Ethylenediaminetetraacetic acid 1.4g 2.8g   Nitric acid (67%) 17.5g 35.0g   Imidazole 14.6g 29.2g   Ammonium sulfite 16.0 g 32.0 g   Potassium metabisulfite 23.1 g 46.2 g   Add water to the total volume 1000 mL 1000 mL   pH (25 ° C, adjusted with nitric acid and aqueous ammonia) 6.00 6.00

[0152] [Rinse solution] [Tank solution] [Replenisher]   Chlorinated sodium isocyanurate 0.02g 0.02g   Deionized water (conductivity 5 μS / cm or less) 1000 mL 1000 mL   pH (25 ° C) 6.5 6.5

[0153]

[Chemical 21]

Example 3 Using the sample prepared in Example 2, image formation was carried out by laser scanning exposure. As the laser light source, a semiconductor laser GaAlAs (oscillation wavelength 808.5 nm)
YAG solid-state laser (oscillation wavelength 94
6 nm) S of LiNbO ₃ having an inversion domain structure
473 nm wavelength-converted and taken out by the HG crystal,
Semiconductor laser GaAlAs (oscillation wavelength 808.7n
LiNb having an inversion domain structure of YVO ₄ solid-state laser (oscillation wavelength 1064 nm) using m) as an excitation light source
Wavelength converted by SHG crystal of O ₃ and extracted 532
nm and AlGaInP (oscillation wavelength about 680 nm: type No. LN9R20 manufactured by Matsushita Electric Industrial Co., Ltd.) were used. The laser light of each of the three colors was moved in a direction perpendicular to the scanning direction by a polygon mirror so that the sample could be sequentially scanned and exposed. Fluctuations in the amount of light due to the temperature of the semiconductor laser are suppressed by using a Peltier device to keep the temperature constant. The effective beam diameter is 80 μm,
The scanning pitch is 42.3 μm (600 dpi), and 1
The average exposure time per pixel was 1.7 × 10 ⁻⁷ seconds. After the exposure, the color development processing B was performed, and the same results as those of the high illuminance exposure in Examples 1 and 2 were obtained, and it was found that it is also suitable for image formation using laser scanning exposure. It was Instead of the above laser light source, a blue semiconductor laser with a wavelength of about 440 nm (presented by Nichia at the 48th Joint Lecture in Applied Physics, March 2001), a semiconductor laser (oscillation wavelength: about 1060)
nm) having a waveguide-like inversion domain structure
Approximately 53 wavelength converted by O ₃ SHG crystal
A similar experiment was performed using a 0 nm green laser and a red semiconductor laser (Hitachi type No. HL6501MG) having a wavelength of about 650 nm, and the same results as above were obtained.

[0155]

The emulsion of the present invention is a silver halide emulsion having high sensitivity, high contrast, small sensitivity fluctuation due to difference in humidity conditions at the time of exposure, excellent reciprocity law characteristics at high illuminance, and stable production. Suitable for

Claims (3)

[Claims] 1. A silver halide emulsion characterized in that a compound releasing a compound having a chalcogen atom-metal atom bond is added and reacted. 2. The silver halide emulsion according to claim 1, wherein the compound that releases the compound having a chalcogen atom-metal atom bond is a compound that releases Au ^I Ch ⁻ ions. Ch represents an S atom, a Se atom or a Te atom. However, as a compound that releases Au ^I Ch ⁻ ions,
Excludes gold (I) thioglucose having β-type as a main component. 3. A silver halide emulsion characterized by being chemically sensitized by a compound releasing a compound having a chalcogen atom-metal atom bond.