JPH0473740A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the photosensitive material which is improved in safe light characteristic and has a high sensitivity and excellent preservable property by incorporating silver halide particles of the dyes expressed by specific formula into at least one layer of silver halide emulsion layers. CONSTITUTION:This photosensitive material contains at least one layer of the silver halide emulsion layers on a base and contains the silver halide particles spectrally sensitized by at least one kind of the dyes expressed by formula I in at least one layer of the silver halide emulsion layers. In the formula, R<1>,R<2> denote an alkyl group; R<3>, R<4>, R<5>, R<6>, R<7>, R<8>, R<9>, R<10> denote a hydrogen atom, alkyl group, halogen atom, alkoxy group; R<5> denotes an alkyl group of 544 value of S expressed by S=3.536L-2.661B+535.4. Z denotes the nonmetallic atom group necessary for forming a 5- or 6-membered carbon ring. X(-) denotes an acid anion: l1 dentoes 0 or 1.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide photographic material, and more specifically, a silver halide photographic material that has excellent safelight properties, high sensitivity, and good storage stability. Regarding materials (hereinafter referred to as photosensitive materials).

[Background of the Invention] In recent years, from various viewpoints, there has been an increasing demand for photosensitive materials with high image quality, and therefore, research has been carried out on improving image quality from various angles.

It is well known that specific sensitizing dyes are used to expand the wavelength range to which silver halide emulsions are uniquely sensitive and to spectrally sensitize them to the visible light range to which they are not originally sensitive.

The sensitizing dye used for the above purpose should be in the appropriate spectral sensitizing wavelength range, have high sensitivity, cause less dye staining after processing, and should not affect other photosensitive layers. Those having favorable properties such as no diffusion or interaction with additives other than sensitizing dyes are selected.

Further, as more preferable conditions, it is required that a light-sensitive material containing the sensitizing dye should have less decrease in sensitivity and less occurrence of fog when stored.

It is known that certain pentamethine dyes used in red-sensitive emulsions are very effective as such spectral sensitizing dyes, but depending on the conditions of use, (1) safelight around 590 nm Because it has unfavorable sensitivity to light, safelight causes fogging (hereinafter, the difficulty of causing fogging is referred to as "safelight property"). Safelight cannot be used for brightness.

(2) Because the absorption spectrum of the anti-irradiation dye and the spectral sensitivity distribution of the red-sensitive emulsion do not match,
Sharpness is not sufficiently improved.

It had drawbacks such as.

That is, the characteristics required of recent photosensitive materials are high image quality and, furthermore, ease of handling. With conventional dyes, when the spectral sensitivity distribution is shortened with the intention of matching the absorption spectrum of the anti-irradiation dye with the spectral sensitivity distribution of the red-sensitive emulsion for the purpose of improving sharpness, the spectral sensitivity region is shortened. The situation is such that the wavelength edge overlaps with the wavelength of safelight light around 590 nm, causing deterioration of safelight properties, and a sensitizing dye that satisfies both sharpness and safelight properties has not been obtained.

Furthermore, in recent years, color paper has been required to have higher sensitivity in order to improve the efficiency of printing operations.

However, with conventional dyes, although it is possible to create a highly sensitive material by increasing the amount of dye added, it also causes an increase in residual color contamination and degrades other properties. At present, no dye has been obtained that achieves high sensitivity.

As a result of extensive studies, the present inventors found that by using a sensitizing dye in which a substituent having a specific sterimole parameter was introduced into a photosensitive material at a specific substitution position, the safelight property was improved, and the above-mentioned The inventors have discovered that a photosensitive material can be obtained that can satisfy various properties at the same time, and have completed the invention.

[Object of the Invention] Therefore, an object of the present invention is to provide a photosensitive material containing a novel pentamethine dye that sensitizes in the red region, having improved safelight properties, high sensitivity, and excellent storage stability. .

[Structure of the Invention] The above object of the present invention is to provide a silver halide photographic material comprising at least one silver halide emulsion layer on a support, in which at least one of the silver halide emulsion layers has the following general formula [I This is achieved by a silver halide photographic light-sensitive material characterized by containing silver halide grains spectrally sensitized with at least one of the dyes shown below.

In general formula [I], R1 and R2 are alkyl groups (
For example, it represents a methyl group, an ethyl group, a propyl group, a methoxyethyl group, an ethoxyethyl group, a 4-sulfobutyl group, a 3-sulfopropyl group, a carboxymethyl group, and preferably an alkyl group containing no acid group.

R3R4R6R7R11R9 and RIO are hydrogen atoms, alkyl groups (e.g. methyl group, ethyl group, hensyl group, methoxyethyl group), halogen atoms (e.g. fluorine atom,
base atom, bromine atom, iodine atom), and an alkoxy group (eg, methoxy group, ethoxy group).

R5 represents an alkyl group in which the value of S is 544 or less and is represented by S-3,538L-2,6[I1B + 535.4.

Here, L is Verloop, Hoperestraten, Tapker (A, Verloop, W, Hoogenstr.
aaten.

J. Tipker), “Drug Design (Dr.
ugDesing) J Volume 7, [edited by E, J, Ar1ens] Academic
B is the sum of the sterimolar parameters (B is the sum of the sterimolar parameters)
Represents the smaller value of 1+B4 and B2+B (unit is in).

R3, R4R7, R8R8, R9R9 and R'' may cooperate to form a ring.

Moreover, these rings may have a substituent.

Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered carbon ring.

Examples of these carbocycles include 5,5-dimethyl-2-cyclohexene ring, 4,4,6,6-tetramethyl-2-cyclohexene ring, and 5,5-dimethyl-2-cyclohexene ring.
-cyclohexene ring is preferred.

X1@ represents an acid anion, specifically a halogen ion (e.g. chloride ion, bromide ion, iodine ion), p
-) Luenesulfonate ion, p-chlorotoluenesulfonate ion, perchlorate ion, boron tetrafluoride ion and the like. g.

represents O or 1, and gl is 0 when forming an inner salt.

As a sensitizing dye having a substituent defined by a specific sterimolar parameter, JP-A-63-163843
No. 83-167348, No. 63-197936, No. 83-218941, No. 83-239436,
The one disclosed in Publication No. 63-30334°C is known. However, all of these disclosures are benzoxazolocarbocyanine derivatives, and nothing is disclosed about benzothiazolodicarbocyanine dyes.

In addition, in these inventions, the substituents defined by the sterimole parameter act to shorten the spectral sensitivity distribution, and the substituents are intended to act to eliminate the shortwave side of the spectral sensitivity distribution. This is completely different from an invention.

Therefore, the present invention uses a benzothiazolodicarbocyanine dye having a substituent defined by the sterimolar parameter, and thereby achieves the effect of lowering the sensitivity on the short wavelength side of the spectral sensitivity distribution. It's completely different.

The dye represented by the general formula [I] can be further expressed by the following general formula [I1
] When used in combination with at least one of the dyes shown below, the effects of the present invention can be further enhanced.

General formula [I1] In general formula [II], R11 and R12 are alkyl groups (e.g. methyl group, ethyl group, propyl group, methoxyethyl group, ethoxyethyl group, 4-sulfobutyl group,
3-sulfopropyl group, 2-sulfoethyl group, carboxynemethyl group), and an alkyl group containing no acid group is more preferable.

Z2 is a nonmetallic atomic group necessary to form a 5- or 6-membered carbon ring (e.g., 5,5-dimethyl-2-cyclohexene ring, 4,4,6°6-tetramethyl-2-cyclohexene ring) represents. Preferably it is a 5,5-dimethyl-2-cyclohexene ring.

Z3 and Z4 represent a group of nonmetallic atoms necessary to form a benzene ring or a naphthalene ring, and the rings formed by Z3 and Z4 may be the same or different.

The benzene ring or naphthalene ring formed by z 3 Z4 includes those each having a substituent.

Examples of the heterocyclic moiety formed by fused benzene or naphthalene rings formed by Z3 and Z4 include benzothiazole, 5-chlorobenzothiazole, 5-methylbenzothiazole, 5-bromobenzothiazole,
5-fluorobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 5-butoxybenzothiazole, 5-nitrobenzothiazole, 5
- trifluoromethylbenzothiazole, 5-hydroxybenzothiazole, 5-carboxybenzothiazole, 6-methylbenzothiazole, 6-chlorobenzothiazole, 6-nitrobenzothiazole, 6-methoxybenzothiazole, 6-amyloxybenzothiazole,
6-hydroxybenzothiazole, 5,6-dimethylbenzothiazole, 4,6-dimethylbenzothiazole,
5-ethoxybenzothiazole, naphtho [2,1-d
lthiazole, naphtho[I,2-d]thiazole, naphtho[2,3-d]thiazole, 5-nitronaphtho[2,
1-d]thiazole, and the like.

Furthermore, the most preferred examples of the heterocyclic moiety fused with the benzene ring or naphthalene ring include 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-fluorobenzothiazole, 5-phenylbenzothiazole, 5-
Methoxybenzothiazole, 5,6-dimethylbenzothiazole, naphtho[2,1-d]thiazole, naphtho[
I<2-d]thiazole, naphtho[2,3-d]thiazole, and the like.

X2″ represents an acid anion, specifically a halogen ion (e.g. chloride ion, bromide ion, iodide ion), p
Examples include -toluenesulfonate ion, p-chlorotoluenesulfonate ion, perchlorate ion, boron tetrafluoride ion, and the like.

g2 represents O or 1, and when forming an inner salt, g
2 is O.

Specific examples of the sensitizing dyes represented by the general formulas [I] and [n] are shown below, but the sensitizing dyes according to the present invention are not limited to these compounds.

The following margin is the following margin: General formula [I] and general formula [II] used in the present invention
The sensitizing dye represented by is described, for example, in "The Chemistry of Heterocyclic Compounders J" by Palmer, F.
laterocyclic compounds) 1st
Volume 8, [The Cyanine Dye and Related Compounds J
s and Re1ated Compound-ds)
(A, Weissherger ed., Inter
Science, New York 1984)
It can be easily synthesized by the method described in .

The optimum amount of the sensitizing dyes of the general formulas [I] and [II] can be determined by methods known to those skilled in the art. These methods include, for example, a method in which the same emulsion is divided, each emulsion contains a different concentration of sensitizing dye, and the performance of each emulsion is measured.

The amount of the sensitizing dye added in the present invention is not particularly limited, but it ranges from 2X1.0-' mol to 1 mol per mol of silver halide.
It is preferable to use ×10 to 2 moles, and more preferably 5 ×
Preferably, to-6 moles to 5 X 10-3 moles are used.

Methods well known in the art can be used to add the sensitizing dye to the emulsion. For example, these sensitizing dyes can be dispersed directly in the emulsion, or dissolved in a water-soluble solvent consisting of pyridine, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, or mixtures thereof, or diluted with water. Alternatively, they can be dissolved in water and added to the emulsion in the form of a solution.

Ultrasonic vibrations can also be used during the dissolution process.

Alternatively, as described in U.S. Pat. No. 3,469.987, the dye is dissolved in a volatile organic solvent, this solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. A method is also used in which a water-insoluble dye is dispersed in a water-soluble solvent without being dissolved, and this dispersion is added to an emulsion, as described in Japanese Patent Publication No. 4B-24185. The dye can also be added to the emulsion in the form of a dispersion by an acid dissolution and dispersion method. Other additions to emulsions include U.S. Patent Nos. 2,912,345 and 3,3
No. 42,605, No. 2,99B, No. 287 and No. 3,
It is also possible to use the methods described in each specification of No. 425,835.

The general formula [N and general formula [I1] used in the present invention
The sensitizing dye represented by ] can be added to the emulsion at any time during the manufacturing process from the time of silver halide grain formation to just before coating on the support.

Specifically, before the formation of silver halide grains, during the formation of silver halide grains, after the completion of silver halide grain formation until the start of chemical sensitization, at the start of chemical sensitization, during chemical sensitization, and during chemical sensitization. It can be added at any time selected from the end of chemical sensitization and the time of application. Further, the addition may be carried out once or in multiple parts. or,
The sensitizing dye according to the present invention can also be used in combination with other sensitizing dyes. In this case, each sensitizing dye is dissolved in the same or different solvent, and prior to addition to the emulsion,
These solutions may be mixed or added separately to the emulsion. When adding them separately, the order and time interval can be arbitrarily determined depending on the purpose.

Higher spectral sensitivity can be obtained by using the sensitizing dye used in the present invention in combination with a compound that provides supersensitizing action.

Examples of compounds having such a supersensitizing effect include U.S. Pat. Nos. 2,933,390 and 3,418,9.
No. 27, No. 3゜511,864, No. 3,815,61
No. 3, No. 3,615.632, No. 3,835,721
Compounds having a pyrimidylamino group or a triazinylamino group described in each specification, British Patent No. 1,137.5
Aromatic organic formaldehyde condensates described in No. 80, halogenated benzito+7 azole derivatives described in U.S. Pat.
No. 541, bispyridinium compounds described in No. 59-188841, aromatic heterocyclic quaternary salt compounds described in JP-A-59-191032, JP-A-Sho BO-793
Electron-donating compound described in Publication No. 48, U.S. Patent No. 4,3
Polymer containing aminoallylidenemalononitrile units described in No. 07.1133, JP-A-55-149937
1,3-oxadiazole derivatives described in U.S. Pat. No. 3,815.833, amino 1.2. Examples include 3,4-thiatriazole derivatives.

There is no particular restriction on the timing of addition of these supersensitizers, and they can be added at any time according to the timing of addition of the sensitizing dyes. The amount added is from IX10-' per mole of silver halide]X10-
The sensitizing dye is selected in the molar range from 1/1O to 10
It is used at an addition molar ratio of /1.

The sensitizing dye of the present invention is preferably used in combination with a phenol resin having a repeating unit represented by the following general formula [III] from the viewpoint of sensitivity and raw sample storage stability.

General formula [m] [wherein RA is a hydrogen atom, a halogen atom, an alkyl group,
Alkenyl group, cycloalkyl group, aryl group, alkoxy group, hydroxyl group, amino group, acyl group or -5
O2RC represents a hydroxyl group, an alkoxy group, an alkyl group, an aryl group, an amino group or a hydrazino group.

R8 represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. m represents an integer from 0 to 3. ] The silver halide grains contained in the silver halide emulsion layer according to the present invention may be any one of silver chloride, silver chlorobromide, silver bromide, silver iodobromide, and silver chloroiodobromide. , or a mixture of these particles. Among these, silver chloride-containing emulsions are more preferred.

The composition of the silver halide grains used in the present invention may be uniform from the inside to the outside of the grain, or
The composition inside and outside the particle may be different. Further, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

The particle size of the silver halide grains used in the present invention is not particularly limited, but in consideration of sensitivity and other photographic performance, it is preferably 0.2 to 1.6 μl, more preferably 0.2 μl to 1.6 μl, and more preferably 0.2 to 1.6 μl.
It is in the range of 25 to 1.2 μm.

The above particle size can be measured by various methods commonly used in the technical field.

A typical method is Labrant's "Particle Size Analysis Method JA
, S, T, M Symposium on Light, Microcopy 1955, pp. 94-122, or chapter 2 of ``Theory of the Photographic Process'' by Mies and James, 3rd edition, Macmillan Publishing Co., Ltd. (1966). Are listed.

Particle size can be measured using the projected area of the particle or a direct approximation.

If the particles are of substantially uniform shape, the particle distribution can be expressed fairly accurately as diameter or projected area.

In the present invention, the grain size distribution of the silver halide grains may be polydisperse or monodisperse, but preferably a monodisperse emulsion. More preferably, the particle size distribution of the silver halide grains has a coefficient of variation of 0.22 or less,
More preferably 0.15 or less, particularly preferably 0.10
The following monodisperse silver halide grains are shown below.

Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution,
It is defined by the following equation.

Here, ri represents the particle size on each side of the particle, and ni represents the number of particles having the particle size of ri. In the case of spherical silver halide grains, the grain size referred to here means the diameter, and in the case of grains with shapes other than cubic or spherical, the diameter when the projected image is converted into a circular image of the same area. .

The silver halide grains according to the present invention may be obtained by any of the acid method, neutral method, and ammonia method. The particles may be grown all at once, or may be grown after seed particles are produced.

The method of creating and growing the seed particles may be the same or different.

The soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferred. Furthermore, as a form of simultaneous mixing method,
It is also possible to use the pAg-chondrol double jet method described in No. 48521 and the like.

Furthermore, if necessary, a silver halide solvent such as thioether may be used.

Further, compounds such as mercapto group-containing compounds and nitrogen-containing heterocyclic compounds may be added during or after the formation of silver halide grains.

Any shape of the silver halide grains according to the present invention can be used.

One preferred example is a cube having the f1001 plane as a crystal surface. Also, U.S. Patent No. 4,183,756, U.S. Pat.
No. 9, specifications and gazettes such as Special Publication No. 55-42737,
The Journal of Photographic Science” (J, photogr, Sci,), 21.39
(1973), particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be produced and used.

Furthermore, particles having twin planes may be used.

The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains according to the present invention can be produced by cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or a complex salt thereof, rhodium salt or a complex salt thereof, iron salt or a complex salt thereof, in the process of forming and/or growing the grain. Metal ions can be added using complex salts to be included inside the particles and/or on the surface of the particles, and by placing them in a suitable reducing atmosphere.
Reduction sensitizing nuclei can be provided inside the particles and/or on the surface of the particles.

It is preferable to include an iridium salt or a complex salt thereof inside the particles and/or on the particle surface since illuminance failure characteristics during exposure are improved.

In the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may remain contained.

In the case of removing the salts, it can be carried out based on the description in Research Disclosure No. 17643.

The silver halide grains used in the present invention may be grains in which a latent image is mainly formed on the surface, or grains in which a latent image is mainly formed inside the grain. Preferably, the particles are particles on which latent images are mainly formed.

In the present invention, chemical sensitizers, such as chalcogen sensitizers, can be used. The chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred.

As the sulfur sensitizer, known ones can be used.

For example, thiosulfate, allylthiocarbazide, thiourea,
Examples include allyl isothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Others: U.S. Patent Nos. 1,574,944 and 2,410,689
No. 2,278,947, No. 2,728゜668, No. 3,5 (No. 11,313, No. 3,656,955, OLS) l-, 422,869
Sulfur sensitizers described in the specifications or publications of JP-A-56-24937 and JP-A-55-45016 can also be used.

The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH and temperature, and the size of silver halide grains, but as a guide, it is 1 mol of silver halide.
(1-' mol to 10-' mol is preferred.

A selenium sensitizer can also be used instead of a sulfur sensitizer. Examples of selenium sensitizers include aliphatic isoselenocyanates such as allyl isoselenocyanate, selenoureas, selenoketones, selenoamides, selenocarboxylic acid salts and esters, selenophosphates, diethylselenide, and diethylselenide. Selenides such as
．． No. 574,944, No. 1,602,592, No. 1,
No. 623,499, each specification, etc. Furthermore, reduction sensitization can also be used together. The reducing agent to be used is not particularly limited, but includes known stannous chloride, thiourea dioxide, hydrazine, polyamine, and the like.

Also, noble metal compounds such as platinum compounds and palladium compounds can be used.

As the gold sensitizer, the oxidation number of gold may be +1 or +3, and other types of gold compounds may also be used.

Typical examples include chloraurate, potassium chloroaurate, auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyanoauric azide, ammonium aurothiocyanate, pyridyl trichlorogold, gold sulfide, and gold selenide. Can be mentioned.

The amount of gold sensitizer added varies depending on various conditions, but as a guideline it is from 10@-8 mol to 10@-1 mol, preferably from 10@-' mol to 10@-2 mol. These compounds may be added at any time during silver halide grain formation, during physical ripening, during chemical ripening, or after completion of chemical ripening.

In the present invention, when a gold compound is used, it is possible to obtain a photosensitive material having better raw sample preservation properties.

In the present invention, silver halide emulsions are added during chemical sensitization, for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of light-sensitive materials, and/or to maintain stable photographic performance. Compounds known in the photographic industry as antifoggants or stabilizers can be added at at least one point after the end of chemical sensitization and before coating the silver rhodanide emulsion. .

Examples of stabilizers that can be used in the present invention include tetrazaindene compounds such as 7-hydroxy-5-methyl-1,3°4.7a-tetrazaindene.

In the present invention, the antifoggant that can be effectively used has a solubility product (Ksp) with silver ions of CalX 10-
``Hereinafter, preferably Ksp is I x 10-11 or less. Compounds with a solubility product exceeding this, that is, compounds with a smaller ability to form salts with silver ions, may not have the desired effect. .

For measurements and calculations of solubility products, refer to “New Experimental Chemistry Course Volume 1” (
You can refer to pages 233-250 (published by Maruzen).

Examples of antifoggants include "Chemical &
"Pharmaceutical Piurethane" (Chemical
al and Pharmaceutical Bul
letin) (Tokyo) Volume 26, 314 (1
97g), JP-A-55-79436, [Berichte・
Berjchte der Deutsch
en Chemischen Ge5ellsdraft
t) 82.121 (1,948), U.S. Patent No. 2.84
No. 3,491, No. 3,017,270, British Patent No. 9
40, No. 1.69, JP-A-51-102639, “
Journal of the American Chemical Society, 44.1502-1510,
J (Beilsteins Handbuch
der OrganlschenChewle) 2
B, 41.43.58, etc., and can be synthesized according to the methods described in these documents.

When the present invention is applied to color light-sensitive materials, various dye-forming substances are used, and a typical example is a dye-forming coupler.

As the yellow dye-forming coupler, various acylacetanilide couplers can be preferably used.

Among these, benzoylacetanilide and pivaloylacetanilide compounds are advantageous.

Specific examples of yellow couplers that can be used include British Patent 1,0
No. 77.874, Japanese Patent Publication No. 45-40757, Japanese Patent Application Publication No. 4
No. 7-1031, No. 47-28133, No. 48-94
No. 432, No. 50-87650, No. 51-3631, No. 52-115219, No. 54-99433, No. 54-133329, No. 5B-30127, U.S. Patent No. 2.875,057, No. 3 , No. 253.924, No. 3.265,506, No. 8,408,194, No. 3
, No. 551.155, No. 3,551,156, No. 3.
[! No. 64.841, No. 3,725.072, No. 3
, 730.

No. 722, No. 3.891.445, No. 3,900,4
No. 83, No. 3929.484, No. 3,933.50
No. 0, No. 3,973,968, No. 3,990.896
No. 4,012,259, No. 4,022,620, No. 4,029,508, No. 4,057,432,
4,108゜942, 4,133,958, 4,269,936, 4゜2H,053, 4,
No. 304,845, No. 4,314,023, No. 4,3
No. 38,327, No. 4,356,258, No. 4.38
No. 6,155, No. 4,401,752, etc.

The diffusion-resistant yellow coupler used in the light-sensitive material of the present invention is preferably represented by the following general formula [Y].

General formula [Y] CHi l+ In the formula, R8 represents a halogen atom or an alkoxy group.

R2 represents a hydrogen atom, a halogen atom, or an alkoxy group which may have a substituent.

R3 is an acylamino group, an alkoxycarbonyl group, an alkylsulfamoyl group, an arylsulfamoyl group, an arylsulfonamide group, an alkylureido group, an arylureido group, a succinimito group, an alkoxy group, or an aryl group, which may have a substituent. Represents an oxy group.

Zl represents a hydrogen atom or a substituent that leaves when coupled with an oxidized color developing agent.

In the present invention, couplers represented by the following general formulas [a] and [a1] can be preferably used as magenta dye image-forming couplers.

General formula [a] represents Ra+ -NHCO- (N atom is bonded to the carbon atom of the pyrazolone nucleus) or -NHCONH-, and m is 1 or 2.

Preferred examples of the compound represented by general formula [a] are as follows.

The following margin is Ar [where Ar represents an aryl group, Ra represents a hydrogen atom or a substituent, and Ra2 represents a substituent.

Y represents a hydrogen atom or a substituent that leaves by reaction with an oxidized product of a color developing agent; It represents a group of nonmetallic atoms necessary to form a ring, and the ring formed by Za may have a substituent. X represents a hydrogen atom or a substituent that can be separated by reaction with an oxidized product of a color developing agent. Moreover, Ra represents a hydrogen atom or a substituent. ] As the substituent represented by Ra, for example, a halogen atom,
Alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, acyl group, sulfonyl group, sulfinyl group, phosphonyl group, carbamoyl group, sulfamoyl group, cyano group,
Spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, peterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group, imide group, ureido group , sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

These include, for example, U.S. Pat. No. 2,600.788;
゜OB 1. , No. 432, No. 3,062,653,
3,127.2 [i9, 3,311,476,
No. 3,152,896, No. 3,419.391, No. 3,159,429, No. 3,555,318, No. 3
．． No. 684514, No. 3,888,680, No. 3,9
No. 07.571, No. 3928.044, No. 3,93
No. 0,881, No. 3,930, 1R3fi, No. 3,9
33,500, etc., JP-A-49-29639
No. 49-111831, No. 49-129538, No. 50-13041, No. 52-58922, No. 5
No. 3-62454, No. 55-118034, No. 5B-
No. 38043, No. 57-35858, No. 60-231
Publications No. 1155, British Patent No. 1,247,493,
Specifications of Belgian Patent No. 769116, Belgian Patent No. 792,525, West German Patent No. 2,158.1.11, Japanese Patent Publication No. 1973
-80479, JP-A-59-125732, JP-A No. 59
-228252, 59-162548, 59-
No. 171956, No. 80-33552, No. 60-43
No. 659, West German Patent No. 1,070,030, and US Patent No. 3,725.067.

Typical specific examples of the magenta coupler represented by the general formula Ea13 used in the present invention are listed below.

2H5 Below margin* -OH M-11 M-15 C8H17(1) M-]6 H3 Cyan dye image-forming couplers include phenolic,
Naphthol type 4-equivalent or 2-equivalent type cyan dye image-forming couplers are typical, and U.S. Pat.
No. 0, No. 2,356,475, No. 2,362.598
No. 2,367.531, No. 2,369,929, No. 2,423.730, No. 2,474.239,
2,476.008, 2.498.4136,
2,545.687, 2,728.1360,
2,772,182, 2,895,826, 2.971(,146, 3,002.838, 3,419.390, 3,448゜622, 3
, 476.583, 3,737.316, 3゜758.308, 3,839.044, British Patent No. 478.991, 945,542, 1,084
, No. 480, No. 1,377.233, No. 1. :118
Specifications of No. 8.024 and No. 1,543,040,
and JP-A-47-37425, JP-A No. 50-10135.
No. 50-25228, No. 50-112038,
No. 50-117422, No. 50-130441, No. 51-6551, No. 5l-37Ei47, No. 51-
No. 52828, No. 51-108841, No. 53-10
No. 9630, No. 54-48237, No. 54-8612
No. 9, No. 54-131931, No. 55-32071, No. 59-148050, No. 59-31953, and No. 60-117249.

As the cyan image forming coupler, a coupler represented by the following general formula [E] or [F] can be preferably used.

General formula [E] 21M In the formula, R and E represent an aryl group, a cycloalkyl group, or a heterocyclic group. R2E represents an alkyl group, an aryl group, a cycloalkyl group or a heterocyclic group.

R and E represent a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. ztE represents a hydrogen atom, a halogen atom, or a group that can be separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

General formula [F] H In the formula, R4F represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, nonyl group, etc.). R5F
represents an alkyl group (eg, methyl group, ethyl group, etc.).

R6F represents a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group (eg, methyl group, ethyl group, etc.).

22F represents a hydrogen atom, a halogen atom, or a vine group that is separated by reaction with an oxidized product of an aromatic primary amine color developing agent.

In the present invention, silver halide is dispersed in a hydrophilic colloid. It is advantageous to use gelatin as the hydrophilic colloid, but other hydrophilic colloids can also be used.

Examples of preferred hydrophilic colloids include gelatin such as alkali-treated gelatin or acid-treated gelatin, which is most commonly used; however, a portion of this gelatin may be substituted with derivative gelatin such as phthalated gelatin, phenylcarbamoyl gelatin, albumin, agar, Arahiacom, alginic acid, partially hydrolyzed cellulose derivative, partially hydrolyzed polyvinyl acetate,
It can also be replaced with polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds.

The light-sensitive material of the present invention can contain various known photographic additives. For example, such an example is
UV absorbers (e.g. benzophenone compounds and benzotriazole compounds), dye image stabilizers (e.g. phenol compounds, bisphenol compounds, hydroxychroman compounds, bisspirochroman compounds, etc.)
hydantoin compounds, dialkoxybenzene compounds, etc.), stain inhibitors (e.g. /S hydroquinone derivatives, etc.), surfactants (e.g. sodium alkylnaphthalene sulfonate, sodium alkylbenzene sulfonate, sodium alkylconophosphate ester sulfonate, polyalkylene glycols, etc.), water-soluble anti-irradiation dyes (e.g. azo compounds, styryl compounds, triphenylmethane compounds, oxonol compounds, anthraquinone compounds, etc.), hardeners (e.g. triazine compounds, vinyl sulfones), compounds, acryloyl compounds, ethyleneimino compounds, N-methylol compounds, epoxy compounds, water-soluble aluminum salts, etc.), film property improvers (e.g. glycerin, aliphatic polyhydric alcohols, polymer dispersions (latex) ), solid/or liquid paraffin, and colloidal silica), optical brighteners (eg, diaminostilbene compounds), and various oil-soluble dyes.

In addition to each emulsion layer, the photographic constituent layers constituting the light-sensitive material of the present invention include a subbing layer, an intermediate layer, a yellow filter layer, an ultraviolet absorbing layer, a protective layer, an antihalation layer, etc., as appropriate. can be provided.

Examples of the support for the photosensitive material of the present invention include supports such as paper, glass, cellulose acetate, nitrocellulose, polyester polyamide, and polystyrene, and laminates of paper and polyolefin (such as polyethylene and polypropylene). A laminate of more than one type of substrate can be used as appropriate depending on the purpose.

The support is then generally subjected to various surface treatments to improve adhesion to the silver halide emulsion layer, such as
Treatment to roughen the surface mechanically or with a suitable organic solvent;
Surface treatment such as electron impact treatment or flame treatment or subbing treatment is performed.

Images can be formed on the photosensitive material of the present invention by subjecting it to a development process known in the art.

The black and white developing agent used in black and white development processing is T.
, II, The Theory of Photographic Processes by J.
y orPhotogr-apic Process
) can be used as described on pages 291 to 326 of the 4th edition.

The color developing agents used in the color development process include those known and widely used in various color photographic processes.

These developing agents include aminophenol and p-phenylenediamine derivatives. Since these compounds are more stable than in the free state, they are generally used in the form of salts, such as hydrochlorides or sulfates. In addition, these compounds are generally used in an amount of about 0.1 g to about 30 g per gram of color developer.
g concentration, preferably from about 1 g to 1 g of color developer.
Use at a concentration of approximately 15g.

Examples of aminophenol-based developing agents include 0-aminophenol, p-aminophenol, and 5-amino-2
-hydroxy-toluene, 2-amino-3-hydroxytoluene, 2-hydroxy-3-amino-1,4-dimethylbenzene, and the like.

Particularly useful primary aromatic amine color developing agents are N, N
It is a '-dialkyl-p-phenylenediamine compound, and the alkyl group and phenylene group may be substituted with any substituent.

Among them, N is a particularly useful compound example.

N'~dimethyl-p-phenylenediamine hydrochloride, N-
Methyl-p-phenylenediamine hydrochloride N.

N'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N,N'-diethylaniline, 4
-amino-N-(2-methoxyethyl)-N-ethyl-
Examples include 3-methylaniline-p-toluenesulfonate.

In addition to the above-mentioned developing agent, known developer component compounds can be added to the developer applied to the processing of the photosensitive material of the present invention.

For example, alkaline agents such as sodium hydroxide and potassium carbonate, alkali metal sulfites, alkali metal bisulfites,
Alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included.

The temperature of the development process is 15°C or higher, generally 20°C to 50°C.
℃, and for rapid processing, it is also preferable to carry out the treatment at 30'C or higher. The pH of the developer is usually above 7, most commonly about 9-12.

In carrying out the present invention, when using a light-sensitive material containing a high silver chloride emulsion as a silver halide emulsion, it is preferable to use a developer that does not substantially contain bromide ions. This is because the presence of bromine ions significantly impairs rapid developability.

A developing solution that does not substantially contain bromide ions refers to a developing solution that contains only l x 10 -3 mol/p or less of bromide ions.

In addition to silver chloride, high chloride silver halide includes some silver bromide,
May contain silver iodide. When silver bromide is contained, a small amount of bromide ions are eluted into the developer during development. This eluted bromide ion partially replaces the chlorine ion in the high chloride silver halide, which is not developed even in the developer, and the solubility of silver in areas other than the image area, which is not developed even in the developer. It is possible that bromine ions are retained in the material and taken out to the next process, but as mentioned above, when high chloride silver halide is developed, bromine ions may be eluted into the developer, albeit in small amounts. However, it is impossible to maintain the bromide ion concentration in the developer at completely zero.

"Substantially not containing bromine ions" means that only bromine ions that are unavoidably mixed in, such as trace amounts of bromine ions eluted during development, are contained, and the above-mentioned IX
"to-3 moles" indicates the upper limit of the concentration of unavoidably mixed bromide ions.

The light-sensitive material of the present invention may contain these color developing agents in the hydrophilic colloid layer as color developing agents themselves or as precursors thereof, and may be processed in an alkaline activation bath.

Color developing agent precursors are compounds that can produce color developing agents under alkaline conditions, and include Schiff base type precursors with aromatic aldehyde derivatives, polyvalent metal ion complex precursors, phthalic acid imide derivative precursors, phosphoric acid amide derivative precursors, and sugar amine reactions. Precursors include urethane precursors.

Precursors for these aromatic primary amine color developing agents are described, for example, in U.S. Pat.
7.114, 2,695,234, 3,719
．． No. 492, specifications of British Patent No. 803,784, Japanese Patent Application Publication Nos. 53-185828 and 54-79035, Research Disclosure Magazine No. 15159,
It is described in No. 12146 and No. 13924.

These aromatic primary amine color developing agents or their precursors need to be added in such an amount that sufficient color development can be obtained upon activation treatment.

This amount varies greatly depending on the type of photosensitive material, but is generally between 0.1 mol and 5 mol, preferably between 0.5 mol and 3 mol, per mol of silver halide. These color developing agents or their precursors can be used alone or in combination.

To incorporate these color developing agents or their precursors into light-sensitive materials, they can be dissolved in a suitable solvent such as water, methanol, ethanol, acetone, etc., and added. It can be added as an emulsified dispersion using a high boiling point organic solvent such as, or it can be added by impregnating a latex polymer as described in Research Disclosure No. 14850.

In the case of a color photosensitive material, the photosensitive material of the present invention is subjected to a bleaching process and a fixing process after color development. Bleaching treatment may be performed simultaneously with fixing treatment.

Many compounds are used as bleaching agents, but iron (
■), cobalt (■), copper (■), etc., multi-reef metal compounds, especially complex salts of these polyvalent metal cations and organic acids,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid,
Aminopolycarboxylic acids such as N-hydroxyethylethylenediaminediacetic acid, malonic acid, tartaric acid, malic acid,
Metal complex salts such as diglycolic acid and dithioglycolic acid, ferricyanates, dichromates, etc. are used alone or in appropriate combinations.

As the fixing agent, a soluble complexing agent that solubilizes silver halide as a complex salt is used. Examples of the soluble complexing agent include sodium thiosulfate, ammonium thiosulfate, potassium thiocyanate, thiourea, and thioether.

After the fixing process, a washing process is usually performed.

Furthermore, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

The stabilizing liquid used in the stabilization treatment can contain a pH adjuster, a chelating agent, an anti-spill agent, and the like. For these specific conditions, reference may be made to JP-A-58-134636 and the like.

The effects of the present invention are effectively exhibited when the photosensitive material of the present invention is a black-and-white or color photosensitive material, such as black-and-white photographic paper, color photographic paper, color reversal film, color reversal vapor, or the like.

[Example] The present invention will be described in more detail below with reference to Examples, which are just one specific example of the present invention, and the present invention is not limited thereto.

Example 1 [Preparation of silver halide emulsion E m -A -D] A solution containing a silver nitrate solution, potassium bromide and sodium chloride was added to an inert gelatin aqueous solution by a double jet method to maintain the conditions listed in Table 1. and added.

Next, desalting and washing with water were carried out by a conventional method to prepare silver chlorobromide emulsions E m -A -D shown in Table 1, respectively.

Multilayer photosensitive material samples 101 to 125 were prepared using the above emulsions and subjected to the following treatments, and each was evaluated for safelight property, sensitivity, and raw sample storage stability as shown below.

A multilayer photosensitive material, sample 101, was prepared by sequentially coating the following seven layers on polyethylene resin-coated paper.

Note that the amounts added below are expressed per unit unless otherwise specified.

Layer 1...1, 2 g of gelatin, 0.35 g (metallic silver equivalent, same hereinafter) of blue-sensitive silver chlorobromide emulsion (Em-A was sensitized with sensitizing dye 5D-1), and 0.9 g of yellow coupler (YC-1) and 0.015g of 2,5
- A layer containing dioctyl phthalate (hereinafter referred to as DOP) in which di-t-octylhydroquinone (hereinafter referred to as HQ-1) is dissolved.

Layer 2...0.7g gelatin and 0.08g HQ-
A layer containing DOP 1 dissolved therein.

Layer 3: 1.25 g gelatin, 0.45 g green-sensitive silver chlorobromide emulsion (Em-B sensitized with sensitizing dye 5D-2) and 0.53 g magenta coupler (MC-3).
) and O, a layer containing DOP in which 12 g of (A-1), 0.2 g of (A-2) and 0.015 g of HQ-1 were dissolved.

Layer 4...1.3g gelatin and 0.08g HQ-
D in which 1 and 0.5g of ultraviolet absorber (UV-1) were dissolved.
Layer containing OP.

Layer 5: 1.4 g of gelatin, 0.3 g of red-sensitive silver chlorobromide emulsion (Em-B) was optimally sensitized at 57°C using sodium thiosulfate and chloroauric acid, and the sensitizing dye ( S-1),
phenolic resin C55) and 4-hydroxy-6-methyl-1,3゜3a,7-chitrazaindene as a stabilizer) and 0.3 g of cyan coupler (CC
-1) and 0.2g of (CC-2) and 0.02g of HQ-
A layer containing DOP in which 1 and 1 are dissolved.

Layer 6...1. Og gelatin and 0.032g HQ
-1 and 0.2g of (UV-1) dissolved in 0.14g
A layer containing a DOP of.

Layer 7: 0.003 g of silicon dioxide and 0.00 g of gelatin.
A layer containing 5g.

As a hardening agent, (H-1) was added at 5II1g per tg of gelatin.
, (H-2) was added in an amount of 10 mg per 1 g of gelatin.

Furthermore, in the preparation of sample 101, the sensitizing dye (S-
Samples 102 to 125 were prepared in the same manner except that 1) was changed as shown in Table 2.

Below margin (A-1) (A (UV-1) H (YC-1) (CC-1) (H-1) Shi! (H-2) C (CHz302C)1=CHz)4・NH2CH2C
I (2SO3K (SD-1) adduct C6H1, (b) (SD-2) I (SS) The obtained sample was evaluated as follows.

(1) Evaluation of safelight properties Safelight properties were evaluated using an IOW light bulb by exposing the sample to light for 5 minutes from a distance of 1m through an Eastman Kodak 111fl13 filter, and then treating it according to the processing steps shown below. The fog density was determined by measuring the fog density.

Safelight property - cyan cuff'1 value of exposed sample - cyan fog value of unexposed sample [Color development process] [I] Color development 38°C 3 minutes 30 seconds [2 bleach-fixing 33°C 1 minute 30 seconds [3] Washing treatment 25°C to 30°C 3 minutes [4] Drying 75
℃～80℃ Approximately 2 minutes [Processing liquid composition] (Color developer) Benzyl alcohol 15ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide
1.3g sodium chloride
0.2g potassium carbonate
30.0g hydroxylamine sulfate 3.
0g polyphosphoric acid (TPPS) 2.5g
3-Methyl-4-amino-N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 5.5g Fluorescent brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.0g water potassium oxide
Add 2.0g water to make a total volume of 1fI, p
Adjust to H10,20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 80g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% aqueous solution) 100ml ammonium sulfite (40% aqueous solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid. Add water to bring the total amount to 1 g.

(2) Evaluation of relative sensitivity Each sample was measured using a photosensitive needle KS-7 type (Konica Corporation).
After being exposed to red light using a primary color separation filter, it was processed according to the same processing steps as in (1). After processing, PD
Sensitometric measurements were performed using an A-65 type densitometer (manufactured by Konica).

The results were determined as relative sensitivity, with the sensitivity of sample No. 101 being 100. The optical density reference point from which the sensitivity was determined was [fog +0.20].

(3) Evaluation of raw sample storage stability Raw sample storage stability is evaluated by the change in sensitivity before storage and after storage at 25°C and 60% (relative humidity) for one month, and the rate of change in sensitivity is calculated using the following formula: I asked for it. The sensitivity was determined by performing the same exposure as above, then performing the same development process as in (1), and measuring the cyan density.

Sensitivity change due to storage (%) The obtained results are summarized in Table-2.

The following margin comparison dyes *: S-1 *: S-2 *: S-3 The sensitizing dyes were added in an amount of 4 x 10' mol per 1 mol of silver halide.

When used together, the total amount was added in this amount. The ratio at that time is shown in ().

2H5 5HL1 As is clear from Table 2, the samples using the sensitizing dye of the present invention were found to be excellent in safelight properties, sensitivity, and raw sample storage properties, which are the effects of the present invention.

Example 2 Em-A used in the first layer of samples 101 to 125 prepared in Example 1 was replaced with Em-C, and E used in the third and fifth layers was replaced with Em-C.
A sample was prepared in the same manner except that m-B was replaced with E m -D. Further, safelight property, sensitivity, and raw sample storage stability were evaluated in the same manner as in Example 1 except that the following treatment steps were performed, and the same results as in Example 1 were obtained.

Even when the sensitizing dye of the present invention is rapidly processed, the effects of the present invention can be obtained.

<Processing process> Processing temperature Time color development 35±0.3℃ 45 seconds bleach fixing
35±0.5℃ 45 seconds stabilization 30~3
Dry for 90 seconds at 4℃ 60-80℃ 60
Seconds (color developer) Pure water
800 ml triethanolamine
10g N,N-diethylhydroxylamine 10g potassium chloride 2g potassium sulfite
0.3g 1-hydroxyethylidene-1゜1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid 1. (1g catechol-
Disodium 3,5-disulfonate 1.0g N-ethyl-N-β~methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.5g optical brightener (4,4'-diaminostilbenesulfone acid derivative) 1, Og
Add water to bring the total volume to 111, and adjust the pH to 1 with potassium hydroxide.
o, adjust to lO.

(Bleach-fix solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Adjust the pH to 8.2 with potassium carbonate or glacial acetic acid. , add water to bring the total volume to 1 fI.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0g ethylene glycol 1. ogl-hydroxyethylidene-1゜1-diphosphonic acid 2.0g ethylenediaminetetraacetic acid 1.0g aqueous ammonia (20% aqueous solution) 3.0g ammonium sulfite
3.0g optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.5g, add 1g water, add sulfuric acid or potassium hydroxide to pH 7
, adjust to 0.

[Effects of the Invention] By using the sensitizing dye represented by the general formula [I] or the sensitizing dye and the sensitizing dye represented by the general formula [n] according to the present invention, fog due to safelight is reduced, and A photosensitive material with high sensitivity and excellent storage stability for raw samples can be obtained.

Applicant Co., Ltd.

Claims (2)

[Claims] (1) In a silver halide photographic material comprising at least one silver halide emulsion layer on a support, at least one of the silver halide emulsion layers has the following general formula [I]
A silver halide photographic light-sensitive material comprising silver halide grains spectrally sensitized with at least one of the dyes represented by: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 represent an alkyl group. R^3,
R^4, R^6, R^7, R^8, R^9, R^1^0
represents a hydrogen atom, an alkyl group, a halogen atom, or an alkoxy group, and R^5 represents an alkyl group having an S value of 544 or less, represented by S=3.536L-2.661B+535.4. Here L
represents the sterimolar parameter L (unit: Å), and B is the sum of the sterimolar parameters B_1+B_4, B_2+B
Represents the smaller value of _3 (unit: Å). Also, R^3 and R^4, R^7 and R^8, R^8 and R^
9. R^9 and R^1^0 may cooperate to form a ring. Z represents a group of nonmetallic atoms necessary to form a 5- or 6-membered carbon ring. X^1^Θ represents an acid anion, and l_1 represents 0 or 1. ] (2) The silver halide photograph according to claim 1, which contains at least one compound represented by general formula [II] together with at least one compound represented by general formula [I]. photosensitive material. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1^1 and R^1^2 represent an alkyl group. Z^2 represents a group of nonmetallic atoms necessary to form a 5- or 6-membered carbon ring. Z^3 and Z^4 represent a group of nonmetallic atoms necessary to form a benzene ring or a naphthalene ring, and the rings formed by Z^3 and Z^4 may be the same or different. good. X^2^Θ represents an acid anion, and l^2 represents 0 or 1. ]