JPS6323146A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having a large inter-image effect, without impairing an another photographic characteristics by incorporating a silver halide emulsion having <=0.7mum mean particle size to a photosensitive silver halide emulsion layer, and a kind of a specific compd. to the photosensitive silver halide emulsion layer and/or a nonphotosensitive layer. CONSTITUTION:In the titled material mounted at least one layer of the photosensitive silver halide emulsion layer on a substrate, said layer contains the silver halide emulsion having <=0.7mum mean particle size, and the photosensitive silver halide emulsion layer and/or the non-photosensitive layer contains at least one kind of the compd. shown by formulas I and II. In the formulas, R is a straight or a branched alkylene or alkenylene group, etc., Z and Z' are each a polar substituent, R1 is hydrogen atom, a substd. or an unsubstd. alkyl or aryl group, X is hydrogen atom, an alkaline metal atom, ammonium group or a group capable of cleaving at alkaline condition, (n) is 0 or 1.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic material with improved interimage effect and improved sharpness and graininess.

(Prior art) By color-developing a silver halide color photographic light-sensitive material, the oxidized aromatic-amine color developing agent and coupler react to produce indophenol, indoaniline, indamine, azomethine, and phenoxazine. , phenazine and similar dyes are known to form color images. In this system, subtractive color reproduction is usually used for color reproduction, with silver halide emulsions selectively sensitive to blue, green, and red, and yellow, magenta, and cyan color image-forming agents, which are complementary colors, respectively. is used. To form a yellow image, for example, acylacetanilide or dibenzoylmethane couplers are used, and to form a magenta image, pyrazolone, pyrazolobenzimidazole, pyrazolopyrazole, pyrazolotriazole, cyano Acetophenone or indacylon couplers are used, and phenolic or naphthol couplers are primarily used to form cyan images.

By the way, the dyes produced from these couplers do not have ideal spectral absorption spectra; magenta and cyan dyes in particular have broad absorption spectra or have sub-absorption in the short wavelength region, making it difficult for color photographic materials to be used. Unfavorable for color reproduction.

In particular, sub-absorption in the short wavelength region tends to cause a decrease in chroma. As a means of improving this, it is possible to improve it to some extent by creating an interimage effect.

Regarding the interimage effect, see, for example, Hanson (
Hanson et al., 'Journal of the Optical Society of America
l of the 0ptical 5ociety
of America)', Volume 42, Pages 663-6
69 pages, and A. Thiels (^, Th1efs
), 'Zeitschrift für Weissenschaftliche Fotografie Fotophysik.
Lant Photohiemy (Zeitschrift)
f'UrWissenschaftliche P
photography.

Photophysique and Photo-
chemie), Vol. 47, pp. 106-118 and pp. 246-255.

U.S. Pat. No. 3,536,486 discloses that by introducing diffusible 4-thiazoline-2-thione into exposed color reversal photographic elements, U.S. Pat.
No. 487 describes a method for introducing diffusive 4-thiazoline-2-thione into an unexposed color reversal photographic element to obtain desirable interimage effects.

Furthermore, in Japanese Patent Publication No. 4B-34169, N-2
It has been described that the presence of a substituted-4-thiazoline-2-thione compound produces a significant interimage effect.

Also, the provision of a colloidal silver-containing layer between the cyan and magenta layers of color reversal photographic elements to obtain desirable interimage effects is discussed in Research Disclosure, Vol. 13.
1, Section 13116 (1975).

Furthermore, U.S. Pat. No. 4,082,553 discloses a color reversal photosensitive material having a layer arrangement that allows movement of iodide ions during development, in which one layer contains latent image-forming silver haloiodide grains. , latent image-forming silver halide grains in another layer;
A method is described for obtaining good interimage effects by including silver halide grains whose surfaces are caplasied so that they can be developed independently of imagewise exposure.

However, in the above method, the interimage effect is insufficient, the use of a colloidal silver-containing layer, the introduction of fogged silver halide grains, etc., lead to a decrease in color density in color reversal light-sensitive materials. It has its drawbacks.

In addition to the above, there are known couplers (DIR couplers) that can release development-inhibiting substances such as benzotriazole derivatives and mercapto compounds during a coupling reaction with an oxidized form of a color developing agent during a color development process. However, this effect is hardly exhibited in color reversal photosensitive materials. It is also known that interimage effects can be produced by using hydroquinone compounds that can release development-inhibiting substances such as iodide ions and mercapto compounds during development. Their use has been limited because they are accompanied by significant color loss and result in a decrease in color density.

OBJECTS OF THE INVENTION The first object of the present invention is to provide a multilayer color photographic material that has a large interimage effect without impairing other photographic properties.

A second object of the present invention is to provide a silver halide photographic material with excellent sharpness.

(Structure of the Invention) An object of the present invention is to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, in which the light-sensitive silver halide emulsion layer has an average grain size of 0. Contains a silver halide emulsion of 7 μm or less, and contains at least one compound represented by the following general formulas (1) and (n) in the photosensitive silver halide emulsion layer and/or non-photosensitive layer. This was achieved using a silver halide photographic material characterized by the following.

General formula (1) General formula (n) In the formula, R represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group, and Z and Z' represent a polar substituent.

R1 is a hydrogen atom, a substituted or unsubstituted alkyl group,
Represents an aryl group, alkenyl group, or aralkyl group. X represents a hydrogen atom, an alkali metal atom, an ammoniamyl group, or a group that cleaves under alkaline conditions. n
represents O or 1.

More specifically, R is a linear or branched alkylene group (
For example, methylene group, ethylene group, propylene group, butylene group, hexylene group, 1-methylethylene group, etc.)
Linear or branched alkenylene groups (e.g., vinylene, 1-methylvinylene, etc.), linear or branched aralkylene groups (e.g., benzylidene, etc.), arylene groups (e.g., phenylene, naphthylene, etc.) ).

As the polar a tlA group represented by Z and Z',
For example, quaternary ammoniamil groups (e.g., trimethylammonylamyl chloride group, dimethylbenzylammonylamyl chloride group, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, 2-methoxyethoxy group, etc.), alkylthio groups (e.g., Methylthio group, butylthio group,
), arylthio group (e.g., phenylthio group, etc.)
, heterocyclic oxy group (e.g., 2-pyridyloxy group,
2-imidazolyloxy group, etc.), heterocyclic thio group (e.g., 2-benzthiazolylthio group, 4-virazolylthio group, etc.), carbamoyl group (e.g., unsubstituted carbamoyl group, methylcarbamoyl group, etc.), sulfamoyl group groups (e.g., unsubstituted sulfamoyl group, methylsulfamoyl group, etc.), acyloxy groups (e.g., acetyloxy group, benzoyloxy group, etc.), ureido groups (e.g., unsubstituted ureido group, methylureido group, ethyl ureido group, etc.), thioureido group (e.g., unsubstituted thioureido group, methylthioureido group, etc.), sulfonyloxy group (e.g., methanesulfonyloxy group, p-
toluenesulfonyloxy group, etc.).

Furthermore, Z' is a substituted or unsubstituted amino group (including salt form; for example, an amino group, a hydrochloride of an amino group, a methylamino group, a dimethylamino group, a hydrochloride of a dimethylamino group, a diethylamino group, a diethylamino group) hydrochloride, dibutylamino group, dipropylamino group, N-dimethylaminoethyl-N-methylamino group, etc.), oryloxy group (e.g., phenoxy group, etc.), heterocyclic group (e.g., 1- morpholino group, 1-piperidino group, 2-pyridyl group, 4-pyridyl group, 2-chenyl group, 1-pyrazolyl group, 2-imidazolyl group, 2-tetrahydrofuryl group, tetrahydrochenyl group, etc.), cyano group There may be. Here, Z' is a sulfonic acid group, a carboxylic acid group, a hydroxy group, and an alkoxycarbonyl group (for example,
methoxycarbonyl group, ethoxycarbonyl group, etc.).

R represents a hydrogen atom, a substituted or unsubstituted alkyl group (e.g., methyl group, ethyl group, propyl group, 2-dimethylaminoethyl group, etc.), a substituted or unsubstituted aryl group (e.g., phenyl group, 2-dimethylaminoethyl group, etc.), methylphenyl group, etc.)
, a substituted or unsubstituted alkenyl group (eg, propenyl group, 1-methylvinyl group, etc.), or a substituted or unsubstituted aralkyl group (eg, benzyl group, phenethyl group, etc.).

X is a hydrogen atom, an alkali metal atom (e.g., sodium atom, potassium atom, etc.), an ammoniamyl group (e.g., trimethylammonylamyl chloride group, dimethylbenzylammonylamyl chloride group, etc.), or a group that cleaves under alkaline conditions It represents a group (a group that can become X=H or an alkali metal under alkaline conditions, such as an acetyl group, a cyanoethyl group, a methanesulfonylethyl group, etc.).

In general formula (I) or (II), preferably R
is an alkylene group and n-1 in general formula (1).

The first developer of the color reversal light-sensitive material contains a silver halide solvent, and the presence of this solvent causes dissolution physical development in the first development.

The smaller the grain size of the silver halide emulsion, the greater the dissolution by a silver halide solvent. The interaction of the compound represented by the general formula (1) or [■] of the present invention with iodide ions in the silver halide emulsion suppresses dissolution by the silver halide solvent, and the silver halide emulsion is developed. is suppressed.

It is believed that the interaction between the compound represented by formula (1) or [■] and iodide ions in the silver halide emulsion produces a large interimage effect.

That is, when a silver halide emulsion layer (hereinafter referred to as "receiving layer") and/or a non-light-sensitive layer that undergoes an interimage effect contains a compound represented by the above general formula (1) or When the N that provides the effect (hereinafter referred to as "imparting layer") is developed and iodine ions diffuse from the providing layer to the receiving layer, development of the receiving layer is greatly inhibited.

On the other hand, if the donor layer is not developed and iodine ions are not diffused from the donor layer to the receptor layer, the development trn of the receptor layer is small.

This large difference in development suppression produces a large inter-image effect.

However, if the grain size of the silver halide emulsion in the receiving layer is large, dissolution by the silver halide solvent in the first developer is low, so that the compound represented by the general formula CI) or (II) and the iodide ion interact with each other. The effect of inhibiting development due to this action is small, and the interimage effect is also small.

According to research conducted by the present inventors, as in the present invention, the average grain size of the silver halide emulsion in the receiving layer is set to 0.7 μm or less, preferably 0.6 μm or less, and more preferably 0.7 μm or less.
55 μm or less, and the silver halide emulsion layer (a layer containing a silver halide emulsion with an average grain size of 0.7 μm or less)
and/or by having at least one of the compounds represented by formulas (1) and (II) endogenously present in the non-photosensitive layer (preferably, the silver halide emulsion layer and/or its adjacent layer). We were able to create a large interimage effect.

Effects similar to those of the color anti-transfer through-hole optical material were also found in other color photographic materials and black and white photographic materials.

In the case of spherical silver halide grains, the average grain size referred to here is the average diameter of the grains, and in the case of grains with shapes other than cubic or spherical, the projected image is converted into a circular image of the same area. 7 is defined by the following formula when the individual particle diameter is r8 and the number is ni.

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

A typical method is Loveland
), "Particle Size Analysis Methods J A, S, T, M, Symposium on Light Microscopy, 1955, pp. 94-122," or "Photographic Process Theory" by Mies and James, 3rd edition, Macmillan Publishing. Issue (1
966), Chapter 2.

Specific examples of the compounds represented by the general formula CI) or (n) are shown below, but the compounds of the present invention are not limited thereto.

・HCI ・HCI ・HCl ・H(1 ・HCI ・2H(1 l ・HCI ・HCI! ・HCI) The compound represented by the general formula (1) used in the present invention is:
“Advances in Heterocyclic Chemistry”
icChemistry), Vol. 9, pp. 165-209 (1968).

Typical synthesis examples are shown below.

Synthesis Example 1 Synthesis method of compound (2) 15g of 2,5-dimercapto-1,3,4-thiadiazole was added to 300mJ of acetone, and then 22ml of
28% solution of sodium methoxide and 12 g of β-chloropropionamide were added.

Furthermore, 15 g of sodium iodide was added to this reaction solution for 20
The mixture was heated to reflux for an hour. After cooling, the obtained crystals were collected by filtration and washed with water. The crystals were recrystallized from a mixed solvent of dimethylformamide and methanol to obtain compound (2).

Yield 12.0g Melting point 175-177°C Synthesis Example 2 Synthesis method of compound (4) 2.5-dimercapto-1,3,4-thiadiazole 1
5.0g, 28% sodium methoxide solution 20mj+
Add to 100ml of ethyl alcohol, dissolve by heating,
-13.5 g of chloroethyl urea was added dropwise. After the addition, the mixture was heated under reflux for 4 hours. After the reaction, the reaction solution was poured into 700 ml of ice water, the precipitated crystals were collected by filtration, and recrystallized from metallurgy.
Target object (4) was obtained.

Yield 16.4g Melting point 174-176℃ Synthesis Example 3 Synthesis method of compound (3) After adding 17.6g of 1-(3-dimethylaminopropyl)thiosemicarbazide to 150mf of ethyl alcohol, 7.9g of potassium hydroxide was added. was added and dissolved. Subsequently, 34.3 g of carbon disulfide was added dropwise at room temperature and then heated under reflux for 5 hours. After cooling, the obtained crystals were collected by filtration and recrystallized from methyl alcohol and concentrated hydrochloric acid to obtain the desired product (3).

Yield: 11.3 g Melting point: 204-205°C Synthesis Example 4 Synthesis method of compound (5) 30.0'g of 2,5-dimercapto-1,3°4-thiadiazole, 2128% molten sodium methane t(1,
40 ml was added to 200 ml of ethyl alcohol, dissolved by heating, and 20.8 g of methoxyethyl chloride was added dropwise. After the addition, the mixture was heated under reflux for 2 hours. After the reaction, the reaction solution was filtered, the filtrate was dried under reduced pressure, and then recrystallized from ethyl acetate and n-hexane to obtain the desired product (5).

Yield 29.8g Melting point 59-60'C Synthesis Example 5 Synthesis method of compound (7) 10.5g of 2,5-dimercapto-1,3°4-thiadiazole, sodium methoxide 28%? 8114m
Add 1 to 100mj+ of ethyl alcohol and dissolve by heating.
8.5 g of methylthioethyl chloride was added dropwise. After the dropwise addition, the mixture was heated under reflux for 3 hours.

After the reaction, the reaction solution was poured into ice water 11 and the precipitated crystals were collected by filtration.
Recrystallize from ethyl acetate and n-hexane to obtain the desired product (7)
I got it.

Yield 8.6g Melting point 75-76°C Synthesis Example 6 Synthesis method of compound (29) 15.0g of 2,5-dimercapto-1,3°4-thiadiazole, 17.4g of 2-chloroethyltrimethylammonium chloride was added to n- Butyl alcohol 100ml
The mixture was heated and dissolved, and 7.8 ml of pyridine was added dropwise. After the dropwise addition, the mixture was heated under reflux for 3 hours. After the reaction, the reaction solution was cooled, and the precipitated crystals were collected by filtration and recrystallized from methyl alcohol to obtain the desired product (29).

Yield: 118.1g Melting point: 222-225°C When the compound represented by the general formula (1) or (If) of the present invention is used in a multilayer color photographic material, the average particle size is 0.7.
It is preferably contained in at least one of the silver halide emulsion layers and/or non-photosensitive layers (for example, yellow filter layer, antihalation layer, intermediate layer, or protective layer) containing a silver halide emulsion of micrometer or less. teeth,
This is the case when it is contained in the silver halide emulsion layer and/or its adjacent layer. Most preferably, it is contained in the silver halide emulsion layer.

Furthermore, when applying the present invention to black and white photographic materials,
A compound represented by the general formula (1) or (If) is contained in a silver halide emulsion layer and/or a protective layer containing a silver halide emulsion having an average grain size of 0.7 μm or less.

The compounds of the present invention represented by general formulas (1) and (If) differ depending on the nature, purpose, or development method of the silver halide photographic material to which they are applied, but generally the halogenated compounds present in the same layer or adjacent layer are 1 mole of silver
0-1 to 10-5 mol, preferably 3X10-
"~3X10-' moles.

In order to introduce the compounds represented by the general formulas (1) and (I[) of the present invention into a light-sensitive material, a solvent commonly used in photographic light-sensitive materials such as water, methanol, ethanol, propatool, or fluorinated alcohol can be used. and then added to the hydrophilic colloid. When included in the silver halide emulsion layer, when forming grains of the silver halide emulsion,
During physical ripening, immediately before chemical sensitization, during chemical sensitization, after chemical sensitization,
Alternatively, it may be used at the time of preparing the coating solution, and is selected depending on the purpose.

The photosensitive materials to which the present invention is applied include, for example, color negative films, color reversal films (inner and outer molds), color papers, color positive films, color reversal papers,
Any of color photographic materials such as color diffusion transfer process and Gouy transfer process, black and white photographic materials such as black and white negative film, black and white photographic paper, X-ray film, and lithographic film may be used, but color reversal film and color reversal paper may be used. It is preferable to apply it to

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. The preferred silver halide is silver iodobromide or silver iodochlorobromide containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide containing from about 0.5 mole percent to about 10 mole percent silver iodide.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof. Also, mixtures of particles of various crystal forms may be used.

Even in monodispersed emulsions with a narrow silver halide grain size distribution,
Alternatively, a polydisperse emulsion having a wide distribution may be used.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
Volume 176, No. 17643 (December 1978), 2
pp. 2-23, “1. Emulsion production (Ea+ulsion P
187, No. 18716 (November 1979)
May), 648, the method described above can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimie et Phys
ique Photographique.

Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, for Focal Press (G, F, D
uffin.

Photographic Emulsion Che
mrstry, Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, for Focal Press (V, L, Zelikmane
tal, Making and Coating
Photographic emulsion, F
ocal Press, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

In addition, known silver halide solvents (for example, ammonia, Rodankali or U.S. Pat.
-No. 144319, No. 54 [00717 or No. 5]
Physical ripening can also be carried out in the presence of thioethers and 1,000-ion compounds (described in No. 4-155828, etc.).

This method also yields a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling I3Ag and pH during grain formation. For more information, please see Photographic Science
and Engineering (Photographic
5science and engineering
), Volume 6, pp. 159-165 (1962); Journal of Photographic Science (Jour
nal ofPhotographic 5cienc
el 12, pp. 242-251 (1964), U.S. Patent No. 3. 655. No. 394 and British Patent No. 1
, No. 413,748.

Furthermore, as a monodisperse emulsion, silver halide grains having an average grain diameter of more than about 0.1 micron, at least 9
Emulsions in which 5% by weight are within ±40% of the average grain diameter are typical. The average grain diameter is 0.25 to 2 microns, and at least 95% by weight or (number of grains) less than
Emulsions such as those within the range of 0% can be used in the present invention.

A method for producing such an emulsion is described in U.S. Pat. No. 3,574.6.
No. 28, No. 3,655,394 and British Patent No. 1,
No. 413,748. Also, JP-A-48-
No. 8600, No. 51-390'27, No. 51-830
No. 97, No. 53-137133, No. 54-48521
No. 54-99419, No. 1-37635, No. 5
Monodisperse emulsions such as those described in No. 8-49938 can also be preferably used in the present invention.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineering (
Gutoff, Photographic 5ci-
ence and Engineering), No. 14
Vol. 248-257 (1970); U.S. Patent No. 4.
434. No. 226, No. 4,414,310, No. 4
, 433°048, 4,439,520 and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency with aggravating dyes, and the above-mentioned U.S. Pat.
．． No. 434,226 describes this in detail.

The crystal structure may be --like, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Patent No. 3,505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Patent Application No. 58-248469.

Further, silver halides having different compositions may be joined by epitaxial joining, and for example, silver halides of different compositions may be joined by epitaxial joining.
It may be bonded with a compound other than silver halide, such as lead oxide. These emulsion grains are described in U.S. Patent No. 4,094.
, No. 684, No. 4,142.900, No. 4,459,
353, British Patent No. 2,038,792, U.S. Patent No. 4,349.622, U.S. Patent No. 4,395.478, U.S. Patent No. 4,433.501, U.S. Patent No. 4,463,087, U.S. Patent No. 3
．． It is disclosed in No. 656.962, No. 3,852.067, Japanese Unexamined Patent Publication No. 162540/1983, and the like.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present.

These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains.

In order to remove soluble root salts from the emulsion before and after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method, etc. are used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening, and spectral enhancement.

The additives used in such processes are based on the research and research mentioned above.
Disclosure No. 17643 (December 1978
) and No. 18716 (November 1979)
The relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the two Research Disclosures mentioned above, and their locations are shown in the table below.

Additive type RD17643 RD1B7
161 Chemical sensitizers Page 23 Page 648 Right column 2 Sensitivity enhancers Same as above 3 Spectral sensitizers, Pages 23-24 Page 648 Right column - Super sensitizers Page 649 Right column 4 Brighteners
Page 24 5 Antifogging agent Pages 24-25 Page 649 right column and stabilizer 6 Light absorber, fi 25-26 True Page 649 right column ~
Luther dye, page 650 left UV absorber 7 stain inhibitor page 25 right MA6sog left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder 26 pages Same as above 11
Plasticizer, lubricant Page 27 Page 650 Right column 12
Coating aid, pages 26-27 Surfactant as above Various color couplers can be used in the present invention, specific examples of which can be found in Research Disclosure N.
o, 17643, ■-〇-G. As dye-forming couplers, couplers that give the three primary colors (i.e., yellow, magenta, and cyan) in subtractive color development are important, and specific examples of diffusion-resistant, hydrophobic, 4-equivalent or 2-equivalent couplers are mentioned above. Research Disclosure No. 17643, ■-
In addition to the couplers described in the patents C and 0, the following can be preferably used in the present invention:

A representative example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
407,210, 2,875.057 and 3
, No. 265, 506, etc. The use of two-equivalent yellow couplers is preferred for the present invention and are described in U.S. Pat. No. 3,408.194, U.S. Pat. Oxygen atom separation type yellow coupler or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4.401
．． No. 752, 4. 326. No. 024, RD180
53 (April 1979), UK Patent No. 1,425,02
0 Now, West German Application No. 2゜219.917, 2.2
61.361, 2.329,587 and 2.
433. A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 812. α
- Pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic indacylon- or cyanoacetyl-based couplers, preferably 5-pyrazolone- and pyrazoloazole-based couplers, which have a ballast group. The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye.
No. 311.082, No. 2,343,703, No. 2゜6
No. 00.788, No. 2,908,573, No. 3.06
No. 2,653, No. 3,152,896 and No. 3,9
No. 36,015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, U.S. Pat.
Particularly preferred are the nitrogen leaving groups described in US Pat. No. 10.619 or the arylthio groups described in US Pat. No. 4,351.897. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density. As a pyrazoloazole coupler, US Patent No. 3. 061. 432, preferably the pyrazolobenzimidazoles described in U.S. Pat.
．． Pyrazo O[5,1-c described in No. 725.067
] [1,2,4] Triazoles, research
Disclosure No. 24220 (June 1984
) and pyrazolotetrazoles and research disclosure described in JP-A No. 60-33552,
No.

24230 (June 1984) and Japanese Patent Publication No. 1986-43
Examples include the pyrazolopyrazoles described in No. 659.
U.S. Pat. 500. The imidazo[1,2-bl pyrazoles described in EP 630 are preferred, and the pyrazolo[1,5-b] described in EP 119,860A
[1,2,4] Triazoles are particularly preferred.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol and phenolic couplers, as described in US Pat. 474°293, preferably the naphthol couplers described in U.S. Pat. No. 4,052.
, No. 212, No. 4,146.396, No. 4,228.
Typical examples include the oxygen atom elimination type di-power naphthol couplers described in No. 233 and No. 4,296.200. Specific examples of phenolic couplers include U.S. Pat. No. 2,369,929 and U.S. Pat.
No. 71, No. 2,772,162, No. 2.895.82
It is stated in issue 6 etc.

Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as follows: Phenolic cyan coupler with groups, U.S. Pat. No. 2,772,162
No. 3,758゜308, No. 4,126.396, No. 4,334.011, No. 4,327,173,
2,5-diacylamino substituted phenolic couplers such as those described in West German Patent Application No. 3.329.729 and European Patent No. 121.365, and U.S. Pat. No. 3,4
No. 46.622, 4. 333. No. 999, same 4,
451,559 and 4,427.767, etc., which have a phenylureido group at the 2-position and have a 5-
These include phenolic couplers having an acylamino group in the position.

In order to correct unnecessary absorption of color pigments, it is preferable to use a colored coupler in combination with a color negative sensitive material for photographing to perform masking. Yellow-colored magenta couplers described in U.S. Pat.
No. 29, No. 4,138.258 and British Patent No. 1.
146. Typical examples include the magenta-colored cyan coupler described in No. 368. Other colored couplers are from the aforementioned Research Disclosure.

No. 17643, described in section ■-G.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
U.S. Patent No. 4.366.237 and British Patent No. 2.
Specific examples of magenta couplers are given in No. 125.570, as well as in European Patent No. 96,570 and German Published Application No. 3,2
No. 34,533 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451,82.
No. 0 and No. 4. 080. It is described in No. 211. Specific examples of polymerized magenta couplers are described in British Patent No. 2. 102. No. 173 and U.S. Patent No. 4,36
7.282.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. As the DIR coupler that releases the development control agent, the patented coupler described in the aforementioned Research Disclosure, No. 17643, Section 1-F is useful.

Preferred in combination with the present invention is JP-A-57-
151944; U.S. Patent No. 4,248.962 and Japanese Patent Application Laid-Open No. 154234/1983
Timing type represented by No. 1987-39653
Particularly preferred are JP-A-57-151944, JP-A-58-217932,
Liquid deactivation type DIR couplers described in Japanese Patent Application No. 59-75474, Japanese Patent Application No. 59-82214, Japanese Patent Application No. 59-82214, Japanese Patent Application No. 59-90438, etc. and Japanese Patent Application No. 1987
This is a reactive DIR coupler described in No.-39653 and the like.

The coupler used in the present invention can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, after dissolving either a high-boiling organic solvent with a boiling point of 175°C or higher and a so-called auxiliary solvent with a low boiling point, either alone or in a mixture of both, water or gelatin is dissolved in the presence of a surfactant. Finely dispersed in aqueous media such as aqueous solutions. Examples of high boiling point organic solvents are U.S. Pat.
．． It is described in No. 027, etc.

Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating.

Specific examples of latex dispersion process steps, effects, and latex for impregnation are described in U.S. Pat.
, No. 541, 230, etc.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color capri-preventing agents or color-mixing preventive agents. It may also contain derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic antifading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans Lp-alkoxyphenols, hindered phenols mainly including bisphenols,
Representative examples include gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The arrangement of these layers can be arbitrarily selected as required. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or blue sensitivity, red sensitivity, and green sensitivity from the support side. Furthermore, each of the above-mentioned emulsion layers may be composed of two or more emulsion layers having different sensitivities (and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivities). .

Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, antihalation layer,
It is preferable to provide an auxiliary layer such as a back layer as appropriate.

In the photographic material of the present invention, the photographic emulsion layer and other layers are coated on a flexible support such as plastic film, paper, or cloth, or a rigid support such as glass, ceramic, or metal that is commonly used in photographic materials. be done. Useful flexible supports include cellulose derivatives (cellulose nitrate,
cellulose acetate, cellulose acetate butyrate, etc.), films made of synthetic polymers (polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, etc.), baryta layers or α-olefin polymers (e.g. polyethylene, polypropylene, ethylene/butene copolymers), etc. Paper coated or laminated with The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion to photographic emulsion layers and the like.

The surface of the support may be subjected to glow discharge, corona discharge, ultraviolet irradiation, flame treatment, etc. before or after the undercoating treatment.

For coating the photographic emulsion layer and other hydrophilic colloid layers, for example, dip coating, roller coating, curtain coating,
Various known coating methods such as extrusion coating can be used. U.S. Patent No. 2,681.29 as appropriate.
No. 4, No. 2,761゜791, No. 3,526,528
Multiple layers may be applied simultaneously using coating methods such as those described in No. 3,508.947.

The color photographic material according to the present invention is described in the aforementioned Research Disclosure, No. 17643, 28-29.
Development processing can be carried out by the usual method described in the left column to the right column of page 651 of the same publication, No. 18716. The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment.

In the washing process, two or more tanks are generally used for countercurrent washing to save water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this process, 2 to 9
A tank countercurrent column is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing the image9. For example, various buffers (e.g. borate, metaborate, Borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia,
Typical examples include monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. (used in combination) and formalin. In addition, water softeners (
Inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (benzisothiazolinones, birithiazolones, 4-
Various additives such as thiazoline benzimidazoles, halogenated phenols, etc.), surfactants, optical brighteners, hardeners, etc. may be used (or combinations of two or more compounds for the same or different purposes) may be used. It's okay.

Further, it is preferable to add various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium thiosulfate, etc. as a pH adjustment agent for the membrane after treatment.

(Examples) Hereinafter, the present invention will be further explained with reference to Examples, but the present invention is not limited thereto.

Example 1 On a triacetate film base, the first
- Sample 101 was created by applying the twelfth layer.

First layer; antihalation layer (gelatin layer containing black colloidal silver).

Second layer; gelatin middle layer.

2.5-di-t-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate, and 2 kg of the emulsion obtained by stirring at high speed with 1 kg of an aqueous solution of 10% gelatin was mixed into a non-chemically sensitized fine grain emulsion ( Grain size 0.06 μm, 1 mol% silver iodobromide emulsion) 1 kg
The mixture was mixed with 1.5 kg of 10% gelatin and applied to a dry film thickness of 2 μm (SNNO: 34 g/m).

Third layer: low-sensitivity red-sensitive emulsion layer 100 g of 2-(heptafluorobutyramide)-5-(2'-(2",4"-di-t-aminophenoxy)butyramide)-phenol, which is a cyan coupler, 100 cc of tricresyl phosphate and 100 cc of ethyl acetate
cc and stirred at high speed with 1 kg of a 10% aqueous gelatin solution, 500 g of the emulsion obtained was mixed with an average particle size of 0.
75μm red-sensitive silver iodobromide emulsion 1kg C3F210
g, contains 60 g of gelatin, and has an iodine content of 4 mol%)
The mixture was mixed and applied to a dry film thickness of 1 μm.

(S content: 0.5 g/m) 4th layer; high-range red-sensitive emulsion layer cyan coupler 2-(heptafluorobutyramide)-5-(2'-(2',4"-di-t- Aminophenoxy)butyramide) - 100 g of phenol was dissolved in 100 cc of tricresyl phosphate and 100 cc of ethyl acetate, and 1000 g of the emulsion obtained by stirring at high speed with 1 kg of a 10% gelatin aqueous solution was mixed with 1 kg of red-sensitive silver iodobromide emulsion. (Contains 70 g of silver, 60 g of gelatin, iodine content is 2.5 mol%, average particle size is 0.55 μm)
) and applied to a dry film thickness of 2.5 μm.

(Amount of silver: 0.7 g/i) Fifth layer; Intermediate layer: 2.5-di-t-octylhydroquinone was dissolved in 100 cc of dibutyl phthalate and 100 cc of ethyl acetate, and the solution was stirred at high speed with 1 kg of a 10% gelatin aqueous solution. 1 kg of the emulsion obtained was mixed with 1 kg of 10% gelatin, and the mixture was applied to a dry film thickness of 1 μm.

6th layer: low-range green-sensitive emulsion layer 1-(, which is a magenta coupler instead of a cyan coupler)
2,4,6-trichlorophenyl)-3-(3-(2,
4-di-t-amylphenoxyacetamide)benzamide) -5-viladuron was used, but 300 g of the emulsion obtained in the same manner as the emulsion of the third layer was added to a green-sensitive emulsion with an average particle size of 0.75 μm. 1 kg of silver iodobromide emulsion (70 g of silver
, gelatin (60 g, iodine content: 3 mol %) and coated to a dry film thickness of 1.3 μm.

(S reaction amount 0.7 g/m) 7th layer; high-range green-sensitive emulsion layer 1-(
2,4,6-trichlorophenyl)-3-(3-(2,
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that -5-brassilone (4-di-t-amylphenoxyacetamido)benzamide) was used, and 1 kg of a green-sensitive silver iodobromide emulsion was added. (Contains 70 g of silver, 60 g of gelatin, iodine content is 2.5 mol%, average particle size is 0.60 μm)
) and applied to a dry film thickness of 3.5 μm. (Sri amount: 0.8 g/I) 8th layer: Yellow filter layer An emulsion containing yellow colloidal silver was coated to a dry film thickness of 1 μm.

9th layer: low-anger blue emulsion layer α-( yellow coupler instead of cyan coupler)
pivaloyl)-α-(1-benzyl-5-nitoxy3
-Hydantoinyl)-2-chloro-5-dotecyloxycarbonylacetanilide was used, but 1000 g of the emulsion obtained in the same manner as the emulsion of the third layer was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (70 g of silver Contains 60g gelatin, iodine content 2.5 mol%, average particle size 0.50
μm) and dry film thickness 1. It was coated to a thickness of 5 μm. (Amount of silver: 0.6 g/n?) 10th layer: Highly sensitive blue-sensitive emulsion layer α-(
pivaloyl)-α-(1-benzyl-5-ethoxy-3
1000 g of an emulsion obtained in the same manner as the emulsion of the third layer except that 2-chloro-5-dotecyloxycarbonylacetanilide (hydantoinyl)-2-chloro-5-dotecyloxycarbonylacetanilide was used was mixed with 1 kg of blue-sensitive silver iodobromide emulsion (70 g of silver Contains 60g of gelatin,
Iodine content is 2.5 mol%, average particle size 1.0 μm
) and coated to a dry film thickness of 3 μm.

(iIffil, 1 g/rd) 11th N;
2nd protective layer: 1 kg of ultraviolet absorber emulsion, 1 kg of 10% gelatin
The mixture was mixed and applied to a dry film thickness of 2 μm.

12th layer: Fine grain emulsion covered with the surface of the first protective layer (grain size 0° 06 μm)
, 1 mol % silver iodobromide emulsion) in a 10% aqueous gelatin solution with a silver coating amount of 0.1 g/m and a dry film thickness of 0. It was coated to a thickness of 8 μm.

A gelatin hardener and a surfactant were added to each layer, respectively.

Preparation of sample 102: Sample 101 and all samples (same as sample 102) except that the average grain size of the photosensitive silver halide emulsions in the third and sixth layers of sample 101 were changed from 0.75 μm to 0.50 μm. was created.

Preparation of sample 103.104.107.108: Sample 10
Samples 103, 104, 107, and 108 were prepared in exactly the same manner as Sample 101, except that the compounds shown in Table 1 were added to the third and sixth layers of Sample 1 in the amounts shown in Table 1.

Preparation of samples 105, 106, 109 to 115: Sample 10
Samples 105, 106, and 109 to 115 were prepared in exactly the same manner as Sample 102, except that the compounds shown in Table 1 were added to the third and sixth layers of Sample No. 2 in the amounts shown in Table 1.

Preparation of Sample 116: Sample 116 was prepared in exactly the same manner as Sample 102, except that the compounds shown in Table 1 were added in the amounts shown in Table 1 to the first layer, No. 6N of Sample 102.

For these samples 101 to 116, each negative part was exposed to red light through a continuous wedge, another part was exposed to green light through a continuous wedge, and another part was exposed to white light (red + green + blue light). The red exposure amount during white light exposure and the exposure amount during red light exposure were equivalent. Further, the amount of green light exposure during white light exposure and the amount of exposure during green light exposure were equivalent.

These exposed samples were subjected to color development processing.

The development process in this case was carried out at 38°C as described below.

Processing process 1 time - temperature 1st development
6 minutes Wash with water at 38℃ 2 minutes 1 inversion 2 minutes
〃Color development 6 minutes 〃Adjustment 2 minutes 〃Bleaching
Arrive in 6 minutes
4 minutes Wash with water 4 minutes
〃Stability 1 minute Drying at room temperature The composition of the processing solution used is as follows.

Second developer water 700a+
1 Nitrilo-N, N, N-)rimethylenephosphonic acid pentasodium salt 3g Sodium sulfite
20g hydroquinone monosulfonate 30g sodium carbonate (monohydrate) 30g 1-phenyl-
4-Methyl-4-hydroxymethyl-3-pyrazolidone 2g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide (0,1
% solution) Add 2ml water
1000m1 Inverted liquid water 700m1
Nitrilo-N,N,N-trimethylenephosphonic acid pentasodium salt 3g stannous chloride (dihydrate) Igp-aminophenol 0.1g sodium hydroxide
8g glacial acetic acid
Add 15ml water
1000ml Color developer water 700ml
Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 3g Sodium sulfite
7g Sodium phosphate (12 hydrate) 36g Potassium bromide
1g potassium iodide (0.1% solution)
90ml Sodium hydroxide 3
g Citrazic acid 1.5g N-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 11g ethylenediamine 3g Add water
1000ml training liquid water 700ml
Sodium sulfite 12g Sodium ethylenediaminetetraacetate (dihydrate) 8g Thioglycerin 0. 4ml glacial acetic acid
Add 3ml water
100100O liquid
·water
800g Sodium ethylenediaminetetraacetate (dihydrate) 2g Iron ethylenediaminetetraacetate ([1) Ammonium (dihydrate) 120g Potassium bromide 100g Add water 10100O fixed water 800ml
Sodium thiosulfate 80.0g Sodium sulfite 5.0g Sodium bisulfite 5.0g Add water
1000ml stable water 800ml
Formalin (37% by weight) 5. 0ml
Add 5.0 ml of Fuji Drywell (Fuji Film side type surfactant) water, compare cyan exposed to 1000 ml red light and cyan exposed to white light, and measure log E for the difference in exposure at a density of 1.0. did.

In addition, △1ogE was measured in the same manner in the case of green light exposure. These results are shown in Table 1.

Compound A: HOOCH (Compound described in Japanese Patent Publication No. 46-12677) Compound B: H3 (Compound described in Japanese Patent Publication No. 48-34169) From these results, it can be concluded that the present invention has a greater interimage effect than the comparative example. is obvious.

Example 2 Preparation of Emulsion A: Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring to prepare a silver iodobromide emulsion (Agl-3 mol %) with an average grain size of 0.8 μm. , after desalination,
Silver iodobromide emulsion A was prepared by optimally gold/sulfur sensitization using chloroauric acid and sodium thiosulfate.

Similarly, emulsion B (average grain size 1.2 μm, AgI=3
(mol%) was prepared.

As a sample, a black-and-white photographic window light material consisting of each layer having the composition shown below was prepared on a cellulose triacetate film support.

1st layer: Low-temperature silver halide emulsion layer Emulsion A (Coated silver amount: 1 g/n?) 2nd N = High-temperature silver halide emulsion layer Emulsion B (Coated silver amount: 2.5 g/m) 3rd layer: Protective layer gelatin (1.3 g/m) Polymethyl methacrylate particles (diameter 1.5 trm) (0.05 g/n?) In addition to the above composition, each layer contains gelatin hardener, surfactant, and thickener polystyrene. Sodium sulfonate was added. The sample prepared as described above was designated as sample 201.

Preparation of sample 202: Sample 2 except that the average grain size of the silver halide emulsion in the first layer of sample 201 was changed from 0.80 μm to 0.850 μm.
Sample 202 was prepared in exactly the same manner as Sample 01.

Preparation of sample 203.204.207.208: Sample 20
Samples 203, 204, 207, and 208 were prepared in exactly the same manner as Sample 201, except that the compounds shown in Table 2 were added in the amounts shown in Table 2 to the first layer of Sample 1 when preparing the coating solution. .

Preparation of samples 205, 206, 209 to 215: Sample 20
Samples 205, 206, and 209 to 215 were prepared in exactly the same manner as Sample 202, except that the compounds shown in Table 2 were added in the amounts shown in Table 2 to the first layer of Sample 2 when preparing the coating solution. .

These samples were exposed to light through a pattern for measuring graininess or a pattern for measuring sharpness, and then subjected to the development treatment described below.

Developer: Metol 2g Sodium sulfite 100g Hydro-Non
5g Borax・5H201,
Add 53g water 11 Stationary solution: Ammonium thiosulfate 200.0g Sodium sulfite (anhydrous) 20.0g Boric acid
8.0g disodium ethylenediaminetetraacetate 0.1g aluminum sulfate 15.0g sulfuric acid
2.0g glacial acetic acid
Add 22.0g water
1.01 (pH adjusted to 4.2) Black and white development was performed at 20° C. for 17 minutes using the above developer.

Granularity (RMS granularity) is the standard deviation of the density variation that occurs when scanning with a microdensitometer.
Displayed as a double value.

Moreover, the sharpness was measured using MTF.

These results are shown in Table 2.

As shown in Table 2, the present invention has lower graininess and lower graininess than the comparative example.
It can be seen that the sharpness has been improved.

Claims (1)

[Scope of Claims] A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the light-sensitive silver halide emulsion layer is a halogenated material having an average grain size of 0.7 μm or less. A halogen containing a silver emulsion and containing at least one compound represented by the following general formulas [I] and [II] in the photosensitive silver halide emulsion layer and/or non-photosensitive layer. Silver chemical photographic material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ General formula [II] In the formula, R represents a linear or branched alkylene group, alkenylene group, aralkylene group, or arylene group, and Z and Z' represents a polar substituent. R_1 represents a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkenyl group, or aralkyl group. X represents a hydrogen atom, an alkali metal atom, an ammoniumyl group, or a group that cleaves under alkaline conditions. n represents 0 or 1.