JPS62175746A - Color image forming method - Google Patents

Abstract

PURPOSE:To obtain the excellent color image for a short period by processing a photographic sensitive material contg. a specific compd. according to a prescribed operation, substantially without using benzyl alcohol. CONSTITUTION:The titled method lies in developing the silver halide color photographic sensitive material which forms a photographic layer contg. the compd. shown by the formula on a reflective substrate, with a color developer which does not substantially contain benzyl alcohol for <=2.5min, after exposing it. In the formula, R1 is an alkyl, a substd. alkyl, an aryl or a substd. aryl group, M is hydrogen atom, ammonium or a metallic atom, (n) is an integer of 1-5. The surface active agent shown by the formula can be jointly used with a so-called anionic surface active agent and/or nonionic surface active agent. Thus, the preparation of the developer is simplified by using substantially no benzyl alcohol. The lowering of the optical density of an image due to restricting a cyan coloring matter to leuco base is reduced.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a color image forming method using a silver halide color light-sensitive material, and in particular to a color image forming method that does not use benzyl alcohol and has a shortened processing time. Regarding.

(Prior Art) In order to form a color photographic image, photographic couplers of three colors, yellow, magenta and cyan, are contained in a photosensitive layer, and after exposure, the layer is processed with a color developing solution containing a color developing agent. In this process, the oxidized product of the aromatic primary amine undergoes a camping reaction with the coupler to give a colored dye, but in this case, it is necessary to give as high a color density as possible within the limited development time. It is.

To obtain high color density, use couplers with as high a coupling rate as possible, or couplers that are easily developed and
And development wc per unit coating amount! ! This is usually achieved by using a silver halide emulsion with a high content of silver halide or by using a color developing solution with a high development speed.

(Problems to be Solved by the Present Invention) In order to speed up the development of a silver halide emulsion, it is easy to think of increasing the silver chloride content of the silver halide, but as the silver chloride content increases, the sensitivity increases. It has the disadvantage that deterioration and fogging easily occur.Also, in order to increase the amount of developed silver, it is possible to increase the above-mentioned silver chloride content or strengthen chemical sensitization, but in this case as well. It has the disadvantage that fog is likely to occur.Reducing the grain size of the silver halide emulsion is also a means of speeding up development, but it has the fatal disadvantage of decreasing sensitivity.Method using silver chloride emulsion For example, JP-A-58-953
No. 45, No. 59-232342 and No. 60-191
No. 40, however, the fog is high and it is not suitable for practical use.

On the other hand, various measures have been conventionally taken regarding color developing solutions to speed up development. Among them, various additives have been studied in order to accelerate the penetration of the color developing agent into the color coupler-dispersed oil droplets and promote color development.In particular, a method of adding benzyl alcohol to the color developer to accelerate color development has been proposed. Because of its great color development promoting effect, it is currently widely used in the processing of color photographic materials, especially color papers.

However, when benzyl alcohol is used, diethylene glycol, triethylene glycol, alkanolamine, etc. are required as a solvent due to its low water solubility. However, since these compounds, including benzyl alcohol, have high pollution load values such as BOD and COD, it is preferable to remove benzyl alcohol for the purpose of reducing the pollution load.

Furthermore, even if this solvent is used, it takes time to dissolve benzyl alcohol, so it is better not to use benzyl alcohol in order to reduce the preparation work.

Furthermore, if benzyl alcohol is brought into the bleaching bath or bleach-fixing bath, which is a post-bath, it causes the formation of a leuco dye, which is a cyan dye, and causes a decrease in color density. Furthermore, since the washing-out speed of the developer components is delayed, the image storage stability of the photosensitive material may be adversely affected.

Therefore, also for the above reasons, it is preferable not to use benzyl alcohol.

Conventionally, color development was generally processed in 3 to 4 minutes, but with recent shortening of finishing delivery times and reduction of laboratory work, there has been a desire to shorten processing times. .

However, if benzyl alcohol, which is a color development accelerator, is removed and the development time is shortened, it is inevitable that the color density will be significantly reduced.

In order to solve this problem, various color development accelerators (for example, U.S. Pat. No. 29,950,970, U.S. Pat. No. 2,515.
No. 147, No. 2,496.903, No. 2,304,9
No. 25, No. 4,038.075, No. 4,119,46
2, British Patent No. 1,430°998, British Patent No. 1,455.
No. 413, JP-A-53-15831, JP-A No. 55-624
No. 50, No. 55-62451, No. 55-62452, No. 55-62453, Special Publication No. 51-12422,
Even when used in combination with the compound described in No. 55-49728, sufficient color density could not be obtained.

Methods of incorporating 3-pyrazolidones (e.g., JP-A-60
No. -26338, No. 60-158444, No. 60-1
Even if the method described in No. 58446 is used, there are disadvantages in that the sensitivity decreases at the diameter of the body and fog occurs.

Also, a method of incorporating a color developing agent (for example, U.S. Pat. No. 37
No. 19492, No. 3342559, No. 3342597
No., JP-A-56-6235, JP-A No. 56-16133,
Even if the method described in Japanese Patent No. 57-97531, Japanese Patent No. 57-83565, etc. is used, it is not an appropriate method because it has drawbacks such as slow color development and fogging.

As described above, no method has been found for obtaining sufficient color images in a short time using a color developing solution that does not substantially contain benzyl alcohol.

(Means to solve the problem) The object of the invention was achieved by the method described below.

After exposure, a silver halide color photographic light-sensitive material having a photographic layer containing a compound represented by the general formula (I) provided on a reflective support was developed for 2 minutes and 30 minutes in a color developer substantially free of benzyl alcohol. A color image forming method characterized by developing in less than a second.

General formula (I) R1 represents an alkyl group, substituted alkyl group, aryl group or substituted aryl group, M represents a hydrogen atom, ammonium or a metal atom, and n represents an integer of 1 to 5.

Here, R1 is a straight chain or branched alkyl of C7 to CZS, or a substituted alkyl group substituted with halogen, aryl, amino, amido, sulfamidoalkyloxy, hydroxy, etc., or an aryl group (e.g., phenyl , naphthyl)
, represents a substituted aryl group (alkyl, substituted alkyl, substituted aryl substituted with halogen, amino, amidoalkyloxy, hydroxy, etc.).

M represents hydrogen, ammonium, or an organic or inorganic cation.

n represents an integer from 1 to 5.

Next, general formula (I) that can be used in the present invention
Specific examples of compounds represented by are shown below.

Compound Example 1, C? II +sCOON a 2 , Cq H+ q COON a3 , C+
+ Hz 3 COON a4- C++HzCOO
K5, CI3Hz? COON a6, C+
s H, lICOOR 7, CI? 835 COON a 8, C,, H,, C00Na 9, Cz+H4zCOONa 10, CzsHs+C00Na 14, C+zHzsCONHCHCOOH6H□CH,
C0OH'CHz) 14CO\N CH2CHz COON a CxH7' 16, C1(CH2)+tCOONa 17, Ct+ T(,,<"soCOONa24, saponin Na The compound of general formula (I) used in the present invention can be used alone. Rather than using it alone, it can be used in combination with other surfactants.In some cases, it may be preferable to use it in combination with certain other surfactants rather than using it alone.

The compound of general formula (I) used in the present invention can be used in combination with so-called anionic surfactants and/or nonionic surfactants.

The anionic surfactant has a hydrophobic group having 8 to 30 carbon atoms in one molecule and -503M or -03
It is preferable to use a compound having a 03M group (M has the same meaning as in (I) above). This type of compound is described in "Synthesis and Application of Surfactants J. by Ryohei Oda and Hiroshi Teramura.
(vA bookstore version) and A. W. Perry “
Surface A
active Agents) Jscience r'
publications Inc., New York
k) (Yes.

As the above-mentioned nonionic surfactant, JP-A-48-30
It is preferable to use the nonionic surfactant described in No. 933 and the fatty acid ester surfactant of polyhydric alcohol. The polyhydric alcohol fatty acid ester surfactant preferably has at least two, preferably at least three, hydroxyl groups, and preferably has 6 to 25 fatty acid carbon atoms. Specifically, a sorbitan fatty acid ester nonionic surfactant described in US Pat. No. 3,676,141 is advantageously used in the present invention.

Specific examples of the anionic surfactant include the following compounds.

(A I) C+zHzsOSOJa(A
2) C+ JzzO5O3Na(,～---
3) Funnel oil (l~-4) C+ zllzsCONllCH
zCllzOSOJa(A 5 ) C+ z
tlzssOJa(A 6 ) C1aHzq
sO3Na(A 8 ) Na03S cl
l C00CsH+ 7CH2COOC8+11? In the present invention, at least one compound of the general formula (I) used in the present invention has a hydrophobic group having 8 to 30 carbon atoms in one molecule and a -3OzM or -3OIM group (M is the above ([) It is preferable to use at least one anionic surfactant having the same meaning as (with the same meaning as inside) and/or at least one fatty acid ester nonionic surfactant of sorbitan.

In the present invention, the coupler must be heated and melted or dissolved in an organic solvent to make it liquid before the emulsification operation. Compounds that can be directly emulsified by melting are limited to compounds with a melting point of about 90°C or less.

As the organic solvent (ie, so-called oil) used to finely disperse the coupler in the aqueous medium, it is useful to use one that is virtually insoluble in water and has a boiling point of 190° C. or higher at normal pressure. Such organic solvents can be selected from carboxylic esters, phosphoric esters, carboxylic amides, ethers and substituted hydrocarbons. Specific examples include di-n-butylfucuric acid ester, diisooctylfucuric acid ester, dimethoxyethylfucuric acid ester, di-n-butyladipic acid ester,
Diisooctyl azelenate, tri-n-butylphthalate, butyl laurate, di-
n-sebacic acid ester, tricresyl phosphate,
Tri-n-butyl phosphate ester, triisooctyl g:
fJ1 ester, N/N-diethylcaprylic acid amide,
N-N-dimethylpalmitic acid amide, n-butyl-m
-Pentadecylphenyl ether, ethyl-2.4-t
Examples include er t-butylphenyl ether and chlorinated paraffin.

In the present invention, in addition to such a solvent, it is advantageous to use a low boiling point solvent (boiling point below 130° C. at room pressure) or a water soluble high boiling point solvent in order to dissolve the coupler. Sometimes. For example, propylene carbonate, ethyl acetate, butyl acetate, ethyl propionate,
5ec-butyl alcohol, tetrahydrofuran, cyclohexanone, dimethylformamide, diethyl sulfoxide, methyl cellosolve, etc.

As the emulsification device used to carry out the present invention, one that applies a large shearing force to the processing liquid or one that applies high-intensity ultrasonic energy is suitable. In particular, an emulsifying device having a colloid mill, a homogenizer, a capillary emulsifying device, a liquid siren, an electromagnetic strain ultrasonic generator, and a Ballmann whistle can give good results.

The photographic layer containing the compound of general formula (I) used in the present invention is preferably a silver halide emulsion layer and/or a layer adjacent thereto, and particularly preferably a silver halide emulsion layer.

The amount of the compound of general formula (I) used in the present invention depends on the type of coupler used, the type of other additives coexisting, the type of dispersion solvent, and, in some cases, other surfactants used in combination. Generally, the amount is preferably 0.2 to 50% by weight of the dispersion 'ff (i.e., a solution in which couplers and other oil-soluble photographic additives are dissolved in a dispersion solvent), although it varies depending on the type and amount of the additive.

As substances that coexist with the coupler, oil-soluble photographic additives such as anti-fading agents, ultraviolet absorbers, DIR couplers, and antioxidants can be included.

In the present invention, containing substantially no benzyl alcohol means that the concentration of benzyl alcohol during development is 0. 5
m7! means the following:

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Examples include those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. For example, balike paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, polyamide There are films, polycarbonate films, polystyrene films, etc., and these supports can be appropriately selected depending on the purpose of use.

Next, a processing step (image forming step) in the present invention will be described.

The color development processing step in the present invention has a short processing time of 2 minutes and 30 seconds or less. The preferred treatment time is 1 to 2 minutes. The processing time herein refers to the time from when the photosensitive material comes into contact with the color developer until it comes into contact with the next bath, and includes the transit time.

The color developing solution used in the development process of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. As this color developing agent, p-phenylenediamine compounds are preferably used, and representative examples thereof include 3-methyl-4-amino-N, N-diethylaniline, and 3-methyl-4-amino-N-ethyl-
N-β-hydroxylethylaniline, 3-methyl-4
-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphates or p- Toluenesulfonate, tetraphenylborate, p-(t-octyl)
Examples include benzenesulfonate.

Examples of aminophenol derivatives include 〇-aminophenol, p-aminophenol, 4-amino-2-
These include methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by F. A. Meson, Focal Press (1966) (L. F. A.)

Mason, “Photographic Processes
sing Chemistry”.

Focal Press), pages 226-229, US Pat. No. 2,193,015, US Pat. If necessary, two or more color developing agents may be used in combination.

The processing temperature of the color developer in the present invention is 30°C to 5°C.
The temperature is preferably 0°C, more preferably 33°C to 45°C.

Further, as the development accelerator, various compounds may be used, except that they do not substantially contain benzyl alcohol. For example, U.S. Patent No. 2,648.604, Japanese Patent Publication No. 44-95
03, U.S. Patent No. 3,171.247, various birimidium compounds and other coloronic compounds, cationic dyes such as phenosafranine, neutral salts such as chlorine nitrate and potassium nitrate, and Japanese Patent Publication No. 1983-930.
No. 4, U.S. Patent No. 2,533.990, U.S. Patent No. 2,531.
No. 832, No. 2,950,970, No. 2.577.1
Nonionic compounds such as polyethylene glycol and its derivatives and polythioethers described in No. 27, US Patent No. 3
, 201, 242, and other compounds described in JP-A-58-156934 and JP-A-60-220344.

In addition, in short-time development processing as in the present invention,
An important issue is not only a means to accelerate development, but also a technique to prevent development fog. Preferred antifoggants in the present invention include alkali metal halides such as potassium bromide, sodium bromide, and potassium iodide, and organic antifoggants.

Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, hydroxyazaindolizine, and l-phenyl-
Mercapto-substituted heterocyclic compounds such as 5-mercap 1-tetrazole, 2-mercaptohenzimidazole, 2-mercaptobenzothiazole, as well as mercapto-substituted aromatic compounds such as thiosalicylic acid can be used. Particularly preferred are halides. These antifoggants are eluted from color photosensitive materials during processing, and
May accumulate in color developers.

In addition, the color developer in the present invention includes a pH buffering agent such as an alkali metal carbonate, borate or phosphate; preservatives such as compounds, sulfites or bisulfites; organic solvents such as diethylene glycol; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; auxiliaries such as l-phenyl-3-pyrazolidone. Developer; Viscosifier; Ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminoniacetic acid, N-hydroxymethylethylenediaminetriacetic acid,
Diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, aminopolycarboxylic acids such as the compounds described in JP-A-58-195845, l-hydroxyethylidene-1,1'-diphosphonic acid, research
Disclog + - (Research Disc
organic phosphonic acid, aminotris (methylenephosphonic acid), ethylenediamine-N, N, N", N'-
Aminophosphonic acids such as tetramethylenephosphonic acid, JP-A Nos. 52-102726, 53-42730, 54-121127, 55-4024, 55-
No. 4025, No. 55-126241, No. 55-65
No. 955, No. 55-65956, and Research Disclosure.
(sure) A chelating agent such as phosphonocarboxylic acid described in Na18170 (May 1979) can be contained.

In addition, the color developing bath can be divided into two or more parts as necessary.
Replenish color developer replenisher from the first bath or last bath,
The development time may be shortened or the amount of replenishment may be reduced.

After color development, the silver halide color photosensitive material is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment (bleaching and fixing) or may be carried out separately. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (I), cobalt (■), chromium (■), and copper (II), peracids, quinones, and nitroso compounds. For example, ferricyanide, dichromate, organic complex salts of iron(III) or cobal l-(nl), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propatoltetraacetic acid Aminopolycarboxylic acids such as or complex salts of organic acids such as citric acid, tartaric acid, and malic acid; persulfates, manganates; nitrosophenols, and the like can be used. Among these, potassium ferricyanide, sodium iron(III) ethylenediaminetetraacetate, ammonium iron(I[I) ethylenediaminetetraacetate, ammonium iron(II[) triethylenetetraminepentaacetate], and persulfates are particularly useful. Ethylenediaminetetraacetic acid iron (nl) complex salts are useful in both stand-alone bleach solutions and -bath bleach-fix solutions.

Further, various accelerators may be used in combination with the bleaching solution and the bleach-fixing solution, if necessary. For example, in addition to bromide ion and iodide ion, U.S. Pat.
No. 6, No. 49-26586, JP-A-53-32735
Thiourea-based compounds as shown in JP-A No. 53-36233 and JP-A No. 53-37016;
No. 3-57831, No. 53-32736, No. 53-6
No. 5732, No. 54-52534 and U.S. Patent No. 3,
Thiol-based compounds as shown in 893,858, etc., or JP-A-49-59644 and JP-A-50-
No. 140129, No. 53-28426, No. 53-14
No. 1623, No. 53-104232, No. 54-357
Heterocyclic compounds described in JP-A No. 27, etc.; thioether compounds described in JP-A-52-20832, JP-A-55-25064, and JP-A-55-26506; Quaternary amines described in No. 48-84440 or 1. 'F Kaisho 49-423
Compounds such as thiocarbamoyls described in No. 49 may also be used.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides, but thiosulfates are generally used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After the bleach-fixing process and the fixing process, a washing process is usually performed. In the water washing process, various known compounds may be added for the purpose of preventing precipitation and saving water. For example, water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid to prevent precipitation, fungicides and anti-spiking agents to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum salts. Typical hardeners, surfactants for preventing drying load and unevenness, etc. can be added as necessary. Or L.E. West (L,
E, West), Photographic Science and Engineering (Photo.

3ci, and Eng,), Volume 9, No. 6, (I
965) and the like may be added.

Particularly effective is the addition of chelating agents and anti-piping agents.

It is also possible to save water by using a multistage (for example, 2 to 5 stages) countercurrent method in the water washing process.

Also, after or instead of the water washing process, JP-A-57-
A multi-stage countercurrent stabilization treatment process such as that described in No. 8543 may be performed. In the case of this step, 2 to 9 free-flow baths are required. Various compounds are added to this stabilizing bath for the purpose of stabilizing the image.

For example, III buffers to adjust the pH (e.g.
borate, metaborate, borax, phosphate, carbonate,
Examples include potassium hydroxide, thorium hydroxide, ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), disinfectants (proxel, isothiazolone, 4-thiazolylbenzimidazole, halogenated phenol benzotriazoles, etc.), a surfactant, a fluorescent brightener, a hardening agent, etc. may be added.

Furthermore, various ammonium salts such as ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, ammonium periosulfate, etc. can be added as a membrane pH 2)4 adjuster after treatment.

The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-star color coupler substituted with a leaving group can reduce the amount of silver coated than a double-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon the campling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2,40
No. 7,210, No. 2,875.057 and No. 3
, No. 265, 506, etc. The use of diagonal yellow couplers is preferred for the present invention; U.S. Pat.
No. 3,933,501 and No. 4,022゜62
0, etc., or Japanese Patent Publication No. 58-10739, U.S. Patent No. 4,
No. 401,752, No. 4,326.024, RD1
8053 (April 1979), British Patent No. 1.425
, No. 020, West German Application Publication No. 2.219,917, No. 2. 261. No. 361, No. 2,329.587
Typical examples thereof include the nitrogen atom separation type yellow couplers described in No. 2 and No. 2 433.5 t2q. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness;
- Benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. 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, and representative examples thereof include U.S. Pat. Same No. 2゜3
No. 43.703, No. 2,600.788, No. 2.
No. 908,573, same No. 3. 062. No. 653, No. 3,152,896 and No. 3936.015
It is written in the number etc. As a leaving group for diagonal 5-pyrazolone couplers, U.S. Patent No. 4,310,619
No. 4.3 or U.S. Patent No. 4.3.
The arylthio group described in No. 51.897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73,636 provides high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
369,879, preferably pyrazolo(5,1-c)(I,2,4) l-lyazoles as described in U.S. Pat. 24220
(June 1984) and Research Disclosure 24230 (I
Examples include pyrazolopyrazoles described in June 1984). The imidazo(I,2-b)pyrazoles described in European Patent No. 119.741 are preferable from the viewpoint of low yellow side absorption of coloring dyes and light fastness, and European Patent No. 1
Pyrazolo [1°5-b) described in No. 19,860 (
I,2,4)) Riazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat.
, No. 212, No. 4゜146.396, No. 4,22
Typical examples include the oxygen atom elimination type divalent naphthol couplers described in No. 8,233 and No. 4.296.200. Further, specific examples of phenolic couplers are given in U.S. Patent Nos. 2,369,929 and 2.
No. 801,171, No. 2,772゜162, No. 2
, No. 895, 826, etc. Humidity and temperature robust cyan couplers are preferably used in the present invention, exemplified by U.S. Pat. No. 3,77
2.002, a phenolic cyan coupler having an alkyl group greater than or equal to an ethyl group at the meta-position of the phenol nucleus, U.S. Pat. No. 2.772.162, U.S. Pat. No. 3.7
No. 58,308, same No. 4. 126. No. 396, No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3. 329. No. 729 and patent application 1977
8-42671, etc., and U.S. Pat. No. 3,4.
No. 46,622, No. 4,333,999, No. 4.
451. These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, which are described in No. 559 and No. 4,427,767.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in U.S. Pat. Specific examples of magenta couplers are given in No. 366.237 and British Patent No. 2.125.570, and examples of yellow, magenta or cyan couplers are given in European Patent No. 96.570 and German Published Application No. 3.234.533. Specific examples are described.

The dye-forming couplers and the specialty couplers described above may form bilayer or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,415,82.
No. 0 and No. 4,080°211. Specific examples of polymerized magenta couplers are described in British Patent No. 2. 102. No. 173 and U.S. Pat. No. 4,367
．． It is described in No. 282.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

Typical usage amounts of color couplers range from 0.001 to 1 mole per mole of photosensitive silver halide, preferably 0, Ol to 0.00 for yellow couplers.
5 mole, 0°003 to 0.3 for magenta coupler
moles, and for cyan couplers 0.002 to 0.3
It is a mole.

The photosensitive material produced using the present invention contains hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic fI! It may contain IS derivatives, colorless couplers, sulfonamidophenol derivatives, and the like.

Known anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
6-hydroxychroman tL5-hydroxycoumarans, spirochroman Lp-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and each of these compounds. Typical examples include ether or ester derivatives in which phenolic hydroxyl groups are silylated or alkylated. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

To prevent yellow dye images from deteriorating due to heat, humidity and light.
U.S. Patent No. 4,268. A compound having a partial structure of a hindered amine and a hindered phenol in the same molecule, as described in '593, gives good results.

In addition, in order to prevent deterioration of the agenta dye image, especially deterioration caused by light, the substitution of spiroindanes described in JP-A-56-159644 and hydroquinone diether or monoether as described in JP-A-55-89835 is recommended. chromans give favorable results.

In order to improve the storage stability of cyan images, especially the light fastness, it is preferable to use a benzotriazole ultraviolet absorber in combination. This UV absorber may be co-emulsified with the cyan coupler.

The amount of ultraviolet absorber applied should be sufficient to impart photostability to the cyan dye image, but if too much is used, it may cause yellowing of the unexposed areas (white areas) of the color photographic light-sensitive material. Therefore, it is usually preferably 1X10-' mol/d to 2X10-' mol/d, especially 5X10-' mol/d.
It is set in the range of M to 1.5×10 −3 mol/d.

In the conventional light-sensitive material layer structure of color paper, an ultraviolet absorber is contained in one of the layers on both sides adjacent to the cyan coupler-containing red-sensitive emulsion layer, preferably in both layers. When an ultraviolet absorber is added to the intermediate layer between the green-sensitive layer and the red-sensitive layer, it may be co-emulsified with a color mixing inhibitor. When a UV absorber is added to the protective layer, another protective layer may be applied as the outermost layer. The rice protection layer can contain a matting agent of any particle size.

In the photosensitive material of the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer.

The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the invention may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener.

Water-soluble brighteners may be used, and water-insoluble brighteners may be used in the form of dispersions.

The present invention, as described above, is 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 order of these layers can be arbitrarily selected as necessary. Furthermore, each emulsion layer in the first stage may be composed of two or more emulsion layers with different sensitivities, and a non-light-sensitive layer may exist between two or more emulsion layers with the same sensitivities. good.

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 pack layer as appropriate.

As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, etc., sugar derivatives such as sodium alginate, starch derivatives;
Various synthetic hydrophilic polymeric substances such as single or copolymers of polyvinyl alcohol, polyvinyl alcohol partial acetal, vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. can be used.

Gelatin includes lime-processed gelatin, acid-processed gelatin, Bull, Soc, and Sci.

Phot, Japan, N [Li2.30 pages (I966
Enzyme-treated gelatin as described in ) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used.

In addition to the above-mentioned additives, the photosensitive material of the present invention further contains various stabilizers, anti-staining agents, developers or their precursors,
Development accelerators or precursors thereof, lubricants, mordants, matting agents, antistatic agents, plasticizers, and other various additives useful for photographic materials may be added. Representative examples of these additives are Research Disclosure 1764
3 (December 1978) and 18716 (I9
(November 1979).

The silver halide emulsion used in the present invention is silver bromide, silver chlorobromide, or silver chloride that does not substantially contain silver iodide, and the silver halide preferably used contains 2 to 80 mol% of silver chloride. Contains silver chlorobromide.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle diameter is the particle size, and in the case of cubic particles, the particle size is the particle size, and the average particle size is based on the projected area) is preferably 2 μ or less and 0.1 μ or more, but it is particularly preferable. is 1μ or less 0.15μ
That's all. The grain size distribution may be narrow or wide, but the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is 20.
It is preferred to use so-called monodispersed silver halide emulsions within 15%, particularly preferably within 15%. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, -dihedral, dodecahedral, etc.).
), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/Pf ratio of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains.

An emulsion consisting of a mixture of these various crystal forms may also be used. 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.

The photographic emulsion used in the present invention is manufactured by Glafkides [Chemistry and Physics of Photography J (P., Glafkides).

Chimie et PhysiquePhoto
graphique (published by Pau1Monte1, 1
967)], Duffin, “Photographic Emulsion Chemistry J (C,
, F.Duf inPhotographic
Emulsion Chemistry (Focal
Press, 1966)], Zelikman et al.
Production and coating of photographic emulsions J (V, L, Zelikma
Making and Coat by n etal
ingPhotographic Emulsion
(Focal 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.

Furthermore, emulsions produced using gPI by the so-called conversion method, which includes a process of converting silver halide that has already been formed before the completion of the silver halide grain formation process to silver halide with a smaller solubility product, and Emulsions subjected to similar halogen exchange after the completion of the silver grain formation process can also be used.

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.

After grain formation, silver halide emulsions are usually subjected to physical ripening, desalting and chemical ripening before being used for coating.

Known silver halide solvents (for example, ammonia, Rodankali or U.S. Pat. No. 3,271,157, JP-A-5
1-12360, JP-A-53-82408, JP-A-53-144319, JP-A-54-100717 or JP-A-54-155828, etc.) by precipitation, It can be used for physical ripening and chemical ripening. In order to remove soluble root salts from the emulsion after physical ripening, washing with water, flocculage sedimentation, ultrafiltration, etc. are performed.

The silver halide emulsion used in the present invention contains active gelatin and sulfur-containing compounds that can react with silver (for example, thiosulfate,
Sulfur aggravation method using reducing substances (e.g. stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); Metal compounds ( For example, in addition to gold complex salts, Pt, Ir, , Pd, Rh5Fe
A noble metal sensitization method using complex salts of Group 1 metals of the periodic table, such as complex salts of metals of Group 1 of the periodic table, etc. can be used alone or in combination.

Among the above chemical sensitizations, sulfur sensitization alone is more preferred.

The premalignant, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and other dyes so as to have color sensitivity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazolidine, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nucleus 1 in which an alicyclic hydrocarbon ring is fused to these nuclei, and these Nuclei in which an aromatic hydrocarbon ring is fused to the nucleus, i.e., indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus , quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbyl nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. A typical example is the United States - Patent 2
, No. 688.545, No. 2゜977.229, No. 3,
397.060, 3.522.052, 3.5
No. 27,641, No. 3,617,293, No. 3,62
No. 8.964, No. 3,666.480, No. 3. 67
2. No. 898, No. 3,679,428, No. 3. 7
03゜377, 3,769.301, 3,81
4.609, 3,837.862, 4゜026
．． 707, British Patent No. 1,344.281, 1.5
No. 07.803, Special Publication No. 43-4936, No. 53-1
No. 2375, JP-A-52-110618, JP-A No. 52-1
No. 09925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

(Examples) The present invention will be explained in detail below using Examples, but the present invention is not limited thereto.

Example 1゜Yellow coupler (Y-1) 24. Og to ethyl acetate 3
5 ml and 12 ml of dibutyl phthalate as a solvent were added and dissolved, and this solution was added as an emulsifying dispersant to 160 ml of a 12% gelatin aqueous solution containing 10 ml of dibutylnaphthalene sulfone (comparative compound R-1 shown below), and mixed with a high-speed stirrer. The mixture was emulsified and dispersed.

The entire amount of this emulsified dispersion was added to a silver chlorobromide emulsion (containing 70 g/kg of Ag) consisting of 80% Br, and paper was laminated on both sides with polyethylene so that the silver coating amount was 0.31 g/nf. A comparative sample (A) was prepared by coating on a support and providing a gelatin layer on top of this coating layer.

Next, samples (B) to (R) were prepared as follows.

The same sample as sample (8) was used except that 1.0 g of the exemplary compound (4) of the present invention was used instead of R-1 as an emulsifying dispersant. The same sample as sample (8) except that 1.0 g of the exemplified compound (I1) of the present invention was used instead of R-1. The same sample as sample (A) except that .0g was used. Same as sample (A) except that 1.0g of the exemplary compound (21) of the present invention was used instead of R-1 as an emulsifying dispersant. Sample 1 Genjo Doin - The same sample as sample (A) except that 1.0 g of the exemplary compound (25) of the present invention was used instead of R-1 as an emulsifying dispersant, and samples (A) to (F )'s yellow coupler (Y-1)
Instead, samples (G) to (L) and (M) to (R) were created using magenta coupler (M-1) and cyan coupler (C-1).

When magenta coupler is used, the amount of coated coupler C is 0.37 g/m, the amount of silver coated in a silver chlorobromide emulsion consisting of 75 mol% Br is 0.20 g/a, and the amount of cyan coupler coated is 0.33 g/m. n? .

The silver coating amount of the silver chlorobromide emulsion consisting of 70 moff% Br was 0.28 g/nl.

SO, Na These samples were given a stepwise exposure for sensitometry. Thereafter, experiments of treatments A and B were conducted using color developing solutions (A) and CB) as shown below.

The contents of treatments A and B are distinguished by the difference in the contents of color developing solutions (A) and (B), and the contents of other treatment steps are the same for both A and B.

(Shinko Co., Ltd.) (OnyD (I) developer solution 38℃ 2.0 minutes Bleach-fix solution
Wash with water for 1.5 minutes at 33℃
28-35°C 3.0 minutes Image solution formulation) Color developer (A) Diethylenetriamine pentaacetic acid 5Na salt
2.0g benzyl alcohol
15ml diethylene glycol
10m1 Nat SOi
2. OgKBr
005g Hydroxylamine Sulfate
3.0g4-amino-3-methyl-N-ethyl-N=[
β-(Methanesulfonamido)ethyl]-p-phenylenediamine, sulfur salt 5.0 g Naz CO3 (I Ei Takumi 30. Og Fluorescent whitening ff
l+ (stilbene type)
Add 1.0g water to total amount
1000ml (I00O, 1) Color developer (B) Diethylenetriaminepentaacetic acid 5N a kg
2゜0g Na25O8l
2. OgKBr
O, 5g Hydroxylamine sulfate 3.0g
4-Amino-3-methyl-N-ethyl-N-Cβ-(methanesulfonamido)ethinolyp-phenylenediamine sulfate 5.0gNaz CO* (I hydrate)
30.0g fluorescent brightener (stilbene type) 1. 0g
Add water to make a total of 1
000ml (I00O, 1) (Bleach-fixing solution formulation) Ammonium (54wt%)
150m1Naz SC)+
15 gNH4[Fe
(flT) (EDTA))
55g EDTA-2Na
Add 4g water to make the total amount
1000ml100O, 9) Photographicity evaluation is based on maximum density (Dmax) and minimum density (D
The test was conducted using two items: min). The results are shown in Table 1.

From the results in Table 1, it can be seen that regardless of whether yellow coupler, magenta coupler, or cyan coupler is used, the sample of the present invention has a higher maximum concentration than the comparative sample, and even treatment B, which does not contain benzyl alcohol, has almost the same color development as treatment A. It can be seen that this shows that

Example 2 Comparative multilayer color printing paper (A) having the layer structure shown in Table 2 was prepared on a paper support laminated on both sides with polyethylene.

The coating liquid was prepared as follows.

Daiichi Shun-ton +1 Yellow coupler (a) 19.1g and color image stabilizer (b
) 4.4g to ethyl acetate 27.2m/and solvent (c) 7
．． 9m6 was added and dissolved, and this solution was mixed with 10% sodium dibutylnaphthalene sulfonate (R
1) 10% gelatin aqueous solution 185mj containing 12mj+
! and emulsified and dispersed using a continuous stirrer to obtain an emulsified dispersion.

On the other hand, silver chlorobromide emulsion (silver bromide 80 mol%, silver 70 g/
kg gold-containing blue-sensitive sensitizing dye shown below in silver chlorobromide
90 g of a blue-sensitive layer emulsion was prepared by adding 7.0×10 −' moles per mole.

The emulsified dispersion and the emulsion were mixed and dissolved, and the gelatin concentration was adjusted to have the composition shown in Table 2 to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were also prepared in the same manner as the first layer coating solution.

The gelatin hardening agent for each layer is l-oxy-3°5-
Dichloro-5-1-riazine sodium salt was used.

The following spectral sensitizers were used in each emulsion.

Blue-sensitive emulsion layer (per 1 liter of silver halide 7.0 x 10-' (transfer) 1
Addition)■ 5OJN(Ctlls)3 (per mol of halogenated 211 7.OX 10-
'＋++ol addition) (per mol of halogenated tl 1
．． (Addition of OX 10-'n5ol) The following dyes were used as anti-irradiation dyes in each emulsion layer.

Green-sensitive emulsion layer: Red-sensitive emulsion FJ: The structural formulas of the compounds used in the woodcarrier array, such as couplers, are as follows.

(a) Yellow coupler (b) Color image stabilizer (C) Magenta coupler (2) 2:1 mixture (weight ratio) on the color image stabilizing side (h) Ultraviolet absorber (i) Color mixing inhibitor H (j) Solvent (iso CJIBO)yP=0 (k) Cyan coupler C511+ (t) (I) Ultraviolet absorber I Next, photosensitive materials (B) to (D) were prepared as follows.

Once in No. 1.3.5N of the photosensitive material (A), exemplified compound (4) of the present invention was added as an emulsifying dispersant instead of R-1.
．． The exemplified compound of the present invention was used as an emulsifying dispersant instead of R-1 in the 1st, 3, and 5th layer of the photosensitive material (A). The same photosensitive material as photosensitive material (A) except that 1.2 g of (I7) was used. The same photosensitive material as photosensitive material (A) was used, except that 1.2 g of the exemplified compound (25) of the present invention was used.
WH type, color temperature of light source 3,200°K)
Gradation exposure for sensitometry was provided through green and red filters. The exposure at this time was carried out so that the exposure time was 0.5 seconds and the exposure amount was 250 CMS.

After this, use color developing solutions (A) and (B) as shown below.
Experiments for treatments A and B were conducted using the following.

The processing consisted of the steps of color development, bleach-fixing, and washing with water, and the photographic properties were evaluated by changing the development time to 1 minute, 2 minutes, and 3 minutes. The contents of treatments A and B represent the differences between the color developing solutions A and B, and the other treatment contents are the same for both A and B.

The evaluation of photographic properties was based on relative sensitivity, gradation, maximum density (D l1
The test was carried out using four items: lax) and minimum concentration (Dmin).

The relative sensitivity is a relative value based on 100, which is the sensitivity when the color development time in Process A of each photosensitive layer of each photosensitive material is 2 minutes. Sensitivity was expressed as a relative value of the reciprocal of the exposure amount required to provide the minimum density plus 0.5. The gradation was expressed as the difference in density from the sensitivity point to the point where the logarithm of the exposure amount (JogE) increased by 0.5.

The results are shown in Table 3.

(Processing 1 aid (warm m)
Ci Temple Developable Solution 38℃ 1.0~3.0
Bleach-fix solution 33℃
1.5 minutes water washing 28-35℃ 3.0 fraction image solution formulation) Color developer (A) diethylenetriamine pentaacetic acid 5Na salt
2.0g benzyl alcohol
15ml diethylene glycol
) OmlNaz SOx
2. OgKBr
005g
Hydroxylamine sulfate F? m
3. 0'g4-Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]
-p-phenylenediamine sulfate
5.0gNa2CO3(I*@
30.0g Fluorescent brightener (stilbene type)
1. Add 0g water to total amount
1000ml color developer (B) diethylenetriaminepentaacetic acid 5Na salt
2. OgNaz 503
2. OgK B r
(), 5 g hydroxylamine sulfate 3.
0g4-amino-3-methyl-N-ethyl-N-[β-
(methanesulfonamide) ethynolyp-phenylenediamine sulfate 5. ogNaz CO* (I*
fg) 30.0g fluorescent whitening agent (stilbene type)
1. Add 0g water to total amount
1000ml (I00O, 1) (Bleach-fix solution formulation) Ammonium thiosulfate (54wt%)
150m1NazS03
15gN11a (Fe (m)
(EDTA)) 55gED
TA・2Na
Add 4g water to make the total amount
1000ml As is clear from Table 3, the photographic properties of the photosensitive materials (B) to (D) of the present invention in processing B are smaller in relative sensitivity, gradation, and maximum density compared to the comparative photosensitive material (A). Treatment B does not contain benzyl alcohol, but treatment A
It can be seen that the performance is comparable to that of

Further, the light-sensitive materials (B) to (D) of the present invention exhibited good photographic properties even in Process B, which did not contain benzyl alcohol, with a developing time of 2 minutes.

Effects of the present invention> By implementing the present invention, benzyl alcohol is substantially eliminated, reducing the pollution load and reducing liquid preparation work.
It has the effect of eliminating the decrease in density caused by cyan dye remaining as a leuco body. Further, by using the silver halide emulsion of the present invention, it is possible to obtain photographic properties with high Dmax, low Dmin, and little change in sensitivity and gradation even if benzyl alcohol is eliminated.

Hand, Zokune city official book (method) %formula% 2. Name of the invention Color image forming method 3. Person making the amendment 4. Agent

Claims (1)

[Claims] A silver halide color photographic light-sensitive material having a photographic layer containing a compound represented by the general formula (I) provided on a reflective support is subjected to color development substantially free of benzyl alcohol after exposure. 1. A color image forming method characterized by developing with a liquid in a time of 2 minutes and 30 seconds or less. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ R_1 represents an alkyl group, substituted alkyl group, aryl group, or substituted aryl group, M represents a hydrogen atom, ammonium or metal atom, and n is 1 to 5 represents an integer.