JPH03101663A - Novel 1-aryl-3-pyrazolidone-based compound - Google Patents

Abstract

NEW MATERIAL:A 1-aryl-3-pyrazolidone-based compound having a substituent group expressed by the formula (R is 1-18C alkyl or phenyl; X is CO, OCO, OCOCO, SO2 or NHCO; R' and R'' are H or OH). EXAMPLE:4-Benzoyloxymethyl-4-methyl-1-phenyl-3-pyrazolidone. USE:A development promoting agent causing no muddiness of color, having excellent developing properties without accompanying the formation of fog and softening tendency on picture performance and especially useful in improving the developing properties of activated silver halide colored picture-sensitive material. PREPARATION:4-Hydroxymethyl-1-aryl-3-pyrazolidone is reacted with an acid chloride such as benzoyl chloride, sulfonyl chloride, isocyanate, etc., in a solvent such as acetonitrile to provide the compound expressed by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel l-aryl-3-pyrazolidone compound, and particularly to a novel l-aryl-3-pyrazolidone compound that improves the developability of silver halide photographic materials.

Fogging the oxidized first aromatic amino color developer with a dye-form compound or a fogging compound to form a color photographic image by obtaining indoaniline, indophenol and azomethine dyes. is well known. In these methods, subtractive color development is usually used, and the image dyes typically removed are cyan, magenta, and yellow. The colors of these pigments have a complementary color relationship with respect to the primary colors red, green, and blue.

Typically, phenolic or natol couplers are used to obtain cyan dye images, virazolone or cyanoacetyl couplers are used to obtain magenta dye images, and acylacetamide couplers are used to obtain yellow images. is used.

In the present invention, when these couplers are non-spreading couplers that have been mixed in the emulsion layer in advance, l-aryl-5-pyrazolidone-based couplers are added to the emulsion layer or a layer adjacent thereto to improve developability. It concerns compounds.

It is known to use a development accelerator when developing with a primary aromatic amino color developer. Although various compounds have been widely used for this purpose in the past, compounds with a high degree of activity as development accelerators often have the disadvantage of causing fog. However, among such compounds, certain black-and-white developing agents exhibiting super-additive properties in color development can provide a development accelerating effect with relatively low fogging compared to other development accelerators. Examples of such black and white developing agents include N-methyl-p-aminophenol described in U.S. Pat. No. 2,417.514, British Patent No. 811, . No. 185 No. 1-phenyl-3-pyrazolidone, JP-A-1983-1
Examples include N,N,N',N'-tetramethyl-p-7 enylenediamine described in No. 5554. Also, regarding the mechanism of super-abrasive development in color development, see G. F. v
by anV eelen J. P. 5.20, page 94 (1972).

However, although the above-mentioned black and white developing agent has satisfactory performance in terms of the development accelerating effect, it has the following drawbacks. That is, for example, 1-phenyl-3-pyrazolidone (hereinafter 7
It's called Enidon. ) is effective as an accelerator in the developer of the 110,000 aromatic amino group color developer when added to the color developer, but this compound has the drawback of causing so-called color turbidity. However, it also has the disadvantage of deteriorating the storage stability of color developers. The same drawback is N-methyl-p
- Also found in aminophenols. On the other hand, the above N, N,
When N',N'-tetramethyl-p-phenylenediamine is added to a color developer, it causes less color turbidity than 7-enidone, but it stains the processed silver halide color light-sensitive material when left alone. It has the disadvantage of deteriorating the storage stability of color developers.

On the other hand, it is also known to add the black and white developing agent to a silver halide color photographic material in advance. As an example of this, for example, in JP-A-49-102340, there is an example in which 4-methyl-4-hydroxymethyl-1-7enyl-3-pyrazolidone is added as a phenidone compound to the light-sensitive material. However, in such a case,
If this phenidone compound is added before it has a sufficient development accelerating effect, it not only has the disadvantage of causing color turbidity, which is seen when added to a color developer, but also deteriorates gradation in terms of photographic performance. This has the disadvantage of causing a phenomenon of softening the tone. Furthermore, N,N,N',N'-tetramethyl-p-
When phenylenediamine is contained in the light-sensitive material, it causes significant desensitization and cannot be used practically.

An object of the present invention is to solve these drawbacks and provide a development accelerator useful for providing a silver halide color photographic light-sensitive material in which color development is accelerated.

That is, an object of the present invention is to provide a silver halide color photographic light-sensitive material that does not cause color turbidity and has excellent developability without producing capri or softening in photographic performance;
The object of the present invention is to provide a development accelerator useful for the following purposes.

The object of the present invention is to provide a silver halide color photographic light-sensitive material in which the following general formula [■
] is achieved by containing at least one type of 1-aryl-3-pyrazolidone compound having a substituent represented by I;

General formula [l] [In the formula, R represents an alkyl group having 1 to 18 carbon atoms or a phenyl ring group, and X is -CO-, -OCO-, -ococ
It represents any group selected from o-, -S01, and -NHCO-, and R' and R // represent a hydrogen atom or a methyl group. ] Next, the l-aryl-3-pyrazolidone compound according to the present invention (hereinafter simply referred to as the compound of the present invention)
Specific examples will be given, but the compounds of the present invention are not limited to these (2) (3) (4) (5) (l2) (l5) (6) (7) (9) (l6) (l7) (19) (20) UH, (2l) (22) (23) (29) (30) (3l) (32) (25) (26) (27) (28) The compounds of the present invention correspond to It is obtained by reacting 4-hydroxymethyl-1-aryl-3-pyrazolidone with acid chloride, sulfonyl chloride, incyanate, etc., and specific synthesis examples thereof are shown below.

Synthesis Example [1] Preparation of Exemplified Compound (5) (Preparation of 4-penzoyloxymethyl-4-methyl-1-phenyl-3-pyrazolidone) 41.
To 2 g of 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone was added 300 mQ of acetonitrile. Cool the external bath with ice water to lower the internal temperature.
31.0 g of penzoyl chloride was gradually added dropwise to the mixture while stirring under a nitrogen stream. After 30 minutes were required for the dropwise addition, the external bath was removed, and the mixture was stirred at room temperature for 3 hours and then left under a nitrogen atmosphere overnight. The reaction solution was concentrated to dryness, then dissolved in ethyl acetate, washed with 3% NaHCO 3 aqueous solution, and further washed with water. Transformation I:n-
Recrystallized from hexane/ethyl acetate.

Yield: 10.5 g As a result of NMR and IR measurements and elemental analysis, the obtained compound supported the structure of the target product.

(2) Synthesis of A-form exemplified compound (15) (4-butoxylponyloxymethyl-4-methyl-
Combination of 1-7 enyl-3-pyrazolidones fR) 01112
of acetonitrile was added. The outer bath was cooled with ice water, but the internal temperature was maintained at 10°C, and the temperature was increased to 30.0°C while stirring under a nitrogen stream.
g of butyl chloroformate was gradually added dropwise. After 30 minutes had passed for the dropwise addition, the external bath was removed, the mixture was stirred at room temperature for 3 hours, and then left overnight under a nitrogen atmosphere.

The reaction solution was concentrated to dryness, then dissolved in ethyl acetate, and 3% Na
After washing with an aqueous HCOs solution and further washing with water, the acetic acid phase was dried with Glauber's salt, concentrated to dryness, and crystallized with petroleum ether.
It was recrystallized from hexane/ethyl acetate.

Yield: 8.7 g As a result of NMR and IR measurements and elemental analysis, the obtained compound supported the structure of the target product.

(3) Synthesis of exemplified compound (28) (4-anilinocanolebonyloxymethinole 4-1
-7enyl-3-pyrazolidone) In 1 Q of four-headed kolben, 38.4 g of 4-hydroxymethyno-4-methynole-1-phenynoley-3-pyrazolidone was added to 41.2 g of 4-hydroxymethyl- in 30 If of four-headed kolben. 4-
300+n of methyl-l-phenyl-3-pyrazolidone
4 was dissolved in thoroughly dried tetrahydrofuran.

While the outer bath was cooled with ice water and kept at an internal temperature of 10° C. and stirred under a nitrogen stream, 26.2 g of a 7-enyl isocyanate solution dissolved in 80 m<2 of tetrahydrofuran was gradually added dropwise. After 30 minutes were required for the dropwise addition, the external bath was removed, the mixture was stirred at room temperature for 3 hours, and left overnight under a nitrogen atmosphere.

After the reaction solution was concentrated to dryness, it was dissolved in ethyl acetate and 3% N
Washing with aHCO and then water was performed. #l:a The ethyl phase was dried over Glauber's salt, concentrated to dryness, crystallized from methanol/water, and further recrystallized from n-hexane/ethyl acetate.

Yield: 12.2 g As a result of NMR and IR measurements and elemental analysis, the obtained compound supported the structure of the target product.

(4) Synthesis of exemplified compound (32) (4-benzenesulfoninoleoxy-4-methynole-1
-Phenyl-3-pyrazolidone) t + -v: A series, 41.2 g of 4-hydroxymethyno-4-methyno-1-7 enyno-3-pyrazolidone in 1Q of four-headed corpen 300 ml of 2-tetrahydrofuran While cooling the external bath dissolved in ice water with ice water, maintain the internal temperature at 10'C,
While stirring under a nitrogen stream, 38.8 g of benzenesulfonyl chloride was gradually added dropwise. After 30 minutes were required for the dropwise addition, the external bath was removed, and the mixture was stirred at room temperature for 3 hours, and then allowed to stand overnight under a nitrogen atmosphere. The reaction solution was concentrated to dryness, then dissolved in ethyl acetate, washed with a 3% aqueous NaHCO3 solution, and then washed with water. The ethyl acetate phase was dried over Glauber's salt, concentrated to dryness, crystallized from methanol/water, and further recrystallized from n-hexane/ethyl acetate.

Yield: 9.7 g As a result of NMR and IR measurements and elemental analysis, the obtained compound supported the structure of the target product.

(5) Synthesis of exemplified compound (2l) (4-7 enoxyoxalyloxymethyl-4-methyl-1-phenyl-3-pyrazolidone) In lf2's four-headed colben, 41.2 g of 4-hydroxymethyl-4 - Add methyl-l-phenyl-3-pyrazolidone, 300 m
12 of acetonitrile was added. While cooling the outer bath with ice water, the internal temperature was maintained at lO<0>C, and 40.6 g of 7-enoxyoxalyl chloride was gradually added under a nitrogen stream with stirring. After 30 minutes of dripping, remove the external bath,
After stirring at room temperature for 3 hrs, the mixture was allowed to stand overnight under a nitrogen atmosphere. The reaction solution was concentrated to dryness, dissolved in ethyl acetate, and diluted with 3% N
It was washed with an aHCOs aqueous solution and further washed with water. (The ethyl acetate phase was dried with Glauber's salt; then concentrated to dryness, crystallized with ligroin, and further recrystallized with n-hexane/ethyl acetate.

Yield 17.3g Melting point 107-109°CNMR, I
As a result of R measurement and elemental analysis, the obtained compound supported the structure of the target product.

The l-aryl-3-pyrazolidone compound used in the present invention, in which the 4-position is substituted with a substituent of the general formula CI), is different from the conventionally known 7-enidone compound because of its photographic performance, which causes color turbidity. It is clearly distinguished from the conventional literature and patents that the object of the present invention can be achieved by substituting the 4-position with a specific substituent defined in the present invention. etc., is not taught at all.

The amount of the 1-aryl-3-pyrazolidone compound of the present invention to be added to the silver halide color photographic light-sensitive material is generally within the range of 1 mg = log per 1 m2, but a more pronounced effect can be obtained. Preferably l m2
It is recommended to use 5 mg to 2 g per serving. This amount varies depending on the amount of silver halide used to increase the development speed, so it varies depending on the amount of photosensitive silver halide, but if it is within the above range, a noticeable effect can be obtained. be able to. If the 1-aryl-3-pyrazolidone compound of the present invention is to be added to a light-sensitive silver halide emulsion layer, a remarkable effect can be obtained by adding approximately 1-100 g per mol of silver halide. I can do it. A certain range was set as an upper limit because - If the amount of fish to be added is too large, silver halide development itself may occur, but it will not contribute to the color reaction and a dye image with low density will be obtained. It is from.

The effects of the present invention can be obtained even when the 1-aryl-3-pyrazolidone compound of the present invention is contained in any layer constituting the silver halide color photographic light-sensitive material. That is, it may be contained in an intermediate layer of a photosensitive silver halide emulsion layer, a yellow filter layer, a protective layer, an antihalation layer, a subbing layer, etc. Among them, when it is contained in a light-sensitive silver halide emulsion layer or a non-light-sensitive layer adjacent to a light-sensitive silver halide emulsion layer and close to the support, the development speed of the light-sensitive silver halide emulsion layer is maximized. can be done.

In order to incorporate the 1-aryl-3-pyrazolidone compound of the present invention into a desired structural layer of a silver halide color photographic light-sensitive material, 1-aryl-3-pyrazolidone is added to the coating solution for forming the structural layer. A pyrazolidone compound may be dissolved in a suitable organic solvent such as methanol, ethanol, ingropanol, acetone, methyl ethyl ketone, dimethyl formamide, dioxane, ethyl acetate, etc. It may be added by emulsifying and dispersing it in a hydrophilic colloid solution using a high boiling point organic solvent such as dimethyl 7-thalerate or tri-101-talesyl 7-osphate, or it may be added in a photosensitive emulsion layer. Alternatively, the coupler can be emulsified and dispersed at the same time as the coupler, and then added to the coating solution.

In the case of a photosensitive layer, the l-aryl-3-pyrazolidone compound may be added to the coating solution after the preparation of the photosensitive silver halide emulsion. If the emulsion is of the surface latent image type, it is sufficient that it has been chemically ripened and optically sensitized; if the light-sensitive silver halide emulsion is of the internal latent image type, the silver halide emulsion is Any period after conditioning and optical sensitization is acceptable. On the other hand, when the -aryl-3-pyrazolidone base material is added to the non-photosensitive emulsion layer, it can be added at any time before coating. However, it is generally preferable to add it immediately before coating.

The silver halide color photographic light-sensitive material containing the 1-aryl-3-pyrazolidone compound of the present invention undergoes a normal color development process, followed by bleaching, fixing (or bleach-fixing), washing with water, and stabilization if necessary. A color image can be obtained by processing in each step. In the color development step of this processing step, the first aromatic amino color developer includes known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine compounds. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds generally have a concentration of about 0.1 g to about 30 g for color developer IQ;
More preferably, a concentration of about 1 g to about 15 g for color developer 112 is used.

Examples of aminophenol-based developers include 0-amino-7enol, p-aminophenol, and 5-amino-2-
These include oxytonoleene, 2-amino-3-oxytonoleene, 2-oxy-3-amino-1,4-dimethyl-benzene, and the like.

A particularly useful primary aromatic amino color developer is an N,N-dialkyl-p-7 enylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among these, particularly useful compounds include N,N-diethyl p-7 enylenediamine hydrochloride, N-methyl p-phenylenediamine hydrochloride, N,N-';methyl p-7 enylenediamine hydrochloride. , 2-amino-5-(N-ethyl-N-t'y'cinoleamino)-tonoleene, N-ethyno-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N- Examples include β-hydroxyethylaminoaniline, 4-amino-3-methyl-N,N-diethylaniline, 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluenesulfonate, and the like. can.

Furthermore, useful primary aromatic amino color developers include:
It is also possible to use an inert color developer that cannot substantially develop silver halide with a normal color developer. Research Dis
Closure 15167 and R. L. BENT1J.
C. D E S S L O C H,F. C. DUE
NNERBIER%D. W. FASSETT, D. B
．． GLASS, T. H. JAMES%D. B. JUL
TAN, W. R. RUBY%J. lJ. SNELL,
J. H. STERANER, J. R. THIRTLE
SP. W. VITTUM and A. WAI SSB
ERGER et al., J. Am. Chem. Soc. 73 3
100 (195l) can be used.

The alkaline color developing solution used in developing the silver halide photosensitive material containing the compound of the present invention is
In addition to the aromatic amino color developer, various additives that are usually added to color developers, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal sulfites, and alkali metal heavy salts, may also be added. Sulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pH value of this color developer is usually 7 or higher, most commonly about 10 to about 13.
It is. Further, the silver halide color photographic light-sensitive material containing the compound 1-aryl-3-pyrazolidone of the present invention can be used in a color-forming material containing both a primary aromatic amino-based color developing agent and an oxidizing agent for subjecting a metallic silver image to a redox reaction. A color image can also be obtained by performing color development using a developer, followed by fixing treatment and washing as required.

When these color developing solutions are used, the color developing agent is oxidized by an oxidizing agent and then coupled with a photographic color coupler to form a dye image.

Such a color developing solution is disclosed in, for example, Japanese Patent Application Laid-Open No. 48-9729, and is it preferable for this purpose? The oxidizing agent is a cobalt complex salt with a coordination number of 6. Color photographic processing using such a color developer is particularly effective for so-called silver-saving color photographic materials, which have a smaller amount of silver than ordinary silver halide color photographic materials.

Particularly useful cobalt complex salts include ethylenediamine, diethylenetriamine, triethylenetetraamine, amines,
contains a ligand selected from the group consisting of nitrate, nitrite, azide, chloride, thiocyanate, inthiocyanate, water and carbonate, and (1) at least two ethylenediamine ligands or (2) at least 5-position amine ligand or (3) at least l
It is also possible to have several triethylenetetraamine ligands. A particularly preferred cobalt complex salt is, for example, a complex salt represented by the following formula.

(Co(En)z(Ns)z)X; [Co(En)
x(4(NCS)X ;(Co(En)z(NHs)N
s)X; (Co(En)gcfft)X;(Co
(En)*(SON)z)X; [Co(En)*(N
CS)*)X; and (Co(NHx)s)X - In the above formula, En represents ethylenediamine, and
Represents at least one anion selected from sulfate, hydrochloride, thiocyanate, inthiocyanate and hydroxide. The most preferred complex salts are the hexaamine salts of cobalt, such as chloride, bromide, sulfite, sulfate, perchlorate, nitrite and acetate. The cobalt complex salt used in the color developer is generally used in a concentration range of about 0.1 g to about 50 g, more preferably about 1 g to about 15 g, for color developer 1a.

Further, a silver halide color photographic light-sensitive material containing the l-aryl-3-pyrazolidone compound of the present invention is used as a first
A color image can also be obtained by processing an aromatic amino color developer and a metallic silver image with a so-called monobath development bleach-fix solution (hereinafter referred to as monopass) containing an oxidizing agent and a fixing agent for subjecting to a redox reaction. Any silver halide solvent can be used as the fixing agent used in the monobath. Representative useful bath media include water-soluble thiosulfates or thiocyanates such as sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, thiourea, 3.6-
Diols such as dithia 1,8-octanediol and 3,6-dioxa-9,12-dithia 1,14-tetradecanediol are included.

A silver halide color photographic light-sensitive material to which the compound of the present invention, which increases the development speed, is added gives particularly favorable results when processed in the above-mentioned monobath.

This is because, in general, in a monobath, the color development reaction and the fixing reaction occur competitively, and if the developing speed is relatively slow compared to the fixing speed, only a poorly colored image can be obtained. When the silver halide color photographic light-sensitive material of the present invention is processed in a monobath, the color development reaction is significantly accelerated, so that a color image with sufficient density can be obtained.

Further, in the 1-aryl-3-pyrazolidone compound of the present invention, the silver halide emulsion is an internal latent image type emulsion, and after exposure,
Contained in a direct positive silver halide photographic light-sensitive material that undergoes color development to directly obtain a reversal image by coexisting a fogging agent in the presence of a first aromatic amine color developer or developing by light fogging. It is also possible to do so. In this case as well, the development speed is improved and a colored image with high density can be obtained, which is very advantageous.

Non-diffusive couplers used in silver halide color photographic light-sensitive materials to which the compound of the present invention is added include open-chain β-ketomethylene compounds, pyrazolone compounds, indazolone compounds, virazolinobenttriazole compounds, phenolic compounds, and Known color photographic couplers such as a-naphthol compounds can be used.

The light-sensitive silver halide emulsions used in silver halide photographic light-sensitive materials to which the compound of the present invention is added include silver chloride, silver iodide, silver bromide, silver iodobromide, silver chlorobromide, and silver chlorobromide. Any type of silver halide, such as silver oxide, can be used as a photosensitive agent. If these silver halide emulsions are surface latent image emulsions, ruthenium, rhodium,
Various surface sensitization methods include noble metal sensitization using metal layer salts such as palladium, iridium, platinum, and gold, sulfur sensitization using sulfur compounds, selenium sensitization using selenium compounds, and reduction sensitization using tin salts, polyamine salts, etc. A feeling can be applied. On the other hand, when silver halide emulsions are used as internal latent image type emulsions, conversion emulsions, internal chemically sensitized emulsions, emulsions doped with polyvalent metal ions inside the grains, and even emulsions with different silver halide compositions inside the grains are used. A layered emulsion having a phase interface can be used. These 8I emulsions can also be optically sensitized with cyanine dyes, merocyanine dyes, etc., and can also be optically sensitized with triazole compounds,
Azaindene compounds, benzthiazolium compounds,
A zinc compound stabilizer and various other photographic additives can be added.

Gelatin is preferable as the pie goose forming the structural layer of the silver halide color photographic material to which the compound of the present invention is added, but in addition to gelatin, there may be used gelatin such as heptadated gelatin and phenylated gelatin. derivative gelatin,
Alpmin, agar, gum arabic, alginic acid, casein, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinylpyrrolidone, and copolymers of these vinyl compounds can also be used in part. In addition, for the hardening film of the binder mainly composed of gelatin, a known hardening agent used for hardening the gelatin film of ordinary silver halide color photographic light-sensitive materials can be used.For example, an epoxy thread hardening agent can be used. , ethyleneimino hardeners, activated vinyl hardeners, methanesulfone hardeners, N-methylol hardeners, carposiimide hardeners, halogen-substituted monotriazine hardeners, and other organic hardeners. ,
Alternatively, inorganic hardeners such as aluminum salts, chromium salts, zirconium salts, etc. can be used.

Examples of the support used in the silver halide color photographic material of the present invention include nitrocellulose film,
Examples of suitable materials include acetyl cellulose 7 film, polyvinyl acetal film, polycarbonate film, polystyrene film, polyethylene terephthalate film, paper, and polymer-coated paper such as hypholyethylene.

Next, the present invention will be explained in more detail with reference to Example I. It goes without saying that the present invention is not limited thereto.

Example i A silver halide color photographic material was prepared by sequentially coating the following layers on a triacetyl cellulose support.

(In all examples below, the amounts added to silver halide color photographic materials are shown per 100 cm.) (1) 40 mg gelatin, 16 mg red-sensitive silver iodobromide emulsion, and 2.6 mg of silver halide silver iodobromide emulsion. 1-hydroxy-4'
~(4-tert-butylphenoxy)-4-phenylazo-2-naphthanilide and 14 mg of 1-hydroxy=N-(α-1(2.4-tertiarybutylphenoxy)butyl)-2-naphthamide were dissolved. layer containing 13 mg di-n-butyl phthalate coupler solvent; (2) 8.4 mg gelatin, 0
．． Gelatin interlayer containing 3 mg dioctylhydroquinone; (3) 40 mg gelatin; 22.
5 mg of green-sensitive silver iodobromide emulsion, and 1.2 mg of 1-
(2,4.6- 1-liqa 7 enyl) -3
- (3- (α-(2,4-diteramylphenoxy)acetamido)benzamide]-4-(4
'-Methoxyphenylazo)-5-vilazolone and 22m
g of 1-(2.4.6-trichlorophenyl)
-3-'(3-iα-(2.4-diteramylphenoxy)acetamide}benzamide]-5-
Pyrazolone, O. as an image improver. 18 mg of 2(1-
722-5-tetrazolylthio)-4-(2,4-tert-amylphenoxyacetamide)-1-
A layer containing 17 mg of tricresyl phos7ate coupler solvent in which indanone and 0.27 of dioctyl hydroquinone were dissolved as a contamination protection agent; (4) 8.1 mg of gelatin, Q. Gelatin layer containing 25 mg of dioctylhydroquinone and yellow filter dye: (5) 49 mg of gelatin, 25.5 mg of blue-sensitive iodobromide emulsion, and 17.5 mg of N-(p-penzoylacetamidobenzenesulfonyl). ) -N- (
(6) 18.5 mg of gelatin; Gelatin protective layer containing; However, the following 78 regarding the present invention! A methanol solution of 1-aryl-3-pyrazolidone compounds was added to each of the layers shown in Table 1 immediately before coating.

As a comparison sample, l-phenyl-3-pyrazolidone (
PP), 4-methyl-4-hydroxymethyl-1-7enyl-3-lazolidone (MHPP) and l
A sample to which no -aryl-3-pyrazolidone compound was added was also prepared at the same time.

Light wedge exposure was carried out according to the sensitometric method in Table 1 and then processed at a temperature of 38°C according to the following sequence.

Processing process Color development 1 minute, 2 minutes, 3 minutes Bleach 6 minutes 30 seconds Water wash 3 minutes 15 seconds Fixation 6 minutes 30 seconds Water wash 3 minutes I 5 seconds Stable 1 minute 30 seconds Color developer As the bleaching solution, fixing solution, and stabilizing solution, processing solutions having the following formulations were used.

Color developer formulation Anhydrous sodium carbonate 26.0g Anhydrous sodium bicarbonate 3.5g Potassium sulfite (dihydrate) 18.0g Potassium bromide
1.3g non-chloride sodium
0.2g sodium ditrilotriacetate (1
water salt) 2.0g potassium hydroxide
0.4g hydroxylamine sulfate 2
．． 0g4-amino-3-methyl-N-methyl-N-(β
-Hydroxyethyl) Aniline sulfate Add 5.0g of water and dissolve (pH: IO'.
5) Bleach solution formulation Ethylenediaminetetraacetic acid iron ammonium salt 100g Ethylenediaminetetraacetic acid 2 Ammonium salt 10.0g Ammonium bromide 1 50g Ice Vinegar
Acid 100mQ
Add water and lα (pH: 6.0
) Fixer formulation ammonium thiosulfate (70% aqueous solution) 175.0
m (2 anhydrous sodium sulfite 8.6g
Sodium metasulfite 2.3g Add water l Q (pH: 6.0) Stable solution formulation 37% aqueous formaldehyde solution 1.5mQ Conidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml Add water IQ Above treatment When developed during the process, yellow, magenta, and cyan images were formed as a result.

These samples were subjected to sensitometry using monochromatic light of blue (B), green (C), and red (R) to determine sensitivity and fog. The results are shown in Table 2. In the table, sensitivity is comparative sample A-
As can be seen from this table, the sensitivity of B, G, and R obtained when developing 11 for 3 minutes is 100.
Sample A containing aryl-3-pyrazolidone compound
-1-A-10 all increase the development speed of the red-sensitive layer. On the other hand, the gradation when developing for 3 minutes (D-0.3 ~
The slope of 1.0) is shown in the table below.

From this table, comparative sample A-9. It can be seen that a significant softening of the tone occurs in A-10.

It can be seen that sample AI-A8 according to the present invention has a preferable development speed without fogging and without softening of tone as observed in the comparative samples.

Example 2 A silver halide color photographic material was prepared by sequentially coating the following layers on polyethylene resin coated paper.

(1) 20 mg of gelatin, 5 mg of blue-sensitive silver chlorobromide emulsion, and 8 mg of 2-(l-benzyl-2,4
-dioxyimitasolidin-3-yl)-2-piparyl-2'-chloro5'- (4-(2,4-di-tert-amylphenoxy)putanamido)acetanilide, 0.5 mg of 5,5-dimethyl - a layer containing 34 mg di-n-butylphthalate coupler solvent in which 1,3-cyclohexanedione and 0.1 mg 2,5-tertiary octylhydroquinone are dissolved; (2) 10 mg gelatin, 0.5 mg (3) 18 mg gelatin, 4 mg green-sensitive silver chlorobromide emulsion, and 5 mg 3-{2-chloro5-(l- octadecinoresuccinimide)anilino} −1 (2,
1.6 mg of tricresylphos 7 in which 4.6-tricorophenyl)-5-pyrazolone and 0.15 mg of 2,5-tertiary octylhydroquinone were dissolved.
layer containing ate coupler solvent; (4) gelatin middle layer containing 15 mg gelatin, 0.8 mg 2,5-tertiary octylhydroquinone; (5) 16 mg gelatin, 4 mg red sensitive salt odor Silveride emulsion, 3.5 mg of 2-(2-(2,4-diteramylphenoxy)butylamide)-4
．． 6-dichloro-5-methyl 7enol and 0.1 m
(6) A gelatin protective layer containing 9 mg of gelatin; However, according to the present invention, The following five types of 1-aryl-3-vilazonadone compounds were respectively added as a methanol solution to the first blue-sensitive emulsion layer immediately before coating.

As comparative samples, a total of three samples were used, one to which PP and MHPP were added and the other to which no 1-aryl-3-pyrazolidone was added, as in Example 1.

Table 4 The 28 types of silver halide color photographic materials listed in Table 4 were subjected to light wedge exposure according to the sensitometric method, and then
Treatments were carried out at a temperature of 33°C according to the following sequence.

Processing steps Color development 1 minute 30 seconds, 2 minutes 30 seconds, 3 minutes 30 seconds Bleach-fixing 1 minute 30 seconds Water washing 3 minutes As the color developer and bleach-fix solution, processing solutions having the following formulations were used.

Color developer formulation N-ethyl-N-β-methanesulfonamidoethyl-3
-Methyl-4-aminoaniline sulfate 4.9g Hydroxylamine 2.0g Potassium carbonate 25.0g Sodium chloride 0.1g Sodium bromide
0.3g anhydrous sodium sulfite
2.0g benzyl alcohol
13mα polyethylene glycol (average degree of polymerization 40
0)3. flnQ Add water to bring the volume to 1Q, pH 0.0 with sodium hydroxide, 60g of ethylenediaminetetraacetate sodium salt, ammonium thiosulfate, 100g, sodium bisulfite, 10g, sodium metabisulfite, 3g, add water to bring the volume to 1Q, and adjust the pH to 7.0 with aqueous ammonia. Development was performed during processing, resulting in yellow magenta and cyan images.

By using a bleach-fix solution formulation that adjusts the sensitometry of the obtained color images B, G, and R, the sensitivity was determined by sensitometry using monochromatic light for each of B, G, and R at a development time of 3.5 minutes for comparative sample B-8. This is the relative sensitivity when each sensitivity is 100 L. Also r4! The tone shows the slope of the reflection density between 0.5 and 1.5.

As can be easily seen from this table, the sample according to the present invention is 1
- Comparative sample B containing no aryl-3-pyrazolidone
The developability of the blue-sensitive layer is superior to that of Sample -8, and on the other hand, there is no softening as seen in Comparative Samples B-6 and B-7 to which Comparative Compound PP or MHPP was added.

Example 3 Among the samples used in Example 2, B-1, B-4, B-
6, B-8 were selected, three samples of each were separately exposed to blue, green, and red monochromatic light, and processed using the color development method of Example 12 (development time: 3 minutes and 30 seconds). death,
Yellow, magenta, and cyan color images were obtained, respectively.

For each of the obtained samples, the reflection density was measured using each monochromatic light of B, G, and R, and as a standard for the degree of color staining, DG/DB, DR/DB, DG/DB, D R/DB,
For the magenta image, DB/DG DR/DG; for the cyan image, DB/DR and DG/DR were calculated. The results are shown in the table below. Here, DB1DG and DR indicate the reflection densities measured in blue, green, and red, respectively.

From the above table, yellow magenta of samples B-1 and B-4 to which the 1-aryl-3-pyrazolidone compound of the present invention was added,
The cyan colored image has almost the same spectral composition as the comparison, whereas in the sample to which PP, which is a 1-aryl-3-pyrazolidone outside of the present invention, is added, for example, there is a higher blue density and red color in the magenta dye image. It can be seen that yellow, magenta, and cyan pigments with high chroma and density cannot be obtained.

This example also shows that the 1-aryl-3-pyrazolidone compounds of the present invention have properties that are clearly different from conventional 7-aryl-3-pyrazolidones and give favorable results.

Example 4 A silver halide color photographic material was prepared by sequentially coating the following layers on polyethylene resin coated paper.

(1) 20n+g gelatin, 1.5mg blue-sensitive silver chlorobromide emulsion, and 8mg 2-(1-benzyl-
2,4-dioxyimitasolidine-3-inole)-2-
pivalinole-27-chloro5'-(4- (2.4-
5.5-dimethyl-1.3 of 5,5-dimethyl-1.3
-cyclohexanedione, and 0.1 mg of 2.5-
Dissolved Geetashary Octyl Hydroquinone 3
(2) gelatin intermediate layer containing 1.0 mg of 2,5-tertiary octylhydroquinone; (3) 18 mg of gelatin; gelatin, 1.2 mg of green-sensitive silver chlorobromide emulsion, and 5 mg of 3-(2-chloro-5-(l-
-1-(
2,4.6-tricoo7enyl)-5-vilazolone,
a layer containing 0.5 mg of 5,5-dimethyl-1,3-cyclohexanedione, and 1.6+ug of tricresylphos 7-tocoupler solvent in which 0.15 mg of 2,5-tertiary octylhydroquinone was dissolved; (4) 1.5 mg of gelatin, 1. 2mg of 2
(5) 16 mg gelatin, 2.0 mg red-sensitive silver chlorobromide emulsion, 3.5-2-(2-(2.4-Jeter)); Sharyamylphenoxy)butylamide) -4
．． 6-dichloro-5-methylphenol, 0.50mg
of 5,5-dimethyl-13-cyclohexanedione, and 1.9 mg of tricresyl phosphate coupler solvent in which 0.20 mg of 2,5-ditertiary octylhydroquinone was dissolved; (6) 18 mg; Gelatin protective layer containing gelatin: However, the following 1-aryl-3-pyrazolidone compound was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer, and l- At the same time, a sample to which no aryl-3-pyrazolidone was added was prepared.

Table 7 These five types of silver halide color photographic light-sensitive materials were subjected to light wedge exposure according to the sensitometric method and then processed at a temperature of 35° C. according to the following sequence.

Bath 4 minutes Wash with water 5 minutes drying The set of baths is as shown in the recipe below.

Pure water
800m4 benzyl alcohol I
O. Omff Sodium Sulfite 2
．． 0g 4-amino-3-methyl-N-ethyl-N-β-(methanesulfonamide) Ethylaniline 5.0g Sodium carbonate 20.0g Diaminoprobanoltetraacetic acid 10.0g Sodium thiosulfate 5.0mg Cobalt hexamine chloride 2. IQ with 0mg pure water and pH-12
．． Adjust to 5.

When development was performed in the processing step, as a result,
Yellow, magenta and cyan images were cast onto each sample. The maximum density and fog of the obtained sample were measured and the results shown in the following table were obtained.

From the results in the table above, samples C-1-C-4 are compared to comparative sample C-5.
It shows a higher maximum density without an increase in fog compared to Sample C-1-C-4, which is thought to be because Sample C-1-C-4 exhibits higher developability than Comparative Sample C-5. It will be done.

As can be seen from this example, the silver halide color photographic light-sensitive material to which the 1-aryl-3-pyrazolidone compound of the present invention is added can provide a desirable color image with a high maximum density even when processed in one bath. Recognize.

Claims (1)

[Scope of Claims] A 1-aryl-3-pyrazolidone compound having a substituent represented by the following general formula [1]. General formula [1] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R represents an alkyl group having 1 to 18 carbon atoms or a phenyl ring group, and
It represents any group selected from O-, -SO_2-, and -NHCO-, and R' and R'' represent a hydrogen atom or a methyl group.]