JPH08262664A - Phosphoryl hydrazine compound, and silver halide color photographic material using it - Google Patents

Abstract

PURPOSE: To provide a novel phosphoryl hydrazine compound and a photosensi tive material improved in color contamination, color fog and life. CONSTITUTION: In a silver halide color photographic material having at least one photosensitive silver halide emulsion layer on a support body, at least one compound represented by the formula is contained. In the formula, R<1> represents an aryl group or a heterocyclic group, R<2> represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group, A<1> , A<2> each represent a hydrogen atom or a hydrolyzable group, G represents a carbon atom or phosphor atom, X represents an oxygen atom or sulfur atom, (m) and (n) represent 2 and 0, respectively, when G is a carbon atom, (m) and (n) represent 2 and 1, or 3 and 0, respectively, when G is a phosphor atom, and a plurality of R<1> N(A<1> )N(A<2> )-may be the same or different when (m) is an integer of 2 or more.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light-sensitive material and a phosphorylhydrazine compound having improved color contamination, color fog generation and storage stability.

[0002]

2. Description of the Related Art In silver halide color photographic light-sensitive materials,
It is well known in the art to cause undesired color contamination between different color-sensitive layers. As means for preventing these, for example, a method using a hydroquinone compound has been proposed in US Pat. No. 4,732,845. Certainly, these have some effect on preventing color contamination, but the effect is small, and after producing the preventive effect, a colored product is produced, which causes a change in photographic performance during the production of a light-sensitive material and during storage. There was such a problem.

On the other hand, EP033875A2 and JP-A-3-
Nos. 164735 and 5-232651 disclose the use of a diffusion-resistant hydrazine compound as an antifoggant. Among these, examples of phosphorylhydrazine compounds are shown, but these effects are weak, and further improvement is required. Also, Japanese Patent Application Laid-Open
-140340, 63-223744, 63-
286840, 63-223744, 63-2
No. 34244, No. 63-306438, JP-A 5-1.
65134, No. 5-197091, No. 5-14268.
No. 8, 2-1834, etc., a hydrazine compound is used as a nucleating agent in a photographic system, and some phosphorylhydrazine compounds are presented. However, these compounds are not suitable for this purpose because they act directly on silver halide and cause sensitivity variations. On the other hand, except for photographic systems, US Pat. No. 4,203,932 shows that phosphorylhydrazines are effective as insecticides. However, none of the above-mentioned patents describes a compound having the structure of the present invention in which two or three hydrazine moieties are directly bonded to a phosphorus atom, and therefore the compound of the present invention is structurally novel. It was unexpected that the compound of the present invention could solve the above-mentioned problems in a photographic system.

[0004]

SUMMARY OF THE INVENTION The first object of the present invention is to:
Second, to provide a light-sensitive material having less color contamination and color fog and excellent in color reproducibility. Second, to provide a light-sensitive material having less change in photographic performance during manufacturing and storage. And to provide a compound for realizing the above light-sensitive material.

[0005]

[Means for Solving the Problems] The above-mentioned problems are as follows.
Solved by (I) A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, containing at least one compound represented by the following general formula (I). Silver halide color photographic light-sensitive material.

[0006]

[Chemical 7]

In the formula (I), R ¹ represents an aryl group or a heterocyclic group, R ² represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group, and A ¹ , A ² represents a hydrogen atom or a hydrolyzable group, G represents a carbon atom or a phosphorus atom, X represents an oxygen atom or a sulfur atom, and when G is a carbon atom, m represents 2 and n represents 0, M when G is a phosphorus atom
Is 2, n is 1, or m is 3, and n is 0. When m is 2 or more, a plurality of R ¹ N (A ¹ ) N (A ² )-may be the same or different.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the compound represented by formula (I) will be described in detail.

In the general formula (I), R ¹ is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, and the aryl group preferably has 6 to 30 carbon atoms. Is phenyl, naphthyl, etc., and the heterocyclic group is preferably a 3- to 8-membered ring and contains an oxygen atom, a nitrogen atom or a sulfur atom as a hetero atom in the ring-constituting atoms, specifically 2-pyridyl, Two
-Furyl, 2-benzoxazolyl, 2-thienyl and the like. Particularly preferred as R ¹ is an aryl group.

When R ¹ has a substituent, the substituent is specifically an alkyl group, an aryl group or an acylamino group (having 2 to 60 carbon atoms. For example, acetylamino, n
-Butanoylamino, octanoylamino, 2-hexadecanoylamino, 2- (2 ', 4'-di-t-amylphenoxy) butanoylamino, benzoylamino, nicotinoylamino), alkoxy group (having 1 carbon atom) ~ 60.
For example, methoxy, ethoxy, butoxy, n-octyloxy, hexadecyloxy, 2-methoxyethoxy), aryloxy group (having 6 to 60 carbon atoms. For example, phenoxy, 2,4-t-amylphenoxy, 4-t- Butylphenoxy, naphthoxy), alkylthio group (having 1 to 60 carbon atoms, for example, methylthio, ethylthio, butylthio, hexadecylthio), arylthio group (having 6 carbon atoms)
~ 60. For example, phenylthio, 4-todecyloxyphenylthio), an acyl group (having 1 to 60 carbon atoms, for example, acetyl, benzoyl, butanoyl, dodecanoyl), a sulfonyl group (having 1 to 60 carbon atoms, for example, methanesulfonyl, butanesulfonyl, Toluenesulfonyl), a sulfonylamino group (having 1 to 60 carbon atoms, methanesulfonylamino, phenylsulfonylamino), a cyano group, an alkoxycarbonyl group (having 2 to 60 carbon atoms, for example, ethoxycarbonyl, hexyloxycarbonyl, dodecyloxycarbonyl), Aryloxycarbonyl group (having 7 to 30 carbon atoms, for example, phenoxycarbonyl, naphthyloxycarbonyl), carbamoyl group (having 1 to 6 carbon atoms)
0. For example, N, N-dicyclohexylcarbamoyl)
Alternatively, a sulfamoyl group (having 0 to 60 carbon atoms. For example,
N, N-dimethylsulfamoyl), a carboxyl group,
Examples thereof include a halogen atom and a hydroxyl group. Preferred substituents are an alkyl group, an alkoxy group, an aryloxy group, an acylamino group and a sulfonylamino group, and particularly preferred groups include an alkoxy group, an acylamino group and a sulfonylamino group.

These substituents may be further substituted with these substituents, and if possible, these substituents may be linked to each other to form a ring.

When R ² represents an alkyl group, it is a substituted or unsubstituted alkyl group, preferably having 1 to 6 carbon atoms.
0, specifically, methyl, ethyl, propyl, is
o-propyl, tert-butyl, 2-ethylhexyl,
Nonyl, undecyl, pentadecyl, n-hexadecyl, 3-decanamidopropyl and the like. When R ² represents a cycloalkyl group, it is a substituted or unsubstituted cycloalkyl group, preferably having 3 to 60 carbon atoms, specifically, cyclopropyl, 1-ethylcyclopropyl,
Examples include cyclopentyl and cyclohexyl. When R ² is an aryl group, the aryl moiety is synonymous with the aryl group and its substituent explained in R ¹ . When R ² is a heterocyclic group, the heterocyclic moiety is specifically R ¹
It has the same meaning as the heterocyclic group and the substituents thereof described above.

Each group of R ² may have a substituent, and as the substituent, the substituents listed for R ¹ can be applied. The substituent is more preferably an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfonyl group, a sulfamoyl group, a cyano group, a carboxyl group or a hydroxyl group, and a particularly preferable group. Are an alkyl group, an alkoxy group and an alkyloxycarbonyl group.

When A ¹ and A ² represent a hydrolyzable group,
Specifically, it represents a sulfonyl group, an acyl group, an oxalyl group or the like. A hydrogen atom is preferable as A ¹ and A ² .

At least one of R ¹ and R ² preferably has a ballast group, which is commonly used in a non-moving photographic additive such as a coupler, incorporated therein.
The ballast group is a group having 8 or more carbon atoms and is inert to photographic properties, and examples thereof include an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amide group, a ureido group,
It can be selected from the group consisting of sulfonamide group, ester group, sulfonyl group, acyl group, hydroxy group and the like, and combinations of these groups.

A combination of R ¹ and R ² is R
Preferred is when ¹ is an aryl group and R ₂ is an aryl group.

Among the compounds represented by the general formula (I), preferred compounds are represented by the formula (II).

[0018]

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[0019] formula (II), R ² is R ² of formula (I)
Synonymous with, m represents 2 or 3, n represents 1 when m is 2, represents 0 when m is 3, r represents 0 to 5, R ³ represents a substituent, When r is an integer of 2 or more, R
³ may be the same or different.

In the formula (II), R ³ is the R in the formula (I).
Those listed as the substituents on ¹ are preferable, an acylamino group, a sulfonamide group, an alkoxy group, an alkyl group,
Alternatively, chlorine atom is more preferable.

In the formula (II), r is 1, 2 or 3
Is preferred.

Among the compounds represented by the general formula (II), a preferable compound is represented by the formula (III).

[0023]

[Chemical 9]

[0024] In the formula (III), R ⁴ is an alkyl group or an aryl group, R ³ and r R ³ of formula (II)
And r are synonymous.

In the formula (III), the alkyl group and Rall group of R ⁴ are preferably selected from the alkyl group and the aryl group represented by R ² of the formula (I).

In the formula (III), when R ⁴ is an alkyl group, it is more preferably a secondary alkyl group having 3 to 30 carbon atoms or a cycloalkyl group.

In formula (III), when R ⁴ is an aryl group, it is more preferably a substituted or unsubstituted phenyl group, and the substituent on the phenyl group is
Examples of the substituent contained in R ¹ of the formula (I) are mentioned, and preferably an alkyl group (having 1 to 16 carbon atoms.
Methyl, isopropyl, tert-butyl, 2-ethylhexyl, cyclohexyl, dodecyl, etc.), alkoxy group (1 to 16 carbon atoms, methoxy, isopropoxy, cyclohexyloxy, hexadecyloxy, etc.), or halogen atom (chlorine, bromine, fluorine). ).

In the formula (III), r is preferably 1.

Specific examples of the compound contained in the formula (I) of the present invention are shown below, but the present invention is not limited thereto.

[0030]

[Chemical 10]

[0031]

[Chemical 11]

[0032]

[Chemical 12]

[0033]

[Chemical 13]

[0034]

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[0035]

[Chemical 15]

Representative synthetic examples and identification data for compounds of the present invention are shown.

Synthesis Example 1. 2-Pentadecyl bis [4-
Synthesis of (phenylsulfonylamino) phenylhydrazide] phosphate (6)

A solution of 11.3 ml of 2-pentadecanol in 20 ml of methylene chloride was added dropwise to a solution of 4.6 ml of phosphorus oxychloride in 50 ml of methylene chloride at 0 ° C., and the mixture was stirred at room temperature for 3 hours. To this solution, 33.0 g of 1,5-naphthalenedisulfonate of 4- (phenylsulfonylamino) phenylhydrazine and 14 ml of triethylamine were added,
Stir at room temperature for 5 hours. Add the reaction mixture to 100 ml of water,
It was extracted with ethyl acetate according to a conventional method. Concentrate the extract,
The residue was purified by silica gel column chromatography (n-hexane / ethyl acetate) to obtain exemplary compound (6) (yield 1
2.8 g, yield 78%).

Synthesis Example 2. Synthesis of tris (4-methoxyphenylhydrazide) phosphorus (9)

To a solution of 0.92 ml of phosphorus oxychloride in 50 ml of methylene chloride, 5.1 g of 4-methoxyphenylhydrazine hydrochloride and 6 ml of triethylamine were added, and the mixture was stirred at room temperature for 5 hours. The reaction solution was added to 100 ml of water and extracted with ethyl acetate according to a conventional method. The extract was concentrated, the residue was purified by silica gel column chromatography (n-hexane / ethyl acetate), crystallized with ethanol and dried to obtain Exemplified compound (9) (yield 3.4 g, yield 77%). .

Other compounds can be synthesized by the same method or a method analogous thereto.

Identification data (10 kinds, NMR, mp are shown in a table)

[0043]

[Table 1]

[0044]

[Table 2]

The compounds of the present invention may be used in combination of two or more kinds.

The compound of the present invention is a protective layer in a light-sensitive material,
It can be used by being contained in at least one layer such as a photosensitive silver halide emulsion layer, a non-photosensitive fine grain silver halide emulsion layer, an intermediate layer, a filter layer, an undercoat layer and an antihalation layer. / Or it is preferably used as an intermediate layer between two photosensitive emulsion layers (color sensitivity may be the same or different), and most preferably is used as the intermediate layer.

When the compound of the present invention is added to the non-photosensitive layer, the coating amount of the non-photosensitive gelatin is 0.2-2.
0 g / m ² are suitable, preferably a 0.3~1.2g / m ^2, further preferably 0.4~1.0g / m ^2. The compound of the present invention may be added to these layers as it is in the coating solution or after being dissolved in a low boiling point organic solvent such as alcohol (eg, methyl alcohol) which does not affect the silver halide color photographic light-sensitive material. You can also do it. Further, it may be dispersed or impregnated in a polymer such as latex, or may be dissolved in a high boiling point organic solvent and emulsified and dispersed in an aqueous solution.

The total amount added to the light-sensitive material of the present invention is usually 0.
001 to 0.8 g / m ² , preferably 0.005
To 0.5 g / m ² , more preferably 0.01 to 0.3 g
/ M ² .

Regarding the various techniques and inorganic / organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same, Research Disclosure No. 308119 (19) is generally used.
1989) can be used.

In addition to this, more specifically, for example,
Techniques and inorganic / organic materials that can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following parts of EP 436,938A2 and the patents cited below. There is.

Item This section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Silver halide emulsion Page 147, line 26 to page 148, line 12 3) Yellow coupler No. Page 137, line 35 to page 146, line 33, page 149, line 21 to line 23 4) Magenta coupler, page 149, line 24 to line 28; EP 421,453A1 Page 3, line 5 to page 25, line 55 5) Cyan coupler page 149, line 29 to line 33; European Patent 432,804A2, page 3, line 28 to page 40, line 6) Polymer coupler, page 149, lines 34 to 38; EP 113, line 113, page 39 to page 123, line 37; 7) Colored coupler, page 53, line 42 to page 137, line 34. Page 149, lines 39-45 8) Other functionality Page 7, line 1 to page 53, line 41, page 149, line 46, coupler line to page 150, line 3; EP 435,334 4A2, page 3, line 1 -Page 29, line 50 9) Antiseptic / mildew agent page 150, lines 25-28 10) Formalin page 149, lines 15-17 17 Scavenger 11) Other additives, page 153, line 38 ~ Line 47; page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40 of European Patent 421,453A1 12) Dispersion method page 150, line 4 ~ Line 24 13) Support page 150 line 32 to line 34 14) Film thickness and film physical properties page 150 line 35 to line 49 15) Color development step page 150 line 50 to page 151 47th line 16) Desilvering process, page 151, line 48 to page 152, line 53 17) Automatic processor, page 152, 54 Eyes - page 153, line 2 18) washing and stabilizing steps page 153, line 3 to 37 row

[0052]

EXAMPLES The present invention will now be specifically described with reference to examples, but the invention is not limited thereto.

Example 1 Preparation of Sample 101 Sample 101 was prepared by preparing a multilayer color light-sensitive material having the following compositions on a cellulose triacetate film support having a thickness of 127 μ and having an undercoat. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.10 g Gelatin 1.90 g UV absorber U-1 0.10 g UV absorber U-3 0.040 g UV absorber U-4 0.10 g High boiling organic solvent Oil-1 0.10 0.10 g of a microcrystalline solid dispersion of Dye E-1

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg Compound Cpd-K 3.0 mg High boiling point organic solvent Oil-3 0.10 g Dye D-4 0.80 mg

Third layer: intermediate layer Fine grained silver iodobromide emulsion with the surface and inside fogged (average grain size 0.06 μm, coefficient of variation 18%, AgI content 1 mol%) silver amount 0.050 g yellow colloidal silver silver amount 0.030 g gelatin 0.40g

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A Silver amount 0.30 g Emulsion B Silver amount 0.20 g Gelatin 0.80 g Coupler C-1 0.15 g Coupler C-2 0.050 g Coupler C-3 0.050 g Coupler C-9 0.050 g Compound Cpd-C 5.0 mg Compound Cpd-J 5.0 mg High boiling point organic solvent Oil-2 0.10 g Additive P-1 0.10 g

Fifth layer: Medium-sensitive red-sensitive emulsion layer Emulsion B Silver amount 0.20 g Emulsion C Silver amount 0.30 g Gelatin 0.80 g Coupler C-1 0.20 g Coupler C-2 0.050 g Coupler C-3 0.20 g High boiling point organic solvent Oil-2 0.10g Additive P-1 0.10g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.40 g Gelatin 1.10 g Coupler C-1 0.30 g Coupler C-2 0.10 g Coupler C-3 0.70 g Additive P-1 0.10 g

Seventh layer: intermediate layer Gelatin 0.50 g Additive M-1 0.25 g Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-J 5.0 mg High boiling organic solvent Oil-3 0.020 g

Eighth layer: intermediate layer Silver iodobromide emulsion with a fogged surface and inside (average grain size 0.06 μm, coefficient of variation 16%, AgI content 0.3 mol%) Silver amount 0.020 g Yellow colloidal silver Silver amount 0.020 g Gelatin 0.80g Additive P-1 0.20g Color mixing inhibitor Cpd-A 0.20g

Layer 9: Low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.10 g Emulsion F Silver amount 0.30 g Emulsion G Silver amount 0.20 g Gelatin 0.50 g Coupler C-4 0.10 g Coupler C-7 0.050 g Coupler C-8 0.10 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-J 10 mg High boiling point organic solvent Oil-1 0.10 g High boiling point organic solvent Oil-2 0.10 g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.30 g Emulsion H Silver amount 0.10 g Gelatin 0.60 g Coupler C-4 0.070 g Coupler C-7 0.050 g Coupler C-8 0.050 g Compound Cpd-B 0.030g Compound Cpd-D 0.020g Compound Cpd-E 0.020g Compound Cpd-F 0.050g High boiling organic solvent Oil-2 0.010g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion I Silver amount 0.50 g Gelatin 1.00 g Coupler C-4 0.20 g Coupler C-7 0.10 g Coupler C-8 0.050 g Compound Cpd-B 0.080 g Compound Cpd-E 0.020 g Compound Cpd-F 0.040 g Compound Cpd-K 5.0 mg High boiling point organic solvent Oil-1 0.020 g High boiling point organic solvent Oil-2 0.020 g

Twelfth layer: intermediate layer Gelatin 0.50 g Additive M-1 0.050 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.080 g Gelatin 1.00 g Anti-color mixing agent Cpd-A 0.10 g High boiling point organic solvent Oil-1 0.10 g Microcrystalline solid dispersion of dye E-2 0.050 g

14th layer: intermediate layer gelatin 0.50 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.20 g Emulsion K Silver amount 0.30 g Gelatin 0.80 g Coupler C-5 0.20 g Coupler C-6 0.10 g Coupler C-10 0.20 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.30 g Emulsion M Silver amount 0.30 g Gelatin 0.90 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g

Layer 17: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.20 g Emulsion O Silver amount 0.20 g Gelatin 1.20 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.60 g High boiling organic solvent Oil-2 0.10g

Eighteenth layer: First protective layer Gelatin 0.70 g UV absorber U-1 0.20 g UV absorber U-2 0.050 g UV absorber U-5 0.30 g Formalin scavenger Cpd-H 0.40 g Dye D-1 0.15 g Dye D-2 0.050g Dye D-3 0.10g

Layer 19: Second protective layer Colloidal silver Silver amount 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.10 g Gelatin 0.40 g

20th layer: 3rd protective layer Gelatin 0.40 g Polymethyl methacrylate (average particle size 1.5 μ) 0.10 g Copolymer of methyl methacrylate and acrylic acid 4: 6 (average particle size 1.5 μ) 0.10 g Silicone oil 0.030g Surfactant W-1 3.0mg Surfactant W-2 0.030g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

[0075]

[Table 3]

[0076]

[Table 4]

[0077]

[Table 5]

[0078]

Embedded image

[0079]

[Chemical 17]

[0080]

Embedded image

[0081]

[Chemical 19]

[0082]

Embedded image

[0083]

[Chemical 21]

[0084]

[Chemical formula 22]

[0085]

[Chemical formula 23]

[0086]

[Chemical formula 24]

[0087]

[Chemical 25]

[0088]

[Chemical formula 26]

[0089]

[Chemical 27]

[0090]

[Chemical 28]

[0091]

[Chemical 29]

[0092]

Embedded image

Preparation of Samples 101 to 116 In Table 101, instead of the color mixing inhibitor Cpd-A used in the eighth and thirteenth layers, Comparative Compound A, Comparative Compound B and the compound of the present invention are shown in Table 6. Sample 10 was prepared in the same manner as Sample 101 except that equimolar amounts were added as shown.
2-116 were produced. The obtained samples 101 to 116 were cut into strips and then wedge-exposed through a red filter to evaluate the color mixture from the green-sensitive layer to the red-sensitive layer based on the minimum density value of the cyan color-forming layer. Further, wedge exposure was performed through a green filter to evaluate the color mixture from the blue-sensitive layer to the green-sensitive layer based on the minimum density value of the magenta coloring layer. Next, under the condition of 45 ° C. and 80% RH, the sample 101
~ 116 was stored for 1 week. After storage, the wafer was exposed to wedge light with white light and compared with a sample stored at 25 ° C. to evaluate the storage stability. The treatment process was performed according to the following formulation. The obtained results are shown in Table 6.

Treatment process time Temperature First development 6 minutes 38 ° C Water washing 2 minutes 38 ° C Reversal 2 minutes 38 ° C Color development 6 minutes 38 ° Pre-bleaching 2 minutes 38 ° Bleach 6 minutes 38 ° C fixing 4 minutes 38 ° C Washing with water 4 minutes 38 ℃ Final rinse 1 minute 25 ℃

The composition of each processing liquid was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g Diethylenetriaminepentaacetic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 15 g Bicarbonate Sodium 12g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide 2.0mg Diethylene glycol 13g Water was added to 1000 ml pH 9. 60 pH was adjusted with sulfuric acid or potassium hydroxide.

[Inversion Liquid] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 3.0 g stannous chloride / dihydrate 1.0 g p-aminophenol 0.1 g sodium hydroxide 8 g glacial acetic acid 15 ml water was added to 1000 ml pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[Color Developer] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g sodium sulfite 7.0 g trisodium phosphate dodecahydrate 36 g potassium bromide 1.0 g potassium iodide 90 mg Sodium hydroxide 3.0 g Citrazine acid 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6-dithiaoctane -1,8-diol 1.0g Water was added and 1000 ml pH 11.80 pH was adjusted with sulfuric acid or potassium hydroxide.

[Pre-bleaching] Ethylenediamine tetraacetic acid / disodium salt / dihydrate 8.0 g Sodium sulfite 6.0 g 1-thioglycerol 0.4 g Sodium formaldehyde bisulfite adduct 30 g Water was added to 1000 ml pH 6.20 The pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching Solution] Ethylenediaminetetraacetic acid / sodium salt / dihydrate 2.0 g Ethylenediaminetetraacetic acid / Fe (III) -ammonium / dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water 1000 ml pH 5 The .70 pH was adjusted with nitric acid or sodium hydroxide.

[Fixing Solution] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with acetic acid or aqueous ammonia.

[Final Rinse Solution] 1,2-Benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 g Polymaleic acid (average molecular weight 2,000) 0 Add 1,000 g water 1000 ml pH 7.0

As is clear from Table 6, the samples 104 to 116 using the color mixing inhibitor of the present invention are excellent in the ability to prevent color mixing between layers, have a small change in the coloring density of the magenta coloring layer during storage, and have a gradation change. It turns out that there are few. It is clear that among the present invention, Samples 109 to 116 are further excellent in color mixing prevention ability and storage stability.

[0103]

[Table 6]

Example 2 Compound Cpd-1 of the sixth and tenth layers in Example 101, Sample 101 described in JP-A-6-236014
Samples A, B and C were prepared in the same manner as in Sample 101, except that was replaced with the compounds (1), (8) and (13) of the present invention. When the samples A, B and C were exposed and developed by the method described in Example 1 of the above publication, the same results as in Example 1 of the present invention were obtained.

Example 3 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 10
0 parts by weight and Tinuvin P.326 (Ciba
2 parts by weight of Geigy (Ciba-Geigy)
After melting at 300 ° C, extruded from a T-die and longitudinally stretched 3.3 times at 140 ° C, then laterally stretched 3.3 times at 130 ° C, and further heat set at 250 ° C for 6 seconds. A PEN film having a thickness of 90 μm was obtained. The PEN film contains a blue dye, a magenta dye and a yellow dye (I-1 and I-described in Official Technical Report No. 94-6023).
4, I-6, I-24, I-26, I-27, II-5) was added in an appropriate amount. Furthermore, the support was wound around a stainless steel core having a diameter of 20 cm and subjected to a heat history of 110 ° C. for 48 hours to obtain a support having less curling tendency.

2) Coating of undercoat layer The above support was subjected to corona discharge treatment, UV discharge treatment and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-on each side. Sulfodi-2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p-chlorophenol 0.2 g / m ² ,
(CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.012 g / m ² , polyamide-epichlorohydrin polycondensate 0.02 g / m ² Apply an undercoat liquid (10 cc / m ² , using a bar coater) ), The undercoat layer was provided on the high temperature side during stretching. Drying was carried out at 115 ° C for 6 minutes (rollers and conveyors in the drying zone are
15 ° C). 3) Coating of back layer On one surface of the above-mentioned support after undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer were coated as a back layer.

3-1) Coating of Antistatic Layer A dispersion of fine particle powder having a specific resistance of 5 Ω · cm of a tin oxide-antimony oxide composite having an average particle size of 0.005 μm (secondary agglomerated particle size of about 0.08 μm) ) and 0.2 g / m ^2, gelatin _{^{0.05g / m 2, (CH 2}} = CHSO 2 CH 2 CH 2 NHCO) 2 CH 2 0.0
2 g / m ² , poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.005 g / m ² and resorcin. 3-2) Coating of magnetic recording layer 3-Corbato-γ-iron oxide (specific surface area 43 m ² / g, coated with poly (degree of polymerization of 15) oxyethylene-propyloxytrimethoxysilane (15% by weight)) Long axis 0.
14μm, uniaxial 0.03μm, saturation magnetization 89emu / g, Fe
^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with aluminum oxide silicon oxide at 2% by weight of iron oxide) 0.06 g / m ² of diacetyl cellulose 1.2 g / m ² (dispersion of iron oxide Was performed with an open kneader and a sand mill), C ₂ as a curing agent
H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NCO) ₃ 0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent, and a magnetic film with a thickness of 1.2 μm was applied. A recording layer was obtained. Silica particles (0.3μ as matting agent
m) and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) treated and coated with aluminum oxide (0.15 μm) as an abrasive at a concentration of 10 mg / m ^2. did. Drying at 115 ℃, 6
Min. (115 ° C. for all rollers and conveyance devices in the drying zone). The color density increase of D ^B of the magnetic recording layer by X-light (blue filter) was about 0.1, the saturation magnetization moment of the magnetic recording layer was 4.2 emu / g, and the coercive force was 7.3.
It was × 10 ⁴ A / m and the squareness ratio was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀
H ₂₀ COOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH
_{A 2} O) ₁₆ H (compound b, 9 mg / m ² ) mixture was applied. This mixture was prepared by melting it in xylene / propylene monomethyl ether (1/1) at 105 ° C. and pouring and dispersing it in propylene monomethyl ether (10 times the volume) at room temperature. Average particle size 0.01μ
m) and then added. Silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (15) as an abrasive.
Aluminum oxide (0.15 μm) coated by weight% was added to a concentration of 15 mg / m ² . Drying is 115
C., 6 minutes (115.degree. C. for all rollers and conveyors in the drying zone). The sliding layer has a dynamic friction coefficient of 0.06 (5
mmφ stainless steel ball, weight 100g, speed 6cm /
Min), the coefficient of static friction was 0.07 (clip method), and the coefficient of dynamic friction between the emulsion surface and the sliding layer described later was 0.12.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, the same emulsion layers as those of Samples 101 and 116 of Example 1 were multilayer-coated to prepare Samples 201 and 220. . 5) Evaluation These samples were evaluated in the same manner as in Example 1, and as a result, it was apparent that Sample 220 had the effect of improving color turbidity, photobleaching, and preservability with respect to Sample 201.

Claims (6)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, containing at least one compound represented by the following general formula (I). And a silver halide color photographic light-sensitive material. Embedded image In the formula (I), R ¹ represents an aryl group or a heterocyclic group, R ² represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group, and A ¹ and A ² are Represents a hydrogen atom or a hydrolyzable group, G represents a carbon atom or a phosphorus atom, X represents an oxygen atom or a sulfur atom, and when G is a carbon atom, m represents 2, n represents 0, and G represents phosphorus. When an atom, m is 2, n is 1, or m is 3, and n is 0, and when m is an integer of 2 or more, a plurality of R ¹ N (A ¹ ) N (A ² )-are the same or different. May be. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (I) is represented by the general formula (II). Embedded image In formula (II), R ² has the same meaning as R ² in formula (I), m represents 2 or 3, n is m represents 1 when 2, m represents 0 when 3, r Represents an integer of 0 to 5, R ³ represents a substituent, and when r is 2 or more, a plurality of R
³ may be the same or different. 3. The silver halide color photographic light-sensitive material according to claim 2, wherein the compound represented by the general formula (II) is represented by the general formula (III). Embedded image In formula (III), R ⁴ represents an alkyl group or an aryl group, R ³ and r are the same and R ³ and r of formula (II). 4. A compound represented by the general formula (I). [Chemical 4] In the formula (I), R ¹ represents an aryl group or a heterocyclic group, R ² represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, an alkoxy group or an aryloxy group, and A ¹ and A ² are Represents a hydrogen atom or a hydrolyzable group, G represents a carbon atom or a phosphorus atom, X represents an oxygen atom or a sulfur atom, and when G is a carbon atom, m represents 2, n represents 0, and G represents phosphorus. When an atom, m is 2, n is 1, or m is 3, and n is 0, and when m is an integer of 2 or more, a plurality of R ¹ N (A ¹ ) N (A ² )-are the same or different. May be. 5. The compound according to claim 4, which is represented by the general formula (II). Embedded image In formula (II), R ² has the same meaning as R ² in formula (I), m represents 2 or 3, n is m represents 1 when 2, m represents 0 when 3, r Represents 0 to 5, and R ³
Represents a substituent, and when r is an integer of 2 or more, a plurality of R ³
May be the same or different. 6. The compound according to claim 5, which is represented by the general formula (III). [Chemical 6] In formula (III), R ⁴ represents an alkyl group or an aryl group, R ³ and r are the same and R ³ and r of formula (II).