JPH05194788A - Cellulose ester film, photosensitive silver halide material and treatment method - Google Patents

Abstract

PURPOSE:To produce the title film excellent in strengths, flame retardance, resistance to bleeding, and storage stability by incorporating a specific plasticizer and a specific degradation preventive into a cellulose ester film contg. triphenyl phosphate as a plasticizer. CONSTITUTION:A cellulose ester film contg. triphenyl phosphate as a plasticizer, another plasticizer of formula I (e.g. a compd. of formula II or III), and at least one degradation preventive selected from the group consisting of a peroxide-decomposing agent (e.g. a compd. of formula IV), a free radical chain transfer inhibitor (e.g. a compd. of formula V), a metal deactivator (e.g. a compd. of formula VI), and an acid acceptor (e.g. a compd. of formula VII) is provided. The plasticizer of formula I prevents bleeding, and the degradation preventive improves the storage stability of the film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cellulose ester film, and more particularly to a cellulose ester film suitable as a support for a silver halide light-sensitive material having improved storage stability and a method for preventing deterioration thereof.

[0002]

2. Description of the Related Art Conventional cellulose ester supports used in photographic light-sensitive materials include cellulose acetate, cellulose acetate butyrate and cellulose acetate propionate. Among them, cellulose triacetate is often used because of its excellent dimensional stability, transparency and gloss. Generally, cellulose acetate film has weak tear strength, folding endurance, impact strength,
Especially under low humidity conditions, it becomes very hard and brittle, and easily cracks.

It has long been well known to add low molecular weight plasticizers to improve these properties.
Typical plasticizers include triphenyl phosphate,
Examples include tricresyl phosphate, octyl diphenyl phosphate, triethyl phosphate, tributyl phosphate, diethyl phthalate, dimethoxyethyl phthalate, ethyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate and triacetin. Especially for triacetyl cellulose, triphenyl phosphate is mainly used. However, it can be said that the strength required for the support increases year by year as the printer speed increases, and the strength is still insufficient.

By increasing the addition amount of triphenyl phosphate, which is excellent in terms of strength physical properties, flame retardancy, etc., it is possible to achieve further improvement in strength physical properties and a reduction in dimensional change, but in terms of volatility and migration property. Therefore, there is a problem of so-called bleed-out, in which the plasticizer is deposited on the film surface during use or storage of the photographic light-sensitive material.

In addition, when the cellulose acetate is hermetically stored under high temperature and high humidity conditions, the degree of acetylation and the molecular weight of the cellulose acetate are lowered, and the physical properties of the film are remarkably lowered.
There is also a problem that increasing the amount of triphenyl phosphate accelerates deterioration.

Generally, fatty acid cellulose esters such as cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate are usually produced by using sulfuric acid as a catalyst. This sulfuric acid reacts with a hydroxyl group of cellulose to form a sulfuric ester. to make. The bound sulfuric acid and the free sulfuric acid remaining in the fiber tissue are desorbed and removed as much as possible by the boiling stabilization treatment, but a very small amount of sulfuric acid ester and free sulfuric acid remain in the fatty acid cellulose ester. Since it serves as a catalyst for hydrolysis, it is a main cause of deterioration due to long-term storage, particularly poor thermal stability, that is, deterioration such as coloring or decomposition due to heat and breakage of molecular chains.

On the other hand, a method of neutralizing and stabilizing treatment by adding acetates, carbonates, oxalates, etc. of potassium, sodium, calcium, barium, aluminum, etc. (US Pat. Nos. 3,047,561, 30898).
No. 71, No. 2614941, etc.) are known. However, since salts of these weak acids are often added in excess when industrially producing fatty acid cellulose esters, they remain in the fiber tissue without binding to the sulfuric acid ester or free sulfuric acid, and if they are decomposed, the molecular chain is temporarily decomposed. Even if it is possible to prevent deterioration such as cutting, it acts as a catalyst for the formation of a coloring substance, which is disadvantageous in that the hue is significantly impaired.

As described above, in order to obtain a fatty acid cellulose ester having excellent transparency and heat resistance, cellulose having a high degree of purification is used as a raw material, and sulfuric acid as a reaction catalyst is formed into a fiber in the form of bound sulfuric acid. It is desirable to use a fatty acid cellulose ester that has a small amount of residual ash and ash content in the tissue, and is free from coloring-causing substances, and the fatty acid cellulose ester usually contains a plasticizer. It is desirable to use an additive having high heat stability.

However, there is a technical and economical limit in the direction of solving the deterioration prevention of the fatty acid cellulose ester only by the purity and quality of the constituent raw materials as described above. Therefore, in general, a combination of suitable deterioration inhibitors has been carried out, and conventional epoxy compounds, weak organic acids, as deterioration inhibitors for fatty acid cellulose esters,
Antioxidants for saturated polyhydric alcohols and general organic materials such as phosphite ester compounds, hindered phenols, sulfur antioxidants such as thioethers, ultraviolet absorbers, light stabilizers, metal deactivators, etc. Are known (US Pat. Nos. 2,917,398 and 3,723,147).
Nos. 4,269,629 and 4,137,201
No. 3,723,147, JP-A-63-12803.
No. 6, No. 57-78431, No. 55-13765,
JP-B-61-45654, JP-A-59-12703
No. 56-18940, JP-A-1-339803, etc.)

In the neutralization stabilization treatment with a weak acid salt, the effect of preventing the resin from being colored when the ash content of the fatty acid cellulose ester is as high as 0.01% by weight or more is exhibited, but the fatty acid cellulose ester is shown. Since it has a function of cutting the molecular chain of, the degree of polymerization was extremely lowered and the physical properties were deteriorated. Further, when a weak organic acid, an epoxy compound and a phosphite ester compound are added to the fatty acid cellulose ester, the physical property deterioration is considerably improved as compared with the case where the weak organic acid and the phosphite ester compound are added, but still not. It was not completely satisfactory, and the colorability upon heating deteriorated. Further, even when a saturated polyhydric alcohol was added to this, when it was placed in an iron container which is a standard storage container for a silver halide light-sensitive material having a fatty acid cellulose ester as a support, the deterioration characteristics were deteriorated by heat treatment by moistening. ..

[0011]

The object of the present invention is strength,
It is an object of the present invention to provide a cellulose ester film excellent in flame retardancy and bleed-out and at the same time excellent in storage stability, and a method for preventing deterioration thereof.

[0012]

Means for Solving the Problems These problems include a cellulose ester film using triphenyl phosphate as a plasticizer containing a plasticizer represented by the following general formula (1), and (A) to (D) below. (4) A cellulose ester film characterized by containing at least one deterioration inhibitor. General formula (1)

[0013]

[Chemical 5]

In the formula, R represents an alkyl group or an alkenyl group having 4 or less carbon atoms, and n represents 3 or 4. (A) Peroxide decomposer (B) Radical chain inhibitor (C) Metal deactivator (D) Acid scavenger Cellulose containing triphenyl phosphate and a plasticizer represented by the general formula (1) In the case of a silver halide light-sensitive material having an ester film as a support, the deterioration inhibitor may be contained in the subbing layer and / or the back layer, or it may be immersed in a processing bath containing the deterioration inhibitor. I was able to achieve it. According to the present invention, the amount of triphenyl phosphate can be increased, and the mechanical strength can be greatly improved. In addition, the compound of the present invention itself has good compatibility with cellulose ester, and is unlikely to bleed out. When R is described in more detail, methyl, ethyl, propyl, butyl and propenyl allyl are preferable, and these alkyl and alkenyl are halogen,
It may be substituted with methoxy, hydroxy and the like. Further, in the general formula [I] of the present invention, the methyl ester and ethyl ester of trimellitic acid are particularly preferable. Specific examples of the plasticizer preferably used in the present invention will be described below, but the present invention is not limited thereto.

[0015]

[Chemical 6]

[0016]

[Chemical 7]

The plasticizer of the present invention can be obtained by various synthetic methods. For example, a carboxylic acid anhydride or a carboxylic acid (eg (anhydrous) trimellitic acid, trimesic acid, (anhydrous) pyromellitic acid) is used in the presence of an alcohol with a catalyst (eg sulfuric acid, hydrochloric acid, tetrabutoxytin, pyridine etc.). It can be easily synthesized by esterification.
Alternatively, the ester obtained in advance may be transesterified in the presence of the desired alcohol under the above catalyst. Generally, the above reaction is preferably carried out at high temperature. Furthermore, the polyfunctional carboxylic acid as a raw material may be converted into an acid chloride with phosphorus oxychloride, thionyl chloride or the like, and the alcohol may be esterified under a base catalyst (for example, pyridine or triethylamine). These general synthetic methods are described in JP-B Nos. 36-22593 and 37-7227.
No. 3,058,942 and the like. In addition, the plasticizer in the present invention has a small refractive index as a side effect, and contributes to the improvement of the light piping characteristics which causes fog. Further, it became clear that since the ratio of the plasticizer can be increased, the drying efficiency of the solvent in the film forming process is increased, and there is also a process merit.

The cellulose ester used in the present invention includes cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate, and the like. Particularly preferred is a cellulose acetate having a polymerization degree of 250 to 400 and a bound acetic acid amount of 54 to 62%. Is preferred. As a plasticizer, it is possible to use a low molecular weight plasticizer or a high molecular weight plasticizer together with triphenyl phosphate and the compound of the present invention depending on the use conditions. The total amount of plasticizer added is 5 to 30% by weight with respect to the cellulose ester.
Is preferably used. The addition amount of the compound of the present invention to triphenyl phosphate is preferably 3 to 50% by weight, particularly preferably 5 to 30% by weight.

As the solvent, lower aliphatic hydrocarbon chloride such as methylene chloride, lower aliphatic alcohol such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, cyclohexane, dioxane and the like are used. Be done. As a solvent composition, 70 to 100% by weight of methylene chloride and 30 to 0% by weight of other solvents are preferably used. The concentration of the cellulose ester is 10 to 50% by weight.
Is preferably used. If necessary, a peeling accelerator or dye may be added to the cellulose ester solution from the casting support.

The method for producing the cellulose ester film in the present invention is not particularly limited, and a method generally used in the art can be preferably used. Regarding the production method of the cellulose ester film, for example, US Pat. Nos. 2,492,978, 2,739,070 and 2,
739069, 2492977, 2336
No. 310, No. 2366603, No. 2492978.
No. 2,607,704 and British Patent No. 640731.
No. 735892, No. 45-9074, No. 49-4554, No. 49-5614, and JP-A No. 62-62.
The description of No. 115035 can be referred to. The thickness of the cellulose ester film is 10 to 500
It is preferably μ, and particularly preferably 50 to 200 μ.

Next, the deterioration preventing agent used in the present invention will be described. In the present invention, the (A) peroxide decomposer is a compound represented by the general formula (AI), (A-II) or (A-III), and the (B) radical chain inhibitor is ,
A compound represented by the general formula (BI):
The metal deactivator is represented by the general formula (C-I), (C-II),
The (D) acid scavenger is a compound represented by (C-III), and is represented by the general formulas (D-I), (D-II), (D-III),
(D-IV), (D-V), (D-VI), (D-VII),
It is a compound represented by (D-VIII).

[0022]

[Chemical 8]

[0023]

[Chemical 9]

[0024]

[Chemical 10]

In the general formulas (AI) to (D-VIII), X represents a hydrogen atom, an alkali metal or an alkaline earth metal. R ₁₀ represents an alkyl group, an alkenyl group or an aryl group. R ₂₀ , R ₂₁ and R ₂₂ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenoxy group, an aryloxy group, an alkylthio group, an alkenylthio group or an arylthio group. R ₃₀ and R ₃₁ may be the same or different and each represents an alkyl group, an alkenyl group or an aryl group. R ₄₀ represents an alkyl group. R
₄₁ , R ₄₂ and Y may be the same or different from each other and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an alkenoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthio group, Alkenylthio group, arylthio group, hydroxy group, optionally substituted amino group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, halogen atom, nitro group, cyano group, acyl group and acyloxy group Represents. m represents an integer of 0 to 2. R ₆₀ and R _{61, which} may be the same or different, each represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Z represents a group defined by Y, and n represents an integer of 0-4. When m is 2, a plurality of Y's may be the same as or different from each other, and similarly, n is 2
In the case of ~ 4, a plurality of Z may be the same as or different from each other.
R ₂₀ and R ₂₁ , R ₃₀ and R ₃₁ , R ₁ and R ₂ , R ₉₁ and R ₉₂ , R
₉₃ and R ₉₄ may combine with each other to form a 5- to 7-membered ring.

R ₁ , R ₂ and R _{3, which} may be the same or different, are each a hydrogen atom, an aliphatic group, an aromatic group,
Represents a heterocyclic group or an amino group. At least two groups out of R ₁ , R ₂ and R ₃ are bonded to each other to form 5 to 8
You may form a member ring. R ₁ and R ₂ may be combined with each other to form an unsaturated group, and R ₃ and R ₃ may combine with each other to form a 5- to 8-membered ring. However, R ₁ , R ₂ and R ₃ are not hydrogen atoms at the same time.

M ₁ represents an alkali metal or an alkaline earth metal, and q is ₁ when M ₁ is an alkali metal and 2 when M ₁ is an alkaline earth metal. R ₈₁ and R ₈₂ may be the same or different from each other, and each represent an alkyl group,
It represents an alkenyl group, an aryl group, and a heterocyclic group. M ₂ represents an alkali metal, and M ₃ represents an alkali metal or alkaline earth metal. u is 1 when the M ₃ of 2, M ₃ is an alkali earth metal when the alkali metal. R ₉₁ , R ₉₂ , R ₉₃ , and R _{94, which} may be the same or different, each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. R ₉₁ , R
_At least two groups out of ₉₂ , R ₉₃ , and R ₉₄ may combine with each other to form a 5- to 8-membered ring.

The compounds represented by formulas (A-I) to (D-VIII) will be described in more detail. X is a hydrogen atom,
Represents alkali metals (eg lithium, sodium, potassium) and alkaline earth metals (eg calcium, barium, magnesium). R ₁₀ , R ₂₀ , R ₂₁ ,
R ₂₂ , R ₃₀ , R ₃₁ , R ₄₀ , R ₄₁ , R ₄₂ , Y, R ₈₁ ,
The alkyl group defined by R ₈₂ , R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₆₀ and R ₆₁ is a linear, branched or cyclic alkyl group (for example, methyl, ethyl, propyl, i-propyl, t
- butyl, cyclohexyl, t-represents hexyl, t-octyl, dodecyl, hexadecyl, octadecyl, _{benzyl), R 10, R 20,} R 21, R 22, R 30, R 31,
R ₄₁ , R ₄₂ , Y, R ₈₁ , R ₈₂ , R ₉₁ , R ₉₂ , R ₉₃ ,
The alkenyl group defined by R ₉₄ , R ₆₀ and R ₆₁ is a straight chain,
Branched or cyclic alkenyl groups (eg vinyl, allyl, 2-pentenyl, cyclohexenyl, hexenyl,
Dodecenyl, octadecenyl), R ₁₀ , R ₂₀ ,
R ₂₁ , R ₂₂ , R ₃₀ , R ₃₁ , R ₄₁ , R ₄₂ , Y, R ₈₁ ,
The aryl group of R ₈₂ , R ₉₁ , R ₉₂ , R ₉₃ , R ₉₄ , R ₆₀ and R ₆₁ represents a benzene monocyclic or condensed polycyclic aryl group (eg, phenyl, naphthyl, anthranyl), R ₄₁ ,
R ₄₂ , Y, R ₆₀ , R ₈₁ , R ₈₂ , R ₉₁ , R ₉₂ , R ₉₃ ,
The heterocyclic group defined by R ₉₄ and R ₆₁ is a 5- to 7-membered cyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom (for example, furyl, pyrrolyl, imidazolyl, pyridyl). , Purinyl, chromanyl, pyrrolidyl, morpholinyl).

R ₁₀ represents an alkyl group, an alkenyl group or an aryl group. R ₂₀ , R ₂₁ and R ₂₂ may be the same or different from each other, and each is an alkyl group, an alkenyl group, an aryl group or an alkoxy group (for example, methoxy, ethoxy, methoxyethoxy, octyloxy, benzyloxy, cyclohexyloxy, i-propoxy). , Tetradecyloxy, octadecyloxy), alkenoxy groups (eg vinyloxy, propenyloxy, cyclohexenyloxy, dodecenyloxy, octadecenyloxy), aryloxy groups (eg phenoxy, naphthoxy), alkylthio groups (eg methylthio, ethylthio, i -Propylthio, cyclohexylthio, benzylthio, octylthio, dodecylthio, hexadecylthio, octadecylthio), alkenylthio groups (eg vinylthio, allylthio, cyclohexenyl) Thio, hexadecenylthio) and arylthio groups (eg phenylthio, naphthylthio). R ₃₀ and R ₃₁ may be the same or different and each represents an alkyl group, an alkenyl group or an aryl group. R ₄₀ represents an alkyl group. R ₄₁ , R ₄₂ and Y may be the same or different and each is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group similar to R ₂₀ , an alkenoxy group, an aryloxy group, an alkylthio group. , An alkenylthio group, an arylthio group, a heterocyclic oxy group (for example, imidazolidinyloxy, morpholinyloxy, tetrahydropyran-3-yloxy, 1,3,3
5-triazin-2-yloxy), a hydroxy group, an amino group which may have a substituent (for example, amino, alkylamino, arylamino, dialkylamino, acylamino, sulfonamide, ureido, urethane), carbamoyl group (for example, N -Methylcarbamoyl, N-phenylcarbamoyl, N, N-diethylcarbamoyl), sulfamoyl group (for example, N-ethylsulfamoyl, N
-Phenylsulfamoyl), an alkoxycarbonyl group (for example, methoxycarbonyl, butoxycarbonyl, cyclohexyloxycarbonyl, octyloxycarbonyl, hexyloxycarbonyl, octadecyloxycarbonyl), an aryloxycarbonyl group (for example, phenyloxycarbonyl, naphthyloxycarbonyl), It represents a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), nitro group, cyano group, acyl group (eg, acetyl, benzoyl, naphthoyl), acyloxy group (eg, acetyloxy, benzoyloxy, naphthoyloxy). m represents an integer of 0 to 2. R ₆₀ and R ₆₁ may be the same or different and each represents an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. Z represents a group defined by Y, and n represents an integer of 0-4. When m is 2, a plurality of Ys may be the same as or different from each other, and similarly, when n is 2 to 4, a plurality of Zs may be the same or different from each other. R ₂₀ and R ₂₁ , and R ₃₀ and R ₃₁ may combine with each other to form a 5- to 7-membered ring.

R ₁ , R ₂ and R _{3, which} may be the same or different, each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group or an amino group. At least two groups out of R ₁ , R ₂ and R ₃ may combine with each other to form a 5- to 8-membered ring. Further, R ₁ and R ₂ may be combined with each other to form an unsaturated group, and R 3 and R 3 may combine with each other to form a 5- to 8-membered ring. However, R ₁ , R ₂ and R ₃ are not hydrogen atoms at the same time. The term "aliphatic group" as used herein means a linear, branched or cyclic alkyl group (for example, methyl, ethyl, propyl, i-propyl, t-butyl, cyclohexyl, t
-Hexyl, t-octyl, dodecyl, hexadecyl,
Octadecyl, benzyl), an alkenyl group (for example, vinyl, allyl, 2-pentenyl, cyclohexenyl, hexenyl, dodecenyl, octadecenyl), an alkynyl group (for example, propynyl, hexadecynyl), which may be substituted with a substituent. Good. The aromatic group as used herein represents a benzene monocyclic or condensed polycyclic aryl group (eg, phenyl, naphthyl, anthranyl). These rings may have a substituent. The heterocycle referred to herein is a 5- to 7-membered cyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom, and an oxygen atom as a ring-constituting atom (for example, furyl, pyrrolyl, imidazolyl, pyridyl,
Purinyl, chromanyl, pyrrolidyl, morpholinyl). The amino group as used herein may be a simple amino group or an N-substituted amino group having a substituent.
Examples of the substituent of the amino group include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, a sulfonyl group, a sulfamoyl group and a carbamoyl group. A 5- to 8-membered ring in which at least two groups out of R ₁ , R ₂ and R ₃ are bonded to each other (for example, a pyrrolidine ring, an imidazoline ring, an imidazolidine ring, a pyrazolidine ring, a piperazine ring, a piperidine ring, a morpholine ring). , Indoline ring, quinuclidine ring). R ₁ and R ₂ may cooperate with each other to form an unsaturated group, and R ₃ and R ₃ may combine with each other to form a 5- to 8-membered ring (for example, a pyridine ring, a quinoline ring, a pteridine ring, or a phenanthroline ring).

M ₁ represents an alkali metal (eg, lithium, sodium, potassium) or an alkaline earth metal (eg, calcium, barium, magnesium). R ₈₁ and R ₈₂ represent an alkyl group, an alkenyl group, an aryl group and a heterocyclic group, respectively. These may be the same or different from each other. The alkyl group referred to herein is a linear, branched or cyclic alkyl group (for example, methyl, ethyl, propyl, i-
Propyl, t-butyl, cyclohexyl, t-hexyl, t-octyl, dodecyl, hexadecyl, octadecyl, benzyl), and the alkenyl group is a linear, branched or cyclic alkenyl group (eg vinyl, allyl,
2-pentenyl, cyclohexenyl, hexenyl, dodecenyl, octadecenyl), and the aryl group is a benzene monocyclic or condensed polycyclic aryl group (for example, phenyl,
Naphthyl, anthranyl), and the heterocyclic group is a 5- to 7-membered cyclic group containing at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom as a ring-constituting atom (for example, furyl, pyrrolyl, imidazolyl, pyridyl, purinyl). , Chromanyl, pyrrolidyl, morpholinyl). M ₂ represents an alkali metal (eg, lithium, sodium, potassium). M ₃ represents an alkali metal (eg, lithium, sodium, potassium) or an alkaline earth metal (eg, calcium, barium, magnesium). )

R ₉₁ , R ₉₂ , R ₉₃ and R ₉₄ represent an alkyl group, an alkenyl group, an aryl group and a heterocyclic group, respectively. These may be identical to each other,
It may be different. As used herein, the alkyl group is a linear, branched or cyclic alkyl group (for example, methyl,
Ethyl, propyl, i-propyl, t-butyl, cyclohexyl, t-hexyl, t-octyl, dodecyl, hexadecyl, octadecyl, benzyl), and the alkenyl group is a linear, branched or cyclic alkenyl group (for example, vinyl, Allyl, 2-pentenyl, cyclohexenyl, hexenyl, dodecenyl, octadecenyl), the aryl group represents a benzene monocyclic or condensed polycyclic aryl group (eg, phenyl, naphthyl, anthranyl), and the heterocyclic group represents a ring-constituting atom. Contains at least one atom selected from nitrogen atom, sulfur atom and oxygen atom as 5
~ 7-membered cyclic group (for example, furyl, pyrrolyl, imidazolyl, pyridyl, purinyl, chromanyl, pyrrolidyl, morpholinyl).

Of the compounds represented by the general formula (A-II), it is preferable that all of R _{20 to} R ₂₂ are selected from an alkyl group, an aryl group, an alkoxy group and an aryloxy group. It is more preferable that all of R _{20 to} R ₂₂ are selected from an alkyl group, an aryl group, and an aryloxy group. Among these, in the case of having an aryloxy group, a substituent is attached to the ortho position of the benzene ring of the aryloxy group. Those having are preferable. Also, at least 2 of R _{20 to} R ₂₂
In the case where each of them is an aryloxy group, it is preferable that the two benzene rings of the two aryloxy groups are bonded to each other at the ortho positions or the substituents at the ortho positions.

Of the compounds represented by the general formula (BI), preferred compounds are the following general formulas (BI-I) and (BI-
It can be represented by I-II).

[0035]

[Chemical 11]

In the formula, R ₄₀ ′ represents a tertiary alkyl group, and R ₄₀ ″ and R ″ ′ may be the same or different and each represents an alkyl group. L is a single bond

[0037]

[Chemical 12]

Represents Here, R ₄₃ represents a hydrogen atom, an alkyl group or an aryl group. R ₄₄ and R ₄₅ may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group. R ₄₁ , R ₄₂ , Y and m have the same meanings as in formula (BI), and Y ′ has the same meaning as Y. m ′ and m ″ have the same meaning as m.

Among the compounds represented by the general formula (D-I), more preferable ones are those having a pKa of 4 or more, more preferably 4 or more and 9 or less, still more preferably 5 or more. And 8 or less. Most preferred are amine compounds having a pKa of 5 or more and 7 or less. The pKa is a dissociation constant of a conjugate acid of an amine compound, and is a value obtained with a mixed solvent of EtOH / H ₂ O = 4/1 at room temperature. Generally, this value can be obtained by a titration method. Further, the amine compound is preferably a lipophilic compound, and the total number of carbon atoms is preferably 8 or more, more preferably 15 or more. Further, this amine compound is preferably a tertiary amine. General formula (D-I)
Among the compounds represented by, most preferred are the lipophilic compounds represented by the general formula (D-I-I) and having a pKa of 4 or more.

[0040]

[Chemical 13]

In the formula, R ₁ and R ₂ are represented by the general formula (DI)
Represents the same group as. R _{b1 to} R _b5 may be the same or different and each is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, an aliphatic thio group, an aromatic group. Group thio group, heterocyclic thio group, hydroxy group, halogen atom, cyano group, nitro group, optionally substituted amino group, sulfonyl group, acyl group, acyloxy group, sulfamoyl group, carbamoyl group, ester group .. R ₁ and R ₂ , R ₁ and R _b5 , R ₂ and R
_b1 or by bonding group at the ortho position to each other of R _b1 to R _b5, may form a 5- to 8-membered ring. General formula (B)
Of the compounds represented by, more preferably, the pKa is 4
The above compounds are 9 or less, more preferably 5 or more and 8 or less, most preferably pKa of 5 or more and 7 or less. Among the amine compounds of the present invention, preferred examples include those represented by the following general formula (D-VIII) in addition to the above. These will be described in more detail.

[0042]

[Chemical 14]

In the formula, X represents a single bond or a divalent to trivalent organic residue, and Ba represents an aryl group having an amino group, an aryloxy group, or a nitrogen-containing heterocyclic group. However,
X is _{-O -, - (CH 2)} 4 - is not a. m represents 2 or 3. The X single bond, 2 or trivalent residue which connects the Ba carbon atom, a nitrogen atom or a phosphorus _{atom, -S -, - SO 2 -} , - O-Ar-O -, - O-A
_{r- (CR 4 R 5) n} -Ar-O- (R 4, R 5 is an alkyl group), - O-Ar-SO 2 -Ar-O -, - O-C
_{H 2 -Y-CH 2 -O- (} Y is CR ₄ R _5, -CH ₂ O
A divalent linking group such as CH ₂ —) can be mentioned. B
a is an aryl group, an aryloxy group, or a nitrogen-containing heterocyclic group having an amino group having a pKa (measured in a mixed solvent of ethanol / water = 4/1) of 4 or more. The amino group here may be unsubstituted or may have a substituent. Examples of the substituent of the amino group include an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group and a heterocyclic group. In the present invention, a tertiary amino group is particularly preferable, and a cyclic tertiary amino group is also preferably used. Examples of the nitrogen-containing heterocyclic group include a pyrrolidino group and a piperidino group.
Morpholino group, piperazino group, pyridyl group, pyrimidyl group, quinolyl group, imidazolyl group, pyrrolyl group, indolino group, tetrahydroquinolyl group, imidazolenyl group,
Examples thereof include a thiazolinyl group, an imidazolidinyl group and a thiazolidinyl group. The above amino acid and nitrogen-containing heterocyclic group may further have other substituents.

In the amine compound represented by the general formula (D-VIII) of the present invention, a more preferable compound has a molecular weight of 30.
It is 0 or more and has substantially no volatility.

In the amine compound represented by the general formula (D-VIII) of the present invention, the most preferable compound is a compound having substantially no volatility and having a molecular weight of 200 or less per basic group.

The general formulas (AI) to (D- of the present invention will be described below.
Specific examples of the compound represented by VIII) are shown below, but the present invention is not limited thereto. First, the general formula (A-
Specific examples of the compounds I) to (A-III) are shown below.

[0047]

[Chemical 15]

[0048]

[Chemical 16]

[0049]

[Chemical 17]

[0050]

[Chemical 18]

[0051]

[Chemical 19]

[0052]

[Chemical 20]

[0053]

[Chemical 21]

[0054]

[Chemical formula 22]

Specific examples of the compound represented by formula (BI) are shown below.

[0056]

[Chemical formula 23]

[0057]

[Chemical formula 24]

[0058]

[Chemical 25]

[0059]

[Chemical formula 26]

[0060]

[Chemical 27]

[0061]

[Chemical 28]

[0062]

[Chemical 29]

[0063]

[Chemical 30]

[0064]

[Chemical 31]

Specific examples of the compounds represented by the general formulas (CI) to (C-III) are shown below.

[0066]

[Chemical 32]

[0067]

[Chemical 33]

Next, specific examples of the compound represented by formula (DI) will be shown.

[0069]

[Chemical 34]

[0070]

[Chemical 35]

[0071]

[Chemical 36]

[0072]

[Chemical 37]

[0073]

[Chemical 38]

[0074]

[Chemical Formula 39]

[0075]

[Chemical 40]

[0076]

[Chemical 41]

[0077]

[Chemical 42]

[0078]

[Chemical 43]

[0079]

[Chemical 44]

[0080]

[Chemical 45]

[0081]

[Chemical 46]

[0082]

[Chemical 47]

[0083]

[Chemical 48]

[0084]

[Chemical 49]

[0085]

[Chemical 50]

[0086]

[Chemical 51]

Specific examples of the compound represented by formula (D-II) are shown below. Among these are calcium hydroxide, barium hydroxide, magnesium hydroxide and the like. Next, specific examples of the compounds represented by formulas (D-III) to (D-VI) are shown.

[0088]

[Chemical 52]

[0089]

[Chemical 53]

Specific examples of the compound represented by formula (D-VII) are shown below.

[0091]

[Chemical 54]

Specific examples of the compound represented by formula (D-VIII) are shown below.

[0093]

[Chemical 55]

[0094]

[Chemical 56]

[0095]

[Chemical 57]

[0096]

[Chemical 58]

[0097]

[Chemical 59]

[0098]

[Chemical 60]

[0099]

[Chemical formula 61]

[0100]

[Chemical formula 62]

[0101]

[Chemical 63]

[0102]

[Chemical 64]

[0103]

[Chemical 65]

[0104]

[Chemical 66]

Since most of these compounds are commercially available, they can be easily obtained. In addition, the general formula (D-
I), other preferred compounds and synthetic methods of the amine compounds represented by (D-VIII) are described in US Pat. No. 4,483,91.
No. 8, No. 4,555,479, No. 4,585,7
No. 28, No. 4,639,415, European Patent Publication No. 2
64,730, JP-A-58-102231, 59.
-229557, 61-73152, 63-9
8662, 63-115167, 63-267
No. 944, etc.

Next, the method of adding these deterioration inhibitors to the silver halide photographic light-sensitive material will be described. These deterioration inhibitors may be contained in the support by any of the following methods. (Addition method A) When a support is formed into a film, these deterioration inhibitors are added to the dope and cast to obtain a support containing the deterioration inhibitor. The deterioration inhibitor may be added after preparation of the dope, or may be added together at the time of preparation of the dope from the beginning. The amount of the deterioration inhibitor added is preferably 0.05 to 2.0% by weight, more preferably 0.1 to 1.0% by weight, based on the solid content in the dope. If the amount of the deterioration inhibitor is too small, a sufficient deterioration preventing effect cannot be obtained.On the other hand, if the amount is too large, the support is colored, the deterioration inhibitor is projected on the surface, haze occurs, and transparency is deteriorated. It is not preferable because it decreases.

(Addition method B) After forming the support, a subbing layer,
At least one of the back layers is coated with a deterioration inhibitor.

(Addition method C) A photosensitive layer is coated on a support,
After taking a picture using this, a deterioration inhibitor is added to at least one of a photographic developing solution, a bleaching solution, a washing solution, a fixing solution and a stabilizing solution at the time of development processing. This impregnates the support with the deterioration inhibitor.

(Addition method D) A photographic light-sensitive material which has been subjected to photographic development processing is impregnated with a solution containing a deterioration inhibitor. This impregnates the support with the deterioration inhibitor.

Regarding the method of adding these deterioration preventing agents,
The details will be described. First, (addition method A) will be described.
Cellulose ester, plasticizer, deterioration inhibitor, solvent and other additives are put into a pressure vessel. The type of the pressurized container is not critical, as long as it can withstand a predetermined pressure. This pressure vessel needs to be able to pressurize as well as agitate. Pressurization may be performed by injecting an inert gas such as nitrogen gas, or may be performed only by increasing the vapor pressure of the solvent by heating. In addition, it is also possible to utilize the decrease in the volume of the gas phase in the container by press-fitting a part or all of the cellulose ester plasticizer, the solvent, the deterioration inhibitor, etc. after sealing the pressurized container. The heating is preferably performed from the outside, and for example, a jacket type is suitable.
In addition, it is also possible to heat by providing a plate heater or the like outside and connecting them with piping to circulate them.

The stirring blade is preferably long enough to reach the vicinity of the container wall, and a scraping blade is preferably provided at the end for renewing the liquid film on the container wall. In addition to the pressure vessel, other instruments such as a pressure gauge and a thermometer are properly installed. The above raw materials are put in a pressure vessel and heated under pressure. The heating temperature is a temperature which is equal to or higher than the boiling point of the solvent and does not boil the solvent. This temperature is preferably 60 ° C. or higher, and particularly preferably about 80 to 110 ° C. The pressure is set so that the solvent does not boil at this set temperature. After the dissolution, the solution is cooled and then taken out from the container, or taken out from the container with a pump or the like and cooled with a heat exchanger or the like, and then used for film formation. In this dissolution method, by applying pressure, it is possible to heat above the boiling point at normal pressure, and to prevent gelation by suppressing boiling and preventing an over-concentrated state.
The heating increases the solubility and the dissolution rate, and enables complete dissolution in a short time. The dope thus obtained is cast to form a film. The dope casting method may be either a band casting method or a drum casting method. When cooling the casting part, JP-A-62-37
As disclosed in No. 113, a method using a refrigerant or cold air, a method using a heat pipe, or the like can be used. The cooling temperature is such that the surface temperature of the support is 10 ° C. or lower, preferably 5 ° C. or lower. Dry air may not be used, but may be used as long as the surface temperature of the support is not increased. After peeling after casting, JP-A-62-1150
As disclosed in No. 35, it is preferable that the film is dried while applying a constant tension in the width direction of the film, and is manufactured in a state where a predetermined residual solvent is contained in the film. In this way, a support containing a deterioration inhibitor can be obtained. This (addition method A) has a feature that the effect is greatest because the deterioration inhibitor is directly added to the support.

Next, (addition method B) will be described. A support comprising a plasticizer and cellulose acetate is obtained in the same manner as the method described in the above (Addition method A). A subbing layer and a back layer to which a deterioration preventing agent is added are coated on this. When applying a subbing layer or a back layer, in order to improve the adhesive strength, chemical treatment, mechanical treatment, or
Corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment,
Surface activation treatment such as glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment may be performed. For the subbing layer, make a gelatin solution dispersed in a methylene chloride / ketone / alcohol mixed organic solvent,
It can be obtained by adding a deterioration inhibitor to this and applying it in a single layer. Gelatin hardeners include chromium salts (chrome alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-s-).
Triazine, etc.), epichlorohydrin resin, and the like. If necessary, various additives may be contained in these sap solutions. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. When using the submersion solution of the present invention, resorcin, chloral hydrate,
An etching agent such as chlorophenol may be contained in the submersion liquid.

This subbing layer may contain inorganic fine particles such as SiO 2 or TiO 2 or polymethylmethacrylate polymer fine particles (1 to 10 μm) as a matting agent. Such an undercoating liquid is generally well-known coating method, for example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat.
It can be applied by an extrusion coating method or the like using a hopper described in Japanese Patent No. 681,294. US Pat. No. 2,761,791, if desired,
Two or more layers by the method described in 3,508,947, 2,941,898, and 3,526,528, and Yuji Harasaki, "Coating Engineering", page 253 (published by Asakura Shoten in 1973). Layers can be applied simultaneously.

The back layer is usually coated on the back side of the photosensitive layer in order to impart functions such as antistatic property, antihalation property, slippery property, scratch resistance and the like. When applying this layer, a deterioration inhibitor may be added together. As the antistatic agent referred to here, particularly, JP-A-62-109044
Nos. 62-215272, and fluorine-containing surfactants or polymers described in JP-A Nos. 60-76742 and 60.
-80846, 60-80808, and 60-80
No. 839, No. 60-76741, No. 58-20874
No. 3, No. 62-172343, No. 62-173459.
No. 62-215272 and the like, or nonionic surfactants described in JP-A-57-204.
The conductive polymers or latexes described in No. 540 and No. 62-215272 (nonionic, anionic, cationic, amphoteric) can be used. Inorganic antistatic agents include ammonium, alkali metal, alkaline earth metal halides, nitrates, perchlorates, sulfates, acetates, phosphates, thiocyanates, and the like. 5
It is possible to preferably use a conductive tin oxide, a zinc oxide, or a composite oxide obtained by doping an antimony or the like in a metal oxide thereof such as those described in No. 7-118242. Further, various charge transfer complexes, π-conjugated polymers and their doping materials, organometallic compounds, intercalation compounds and the like can also be used as antistatic agents, such as TCNQ / TTF, polyacetylene and polypyrrole. These are Morita et al., Science and Industry 59 (3), 103-111 (1985), 59.
(4), 146-152 (1985).

Further, various surfactants are used for imparting slipperiness and scratch resistance. For example, saponin (Stayrod type), alkylene oxide derivative (for example, polyethylene glycol, polyethylene glycol / polypropylene glycol condensation spots, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol). Alkylamines or amides,
Polyethylene oxide adducts of silicones), nonionic surfactants such as glycidol derivatives (eg alkenyl succinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates , Alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-
N-alkyl taurines, sulfosuccinates,
Such as sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphates, etc., carboxy group, sulfo group, phospho group,
Anionic surfactants containing acidic groups such as sulfuric acid ester groups and phosphoric acid ester groups; amphoteric surfactants such as amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or phosphoric acid esters, alkyl betaines, amine oxides; Alkylamine salts, aliphatic or aromatic fourth
Cationic surfactants such as quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing an aliphatic or heterocyclic ring can be used. These are Ryohei Oda et al. "Surfactants and their applications" (1964), Hiroshi Horiguchi "New surfactants" (Sankyo Publishing Co., Ltd., 1975).
Year) or "Mac Cation's Day Tanger and Emulsion Fires" (Mc Cation Divisions, MC Publishing Company)
1985) ("McCutcheon's Detergents & Emulsif
iers ”(Mc Cutcheon Divisions, MC Publishing Co.1
985)), JP-A-60-76741, and JP-A-62-172.
No. 343, No. 62-173459, No. 62-2152.
72, etc.

For antihalation, carbon black or various dyes such as oxonol dye, azo dye, arylitene dye, styryl dye,
Examples thereof include anthraquinone dye, merocyanine dye and tri (or di) allylmethane dye. Cationic polymers or latices may then be used to prevent the dye from diffusing from the antihalation layer. These are Research Disclosure, Volume 176, No. 1764.
3, section VIII (December 1978). Further, in order to improve the color tone of developed silver, JP-A-61-285
Magenta dyes such as those described in No. 445 may also be used.

These additives are mixed with the deterioration preventive agent of the present invention and applied. These additives and deterioration inhibitors are dissolved in a solvent such as acetone, methanol, dichloromethane, cyclohexanone, ethyl acetate, toluene, xylene, butyl acetate, chloroform, benzene, isopropanol, methyl ethyl ketone, etc., and a mixed solution of these solvents. And apply. These compounds may be applied as a single layer or may be applied as divided into two or more layers. The coating method can be the same as that for the undercoat layer.

The deterioration preventing agent may be added to either one of the subbing layer and the back layer, or may be added to both layers. The preferred amount of the anti-degradation agent applied is 200 mg to 10 g, and more preferably 400 mg to 5 g, based on 1 m ^{2 of the} support. If the amount of the anti-deterioration agent is too small, the anti-deterioration ability is insufficient, and if it is too large, it causes an increase in haze, a decrease in adhesion, a decrease in slipperiness and a decrease in antistatic ability. In (addition method A), since the deterioration inhibitor is directly added to the dope, the type and amount of the deterioration inhibitor to be added may be limited from the viewpoint of phase separation, but in this (addition method B), However, the deterioration inhibitor can be selected in a wider range without these concerns.

Next, (addition method C) will be described. The characteristic point of this method is that an operation of diffusing and permeating the deterioration inhibitors (A) to (D) into the silver halide photographic light-sensitive material and incorporating it in the support is incorporated in the processing step of the light-sensitive material. is there. Incorporation in the processing step means that the stability improving compound of the present application does not intervene in various steps from the production of the support to the coating of the photosensitive layer, the storage of the finished photosensitive material, and the photographing. Therefore, this compound does not affect the characteristics of the light-sensitive material such as photographic performance. This is advantageous because it broadens the choice of compounds. Also, inclusion in the treatment bath and incorporation by diffusion and penetration depends on the properties of the compound,
It is also advantageous in that the applicability is widened in that the concentration, the auxiliary agent, the dispersion or dissolution method, and the selection of the coexisting substance can be devised.

Further, this method is not limited to a specific light-sensitive material and can be simultaneously applied to various light-sensitive materials having a cellulose ester as a support, and of course, the light-sensitive material of any manufacturer may be used. The point is also a big advantage. It is also an advantage of the present invention that by incorporating it into the process step, the stabilization objective can be reached without adding new steps. However, a bath containing a deterioration inhibitor may be newly provided before the final bath. The treatment bath to contain the compound of the present invention may be any treatment bath as long as an appropriate addition method is adopted depending on the properties of the compound. But,
Of course, a processing bath closer to the end of the processing step is more convenient, and it is desirable to add it to the final bath, that is, the image stabilizing bath, the water-saving type rinsing bath, or the anhydrous washing type stabilizing bath.

The photographic light-sensitive material is subjected to appropriate processing such as development according to the type. In the present invention, the process of processing peculiar to a light-sensitive material is called a processing bath, and the processing bath newly provided after the specific processing and before drying is called a post-processing bath. The method of adding the compound is variously devised depending on the properties of the compound. The methods are roughly classified into two: (1) a liquid bath in the form of a homogeneous phase, and (2) a form of a dispersion liquid. The former can be applied to compounds having relatively high water solubility. However, the compounds of the present invention generally have low solubility in water, and thus it is often difficult to form an aqueous solution having a sufficient concentration. Therefore, it is preferable to increase the solubility by using a dissolution aid together. The latter is used in the form of oil / water type dispersion utilizing a solvent having a property of dissolving the compound.

The former solubilizing agent includes (a) benzyl alcohol, phenylethyl alcohol,
Phenyl-substituted lower alkyl alcohols such as phenylpropyl alcohol (b) Aliphatic polyalcohols consisting of lower alkyl groups such as ethylene glycol, triethylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol (c) Ethanolamine, triethanolamine , Alkanolamines such as pentanolamine (d) Aliphatic alcohols such as methanol, ethanol, propanol, butanol, and ethylhexyl alcohol (c) Water-soluble low-molecular organic solvents such as acetone, methyl cellosolve, cellosolve, and methyl ethyl ketone (however, ,
Naturally, the solvents belonging to (d) and (e) should not be in an amount that adversely affects the support. However, an amount such that the support is slightly swollen is convenient because it promotes uptake of the compound of the present invention. )

Although not a solvent, the solubility can be increased by the addition of a small amount of a surfactant, possibly by solubilization by micelle formation. For such purposes (f) nonionic surfactants such as polyethylene glycol nonyl phenyl ether (n = 10 to 100), polyethylene / propylene glycol (Pluronics etc.) (g) alkylbenzene sulfonic acid such as sodium dodecylbenzene sulfonate, Anionic surfactants represented by carboxylic acid salts such as alkylsulfates, sodium stearate, sodium palmitate and sodium laurylate (h) Quaternary ammonium, pyridinium and phosphonium type cationic surfactants. Further, in order to process the compound of the present application in a dispersion state, the following high boiling point solvent is used as a dispersion medium. That is, the phosphoric acid ester compound represented by the following general formula (P) is represented by the general formula (P)

[0124]

[Chemical 67]

(R, R ₁ and R ₂ represent an alkyl group, a cycloalkyl group or an aryl group, and they may be the same or different.) For example, tricresyl phosphate or dimethyl. Phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate, glycerol triacetate, o- or p-tolueneethyl sulfonamide, butylphthalylbutyl glycolate, ethylphthalylethyl glycolate, methylphthalylethylglycol Examples include compounds such as rate. The compound is dissolved in these organic solvents, solubilizing agents such as propanol, ethanol and ethyl acetate are added if necessary, and a suitable surfactant as shown in (f) (g) (h) is used. To make an oil drop / water dispersion.

The above-mentioned homogeneous aqueous solution or dispersion contains antibacterial agents, fungicides, pH adjusters, pH buffers, formaldehyde or its precursors, optical brighteners, water-removing surfactants, and image-fastening agents. Agents and the like are added. The above-mentioned various dissolution aids and dispersion aids can be used alone or in combination. Further, a higher concentration liquid can be prepared by an appropriate combination between the homogeneous liquid phase type and the dispersion type, that is, (a)-(h). Therefore (a)
An appropriate amount of the (-) auxiliary agent is selected depending on the properties of the compound. That is, (a)-(e) is 0.1 to 300% with respect to water, preferably (a) 0.2 to 5%,
(B) 0.3 to 200%, (c) 0.3 to 100%,
(D) and (e) are 0.2 to 150%, (f) and (g)
(H) is 0.1 to 10%, high boiling point solvent is 0.5 to 200
% Is desirable. The higher the concentration of the compound, the better, but it depends on the nature. Generally, (A) or (B) or (C) or (D) is 0.2 to 100 per liter of liquid bath.
g, preferably 0.5 to 20 g is desirable. 100 g /
In the case of a concentrated liquid such as liter, it is convenient to apply a coating process instead of the immersion process.

(A) (B) (C) (D) in the present invention
If the addition amount is less than this, the deterioration preventing effect is not sufficiently exhibited, and if the addition amount increases, the deterioration preventing effect gradually increases, but if the addition amount exceeds a certain limit, the deterioration preventing effect only decreases. In particular, (C) exceeds the compatibility limit, becomes cloudy, and bleeds on the product surface.
It is not appropriate to add more than the above amount. The duration of the treatment bath of the compound of the present application is performed according to the schedule of the designed treatment process. In other words, the present application is applied to a rapid processing color photographic paper processing (for example, CP2 of Fuji Photo Film Co., Ltd.).
5Q, CP40FA, CP43FA), it is performed in 60 to 80 seconds depending on the final rinse step. When applied to the CN-16 processing of color negative films, the image stabilizing bath time is 60 seconds.

Further, some color photographic papers and black-and-white films may be subjected to a non-water-saving rinsing step and then a drying step, which does not have a liquid bath step similar to a stabilizing bath. For such treatment, it is preferable to provide the liquid bath step of the present invention having the above-mentioned composition. The length of the liquid bath is preferably selected so as to be in harmony with the design process of the target treatment, and is generally about 10 seconds to 5 minutes, preferably about 20 seconds to 1 minute. For example,
In the case of applying to the microfilm treatment step, if the washing step is a 3-tank processor, it is preferable to switch the final washing bile section to the liquid bath step of the present invention to make a 2-tank washing treatment plus a base stabilizing bath. .. Needless to say, even when the present application is carried out in the form of a concentrated liquid application process, the application process time is 1 to 2 seconds, regardless of the above.

As a method of diffusing and permeating the compound of the present invention, a method of adding it to a treatment bath is first mentioned. Since high solubility in the liquid of the treatment bath is desirable for diffusion and penetration, for example, (A-44), (A-45), (A-
46), (B-I-31), (B-I-32), (C-
9), (C-10), (D-I-8), (D-I-4)
3), (D-I-62), (D-I-63), (D-I
Water-soluble compounds such as -64) are preferred for addition to the treatment bath. Here, the processing bath is (a) color developing bath, (b)
Black-white development bath, (c) bleaching bath, (d) fixing bath, (e) bleach-fixing bath, (f) water washing bath, (ki) stabilizing bath, (h) pre-hardening bath, (ke) various accelerating baths, etc. Refers to. The compositions of the processing solutions used in (a)-(v) are shown below, taking the case of a silver halide color photographic light-sensitive material as an example.

The color developing solution used in (a) is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. .. Two or more kinds of these compounds can be used in combination depending on the purpose.

The color developing solution contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It is common to include agents or antifoggants. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazides, triethanolamine, catecholsulfonic acids, triethylenediamine (1,4-diazabicyclo [2,2,2] octane) s, etc. Various preservatives, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. , Chelating agents such as auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, for example, Ethylenediamine tetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo -
N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'-tetramethylenephosphonic acid,
Ethylenediamine-di (o-hydroxyphenylacetic acid)
And their salts may be mentioned as representative examples.

When the reversal process is carried out, black and white development is usually carried out and then color development is carried out. The black-and-white developer used in this (a) includes dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol. The developing agents can be used alone or in combination. The color developing solution and the black and white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but in general, the light-sensitive material 1
Less than 3 liters per square meter, 500 ml by reducing the bromide ion concentration in the replenisher
It can also be: When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process (bleach-fixing process) or separately. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out. Examples of bleaching agents include iron (III) and cobalt
(III), chromium (VI), compounds of polyvalent metals such as copper (II),
Peracids, quinones, nitro compounds and the like are used. Typical bleaching agents are ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Cyclohexanediaminetetraacetic acid, methyliminodiacetic acid,
Aminopolycarboxylic acids such as 1,3-diaminopropane tetraacetic acid and glycol ether diamine tetraacetic acid, or complex salts such as citric acid, tartaric acid and malic acid; persulfates;
Bromate; permanganate; nitrobenzenes and the like can be used. Of these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediaminetetraacetic acid iron (III) complex salts and persulfates are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron (III)
Complex salts are particularly useful in bleaching solutions and bleach-fixing solutions. The pH of a bleaching solution or a bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5.
However, the treatment can be performed at a lower pH for speeding up the treatment.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications: US Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-95,630,
Research Disclosure No. 17,129 (1
Compounds having a mercapto group or a disulfide bond described in, eg, 1978); JP-A-50-140,12;
Thiazolidine derivatives described in No. 9; US Pat. No. 3,70
Thiourea derivatives described in 6,561; JP-A-58-1
Iodide salt described in 6,235; West German Patent No. 2,74
The polyoxyethylene compounds described in JP-B No. 8,430; the polyamine compounds described in JP-B-45-8836; the bromide ion and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95,63.
The compounds described in No. 0 are preferable. Furthermore, US Pat.
The compounds described in No. 552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photographing.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodide salts. The use of thiosulfates is common, and ammonium thiosulfate is particularly preferable. Can be used most widely. As a preservative for the bleach-fixing solution, sulfite, bisulfite, sulfinic acid or carbonyl bisulfite adduct is preferable. The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the rinsing water, the number of rinsing tanks (the number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. It can be set in a wide range. Of these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion Pictur.
e and Television Engineers Volume 64, P. 248-253
(May, 1955 issue).

According to the multistage countercurrent system described in the above-mentioned document,
Although the amount of washing water can be significantly reduced, the increase in the residence time of water in the tank causes problems such as bacteria breeding and adhered floating substances to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, the method of reducing calcium and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. In addition, JP-A-57
-8,542, isothiazolone compounds, siabendazoles, chlorinated germicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents", Sanitary Technical Association The sterilizing agents described in "Microbial Sterilization, Sterilization, and Antifungal Techniques", edited by the Society for Antibacterial and Antifungal Society, "Encyclopedia of Antibacterial and Antifungal Agents" can be used.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but generally, at 15-45 ° C. for 20 seconds-10 minutes,
Preferably, a range of 30 seconds-5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilizing treatment, Japanese Patent Laid-Open No. 57-8,543, 58
All known methods described in Nos. 14,834 and 60-220,345 can be used. In addition, there is a case where a stabilizing treatment is further performed after the water washing treatment, and an example thereof is a stabilizing bath containing formalin and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. .. Various chelating agents and antifungal agents can also be added to this stabilizing bath. The preferred use form of the present invention is
This is the case where it is applied to either the water-saving type washing bath (called a rinse bath) or the stabilizing bath. Alternatively, these baths may be followed by a second rinse or stabilizing bath. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step.

The silver halide color light-sensitive material may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example, US Pat. No. 3,34
Indoaniline compounds described in No. 2,597, No. 3,
342, 599, Research Disclosure 1
Schiff base type compounds described in 4,850 and 15,159, aldol compounds described in 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and JP-A-53-135628. The urethane compounds described in No. 1 can be mentioned. Further, the silver halide color light-sensitive material may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary. Typical compounds are JP-A-56-64,339, JP-A-57-144,547, and JP-A-58-115,43.
No. 8 etc. are described. Various treatment liquids in the present invention are 1
Used at 0 ° C to 50 ° C. Normally 33 ° C-38
Although the temperature of ℃ is standard, it can be raised to accelerate the treatment to shorten the treatment time, and conversely, to lower the temperature to improve the image quality and the stability of the treatment liquid. Also, in order to save silver in the light-sensitive material, West German Patent No. 2,226,77
Treatment with cobalt intensification or hydrogen peroxide intensification described in No. 0 or US Pat. No. 3,674,499 may be performed.

Next, (addition method D) will be described. This is a method in which the photographic light-sensitive material after the processing step is dipped in a bath in which the deterioration inhibitors (A) to (D) are dissolved, and these are incorporated into a support. The feature of this method is that a deterioration inhibitor can be newly added to the photographic light-sensitive material which is being stored after processing. The dipping solution in the present invention is 10
Used at -50 to 50 ° C. Normally 33 ° C to 38 ° C
Although the temperature is standard, the temperature can be raised to accelerate the treatment to shorten the dipping time, or conversely, to lower the temperature to improve the image quality and improve the stability of the solution. In the present invention, each of the deterioration inhibitors (A) to (D) may be used alone, or two or more of them may be used in combination. In any case, it is desirable that the addition amount is dissolved so that the total amount becomes 0.02 to 2 parts by weight.

(A) (B) (C) (D) in the present invention
If the addition amount of is less than this, the deterioration prevention effect is not sufficiently exerted, and if the addition amount increases, the deterioration prevention effect gradually increases, but if the addition amount exceeds a certain limit, the deterioration prevention effect only decreases. However, it exceeds the limit of compatibility, becomes cloudy, and bleeds on the product surface. Therefore, it is not appropriate to add more than the above-mentioned addition amount. Next, the immersion time and the subsequent drying conditions will be described. Immersion time is 1 minute to 120
The range of minutes is preferable, and more preferably between 1 minute and 60 minutes. When the immersion time is shorter than the above, the deterioration inhibitor cannot sufficiently penetrate into the support, and even when the immersion time is longer than that, the concentration of the deterioration inhibitor in the support hardly changes. The drying conditions should be so severe that the immersion liquid component in the support can be removed, but must be mild enough not to cause deterioration of the support. Therefore, the drying temperature is preferably in the range of 40 to 120 ° C, more preferably 60 to 120 ° C. The drying time is preferably in the range of 1 minute to 120 minutes, more preferably 1 minute to 60 minutes.

Next, the immersion liquid will be described. A non-aqueous solvent or a mixed solvent of a non-aqueous solvent and water can be considered as the immersion liquid having good permeability to the support. As the non-aqueous solvent, methyl alcohol, ethyl alcohol,
Examples thereof include alcohols having 1 to 8 carbon atoms such as isopropyl alcohol, ketones such as acetone and methyl ethyl ketone, halogenated hydrocarbons such as chloroform and methylene chloride, and cellosolve and methyl cellosolve. These may be used alone or in combination of two or more. The solvent composition in the solution is (1) alcohols having 1 to 8 carbon atoms 10 to 17% by weight (2) ketones such as acetone and methyl ethyl ketone 10 to 17% by weight (3) halogenated hydrocarbons such as chloroform and methylene chloride 0 to 10% by weight (4) cellosolve, methyl cellosolve 0 to 20% by weight (5) water 0 to 50% by weight In order to select a non-aqueous solvent, the permeability of these solvents to the support and the deterioration inhibitor are selected. Although solubility is taken into consideration, examples of desirable solvent compositions include isopropyl alcohol 50% by weight water 50% by weight or acetone 50% by weight water 50% by weight.

If necessary, an additive such as a plasticizer may be added to the solution. By adding the plasticizer used in the support, the elution of the plasticizer from the support into the immersion liquid can be prevented, and it is effective in preventing shrinkage and curling after immersion. Common examples of this plasticizer include dimethyl phthalate, diethyl phthalate, triphenyl phosphate, dimethoxyethyl phthalate, glycerol triacetate, o-, or p-toluene ethyl sulfonamide, butylphthalyl butyl glycolate, ethyl phthalate. Examples thereof include ruethyl glycolate and methylphthalyl ethyl glycolate. The amount of the plasticizer added is preferably a saturated amount of the plasticizer with respect to the immersion solvent. For example, in the case of triphenyl phosphate with respect to a 50% by weight aqueous solution of isopropyl alcohol, 7
% By weight. A deterioration inhibitor is added to these solutions. Since high solubility in the liquid of the treatment bath is desirable for diffusion and penetration, for example, (A-44), (A-
45), (A-46), (B-I-31), (B-I-
32), (C-9), (C-10), (DI-8),
(D-I-43), (D-I-62), (D-I-6)
Water-soluble compounds such as 3) and (D-I-64) are preferable for addition to the treatment bath.

Although the addition method of the deterioration preventing agent in the present invention has been described above, these addition methods may be used alone or in combination of two or more kinds. Moreover, the present invention is not limited by these descriptions.

The silver halide emulsion and the photographic light-sensitive material when the cellulose ester film of the present invention is used as a support for the photographic light-sensitive material will be described.

Various hydrophilic colloids are used in the photographic light-sensitive material. Examples of the hydrophilic colloid used as a binder for photographic emulsion and / or other photographic constituent layers include gelatin, colloidal albumin, casein, carboxymethyl cellulose. , Cellulose derivatives such as hydroxyethyl cellulose, sugar derivatives such as agar, sodium alginate and starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives thereof. Partial hydrolysis and the like can be mentioned. If desired, compatible mixtures of two or more of these colloids are used. The most commonly used of these is gelatin.

In the photographic emulsion layer and other layers, a synthetic polymer compound, for example, a latex-like water-dispersed vinyl compound weight, particularly a compound which increases the dimensional stability of the photographic material, may be used alone or as a mixture (heterogeneous polymer). ) Or in combination with a hydrophilic water-permeable colloid.
There are many polymers, for example US Pat.
No. 376,005, No. 2,739,137, No. 2,8
53,457, 3,062,674, 3,41
1,911, 3,488,708, 3,52
5,620, 3,635,715, 3,60
7,290, 3,645,740, British Patent Nos. 1,186,699, 1,307,373 and the like. Among them, alkyl acrylate, alkyl methacrylate, acrylic acid,
Methacrylic acid, sulfoalkyl acrylate, sulfoalkyl methacrylate, glycidyl acrylate,
Glycidyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate,
Copolymers and homopolymers selected from alkoxyalkyl acrylates, alkoxymethacrylates, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride, and itaconic anhydride are commonly used.

Hardening treatment of the photographic emulsion and / or other photographic constituent layers can be carried out by a conventional method. Examples of the curing agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3. , 5
-Triazine and others U.S. Pat. No. 3,288,775
No. 2,732,303, British Patent 974,7
23, No. 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine,

In addition, US Pat. No. 3,635,718
No. 3,232,763, No. 3,490,91
No. 1, 3,642,486, British Patent No. 994.
Compounds having a reactive olefin as shown in No. 869, N-hydroxymethylphthalimide,
Other US Pat. Nos. 2,732,316 and 2,58
N-methylol compounds as shown in US Pat. No. 6,168, etc., isocyanates as shown in US Pat. No. 3,103,437, US Pat. No. 3,017,
280, 2,983,611, and the like, aziridine compounds, US Pat. No. 2,725,2
No. 94, No. 2,725,295, etc., acid derivatives,

Carbodiimide compounds as shown in US Pat. No. 3,100,704, epoxy compounds as shown in US Pat. No. 3,091,537, US Pat. No. 3 , 321, 313 and 3,543, 292, isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, N-carbamoyl. Pyridinium salts, haloamidinium salts, and also inorganic hardeners such as chromium alum and zirconium sulfate. Instead of the above compounds, precursors in the form of precursors, for example, alkali metal bisulfite aldehyde adducts, hydyltoin methylol derivatives, primary fatty acid nitroalcohols and the like may be used.

A silver halide photographic emulsion is usually prepared by mixing a water-soluble silver salt (eg silver nitrate) solution and a water-soluble halogen salt (eg potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. Was given. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as chlorobromide, iodobromide and silver chloroiodobromide can be used.

For the above photographic emulsion, the process for producing a light-sensitive material,
Various compounds can be added in order to prevent sensitivity deterioration and fog generation during storage or processing. Those compounds are 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene, 3-methyl-benzothiazole,
Many heterocyclic compounds including 1-phenyl-5-mercaptotetrazole, mercury-containing compounds, mercapto compounds,
An extremely large number of compounds such as metal salts have been known since ancient times.

The silver halide emulsion can be chemically sensitized by a conventional method. Chemical sensitizers include, for example:
Chloraurate, gold compounds such as gold trichloride, salts of precious metals such as platinum, palladium, iridium, rhodium and ruthenium, sulfur compounds that react with silver salts to form silver sulfide, stannous salts, amines, Other reducing substances may be mentioned.

The photographic emulsion can be spectrally sensitized or supersensitized, if necessary, by using cyanine dyes such as cyanine, merocyanine and carbocyanine alone or in combination, or by using them in combination with a styryl dye. .. Photosensitive materials include stilbene, triazine, oxazole and coumarin compounds as whitening agents in the non-photosensitive photographic constituent layers: benzotriazole, thiazolidine, cinnamic acid ester compounds as ultraviolet absorbers: high absorption Various photographic filter dyes known as agents may be contained.

If necessary, as other sliding agent or anti-adhesive agent, for example, US Pat.
Amides or esters and polyesters of fatty acids, such as those described in 042399, 3112060 and British Patent 14466304, and also in British Patents 1,320,564, 1,320,565, British Patents. Water insoluble materials such as those described in US Pat. No. 3,121,060 and surface active materials such as those described in US Pat. No. 3,617,286 can be included.

The photographic light-sensitive material is used as a photographic constituent layer such as a photographic emulsion layer, in particular, as an antistatic layer provided on the outermost side of a photographic light-sensitive material.
725, 297, 2,972,535, 2,9
72,536, 2,972,537, 2,97
2,538, 3,033,679 and 3,073
No. 2,484, No. 3,262,807, No. 3,52
No. 5,621, No. 3,615, 531, No. 3,63
0,743, 3,653,906, 3,65
Hydrophilic polymers such as those described in US Pat. Nos. 5,384,3,655,386, and British Patents 1,222,154, 1,235,075 are described in, for example, US Pat. , 263, 2,976,148, and the like, for example, biguanides as described in US Pat. Nos. 2,584,362 and 2,591,590. The compound

For example, US Pat. No. 2,639,234,
No. 3,649,372, No. 3,201,251, No. 3,457,076, the sulfonic acid type anion compound as described in, for example, US Pat. No. 3,317,
Phosphoric acid esters and quaternary ammonium salts as described in U.S. Pat. No. 344,344,291 and U.S. Pat.
No. 51, No. 3,399,995, No. 3,549,36
Cationic compounds such as those described in US Pat. No. 3,625,043 and US Pat.
Nonionic compounds such as those described in U.S. Pat. No. 695, and amphoteric compounds such as those described in U.S. Pat. No. 3,736,268, such as U.S. Pat. No. 2,647,836. Such complex compounds may include organic salts such as those described in US Pat. Nos. 2,717,834 and 3,655,387.

The cellulose ester film of the present invention can be applied to a support for all kinds of photographic light-sensitive materials regardless of black and white or color. The silver halide emulsion includes an ortho emulsion, a panchromatic emulsion, an infrared ray emulsion, an X-ray or other invisible light recording emulsion, a color photographic emulsion such as an emulsion containing a color-forming coupler, an emulsion containing a dye developing agent and a bleachable dye. Various silver halide photographic emulsions such as contained emulsions are included.

The color photographic emulsion may contain 2 equivalents or 4 equivalents of a color-forming coupler. For example, an open-chain ketomethylene yellow-forming coupler such as a benzoyl acetanilide type or a pivaloyl acetanilide type,
Pyrazolone-based or indazolone-based Kodoki magenta color-forming couplers and phenol- or naphthol-based cyan-forming couplers are preferably used. For example, a yellow coupler represented by the general formula [I] described in JP-B-48-18256, a magenta coupler described in JP-B-48-38416, a cyan coupler described in JP-A-48-42732, a U.S. Pat. No. 054, No. 2,449,966, No. 2,455,170, No. 2,600,788, No. 2,983,608, No. 3,148,062, etc. The separation-inhibiting coupler described in Japanese Patent No. 3,227,554 can be used.

The evaluation method will be described below. (1) Measurement of folding endurance The number of reciprocations up to cutting by bending was measured in accordance with the ISO8776-1988 standard using a MIT rub resistance tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.). (2) Evaluation of bleed-out Put 5 cc of ether in a 25 cc weighing bottle, cover with a film, cover with a glass plate on top, seal, leave for 2, 4 or 8 minutes, then remove, 30 at 25 ° C, 60% RH. After leaving for a minute, the bleed-out state of the plasticizer was visually measured. ◎: No bleed-out ○: Almost no bleed-out △: Bleed-out is conspicuous ×: Bleed-out is seen on the entire surface (3) Evaluation of deterioration preventing effect (measurement of viscosity retention rate) 2.0 g of sample 15 ml Put it in a glass container at 90 ℃,
After conditioning the humidity for 24 hours under the condition of relative humidity of 100%, the container is hermetically sealed and subjected to wet heat treatment at 90 ° C. for 100 hours under the condition of relative humidity of 100%. In the support of the photographic light-sensitive material thus deteriorated, the main chain and side chains of the polymer are mainly cleaved. This degree was evaluated by measuring the viscosity.
The viscosity was measured by the following method. That is, a sample degraded by the above method is used as a protein degrading enzyme (Bioprase S).
P4: Immerse in a 1% aqueous solution of Nagase Seikagaku Co., Ltd. at room temperature overnight and wash well with water to remove the emulsion layer. After this 40
Immerse in a methanol bath at ℃ for 30 minutes. This is repeated 4 times for rinsing to remove low molecular weight degradation products contained in the sample. After that, vacuum drying is performed at 50 ° C. for 15 hours to volatilize residual methanol.

An absolutely dry sample obtained after the rinsing and drying operations is used as a trifluoroacetic acid solution having a concentration of 1 g / 100 ml.
The solution was stored refrigerated at 5 ° C until measurement, and had a pore size of 0.5 μm.
After filtration with a PTFE filter (Milex LS, Millipore), measure the relative viscosity of the solution. That is, about 10 ml of the solution is put into an Ubbelohde viscometer (having a falling time of about 30 seconds in water at 30 ° C.), and the flowing time is measured. The flow down time obtained for the sample solution is divided by the flow down time obtained by measuring only the trifluoroacetic acid solvent to obtain the ratio of the solution flow down time to the solvent flow down time. This is the relative viscosity, which is a value corresponding to the degree of polymerization of the sample.

The deterioration prevention effect was evaluated by increasing the {(relative viscosity) -1}, that is, the specific viscosity of the sample after the wet heat treatment with the {(relative viscosity) -1}, that is, the specific viscosity of the sample before the wet heat treatment. The ratio of the specific viscosity after the treatment to that before the treatment, which is obtained in this way, is expressed in percentage. This is defined as the viscosity retention rate (%) and is used as an index of the decrease in the degree of polymerization of the sample. That is, viscosity retention rate (%)
Is closer to 100, the degree of polymerization is not lowered even by the wet heat treatment, which means that the deterioration preventing effect is large. Although this evaluation method is significantly more severe than the actual storage conditions, the effect of preventing deterioration under the actual storage conditions can be evaluated in a short time. Further, the fact that it is an index of the decrease in the degree of polymerization corresponds to the index of the decrease of important physical properties of the film (folding strength, tear strength, etc.), and the closer the viscosity retention rate (%) is to 100, It shows that the physical properties of the film are not easily deteriorated.

[0162]

【Example】

Example 1. Acetyl cellulose (degree of acetylation 60.8, degree of polymerization 262) was dissolved in a mixed solvent consisting of 82 parts by weight of methylene chloride, 15 parts by weight of methanol and 3 parts by weight of n-butanol with stirring to give a 15% by weight solution. did.
Add the plasticizers listed in Table 1 to acetyl cellulose 100
The parts were mixed according to the formulation shown in Table 1 with respect to parts by weight, and the solution was cast on a metal support to obtain a film having a thickness of 135 μm. Next, the coating solution shown below was applied at 35 cc / m ^{2 and} dried at 90 ° C. for 3 minutes to form a backing layer.

(Coating liquid) -Carbon black (average particle size of primary particle size: 20 mμ) 9.6 parts-Hydroxypropylmethyl cellulose hexahydrophthalate hexahydrophthalic acid 38 mol% 20 parts Hydroxypropyl group 8 mol% Methoxy group 16 mol % -Acetone 600 parts-Methyl cellosolve 150 parts-Methanol 200 parts

An undercoat layer was provided on the opposite side of the obtained backing layer, and a multi-layer color light-sensitive material consisting of each layer having the composition shown below was prepared thereon. First layer: blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 0.2 mol%) ............... coated silver amount 1.0 g / m ² Sensitizing dye (I) ............... silver 3 × 10 -4 mol coupler / mol 1 mol silver 2 × 10 -1 mol coupler EX-2 …………………………………… .. -1 mol

Second layer: intermediate layer Gelatin layer containing emulsified dispersion of 2,5-di-t-octylhydroquinone ........................ Gelatin 0.5 g / m ² Third layer: Red sensitive emulsion layer Chlorobromide Silver emulsion (silver bromide: 30 mol%) Coating amount: 0.5 g / m ² Sensitizing dye (II): 6 × 10 -5 mol coupler EX to 1 mol of silver Coupler EX -3 …………………………………………………………………………………… ..1 × 10 −1 mol coupler EX-4 …………………… for 1 mol silver 4 × 10 −1 mol

Fourth Layer: Intermediate Layer Same as Second Layer Fifth Layer: Green Sensitive Emulsion Layer Silver Chlorobromide Emulsion ………… Silver Chromobromide Coating 500g Sensitizing Dye (III) ……………… 1 mol silver To 0.5 × 10 -3 mol Coupler EX-3 ……………… 2 × 10 -1 mol to 1 mol silver

Sixth Layer: Green Sensitive Emulsion Layer Silver Chlorobromide Emulsion: Coating Silver Content 200 mg / m ² Sensitizing Dye (III) ………… 1.0 × 10 −3 per mol of silver Molar coupler EX-5 …………………………………………………………………………………… ..2 × 10 −1 mol per mol silver 7th layer: protective layer gelatin ………… 0.7 g / m ^{2 The} sensitizing dyes and couplers used are as follows. On the street.

[0168]

[Chemical 68]

[0169]

[Chemical 69]

[0170]

[Chemical 70]

35 mm after aging the obtained sample for one week
It was cut into a width and perforated to obtain a roll-shaped film of 400 films. The films obtained were evaluated and the results are shown in the table. The folding endurance is 80 times or more and the bleed-out is 0 or more in the practical range.

[0172]

[Table 1]

Example 2 Acetyl cellulose (acetylation degree 60.8%, degree of polymerization 262) 100 parts by weight triphenyl phosphate 16 〃 P-11 〃 methylene chloride 290 〃 n-butanol 20 〃 methanol 40 〃

The dope obtained from the raw material having the above composition was dried using a band casting machine having an effective length of 6 m to give a dry film thickness of 135 μm.
It was cast to become. The surface temperature of the band is 5 ℃,
After casting, it was dried at a temperature of 60 to 130 ° C. and wound. A subbing layer and a back layer were coated on the support. In this example, one or both of the deterioration inhibitors (A) to
(D) was added.

(Undercoat layer) Acetone / methanol / dichloromethane / water (composition ratio 70)
/ 20/10/2 (melting ratio) was used as a coating solvent, and coating was performed using a slide bead coater. Cellulose diacetate 0.1 mg / m ² Gelatin 50 mg / m ² Formaldehyde 3.9 mg / m ² Citric acid diethyl 26 mg / m ² of salicylic acid 15 mg / m ² antidegradant (Table ^{2) 600mg / m 2 (A} ) ~ (D Further, as a comparative example, a composition obtained by removing the deterioration inhibitor from the above composition was applied by the same method.

(Back layer) As the back first layer, methanol / acetone / dichloromethane / ethylene glycol (composition ratio 6) was applied on the side opposite to the underlayer so that the coating amount was as follows.
/2/2/0.5 (melting ratio) was used as a coating solvent and coating was performed with a slide bead coater.

[0177]

[Chemical 71]

On top of this, as a back second layer, acetone / methanol (composition ratio 85 /
15 (melting ratio) was used as a coating solvent, and coating was performed with a wire bar coater. Cellulose diacetate 200 mg / m ² colloidal silica 13.5 mg / m ² deterioration inhibitor (Table 2) 500 mg / m ² (total amount of (A) to (D)) As a comparative example, the deterioration inhibitor was removed from the above composition. The composition was applied in a similar manner. These are summarized in Table 2.

[0179]

[Table 2]

Preparation of Photosensitive Layer: Next, a photosensitive layer was provided on the obtained undercoat layer. (Preparation of emulsion) A surface latent image type emulsion was prepared by the following method. Solution I 75 ° C. Inert gelatin 24 g Distilled water 900 ml KBr 4 g 10% aqueous phosphoric acid solution 2 ml Sodium benzenesulfinate 5 × 10 −2 mol 2-mercapto 3,4-methylthiazole 2.5 × 10 −3 g Solution II 35 ° C. Silver nitrate 170 g Distilled water was added to 1000 ml Solution III 35 ° C. KBr 230 g Distilled water was added to 1000 ml Solution IV Room temperature potassium hexacyanoferrate (II) 3.0 g Distilled water was added to 100 ml Solution I was stirred well And solution III at the same time 45
When the total amount of the solution II and the solution II was completely added, a cubic monodisperse emulsion having an average grain size of 0.28 μm was finally obtained.

At this time, the addition rate of the solution III was adjusted such that the pAg value in the mixing vessel was always 7.50 with respect to the addition of the solution II. The solution IV was added for 5 minutes from 7 minutes after the addition of the solution II was started. Solution II
After completion of the addition, the product was washed with water and desalted by a sedimentation method, and then dispersed in an aqueous solution containing 100 g of inert gelatin. To this emulsion, 34 mg each of sodium thiosulfate and tetrachloroauric acid tetrahydrate were added per mol of silver, and the pH and pAg values were adjusted to 7.0 and 8.9 (40 ° C.), respectively, and then 75 ° C.
Was chemically sensitized for 60 minutes to obtain a surface latent image type silver halide emulsion. A comparative antihalation (AH) layer, AH-1, emulsion layer and protective layer were coated in this order on the support. <AH-1> Gelatin 1.7 g / m ² polymer mordant (below) 167.8 mg / m ² dye Em (〃) 72.4 mg / m ² dye Fm (〃) 68.5 mg / m ² dye Gm (〃) ) 68.5 mg / m ²

[0182]

[Chemical 72]

<Emulsion layer> Silver halide emulsion (as silver amount) 1700 mg / m ² Sensitizing dye Am 238 〃 5-methylbenzotriazole 4.1 〃 Sodium dodecylbenzene sulfonate 5 〃 1,3-divinylsulfonyl- 2-propanol 56〃 sodium polystyrene sulfonate 35〃

[0184]

[Chemical formula 73]

<Protective Layer> Inert gelatin 1300 mg / m ² colloidal silica 249 〃 Liquid paraffin 60 〃 Barium strontium sulfate (average particle size 1.5 μm) 32 〃 Proxel 4.3 〃 N-perfluorooctanesulfonyl-N-propyl Glycine potassium salt 5.0 〃 1,3-divinylsulfonyl-2-propanol 56 〃 The following compounds 15 〃

[0186]

[Chemical 74]

Development Processing Each of the photographic light-sensitive materials prepared in this manner was exposed under constant conditions, and then developed in the same manner according to the following method. Developed by Allen Products Company F-
A 10-deep tank automatic processor was used under the following conditions using a commercially available general-purpose processing solution for microfilm (FR-537 developer manufactured by FR Chemicals, USA).

[0188]

[Table 3]

The sample subjected to the development treatment was evaluated in the same manner as in (Example 1). The results are shown in Table 2. Thus, by adding the deterioration preventing agent of the present invention to at least one of the subbing layer and the back layer, a remarkable deterioration preventing effect was obtained.

Example 3 The dope of the formulation of Sample No. 3 in Table 1 was adjusted, and a film forming process, an undercoating process, a backing layer and a photosensitive emulsion layer were formed in the same manner as in Example 1. The photographic light-sensitive material thus prepared was exposed under constant conditions, and then developed under the same conditions according to the following method. The development processing was carried out in the same manner as in Example 1, and the development was carried out according to the processing step specifications according to the ECP-2A processing recipe (Table 2). However, for the stabilizing bath, the following liquid was prepared and treated at 38 ° C. for 40 seconds.

Deterioration inhibitor (Table 4) 20 g (or 0) (total amount of (A) to (D)) Formalin (37% solution) 7.5 ml Hexylene glycol 130 g Isopropanol 400 g Water 400 g Polyoxyethylene-P-mono Phenyl ether 1.0 g (average degree of polymerization 10) Ethylenediaminetetraacetic acid 2-sodium salt 0.05 g In preparing a stabilizing bath, first, the deterioration inhibitor (A),
(B), (C), and (D) were thoroughly mixed, isopropanol, hexylene glycol, and a nonionic activator were added to this, and the mixture was stirred. Finally, the remaining components were added while stirring. The developing machine and line speed at the time of development are the same as those in Example 1.
The same conditions were used.

Evaluation of Deterioration Prevention Effect Evaluation was carried out in the same manner as in Example 1. The results are shown in Table 4.

[0193]

[Table 4]

As described above, it was revealed that a sufficient deterioration preventing effect can be obtained also by diffusing the deterioration preventing agent from the processing solution into the support during the development processing.

Example 4 A silver halide photosensitive material was prepared in the same manner as in Example 3,
The same development process as in Example 2 was performed. After the completion of all the processing steps, the photographic light-sensitive material which had been subjected to the development treatment was dipped in a solution containing the deterioration inhibitor to diffuse the deterioration inhibitor in the support and to obtain its effect. A deterioration preventing bath having the following composition was prepared. Deterioration inhibitor (Table 5) 20 g (or 0 g) (total amount of (A) to (D)) Isopropanol 400 g Water 400 g Polyoxyethylene-P-monophenyl ether 1.0 g (Average degree of polymerization 10) Immersion of photographic light-sensitive material Was performed by heating this solution to 38 ° C. and then immersing it for 5 minutes. After this, it was dried at 60 ° C. for 30 minutes.

Evaluation was carried out according to Example 1. The results are shown in Table 5.

[0197]

[Table 5]

As described above, even in the photographic light-sensitive material which has been subjected to the development processing, the deterioration preventing agent is effectively immersed by immersing the deterioration preventing agent into the support. It turned out to be obtained.

[0199]

Various plasticizers have been studied in order to solve problems such as weak mechanical strength and exudation of the plasticizer, which were the drawbacks of the cellulose acetate film, and triphenyl phosphate is particularly flame retardant. It is widely used because it excels in However, in order to further improve the strength,
When the amount is increased, bleed-out and storage stability are significantly deteriorated. Bleedout can be prevented by using the compound represented by the general formula (1) of the present invention, and
At least one of the deterioration inhibitor (A) peroxide decomposer, (B) radical chain inhibitor, (C) metal deactivator, and (D) acid scavenger of the present invention is added to (1) dope. Add to form a film. (2) Add to at least one of the subbing layer and the back layer. (3) It is added to the processing solution at the time of development processing and incorporated into the support from there. (4) The developed photographic light-sensitive material is dipped in a bath containing a deterioration inhibitor and incorporated into the support. By doing at least one of these,
The stability over time was insufficient. The stability of these cellulose acetates could be significantly improved.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yukio Shinagawa 210 Nakanuma, Minamiashigara-shi, Kanagawa Fuji Photo Film Co., Ltd.

Claims (5)

[Claims] 1. A cellulose ester film using triphenyl phosphate as a plasticizer, which contains a plasticizer represented by the following general formula (1) and has the following (A):
A cellulose ester film containing at least one deterioration preventive agent selected from the following: General formula
(1) [Chemical 1] In the formula, R represents an alkyl group or an alkenyl group having 4 or less carbon atoms, and n represents 3 or 4. (A) Peroxide decomposer (B) Radical chain inhibitor (C) Metal deactivator (D) Acid scavenger 2. The cellulose ester film according to claim 1, wherein in the general formula [I], R is a methyl group or an ethyl group, and n is 3. 3. A silver halide photographic light-sensitive material having, as a support, a cellulose ester film containing triphenyl phosphate and a plasticizer represented by the following general formula (1), either a subbing layer or a back layer: A silver halide light-sensitive material characterized in that it contains at least one deterioration inhibitor selected from the following (A) to (D). General formula (1) In the formula, R represents an alkyl group or an alkenyl group having 4 or less carbon atoms, and n represents 3 or 4. (A) Peroxide decomposer (B) Radical chain inhibitor (C) Metal deactivator (D) Acid scavenger 4. Triphenyl phosphate and the following general formula
When a silver halide photographic light-sensitive material having a cellulose ester film containing a plasticizer represented by (1) as a support is subjected to development processing, at least one bath until the development processing step is completed, A treatment method characterized by containing at least one kind of deterioration preventive agent of (D). General formula (1) In the formula, R represents an alkyl group or an alkenyl group having 4 or less carbon atoms, and n represents 3 or 4. (A) Peroxide decomposer (B) Radical chain inhibitor (C) Metal deactivator (D) Acid scavenger 5. Triphenyl phosphate and the following general formula
After completion of the development processing step of the silver halide light-sensitive material having a cellulose ester film containing a plasticizer represented by (1) as a support, at least one deterioration inhibitor of the following (A) to (D) By providing a treatment bath containing
A processing method comprising immersing the photosensitive material in a processing bath. General formula (1) In the formula, R represents an alkyl group or an alkenyl group having 4 or less carbon atoms, and n represents 3 or 4. (A) Peracid decomposer (B) Radical chain inhibitor (C) Metal deactivator (D) Acid scavenger