JP2665706B2 - Method for preventing deterioration of cellulose acetate film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a support for photographic light-sensitive materials,
The present invention relates to a method for preventing deterioration of a cellulose acetate film suitable for use in a polarizing plate protective film, an optical filter, a release film, and the like.

[0002]

2. Description of the Related Art Cellulose acetate films are extremely stable under ordinary storage conditions. However, when stored tightly under high temperature and high humidity conditions, both the degree of acetylation and the molecular weight are reduced, and the physical properties of the films are significantly reduced in recent years. It is becoming. This will be described from the viewpoint of the purity of the raw material. In general, fatty acid cellulose esters, such as cellulose acetate, cellulose acetate propionate,
Cellulose acetate butyrate and the like are usually produced using sulfuric acid as a catalyst, and the sulfuric acid reacts with hydroxyl groups of cellulose to form a sulfate ester. The bound sulfuric acid and free sulfuric acid remaining in the fiber tissue are removed and removed as much as possible by the boiling stabilization treatment, but only a trace amount of sulfate ester and free sulfuric acid remain in the fatty acid cellulose ester. Since it serves as a catalyst for hydrolysis, it is a major cause of deterioration due to long-term storage, particularly poor heat stability, that is, deterioration such as coloring or decomposition due to heat and breaking of molecular chains.

[0003] To deal with this, a method of neutralizing and stabilizing by adding an acetate, carbonate, oxalate or the like of potassium, sodium, calcium, barium, aluminum or the like (US Pat. Nos. 3,047,561 and 30898).
Nos. 71 and 2614941). However, when industrially producing fatty acid cellulose esters, these weak acid salts are often added in excess, so they remain in the fibrous tissue without binding to sulfate esters or free sulfuric acid, and temporarily decompose and degrade the molecular chains. Even if degradation such as cutting can be prevented, it acts as a catalyst for the production of colored substances, and therefore has the disadvantage of significantly impairing the hue.

[0004] As described above, in order to obtain a fatty acid cellulose ester having excellent transparency and heat resistance, a highly purified cellulose is used as a raw material, and sulfuric acid, which is a reaction catalyst, is converted into a fiber in the form of bound sulfuric acid. It is desirable to use a fatty acid cellulose ester having a small amount remaining in the tissue and a low ash content, and from which a coloring cause substance has been removed, and the fatty acid cellulose ester usually contains a plasticizer. It is desirable to use additives having high heat stability.

[0005] However, there is a technical and economic limit in the direction in which the prevention of deterioration of the fatty acid cellulose ester is to be solved only by the purity and quality of the constituent materials as described above. Therefore, it is common practice to combine and mix an appropriate deterioration inhibitor. Conventionally, an epoxy compound, a weak organic acid,
Antioxidants for saturated polyhydric alcohols and general organic materials, for example, sulfur-based antioxidants such as phosphite compounds, hindered phenols and thioethers, ultraviolet absorbers, light stabilizers, metal deactivators, etc. (U.S. Pat. Nos. 2,917,398 and 3,723,147)
No. 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 case of neutralization and stabilization treatment with a weak acid salt, even when the fatty acid cellulose ester has an ash content of 0.01% by weight or more and has many impurities, the effect of preventing the resin from being colored during heating appears. Has a function to cut the molecular chain of the polymer, and the degree of polymerization is extremely reduced, and the physical properties are deteriorated. In addition, when a weak organic acid, an epoxy compound and a phosphite compound are added to the fatty acid cellulose ester, the deterioration of physical properties is considerably improved as compared with the case where a weak organic acid and a phosphite compound are added, but still, It was not satisfactory enough, and the colorability at the time of heating deteriorated. In addition, when a saturated polyhydric alcohol was further added thereto, the deterioration property was deteriorated by the wet heat treatment when it was placed in an iron container which was a standard storage container of a silver halide photosensitive material having a fatty acid cellulose ester as a support. .
In the case of an ultraviolet absorber and a light stabilizer, such a method is obviously insufficient, because it is premised on deterioration that occurs even in a dark room. The metal deactivator suppresses the catalytic action of the metal by the chelating effect when stored in a metal container, so that a good inhibitory effect can be obtained in combination with other inhibitors, but it is effective alone in a nonmetal container. Not shown. In addition, because of its high hydrophilicity due to its structure, when it is added to a hydrophobic fatty acid cellulose ester film, compatibility is poor and haze is generated even with a small amount of addition.

From the above, it can be understood that various degradation inhibitors have been studied for the purpose of preventing hydrolysis of cellulose acetate using an acid or a metal as a catalyst. However, an amine compound having a function of trapping an acid has been studied. It has become clear that has not been sufficiently studied in the past. One of the problems is that many amine compounds have a problem in terms of coloring.In other words, it has been considered that although deterioration can be prevented, the compound gradually becomes colored. It is possible that they did not. Now, the present inventors have studied compounds from the viewpoint of insufficient conventional studies, and have reached the present invention.

[0008]

[Problems to be Solved by the Invention] Literature (NS Allen et al.
al., J. Photogr. Sci. 36, 194-198, 1988)
As described in, etc., cellulose acetate film is an excellent material that is very resistant to deterioration when a normal and correct storage method is used.However, it is sealed in a metal case or exposed to high temperature and humidity. If stored or used in, the degree of polymerization and acetylation decrease due to hydrolysis,
Causes significant deterioration of physical properties and devitrification. An object of the present invention is to prevent degradation of cellulose acetate under severe conditions such as in a metal case or stored tightly under high temperature and high humidity.

[0009]

The object of the present invention has been achieved by adding an amine compound having a pKa of 4 or more to a cellulose acetate film. That is, the present invention provides an amine compound having a pKa (negative logarithm of acid dissociation constant) of 4 or more in a cellulose acetate film or a cellulose acetate film having an adjacent layer on the cellulose acetate film or in the adjacent layer. A method for preventing deterioration of a cellulose acetate film, characterized by containing an amine compound having no volatile property and a molecular weight per basic group of 200 or less.

The amine compound of the present invention will be described in more detail. The pKa of the present invention can be defined as the negative logarithm of Ka, which is the dissociation constant of the conjugate acid of the amine compound. This value was determined by measuring at room temperature with a mixed solvent of ethanol / water = 4/1 (volume ratio). Generally, this value can be obtained by titration.

The amine compound of the present invention has a pKa of 4 or more. From the viewpoint of the effects of the present invention, the pKa is preferably 4 or more and 9 or less, more preferably 5 or more and 8 or less. Most preferably, the amine compound has a pKa of 5 or more and 7 or less.

The amine compound of the present invention is preferably a lipophilic compound, and the total number of carbon atoms is preferably 8 or more, more preferably 15 or more.

Among the amine compounds of the present invention, preferred are tertiary amines represented by the following general formula (I), which are lipophilic and have a pKa of 4 or more.

[0014]

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In the formula, R ₁ , R ₂ and R ₃ may be the same or different and represent 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 be bonded to each other to form a 5- to 8-membered ring, and R ₁ and R ₂ may work together to form an unsaturated group, and R ₃ may form a 5- to 8-membered ring. However, R ₁ , R ₂ and R ₃ are not hydrogen atoms at the same time.

The aliphatic group referred to in the present invention is a linear, branched or cyclic alkyl group (eg, methyl, ethyl, propyl, i-propyl, t-butyl, cyclohexyl, t-butyl).
Hexyl, t-octyl, dodecyl, hexadecyl, octadecyl, benzyl), alkenyl groups (for example, vinyl, allyl, 2-pentenyl, cyclohexenyl, hexenyl, dodecenyl, octadecenyl), and alkynyl groups (for example, flopynyl, hexadecynyl). The group may be substituted with a substituent. The aromatic group referred to in the present invention represents a benzene monocyclic or condensed polycyclic aryl group (for example, phenyl, naphthyl, anthranyl). These rings may have a substituent. The heterocyclic ring referred to in the present invention 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 in the present invention 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. At least two groups out of R ₁ , R ₂ and R ₃ are bonded to each other and
An 8-membered ring (eg, a pyrrolidine ring, an imidazoline ring, an imidazolidine ring, a pyrazolidine ring, a piperazine ring, a piperidine ring, a morpholine ring, an indoline ring, and a quinuclidine ring) may be formed. R ₁ and R ₂ may combine with each other to form an unsaturated group, and this and R ₃ may combine to form a 5- to 8-membered ring (for example, a pyridine ring, a quinoline ring, a pteridine ring, a phenanthroline ring).

Among the lipophilic compounds represented by the formula (I), more preferred compounds have a pKa of 4 or more and 9 or less, more preferably 5 or more and 8 or less, most preferably a pKa of 5 or more and 7 or less. The following compounds are used. Further, among the compounds represented by the general formula (I), more preferred are lipophilic compounds having a pKa of 4 or more represented by the general formula (II). Among the amine compounds represented by the general formula (II) of the present invention, the most preferred compounds have a molecular weight of 300 or more and have substantially no volatility.

[0018]

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In the formula, R ₁ and R ₂ represent the same groups as in formula (I). R _{21 to} R ₂₅ may be the same or different and each represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an aliphatic oxy group, a heterocyclic oxy group, an aromatic oxy group, an aliphatic thio group, or an aromatic group. Group thio group, heterocyclic thio group, hydroxy group, halogen atom, cyano group, nitro group, amino group which may have a substituent, sulfonyl group, acyl group, acyloxy group, sulfamoyl group, carbamoyl group, ester group . R ₁ and R ₂ , R ₁ and R ₂₅ , R ₂ and R _21, or R _{21 to} R ₂₅ , may be bonded to each other in the ortho-position to form a 5- to 8-membered ring.

Among the compounds represented by the general formula (Formula 2),
More preferably, the compound has a pKa of 4 or more and 9 or less, further preferably 5 or more and 8 or less, and most preferably a pKa of 5 or more and 7 or less.

Hereinafter, specific examples of the amine compound of the present invention A-
1 to A-73 and pKa values are shown, but the present invention is not limited thereto.

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[0062]

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Among the amine compounds of the present invention, preferred are, in addition to the above, those represented by the following general formula (III). These will be described in more detail.

[0064]

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In the formula, X represents a single bond or a divalent or 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
And a divalent linking group such as CH ₂ —). B
a is an aryl group, an aryloxy group, or a nitrogen-containing heterocyclic group having an amino group with a pKa (measured in a mixed solvent of ethanol / water = 4/1) of 4 or more. The amino group referred to herein 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 preferred, 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, imidazonilyl group,
Examples thereof include a thiazolinyl group, an imidazolidinyl group, and a thiazolidinyl group. The amino acid and the nitrogen-containing heterocyclic group may further have another substituent.

Among the amine compounds represented by the general formula (III) of the present invention, more preferred compounds are those having a molecular weight of 300 or more and having substantially no volatility.

Among the amine compounds represented by the general formula (III) of the present invention, the most preferred compounds have substantially no volatility and have a molecular weight of 200 or less per basic group.

The specific examples B-1 to B-67 of the amine compound represented by the general formula (III) of the present invention are shown below, but the present invention is not limited thereto.

[0069]

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Other preferred examples of the amine compound of the present invention and a synthesis method thereof are described in US Pat. No. 4,483,918,
Nos. 4,555,479 and 4,585,728
No. 4,639,415, European Patent Publication No. 26
4,730, JP-A-58-102231, JP-A-59-102231.
No. 229557, No. 61-73152, No. 63-98
No. 662, No. 63-115167, No. 63-2679
No. 44, etc.

The present invention is characterized in that an amine compound is used. As a method for adding the amine compound to cellulose acetate, there is a method in which the amine compound is added during a solution casting step for obtaining a film molded product. This method is advantageous in terms of production in that deterioration prevention treatment can be performed at the same time during the film forming process, and stability can be imparted to the film alone without requiring any new equipment. In particular, when used as a support for a silver halide photographic light-sensitive material, the adjacent layer becomes a hydrophilic undercoat layer, which prevents bleeding to the light-sensitive layer as a barrier layer, so that the influence on photographic properties is reduced. Is advantageous. Solution casting is a method in which a dope obtained by dissolving cellulose acetate in a solvent is cast on a support to produce a film. The solid content of the dope (1) containing cellulose acetate is 18 to 35%.
(2) The solvent is 65 to 82% by weight, and the solvent composition is (2-1) 75 to 87% by weight of a good solvent such as methylene chloride (2-2) Poor solvent of cellulose triacetate 0 to 0 25
It is preferable to use a mixed solvent consisting of% by weight. The acetyl group of the cellulose acetate used in the present invention is 3
A range of 7 to 62.5% is preferred. As the dope, it is preferable to use a dope having a high concentration of cellulose acetate, and the total concentration of cellulose triacetate and other components which become solid after drying is 18% by weight or more, preferably 20 to 35% by weight. Other components that become solid after drying include cellulose derivatives such as cellulose acetate propionate and cellulose acetate butyrate, plasticizers such as triphenyl phosphate, and various additives that are added as necessary.

The amine compound can be added as one of these additives. The amine compound is preferably blended in an amount of 0.05 to 2.0 parts by weight based on 100 parts by weight of cellulose acetate. More preferably, 0.1-1.
It is preferable to add 0 parts by weight. When the amount of the amine compound in the present invention is less than this, the effect of preventing deterioration is not sufficiently exhibited, and when the amount of addition is increased, the effect of preventing deterioration gradually increases. Not only decreases, but also exceeds the compatibility limit of the additive and becomes cloudy, and bleeds on the surface of the film-forming product,
It is not appropriate to add more than the above-mentioned amount, since coloring cannot be ignored.

Next, the conditions in the film forming step will be described in more detail. As a solvent, a good solvent of cellulose triacetate such as methylene chloride is used. Further, the mixed solvent of the present invention may include a poor solvent for cellulose triacetate such as alcohols having 1 to 4 carbon atoms and cyclohexane. These may be used alone or in combination of two or more. In particular, as described below, in order to promote the gelling of the dope by cooling,
It is desirable to include alcohols such as n-butanol and poor solvents such as cyclohexane. The preferred solvent composition is 75 to 87% by weight of methylene chloride and 0 to 25% by weight of a poor solvent. Regarding the concentration of cellulose triacetate 2 and the composition of the solvent, it is easy to produce a dope by the method described below. Further, cooling the support to a temperature of 10 ° C. or less can cause gelation of the dope, thereby facilitating stripping, which is preferable. In addition,
At this time, the gelling temperature of the dope, which depends on the concentration of cellulose triacetate and the solvent composition, needs to be higher than the temperature of the support. Such a dope is, for example, put the cellulose triacetate and the solvent in a pressurized container and seal the container, and heat the mixture to a temperature not lower than the boiling point of the solvent at normal pressure under pressure and within the range where the solvent does not boil, and agitated. Obtained by:

The cellulose triacetate, the solvent, and other additives to be added as required may be roughly mixed in advance and then charged into a pressure vessel, or may be charged separately. It does not matter what kind of pressurized container is used. In short, any type can be used as long as it can withstand a predetermined pressure. This pressurized container needs to be pressurized and capable of being stirred. After melting, remove from the container after cooling, or withdraw from the container with a pump etc., cool with a heat exchanger, etc.,
This is used for film formation. In this dissolving method, by applying pressure, heating can be performed at a temperature higher than the boiling point at normal pressure, and the generation of gel is prevented by suppressing boiling to prevent an over-concentrated state. Heating increases the solubility and dissolution rate, allowing complete dissolution in a short time.

The casting method of the dope may be either a band casting method or a drum casting method. When the casting part is cooled, a method using a refrigerant or cold air, a method using a heat pipe, or the like can be used as disclosed in JP-A-62-37113. The cooling temperature is such that the surface temperature of the support is 10 ° C. or less, preferably 5 ° C. or less. 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, as disclosed in JP-A-62-115035, it can be dried while applying a constant tension in the width direction of the film, and can be manufactured in a state having a predetermined residual solvent in the film. preferable.

The 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 a decrease in the gas phase volume in the container by sealing a pressurized container and then injecting part or all of cellulose triacetate, a solvent, and other additives. The heating is preferably performed from the outside, 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 and circulating with a pipe. The stirring blade preferably has a length reaching the vicinity of the container wall, and it is preferable to provide a scraping blade at the end for renewing the liquid film on the container wall. Other instruments such as a pressure gauge and a thermometer are appropriately provided in the pressurized container. The aforementioned raw materials are put in a pressurized container and heated under pressure. The heating temperature is a temperature not lower than the boiling point of the solvent and within a range where the solvent does not boil. This temperature is preferably 60 ° C or higher, and particularly preferably about 80 to 110 ° C. The pressure is determined so that the solvent does not boil at this set temperature.

Examples of the cellulose ester used in the present invention include cellulose acetate, cellulose acetate butyrate, cellulose acetate propionate and the like. Particularly preferred are celluloses having a degree of polymerization of 250 to 400 and a combined acetic acid amount of 54 to 62%. Acetate is preferred.

As the plasticizer, a low molecular weight plasticizer and a high molecular weight plasticizer, which are conventionally used, can be used in combination with the compound represented by the general formula (IV) depending on the use conditions.

[0090]

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However, R ₁ , R ₂ , R ₄ and R ₅ each represent a hydrocarbon group which is the same or different and is an alkyl group or an aryl group (phenyl group or the like), and has 1 to 18 carbon atoms. Are preferred, and particularly preferably 2 to 6. The alkyl group may be linear or branched. An aryl group is more preferable, and may be substituted with a hydrocarbon substituent. R ₃ represents an alkylene group, and preferably has 1 to 20 carbon atoms, particularly preferably 2 to 6 carbon atoms. If the number n is too large, the dimensional change due to humidity of the formed cellulose ester film is undesirably large. As a plasticizer conventionally used,
That is, a phosphate ester compound represented by the following general formula (P) can be mentioned.

[0092]

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In the formula, R, R ₁ and R ₂ represent an alkyl group, a cycloalkyl group or an aryl group, which may be the same or different. Representative plasticizers include, for example, triphenyl phosphate, biphenyl diphenyl phosphate, tricresyl phosphate, octyl diphenyl phosphate, triethyl phosphate, tributyl phosphate, or dimethyl phthalate, diethyl phthalate, dibutyl phthalate,
Compounds such as dioctyl phthalate, dimethoxyethyl phthalate, glycerol triacetate, o- or p-tolueneethyl sulfonamide, butyl phthalyl butyl glycolate, ethyl phthalyl ethyl glycolate, methyl phthalyl ethyl glycolate, and triacetin Can be Japanese Patent Publication No. 61-14168 discloses polycaprolactone polyol as a plasticizer for acetylcellulose.
No. 60 discloses that a polyester urethane resin is mixed into a triacetate fiber membrane.
No. 69845 discloses mono- or dialkyl phosphates in which non-esterified hydroxyl groups are in free acid form as plasticizers for cellulose ester films. However, particularly for triacetyl cellulose, triphenyl phosphate is mainly used.

The amount of the plasticizer to be added is preferably 5 to 20% by weight based on the cellulose ester. In particular, noncombustibility is further improved by using triphenyl phosphate or biphenyl diphenyl phosphate in combination with a part of the compound represented by the general formula (IV).

Examples of the solvent include lower aliphatic hydrocarbon chlorides such as methylene chloride, lower aliphatic alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and n-butanol, and cyclohexane and dioxane. Can be The mixing ratio of the solvent composition is as follows: methylene chloride 70 to 1
00% by weight and 30 to 0% by weight of other solvents are preferably used. More preferably, methylene chloride 75-8
7% by weight and 13 to 25% by weight of other solvents.

The concentration of the cellulose ester is 10 to 5
0% by weight is preferably used. If necessary, a peeling accelerator or a dye from the casting support may be added to the cellulose ester solution.

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. 2,429,978, 2,739,070 and 2,
No. 739069, No. 2492977, No. 2336
No. 310, No. 2367603, No. 2492978
No. 2607704, UK Patent No. 640731
No. 7,358,892, JP-B-45-9074, JP-A-49-4554, JP-A-49-5614, and the like.

The cellulose acetate film prepared by the method described above is suitable for use as a support for a silver halide photographic light-sensitive material or as a protective film for a polarizing plate. Therefore, it is possible to easily carry out a measure for preventing deterioration of a cellulose acetate film used as a support of a silver halide photographic material or a protective film of a polarizing plate by a method of adding to a dope.

Here, the polarizing plate protective film will be described in more detail. In recent years, liquid crystal display devices have been used as display devices for televisions and personal computers in addition to electronic desk calculators and wristwatches. A polarizing plate plays an important role in image formation of this liquid crystal display device. That is, a polarizing plate usually has a structure in which a film of polyvinyl alcohol resin is stretched and oriented and adsorbs iodine, and has a property of passing only a specific polarized light. Are formed to form an image. Since the display quality of such a polarizing plate is significantly reduced due to evaporation of iodine and scratches on the surface, it is generally practiced to protect the surface by laminating a transparent and colorless thin film having good flatness. This is called a polarizing plate protective film, and a cellulose acetate film is most often used. As the cellulose acetate film, a film having a thickness of about 0.1 mm produced by the above method is often used. The following method is generally used as a method for bonding the polarizing plate protective film and the polarizing plate. That is, a solution of the pressure-sensitive adhesive is applied on a polyethylene terephthalate film, and the pressure-sensitive adhesive layer obtained by drying is transferred onto a polarizing plate or a polarizing plate protective film, and these are laminated. As a pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer, a rubber-based pressure-sensitive adhesive, an acrylic-based pressure-sensitive adhesive, a vinyl ether-based pressure-sensitive adhesive, a silicone pressure-sensitive adhesive, and the like can be used. Is preferred from the viewpoint of transparency. The acrylic adhesive is not particularly limited,
The main monomers are ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, etc., the comonomers are vinyl acetate, acrylonitrile, acrylamide, styrene, methyl methacrylate, methyl acrylate, etc., and the functional group-containing monomers are methacrylic acid, acrylic Acid, itaconic acid, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl methacrylate, methylol acrylamide, glycidyl methacrylate, maleic anhydride and the like are used. As a solvent for the pressure-sensitive adhesive solution, various organic solvents, for example, toluene, benzene, butyl acetate, ethyl acetate and the like are used alone or as a mixture.

As the method for adding the amine compound to the cellulose acetate film in the present invention, in addition to the above-mentioned method, a layer adjacent to the film, for example, an undercoat layer or a backing layer in a silver halide photographic light-sensitive material,
In the case of a polarizing plate protective film, a method in which the film is contained in a pressure-sensitive adhesive layer applied on one side or both sides and the like and penetrates the film can also be used. In this case, the amine compound is preferably contained in the undercoat layer and / or the backing layer and / or the pressure-sensitive adhesive layer in an amount of 0.01 to 2.00 g / m ² . In particular, an undercoat layer and / or a backing layer and / or
Alternatively, the pressure-sensitive adhesive layer desirably contains 0.1 to 1.0 g / m ² . This method is advantageous in that the compound concentration is highest near the surface where deterioration is likely to occur, so that the effect of preventing deterioration is large and the necessary amount of addition can be reduced.

Next, the silver halide emulsion layer and other light-insensitive photographic constituent layers (protective layer, intermediate layer, backing layer, undercoat layer, etc.) will be described by taking a color photographic light-sensitive material as an example. The silver halide photographic light-sensitive material of the present invention comprises a photographic emulsion layer and other photographic constituent layers including an undercoat layer and / or
Alternatively, it is composed of a backing layer and a support of cellulose acetate. Various hydrophilic colloids are used in the photographic light-sensitive material of the present invention. Examples of the hydrophilic colloid used as a binder for a photographic emulsion and / or a photographic component layer of another non-photosensitive layer include gelatin, colloidal albumin, and the like. Cellulose derivatives such as casein, carboxymethylcellulose, hydroxyethylcellulose, sugar derivatives such as agar, sodium alginate and starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or these Derivatives and partial hydrolysates of these. Optionally, two or more compatible mixtures of these colloids are used. The most commonly used of these is gelatin.

The photographic emulsion layer and other non-photosensitive layers used in the present invention may contain a synthetic polymer compound, for example, a latex-like water-dispersible vinyl compound polymer, especially a compound which increases the dimensional stability of a photographic material. And the like, alone or in combination (of different polymers) or in combination with a hydrophilic water-permeable colloid. There are many polymers, for example, US Pat. No. 2,376,005,
2,739,137, 2,853,457, 3,062,674, 3,411,911, 3,488,708, 3,525,620, and 3 Nos. 3,635,715, 3,607,290, 3,645,740 and British Patent 1,186,699.
No. 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, alkoxyalkyl acrylate, alkoxy methacrylate, styrene, butadiene, vinyl chloride, vinylidene chloride, maleic anhydride, and Copolymers and homopolymers selected from itaconic anhydride are generally used.

The hardening of the photographic constituent layers of the photographic emulsion layer and / or other non-photosensitive layers can be carried out according to a conventional method.
Examples of the curing agent include aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, and bis (2-
Chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine, and other U.S. Pat.
Nos. 288,775 and 2,732,303. Compounds having a reactive halogen, such as those disclosed in British Patent Nos. 974,723 and 1,167,207, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,3 5-triazine, and others, U.S. Patent Nos. 3,635,718 and 3,232,76
No. 3, No. 3,490,911, No. 3,642,4
No. 86, compounds having a reactive olefin such as those described in British Patent No. 994,869, N-hydroxymethylphthalimide, and other U.S. Pat.
N-methylol compounds as shown in U.S. Pat. Nos. 2,316 and 2,586,168;
Isocyanates such as those described in U.S. Pat. No. 3,017,280 and U.S. Pat.
Aziridine compounds such as those described in U.S. Pat.
Acid derivatives as shown in US Pat. No. 5,295, carbodiimide compounds as shown in US Pat. No. 3,100,704, US Pat. No. 3,091,5
Epoxy compounds such as those described in U.S. Pat. Nos. 3,321,313 and 3,543,29;
No. 2 isoxazole compounds, halogenocarboxaldehydes such as mucochloric acid, dioxane derivatives such as dihydroxydioxane and dichlorodioxane, N-carbamoylpyridinium salts, haloamidinium salts, and also inorganic hardened films Chromium van, zirconium sulfate and the like are used as agents. In place of the above compound, a precursor in the form of a precursor such as an alkali metal bisulfite aldehyde adduct, a methylol derivative of hydantoin, or a nitro alcohol of a primary fatty acid 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. Can be As the silver halide, mixed silver halide such as chlorobromide, iodobromide, silver chloroiodobromide and the like can be used in addition to silver chloride and silver bromide. Various compounds can be added to the above-mentioned photographic emulsion in order to prevent a decrease in sensitivity and generation of fog during the production process, storage or processing of the photographic material. The compounds are 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3-methyl-benzothiazole, 1-
Very many compounds such as phenyl-5-mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts have been known for a long time.
The silver halide emulsion can be chemically sensitized by a conventional method. Chemical sensitizers include, for example, gold compounds such as chloroaurate and gold trichloride, salts of noble metals such as platinum, palladium, iridium, rhodium and ruthenium, and sulfur compounds that react with silver salts to form silver sulfide. , Stannous salts, amines, and other reducing substances.
The photographic emulsion can be subjected to spectral sensitization or supersensitization by using cyanine dyes such as cyanine, merocyanine and carbocyanine, alone or in combination, or in combination with a styryl dye or the like, if necessary.

The photographic light-sensitive material of the present invention contains, as a whitening agent, for example, stilbene, triazine, oxazole and coumarin-based compounds in a non-photosensitive photographic component layer: as an ultraviolet absorber, for example, benzotriazole, thiazolidine, cinnamate System compound: It may contain various photographic filter dyes known as light absorbers. In addition to the compounds used in the present invention, if necessary, other slipping agents or anti-adhesion agents, for example, US Pat.
Amides or esters of fatty acids and polyesters as described in U.S. Pat. No. 5,042,399, 3,121,060 and British Patent No. 14466304.
British Patent Nos. 1,320,564 and 1,320,5
No. 65, U.S. Pat. No. 3,121,060, and water-insoluble materials as described in U.S. Pat.
No. 286, may contain a surfactant.

The photographic light-sensitive material of the present invention can be used as an antistatic agent in photographic constituent layers such as a photographic emulsion layer, in particular, in an antistatic layer provided on the outermost side of the photographic material. , 297, 2,972,535,
2,772,536, 2,972,537, 2,972,538, 3,033,679, 3,072,484, 3,262,807, and 3 No. 3,525,621, No. 3,615,531, No. 3,630,743, No. 3,653,906, No. 3,655,384, No. 3,655,386, and British Patent No. 1,222,154, 1,235,0
No. 2,973,263, U.S. Pat.
For example, hydrophobic polymers such as those described in US Pat. No. 48,482, US Pat.
Biguanide compounds as described in US Pat.
For example, US Patent Nos. 2,639,234 and 2,64
9,372, 3,201,251, 3,45
7,076, for example, using a sulfonic acid type anionic compound as described in US Pat. No. 3,317,344.
Phosphate esters and quaternary ammonium salts as described in U.S. Pat. Nos. 3,882,157 and 3,982,651 can be used.
Nos. 3,399,995 and 3,549,369
No. 3,564,043, a cationic compound such as described in U.S. Pat.
95, for example, an amphoteric compound, such as described in U.S. Pat. No. 3,736,268, and the like, for example, U.S. Pat.
Complex compounds such as described in US Pat. No. 647,836 can be used, for example, in US Pat.
Organic salts such as those described in, for example, U.S. Pat.

The present invention can be applied to all kinds of photographic light-sensitive materials regardless of black and white or color. Silver halide emulsions include ortho emulsions, panchromatic emulsions, infrared emulsions, X-ray and other invisible light recording emulsions, color photographic emulsions such as emulsions containing color-forming couplers, emulsions containing dye developers, and dyes that can be bleached. The emulsion layers include various silver halide photographic emulsions. Color photographic emulsions may contain 2 or 4 equivalents of a color forming coupler. For example, an open-chain ketomethylene yellow-forming coupler such as a benzoylacetoanilide-based or pivaloylacetoanilide-based coupler,
Magenta color-forming couplers such as pyrazolone-based or indazolone-based, and cyan-forming couplers such as phenol-based or naphthol-based 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, U.S. Pat. No. 054, 2,449,966, 2,455,170, 2,600,788, 2,983,608, 3,148,062, etc. For example, a coupler capable of suppressing the separation described in Japanese Patent No. 3,227,554 can be used.

The backing layer containing carbon black in the backing layer is used in a pre-bath during development.
It is designed so that it is removed when it enters the washing process. The pre-bath is usually an aqueous alkaline solution having a pH of 9.25 ± 0.10. The alkaline aqueous solution may contain a water-soluble organic solvent. The binder used for the backing layer is a binder that is soluble or swellable in an aqueous alkaline solution. Specific examples include hydroxypropylmethylcellulose hexahydrophthalate, cellulose acetate hexahydrophthalate, hydroxypropylmethylcellulose acetylphthalate, and polyacrylate.

As a method for adding the amine compound to the cellulose acetate film in the present invention, especially when the amine compound is used as a support for a silver halide photographic light-sensitive material, it may be incorporated into a processing step of the light-sensitive material. Incorporation into the processing steps includes the production of the support, the application of the photosensitive layer,
It is that the compound for improving stability of the present invention is not present in various stages from storage of the finished photosensitive material to photography, and therefore, this compound affects the characteristics of the photosensitive material such as photographic performance. There is no such thing. This advantageously increases the range of compound selection. In addition, depending on the properties of the compound, the concentration, auxiliary,
The applicability is widened and advantageous in that the method of dispersing or dissolving and the selection of coexisting substances can be devised. In addition, this method is not limited to a specific photosensitive material, it can be applied simultaneously to various photosensitive materials having a cellulose ester as a support, and of course, it may be a photosensitive material of any manufacturer. A great advantage. It is also an advantage of the present invention that the incorporation into a processing step can achieve the purpose of stabilization without adding a new step.

The treatment bath to contain the compound of the present invention is as follows:
Any treatment bath may be used as long as an appropriate addition method is employed depending on the properties of the compound. However, it is natural that the processing bath near 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 rinsing bath of the water-saving type processing, and the stable bath of the anhydrous washing type processing. Instead of adding to the existing final bath, a new treatment step containing this compound may be provided as a second final bath next to the existing final bath. The photographic light-sensitive material is subjected to appropriate processing such as development depending on the type. In the present invention, a processing step peculiar to the photosensitive material is called a processing bath, and a processing bath newly provided between the peculiar processing and drying is called a post-processing bath. Various methods for adding the compound are used depending on the properties of the compound. The idea is roughly divided into (1) a liquid bath in the form of a uniform phase,
(2) Dispersion is classified into two types.

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 obtain a sufficiently concentrated aqueous solution. Therefore, it is preferable to increase the solubility by using a dissolution aid in combination.

The latter is used in the form of an oil / water dispersion using a solvent having the property of dissolving the compound. The former dissolution aids include (a) phenyl-substituted lower alkyl alcohols such as benzyl alcohol, phenylethyl alcohol, and phenylpropyl alcohol; (b) ethylene glycol, triethylene glycol,
Aliphatic polyalcohols comprising lower alkyl groups such as hexylene glycol, polyethylene glycol and polypropylene glycol (c) alkanolamines such as ethanolamine, triethanolamine and pentanolamine (d) methanol, ethanol, propanol, butanol, Aliphatic alcohols such as ethylhexyl alcohol (c) Water-soluble low molecular weight organic solvents such as acetone, methyl cellosolve, cellosolve, and methyl ethyl ketone (However, solvents belonging to (d) and (e) may adversely affect the support. However, an amount that slightly swells the support is advantageous because it promotes the incorporation of the compound of the present invention.) Although not a solvent, a small amount of a surfactant is added. Possibly by micelle shape It can also increase the solubility by solubilization with.

(F) Nonionic surfactants such as polyethylene glycol nonylphenyl ether (n = 10 to 100) and polyethylene / propylene glycol (Pluronics, etc.) (g) Alkyl benzenes such as sodium dodecylbenzenesulfonate Anionic surfactants represented by carboxylate salts such as sulfonic acid, alkyl sulfate, sodium stearate, sodium palmitate and sodium laurate (h) Various cationic surfactants of quaternary ammonium, pyridinium and phosphonium type. In order to treat the compound of the present invention in the form of a dispersion, the following high-boiling solvent is used as a dispersion medium. That is, a phosphate compound represented by the following general formula (P):

[0114]

Embedded image

In the formula, R, R ₁ and R ₂ represent an alkyl group, a cycloalkyl group or an aryl group, each of which may be the same or different.

For example, tricresyl phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, dimethoxyethyl phthalate, glycerol triacetate, o-,
Or compounds such as p-tolueneethylsulfonamide, butylphthalylbutylglycolate, ethylphthalylethylglycolate, and methylphthalylethylglycolate. The compound is dissolved in these organic solvents, and if necessary, a solubilizing agent such as propanol, ethanol, or ethyl acetate is added, and an appropriate surfactant as shown in (f), (g) and (h) is used. To make an oil / water dispersion. In the above-mentioned homogeneous aqueous solution or dispersion, a bactericidal agent, a fungicide, a pH regulator, a pH buffer, a formaldehyde or its precursor, a fluorescent brightener, a draining surfactant, an image hardening agent, etc., which will be described later, are used. Is added. The various dissolution aids and dispersion aids described above can be used alone or in combination. Further, an even higher concentration solution can be prepared by an appropriate combination from the intermediate between the homogeneous liquid phase type and the dispersion type, that is, (a)-(h).

Accordingly, an appropriate amount of the auxiliary agent (a)-(h) is selected depending on the properties of the compound. That is, (a)-(e) is 0.1-300% with respect to water, preferably (a) 0.2-5%, (b) 0.3-200%,
(C) 0.3 to 100%, (d) and (e) are 0.2 to 1
50%, 0.1 to 10% for (f), (g) and (h), and 0.5 to 200% for the high boiling point solvent. The higher the compound concentration, the better, but it depends on the nature. Generally, it is desirable that the amount of the amine compound is 0.2 to 100 g, preferably 0.5 to 20 g per liter of the liquid bath. In the case of a thick liquid such as 100 g / liter, it is convenient to perform a coating process instead of the immersion process. When the addition amount of the amine compound in the present invention is less than this, the deterioration preventing effect is not sufficiently exhibited, and when the adding amount is increased, the deterioration preventing effect gradually increases, but when the adding amount exceeds a certain amount, the deterioration preventing effect is increased. Not only decreases, but also exceeds the compatibility limit,
Since it becomes cloudy and bleeds on the product surface, it is not appropriate to add more than the above amount.

The treatment bath time of the compound of the present invention is set in accordance with the schedule of the treatment step designed. That is,
Color printing paper processing of rapid processing type (for example, Fuji Photo Film CP25Q, CP40FA, CP43FA)
Is applied in 60 to 80 seconds in accordance with the final rinsing step. Color negative film CN-16
When applied to the processing, the image stabilizing bath is performed for 60 seconds. Further, some color photographic papers and black-and-white films are subjected to a drying step after a non-water-saving type washing step, and do not have a liquid bath step similar to a stabilizing bath. For such a treatment, it is preferable to provide a liquid bath step of the present invention having the composition described above. 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, it is about 20 seconds to 1 minute. For example, when applied to the processing step of microfilm, if the rinsing step is a three-tank processor, the final rinsing tank may be switched to the liquid bath step of the present invention to provide a two-tank rinsing processing plus a base stabilizing bath. Good. Even when the present invention is performed in the form of a thick liquid application process, it goes without saying that the processing step time is 1 to 2 seconds, regardless of the above.

In the photographic processing of the light-sensitive material of the present invention, for example, Research Disclosure 1 is used.
No. 76, pages 28 to 30 (RD-17643), any of known methods and known processing solutions can be applied. This photographic processing may be either photographic processing for forming a silver image (black-and-white photographic processing) or photographic processing for forming a dye image (color photographic processing), depending on the purpose. Processing temperature is usually 18 ° C to 50 ° C
Chosen between. The developer used for black-and-white photographic processing can contain a known developing agent. As the developing agent, dihydroxybenzenes (for example, hydroquinone), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone), aminophenols (for example, N-methyl-p-aminophenol) may be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, and the like, and further, if necessary, a solubilizing agent, a color tone agent, a development accelerator (for example, a quaternary salt, Hydrazine, benzyl alcohol), a surfactant, an antifoaming agent, a water softener, a hardener (for example, glutaraldehyde), a viscosity imparting agent, etc. The light-sensitive material of the present invention and black-and-white reversal photographic processing include: Any of the known processing methods for forming a positive silver image by reversal development can be used. Rukoto can. Processing temperature is usually 18
It is selected between ℃ and 65 ℃, but may be lower than 18 ℃ or higher than 65 ℃.

The reversal development processing usually comprises the following steps.
First development-washing-bleaching-cleaning-overall exposure-second development-fixing-washing-drying. The developer used in the black-and-white photographic processing of the first development can contain a known developing agent. Developing agents include dihydroxybenzenes (eg, hydroquinone), 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone), aminophenols (eg, N-methyl-p-aminophenol), 1-phenyl-3-pyrazolin , Ascorbic acid, and a heterocyclic compound in which a 1,2,3,4-tetrahydroquinoline ring and an indole ring described in U.S. Pat. No. 4,067,872 are condensed, or the like, alone or in combination. it can. In particular, it is preferable to use pyrazolidones and / or aminophenols together with dihydroxybenzenes. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants and the like, and further, if necessary, a dissolution aid, a color tone agent, a development accelerator, a surfactant, an antifoaming agent, It may contain a water softener, a hardener, a viscosity imparting agent and the like. The light-sensitive material of the present invention is usually processed with a developer containing 0.15 mol / l or more of sulfite ion as a preservative.

The pH is preferably 8.5 to 11, particularly preferably 9.5 to 10.5. NaS is used as the first developer.
A silver halide solvent such as CN is used in an amount of 0.5 to 6 g / liter. As the second developer, a general black-and-white developing solution can be used. That is, it has a composition obtained by removing the silver halide solvent from the first developer. The pH of the second developer is preferably 9 to 11, particularly preferably 9.5 to 10.5.
Is preferred. A bleaching agent such as potassium dichromate or cerium sulfate is used in the bleaching solution. Thiosulfate and thiocyanate are preferably used for the fixing solution, and may contain a water-soluble aluminum salt as necessary.

As a special type of development processing, a method may be used in which a developing agent is contained in a light-sensitive material, for example, an emulsion layer, and the light-sensitive material is processed in an aqueous alkaline solution to perform development. Among the developing agents, hydrophobic ones are described in Research Disclosure 169 (RD-16928), US Pat. No. 2,739,890, British Patent No. 813,253 or West German Patent No. 1,547,763. It can be included in the emulsion layer by various methods described above. As the fixing solution, those having a commonly used composition can be used. As a fixing agent, in addition to thiosulfate thiocyanate,
An organic sulfur compound known to have an effect as a fixing agent can be used. The fixer may contain a water-soluble aluminum salt as a hardener.

As a method for diffusing and infiltrating the compound of the present invention, a method of adding the compound to a processing bath can be mentioned. Here, the processing bath includes (A) a color developing bath, (A) a black-and-white developing bath, and (C) a bleaching bath. (D) fixing bath, (e) bleach-fixing bath, (f) washing bath, (g) stabilizing bath, (h) pre-hardening bath, (g) various accelerating baths, etc. The compositions of the processing solutions used in (a) to (g) are shown below, taking the case of a silver halide color photographic material as an example. The color developing solution used in (A) is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used. Typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3-methyl-4-amino-N-diethylaniline. 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 sulfates, hydrochlorides or p-toluenesulfonates thereof. These compounds can be used in combination of two or more depending on the purpose. The color developer is
Includes pH buffers such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromide, iodide, benzimidazoles, benzothiazoles or mercapto compounds It is common. Further, if necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, and triethylenediamine (1,4-diazabicyclo [2,2,2] octane) 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 agent such as sodium boron hydride, 1
An auxiliary developing agent such as -phenyl-3-pyrazolidone,
Viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic 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 salts thereof can be mentioned as representative examples.

When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer used in (A) includes known hydroxyphenols such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, and aminophenols such as N-methyl-p-aminophenol. Black and white 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 replenishing amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the light-sensitive material, and is reduced to 500 liters by reducing the bromide ion concentration in the replenishing solution.
It can be less than ml. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Further, processing in two successive bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. Examples of the bleaching agent include iron (III), cobalt (III), chromium (IV), and copper (II).
Compounds of polyvalent metals such as peracids, quinones, and nitro compounds are used. Typical bleaching agents are ferricyanide; dichromate; iron (III) or cobalt (II
Organic complex salts of I), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol etheraminetetraacetic acid, or citric acid and tartaric acid And persulfates; bromates; permanganates; nitrobenzenes, and the like. Among these, iron (III) complex salts of aminopolycarboxylic acid, such as iron (III) complex salt of ethylenediaminetetraacetate, and persulfate are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 5.5 to 8, but the processing can be carried out at a lower pH in order to speed up the processing. .

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent 1,290,812, JP-A-53-95,630,
Research Disclosure No. 17,129 (1
A compound having a mercapto group or a disulfide bond as described in JP-A-50-140,12
No. 9; thiazolidine derivatives described in US Pat.
Thiourea derivatives described in JP-A-6-561;
Iodide salts described in 6,235; West German Patent No. 2,74
8,430; polyamine compounds described in JP-B-45-8836; bromide ions, and the like. Among them, a compound having a mercapto group or a disulfide group is preferable in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-9563.
Compounds described in No. 0 are preferred. Further, U.S. Pat.
Compounds described in 552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. The use of thiosulfates is generally used, and particularly, ammonium thiosulfate is used. Is the most widely used. As a preservative of the bleach-fixing solution, a sulfite, a bisulfite, a sulfinic acid or a carbonyl bisulfite adduct is preferable. The silver halide color photographic light-sensitive material of the present invention generally undergoes a washing and / or stabilizing step after desilvering. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Of these, the relationship between the number of washing tanks and water volume in the multi-stage countercurrent method is described in the Journal of the Society of Motion Pictu
re and Television Engineers Vol. 64, p. 248
-253 (May 1955).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere 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 ions and magnesium ions described in Japanese Patent Application No. 61-131,632 can be used very effectively. Also, Japanese Unexamined Patent Publication No.
No.-8,542, isothiazolone compounds, thiabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., written by Hiroshi Horiguchi, "Chemistry of Bacterial and Fungicides" It is also possible to use the disinfectant described in "Sterilization, disinfection and fungicide technology of microorganisms", edited by the Japanese Society of Antimicrobial and Fungicide, "Encyclopedia of Antifungal and Antifungal Agents".

The pH of the washing water in the processing of the light-sensitive material of the present invention is 4-9, preferably 5-8. Washing water temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the application, and the like.
Preferably, a range of 25-40 ° C. for 30 seconds-5 minutes is selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilizing process, JP-A-57-8543 and JP-A-57-8543 are used.
All known methods described in JP-A Nos. 8-14,834 and 60-220,345 can be used. Further, after the above-mentioned water washing treatment, a stabilization treatment may be further carried out. For example, a stabilizing bath containing formalin and a surfactant used as a final bath of a color light-sensitive material for photography can be mentioned. . Various chelating agents and fungicides can also be added to this stabilizing bath.

A preferred mode of use of the present invention is a case where the present invention is applied to any of the above-mentioned water-saving type washing baths (called rinsing baths) and stabilizing baths. Alternatively, these baths may be followed by a second rinsing or stabilizing bath. The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.

The silver halide color light-sensitive material may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, US Pat.
No. 2,597, the indoaniline-based compound;
No. 342,599, Research Disclosure 1
Nos. 4,850 and 15,159, Schiff base compounds, aldol compounds described in 13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and JP-A-53-135,628. The urethane-based compounds described in (1) can be cited.

Further, the silver halide color light-sensitive material may contain various 1-phenyl-3-pyrazolidones as needed for the purpose of accelerating color development. Typical compounds are described in JP-A-56-64339 and JP-A-57-14.
No. 4,547, and No. 58-115,438. Various processing solutions in the present invention are 10 ° C to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to. Further, in order to save silver in the photosensitive material, a process using cobalt intensification or hydrogen peroxide intensification described in West German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be performed.

Although the method of adding and blending the raw materials in the present invention has been described above, the present invention is not limited by these methods.

[0133]

The present invention is demonstrated in the following examples, but is not limited thereto. Example 1 As an example of a method of adding to a dope, an amine compound A-
1, A-2, A-3, A-4, A-8, A-9, A-1
5, A-24, A-31, A-36, A-42, A-4
4, A-53, A-55, A-72, A-73, B-
1 and B-13 were added, respectively, to prepare the following compositions. Cellulose triacetate 100 parts by weight Triphenyl phosphate 16 parts by weight Amine compound 1 part by weight Methylene chloride 270 parts by weight Butanol 7 parts by weight Methanol 70 parts by weight

The above composition is put into a closed container, and is stirred and completely dissolved under pressure at 80 ° C.
The dope was then filtered, cast on a rotating 30 cm diameter jacketed drum while cooling and maintaining the temperature at 25 ° C. Since the drum is required to have both heat conductivity, corrosion resistance, and flatness, the surface of the SB material is plated with a Ni layer of about 50 μm and hard chrome plated twice with a thickness of about 40 μm.
Super mirror-polished one of 01-0.05S was used. At this time, the drum is supplied with cold water through the jacket and kept at a surface temperature of 0 ° C. The casting speed was fixed at 3 m / min, and the film was peeled off via a peeling roll at a position rotated 270 degrees in the casting direction from the casting position, and 3.15 m.
The base is scraped off at a rate of / min and cast 5% in the casting direction. The peeled base was fixed on both sides and dried with hot air at 70 ° C. to obtain a film having a thickness of 140 μm. As a comparative example, the composition was prepared by removing the amine compound from the above composition, that is, by the following composition. Cellulose acetate 100 parts by weight Triphenyl phosphate 16 parts by weight Methylene chloride 270 parts by weight Butanol 7 parts by weight Methanol 70 parts by weight A dope having the above composition is formed in the same manner as described above to form a film having a thickness of 14
A 0 μm film was obtained as a comparative example.

Next, a method of evaluating the effect of preventing deterioration will be described. 2.0 g of a sample is placed in a 15 ml glass container, and 90 g
After humidity control for 24 hours at 100 ° C. and a relative humidity of 100%, the container is sealed, and wet heat treatment is performed at 90 ° C. and a relative humidity of 100%. In the case of a single film, the wet heat treatment time is 120 hours, and in the case of a silver halide photographic light
Time. In the case of a polarizing plate protective film provided with a pressure-sensitive adhesive layer, the time is set to 80 hours.

The obtained sample after the treatment is immersed in a methyl alcohol bath at 40 ° C. for 30 minutes. This is repeated four times for rinsing to remove additive components other than cellulose acetate contained in the sample. After removal, vacuum drying is performed at 50 ° C. for 15 hours. In the case of a support of a silver halide photographic light-sensitive material, the emulsion layer is removed before the main rinsing operation. That is, the emulsion layer is immersed overnight in a 1% aqueous solution of a proteolytic enzyme (Biooprase SP4, Nagase Seikagaku Corporation) and washed well with water to remove the emulsion layer. Thereafter, a rinsing operation and drying are performed in the same manner.

An absolutely dried 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 is refrigerated at 5 ° C. until measurement, filtered through a PTFE filter (Mirex LS, Millipore) having a pore size of 0.5 μm, and then the relative viscosity of the solution is measured. That is, about 10 ml
Is placed in a Ubbelohde viscometer (flowing time for water at 30 ° C. for about 30 seconds), and the flowing time is measured. The flow time obtained for the sample solution is reduced by the flow time obtained by measuring only the trifluoroacetic acid solvent to obtain the ratio of the flow time of the solution to the flow time of the solvent. This is the relative viscosity, which is a value corresponding to the degree of polymerization of the sample.

Evaluation of the effect of preventing deterioration was made by gradually decreasing {(relative viscosity) -1} of the sample after the wet heat treatment, that is, the specific viscosity, by {(relative viscosity) -1} of the sample before the wet heat treatment. The ratio of the specific viscosity after the treatment to that before the treatment is expressed in percentage. This is defined as a viscosity retention rate (%) and is used as an index of a decrease in the degree of polymerization of the sample. That is, viscosity retention rate (%)
Is closer to 100, indicating that the degree of polymerization does not decrease even by the wet heat treatment, indicating that the effect of preventing deterioration is greater. Although the present evaluation method is significantly harsher than the actual storage conditions, it is possible to quickly evaluate the effect of preventing deterioration under the actual storage conditions. Further, being an index of a decrease in the degree of polymerization corresponds to being an index of a decrease in important physical properties (such as bending strength and tear strength) of the film. This indicates that deterioration of the film physical properties is unlikely to occur. The results obtained are summarized in Table 4 below.

Comparative Example No. The sample not subjected to the deterioration prevention method shown in FIG. 19 has a low viscosity retention (%) of 30 and shows that the degree of polymerization is significantly lower than that before the wet heat treatment. . As shown in Nos. 1 to 18, the viscosity retention was remarkably large, indicating that the degree of polymerization did not decrease even after the wet heat treatment. In particular, the pKa having a pKa of 5 or more and 8 or less. In the case of the amine compounds of 1 to 5, the effect of preventing deterioration is remarkable. No. 3 is a tertiary amine having a molecular weight of 300 or more and having substantially no volatility. It can be seen that in the cases of Nos. 1 to 4 and 16, the effect of preventing deterioration is remarkable. Further, the compound having a molecular weight of 200 or less per basic group is No. 1. It is also clear that the deterioration prevention effect is remarkable also in the case of 17-18. Accordingly, a cellulose triacetate film having a remarkable effect of preventing deterioration could be obtained by this method. The silver halide photographic light-sensitive material obtained by using this film as a support has no problem in transparency, coloring, and photographic properties, and also hinders its use as a polarizing plate protective film, an optical filter, and a release film. Was not found. That is, it was found that this film could be sufficiently used for these uses, and that the effect of preventing deterioration was recognized.

Example 2 As an example of a method of adding the compound to a layer adjacent to the film, first, an amine compound A was added to a polarizing plate protective film.
-1, A-2, A-3, A-4, A-8, A-9, A-
15, A-24, A-31, A-36, A-42, A-
44, A-53, A-55, A-72, A-73, B-
1 and B-13 were each added by the following method and examined.

An acrylic adhesive containing 2-ethylhexyl acrylate as a main component and vinyl acetate and maleic anhydride as components is dissolved in a mixed solvent of toluene, benzene and ethyl acetate to form a 5% solution. Next, 10 kinds of solutions were prepared by adding 0.03% of the above 10 kinds of amine compounds to the solution. As a comparative example, a composition to which no amine compound was added was prepared.
The solution was applied on a polyethylene terephthalate film with a comma coater and dried to form an adhesive layer having a thickness of 30 μm. The pressure-sensitive adhesive layer was transferred to both sides of a 90 μm cellulose triacetate film prepared by the production method described in JP-A-62-115035. Table 4 summarizes the results of evaluating the effect of preventing the deterioration of the film.

As shown in Table 4, a remarkable deterioration preventing effect was recognized by the addition of the amine compound as in Example 1.
That is, the effect of preventing deterioration was also observed when added to the adjacent layer, as in the case where it was added to the film itself.

Example 3 As an example of a method of adding a film to a layer adjacent to the film, a color positive film for cinema was next used to prepare amine compounds A-1, A-2, A-3, A-4, and A-8. , A-
9, A-15, A-24, A-31, A-36, A-4
2, A-44, A-53, A-55, A-72, A-7
3, the following compositions were prepared for B-1 and B-13, respectively, and coating was performed.

First, 9.6 parts by weight of carbon black 20 parts by weight of hydroxypropylcellulose hexahydrophthalate 20 parts by weight of an amine compound on a 132 μm triacetyl cellulose film prepared by the production method described in JP-A-62-115035 10 parts by weight Acetone 600 parts by weight Methyl cellosolve 150 parts by weight Methanol 200 parts by weight A coating solution having the above composition was applied at 35 cc / m ^{2 and} dried at 90 ° C. for 3 minutes to form a backing layer. 1 to No. 11 was formed.

Next, No. 1 to No. Based on 11, 275 parts by weight of gelatin 12.1 parts by weight of formaldehyde 100 parts by weight of amine compound 82.4 parts by weight of salicylic acid 4372 parts by weight of methanol 22200 parts by weight of methylene chloride 31,000 parts by weight of water 626 parts by weight 20 cc / m ^{2 was} applied and dried at 90 ° C. for 3 minutes to form an undercoat layer.

Next, a photosensitive material layer was provided on the undercoat layer. The photosensitive material layer was applied in the same manner as the photosensitive material layer described in Example 1 of Japanese Patent Application No. 2-264445 to form a multilayer color photosensitive material. Note that the first, third, fifth and sixth layers are arranged in the order of proximity to the support.
The layer is an intermediate layer and the seventh layer is a protective layer. Each sample is 35
After slitting to a width of mm, a silver halide photographic material having a length of 5 m was obtained. In addition, a composition was prepared by coating the composition of the back and undercoat layers except for the amine compound, and the photosensitive material layer was similarly coated thereon to prepare a comparative example.

Each sample obtained as described above, that is, No. Each of Nos. 1 to 11 was photographed and developed using an automatic developing machine ECP-100 (Otomo Seisakusho) in accordance with ECP-2A, a commercially available color positive film processing prescription for movies. The line speed was 75 m / min. Table 1 shows the processing steps of ECP-2A.

[0148]

[Table 1]

The effect of preventing deterioration of the obtained treated sample was evaluated. The results are summarized in Table 4.

As shown in Table 4, similar to Example 1, the addition of the amine compound showed a remarkable effect of preventing deterioration.
That is, the effect of preventing the amine compound of the present invention from deteriorating was also observed when it was added to an adjacent layer.

Example 4 As an example of the method of adding the compound to the layer adjacent to the film, the following method was applied to a multilayer color negative photosensitive material.
2, A-3, A-4, A-8, A-9, A-15, A-
24, A-31, A-36, A-42, A-44, A-
53, A-55, A-72, A-73, B-1, B-1
The following composition was applied to the amine compound of No. 3.

A back layer having the following composition was provided on a 132 μm triacetyl cellulose film prepared by the production method described in JP-A-62-115035 to provide a base for photosensitive materials. (Back layer composition) First layer Cellulose diacetate 0.1 g / m ² Ethylene glycol 0.08 {Compound I 0.5}

[0153]

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Amine compound 0.25 {Second layer Cellulose diacetate 0.32 g / m ² Aerosil 0.02 {(n) C15H31COOC40H81 (n) 0.02} Poly (methyl methacrylate / styrene) (molar ratio 95: 5) , Average particle size 2.0 μm) 0.01 g / m ² amine compound 0.25%

Next, an undercoat layer having the following composition was provided on the side opposite to the back layer. Cellulose diacetate 0.1 g / m ² gelatin 0.05 〃 formaldehyde 0.004 ジ エ チ ル diethyl citrate 0.003 〃 salicylic acid 0.015 〃 amine compound 0.5 ０．５ A composition with the composition removed was prepared and used as a comparative example.

Next, a photosensitive material layer was provided on the undercoat layer. The photosensitive material layer was coated in the same manner as the photosensitive material layer described in Example 1 of JP-A-2-93641, to prepare a sample as a multilayer color negative photosensitive material. Note that the layer structure is such that the first layer is an antihalation layer,
The layer is an intermediate layer, the third to thirteenth layers are sensitizer layers, and the fourteenth to fifteenth layers are protective layers. After slitting each sample to a width of 35 mm, a silver halide color photographic material having a length of 5 m was obtained.

Next, each of the obtained samples, that is, 1 to 1
Sample No. 1 was photographed and subjected to the following development processing. Processing method Step Processing time Processing temperature Replenisher tank capacity Color development 3 minutes 15 seconds 38 ° C 15 ml 20 liter Bleaching 6 minutes 30 seconds 38 ° C 10 ml 40 liter Rinse 2 minutes 10 seconds 35 ° C 10 ml 20 liters Fixed 4 minutes 20 seconds 38 ° C 20ml 30 liters Rinse (1) 1 minute 05 seconds 35 ° C 10 liter countercurrent piping from (2) to (1). Washing with water (2) 1 minute 00 seconds 35 ° C 20 ml 10 liters Stabilization 1 minute 05 seconds 38 ° C 10 ml 10 liters Drying 4 minutes 20 seconds 55 ° C Replenishment amount per 350 cm ² Next, the composition of the processing solution is described.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.04 9.9 Potassium carbonate 30.0 30.0 Potassium bromide 1.4-Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 3.6 4- (N-ethyl-N-β-hydroxyethyl) amino ) -2-Methylaniline sulfate 4.5 7.2 Add water 1.0 liter 1.0 liter pH 10.05 10.10 (Bleaching solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid Ferric ammonium trihydrate 100.0 140.0 Ethylenediaminetetraacetic acid disodium salt 10.0 11.0 Ammonium bromide 140.0 180.0 Ammonium nitrate 30.0 40. By adding aqueous ammonia (27%) 6.5ml 2.5ml Water 1.0 l 1.0 l pH 6.0 5.5

(Fixing solution) Mother liquor (g) Replenisher (g) Ethylenediaminetetraacetic acid disodium salt 0.5 1.0 Sodium sulfite 7.0 12.0 Sodium bisulfite 5.0 9.5 Aqueous ammonium thiosulfate solution (70 170.0 ml 240.0 ml Add water 1.0 liter 1.0 liter pH 6.7 6.6 (wash water) Common for mother liquor and replenisher Tap water is replaced with H-type strongly acidic cation exchange resin (Rohm and Haas) (Amberlite IR-120B, manufactured by Aztec Co., Ltd.) and an OH type anion exchange resin (Amberlite IR-400) were passed through a mixed-bed column to reduce the calcium and magnesium ion concentrations to 3 mg / L or less. Then, 20 mg / l of sodium diisocyanurate and 1.5 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5. (Stabilizer) Mother liquor (g) Replenisher (g) Formalin (37%) 2.0 ml 3.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 0.45 Disodium ethylenediaminetetraacetate 0.05 0.08 Add water 1.0 liter 1.0 liter pH 5.0-8.0 5.0-8.0 The processing machine used is a cine-type automatic made by Fuji Photo Film Co., Ltd. A developing machine FNCP-900 was used. The degradation prevention effect of the obtained photographic film sample was evaluated, and the results are shown in Table 4.

As shown in Table 4, similar to Example 1, the addition of the amine compound showed a remarkable effect of preventing deterioration.

Example 5 As an example of the method of adding to a layer adjacent to the film, next, a microfilm of a black-and-white light-sensitive material was used as an example.
A-1, A-2, A-3, A-4, A-8, A-9, A
-15, A-24, A-31, A-36, A-42, A
-44, A-53, A-55, A-72, A-73, B
The following compositions were prepared and applied to amine compounds B-1 and B-13.

A backing layer having the following composition was provided on a 127 μm cellulose triacetate film prepared by the production method described in JP-A-62-115035 to prepare a support for a photosensitive material. (Back layer composition) First layer Compound I 0.06 g / m ² amine compound 0.25 g / m ² Second layer Cellulose diacetate 0.2 g / m ² Aerosil 0.014 g / m ² Amine compound 0.25 g / m ^Two

Next, an undercoat layer having the following composition was provided on the side opposite to the back layer. Cellulose diacetate 0.1 g / m ² gelatin 0.05 〃 formaldehyde 0.004 ジ エ チ ル diethyl citrate 0.003 〃 salicylic acid 0.015 ア ミ ン amine compound 0.5 〃 A composition with the composition removed was prepared and used as a comparative example.

Next, a light-sensitive material layer was provided on the undercoat layer.
That is, 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% phosphoric acid aqueous 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 179 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

The solution II and the solution III were simultaneously added to the well-stirred solution I over 45 minutes, and when the total amount of the solution II was completely added, a cubic monodispersed emulsion having an average particle size of 0.28 μm was finally obtained. Was. At this time, the pAg value in the mixing vessel was always 7.
It was added while adjusting to 50. The solution IV
Was added over 5 minutes from 7 minutes after the start of the addition of solution II. After the completion of the addition of the solution II, it was washed and desalted by a sedimentation method and then dispersed in an aqueous solution containing 100 g of inert gelatin. To this emulsion were added 34 mg of sodium thiosulfate and 34 mg of chloroauric acid tetrahydrate per mole of silver, respectively.
The g value was adjusted to 7.0 and 8.9 (40 ° C.), respectively, and then subjected to a chemical sensitization treatment at 75 ° C. for 60 minutes to obtain a surface latent image type silver halide emulsion. An antihalation (AH) layer, AH-1, an emulsion layer and a protective layer were sequentially coated on the support to form a sample. <AH-1> Gelatin 1.7 g / m ² Polymer mordant (described below) 167.8 mg / m ² Dye E (〃) 72.4 mg / m ² Dye F (〃) 68.5 mg / m ² Dye G (〃) ) 68.5 mg / m ²

[0166]

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[0167]

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<Emulsion Layer> Silver halide emulsion (in terms of silver) 1700 mg / m ² Sensitizing dye A 238 described below {5-methylbenzotriazole 4.1} sodium dodecylbenzenesulfonate 5} 1,3-divinylsulfonyl- 2-propanol 56 ナ ト リ ウ ム sodium polystyrene sulfonate 35

[0169]

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<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} Compound II (described below) 15}

[0171]

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[0172] Each sample was photographed and used in the US Allen Product
s Co., Ltd. F-10 deep tank automatic developing machine, commercially available general-purpose processing solution for microfilm (FR-5, manufactured by FR Chemicals, USA)
37 developer) under the processing conditions shown in Table 2 below.

[0173]

[Table 2]

Table 4 summarizes the results of evaluating the effect of preventing deterioration of the obtained photographic film samples. As in Example 1, a remarkable deterioration preventing effect was observed by the addition of the amine compound.

Example 6 A commercially available cinema positive film (Fujicolor Positive LP. No. 881) using cellulose triacetate as a support
6) was exposed and developed according to the processing step specifications according to the ECP-2A processing recipe already shown in Table 1. That is, all the specifications except the stabilizing bath followed the specification. A-1 and A for the stabilizing bath
-2, A-3, A-4, A-8, A-9, A-15, A
-24, A-31, A-36, A-42, A-44, A
-53, A-55, A-72, A-73, B-1, B-
13 amine compounds were prepared with the following composition, and 38
The treatment was performed at 40 ° C. for 40 seconds. Triphenyl phosphate 30 g Amine compound 20 g Formalin (37% solution) 7.5 ml Hexylene glycol 130 g Isopropanol 400 g Water 400 g Formalin (37% solution) 7.5 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 1.0 g Ethylenediaminetetraacetic acid 2-sodium salt 0.05 g A liquid having a composition obtained by removing the amine compound from the above composition was prepared and treated at the same temperature and for the same time as Comparative Example.
In preparing the stabilizing bath, first, compounds A, B, C and triphenyl phosphate are sufficiently mixed, and isopropanol, hexylene glycol and nonionic activator are added thereto, and the mixture is stirred. The ingredients were added.

Table 4 summarizes the results of evaluating the effect of preventing deterioration of the obtained developed photographic samples. The same addition of an amine compound as in Example 1 was also possible with the treatment bath as described above, and a remarkable effect of preventing deterioration was confirmed by the addition.

Example 7 Commercially available color negative film using cellulose triacetate as a support (Fujicolor Negative Super HG400)
Was photographed and developed according to the processing step specifications shown in Table 3 below.

[0178]

[Table 3]

The composition of each processing solution is shown below. (Color developing solution) Mother liquor (g) Replenisher (g) Diethyleneditriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.2 Sodium sulfite 4.0 4.0 9 Potassium carbonate 30.0 30.0 Potassium bromide 1.4-Potassium iodide 1.5 mg-Hydroxylamine sulfate 2.4 3.6 4- (N-ethyl-N-β-hydroxyethylamino) -2 -Methylaniline sulfate 4.5 7.2 Add water 1.0 liter 1.0 liter pH 10.05 10.10

(Bleaching solution) Common to mother liquor and replenisher (unit: g) Ferric ammonium diamine tetraacetate ammonium dihydrate 120.0 Disodium ethylene diamine tetraacetate 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching Accelerator 0.005 mol

[0181]

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Ammonia water (27%) 15.0 ml Add water 1.0 liter pH 6.3

(Bleach-fixing solution) Mother liquor (g) Replenisher (g) Ferric ammonium diaminetetraacetate ammonium dihydrate 50.0-Disodium ethylenediaminetetraacetate 5.0 1.5 Sodium sulfite 12.030 0.0 Ammonium thiosulfate aqueous solution (70%, weight / volume) 240.0 mL 400 mL Ammonia water (27%) 6.0 mL-Add water 1.0 L 1.0 mL pH 7.2 7.2

(Stabilizing bath) Amine compounds A-1, A-2,
A-3, A-4, A-8, A-9, A-15, A-2
4, A-31, A-36, A-42, A-44, A-5
3, A-55, A-72, B-1, and B-13 were prepared with the following compositions, respectively. Triphenyl phosphate 30 g Amine compound 20 g Hexylene glycol 107 g Isopropanol 400 g Water 400 g Formalin (37% solution) 2.0 mL Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 1.0 g Ethylenediaminetetraacetic acid 2-sodium salt 0. 05 g Further, a liquid having a composition excluding the amine compound from the above composition was prepared and provided for a comparative example. In preparing the stabilizing bath, first, the amine compound and triphenyl phosphate were sufficiently mixed, and isopropanol, hexylene glycol and nonionic activator were added thereto, followed by stirring, and finally, the remaining components were added with stirring. .

Table 4 summarizes the results of evaluating the effect of preventing deterioration of the obtained developed samples. As in Example 1, a remarkable deterioration preventing effect was observed by the addition of the amine compound.

Example 8 Using a microfilm processor made by Fuji Photo Film with a stabilizing bath by AG Guard [Mini Copy Auto Processor AP-5 (with AG guard bath)], a mini copy film HR- made by Fuji Photo Film was used. II was processed. The developer is Fuji Mini Copy Film Developer MD
The 270 fixer used was Fuji Mini Copy Film High Temperature Rapid Liquid Fixer MF515. The final bath was prepared as follows. That is, the amine compounds A-1, A-2, A-3, A-4, A
-8, A-9, A-15, A-24, A-31, A-3
6, A-42, A-44, A-53, A-55, A-7
2, B-1 and B-13 were prepared with the following compositions, respectively. Triphenyl phosphate 30 g Sodium dodecylbenzenesulfonate 5 g Amine compound 20 g Isopropyl alcohol 300 g Benzyl alcohol 10 g Triethylene glycol 100 g AG guard stock solution 300 g Water 200 g A composition prepared by removing the amine compound from the above composition was prepared and used as a comparative example. did. Not only the stabilization of the silver image by the AG guard but also the same evaluation as in Example 1 showed that the support was also robust. Table 4 summarizes the above results.

[0187]

[Table 4]

[0188]

According to the present invention, a cellulose acetate film having a small decrease in viscosity, that is, a decrease in polymerization degree even under severe conditions such as being sealed in a metal case or under high temperature and high humidity can be obtained. That is, weather resistance, moist heat resistance,
It is possible to obtain a cellulose acetate film having excellent resistance to dark heat and humidity and storage stability.

Claims (5)

(57) [Claims] 1. An amine compound having a pKa (negative logarithm of acid dissociation constant) of 4 or more in a cellulose acetate film or a cellulose acetate film having an adjacent layer on the cellulose acetate film or in the adjacent layer. A method for preventing deterioration of a cellulose acetate film. 2. The method for preventing deterioration of a cellulose acetate film according to claim 1, wherein the amine compound is a tertiary amine. 3. The method for preventing deterioration of a cellulose acetate film according to claim 1, wherein the total number of carbon atoms of the amine compound is 8 or more. 4. The cellulose acetate film according to claim 1, wherein the cellulose acetate film having an adjacent layer on the cellulose acetate film is a support for a silver halide light-sensitive material further having a silver halide emulsion layer. A method for preventing deterioration of a cellulose acetate film. 5. The cellulose acetate film according to claim 1, wherein an adjacent layer of the cellulose acetate film is an undercoat layer or a backing layer of a silver halide photosensitive material, or a pressure-sensitive adhesive layer of a polarizing plate. To prevent deterioration of