JPH05134348A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent a preservative from flowing into a developer liquid during development so as to extend the life of the developer liquid and to prevent environmental pollution by using a specified preservative. CONSTITUTION:This photographic sensitive material contains at least silver halide particles and a pendant-1 type dispersion medium. This pendant-1 type dispersion medium consists of a dispersion medium having covalent bonds with a preservative which satisfies the relation (concn. of preservative in insensitive layers/concn. of preservative in photosensitive layers)>=0.2. Further, the photographic sensitive material contains at least silver halide particles and a pendant-2 type preservative. This pendant-2 type preservative has reactive substituents. The reactive substituents react with functional groups of the dispersion medium in a manner that >=20% of the preservative produces covalent bonds with the dispersion medium when the photosensitive material is delivered and that the preservative satisfies the relation (concn. of preservative in insensitive layers/concn. of preservative in photosensitive layers)>=0.2. Further, the polymer preservative has two or more preservative molecules by covalent bonds in one polymer molecule and satisfies the relation (concn. of preservative in insensitive layers/concn. of preservative in photosensitive layers)>=0.2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to silver halide (hereinafter referred to as A
and a photographic light-sensitive material having a particularly effective antiseptic effect.

[0002]

2. Description of the Related Art When photographic light-sensitive materials and photographic images that have undergone development processing are stored, microorganisms (especially bacteria, molds, yeasts, etc.) adhere to these materials during storage and their performance is degraded. There are many. To prevent this, they usually contain preservatives. Regarding this, for example, JP-A Nos. 59-226343, 59-226344, 59-228247, 58-166343 and 6
0-260952, JP-A-1-253727, 2
-287535, 3-130758, 3-11
The description in No. 9347 and No. 3-140950 can be referred to.

However, the added preservative may interact with the AgX emulsion layer containing various photographic additives to deteriorate the photographic performance. Therefore, it is required to reduce the interaction. Further, when the photosensitive material containing the preservative is developed, the preservative flows out into the processing solution because it is not fixed in the photosensitive material. This is not preferable because of the following points. 1) Preservative accumulates in the developer. When this accumulated amount increases, the developability of the photosensitive material is affected, and the reproducibility of developability deteriorates. Also, the processing amount of the photosensitive material per unit developing solution is limited for that reason. 2) Microorganisms attach to the light-sensitive material from which the preservative has flowed out, and are easily proliferated. Therefore, the deterioration of the image is promoted. 3) Outflow of preservatives into the treatment liquid is not preferable from the viewpoint of environmental pollution.

In order to make up for the drawback 2), it is disclosed that a treatment bath containing a preservative is provided in the treatment step. However, there are problems that it is necessary to provide a new processing bath, and because the preservative has poor solubility in water, it precipitates in the processing bath and adheres to the surface of the photographic light-sensitive material. In addition, a large amount of waste liquid is produced, which poses a problem in terms of environmental protection. Further, when the photograph image is held in a hand and viewed, the preservative adheres to the hand,
Causes problems such as rashes. Furthermore, the other problems mentioned above remain unsolved. It has a defect that an image is deteriorated due to the interaction between the preservative and the image-constituting substance.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material in which an antiseptic agent is fixed in the light-sensitive material, and thus elution into a developing solution during development processing is suppressed. Another object of the present invention is to provide a light-sensitive material in which the preservative is retained in the light-sensitive material even after the development processing, and there is no problem such as precipitation of the light-sensitive material, and image deterioration due to microorganisms is prevented. Another object of the present invention is to provide a light-sensitive material in which the interaction between the antiseptic and the AgX emulsion and the image-constituting substance is reduced and an effective antiseptic effect can be obtained.

[0006]

The objects of the present invention have been achieved by the following items. 1) In a silver halide photographic light-sensitive material having at least silver halide grains and a pendant-1 type dispersion medium, the pendant-1 type dispersion medium is a dispersion medium in which a preservative and a dispersion medium are covalently bonded, and A silver halide photographic light-sensitive material, wherein the concentration of the preservative in the photosensitive layer / the concentration of the preservative in the photosensitive layer is 0.2 or more.

2) In a silver halide photographic light-sensitive material having at least silver halide grains, a dispersion medium and a pendant-2 type preservative, the pendant-2 type preservative is a preservative having a reactive substituent, In addition, the reactive substituent reacts with the functional group of the dispersion medium, and at the time of shipment, 2 of the preservative is added.
0% or more causes covalent bond with the dispersion medium, and (concentration of the preservative in the non-photosensitive layer / concentration of the preservative in the photosensitive layer) is 0.2.
The above is a silver halide photographic light-sensitive material characterized by the above.

3) In a silver halide photographic light-sensitive material having at least silver halide grains, a dispersion medium and a polymer preservative, the polymer preservative has two or more preservative molecules covalently bonded in one molecule. A silver halide photographic light-sensitive material which is an antiseptic and has a (preservative concentration of the non-photosensitive layer / preservative concentration of the photosensitive layer) of 0.2 or more.

The present invention will be described in more detail below. The general formula of the pendant-1 type dispersion medium, pendant-2 type preservative and polymer preservative of the present invention is represented by the following formula. Pendant-1 type dispersion medium Dispersion medium A- (L-preservative) _a (1) Pendant-2 type preservative preservative- (L-reactive substituent) _b (2) Polymer preservative polymer- (L -Preservative) _c (3-1) Preservative- (L-preservative) _c (3-2) Here, L represents a divalent linking group, a is an integer of 1 or more,
c represents an integer of 2 or more, and b represents 1 or 2. First, the preservatives will be described in order.

A. Antiseptic agent In the present invention, the antiseptic agent refers to a chemical agent used to prevent the dispersion medium for a photographic light-sensitive material from undergoing a decomposition reaction due to the growth of the microorganism. More specifically, phenols (for example, phenol, thymol, chlorophenol, bromophenol, chlorobromophenol, cresol, guaiacol, o-phenylphenol, xylenol,
Phenolsulfonic acid, resorcin, pyrogallol, phenoxyethanol, etc.), carboxylic acids or their esters (for example, benzoic acid, monobromoacetate, p-
Hydroxybenzoic acid ester, sorbic acid, sorbic acid ester, etc.), amines (hexamethylenetetramine,
Alkylguanidine, nitromethylbenzylethylenediamine, etc.), disulfides (tetramethylthiuram disulfide, etc.), nitrogen-containing heterocyclic compounds [2-mercaptobenzothiazole, 2- (4-thiazolyl) -benzimidazole, 2-methoxy-carbonylaminobenzo Imidazole and the like, which are described by mother nucleus, are pyrrole, pyridine, pyrimidine, pyrazole, imidazole, benzimidazole, 1,3,5-triazine, hexahydrotriazine, triazole, isoxazole. , Thiazole type, benzthiazole type,
Thiazolin-2-one system, isothiazolin-3-one system, benzisothiazolin-3-one system, benzothiazolin-2-one system, tetrahydrothiadiazin-2-thione system, morpholine system]], organic mercury compound (phenyl Mercury acetate, mercury phenylpropionate, mercury phenyloleate, etc.), antibiotics (neomycin, kanamycin, streptomycin, kanamycin, etc.), alcohols (ethanol, chlorobutanol, isopropanol, etc.), bromine preservatives (eg NC-CH ₂ -CBr ₂ -CONH ₂ , C
₆ H ₅ -CH = CBrNO ₂ , CH ₃ CONHBr, C ₆ H ₅ -CH ₂ OCOCH ₂ Br, C ₆ H ₅ -C
H = CBrCHO, HOH ₂ C-CBr (NO ₂ ) -CH ₂ OH, CH ₂ = CHCOOC ₂ H ₄ OCOCH
₂ Br, etc.], quaternary ammonium salts (benzalkonium chloride, alkyltrimethylammonium chloride, cetylpyridinium chloride, benzethonium chloride, etc.) and JP-A-1
Examples thereof include compounds represented by the general formula (4-1) described in JP-A-253727, phenoxy alcohols described in JP-A-3-130758, and aralkyl alcohol compounds described in JP-A-3-119347.

[0011]

[Chemical 1]

In addition, a symmetric or asymmetric compound obtained by organically bonding these preservatives through a divalent linking group can also be preferably used. The divalent linking group has 20 carbon atoms.
Represents the following divalent linking group, specifically, alkylene,
Arylene, _{alkenylene, -SO 2 -, - SO -} , -
O-, -S-, -CO-, -NR- (R is an alkyl group,
And an aryl group, a hydrogen atom) or a heterocyclic divalent group (for example, a triazine group) alone or in combination.

The definition of these preservatives according to the general formula and specific compounds are described in all the above-mentioned patents, as well as the antiseptic and antifungal handbook, Gihodo Publishing (1986), Horiguchi Hiroshi, Antibacterial and antifungal chemistry, Sankyo. Published (1986), Antibacterial and Antifungal Encyclopedia,
It is described in Japanese Society for Antibacterial and Antifungal (1986).
Among these preservatives, compounds that are non-adsorptive to AgX particles are more preferable. Here, the non-adsorptive property is (the number of molecules adsorbed on the surface of AgX particles / the number of non-adsorbed molecules existing in the dispersion medium) = x is not more than 1 / 1.5, preferably not more than 1/3, more preferably not more than 1/6. The following is shown.

The non-adsorbability can be determined by the following method. A preservative is added to the AgX emulsion with stirring, and after reaching the adsorption equilibrium, the AgX particles are centrifuged. The compound concentration in the supernatant or the separated AgX particle phase may be analyzed by an analytical method such as a light absorption method. Among the above preservatives, preferred compounds are the above compounds excluding alcohols, organic mercurys, antibiotics and quaternary ammonium salts,
More preferred are phenols, nitrogen-containing heterocyclic compounds (particularly thiazolines and isothiazolines), bromine-based preservatives, (4-1) formulas, aralkyl alcohols, phenoxy alcohols, and further more preferred nitrogen-containing compounds. It is a compound excluding a heterocyclic compound. Isothiazoline-
The definitions of 3-one type and benzisothiazolin-3-one type compounds and phenols are described in the above-mentioned Antibacterial and Antifungal Handbook, JP-A-3-119347, and JP-A-59-228.
No. 247, the definition of the formula (4-1) is described in JP-A-1-253.
No. 727, the definition of phenoxy alcohols is JP-A-3.
No. 130758, the definitions of aralkyl alcohols and bromine-based preservatives are described in JP-A-3-119347.

B. Linking Group L The linking group L in the present invention represents a divalent linking group having 30 or less carbon atoms. Alkylene divalent linking group, arylene, _{alkenylene, -SO 2 -, - SO -} , - O
-, S-, -CO-, -NR- (R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group), or a heterocyclic divalent group as described above, alone or in combination. Represents.

C. Pendant-2 type preservative In the present invention, the pendant-2 type preservative (hereinafter referred to as "2-type") is an organic chemistry in which at least the preservative and the reactive substituent are directly present in both substitution departments, or by a linking group. Refers to a chemically bound compound.

1. Reactive Substituent The reactive substituent refers to a substituent that reacts with a functional group of a dispersion medium to form a covalent bond, and is a reactive group that a hardener for gelatin has, or a reactive group that forms a derivative gelatin, And Steiger et al.
The reactive group described in No. 9 can be mentioned. The details of these are described below, and James (THJame
s), Theory of Photographic Process, 4th Edition, Macmillan Publishing, New York (1977), Chapter 2, Section III and AGWard.
and A. Courts, The Science and Technology of Gelatin
(Science and Technology of Gelatin), Chapter 7, Academic Press,
The description in Now York (1977) and Japanese Patent Application No. 3-146503 can be referred to.

Specifically, it refers to the following substituents. Aldehyde group, protected aldehyde group, acid anhydride group, acid halide group, diketone group, active ester group, active halide group, active olefin group, isocyanate group, isothiocyanate group, epoxy group, aziridine group, dioxrazone group , Alkane sultone group, carboxyl azide group, N-
Carbamoyl group, isoxazolium base, aromatic amine acid group, a carboxyl group activated by carbodiimide, preferably an acid anhydride group, an acid halide group, a diketone group, an active halide group, an active olefin group, Epoxy group, aziridine group, alkane sultone group,
Carboxyl azide group, a carboxyl group activated by carbodiimide, more preferably an acid halide group,
An acid anhydride group, an epoxy group, a carbodiimide-activated carboxyl group, an aziridine group, and a carboxylazide group.

The reactive group may have two or more reactive groups like a hardener, and it is more preferable.
Even if one of the reactive groups causes an ineffective reaction, the effect of the present invention can be achieved if the remaining reactive groups cause an effective reaction.

The specific examples including L of the reactive substituent can be referred to the description in Japanese Patent Application No. 3-146503. As specific compound examples of the carbodiimide, N,
N'-disilohexylcarbodiimide, 1-ethyl-
3- (3-dimethylaluminumpropyl) carbodiimide,
1-benzyl-3- (3-dimethylaminopropyl) carbodiimide and the like can be mentioned. In addition, as a method of activating the carboxyl group of the antifoggant,
A method using a condensation reagent such as N-ethyl-5-phenylisoxazolium-3'-sulfonate, an active ester method using pentachlorophenyl chloroacetate, p-nitrophenyl trifluoroacetate, p-nitrophenyl chloroacetate. be able to.

Other reactive substituents include --NH.
₂ , -COOH and -OH groups can be mentioned. In this case, the reactive substituent reacts with the hardener after coating the emulsion, and the hardener crosslinks the preservative and gelatin molecules. The effect of the present invention can be obtained also by this, but the above embodiment is more preferable. In this case, the reactive substituent --COOH is ca.
More preferred is an embodiment activated with rbodiimide. Furthermore, it is more preferable that the -COOH group of the dispersion medium gelatin is also activated by carbodiimide. In this case, carbodiimide
It is more preferable that the existing density of -COOH groups of the gelatin activated by (4) corresponds to the existing density of -COOH groups of the preservative. Corresponding here means that the existence density ratio of both is 10 to 1
/ 10, preferably 3 to 1/3, more preferably 2-1
/ 2. The hardener refers to a known photographic hardener,
For details, the description below can be referred to. It is preferable to select and use those which are easier to synthesize and easily react with the dispersion medium, and in which the reactive group or the reaction product does not adversely affect AgX particles. For example, the addition reaction to the active olefin is preferable because no by-product is generated after the reaction.

2. Specific Compound Examples Next, specific compound examples will be shown.

[0023]

[Chemical 2]

[0024]

[Chemical 3]

3. Fixation of Pendant-2 Type Preservative to Dispersion Medium The preservative having the reactive group reacts with the functional group of the dispersion medium in the light-sensitive material and covalently bonds with the dispersion medium. The chemical reaction is preferably completed before the product is shipped. That is, preferably 20% or more, more preferably 60% or more, still more preferably 80% or more, of the reaction is completed.
The binding reaction mainly proceeds during coating and drying and the subsequent heat treatment as in the case of the conventional hardener. The reaction is accelerated by the effect of increasing the gelatin concentration by drying (that is, the effect of increasing the functional group concentration) and the heat treatment after drying. With respect to the conditions at the time of the binding reaction, the hardening conditions with a conventional hardening agent can be referred to. That is, usually, an AgX emulsion is coated, the coated emulsion is gelled at 0 to 30 ° C, and dried at a relative humidity of 30 to 80% and a temperature of 15 to 40 ° C. Next, it is usually heated at 35 to 55 ° C. and a relative humidity of 80 to 100% or 100%, or after winding the coated film, it is sealed and heated at 35 to 55 ° C. for 1 to 100 hours. , Accelerates the dura reaction. In the case of the present invention, the binding reaction can be promoted according to this. Practically, the optimum conditions can be selected by changing the temperature, humidity and time and examining the elution degree of the preservative at the time of development.

The percentage of the binding reaction can be determined as follows. First, the following comparative samples are prepared as comparative samples. A comparative sample in which y% of the added preservative was fixed in the dispersion medium was prepared by adding (100-y)% preservative to the AgX emulsion.
It is prepared by applying under the same conditions as the sample and drying. Comparative samples with different y values were prepared, and elution experiments of the preservative in the solution were conducted under the same conditions, and the elution concentration VS. Make a graph of y%. Next, the sample is subjected to an elution experiment under the same conditions to obtain the elution concentration, and y% is obtained from the elution concentration value on the graph.

The dispersion medium referred to herein may be a conventionally known hydrophilic dispersion medium, such as gelatin, a graft polymer of gelatin and another polymer, albumin, protein such as casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfate. Cellulose derivatives such as esters, sodium alginate, sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Various synthetic hydrophilic polymer substances such as the above-mentioned single or copolymers can be used alone or in a mixed system. For details, reference can be made to the description in the literature described below. Usually, a gelatin dispersion medium is more preferable, and examples of the gelatin dispersion medium include gelatin and gelatin derivatives. More specifically, in addition to alkali-treated gelatin, acid-treated gelatin, derivative gelatin such as phthalated gelatin, low-molecular weight gelatin (molecular weight 2000 to 100,000, enzymatically-degraded gelatin, acid-alkali hydrolyzed gelatin, thermally-degraded gelatin), Examples thereof include gelatin having a methionine content of 50 μmol / g or less, oxidation-treated gelatin, and a mixture of two or more thereof. As derivative gelatin, gelatin is reacted with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds. What can be obtained by doing so.

However, in the first embodiment of the present invention, the reactive substituent bonded to the preservative reacts with the functional group of the dispersion medium to form a covalent bond, so that the derivative gelatin in which the functional group of the dispersion medium is blocked. Is not preferable. This is because the reaction proceeds more rapidly when the number of functional groups that can be bonded is sufficient.
When the functional group is -COOH, an alkali-processed gelatin in which glutamine or asparagine is converted into glutamic acid or aspartic acid is more preferable. Further, when the functional group is -N
In the case of H ₂ , gelatin in which arginine is converted to ornithine is more preferable. In these cases, the —CONH ₂ group is preferably 30% or more, more preferably 60% or more,
More preferably, gelatin in which 90% or more is converted to -COOH is more preferable. Arginine is preferably 2
Gelatin in which 0% or more, more preferably 40% or more, still more preferably 80% or more is converted to ornithine is more preferable. Although less reactive functional group of arginine, or an alkali treatment to pH 13 or higher, arginine by Arginase enzyme treatment ornithine [functional groups - (CH _{2) 3} NH _2] can be converted into .. The molecular weight of the gelatin is preferably that of conventional photographic gelatin, and gelatin having a molecular weight of 6 × 10 ^{4 to} 1.5 × 10 ⁵ accounts for 50% by weight or more is used. For the details of these and conventionally known hydrophilic dispersion media, the descriptions below and the references can be referred to. The preservative according to claim 2 has a reactive substituent capable of reacting with the functional group of the dispersion medium, and the functional group of the dispersion medium here means an amino group, a carboxyl group, and a hydroxyl group,
Preferred is an amino group, a carboxyl group or a hydroxyl group of gelatin. This is because gelatin has the largest number of amino groups, carboxyl groups and hydroxyl groups as functional groups, and thus the reaction can occur most easily. When -COOH is used as the functional group, carbodii is added to the -COOH.
It is preferable to use gelatin in which the functional group is activated by the action of mide. Regarding this, JP-A-2-305
The description of No. 876 can be referred to. The hardening reaction with a hardening agent can be carried out at the time of the binding reaction as usual.

Further, it is preferable that the functional group species which reacts with the hardener and the functional group species which reacts with type 2 are different from each other. For example, when the reaction partner of the hardener is -NH _2, it is more preferable that the type 2 of the reaction partners to -COOH and -OH. This is because it does not compete with the reaction of the hardener. Further, it is preferable to use the preservative linked by the above-mentioned linking group because the required number of functional groups can be more easily secured. This is because (reactive substitution number / preservative molecule number) is reduced. In the dispersion medium, (the number of functional groups capable of reacting with the reactive substituent / one molecule of the dispersion medium) = Z ₁ is essentially 1 or more, preferably Z> 3, more preferably 8
0 ≧ Z ₁ ≧ 5. Further, the dispersion medium (the number of functional groups capable of reacting with the added hardening agent / one molecule of the dispersion medium) = Z ₂ must be 1 or more, preferably Z ₂ > 3, and more preferably 80 ≧
Z ₂ ≧ 5.

D. Pendant-1 type dispersion medium The pendant-1 type dispersion medium (hereinafter referred to as type 1) in the present invention refers to a dispersion medium in which a preservative and a dispersion medium A are covalently bonded between both substituents. The dispersion medium A refers to a conventionally known hydrophilic dispersion medium for photography, more preferably gelatin. That is, the dispersion medium A is defined by the dispersion medium described in the above C-3. However,
It is essential that the dispersion medium A and the dispersion medium have the same functional group capable of reacting with the same hardener. For example, when glutaraldehyde is added as a hardener, both dispersion medium A and dispersion medium are -NH
It is essential to have a _bifunctional group. Usually, the most preferable embodiment is an embodiment in which both the dispersion medium A and the dispersion medium are gelatin. In the dispersion medium A, (the number of functional groups capable of reacting with the hardener / 1 molecule of the dispersion medium A) = Z ₃ is essentially 1 or more, preferably 3 or more, and more preferably 80 ≧ Z ₃ ≧ 5.

Type 1 is added to the AgX emulsion and / or protective layer solution, coated and dried to cause a hardening reaction. At this time, the type 1 gelatin part reacts with the hardener, cross-links with the dispersion medium gelatin, and is fixed to the dispersion medium. The fixing reaction is also preferably completed before the product is shipped. That is, 20% or more of the reaction is preferable, and 6 is more preferable.
It is preferred that 0% or more, more preferably 80% or more, be completed. Regarding the dura mater reaction, the above description can be referred to. It is obtained by adding type 2 to this type 1 dispersion medium solution and binding the functional group of the dispersion medium and the type 1 reactive substituent. Alternatively, it can be obtained by crosslinking reaction between the reactive substituent and the functional group of the dispersion medium with a hardening agent. The former is more preferable in terms of the bond generation rate. In this case, since the binding reaction is carried out outside the light-sensitive material, the reaction conditions can be selected within a wider range (for example, temperature, pH, etc.), and the binding production rate can be further increased.

The molecular number (a) of the preservative to be bonded to one gelatin molecule depends on the number n of the bonding functional groups in the gelatin molecule. The approximate number of amino acids in one molecule of gelatin having a molecular weight of 96000 is aspartic acid 32, asparagine 11, glutamic acid 45, glutamine 29, serine 40, threonine 16, hydroxyproline 11
2, lysine 34, arginine 52, hydroxylysine 3
Is. The reactivity of the -CONH ₂ group of glutamine and asparagine is low, but almost 100% of the
Can be converted to COOH. Therefore, when the —COOH group is used as the bonding functional group, the —CONH ₂ group is preferably 30 or less.
% Or more, more preferably 60% or more, and further preferably 9
Gelatin in which 0% or more is converted to -COOH is more preferable. This is because n can be increased. Further, when the —NH ₂ group is used as the binding functional group, gelatin in which arginine is converted into ornithine in an amount of preferably 20% or more, more preferably 40% or more, still more preferably 80% or more is more preferable. The maximum number of preservative molecules bound to all these functional groups is about 374. However, when preservative molecules are bound to all the functional groups, the molecules cannot undergo the crosslinking reaction by the hardener in the light-sensitive material. Further, in the case of a non-hydrophilic preservative, the hydrophilicity of gelatin is lost. Therefore, practically, a compound in which the number of a is changed from 1 to n is synthesized, added to a photosensitive material, the characteristics of the photosensitive material, the antiseptic property, and the development processing property are examined, and the compound having the most preferable value is selected. be able to. The optimum number is stored depending on the type of preservative, the molecular weight of gelatin, the type of binding functional group and the like. However, when the bonding functional group is only -COOH, the maximum value of n is about 116.

The value of n also changes depending on the molecular weight of gelatin. Therefore, the preferred range of the bond number a is a /
It is represented by n. The preferable range of a / n is 0 <a / n ≦ 0.
9, more preferably 0.01 <n <0.6, still more preferably 0.03 <n <0.4. The value of a is 1 or more, preferably 2 or more. The molecular weight of the dispersing medium A is 500 or more, preferably 2,000 or more, more preferably 10 ⁴ to 2 × 10
^{Is 4} . The higher the molecular weight, the greater the number of functional groups in the gelatin molecule, and the higher the probability that it will react with the hardener in the light-sensitive material and be fixed in the gelatin film. That is, it is cross-linked with other gelatin molecules to form a three-dimensional network of gelatin molecules,
Securely fixed in the photosensitive material.

In the above case, 1) an embodiment in which two or more preservative molecules of the same kind are covalently bonded to one molecule of dispersion medium A, 2) 1
A mode in which two or more kinds of preservative molecules are covalently bonded to the molecular dispersion medium A can be mentioned. Usually, one kind of preservative is rarely effective against all microorganisms, and thus 2) is effective against more microorganisms and is preferable. This can be obtained by adding two or more kinds of preservatives having the above-mentioned reactive substituents to the dispersion medium A and covalently bonding with the dispersion medium. The addition may be carried out one by one, or two or more may be added almost simultaneously and combined. It can be used according to each purpose. Next, specific compound examples of the pendant-1 type preservative are shown. However, here, the number of binding molecules a represents the average number of binding molecules.

[0035]

[Chemical 4]

[0036]

[Chemical 5]

E. Polymerization of antiseptic molecules When the antiseptic molecules are polymerized, diffusion resistance and outflow to the developing solution are suppressed. This method has the following two methods. 1) Attach a diffusion resistant group to the preservative molecule. 2) Preservative A preservative having two or more molecules is used. However, in the method of 1), the larger the diffusion resistant group, the more the molecular gabarky becomes, the more the weight ratio of the preservative is added, and the more the film thickness of the photosensitive material is unfavorable. In the method of 2), as the number of preservative molecules increases, the size of the molecule increases and the anti-diffusion property is improved. Therefore, the addition weight ratio of the preservative hardly changes with the diffusion resistance. Therefore, the polymer preservative of the present invention means 2 or more molecules in one molecule, preferably 5 or more molecules, and more preferably 2 molecules or more.
An antiseptic having 0 or more molecules of the antiseptic molecule covalently bonded thereto. Also in this case, (1) two preservative molecules of the same kind are included in one molecule.
The molecule may be a covalently bonded molecule, or (2) two or more preservative molecules may be covalently bonded in one molecule. Similar to the above, (2) is more preferable.

The polymer represented by the formula (3-1) means that the functional group capable of reacting with the preservative of the formula (2) to form a covalent bond is (2 / molecule) or more, preferably (5 / molecule). As described above, more preferably (10 to 100 / molecule) is included. Polysaccharides such as starch having two or more -OH groups as specific examples, the aldehyde derivative, two or more functional groups (-NH ₂ groups, -COOH groups, -OH group) protein having a polyacrylic acid, Examples thereof include polyvinyl amine and polyvinyl alcohol. To the polymer (2)
The preservative of formula (3-1) is added and covalently bonded to obtain the preservative of formula (3-1). However, in the case of the aldehyde, the reactive substituent is an —NH ₂ group. In this case, type 1 and (3-1)
The difference from the formula is as follows. The case where the polymer and the dispersion medium are crosslinked by the hardener is defined as type 1, and the case where the polymer and the dispersion medium are not crosslinked is defined as formula type (3-1). Therefore, for example, when the dispersion medium of the light-sensitive material is gelatin and the hardener is a vinyl sulfone compound, the covalent bond between the polysaccharide and the preservative is (3-1)
It is an expression type.

The formula (3-2) is a preservative having a repeating unit of preservative molecules, and C is 2 or more, preferably 4 or more, more preferably 8 to 50. Next, specific compound examples of the preservatives corresponding to the formulas (3-1) and (3-2) are shown. Here, d is an integer of 1 to 4, e is an integer of 2 or more,
f represents an integer of 2 to e. For example, the equation (8-1) is e
In a polyvinylamine molecule having amino groups,
A mode in which a chlorotriazine group is bonded to f amino groups of e amino groups is shown. The e value is 2 or more, preferably 4 to 30, more preferably 6 to 20. A compound having a preferable e value in terms of compatibility with the coating solution can be selected and used.

[0040]

[Chemical 6]

[0041]

[Chemical 7]

The compound of formula (7-1) is synthesized by the condensation reaction of the phenolic compound and formaldehyde.
In the formula (8-1), polyvinylamine is used as the polymer,
Formula (8-2) is obtained by reacting polyacrylic acid and formula (8-4) is polyvinyl alcohol with the compound of formula (2).

Regarding the synthesis of the compounds of the formulas (1) to (3),
JP-A-51-117619, JP-A-3-109539
No. 3-37643, No. 3-62029, Japanese Patent Application No. 3-146503 and the following documents can be referred to. Stritetwiser (A. Streitw
ieser), Organic Chemistry, Macmillan, New York (1985),
WGade, Organic Chemistry, Prentice Hall, Inglewood, Englewood, U.S.A.
SA) (1987), Nobuo Izumiya et al., Fundamentals and Experiments of Peptide Synthesis, Maruzen (1985), Chemical Society of Japan, New Experimental Chemistry Course 14, I
~ V, Maruzen (1977), El F Feather and M.
Fiser (LFFieser and M.Fieser), Advanced Organic Chemistry
istry), Maruzen, Tokyo (1962)

F. Hardener The hardener in the present invention refers to a photographic hardener, and specific examples are as follows. Chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitalaldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) , Active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N-methylenebis- [β
-(Vinylsulfonyl) propionamide], etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, dioxane Aldehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination. Among them, JP-A-53-4122
No. 1, No. 53-57257, No. 59-162546.
Nos. 60-80846 and the active halides described in US Pat. No. 3,325,287 are preferred. Other examples include polymeric hardeners. As the hardener, a compound that does not release a by-product in the crosslinking reaction, such as an active vinyl compound, is more preferable.
See Research Disclosure, 176 for details.
Volume (Item 17643) (December, 1978), Volume 307 (Item 307105, November, 1989)
), James, Theory of Photographic Process, 4th Edition, Chapter 2
Section III, Macmillan Publishing (1977), JP-A-63-3
05343, 63-229450, 63-26.
Reference can be made to the descriptions in Japanese Patent Application Laid-Open No. 4572, Japanese Patent Application Laid-Open No. 2-2114339, and the documents described later.

G. In addition, the addition amount of these preservatives is 500 to 10 ⁵ p for phenol-based and phenoxyalcohol-based and aralkyl alcohol-based preservatives in a weight ratio with respect to the dispersion medium amount in the light-sensitive material.
pm, (3-1) type preservative, isothiazolin-3-one preservative 50 to 10 ⁴ ppm, bromine preservative 1 to 10 ³ p
pm, 10 to 10 ⁵ ppm for other preservatives. It is preferable to select and use the addition amount as small as possible within the range where a sufficient antiseptic effect is obtained.

The compound of the present invention may be dissolved in a solvent which does not adversely affect photographic performance among organic solvents such as water, methanol, isopropanol, acetone and ethylene glycol, and may be added to the hydrophilic dispersion medium as a solution. Of course, it may be coated on the protective layer. Type 1 is a hydrophilic dispersion medium,
The comb can be directly dissolved in water and then added to the coating solution. The present invention is characterized in that the preservatives of the formulas (1) to (3) are contained in the non-light-sensitive layer of the light-sensitive material. That is, (concentration of the preservative in the non-photosensitive layer / concentration of the preservative in the photosensitive layer) = x is 0.2 or more,
Preferably, it is 0.5 or more. However, the compounds (1) to (3) of the present invention are added to each layer of a light-sensitive material containing a hydrophilic dispersion medium such as AgX emulsion layer, undercoat layer, intermediate layer, filter layer, antihalation layer and protective layer. can do. In this case, it is preferable to minimize the interaction between the photosensitive layer-constituting substances (AgX emulsion particles, photographically effective additives such as couplers) and preservatives. For that purpose, the x value is more preferably 1.
It is preferable to add 2 or more, more preferably 2 to 20. Here, the non-photosensitive layer refers to a layer containing no AgX emulsion grains, and specifically refers to an undercoat layer, an intermediate layer, a filter layer, an antihalation layer, or a protective layer. on the other hand,
The photosensitive layer means a layer (d) containing AgX emulsion grains and a layer (e) containing a photographic image forming substance. Normally, d = e, but in the diffusion transfer type photograph, d ≠ e. Further, in the case of a light-sensitive material, the layer requiring the most preservative is a protective layer. This is because when microorganisms enter the photosensitive material from the outside, they first adhere to the surface of the protective layer. Therefore (concentration of preservative in protective layer /
The average preservative concentration in the layer below the protective layer) = y is preferably 1.2 or more, more preferably 1.5 or more, and further preferably 2 to 20 times.

By reducing the total amount of the preservatives used, it is possible to more effectively inhibit the adherent growth and invasion of microorganisms from the outside. When the preservative of the formula (1) is added in this embodiment, since the preservative is bound to the dispersion medium from the beginning, diffusion to other layers is surely prevented and the embodiment is maintained. After the preservative of formula (2) also forms a bond with the dispersion medium, diffusion to other layers is surely prevented. The preservative represented by the formula (3) has a high molecular weight, so that diffusion into other layers is suppressed. Further, according to the aspect of the present invention, even when the concentration of the preservative in the protective layer is increased, the outflow of the preservative into the development processing solution is prevented. Therefore, this aspect is possible. The magnitude of these effects of the present invention is as follows: Expression (1)> Expression (2)> Expression (3). Therefore, (1) ~
Among the formula (3), the preservatives of the formulas (1) and (2) are more preferable,
Preservatives of formula (1) are more preferred.

JP-A-3-37643 is disclosed as an example of a photosensitive material containing a dispersion medium to which an antifoggant is covalently bonded. Some of the structural regulations of antifoggants fall within the structural regulations of preservatives. However, the patent is intended to add the compound to an AgX emulsion layer and cause it to be adsorbed on AgX grains, not to a non-photosensitive layer. Therefore, it differs from the present invention.

The method of adding the preservative includes (1) to (3)
Only one type of preservative of the formula may be added, two or more types may be added in combination, and the preservatives of the related art may be used in combination. However, when used in the above embodiment, (number of conventional preservative combined molecules / total number of preservatives) = z is 0.6
The following is preferable, and 03 or less is more preferable.

Microorganisms adhering to the photosensitive material are many kinds of microorganisms. On the other hand, preservatives are often effective only against specific microorganisms. For example, phenol is effective against bacteria but less effective against mold and yeast. Organic mercury compounds are effective against fungi, but less effective against bacteria. Therefore, in order to impart an antiseptic effect to all microorganisms, it is more preferable to use two or more antiseptics in combination. Therefore, even when the preservative of the formula (2) is used, it is more preferable to use two or more kinds of the compounds of the formula (2) having different preservative species. Even when the preservative of the formula (1) is used, a mode in which a compound in which two or more kinds of preservative molecules are covalently bonded to one molecule of the dispersion medium is used, and one kind of preservative is covalently bonded to one molecule of the dispersion medium. The case where two or more of the above compounds are used in combination can be mentioned. 2 like this
The combined use of one or more preservatives has not only an additive effect on various fungi but also a synergistic effect. This is because the action mechanism of each preservative against microorganisms is different.
For example, by combining an antiseptic agent that destroys the cell wall of the microorganism with an antiseptic agent that reacts with the nucleic acid of the microorganism, the microorganism can be more effectively inactivated.

These preservatives can be added to the AgX emulsion at any time from grain formation to coating, if necessary. However, it is better to make the interaction with the AgX particles as small as possible. For that purpose, the period from the particle formation to the coating is preferable, and the period before coating is more preferable. In order to further enhance the antiseptic effect of the photographic image after the development processing, it may be immersed in a solution containing an antiseptic. In this case, the concentration of the preservative can be selected as necessary,
It is preferable to reduce the concentration as compared with the conventional one.

In addition to the photographic light-sensitive material of the present invention, a compound in which a photographically effective compound is covalently bonded to a dispersion medium can be added. Here, the photographically effective compounds include sensitizing dyes, antifoggants, dye forming agents, fluorescent whitening agents, color image stabilizers, developers (hydroquinone compounds, etc.), etc. -117619, JP-A 3-1
0953, 3-37643, 3-62029,
The description in Japanese Patent Application No. 3-146503 can be referred to. The photographic light-sensitive material of the present invention contains all conventional additives,
It can be used in combination with technology. Regarding these, the descriptions in the following documents can be referred to.

The silver halide photographic light-sensitive material to which the preservative of the present invention can be added is not particularly limited. However, the preservative is a black and white silver halide photographic light-sensitive material [for example, X-ray sensitive material
Printing sensitizers, photographic papers, negative films, microfilms, direct positive sensitizers, ultrafine particle dry plate sensitizers (for LSI photomasks, shadows, liquid crystal masks)], color photographic light-sensitive materials (eg negative films, photographic prints) It can be used for paper, reversal film, direct positive color photosensitive material, silver dye bleaching method photograph, etc.). Further, a photosensitive material for diffusion transfer (for example,
A color diffusion transfer element, a silver salt diffusion transfer element), a photothermographic material (black and white, color), a high density digital recording light sensitive material, a holographic light sensitive material and the like can also be used. Regarding the details of these, the descriptions in the following documents can be referred to.

Research Disclosure
Disclosure) Volume 176 (Item 17643) (12
Mon, 1978), volume 307 (item 30710)
May, November, 1989), Duffin, Photographic Emulsion Chemistry, Focs
l Press, New York (1966), by Bill (EJBir
r), Stabilization of photographic silver halide emulsions
of Photographic SilverHalide Emulsions), Focal Press, London (1974)
Year), edited by James (TH James), theory of photographic process (Th
e Theory of Photographic Process) 4th Edition, Macmillan, New York (1977)

P. Glafkides, Chemistry and Physics of Photography (Chimie et Physique Photographiques), No. 5.
Edition, EDITION DARIZIN NUVER (Edition de
1 ', Usine Nouvelle, Paris (1987), second edition,
Paul Montel, Paris (1957), VL Zelikman et al., Preparation and coating of photographic emulsions (Makin
g and Coating Photographic Emulsion), Focal Press
(1964), KR Hollister Journal of Imaging Science (Journal of Imagi
ng science), 31 volumes, p.148-156 (1987)
Year), JEMasksky, Volume 30, p.24
7-254 (1986), 32 volumes, 160-177.
(1988), 33 volumes, 10-13 (1989).

Freezer et al., The Basics of Silver Halide Photographic Process (Die Grundlagen Der Photographischen Prozesse
Mit Silverhalogeniden), Academische Verlaggesellschaf (Akademische Verlaggesellschaf)
t), Frankfurt (1968). JCIA Monthly Report, December 1984, p.18-27, Journal of the Photographic Society of Japan, 49, 7-12 (1986), 52
Volume 144-166 (1989), Volume 52, 41-
48 (1989), JP-A-58-113926-11.
No. 3928, No. 59-90841, No. 58-1119.
No. 36, No. 62-99751, No. 60-143331.
No. 60-143332, No. 61-14630,
62-6251, 63-220238, 63.
-151618, 63-281149, 59-
133542, 59-45438, 62-26.
No. 9958, No. 63-305343, No. 59-142.
No. 539, No. 62-253159, No. 62-2665.
No. 38, No. 63-107813, No. 64-26839.
No. 62-157024 and No. 62-192036.

Japanese Unexamined Patent Publication Nos. 1-297649 and 2-127
No. 635, No. 1-158429, No. 2-42, No. 2
No. 24643, No. 1-146033, No. 2-838
No. 2, No. 28286, No. 3-109539, No. 3
-119347, U.S. Pat. No. 4,636,461,
4,942,120, 4,269,927, 4,900,652, 4,975,354, European Patent No. 0355568A2, and Japanese Patent Application No. 2-326222.
No. 4, No. 4-415037, No. 2-266615, No. 2-43791, No. 3-160395, No. 2-14.
No. 2635, No. 3-146503

[0058]

EXAMPLES The present invention will now be described in more detail by way of examples, but the embodiments of the present invention are not limited thereto. Example 1 Preservatives shown in Table 1 were independently added to the surface protective layer liquids shown below, and the preservatives were coated on an undercoated triacetyl cellulose base and dried. Further, the sample was wound up, placed in a sealed can, and kept at 45 ° C. for 15 hours to accelerate the dura reaction. In this way, Samples A to E were prepared. The surface protective layer liquid is 100 g of gelatin, 2000 cc of H ₂ O, hardener (C
H ₂ = CHSO ₂ CH ₂ CONHCH ₂ ) ₂ containing 3.6 g. The coating amount was 3 g / m ² of gelatin. The addition amount was expressed in ppm by weight ratio of the molecular portion of the preservative to the weight of gelatin. When Type 1 was added, the total amount of (Type 1 gelatin amount + added gelatin amount) was the same as the others.

[0059]

[Table 1]

Each of the samples A to E had an independent pH of 10.
It was immersed in an aqueous solution at 0 and 40 ° C. for 30 minutes, and the ultraviolet spectral density of the eluate was measured. The results are shown in Table 1. It was confirmed that the elution of the preservative was remarkably suppressed in the sample of the present invention when the spectral absorption concentration of the eluate of Sample A to which the preservative was added by the conventional method was 100.

Example 2 Emulsion A containing a preservative shown in Table 2 was coated on the undercoated triacetylcellulose base, and surface protection layer solution A containing a preservative shown in Table 2 was further coated. However, the amount of the preservative added to Emulsion A was 1/3 of the amount added to the protective layer.

[0062]

[Table 2]

Emulsion A: Tabular emulsion grains having an average grain size of 1.0 μm and an average thickness of 0.17 μm were prepared and chemically sensitized by a gold-ion sensitization method. Sensitizing dye 1 2.1 mg /
Ag was added at a ratio of 1 g, and 4-hydroxy- was added as a stabilizer.
2x 6-methyl-1,3,3a, 7-tetrazidene
10 ^-3 mol / mol Ag) Coating aid 0.05 mg / Ag of dodecylbenzenesulfonic acid sodium salt, poly-p-
0.5 mg / Ag 1 g of sodium styrenesulfonate,
15 mg of 1,2-bis (vinylsulfonylacetylamino) ethane / g of gelatin was added to give a gelatin content of emulsion of 1.6 g / Ag of 1 g. This is applied Ag amount 1.8
It was applied at g / m ² .

Surface protective layer liquid A: 100 g of gelatin, H ₂ O
1670 cc, di-2-ethylhexyl-Na-sulfosuccinate 3.5 g, sodium poly-p-styrenesulfonate 1.4 g, hardener 1,2-bis (vinylsulfonylacetylamino) ethane 3.6 g are contained. This was coated with ² g / m ² of gelatin. This was dried, the sample was wound up, put in a sealed can, and kept at 45 ° C. for 12 hours.
This was cut into a test sample. 0.015 cc of a suspension of Aspergillus strain was dropped onto Samples A to E. Next, this was left for 3 weeks under the conditions of 20 ° C. and relative humidity of 100%, and the mold generation state was observed. The results are shown in the section before treatment in Table 2. The numerical value represents the diameter (mm) of the area where the hyphae spread. In all of the samples A to D, there is no bacterial growth, indicating that the antiseptic effect is sufficient.

Next, another new sample of A to D was taken out, and a sensitometer (FWH type, FWH type, light source color temperature of 3200 ° K) was used for each sample and passed through transparent glass to
A uniform exposure for a second was given. Each sample was made into an independent developer "Hirendol" manufactured by Fuji Film Co., Ltd. 2
Develop for 4 minutes at 0 ° C. Then add 3% to a 1.5% by weight solution of acetic acid
It was dipped for 0 seconds, fixed with the same Super Fujix for 1.5 minutes, and washed with water for 15 minutes. The sample is dried, and 0.015 cc of a suspension of Aspergillus strain is dropped on Samples A to E,
The same experiment as above was performed. It was confirmed that the preservative of the present invention has an antiseptic effect even after the development processing, as compared with the conventional antiseptics.

[0066]

When the light-sensitive material of the present invention is developed,
The elution of the preservative into the developing solution can be surely suppressed, and the throughput of the light-sensitive material when the same developing solution is used can be increased. Variations in development processing performance are reduced. Further, environmental pollution due to elution of the preservative can be prevented. Since the preservative is retained in the photosensitive material even after the development processing, even after the development processing,
The antiseptic effect of photographic images is maintained. Therefore, the step of immersing the photographic image in the preservative after the development processing can be omitted. Further, since the concentration of the preservative in the non-photosensitive layer, particularly in the protective layer can be increased, the total amount of the preservative used can be reduced and the invasion of microorganisms from the outside can be effectively prevented. Since the concentration of the preservative in the photosensitive layer can be lowered, the interaction between the preservative and the photosensitive layer and the photographic image layer can be further reduced.

If a different type of molecule is covalently bound to the gelatin molecule, it will be difficult to enzymatically decompose. This is because enzymatic degradation occurs at specific amino acid sequences. Microorganisms secrete enzymes to decompose gelatin, but the light-sensitive material of the present invention is also difficult to undergo a decomposition reaction from this point. Particularly, in the case of Type 1 antiseptic, it is a hydrophilic decomposition medium and can be added directly without any organic solvent or dissolved in water. Further, since the preservative molecule is in a molecular form and fixed to the dispersion medium, there is no trouble such as precipitation. In the conventional method in which a preservative is contained by immersing it in a solution of a preservative after the development treatment, when the photographic image is held in the hand, the preservative adheres to the hand and causes a rash. In addition, preservatives on the hands may enter the mouth with food. Since the preservative of the present invention is fixed to the dispersion medium, it does not adhere to the hands and is safe.

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material having at least silver halide grains and a pendant-1 type dispersion medium, wherein the pendant-1 type dispersion medium is a dispersion medium in which a preservative and a dispersion medium are covalently bonded. And a silver halide photographic light-sensitive material characterized in that (concentration of the preservative in the non-photosensitive layer / concentration of the preservative in the photosensitive layer) is 0.2 or more. 2. A silver halide photographic light-sensitive material having at least silver halide grains, a dispersion medium, and a pendant-2 type preservative, wherein the pendant-2 type preservative is a preservative having a reactive substituent, In addition, the reactive substituent reacts with the functional group of the dispersion medium, and at the time of shipment, 20% of the preservative is added.
% Or more of which a covalent bond is formed with the dispersion medium, and (the concentration of the preservative in the non-photosensitive layer / the concentration of the preservative in the photosensitive layer) is 0.2 or more. .. 3. A silver halide photographic light-sensitive material having at least silver halide grains, a dispersion medium and a polymer preservative, wherein the polymer preservative has two or more preservative molecules covalently bonded in one molecule. A silver halide photographic light-sensitive material which is an antiseptic and has a (preservative concentration of the non-photosensitive layer / preservative concentration of the photosensitive layer) of 0.2 or more.