WO2004046816A1 - Method for producing silver halide photosensitive material - Google Patents

Abstract

A method for producing a silver halide photosensitive material using an aqueous coating liquid excellent in preservability, cleanability, productivity, and coating stability without marring the photography performance. The method for producing a silver halide photosensitive material comprising a transparent support and further comprising, over the transparent support, constituent layers including of at least one red-photosensitive silver halide emulation layer, at least one green-photosensitive silver halide emulation layer, at least one blue-photosensitive silver halide emulation layer, and at least one non-photosensitive layer is characterized in that an aqueous composition containing a photography-usable compound for forming the constituent layers contains 5.0 mass% of hydrophilic binder and a compound expressed by general formula (1) or (2).

Description

 Ϊ́ Production method of silver halide photographic light-sensitive material

 The present invention relates to a method for producing a silver halide photographic light-sensitive material produced by using an aqueous coating solution having excellent antiseptic properties, washing properties, productivity and coating stability without impairing photographic performance. Background art

In general, a silver halide photographic light-sensitive material is prepared by coating one or more photosensitive emulsion layers on a support and, if necessary, providing an undercoat layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer, and the like. Is applied. Examples of hydrophilic colloids used as binders for these photographic layers include proteins such as gelatin, albumin, and casein; cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose; agar, sodium alginate, and starch derivatives. Such sugar derivatives and synthetic hydrophilic colloids, for example, polyvinyl alcohol, polyvinyl divinyl pyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof are known. The most commonly used of these is gelatin. On the other hand, these hydrophilic colloids used in silver halide photographic materials are also known to rot or decompose under the action of bacteria, mold, yeast and the like. For example, in the production of photographic materials, when these hydrophilic colloids decay or decompose, the viscosity of the coating solution and the physical strength of the coated film are reduced, and locally Degradation of these hydrophilic colloids may result in loss of uniformity of the coating film, degradation products of the hydrophilic colloids may cause coating failure, or may have a negative effect on photos. .

 To prevent such decay and decomposition of hydrophilic colloids used in silver halide photographic materials by bacteria, molds, yeasts, etc., so-called preservatives and fungicides are used in silver halide photographic materials. At any stage of the production process, it has been added to a liquid containing a hydrophilic colloid as described above.

 In general, as a bactericide or fungicide for such a purpose, for example, an aromatic hydroquine compound such as phenol or a salt thereof, a carboxylic acid or an ester thereof, an amine, a nitrogen-containing heterocyclic compound, an organic Mercury compounds and antibiotics are known, and some of these are also known to be used for the production of silver halide photographic materials.

 In the production of the silver halide photographic light-sensitive material described above, the additive solution and the coating composition are in an environment where microorganisms such as Pacteria fungi tend to be generated during storage or temporary storage during production. As the length of the applied coating increases, the time for which the coating composition is stored in the manufacturing apparatus also increases.

 To cope with the above problems, preservatives for hydrophilic colloids having a specific structure have been proposed (for example, see Patent Documents 1 to 4). However, these preservatives are only described under the condition of low binder concentration or low viscosity of the aqueous coating solution, and have high concentration and high viscosity for high production and high speed coating as required in recent years. No technical suggestion has been made for the aqueous coating liquid.

 (Patent Document 1)

Japanese Patent Publication No. 3—3 2 7 6 9 (Patent Document 2)

 Japanese Patent Publication No. 4-8037 1

 (Patent Document 3)

 JP-A-11-184039

 (Patent Document 4)

 JP 2002-49115 A Disclosure of the Invention

 The above object of the present invention is achieved by each of the following constitutions.

 (1) On a transparent support, each of at least one layer of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a non-light-sensitive layer In a method for producing a silver halide photographic light-sensitive material having a constituent layer comprising: a water-soluble composition containing a photographically useful compound used for forming the constituent layer, the hydrophilic binder concentration is 5.0% by mass or more. A method for producing a silver halide photographic material, comprising a compound represented by the following general formula (1) or (2).

—General formula (1)

Wherein a hydrogen atom, an alkyl group, an alkenyl group, Ararukiru group, Ariru group, a heterocyclic _{group, - CONR (R 5),} -C SNR 4 represents _{(R B), R 2,} R 3 are each Each represents a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkyl group, an alkylsulfoxy group, or an alkylsulfonyl group. R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. General formula (2)

 Br R

 To i

R ₆ — C— CHOH

 I

N0 ₂

[In the formula, R ₆ represents a hydrogen atom, an alkyl group or a hydroxymethyl group, and R represents a hydrogen atom or an alkyl group. ]

(2) including chromatic amount of the aqueous composition of the general formula (1) or (2) a compound represented by the, 5 X 1 0 - and characterized in that the ^beta to 5 X 1 0 one ¹ wt% The method for producing a silver halide photographic light-sensitive material according to (1).

 (3) On a transparent support, each of at least one layer of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a non-light-sensitive layer In the method for producing a silver halide photographic light-sensitive material having a constituent layer, the aqueous coating solution containing an aqueous composition containing a photographically useful compound forming the constituent layer has a hydrophilic binder concentration of 5.0 mass%. % Or more, containing the compound represented by formula (1) or (2), and having a coating solution viscosity of 30 mPa · s or more. Manufacturing method.

() Among the constituent layers, a hardening agent for curing a hydrophilic binder is added to an aqueous coating liquid containing an aqueous composition containing a photographically useful compound constituting the outermost layer. Within 10 minutes of the addition of water, The method for producing a silver halide photographic light-sensitive material according to (3), wherein the viscosity of the hydrophilic coating solution is less than 30 mPa · s.

 (5) The aqueous coating solution containing the aqueous composition containing the photographically useful compound contains a thickener, and the total concentration of the thickener and the hydrophilic binder is 7.0% by mass or more. The method for producing a silver halide photographic light-sensitive material according to (3) or (4), wherein

 (6) The method for producing a silver halide photographic light-sensitive material according to (5), wherein the thickener is dextran sulfate.

(7) The content of the aqueous coating solution of the general formula (1) or (2) a compound represented by the, and Toku徵that is ^{5 X 1 0 _ 6 ~5 X} 1 0- 1 % by weight Yes (3) ~

(6) The method for producing a silver halide photographic material according to any one of the above (1) to (4).

 (8) On a transparent support, each of at least one layer of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a non-light-sensitive layer In the method for producing a silver halide photographic light-sensitive material having a constituent layer, a storage container for an aqueous composition containing a photographic useful compound used for forming the constituent layer, or a photographic useful compound forming the constituent layer A preparation vessel for preparing an aqueous coating solution containing an aqueous composition and a liquid sending line from the preparation vessel to a coating coater were prepared using the compound represented by the general formula (1) or (2). A method for producing a silver halide photographic light-sensitive material, characterized by washing with a contained washing solution.

(9) The silver halide according to (8), wherein the concentration of the compound represented by the general formula (1) or (2) in the cleaning solution is 1 to 100 ppm. Manufacturing method of photographic photosensitive material. BEST MODE FOR CARRYING OUT THE INVENTION

 In the method for producing a silver halide photographic light-sensitive material of the present invention, the aqueous composition containing a photographically useful compound used for forming a constituent layer of the silver halide photographic light-sensitive material has a hydrophilic binder concentration of 5. 0% by mass or more, and contains a compound represented by the general formula (1) or (2), and contains an aqueous composition containing a photographically useful compound forming a constituent layer. The aqueous coating solution to be used has a hydrophilic binder concentration of 5.0% by mass or more, contains the compound represented by the general formula (1) or (2), and has a coating solution viscosity of 3 OmPa. · It is characterized by being at least s. By using the above-mentioned method for producing a silver halide photographic light-sensitive material, an aqueous coating solution having excellent antiseptic properties, detergency, productivity and coating stability without impairing photographic performance is used. Can be manufactured.

 First, the preservative represented by the general formula (1) or (2) according to the present invention will be described.

In the general formula (1), R i is a hydrogen atom, a linear or branched substituted or unsubstituted alkyl group (for example, methyl, ethyl, tert-butyl, n-octadecyl, 2-hydroxyethyl, 2-carboxyethyl, 2-cyanoethyl, sulfoptyl, N, N-dimethylaminoethyl groups, substituted or unsubstituted cyclic alkyl groups (for example, cyclohexyl, 3-methylcyclohexyl, 2-oxocyclopentyl) ), A substituted or unsubstituted alkenyl group (for example, aryl and methylaryl groups), a substituted or unsubstituted aralkyl group (for example, benzyl, p-methoxybenzyl, 0-chlorobenzyl, p— iso—propynole benzyl groups), substituted or unsubstituted aryl groups (for example, phenyl, naphthynol 0 — methynolephine) m- two door Krumlov d two Norre, 3, 4 Jikuro opening full-et-two Norre of Each group), a heterocyclic group (for example, 2-imidazolyl, 2-furyl, 2-thiazolyl, 2-pyridyl), one CONR ₄ (R ₅ ), one C SNR ₄ (R ₅ ), R ₂ and R ₃ are each a hydrogen atom, a substituted or unsubstituted alkyl group (for example, methyl, ethyl, chloromethyl, 2-hydroxyl, tert-butyl, n-octyl), a substituted or unsubstituted cyclic alkyl group; Groups (eg, cyclohexyl, 2-oxocyclopentyl), substituted or unsubstituted aryl groups (eg, phenyl, 2-methylphenyl, 3,4-dichlorophenyl, naphthyl, 4-nitrophenyl)ヽ 4-aminophenyl, 3-acetamidophenyl), cyano, complex (eg 2-imidazolyl, 2-thiazolyl, 2-pyridyl), substituted or unsubstituted alkylthio (Eg, methylthio, 2-cyanoethylthio, 2-ethoxycarbonylthio), substituted or unsubstituted arylthio groups (eg, phenylthio, 2-carboxyphenylthio, p-methoxyphenylthio) A substituted or unsubstituted alkylsulfoxy group (eg, methylsulfoxy, 2-hydroxyhexylsulfoxy group), a substituted or unsubstituted alkylsulfonyl group (eg, methylsulfonyl, 2 -Bromoethylsnolehoninole).

R ₄ and R ₅ are each a hydrogen atom, a substituted or unsubstituted alkyl group (eg, each group of methyl, ethyl, iso-propyl, 2-cyanoethyl, 2-n-butoxycanolebonylethyl, 2-cyanoethyl), substituted or unsubstituted Ariru group (e.g., Fuweniru, naphthyl, 2-main Tokishifueniru, m- Nitorofuweniru, 3, 5 - Jikurorofuweniru, ₃ - each group Asetoami Dofue) yl, a substituted or unsubstituted § aralkyl groups (e.g. Benzyl, phenethyl, p-iso-propylbenzyl, monochlorobenzyl, _m -methoxybenzyl). Hereinafter, typical specific examples of the compound represented by Formula (1) will be shown, but the present invention is not limited thereto.

-1 1-2

-3 1-4

-5 1-6

-9 1-10

-15 1-16 1-8

-9 1-10

-15 1-16

-17 1-18

-19 1—20

-21 1-22

1—23

-17 1-18

-19 1—20

-21 1-22

1—23

1—25 -26

1 -27 1 -28 C ₈ H ₁₇ (n)

Some of the above compounds are commercially available, can be easily obtained, and can be synthesized according to the synthesis method described in French Patent No. 1,555,416. Can be.

 Next, details of the compound represented by the general formula (2) will be described.

In the general formula (2), R ₆ represents a hydrogen atom, a lower alkyl group (for example, methyl, ethyl, is0-propyl), or a hydroxymethyl group, and R ₇ represents a hydrogen atom, a lower alkyl group (for example, , Methyl, n-butyl, is 0-amyl groups). The lower alkyl group is preferably a group having 1 to 5 carbon atoms, particularly preferably a methyl group.

Hereinafter, typical specific examples of the compound represented by the general formula (2) will be shown, but the present invention is not limited thereto. 2-1 2-3

HOCH ₂ — CH ₃

 One

 2-4 2 2-5 H

また、 これらの化合物の一部は三愛石油（株） から市販されている。 また以 下の文献を参考にして合成することができる。 丄 ： H e n r y R e c u e i l d e s a v a u x

Some of these compounds are commercially available from San-ai Oil Co., Ltd. It can also be synthesized with reference to the following documents.丄: H enry R ecueildesavaux

 c h i n i q u e s d e s R a y s— B a s l 6 25 丄

 2: M a s s. C h e m i s c h e s Z en t r a l b l a t t

 1899 I 179

 3: E. S c hm i d t. B e r i c h t e d e r D e u t c h e n

C h e m i s c h e n G e s e l l s c h a f t. 52 397

4: E. S ch m i d i b i d 55 3 17

 5 '-H en r y C h e m i c h e s Z e n t r a l b l a t t,

 1897 II 338

In this case, the synthesis of Exemplified Compound 3-1 should follow References 1, 2 to 3, the synthesis of Exemplified Compound 2-2 should follow Reference 2, the synthesis of 3-3 should follow Reference 5, and the synthesis of 3-4 should follow Reference 2. Good.

 In the present invention, an aqueous composition containing a photographically useful compound, wherein the compound represented by the above general formula (1) or (2) is used for forming a constituent layer having a hydrophilic binder concentration of 5.0% by mass or more. It is preferable to use it by adding it to a product.

 The aqueous composition containing a photographically useful compound referred to in the present invention is a composition in which a photographically useful compound is present in a hydrophilic binder in an emulsified state or a dispersed state. In the case of using a gelatin exhibiting a change, it is dispersed in gelatin, stored in a solidified state in a gel state, and is heated, for example, in a stage of producing a silver halide photographic light-sensitive material. It is added to the aqueous coating solution to be formed.

 Typical aqueous compositions used in the present invention include a silver halide emulsion in which silver halide grains are dispersed, or an oil-soluble additive such as a color-forming coupler, an oil-soluble antioxidant, and an oil-soluble additive. Oil-soluble compounds such as ultraviolet absorbers, antioxidants, and anti-fading agents are dissolved in an appropriate solvent, and emulsified in a medium comprising a surfactant, gelatin, and the like.

 In the present invention, in order to effectively exhibit the preservative effect or the antifungal effect of the compound represented by the general formula (1) or (2), the storage temperature of the aqueous composition is preferably 15 ° C. C or less, more preferably 2 to 10 ° C., and particularly preferably 2 to 5 ° C.

In the present invention, the addition amount of the compound represented by the above general formula (1) or (2) is not particularly limited, but is based on an aqueous composition having a hydrophilic binder concentration of 5.0% by mass or more. it is preferably added in 5 X 1 0 ~5 X 1 0- 1 % by weight range. Under the above conditions, the compound represented by the general formula (1) or (2) is added to the aqueous composition. By adding, even if the aqueous composition is stored for a long period of time, it is possible to prevent deterioration, decay or decomposition by bacteria, bacteria, mold, yeast, etc. of the hydrophilic binder, and to obtain a stable quality at all times. A silver halide photographic light-sensitive material can be produced.

 Further, in the present invention, the compound represented by the above general formula (1) or (2) is prepared by adding a compound having a hydrophilic binder concentration of 5.0% by mass or more and a coating solution viscosity of 30 mPa-s. It is characterized in that it is added to an aqueous coating solution containing an aqueous composition containing a photographically useful compound that forms the constituent layer described above.

The silver halide photographic light-sensitive material according to the present invention comprises at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, at least one blue-sensitive silver halide emulsion layer, and at least one non-light-sensitive layer. Each photosensitive silver halide emulsion layer is composed of a two-layer unit consisting of a high-sensitivity layer and a low-sensitivity layer, or a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer, if necessary. It may be a three-layer unit. As the non-photosensitive material, for example, an antihalation layer, one yellow filter, an intermediate layer, or a protective layer (outermost layer) can be provided. In the present invention, among the above constituent layers, All of the aqueous coating liquids containing the aqueous composition containing the photographically useful compound are characterized by satisfying the above-mentioned conditions defined in the present invention. In the present invention, the content of the aqueous coating liquid of the general formula (1) or (2) a compound represented by, preferred to be a ^{5 X 1 0- 6 ~5 X 1} CT 1 wt% New

After adding the compound represented by the general formula (1) or (2) under the above conditions to an aqueous coating solution containing an aqueous composition containing a photographically useful compound, an aqueous coating solution is prepared. Even if stagnant storage is performed for a long time, the hydrophilic binder It is possible to prevent deterioration, decay or decomposition by bacteria, bacteria, molds, yeasts, etc., and to produce a silver halide photographic light-sensitive material of always stable quality.

 In the present invention, the hydrophilic binder concentration in the aqueous composition or the aqueous coating solution is characterized by being 5.0% by mass or more, preferably 7.0 to 20.0% by mass, More preferably? ~ 15% by mass.

As the hydrophilic binder used in the silver halide photographic light-sensitive material according to the present invention, gelatin is most preferably used, but other hydrophilic binders can also be used in combination. As gelatin, acid-treated gelatin may be used in addition to lime-processed gelatin, and a hydrolyzate of gelatin and an enzymatically decomposed product of gelatin can also be used, but gelatin having a low calcium content is preferably used. Gelatin having a Ca ²⁺ concentration of 100 ppm or less is more preferable, and gelatin of l to 500 ppm is particularly preferable.

 In the aqueous coating solution according to the present invention, a thickener is used together with the hydrophilic binder, and the total concentration of the thickener and the hydrophilic binder is preferably 7.0% by mass or more, more preferably It is preferably from 7.0 to 20% by mass, more preferably from 10 to 20% by mass.

 Examples of the thickener that can be used in the present invention include starch, dextran, dextran sulfate, carboxymethylcellulose, cellulose sulfate, polyacrylamide, alginic acid, sodium polyacrylate, polyvinylpyrrolidone, and styrene-maleic acid copolymer. A wide variety of thickening agents such as dextran sulfate are preferred, although a wide range of thickening agents are used.

Together with the compound represented by the general formula (1) or (2) according to the present invention, By using dextran sulfate as an agent, the effects of the present invention can be further exerted.

 One characteristic of the viscosity of the aqueous coating solution containing the aqueous composition containing the photographically useful compound used in the present invention is that the viscosity is 30 mPas or more at 40 ° C, but preferably 30 to 20 mPas. OmPas, more preferably 30 to 150 mPas.

 In the method for producing a silver halide photographic light-sensitive material of the present invention, a hydrophilic binder is added to an aqueous coating solution containing an aqueous composition containing a photographically useful compound constituting the outermost layer. It is preferable that a hardening agent to be hardened is added by an in-line method within 10 minutes of the start of the application of the aqueous coating solution, so that the viscosity of the aqueous coating solution is less than 30 mPa's.

The hardening agent used for the outermost layer is not particularly limited, and examples thereof include, for example, U.S. Pat. No. 4,678,739, column 41, 4,791,042, and JP-A-59-111. Hardening agents described in Nos. 16655, 62-245261, 61-18942, 61-249054, 61-245153, and JP-A-4-218044. More specifically, aldehyde hardeners (such as formaldehyde), aziridine hardeners, epoxy hardeners, and vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) De) ethane, etc.), N-methylol hardeners (such as dimethyl monourea), boric acid, metaboric acid or polymer hardeners (compounds described in JP-A-62-234157). No. Among these hardeners, it is preferable to use a vinyl sulfone hardener or a chlorotriazine hardener alone or in combination. These hardeners have a hydrophilic binder content of 0.001 to: Lg, preferably 0.005 to 0.5, per lg. Used.

 In the present invention, it is preferable that the above-mentioned hardener is added to the aqueous coating solution for forming the outermost layer by an inline method within 10 minutes when the aqueous coating solution passes through the coating start point. The in-line method is also referred to as in-line addition, and a mixing device therefor is also commercially available as an in-line mixer or a static mixer. For example, a static mixer manufactured by Kenics (Amerikiri), a static mixing element SMV type manufactured by Sulger (Switzerland), a Shimazaki pipe mixer manufactured by Koiritsu Kogyo, and a Hi-M manufactured by Toray. iXer, a static mixer N10 manufactured by Noritake, or the like can be used.

 In the present invention, the viscosity of the aqueous coating solution of the outermost layer after the addition of the hardener is preferably 30 mPas or less, more preferably 10 to 28 mPas. s. By setting the viscosity of the aqueous coating liquid of the outermost layer according to the present invention to the conditions specified above, stable coating conditions can be obtained, and as a result, a coating film with excellent uniformity can be achieved. A remarkable effect is exhibited in the outermost layer coating solution containing the compound represented by the general formula (1) or (2) and the aqueous composition containing the photographically useful compound.

 Next, a washing method using the compound represented by the general formula (1) or (2) according to the present invention will be described.

In the method for producing a silver halide photographic light-sensitive material of the present invention, a storage container for an aqueous composition containing a photographic useful compound used for forming each constituent layer, or an aqueous composition containing a photographic useful compound forming the constituent layer For preparing an aqueous coating solution containing a product and a liquid sending line from the preparation tank to the coating coater are washed with a washing solution containing the compound represented by the general formula (1) or (2). It is characteristic. As described above, an aqueous composition containing a photographic useful compound is prepared, stored in a storage container, and dissolved during the production of a silver halide photographic light-sensitive material, and added to a desired coating solution. However, if the storage container used for storage is contaminated with bacteria, bacteria, mold, yeast, etc., the aqueous composition may deteriorate when stored for a long period of time. By washing with a washing solution containing the compound represented by (1) or (2) before use, it is possible to effectively prevent the growth of bacteria, pacteria, bacteria, yeast and the like.

 In the production of a silver halide photographic light-sensitive material, each aqueous coating liquid prepared by adding a desired additive to a preparation tank is supplied via a liquid feed pipe, a filter, a liquid feed pump, or a coating flow meter. Is sent to the coater and applied on the support.However, when the liquid is stagnated for a long time in the preparation tank or passes through a liquid feed pipe or the like that has been used for a long time, There is a danger that the coating solution will be deteriorated when the coating is performed for a long time due to bacteria, pacteria, lentils, yeasts, etc. attached to the surface. However, the general formula (1) or (2) The use of a washing solution containing the compound represented by formula (1) after washing in advance can effectively prevent the growth of bacteria, bacteria, mold, yeast and the like.

 The concentration of the compound represented by the general formula (1) or (2) in the cleaning solution according to the present invention is preferably 1 to 100 ppm, more preferably 1 to 500 ppm, Particularly preferably, it is 1 to 200 ppm.

The coating method used in the production of the silver halide photographic light-sensitive material of the present invention is not particularly limited. Examples thereof include a bar coater method, a curtain coat method, an immersion method, an air-knife method, a slide hopper coating method, and an next coat method. A known method such as a solution coating method can be used. Of these, the slide hopper is more preferable. —This is a pre-metering type coating method called coating method.

 In the coating method according to the present invention, any method may be used as long as it can coat at least one layer at a time. Preferably, all the constituent layers constituting one surface side of the support of the silver halide photographic light-sensitive material are simultaneously layered. It is preferable to use a coating method. By using the above simultaneous multilayer coating method, the effects of the present invention can be fully exhibited, and a silver halide photographic light-sensitive material having high production and excellent coating quality can be stably produced.

 Next, other components of the photosensitive layer of the silver halide photographic light-sensitive material according to the present invention will be described below.

 For the preparation of the silver halide emulsion according to the present invention, those described in each item described in Research Disclosure 1 (hereinafter abbreviated as RD) No. 308 119 can be used. .

 The places to be described are shown below.

 [Item] [RD3081 Page 19]

 Iodine composition 993 I-1 A

 Production method 993 I-A and 994 E Crystal habit Normal B 993 I-A

 Crystal habit Twin crystal 993 I—A term

 D 993 I—Section A

 Halogen composition uniform 993 I-B

 Halogen composition is not uniform 993 I-1 B

 Halogen Condensation / 994 I-C

Halogen substitution 994 I-C 994 I-D

 Monodisperse 995 I—F term

 Solvent addition 995 I-F section

 Latent image formation position Surface 995 I-G term

 Latent image formation position Inside 995 I-G section

 Applicable silver halide photographic material negative 995 I-H section

 Positive (including internal capri particles) 995 I-H

 995 I-J term mixed with emulsion

 Desalination 995 II-A Section A

 In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitivity is used. Additives used in such a process are described in RDN No. 17643, No. 187 16 and No. 308 119. The places to be described are shown below.

 [Item] [RD308 1 19 page] [RD 17643] [RD 187 16] Chemical sensitizer 996 III-A Section 23 648 Spectral sensitizer 996 IV—A—A,

 B, C, D, 23-24 648-69 H, I, J¾

 Supersensitizer 996 IV—A—E, J

23-24 648-649 Capri inhibitor 998 VI 24-25 649 Stabilizer 998 VI 2 — 25 649 Known photographic additives which can be used in the silver halide photographic light-sensitive material of the present invention. Are also described in the above RD. The relevant sections are described below.

 [Items] [RD308 119 page] [RD 17643] [RD 187 16] Anti-turbidity agent 1002VII-I Section 25 650 Dye image stabilizer 100 1 VII-J Section 25

 Brightener 998 V 24

 UV absorber 1003VIII—I,

 XIII—C section 25-26

 Light absorber 1003VIII 25-26

 Light scattering agent 1003 VIII

 Filter dye 1003VIII 25-26

 Binder 1003 IX 26 65 1 Static inhibitor 1006X1 II 27 650 Hardener 1004X 26 65 1 Plasticizer 1006 ΧΠ 27 650 Lubricant 1006X11 27 650 Activator / Coating aid 1005X1 26-27 650 Matting agent 1007XVI

 Developer (contained in silver halide color photographic materials)

 100 1XXB

 Various couplers can be used in the photosensitive layer according to the present invention, and specific examples thereof are described in the above RD. The relevant sections are described below.

[Items] [RD308 1 19 page] [RD 17643] Yellow coupler 100 1VII-D D VIIC-G Magenta coupler 100 1 VI D section VIIC-G section Cyan coupler 100 1 VII—D section VIIC-G section Color coupler 1002VII—G section VIIG section

 D I R coupler 100 1 VII—F section VIIF section

 BAR power plastic 1002VII-F section

 Release of other useful residues 100 1 VII-F

 Power plastic

 Alkali-soluble coupler 100 Section 1VII-E

 Each of the above additives can be added by a dispersion method described in RD308119 XIV.

 The silver halide photographic light-sensitive material according to the present invention may be provided with an auxiliary layer such as a filter layer or an intermediate layer described in the aforementioned RD 308 119-VII-K. The silver halide photographic light-sensitive material according to the present invention may have various layer constitutions such as a forward layer, a reverse layer, and a unit constitution described in the aforementioned RD 308 119 VII-K.

To develop the silver halide photographic light-sensitive material according to the present invention, it is possible to use, for example, a method described in TH Jiemuzu, Theory of the Photographic Process, 4th Edition (He T heorof T he P hotgraphic Process E). dition), pages 291-334 and Journal Off, The American Chemical Society, 73, No. 3, page 100 (1951). Can be used. In addition, pages 28 to 29 of RD 1 7643 and 6 of RD 187 16 mentioned above Development can be carried out by a usual method described on page 15 and RD 308 119 XIX.

 Hereinafter, the present invention will be described more specifically with reference to Examples, but embodiments of the present invention are not limited thereto.

 Example 1

 (Preparation of aqueous composition)

 A silver iodobromide emulsion was prepared according to the method described in paragraphs [0158] to [0163] of JP-A-2001-242576. The silver iodobromide emulsion was finished so that the gelatin concentration was 9.0% by mass.

The aqueous compositions 1 to 14 to which the respective preservatives are added in a predetermined concentration according to the following table are added to the silver iodobromide emulsion, placed in a 5-liter container washed with hot water, and then placed in a refrigerator at 5 ° C. Each sample was stored for 1 month, 2 months, and 3 months.

Aqueous composition (preservative conditions)

 Addition ratio Total amount added

 (% By mass) Comparative example

2 phenol 10 2 X 10 one ⁷ Comparative Example 3 phenol 10 2 X 10 one ⁴ Comparative Example 4 cresol Ichiru 10 2 X 10- ⁷ Comparative Example 5 cresol Ichiru 10 2 X 10 one ⁴ Comparative Example 6 10 2 X 10 " ⁴ Comparative example 7 compound 1 (* 1) 10 2 X 10- 7 present invention 8 compound 1 (* 1) 10 2 X 10- 4 present invention 9 2- 1 10 2 X 10- ⁷ present invention

10 2- 1 10 2 X 10- ⁴ present invention 1 1 Compound 1 / 2- 1 5/5 2 X 10 - 7 present invention 1 2 Compound 1Z2- 1 5/5 2 X 10 ^"4 present MizunotoAkira 13 Compound 1 Z 2—1 2/8 2 X 10 Invention 14 Compound 1 2—18 / 2 2 X 10 Invention

(* 1) Exemplified compound 1—25: 1—26: 1—27 = 650: 4 (molar ratio)

(Evaluation of aqueous composition)

The bacteriostatic effect of each of the aqueous compositions stored in the refrigerator according to the method described below. Was evaluated.

 The meat extract for medium (nutrient broth pH = 7.0) and agar were dissolved in water, heated, then poured into a sterilized petri dish, and solidified to form a medium for evaluation. 0.1 ml of the aqueous composition stored for each of the above-mentioned predetermined periods was collected, added to the above-prepared medium, and spread on the medium with a sterile concealer stick. After storing each petri dish at room temperature for 7 days, the number of colonies of the bacteria generated in the petri dish was counted, and the bacteriostatic effect was evaluated according to the following criteria.

 ◎: Number of colonies generated is 10 or less and bacteria are extremely controlled

〇: The number of colonies generated is 100 or less, and the bacteria are almost contaminated. Δ: The number of colonies generated is 100 or less, slightly contaminated.

 X: Very high contamination with 100,000 or more colonies

The results obtained above are shown in the table below.

Aqueous composition (bacteriostatic effect)

 1 month storage 2 months storage 3 months storage Remarks

1 X XX Comparative Example 2 △ Δ X Comparative Example 3 〇 Δ X Comparative Example 4 △ XX Comparative Example 5 Δ Δ X Comparative Example 6 △ XX Comparative Example 7 〇 〇 Δ Invention 8 ◎ ◎ ◎ Invention 9 〇 〇 △ Invention

1 0 ◎ ◎ 〇 The present invention 11 1 〇 〇 〇 The present invention 1 2 ◎ ◎ The present invention 13 ◎ © 発 明 The present invention 1 ◎ ◎ 〇 The present invention Example 2

 (Preparation of aqueous coating solution)

A red-sensitive silver halide emulsion layer coating solution (hereinafter also referred to as an aqueous coating solution) having a gelatin concentration of 8.5% and a viscosity at 40 ° C of 45 mPa · s was prepared according to the following method. . Silver iodobromide emulsion (average grain size: 1.50 m, average silver iodide content: 3.1 mol%-average aspect ratio: 6.60) 0.48

SD—1 7.1 1 X 10 ¹⁵

S D- 2 9.78X 10. SD—3 4.72 X 10 C—1 0. 046 C-2 0. 0 1 CC 1 1 0. 0 1 9 AS— 2 0. 00 1 0 IL-2 0 .088 Gelatin 0.84

C-1

C-2

 0 βΗ ·]

C ₈ H ₁₇ (t)

AS— 2

5 OIL— 2

Five OIL— 2

H ₉ C ₄ OOC (CH ₂ ) ₈ COOC ₄ H ₉ Of the above additives, the oil-soluble additives C-1, C-2, CC-1 and AS-2 have 0 IL-2 and an appropriate amount. After dissolving with ethyl acetate, which is a low boiling point organic solvent, the solution was added to an aqueous solution of sodium triisopropylnaphthalenesulfonate and gelatin, ultrasonically dispersed to remove the ethyl acetate, and then added as an emulsion.

Each aqueous coating liquid 1 to 14 was prepared by adding each preservative to the aqueous coating liquid at a predetermined concentration according to the following table, and each aqueous coating liquid was placed in a 5-liter container washed with hot water. Thereafter, the solution was stored at 40 ° C. for 6 hours, 12 hours, and 24 hours while gently stirring.

Aqueous coating solution [Preservative conditions]

 No.Addition ratio Total addition Remarks

 (麵)

1 Comparative example

2 Phenol 10 5 X 10— 7 Comparative example

3 Fuwenonore 10 5 X 10- ⁴ Comparative Example

4 Cresol 10 5 X 1 CT ⁷ Comparative example

5 cresol Ichiru 10 5 X 10 one ⁴ Comparative Example

6 Benzoic acid 10 5 X 10 Comparative example

7 Compound 1 (* 1) 10 5 X 10 ⁷

8 Compound 1 (* 1) 10 5 X 10 - 4 present invention

9 2- 1 10 5 X 10-7

10 2- 1 10 5 X 10- ⁴ present invention

1 1 Compound 1 / 2—1 5/5 5 X 10-7 The present invention

1 2 Compound 1 Z 2- 1 5/5 5 X 10- 4 present invention

13 Compound 1 Z 2- 1 2/8 5 X 10 one ⁴ present invention

1 Compound 1 Z 2— 18/2 5 X 10— ⁴

(* 1) Exemplified compound 1-25: 1 -26: 1-27 = 46: 50: 4 (ratio)

(Evaluation of stagnation stability of aqueous coating liquid)

Each of the aqueous coating solutions, which had been stagnant for the predetermined time, was sterilized according to the following method. The effect was evaluated.

 The meat extract for medium (nutrient broth pH = 7, 0) and agar were dissolved in water, heat-treated, poured into a sterilized petri dish, and solidified to prepare a medium for evaluation. 0.1 ml of the aqueous coating solution subjected to the stagnation treatment for each of the above-mentioned predetermined periods was collected, added to the above-prepared medium, and spread on the medium with a sterilized concealer rod. After each petri dish was stored at room temperature for 7 days, the number of bacterial colonies generated in the petri dish was counted, and the bacteriostatic effect was evaluated according to the criteria shown below.

 ©: The number of colonies is less than 10 and is very controlled.

〇: The number of colonies generated is 100 or less, and almost bacteria are controlled

 Δ: Number of colonies generated is 100 or less, slightly contaminated, but not in a state that causes application failure

 X: Number of colonies generated is 100 or more, extremely contaminated, and easily prone to coating failure

The results obtained above are shown in the table below.

Aqueous coating liquid [bacteriostatic effect: 4 CTC stagnation time]

 6 hours 1 2 hours 2 4 hours

1 X XX Comparative Example 2 Δ XX Comparative Example 3 〇 Δ X Comparative Example 4 XX X Comparative Example 5 Δ Δ X Comparative Example 6 Δ XX Comparative Example 7 〇 △ 発 明 Invention 8 ◎ ◎ ◎ Invention 9 〇 Δ Δ Invention

1 0 ◎ ◎ 〇 The present invention 11 〇 〇 Δ The present invention 1 2 ◎ ◎ ◎ The present invention 13 ◎ ◎ 〇 The present invention 1 ◎ 〇 The present invention Example 3

 (Evaluation of cleanliness of prepared line)

SUS 316 preparation tank, SUS 316 preparation pipe with 30 mm inner diameter, filter box, and liquid pump The red-sensitive silver halide emulsion layer coating solution After circulating for 2 hours, a cycle of easy blanching and drying for 12 hours was carried out continuously for 30 days.

 This liquid transfer line was circulated for 15 minutes with each of the cleaning liquids in the table below at 35 ° C, dried, and then washed again after 6 hours, 12 hours, and 24 hours. Washing water was collected and evaluated as follows.

 (Evaluation of washability)

 The meat extract for medium (nutrient broth pH = 7.0) and agar were dissolved in water, heated, then poured into a sterilized petri dish, and solidified to form a medium for evaluation. 0.1 ml of the washing liquid collected after each of the above standing times was added to the medium prepared above, and spread on the medium with a sterilized concealer stick. After each dish was stored at room temperature for 7 days, the number of colonies of bacteria generated in the dish was counted, and the bacteriostatic effect was evaluated according to the following criteria.

 ◎: The number of colonies generated is 10 or less, and the bacteria are very controlled. 〇: The number of colonies generated is 100 or less, and the bacteria are almost controlled.

 Δ: Number of colonies generated is less than 100, and it is slightly contaminated

 X: Number of colonies generated is 100 or more, extremely contaminated

The results obtained with JiJLb are shown in the table below.

Washing solution [washing solution conditions] [bacteriostatic effect: retention time after washing] Compound addition ratio Total addition amount 6 hours 12 hours 24 hours Remarks

 (P m) 1 Hot water washing X X X Comparative example

2 Phenol 10 100 Δ △ Δ Comparative example

3 Cresol 10 100 Δ Δ X Comparative example

4 Benzoic acid 10 100 Δ X X Comparative example

5 Compound 1 10 100 ◎ ◎ ◎ The present invention 6 2-1 10 100 ◎ ◎ 〇 The present invention

7 * 2 5/5 100 ◎ ◎ The present invention

8 * 2 2/8 100 ◎ ◎ 発 明 The present invention

9 * 2 8/2 100 ◎ ◎ ◎ The present invention

(* 2) Compound 1 + Exemplified Compound 2-1 Example 4

 << Preparation of silver halide photographic light-sensitive material >>

The following preservatives were applied to all the constituent layers described in Example 1 of JP-A-2000-89426 on a triacetyl cell orifice film support having a thickness of 120 m provided with an undercoat layer. Then, using a slide hopper type coater, all layers were simultaneously coated to prepare Samples 101A to 108A, which are silver halide photographic materials. The addition amount of each preservative is coating solution 1 L per 5 X 10- ⁴ g. Next, in samples 101 A to 108 A which are silver halide photographic materials, The aqueous coating solution of each constituent layer was stirred and stagnated at 40 ° C. for 24 hours, and then coated in the same manner to prepare stagnant silver halide photographic light-sensitive materials, Samples 101B to 108B.

 << Evaluation of each sample >>

 (Exposure and development processing)

 Each sample was exposed through a wedge according to JISK 7614-1981, and then subjected to the developing method described in paragraphs [0220] to [0227] of JP-A-10-123652. A color development process was performed. (Characteristic evaluation)

 For each sample subjected to color development by the above method, the transmission Status sM densities of yellow, magenta, and cyan were measured using a densitometer manufactured by X-rite, which is a transmission densitometer. A D-Log E characteristic curve was created.

 Evaluation of stagnant stability>

In the D-L ₀ g E characteristic curve for the photograph created above, the reciprocal of the exposure required to obtain a density of +0.10 from the minimum density on the magenta density characteristic curve is defined as sensitivity, and the sample 101 A ~; When the sensitivity of L08A was set to 100, the relative sensitivities of the samples 101B to 108B were determined. Also, determine the difference between the minimum concentration of the sample 10 1 B~l 08 B to the minimum concentration of the sample 10 1 A~l 08 A, was determined as the Capri variation (Δ D _{mi nl).}

 <Evaluation of storage stability>

Prepare 2 parts of each of the prepared samples 101 A to 108 A, one part was stored at 23 in a 50% RH environment for 7 days and used as a reference sample.The other one was at 40 ° C. , And 80% RH environment, for 1 week. And

The sample subjected to each of the above processes was exposed and developed in the same manner as described above, and the relative sensitivity of each forcedly degraded sample when the sensitivity of each reference sample was 100 was determined. In addition, the difference between the minimum concentration of each reference sample and the minimum concentration of each forcedly degraded sample was determined, and this was determined as the Capri variation ( _ADmin2 ).

 The results obtained above are shown in the table below.

5 ^ materials [Preservatives] [Stagnation stability] [Storage stability]

Compound Relative sensitivity AD _mi Relative sensitivity AD _minl

1 0 1 Phenol 9 3 0.06 84 0.09 Comparative example

1 0 2 Cresol 9 2 0.06 86 0.10 Comparative Example

1 03 Benzoic acid 94 0.07 8 1 0.09 Comparative example

1 04 Compound 1 1 0 0 0. 0 1 98 0.0 3 3

1 0 5 2—1 1 0 1 0.03 9 5 0.04 The present invention

1 0 6 * 2 (5/5) 1 0 1 0. 0 2 97 0. 0 3 The present invention

1 07 * 2 (2/8) 1 0 2 0.02 95 0.04 The present invention

1 08 * 2 (8/2) 1 00 0. 0 1 98 0. 0 2 The present invention

(* 2) Compound 1 + Exemplary compound 2-1. The numerical value in parentheses indicates the mixing ratio of Compound 1 and Exemplary compound 2-1. Evaluation of coating failure>

A 100-fold loupe was applied to the sample surface of the sample 101 B to 108 B prepared above, As a result of observing a coating failure (tailing failure), it was found that in samples 101B to 103B, a tailing failure considered to be caused by the proliferation of the bacterium was scattered, but samples 104B to 108 of the present invention were desired. In B, no outbreak was observed.

Example 5

 In the preparation of Samples 10 1 B and 108 B which were subjected to the coating solution stagnation treatment described in Example 4, the following hardener H-1 was applied to the 14th layer (outermost layer) 5 minutes before the start of application and 15 10 1 C-E and 108 C-E were prepared in the same manner except that they were added 30 minutes before and 30 minutes before, and the following evaluations were made.

 Hardener H—1:

CH ₃ = CH-S 0 ₂ CH ₂ -CH (0 H) -CH ₂ -S 0 ₂ CH = CH ₂ (Evaluation of dispensing failure)

The number of coating failures (tailing failures) on 1 m ^{2 of} each sample surface was measured with a 100-fold loupe.

 (Measurement of film strength)

 Each sample was cut to a size of 3.5 cm in width and 14 cm in length, immersed in the color developing solution at 38 ° C for 3 minutes, and a 0.5 mm diameter sapphire needle was pressed onto the film surface. Then, the load on the needle was continuously changed while moving at a speed of Smm / sec, and the load at which scratching started was determined, and this was used as a measure of the film strength.

 (Evaluation of adhesion resistance)

Four samples of each sample were prepared, stacked in the same direction, sandwiched between cardboards of the same size, fixed with rubber bands, and left for 3 days in an atmosphere at a temperature of 55 ° (88% RH relative humidity. Then, the four samples were peeled off, and the ratio (%) of the area that became hull-shaped due to adhesion to the total area was measured for the three superimposed surfaces. _C indicating that the smaller, adhesion resistance is improved

The results obtained above are shown in the table below. Hardening agent applied | i Early adhesion resistance Remarks No.Addition time (pieces Zm ² ) (g) (%)

10 1 C 5 minutes ago 4 82 32 Comparative example

101 D 15 min 刖 7 76 4 1 Comparative example

101 E 30 minutes ago 1 2 65 49 Comparative Example 108 C 5 minutes ago 0 1 12 1 2 Invention

108 D 15 min 刖 1 104 19 The present invention

1 08 E 30 minutes ago 1 102 2 1 Invention Industrial potential

 As described above, according to the constitution of the present invention, a method for producing a silver halide photographic light-sensitive material produced by using an aqueous coating solution excellent in antiseptic properties, detergency, productivity and coating stability without impairing photographic performance. Could be provided.

Claims

The scope of the claims 1. A layer comprising at least one layer of a red-sensitive silver halide emulsion layer, a layer of a green-sensitive silver halide emulsion layer, a layer of a blue-sensitive silver halide emulsion layer, and a non-light-sensitive layer on a transparent support. In the method for producing a silver halide photographic light-sensitive material having the formula (I), the aqueous composition containing a photographically useful compound used for forming the constituent layer has a hydrophilic binder concentration of at least 5. ◦% by mass, and A method for producing a silver halide photographic light-sensitive material, characterized by containing a compound represented by the formula (1) or (2). General formula (1)

Wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group, a heterocyclic group, —CONR ₄ (R ₅ ), —C SNR ₄ (Rs), and R ₂ and R ₃ represent Each represents a hydrogen atom, an alkyl group, an aryl group, a cyano group, a heterocyclic group, an alkylthio group, an alkylsulfoxy group, or an alkylsulfonyl group. E and each represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group. ] -General formula (2) Br R ₇ R ₆ — C— CHOH N0 ₂ [In the formula, R 6 represents a hydrogen atom, an alkyl group or a hydroxymethyl group, and R represents a hydrogen atom or an alkyl group. ] 2. The content of the compound represented by the general formula (1) or (2) in the aqueous composition is from 5 × 10 to ^{6 to} 5 × ^{10 to 1} % by mass. 3. The method for producing a silver halide photographic light-sensitive material according to item 1.  3. On the transparent support, a constituent layer comprising at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a non-light-sensitive layer In the method for producing a silver halide photographic light-sensitive material having the formula (I), an aqueous coating solution containing an aqueous composition containing a photographically useful compound for forming the constituent layer has a hydrophilic binder concentration of 5.0% by mass or more. A method for producing a silver halide photographic light-sensitive material, characterized by containing a compound represented by the general formula (1) or (2) and having a coating solution viscosity of 30 mPa · s or more. .  4. Among the constituent layers, a hardener for curing a hydrophilic binder is added to an aqueous coating solution containing an aqueous composition containing a photographically useful compound constituting the outermost layer, and the aqueous coating solution is applied at a starting point of application. 4. A silver halide photographic light-sensitive material according to claim 3, wherein the aqueous coating solution has a viscosity of less than 30 mPas within 10 minutes of passing the solution. Manufacturing method.  5. The aqueous coating solution containing the aqueous composition containing the photographically useful compound contains a thickener, and the total concentration of the thickener and the hydrophilic binder is 7.0% by mass or more. 5. The method for producing a silver halide photographic light-sensitive material according to claim 3 or 4, wherein: 6. The method for producing a silver halide photographic light-sensitive material according to claim 5, wherein the thickener is dextran sulfate. 7. The content of the aqueous coating solution of the general formula (1) or (2) a compound represented by, characterized in that a ^{5 X 1 0- e ~5 X 1} 0 one ¹ wt% A method for producing a silver halide photographic light-sensitive material according to any one of claims 3 to 6. 8. On the transparent support, at least one layer composed of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a non-light-sensitive layer In the method for producing a silver halide photographic light-sensitive material having the above, a storage container for an aqueous composition containing a photographic useful compound used for forming the constituent layer, or an aqueous container containing a photographic useful compound forming the constituent layer A preparation vessel for preparing an aqueous coating solution containing the composition and a liquid sending line from the preparation vessel to the coating coater contain the compound represented by the general formula (1) or (2). A method for producing a silver halide photographic light-sensitive material, characterized by washing with a washing liquid. 9. The halogen according to claim 8, wherein the concentration of the compound represented by the general formula (1) or (2) in the cleaning solution is 1 to 100 ppm. A method for producing a silver halide photographic material.