WO2004012008A1 - Silver halide photographic sensitive material - Google Patents

Abstract

A silver halide photographic sensitive material which has improved blocking resistance in a high-temperature high-humidity atmosphere and stably gives high-quality images. The photographic sensitive material comprises a transparent substrate and, formed on one side thereof, at least one red-sensitive silver halide emulsifier layer, at least one green-sensitive silver halide emulsifier layer, at least one blue-sensitive silver halide emulsifier layer, and at least one non-light-sensitive layer, and is characterized in that after development the unexposed area has a spectral absorption density at 370 nm of 3.0 or higher and the ratio of the spectral absorption density thereof at 370 nm to that at 400 nm (370 nm/400 nm) is 0.4 or lower and that the outermost layer of the constituent photographic layers contains a fluorochemical surfactant.

Description

 Description Silver halide photographic material Technical field

 The present invention relates to a silver halide photographic light-sensitive material having improved adhesion resistance under high temperature and high humidity and capable of stably obtaining high quality image quality. Background art

 Even though video cameras and digital (still) cameras are rapidly penetrating, silver halide photosensitive materials (hereinafter simply referred to as photosensitive materials) are still available to users all over the world in terms of convenience, high image quality, and high sensitivity. Widely used. These light-sensitive materials are sold to users from photo-sensitive material manufacturers to dealers around the world, and are stored in various environments before shooting. In the distribution of photosensitive materials, it is desirable that the designed quality is always obtained in a stable manner.For example, in cases where photosensitive materials such as high temperature and high humidity are stored in extremely harsh environments, There have been many attempts to improve storage stability.

For example, if the photosensitive material is left for a long period of time in a high-temperature and high-humidity atmosphere, the films adhere to each other, that is, so-called sticking tends to occur. Sticking is a phenomenon in which the front and back surfaces of the photosensitive material adhere to each other in the patrone camera, especially when stored in a high-humidity atmosphere. This pulling can be done even in the case of Yellow capri was apt to be generated by peeling, and as a result, there was a problem that print quality was impaired.

 In order to prevent this sticking, it is known that a fluorinated surfactant is contained in the photosensitive material in order to reduce the peeling force of the generated tack. It can reduce sticking to some extent, but it is extremely insufficient especially for sticking that occurs when stored for a long time under high temperature and high humidity, and further improvement has been desired.

 The present invention has been made in view of the above problems, and has an object to reduce sticking even under high temperature and high humidity, and to reduce yellow capri even when peeled after sticking occurs. An object of the present invention is to provide a silver halide photographic light-sensitive material capable of maintaining good print quality. ·

Disclosure of the invention

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

 (1) 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 on one side of the transparent support In the silver halide photographic light-sensitive material, the spectral absorption concentration at 370 nm of the unexposed portion after the development processing is 3.0 or more, and the ratio of the spectral absorption concentration between 370 nm and 400 nm (3 70 nm / 400 nm) is 0.4 or less, and the outermost layer of the photographic component layer contains a fluorine-containing surfactant.

(2) On one side of the transparent support, 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 In a silver halide photographic light-sensitive material having a photosensitive layer, the outermost layer opposite to the surface having the silver halide emulsion layer across the support contains a slip agent particle and an inorganic particle. When the average particle diameter of the slip agent particles is a (/ m) and the average particle diameter of the inorganic particles is bm), && b satisfy both of the following formulas (1) and (2). A silver halide photographic material as described in (1) above.

 Equation (1)

 0.0 1≤b≤ 0.20 (μm)

 Equation (2)

 1.2 ≤ a / b ≤ 5.0 Best mode for carrying out the invention

 The silver halide photographic light-sensitive material of the present invention comprises, on one side of a transparent support, at least one red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion. And a non-photosensitive layer, and the unexposed portion after development processing has a spectral absorption density at 370 nm of 3.0 or more, and a ratio of the spectral absorption density of 370 nm to 400 ηm (370 One feature is that (nmZA 00 nm) is 0.4 or less.

The spectral absorption density of the light-sensitive material in the present invention can be measured using a commercially available spectrophotometer after performing the following development processing. That is, the same processing process is used except that a standard developing process, for example, a developing solution obtained by removing the color developing agent from the color developing solution in the color negative film developing process C-141 of Eastman 'Kodak Company is used. Then, the photosensitive material that is not exposed can be processed, and the spectral absorption density can be determined by measuring the spectral absorption density using a commercially available spectrophotometer. In the present invention, the spectral absorption concentration at 370 nm is a force that is 3.0 or more, preferably 3.1 to 3.6. The spectroscopic absorption concentration ratio at 370 iim / 400 nm is 0.4 or less, but preferably 0.30 to 0.38. In the present invention, the means for achieving the spectral absorption concentration specified in the present invention is not particularly limited, but an ultraviolet absorber represented by the following general formula (1) or (2) may be used. Is preferred. In addition, these ultraviolet absorbers can be added to at least the layer located farthest from the silver halide emulsion layer located farthest from the support among the layers constituting the photosensitive material. It is preferable because the effects of the invention can be fully exhibited.

 Hereinafter, the ultraviolet absorber represented by the general formulas (1) and (2) will be described. General formula (1)

In the general formula (1), and R ₂ each represent an optionally substituted alkyl group, and R ₃ represents a hydrogen atom, a halogen atom, an alkyl group or an alkoxy group. In the general formula (1), the alkyl group represented by R ₂ and R ₃ can be any alkyl group, but at least one is a tertiary alkyl group or a secondary alkyl group. Is preferred. In particular, it is preferable that at least one of the alkyl groups represented by R ₂ is a tertiary alkyl group or a secondary alkyl group. In the above alkyl group, the carbon number of the alkyl moiety Is preferably 12 or less. Hereinafter, specific examples of the compound represented by the general formula (1) will be shown.

General formula (2)

 Y

I H H /

 ノ N—— C = C— C = C

Rs ", G ₂

Next, the ultraviolet absorbent represented by the general formula (2) will be described.

Illustrative compounds

No. R ₂ R3

1 — 1 — CH ₃ — C ₄ H ₉ (sec) — H

1 1 2 — C ₄ H ₉ (sec) 1 C ₄ Akebono — C ₄ H ₉ (t)

1 1 3 — C ₄ H9 (sec) — C ₄ H ₉ (t) 4Π9

1 —4 — C ₄ H ₉ (sec) — C ₄ H ₉ (t) One CsH ”(t)

 1 —5 — C4Hg (sec) "~" ^ 5 ^ 11

1 —6

― Hoft)

1 -7!) "5 11 4 ⁿ 9

 1 -8

1 1 9 — C ₅ Hn (t) — C ₅ Hn (t) — CdHq (sec)

1 -10 ― CdHq (t) ― C ₅ H "(t) — C iHofsec)

 1 —11 — CAHq (sec) — (iHq (sec) —— CI

 1 —12

1 -13 ^ 4 9 \ 4 ^H 9

 1 -14 C iHaiS6C) C4H9

1 -15 ― 0 Η _Λ 0000οΗΐ7 ― H

1 16 — C ₄ H ₉ (t) — C ₂ H ₄ COOC ₈ H ₁₇ — — CI

1 17 4 ⁿ 9l ¹ / ― H

 1 1 18 then 2 ^ · lily n; 2 π and "" 9 —— Ple I 1

1 —19

― H

1 one _{20 - C 4 H 9 (t} ) - C2H4COOC2H40C4H9 - CI

1 one 21 ― ^c eHi7 — CH ₃ — H

1 22- ^C 10H21-CH ₃ -H

1-23 ― C12H25 — CH ₃ — H

1 -24 ~~ C ₁₆ H ₃₃ — CH ₃ — H

1 -25 ― ^C 20 ^H 41 — CH ₃ — H

1 -26 ― ^C 22 ^H 45 — CH ₃ — H

1-27 ― ^C 24 ^H 49 — CH ₃ — H

In the general formula (2), 1 ₄ and 1 ₅ each Arukiru group, a Ariru groups or rings alkyl groups may be the same or different from each other. Y is hydrogen source Or an atomic group necessary for bonding with R ₄ to form a 5-membered ring. And G ₂ each represent an electron-withdrawing group, which may be the same or different from each other. In the general formula (2), R ₄ and R ₅ may be the same or different from each other, and the alkyl group includes a substituted alkyl group (eg, a cyanoalkyl group, an alkoxyalkyl group, etc.), and has a carbon atom of 110. Individual. The aryl group also includes a substituted aryl group, and has 620 carbon atoms. 1 ₄ If the及Pi 1 ₅ are integrated together but not assembled, R ₄ and R ₅ are a cyclic amino group, for example a piperidino group, morpholino group, Kisahi Doroazepino groups some have the pin piperazino group pyrrolidino group to, Represents an atomic group necessary to form And the electron-withdrawing group represented by G ₂ include, for example, a cyano group, an alkoxycarbonyl group, a sorbamoyl group or mono-SO ₂ R (R represents an alkyl group or an aryl group). Hereinafter, specific examples of the compound represented by the general formula (2) will be shown.

2-1

2-2

2-3

2-4

2-5

2-6

The ultraviolet absorbers represented by the general formulas (1) and (2) are preferably liquid at room temperature. Usually, a hydrophobic compound represented by the ultraviolet absorber represented by the general formula (1) or (2) is added to a silver halide photographic material as an oil-in-water emulsion using a high boiling organic solvent. Is done.

 The silver halide photographic light-sensitive material of the present invention is characterized in that the outermost layer of the photographic constituting layer contains a fluorine-based surfactant.

 The fluorine-based surfactant in the present invention refers to a surfactant containing a fluorine atom in its structure, and may be any of anionic, cationic, betaine, and nonionic. For example, compounds described in Paragraph Nos. [023] to [0332] of JP-A-5-265154 can be preferably used.

In the silver halide photographic light-sensitive material of the present invention, the outermost layer on the side opposite to the side having the silver halide emulsion layer with the support interposed therebetween is made up of slip agent particles and inorganic particles. When the average particle diameter of the slip agent particles is a (m) and the average particle diameter of the inorganic particles is b (μτη), a and b are both of the above formulas (1) and (2). The feature is to satisfy.

 The slip agent particles according to the present invention will be described.

 The slip agent useful in the present invention is not particularly limited, and a known slip agent can be used. In particular, a compound represented by the following general formula (3) as a higher fatty acid or a derivative thereof is preferable.

 General formula (3)

R! CO R ₂

In the formula, represents a saturated or unsaturated aliphatic hydrocarbon group having 12 or more carbon atoms, preferably represents an alkyl group or an Arkiel group, and particularly preferably has 16 or more carbon atoms. R ₂ represents one OM, one OH, —NH ₂ , or one OR ₃ , and any of these groups can be preferably used in the present invention. Here, M represents an alkali metal such as Na or K, and R ₃ represents a saturated or unsaturated aliphatic hydrocarbon group having 12 or more carbon atoms, preferably an alkyl group or an α / recenyl group.

Specific examples of the compound represented by the general formula (3) include higher fatty acids such as behenic acid, stearic acid amide, and arachidic acid or derivatives thereof, and carnauba containing a large amount of these components as a natural product. Wax, honey, Montattatta, polyorganosiloxane as disclosed in Japanese Patent Publication No. 53-292, and U.S. Pat. No. 4,275,146. Una higher fatty acid amide, Japanese Patent Publication No. 58-33541, British Patent No. 9274446, Japanese Patent Application Laid-open No. 9 0 6 3 3 Fatty acid esters (esters of fatty acids having 10 to 24 carbon atoms and alcohols having 10 to 24 carbon atoms) as disclosed in U.S. Pat. No. 3,933,516 A metal salt of a higher fatty acid as disclosed in JP-A-51-372 17 from a dicarboxylic acid having up to 10 carbon atoms and an aliphatic or cycloaliphatic diol as disclosed in And polyesters such as oligopolyesters of dicarboxylic acids and diols disclosed in JP-A-7-132922. Of these, higher fatty acids such as behenic acid, stearic acid amide, and arachidic acid or derivatives thereof, carnauba wax containing a large amount of these components as natural products, honey, and montan wax can be preferably used.

The amount of silver halide photographic material useful slip agents in the present invention, 2~1 0 O mg Zm ² is preferably a supporting lifting member, more preferably from 3~6 0 mg Z m ^2.

In the present invention, the slip agent is present in the layer in the form of solid particles. In order to incorporate the slipping agent in the form of particles in the silver halide photographic light-sensitive material, it is preferable to include it in the coating liquid as an oZw type (oil-in-water type) dispersion in an emulsified state or a dispersed state. . An oZw type dispersion of a slipping agent (hereinafter, also simply referred to as a slipping dispersion) is a dispersion of a slipping agent which is substantially insoluble or does not mix with water. As a method for obtaining this slip agent dispersion, generally known methods can be used. For example, Tsuji recommends “Emulsification and Solubilization Technology” (Kogaku Tosho Co., Ltd.), Kariya, Koishi, Hidaka Edit You can use the method described in "Emulsification and Dispersion Technology Application Handbook" (Science Forum Edition). More specifically, a method of melting in an organic solvent and emulsifying in water, Examples thereof include a method of emulsification in water, a mechanical dispersion method using a dissolver, a sand grinder, and the like.

 Next, the inorganic particles according to the present invention will be described.

Examples of the inorganic particles used in the present invention include barium sulfate, desensitized silver halide, zinc powder, manganese colloid, strontium barium sulfate, oxidized lithium, sodium oxide, and calcium carbonate. , Z n O, T i 0 2, S n 0 2, A l 2 0 3, I n 2 〇 _3, S i 〇 _{2, Mg O, B a O} , Mo 0 3, V 2 0 5, S b ₂ 0 ₃ at least one selected from among metal oxides, or Ru can be given a fine powder of inorganic substances such as these complex metal oxides. Among these, preferred are S N_〇 ₂ or silicon dioxide (S i 0 _2). S n 0 ₂ particles, Z n, T i, S n, A l, I n, Mg, composite metal oxide containing B a, Mo, V, and at least one metal selected from among S b It may be a thing. Particularly preferred in the present invention are spherical fine particles of S i 0 _2. Specifically, as commercial products, Nippon Shokubai's Seahoster KE-P10 (0.10 μm) KE-P20 (0.20 μηι), AERO SIL 1 of Nippon Aerosil Co., Ltd. 3 0 (0.01 6 m) _N 2 0 0 (0.01 2 μm), OX 5 0 (0.04 0 m) _s TT 6 0 0 (0.04 0 μm) _s MOX 8 0 (0.03 0 m), MOX 17 0 (0.015 5 m) _N R972 (0.016 m), Alum ini um Oide C (0. 0 20 μπι) and Titanium Oide P 25 (0.030 / im).

In order to make the outermost layer or the adjacent layer on the back surface according to the present invention contain the slip agent particles or the inorganic particles, it is preferable to use a binder. Any of these layer binders can be used without particular limitation as long as they can be dispersed well. However, a hydrophobic binder may be used.

 Examples of the hydrophilic binder include natural polymers such as gelatin, agar, sodium alginate, starch, canolepoxmethinoresenorelose, hydroxymethylinoreserulose, polyvinyl alcohol and poly (N-bipyrrolide). And synthetic polymers such as polyacrylamide, aqueous polyester and the like. As the gelatin, any of so-called acid-treated gelatin, lime-treated gelatin, enzyme-treated gelatin, gelatin derivative, and modified gelatin can be used. Examples of the hydrophobic binder include a copolymer of vinyl chloride and vinyl acetate, a copolymer of vinyl chloride and vinyl acetate and bier alcohol, a copolymer of maleic acid and acrylic acid, and a copolymer of vinylidene chloride and vinyl chloride. Polymer, copolymer of butyl chloride and acrylonitrile, copolymer of ethylene and butyl acetate, copolymer of styrene and butadiene, copolymer of butadiene and acrylonitrile, Examples of the cellulose ester derivatives include cellulose acetate propionate or cellulose acetate butylate, methyl methacrylate resin, polyacetal resin, polybutyral resin, polycarbonate resin, polyester polyurethane resin, polyether resin, and polycarbonate. Carbonate polyurethane resin, polyamide resin, silicone resin and the like. Of these, a cellulose derivative, a copolymer of vinyl chloride and vinyl acetate, and a copolymer of vinyl chloride and vinylidene chloride can be preferably used.

Further, the binder used in the present invention may be hardened. Hardening agents that can be used include, for example, aldehyde compounds, ketone compounds, compounds having a reactive halogen, compounds having a reactive olefin, N-methylol Examples include compounds, isocyanates, aziridine compounds, acid derivatives, epoxide compounds, and halogen carboxy aldehydes. In addition, an inorganic hardener can be used, and a carboxyl group-activated hardener can also be used. The amount of the hardener added is from 0.01 to 30% by mass, preferably from 0.05 to 20% by mass, based on the binder.

In the present invention, the ratio of the binder and the lubricant particles or inorganic particles, each layer of the bar Inda one, total 1 0-1 20 mass _^0/0 of the particles, and preferably 20 to 1 00% by weight.

The silver halide emulsion layer of the silver halide photographic light-sensitive material of the present invention is described. _C For the preparation of the silver halide emulsion according to the present invention, Research Disc 1 osure (hereinafter abbreviated as RD) No. 3 Those described in each item described in 0811 can be used.

 The places to be described are shown below.

 [Item] [RD 3 08 1 1 9 page]

 Iodine composition 9 9 3 I-1 A

 Manufacturing method 9 9 3 I-1 A and 9 94 E Crystal habit Normal crystal 9 9 3 A

 Crystal habit Twin crystal 9 9 3 A

 99.3 A

 Halogen composition uniform 9 9 3 B

 Non-uniform halogen composition 9 9 3 B

 Nodogen consonance 9 94 Section C

Halogen substitution 9 94 C Metal content 9 94 I-D section

 Monodisperse 9 9 5 I_F term

 Solvent addition 9 9 5 I_F

 Latent image formation surface Surface 9 9 5 I-1 G

 Latent image formation position Internal 9 9 5 G

 Applicable silver halide photographic light-sensitive material negative 9 9 5 I-1 H

 Positive (including internal capri particles) 9 9 5 I-1 H

 995 J with emulsion

 Desalination 9 9 5 II-1 A

 In the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. Additives used in such a process are described in RD No. 17643, No. 187716 and No. 308119. The places to be described are shown below.

 [Items] [Page of RD 308 1 19] [RD 1 7643] [RD 1 8 7 16] Chemical sensitizer 9 96 III—A section 23 648 Spectral sensitizer 9 96 IV—A— A,

 B, C, D, 23-24 648-649

H, I, J terms

 Supersensitizer 9 9 6 IV—A—E, J

23 to 24 648 to 649 Capri inhibitor 998 VI2: to 25649 Stabilizer 998 VI 24 to 25649 Known photographic materials which can be used in the silver halide photographic light-sensitive material of the present invention. Additives, It is described in the above RD. The relevant sections are described below. [Items] [RD 30 8 1 19] Page [RD 1 7643] [RD 1 8 7 16] Anti-turbidity agent 00 2 VII-I Section 2 5 6 50 Dye image stabilizer 00 1 VII-J Section twenty five

 Brightener 9 9 8 V 24

 UV absorber 00 3 VIII-I,

 XIII-C Section 2 5 26

 Light absorber 00 3 VIII 2 5 26

 Light scattering agent 00 3 VIII

 Filter dye 1 0000 33 2 5— 26

 Binder 1 0000 33 I IXX 26 65 1 Antistatic 1 00 6XIII 2 7 6 50 Hardener 1 004X 26 6 5 1 Plasticizer 1 00 6 XII 2 7 6 50 Lubricant 1 00 6 XII 2 7 6 50 Activator Coating aid 1 00 5 XI 26-2 7 6 50 Matting agent 1 00 7 XVI

 Developer (contained in silver halide photographic materials)

 1 00 1XXB

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

(Items) (RD 3 08 1 19 page) (RD 1 7 6 43) Yellow coupler 00 1 VII—D section VIIC to G magenta coupler 0 0 1 VII—D section niC to G section

 00 1 VII—section D VIIC to G section Colored coupler 00 2VII—G section VIIG section

 D I R coupler 00 1VII—F section VIIF section

 B AR coupler 002VII_ section F

 Release of other useful residues 0 0 1 VII—Section F

 Coupler

 Soluble soluble coupler 100 1 Section VII-E

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

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

The silver halide photographic light-sensitive material of the present invention can be developed by, for example, TH Theorvof Photographic Process, Fourth Edition, by TH James, ed. Known developments described on pages 1-334 and in Journal of the American Chemical Society, Vol. 73, No. 3, page 100 (1951). Use agent be able to. Also, develop by the usual method described in RD 17643, pages 28 to 29, RD18716, page 615 and RD308119XIX. Can be.

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

 [Preparation of Sample 101]

 (Formation of back layer)

 One side (surface) of a triacetyl cellulose film support having a thickness of 120 μπι is subjected to an undercoating process, and then the back surface opposite to the undercoated surface is sandwiched between the supports, the following composition: Were sequentially formed from the support side.

 <Back layer first layer (B C-1)>

The following coating solution for the first layer of the back layer was applied at a rate of 20 ml / m ² and dried at 80 ° C. for 5 minutes.

 Alumina sol A S—100 (manufactured by Nissan Chemical Industries, Ltd.) 40 g acetone 500 million ml methanol / 400 ml l dimethylformamide 100 ml

<Back layer 2nd layer (B C-2)>

On the first layer of the back layer, the following coating solution for the second layer of the back layer was applied so as to be ² Om 1 Zm ² , and dried at 80 ° C. for 5 minutes.

 Diacetinoresenorelose ス g

S i O ₂ fine particles (average particle size 3.0 μ τη) 0.0 2 g acetone 500 ml Ethyl acetate 500ml

<Back layer 3rd layer (BC-3)>

On the second layer of the back layer, the following coating solution for the third layer of the back layer was applied so as to be 20 m 1 / m ² , and dried at 90 ° C. for 5 minutes.

 70 0 ml Methinoletinoketone 300 ml Fluorosurfactant (SU-2) 1

(Formation of photosensitive layer side)

Next, on the surface side (photosensitive layer side) of the support provided with the back layer, each layer having the following composition was formed in order from the support side, and a multilayer photo-sensitive material 101 was prepared. Produced. Incidentally, it is shown in grams per 1 m ² unless otherwise specified addition amount of each material below. Silver halide and colloidal silver are expressed in terms of silver, and sensitizing dyes (indicated by SD) are expressed in moles per mole of silver.

[First layer: anti-halation layer] (gZm ² ) Black colloidal silver 0.13

U V- 1 0.3 0

CM-0

OIL-1 0.2 3 Gelatin 1.20

[Second layer: middle layer]

 O I L-3 0.26 7 Gelatin 0.89 [3rd layer: low-sensitivity red-sensitive layer]

 Silver iodobromide emulsion a 0.3 1 Silver iodobromide emulsion c 0.22

S D- 1 1. 28 X 1 0- 4. SD- 2 1. 78 X 1 0- 5 SD- 3 8. 40 X 1 0- 5

C 1 1 0.3 3 24

C C-1 0. 0 56

D— 1 0. 0 14

A S-2 0.002 O I L-2 0.320 Gelatin 0 6

[4th layer: middle-sensitivity red-sensitive layer]

Silver iodobromide emulsion b 0. 0 8 iodobromide emulsion d 0. 40 SD - 1 2. 5 6 X 1 0- 4 SD - 2 3. 50 X 10- 5 SD- 3 1. 7 2 X 1 0— ⁴ C-1 0 0.2 1 9 cc-1 0 0 44 D— 1 0 0 24 D— 3 0 0 0 2 AS-2 0 0 0 2 OIL-2 0 0 0 1 Gelatin 0 8 4

[Fifth layer: Highly sensitive red-sensitive layer]

 Silver iodobromide emulsion d 0 0 Silver iodobromide emulsion g 0.38 SD-17 X 10 SD-2 9.7 8 X 10 SD-3 4.7 2 X 10 1 5 C-1 0.04 6 C-1 2 0.04 1 CC-1 1 0.0 1 9 D—3 0. 0 0 3 AS—2 0.

 0.8 4 [Sixth layer: middle layer]

 AS— 0.2 0

OIL-0.2 5 Gelatin 0.9 1 [Seventh layer: low-sensitivity green color-sensitive layer]

 Silver iodobromide emulsion b 0.23 Silver iodobromide emulsion c0 0

S D— 4 7 X 10-4 S D— 5 28 X 10 1 5

S D- 6 1.6 1 X 1 0 1 5

M— 1 0. 27 5

CM-1 0. 08 5

D— 2 0. 00 3 D— 3 0. 00 1

A S-2 0.001

X- 2 0.0.06 9

A S-3 0. 0 3 3

O I L-10.4 1 0 Gelatin 14

[Eighth layer: medium-sensitive green color-sensitive layer]

 Silver iodobromide emulsion c 0.09 Silver iodobromide emulsion d 0.33

SD - 4 3. 8 3 X 10- 4 SD- 5 4. 00 X 10- 5

S D- 6 5.00 X 1 0— 5

M— 1 0. 1 0 1

CM—1 0. 0 3 9 D— 2 0. 0 0 1 D— 3 0. 0 1 2 AS— 2 0. 0 0 1 X- 2 0. 0 1 4 AS-3 0. 0 0 7

O I L-10.2 8 0 Gelatin 0 6

[Ninth layer: high-sensitivity green color-sensitive layer]

 Silver iodobromide emulsion b 0.02 Silver iodobromide emulsion f 0.48

S D- 4 1.01 1 X 10

SD- 5 3.7 8 X 10

SD-6 6.3.3 X 10

M— 1 0. 0 5 8 CM- 1 0. 0 2 9

A S— 2 0. 0 0 1

X- 2 0. 0 1 5

A S-3 0. 0 0 7

O I L- 1 0.1 4 1 Gelatin 1.

 [Layer 10: One yellow filter]

 Yellow colloid silver 0.06

AS-1 0. 0 7 OIL-1 0.09 Gelatin 0.90

[First layer: low-sensitivity blue-sensitive layer]

Silver iodobromide emulsion b 0. 1 1 silver iodobromide emulsion d 0. 1 7 silver iodobromide emulsion e 0. 1 7 SD - 7 2. 78 X 1 0 one ^{4 SD - 8 7. 1 7 X} 1 0— ⁵ Y— 1 0.9.25 AS-2 0.003

O I L-1 0.3 7 1 Gelatin 9 1

[First and second layers: high-sensitivity blue-sensitive layer]

 Silver iodobromide emulsion e 0.03 Silver iodobromide emulsion h 0.25

SD - 7 2. 78 X 1 0- 5

SD-883 X 10-5

Y— 1 0. 0 78

AS-2.0.00 1 D—40.0.38

O I L-1 0. 047 Seratin 0.6. 1

[1st 3rd layer: 1st protective layer] Silver iodobromide emulsion i 0.22 uv- 1 0.10

UV- 2 0.0 6 X- 1 0.04 AF-6 0.003 Gelatin 0.70

[1st 4th layer: 2nd protective layer]

 PM-10.0 PM-20.0 0.01 WAX-10.02 SU-10.003 Gelatin 0.55 In addition to the above composition, coating aid SU-2, SU-3, Dispersing aid SU-4, Viscosity modifier V-1, Stabilizer ST-1, Weight average molecular weight: 10,000 and 2 types of polybutylpyrrolidone with weight average molecular weight: 100,000 ( AF-1, AF-2), calcium chloride, inhibitor AF-3, AF-4, AF-5, AF-6, AF-7, hardener H-1, H-2, and preservative A se-1 Was added as appropriate.

The characteristics of each silver iodobromide emulsion used in the preparation of Sample 101 are shown in the table below. The average grain size of silver iodobromide emulsions c, d, e, f, g, and h is the diameter (average value) of a circle having the same projected area (average value). And i are represented by the side length (average value) of the cube. Silver iodobromide emulsion average particle size average iodine content average Asupeku Ratio (mu m) (mol _^0/0) (average particle径NoAtsu of) silver iodobromide emulsion a 0. 2 7 2. 0 ―

Silver iodobromide emulsion b 0.28.20 Silver iodobromide emulsion c o

Silver iodobromide emulsion d 0.893.76.10 Silver iodobromide emulsion e0.9958.03.07 Silver iodobromide emulsion ί1.433.9.6.7 6 Silver iodobromide emulsion g 1.5 0.36.60 Silver iodobromide emulsion h 1.2 37.9.2.8 5.85 Silver iodobromide emulsion i 0.04 31.9

For each emulsion except silver iodobromide emulsion i, after adding each sensitizing dye described above, triphenyl phosphine selenide, sodium thiosulfate, chloroauric acid, potassium thiocyanate, etc. Chemical sensitivity was applied to optimize the sensitivity relationship.

 The details of the compounds used for preparing the sample 101 are shown below.

Y one 1

 CO-CHCONH

 I

N

CM— 1

 D-3

D-4

AS— 1

S-2

S— 3

 OIL— 2 OIL— 3

 Liquid paraffin

H ₉ C ₄ OOC (CH ₂ ) ₈ COOC ₄ H ₉

Ase-1 (a mixture of the following three components)

 (Component A) (Component B) (Component C) Component A: Component B: Component C = 50: 46: 4 (molar ratio)

H-1

_{CH 2 = CHS0 2 - CH 2} CONHC 2 H 4 NHCOCH 2 - S. ₂ CH = CH ₂

H-2

 ONa

 Man

 CI, N 'CI

X-2 Γ ~

H ₂₉ C ₁₄ OOCH ₄ C ₂ —N ^ ^-C ₂ H ₄ COOC ₁₄ H ₂₉ ST— 1 OH ——

H ₃ CN JN

X-1 H

 .丫 丫.

NHCONH2

SU-3 CH ₂ COOCH ₂ CH (C2H ₅ ) C4H9

[Preparation of Sample 102]

Sample 102 was prepared in the same manner as Sample 101 except that the amount of UV-1 used in the thirteenth layer (first protective layer) was changed to 0.35 g / m ² .

 [Preparation of Sample 103]

In the preparation of Sample 102, Sample 103 was prepared in the same manner except that the configuration of the pack layer on the back surface side and the undercoat layer were changed as described below. Subbing layer on one side of a 20 μm thick cellulose triacetate film The coating solution s-1 was applied so that the dry film thickness became 0.1 μπι, and dried at 90 ° C for 20 seconds to obtain an undercoat layer S-1. On the back side, apply a conductive layer coating solution u-1 so that the dry film thickness becomes 0.1 μμπι (100 nm), dry at 80 ° C for 40 seconds, and Apply the outermost layer coating solution p-1 on U-1 to a dry film thickness of 50 nm, and dry at 80 ° C for 12 seconds and then at 75 ° C for 2 minutes. Set to P-1.

 <Undercoat layer coating liquid s-1>

 Gelatin 10 g Water 270 g Methanol 5 20 g Polyamide-epichlorohydrin resin (synthetic product of reaction of adipic acid with diethylenetriamine and epichlorohydrin in a conventional manner)

 0.5 g Polyoxyethylene noninolephenyl ether (degree of polymerization: 10) 0.1 g <Coating solution for conductive layer u-1>

 Vininolebenzinoletrimethinoleammonium mouth lid / ethylene glycol dimethacrylate copolymer (mass ratio 93 3 Z7) 6 g Senorelose diacetate 3 g Acetone 800 g methanol 200 g

<Outer layer coating solution! 1) 1>

 The following lubricant dispersion 1 (average particle size of lubricant particles 0.18 μm)

10 g Inorganic particles (Seahoster KE-P10 average particle size: 0, Ο Ο μπι, manufactured by Nippon Shokubai Co., Ltd.) 0.02 g Senorelose diacetate

 Acetone 500 g Water Total of the following slip agent dispersion 1 and water is 200 g Methanol 300 g << Slip agent dispersion 1 >>

 Canolena Bax 90 g

_{HO (C 2 H 4 O)} 7. One (C ₃ H ₆ 0) ₃₀ H 10 g

 After mixing the above composition, 900 g was emulsified using a high-speed homogenizer to prepare a slip agent dispersion.

 [Measurement and evaluation of each sample]

 (Measurement of spectral absorption characteristics)

 In the developing process described in paragraphs [0220] to [0227] of Japanese Patent Application Laid-Open No. H10-1232652, each of the samples prepared above was used to develop a color developing agent from a color developing solution. A color development process was performed in the same manner, except that. The spectrophotometric absorption concentration of this sample was measured using a Hitachi U-3210 type recording spectrophotometer, and the spectral absorption concentrations at 370 nm and 400 nm were determined.

The following table shows the spectral absorption characteristics of each sample. Sample number 3 70 nm concentration 3 70 nm / 400 nm concentration ratio

1 0 2. 2 0.50

 0 2 3. 1 0. 3 5

 0 3 3. 1 0. 3 5

(Evaluation of adhesion resistance)

Each sample was cut into four pieces of 3 mm width and 70 mm length, and stored for 1 day in an atmosphere of 23 ° C and 80% RH so that they did not come into contact with each other. After that, four sheets are stacked with the photosensitive layer side facing up, sandwiched between cardboards of the same size, and a load of 800 g is applied under an atmosphere of 40 ° C, 80 ° / ₀ RH for 3 days. After storage, the laminated sample was peeled off, the area of the bonded portion was measured, and the adhesion resistance was measured according to the following criteria.

 A: The area of the adhesive part is less than 10%

 B: The area of the bonded part is 10% or more and less than 30%

 C: The area of the bonded part is 30% or more and less than 50%

 D: The area of the adhesive part is 50% or more

 (Evaluation of print quality)

The sample was processed to a size of 135, stored in a metal patrone for the size of 135, and stored at 23 ° C and 80% RH for 1 day. Next, these samples were loaded into a commercially available single-lens reflex camera, and 50 kinds of portrait scenes were shot in a daytime park while changing the scenery such as trees. Next, the photographed sample was subjected to color development processing according to the development processing steps described in paragraphs [0220] to [0227] of JP-A-10-123652. Subsequently, using Konica's Nice Print System NPS 858, it was printed on Konica Corporation's color paper QA type A7. This print is created by 10 print experts, and the ratio of scenes that require correction to the proper print finish [(correction number Z50 scenes) X100] and the correct printing Was calculated for each sample, and the average value was calculated.

 The results obtained above are shown in the table below. Sample No.Adhesion resistance Corrected print Improper print Remarks

 Ratio (%) Ratio (%)

 1 0 C 7 2 3 Comparative example

 0 2 B 8 0.7 .0 The present invention

10 3 A 4 0 .3 0 INDUSTRIAL APPLICABILITY

 As described above, according to the present invention, it is possible to provide a silver halide photographic light-sensitive material having improved adhesion resistance under high temperature and high humidity and capable of stably obtaining high quality image quality.

Claims

The scope of the claims

1. At least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, blue-sensitive silver halide emulsion layer and non-light-sensitive layer on one side of the transparent support In the silver halide photographic light-sensitive material, the spectral absorption density of the unexposed portion after development processing at 370 nm is 3.0 or more, and the ratio of the spectral absorption density of 370 nm to 400 nm ( (3700 nm / 400 nm) is not more than 0.4, and the outermost layer of the photographic component layer contains a fluorine-containing surfactant.

2. At least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer, blue-sensitive silver halide emulsion layer and non-light-sensitive layer on one side of the transparent support In the silver halide photographic light-sensitive material, the outermost layer on the side opposite to the side having the silver halide emulsion layer with respect to the support contains slipping particles and inorganic particles, Where a (/ xm) is the average particle diameter of the particles and b (μ χη) is the average particle diameter of the inorganic particles, the && b satisfy both of the following formulas (1) and (2). The silver halide photographic light-sensitive material according to claim 1.

 Equation (1)

 0.0 1 ≤ b≤ 0.20 (μm)

 Equation (2)

 1.2 ≤ a / b ≤ 5.0