JPS6363035A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the electrostatic charge of a sensitive material without deteriorating the transparency or causing powdering by forming a protective layer having a multilayered structure on the emulsion layer side and by separately incorporating specified substances into the constituent layers. CONSTITUTION:When at least one silver halide emulsion layer is formed on a support to produce a silver halide photographic sensitive material, a protective layer having a multilayered structure is formed on the emulsion layer side. The outermost layer of the protective layer has <=1mum thickness and contains at least one kind of compd. selected among metal oxides such as the oxides of Zn, Ti, Sn, Al, In, Si, Mg, Ba, Mo, W and V, and electrically conductive high molecular compds. A lower layer adjacent to the outermost layer contains at least one of metal oxides such as the oxides of an Zn, Ti, Sn, Al, In, Si, Mg, Ba, Mo, W and V by >=400wt% of the amount of a binder in the layer. The metal oxides used in the form of fine particles have electrical conductivity and <=10<7>OMEGA-cm, preferably <=10<5>OMEGA-cm volume resistivity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material (hereinafter referred to as photographic material) having improved antistatic properties.
In particular, the present invention relates to a photographic material that has improved antistatic properties without deteriorating transparency or powder removal.

(Prior Art) Photographic materials generally consist of an electrically insulating support and a photographic layer, so contact friction or peeling between surfaces of the same or different materials is avoided during the manufacturing process and during use of the photographic materials. By receiving it, Shizuka 1! Electric charge is often accumulated. This accumulated electrostatic charge causes many problems, but the most serious one is the electrostatic charge accumulated before processing! The photosensitive emulsion layer is exposed to light due to the discharge of electric charges, resulting in dot-like spots or dendritic or feather-like streaks when the photographic film is developed. This is what is called a static mark, and it significantly reduces the commercial value of the photographic film, or in some cases completely destroys it. For example, if it appears on medical or industrial X-ray film, it will be easily recognized that it will lead to very difficult judgments at the district attorney's office. This phenomenon becomes apparent only after development, and is one of the most troublesome problems. Furthermore, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the film surface or inability to apply uniformly.

As mentioned above, such electrostatic charges are often accumulated during the production and use of photographic materials.For example, during the production process, electrostatic charges are accumulated due to contact friction between a photographic film and a roller or when the photographic film is wound up.

This occurs due to separation of the support surface and emulsion surface during the unwinding process. In finished products, the separation of the base surface and emulsion surface when the photographic film is wound and changed, or the separation of the X-ray film from mechanical parts in an automatic camera or from a fluorescent screen. This occurs due to contact separation between the parts.

It also occurs when there is contact with the packaging material. Static marks in photographic light-sensitive materials induced by the accumulation of charges become more noticeable as the sensitivity of photographic light-sensitive materials increases and the processing speed increases. Especially recently, photography,
Static marks are more likely to occur as photosensitive materials have become more sensitive and are subjected to harsh handling such as high-speed coating, high-speed photography and high-speed automatic processing.

The best way to eliminate these static electricity disturbances is to increase the electrical conductivity of the material so that the static electricity can be removed before the accumulated charges are discharged.
! The purpose is to dissipate the charge in a short time.

Therefore, methods have been considered to improve the conductivity of supports and various coated surface layers of photographic materials, and attempts have been made to use hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. I've been exposed to it.

For example, U.S. Patent No. 2,112. /J-7-Same.

972, jJjt No. 3. Ot2.71! r number, same 3
．． No. 262,107 - 3. ! /≠, λ9/ issue - same 3.
T/! , Yo 31, 3.7! 3.71t - 3,2
No. 3, No. 9, etc., such as those described in US Pat. Nos. λ, 9♂λ.

JJ-/issue-same 3. Hiroλza, 4 (, tA-bar) 3. ≠
! No. 7.076 - 3. ≠Yo≠, t-ko! No. 3゜! !
Ko, No. 972 - Same J, t! ! , 317, and surfactants such as those described in U.S. Pat. ! 12
! Colloidal silica as described in , t, No. 2/, etc. are known.

However, many of these materials exhibit specificity due to differences in film support properties and photographic compositions, with good results for certain film supports and photographic emulsions and other photographic components, but for other differences. Film supports and photographic components not only are of no use in preventing static electricity, but may also cause poor photographic properties. More importantly, the electrical conductivity of many of these substances is dependent on humidity, and they have a major drawback in that they lose their function as electrically conductive layers under low humidity conditions.

In addition, Japanese Patent Publication No. 33-jA/A describes the technique of using Vi stannic oxide as an antistatic treatment agent.
This technology uses an amorphous tin oxide colloid - a material whose conductivity is humidity dependent and which loses its function as a conductive layer at low humidity, and is essentially the same as described above. It is no different from the various substances.

On the other hand, for example, in U.S. Pat. Crystalline zinc oxide, which has almost no dependence on humidity.
It is known to use metal oxides such as stannic oxide and indium oxide. However, in order to obtain good antistatic properties using these crystalline metal oxide particles in photographic light-sensitive materials, it is necessary to use a large amount of metal oxide in the binder of the constituent layers. As a result, the transparency of the photographic light-sensitive material is extremely reduced, making it unusable as a photographic material, and the metal oxide is separated into powder.

(Objective of the Invention) The first object of the present invention is to provide a photographic material that is well prevented from charging. The first object of the present invention is to provide a photographic material that is antistatic without impairing its transparency. A third object of the present invention is to provide a photographic material that is antistatic without causing dusting of the antistatic agent.

(Disclosure of the Invention) These objects of the present invention, as a result of chain research, have revealed that in a silver halide photographic light-sensitive material having at least one silver halide layer on a support, one emulsion layer side The protective layer consists of two or more layers, and the outermost layer constituting the protective layer has a film thickness/μm of -Zn-Ti-5n-At, In-Si, Mg-B
At least one selected from the group consisting of a metal oxide and a conductive polymer compound whose main component is a-Mo-W-V'
The lower layer containing the seeds and adjacent to the outermost layer is Zn-Ti,
Sn-At-In, Si-Mg-Ba-Mo, W-
This was achieved by a silver halide photographic material characterized by containing at least one metal oxide having V't as a main component in an amount of ≠oo1its or more relative to the binder in the core layer.

Preferred metal oxide particles for the outermost layer used in the present invention are crystalline metal oxide particles, but those containing oxygen defects and small amounts of foreign atoms that form donors for the metal oxide used Generally speaking, these are particularly preferred because they have high conductivity, and the latter are especially preferred because they do not cause fog to the silver halide emulsion. Examples of metal oxides include Zn(l Ti02-5n02, At203,
In2O3, S i O2+ M g O, B a O
, M o 03. V 205 etc.

Alternatively, these composite oxides are good, especially Zn(ITi
02 and 5n02 are suitable sizes. Examples of materials containing different atoms include addition of At, In, etc. to ZnO, and addition of 5n
For 02, addition of Sb-Nb-], Rogen base, etc.
Furthermore, addition of Nb-Ta or the like is effective for T i O2. The amount of these different atoms added is 0.0 layer moL4
〜JOmo1% range is preferable, but −0,/mold〜
/Omo1% is particularly preferable.

The metal oxide fine particles of the present invention have electrical conductivity, and their volume resistivity is preferably 10 7 Ω-σ or less, particularly 10 5 Ω-α or less.

Regarding these oxides, see JP-A-Shojt-/≠31A31.
No. JA-/201/9-No. 5r-x26μ7, etc.

Yet again - Tokko Akira! A conductive material in which the above metal oxide is attached to another crystalline metal oxide particle or fibrous material (for example, titanium oxide) may also be used as described in No. 2J, J.

The particle size that can be used is preferably 10μ or less, but 2μ
If it is below, the stability after dispersion will be good and it will be easy to use. In addition, in order to minimize light scattering, O1! It is very preferable to use conductive particles of μ or less in size because it is possible to form a transparent photosensitive material.

Further, when the conductive material is acicular or fibrous, the length is preferably 30 μm or less and the diameter is 1 μm or less, and particularly preferably the length is 2 μm or less and the diameter is O1jμ or less, and the length/diameter is The ratio is 3 or more.

Father 1 The outermost layer of the present invention can contain all conductive polymer compounds, such as polyvinylbenzenesulfone ekMfA, polyvinylbenzyltrimethylammonium chloride, U.S. Patent No.≠, ior, toλ,
≠ salt polymers described in μ, i/r, r3i, Dohiro, /uA, ≠t7 - ≠, /37,277 - U.S. Patent No. ≠, 070.119, 0L12,130 ,76
Polymer latexes described in No. 7 and the like are preferred.

The metal oxide or conductive polymer compound of the present invention contained in the outermost layer is used by being dispersed or contained in a binder.

Examples of binders include proteins such as gelatin and colloidal albumin-casein as hydrophilic colloids;
Cellulose compounds such as carboxydimethylcellulose and hydroxyethylcellulose; agar-sodium alginate,
Sugar derivatives such as starch derivatives; synthetic hydrophilic colloids such as polyvinyl k'j -l+poly N-vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide or derivatives thereof and partially hydrolyzed dispersions, dextranpo+1 vinyl acetate, Examples include polyacrylic hard ester-rosin. Mixtures of two or more of these colloids may be used if necessary.

Among these, gelatin is the most used, and the gelatin mentioned here is so-called lime-processed gelatin.

Refers to acid-treated gelatin and enzyme-treated gelatin.

In addition to being able to replace part or all of gelatin with synthetic polymeric substances, so-called gelatin derivatives, i.e., amino groups and imino groups as functional groups contained in the molecule, can be used.
A hydroxy group or a carboxyl group treated or modified with a reagent having one group capable of reacting with them, or a graft polymer in which molecular chains of a polymeric substance are bonded may be used in place of the hydroxy group or carboxyl group.

What is the volume ratio of the metal oxide or conductive polymer compound used in the outermost layer and the binder? :9j to uo:to are preferred. Also, the metal moltenide or conductive polymer compound has a ratio of 22 to 22% to the binder of the layer. A 27θ weight f4 is preferable. In that case - the thickness of the outermost layer does not exceed 1 μm gold.

It is particularly preferable that the volume ratio of the metal acid compound and/or the conductive polymer compound to the binder is sr: 7J- to 70
:30, and the film thickness of the outermost layer is 0.0j~/μm.

Next, the protective layer formed adjacent to the outermost layer (referred to as the adjacent layer) will be described. The metal oxide used is exactly the same as that used for the outermost layer. As for the binder used in the adjacent layer, not only can the same binder as the outermost layer be used, but also a part or all of the binder may be replaced with a conductive polymer compound that can be used in the outermost layer. The metal oxide used in a layer has a ≠00
Required for rank I or above.

A preferred form of the adjacent layer is that the monometal oxide is present in an amount of ≠00 to /λ00% by weight based on the binder, and the thickness of the adjacent layer is 0.00% by weight. /～! It is μm. It is particularly preferable that the metal oxide has a weight of UOO~/000 weight relative to the binder! The film thickness of the adjacent layer is Oo-~1 μm.

By applying the above-mentioned protective layer according to the present invention to the emulsion layer side, a photographic light-sensitive material having good antistatic properties can be obtained without impairing transparency or causing any metal oxide powder to fall off. be able to.

In the present invention, even better antistatic properties can be obtained by using a fluorine-containing surfactant in combination. The layer containing the fluorine-containing surfactant used in this case may be present in any of the constituent layers of the photographic light-sensitive material, but the protective layer is preferred, and the outermost layer is particularly preferred.

Preferred fluorine-containing surfactants used in combination with the present invention include fluoro-alkyl groups having a carbon number of μ or more.

J ionic group with alkenyl group or aryl group, 1 anionic group (sulfonic acid (salt), sulfuric acid (salt), carboxylic acid (salt), phosphoric acid (salt)), cationic group (amine salt,
ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt) - hetaine group (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt, phosphoammonium salt) or nonionic group (
Examples include activators having an unsubstituted polyoxyalkylene group, polyglyceryl group, or rubitan residue)'81-.

Are these fluorine-containing surfactants developed by Akihiro? -107--, British Patent No. 1,330.33, JP-A-3-4
≠7/2 issue, same! Hiro-/! , No. 22 Hiro.

same! No. 0-113221, U.S. Patent No. 11-. 33.

, No. 207, No. 44,3417.301, British Patent No. 1, (t/7.ri No. 73, Japanese Patent Publication No. 32-21,417, No. 37-2t7/ri, No. 9-31673- JP-A No. 937, 7♂, 120, 121, tr-, :z.

023! r-fA! 71'A6λ+, r issue, same! ? −
It is described in /ri A Yohiro≠, British Patent No. 1,4t39,110λ, etc.

Preferred specific examples of these are described below.

I − / C3F17SO3■-2C7F 15 C00N a I 3 CBF17CH2CH20SO3Na■
-Hiro C3H7 ■ CsF 175O2N-CH2COOK-t 1-+ I -7C3H7 ■ Ca F 17 So 2 N4-CH2CH20+r
+C) (2qsOa N aC8F17SO2NCH2
CH20P-ONaNa l-9' CxoFt7COOCHzCHCHzS
O3NaH ■-10H(CF2-)TCH200C-CH2H(C
F2icH200cmCHSO3Na knee//Cg
F17CH2CH200C-CH2C4Hg00C-C
HSO3Na CH3 CH3 C1 (3 CH3 SAH CH3 2H5 ■-26 C7F 15COO+CH2CH2O power completion ■(I-27
'Cl0F21COO-1-CH2CH20+Ti5TT
H ■, zz CH3 C3F17SO2N-f-CH2CH20) 9H knee 3
o Cl0H21C8F17SO2N
-4-CH2CH20tHn+m=/ /, j I-J co C3H7 C3F17SO2NJCH2CH20 tomb HI-33C2
H5 C8F, 7802N-1-CH-CH2-0ga → CH2
CH2O beat HC1 (a knee 3t C3H7 C3F17SO2N-CH2COO-4-CH2CH2
0-)T, -H ■-3 CH3 ■-47 HfCF2+TcH2O-CH2CF2H20-CH2
CH2CF2H0+cH2cH2018H ■-μ2 3H7 H It is also possible to use another antistatic agent in the retention layer of the present invention or other layers, and by doing so, a more preferable antistatic effect can be obtained.

Such antistatic agents include - for example, U.S. Pat.

772.137, 2,972.13j, J, O
t2,7. ! r! No. 3.2A2, 107, No. 3,
31 Hiroshi, λri/issue-same J, AI! , j3/issue, same 3,
7j3,71A, 3,931,999-Dohiro, 0
70. /No.19-sameμ, /IIL7゜! ! No. O, German Patent No. -, too, ≠ JJ No., Japanese Patent Application Publication No. 2003-19919 /, /
1! No. ≠♂-94L, ≠33-'49-','
t, No. 733, No. 60-144゜372 - Ta O-ta≠, O No. 3, item 1! Polymers such as those described in US Pat. No. 1, 9! λ,
tri issue, same 3゜It21,4116, same 3. ! 77
．． No. 074, same J,','jμ,buichi! No., same j, j!
, 2. ri No. 72, (Tsukasa J, 666, J♂ No. 7 - Tokkai Sho!
μm/! 9 + No. 23 - Same j7 - 10 Tade 7 July - + Same! -4ti<041-74-/jθ6.2j,
same! Tha! 723/issue, same! Knee 33!2/issue, same! ?
-203413! r issue-same rl-2017413-same! Day/9/031A, same/, /91. It! 0
No., British Patent No. 7744.106, Patent Application Sho&/-/l
O! Surfactants 1, such as those described in US Pat. No. J, OA, 2,700-3. -14t3
．． Metal oxide-colloidal silica, etc., barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, colloidal silica as described in No. r, No. 33, No. j, 12j, jj/, etc. Alternatively, a so-called matting agent made of powdered silica or the like can be mentioned.

Also, ethylene glycol, phlopylene gelicol, '+
't' ) 'J Methylolpropane, etc. JP-A-Sho! ≠−t
? A polyol compound as shown in No. ≦2 can be added to the retention layer or other layer of the present invention, and by doing so, a more preferable antistatic effect can be obtained.

The light-sensitive material according to the present invention is a conventional silver halide light-sensitive material (for example, a black-and-white light-sensitive material for photography).

(Black-and-white sensitive materials for X-ray, black-and-white sensitive materials for printing, etc.) - Ordinary multilayer color photosensitive materials (For example - Color reversal film, Color negative film - Color positive film, etc.) 1 Various photosensitive materials can be mentioned. . It is particularly effective for silver halide photosensitive materials for high-temperature, rapid processing - high-sensitivity silver halide photosensitive materials.

A silver halide photosensitive material according to the present invention will be briefly described below.

A hydrophilic colloid similar to the binder for the photographic layer and the binder for the surface protective layer is used.

Other known surfactants may be added alone or in combination to the X component layer of the present invention. Although they are used as coating aids, they are also occasionally used for other purposes, such as emulsification and dispersion, sensitization, and other improvements in photographic properties.

These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide type, glycerin type-glycidol type, higher alkylamines, and
Ammonium salts - Pyridine and other heterocycles - Cationic surfactants such as phosphonium or sulfoniums: Carboxylic acids - Anionic surfactants containing acidic groups such as sulfonic acid, phosphorus e-am esters, phosphate esters, amino acids - Aminosulfonic acids - Ampholytic surfactants such as sulfuric acid phosphoric acid esters of amino alcohols.

The present invention also includes a smoothening composition, such as U.S. Pat. No. J, 079. 37-$3.01rO.

3 Noah, same No. J, j≠Yu, Ri No. 70, same No. 3゜29≠
, No. 337 and Japanese Published Patent No.! 12-/2ri, 120
Modified silicones such as those shown in No.

The photographic light-sensitive material of the present invention has a photographic constituent layer as described in US Patent No. 3.
'A//, 9// issue, same 3. ≠//, 9/λ, Tokuko Sho≠t-yo JJ/, etc. may be included.

In addition, the photographic material of the present invention contains U.S. 7 in the photographic constituent layer.
% allowance 3rd. ≠ii, ta// issue, same 3. Hiroshi/, ?
/-No.-Tokuko Akira! J'-! The alkyl acrylate latex described in No. 33/ etc. can be included.

The silver halide grains in the emulsion may have a regular crystal shape such as a cube or octahedron, or may have an irregular crystal shape such as a spherical shape, a plate shape, a potato shape, etc.
It may consist of a mixture of particles of two different crystal forms, which may have irregular crystal forms or may have a composite form of these crystal forms. Further, tabular grains having a particle diameter of one or more times the particle thickness are preferably used for the present invention (for details, refer to RESEARCHDISC
LO3URE22j winding tem #22! J II
P, 20-P, J♂, January issue, /23, and JP-A-1-/λ7-2/ issue, 5r-ii Jqxt
(described in the publication).

In the present invention, the photosensitive silver halide emulsion may be a mixture of 12 or more types of silver halide emulsions. The emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc. Substantially non-light sensitive emulsion (
(The surface or interior may or may not be covered) may be used in a mixture or may be separated into separate layers.

For example, in the same layer as a spherical or potato-shaped photosensitive emulsion and a photosensitive silver halide emulsion consisting of tabular grains with a grain size of 5 times or more the grain thickness, or in JP-A-Shoj! -/λ7 Octopus/ may be used in different layers as described in the publication. When used in different layers, the light-sensitive silver halide emulsion consisting of tabular grains may be on the side closer to the support or, conversely, on the side farther away.

The silver halide emulsion layer and other hydrophilic colloid layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardening agents (either singly or in combination). Typical examples include mucochloric acid-formaldehyde-trimethylolmelamine, glyoxalu, 3-dihydroxy-/.

Gudioxane-2,3-dihydroxy=yo-1 methyl/, 4cm dioxane, succinic aldehyde.

Aldehyde compounds such as glutaraldehyde Nidivinyl sulfone-methylene bismaleimide/lJ, j-)
IJ acryloyl-hexahydro-S-triazine-
/, J, z-trivinylsulfonyl-hexahydro-5-)riazine bis(vinylsulfonylmethyl)ether, /, J-bis(vinylsulfonylmethyl)furopanol-2, bis(α-vinylsulfonylacetamido)ethane. Vinyl compounds;,! , Il-dichloro-monohydroxy-5-)riazine sodium salt-co,≠-dichloro-6-medoxyS-)riazine; Ethyleneimine compounds;
etc. can be mentioned.

Silver halide emulsion layer of the photographic light-sensitive material of the present invention.

Types of silver halides used in surface protective layers - Manufacturing methods, chemical sensitization methods, antifoggants - Stabilizers - Hardeners, plasticizers, lubricants, coating aids - Matting agents, brighteners - Spectral enhancement There are no particular restrictions on dyes, dyes, color couplers, etc.; for example, Research Disclosure K (Resea
Reference may be made to the description in ``Rch Disclosure''/Volume 76, pages 22-3 (December 1997Ir).

The present invention will be illustrated below with reference to Examples, but the present invention is not limited thereto.

Example 1 An emulsion layer and a protective layer (consisting of the contact layer and the outermost layer) on one side of a polyethylene terephthalate film support of approximately /7 μm
(emulsion layer side) and back protective layer C on the other side.
Samples /-/ to /-10 consisting of back layer side) were coated and dried according to a conventional method. °The composition of each layer is as follows.

A) Emulsion layer side (a) Emulsion layer (3 μm) Binder; Gelatin 2. j? /m2 Coated silver amount: jf/m2 Silver halide composition; AgI /, r mat c
ir and AgBr 9 r , j mol 4 antifoggant; l-phenyl-yo-mercaptoterrasil 0
．． 3 f/Ag/00 hardness g(agent;/, j-bis(
vinylsulfonyl)-propanol 2/, cof/1
009 gelatin ζ mouth) Adjacent layer 1/μm) Binder; gelatin hard ILHII; /, J-his(vinylsulfonyl)-prono-nor-2/, λf/1009 gelatin (c) outermost layer (0.1 μm) binder; Gelatin coating agent; pt-octylphenoxyethoxyethoxyethanesulfonic acid sodium salt 20m97m2 B) Back layer (approximately 3 μm) Binder; gelatin 1. f/m2 Coating agent: N-oleyl-N-methyltaurine sodium salt 7 ~/m2 Nm agent: /, J-bis(vinylsulfonyl)-propanol-2 /, λq7'1oot gelatin Each sample has its outermost layer , a layer having the composition shown in Table 1 was provided as an adjacent layer.

(1) Static mark test These unexposed samples were conditioned for 2 hours at 104 RH for 2 hours, and the static marks of each sample on various materials were measured in a dark room under the same air conditioning conditions. After rubbing with a rubber roller and a urethane roller to determine whether the static marks were formed or not, the film was developed with the following developer and washed with water for a certain period of time to determine the degree of static mark formation.

(Current liquid composition) Hot water room Sodium tetrapolyphosphate 2.07 Anhydrous sodium sulfite Yo09 Hydroquinone
109 Sodium carbonate C/water salt) Hiro O? /-Phenyl-3-pyrazolidone 0.37 Potassium Bromide 2
．． 02 Add water tooml
(pH 10, 2) The antistatic properties of these samples are shown in Table 1.

In Table 7, the evaluation of the degree of static mark occurrence was divided into the following μ stages.

A: No static marks were observed at all B:
Slightly recognized C:
(2) Transmittance test Using an unexposed sample that was developed and fixed as described in (1), the total light transmittance was measured.

Sample 1-/(control) was set as 100, and the relative values relative to that were shown in Table 1 as relative transmittance. Note that the total light transmittance was measured according to ASTM I)-1003.

(3) Powder removal test The sample was cut into 3.3cm x 3ocm and weighed 2!0C1t.

Humidity was controlled for 3 hours at the relative humidity. The emulsion layer side of the sample.

j A white drawing paper with a load of Kq J crnx J
I rubbed the c1nkt blue color by going back and forth 3 times. The deposits on the drawing paper were evaluated using the following ≠ scale.

A: No deposits were observed at all.

B: I Slightly recognized.

C:　　　　　　Quite acceptable.

D = 1 is observed almost entirely. .

(4) Relative Sensitivity After exposing the sample to tungsten lamp light completely passed through Fuji Film's filter SP-/≠.

It was processed according to the development method described above. Other samples were evaluated as sensitivity 5 (ioo) of sample l-/(contronil).

Compound Ta) Polyacrylic acid sodium salt (molecular weight 100,000) As is clear from Table 1, one sample of the present invention (l-1~/-A) V
i-It has an excellent antistatic effect with almost no static marks on rollers made of two different materials (rubber and urethane) based on their static charge under humidity conditions such as 10% relative humidity. In addition, it has good transmittance, powder drop, and sensitivity. On the other hand, the antistatic property of one control was significantly inferior, and the sample used for comparison / -7 ~ No? Since the outermost layer or the adjacent layer does not contain the compound of the present invention, it is impossible to improve the static mark on both rubber and urethane materials. In addition, in the case of sample/-ta, sufficient antistatic properties could not be obtained because the amount of metal oxide in the adjacent layer was smaller than that of the binder. Although the comparative sample/-IO has improved antistatic properties, it is significantly inferior to the present invention in terms of transmittance and poor powder removal. This is because the comparative sample /-10 does not have an outermost layer and the adjacent layer directly becomes the outermost layer J8.

As described in this example, the present invention is a significant improvement over the conventional antistatic technology, and as a result, a good photographic material could be obtained.

Claims (1)

[Claims] In a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support, the protective layer on the side of the emulsion layer consists of two or more layers, and the outermost layer constituting the protective layer has a thickness of 1 μm. Below, Zn, Ti, Sn, Al, In, Si
, Mg, Ba, Mo, W, contains at least one selected from the group consisting of metal oxides and conductive polymer compounds whose main components are V, and the lower layer adjacent to the outermost layer is Zn.
, Ti, Sn, Al, In, Si, Mg, Ba, Mo,
1. A silver halide photographic material, characterized in that the layer contains at least 400% by weight of at least one metal oxide selected from metal oxides containing W and V as main components, based on the binder in the layer.