JPH02272537A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a good antistatic property without changing with age by using a biaxially stretched polyester film which is formed by applying a specific coating layer on a polyester film, then stretching the film and is 0.01 to 2mum in the thickness of the conductive coating layer and 0.05 to 3mum in the thickness of a vinylidene chloride layer as a base. CONSTITUTION:The biaxially stretched polyester film which is 0.01 to 2mum in the thickness of the conductive coating layer and 0.05 to 3mum in the thickness of the vinylidene chloride layer is formed by applying the conductive coating layer which consists of the vinylidene chloride polymer A and at least one kind B of the metal oxides essentially consisting of Zn, Ti, Sn, Al, In, Si, Mg, Ba, Mo, W, and V and has <=10<7>OMEGA-cm volume resistivity thereof and has 1/99 to 80/20 A/B weight ratio and the coating layer consisting of the vinylidene chloride polymer A on the polyester film, then stretching the film. The film formed in such a manner is used a the base. The photographic sensitive material imparted with the antistatic property without impairing the transparency is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as "sensitive material") that has improved antistatic properties and dust retention after processing, and has strong film strength and dimensional stability. This paper concerns a sensitive material with excellent properties and pinhole resistance.

(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. Electrostatic charges often accumulate due to exposure to This accumulated electrostatic charge causes many problems, but the most serious one is that the photosensitive emulsion layer is exposed to light when the photosensitive emulsion layer is exposed to light due to the discharge of the accumulated static tL charge before processing, and when the photographic film is processed. It causes dot-like spots or dendritic or feather-like cotton clumps. 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, it will be easily recognized that if it appears in a medical or industrial X-ray film, it will lead to a very dangerous judgment. Alternatively, in the case of photosensitive materials for plate making (Graphiso Arts photosensitive materials), static marks may stain the print, or in the case of industrial squirrel window materials, they may cause electronic wiring diagrams to be missing. cause serious trouble. 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. This occurs due to separation of the support surface and emulsion surface, etc. In addition, in the finished product, separation of the base surface and emulsion surface occurs when the photographic film is wound and changed, or mechanical parts in automatic processing machines for X-ray film or fluorescence aggravation This occurs due to contact separation between the parts.

Furthermore, in the case of plate-making photosensitive materials, printer burn-in may be caused by time or corrections. It can also occur due to contact with other packaging materials. Static marks on photographic materials induced by such accumulation of electrostatic charges become more noticeable as the sensitivity of photographic materials increases and processing speed increases. Particularly in recent years, as photographic materials have become more sensitive and are subjected to harsh handling such as high-speed coating, high-speed photographing, and high-speed automatic processing, it has become even more likely that stain marks will occur.

Furthermore, the presence of dust after development has become a serious problem in recent years, and improvement thereof is also important.

The best way to eliminate these electrostatic disturbances is to increase the electrical conductivity of the material so that the electrostatic charge can be quickly dissipated before the accumulated charge is discharged.

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 various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. It's here.

For example, US Pat. No. 2,882,157, US Pat. No. 2,972.
No. 535, No. 3,062,785, No. 3.262,8
No. 07, No. 3,514,291, No. 3,615.53
No. 1, No. 3,753,716, No. 3,938.999
For example, polymers such as those described in U.S. Patent No. 2.982651, U.S. Pat.
552.972, 3,655.387, etc. and surfactants such as those described in U.S. Pat.
Colloidal silica as described in No. 25,621 is known.

However, many of these materials exhibit specificities depending on the type of film support and photographic composition, giving good results for certain film supports and photographic emulsions and other photographic components, but not for other different films. Not only are supports and photographic components completely useless for antistatic purposes, but photographic properties may also be adversely affected.

Furthermore, it has the disadvantage that it loses its antistatic properties during development.

In addition, Japanese Patent Publication No. 35-6616 describes a technology using tin oxide as an antistatic treatment agent, but this technology uses amorphous tin oxide colloid, and its conductivity It is a material that has humidity dependence and loses its function as a conductive layer under low humidity, and in terms of wood quality, it is no different from the various substances mentioned above.

Furthermore, a technique for preventing static electricity by providing a conductive polymer on a support is described in JP-A No. 64-65180, but this technique has the major disadvantages of humidity dependence and extremely low film strength. Ta.

On the other hand, for example, in U.S. Patent No. 3,062,700 and Japanese Patent Application Laid-Open No. 143431/1989, the conductivity of the conductive material is almost dependent on temperature as a conductive material used as a conductive support for photographic light-sensitive materials or electrostatic recording materials. Not crystalline zinc oxide,
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.

Furthermore, as an improvement on this, a method of containing a crystalline conductive metal oxide in the undercoat layer is disclosed in JP-A-57-104931 and JP-A-57-104931.
No. 7-118242, No. 58-62646, No. 58-
It is described in No. 62647, etc.

It is true that these methods have improved transparency, but the adhesion between the support and the conductive layer containing the metal oxide is insufficient, resulting in the drawback that the film of the developed film may fall off during the development process or after it has been developed. It was something that I had. Another drawback is that white pinholes are generated on the image due to scratches during development.

Furthermore, these techniques have the disadvantage that the dimensions tend to change depending on storage conditions, development processing methods, and conditions.

(Objective of the Invention) The first object of the present invention is to
An object of the present invention is to provide a photographic material that is well prevented from charging. A second 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 an antistatic photographic material that has excellent film strength and does not generate pinholes.

A fourth object of the present invention is to provide a photographic material with improved dust retention after processing.

A fifth object of the present invention is to provide a photographic material with improved dimensional stability and excellent antistatic properties.

(Disclosure of the Invention) These objects of the present invention are to provide a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on at least one side of the support. Vinylidene chloride polymer (A) and Zn, Ti, Sn, AIS In, St on at least one side.
, Mg, , Ba.

The main components are Mo, W, ■, and the volume resistivity is 10.
Consisting of at least one type (B) selected from metal oxides having a resistance of Ω-1 or less, (A)/(B) is 1/9 by weight
After applying a coating layer consisting of a conductive coating layer with a ratio of 9 to 80/20 and a vinylidene chloride polymer (A), the coating layer is stretched in at least one direction, and the thickness of the conductive coating layer is 0.01 to 2 μm and This was achieved by a silver halide photographic material characterized by having as a support a two-wheel stretched polyester film having a vinylidene chloride layer of 0.05 to 3 .mu.m.

The present invention will be described in detail below.

The polyester film used in the present invention has a polyethylene terephthalate (hereinafter abbreviated as PET) component of 90%.
A film made of a copolymer having the above.

The vinylidene chloride copolymer (A) used in the present invention is 70 to 99.5% by weight, preferably 85 to 90% by weight.
Copolymer containing vinylidene chloride units of JP-A-51-1
A copolymer of vinylidene chloride/acrylic acid ester/vinyl monomer having an alcohol in the side chain described in No. 35526, a copolymer of vinylidene chloride/alkyl acrylate/acrylic acid described in U.S. Pat. No. 2,852.378 , copolymer of vinylidene chloride/alkyl acrylate/itaconic acid described in U.S. Pat. No. 3,788.856, copolymer of vinylidene chloride/acrylonitrile/itaconic acid described in U.S. Pat. No. 2,698.235, patent application No. 63-174698, patent application 1986-174
Examples include core-shell type vinylidene chloride copolymers described in No. 699. Specific compounds include the following, but the present invention is not limited thereto. (
All numbers in ) represent weight ratios.

A-1 Copolymer of vinylidene chloride: methyl acrylate hydroxyethyl acrylate (83 12: 5) A-2 Copolymer of vinylidene chloride: ethyl methacrylate: hydroxypropyl acrylate (8210: 8) A-3 Vinylidene chloride: hydroxy diethyl Copolymer of methacrylate (92:8) A-4 vinylidene chloride;
Methyl methacrylate; acrylonitrile (90:8:
2) Copolymer A-5 Vinylidene chloride; Butyl acrylate; Copolymer A-6 of acrylic acid <94:4:2> Vinylidene chloride:
Copolymer A-7 of butyl acrylate: itaconic acid (75:20:5) Vinylidene chloride: Methyl acrylate: Itaconic acid (90: 8: 2) Copolymer A-8 Vinylidene chloride; Methyl acrylate: Methacrylic acid ( 94:4=
2) Copolymer A-9 Copolymer A-10 of vinylidene chloride: itaconic acid monoethyl ester (96: 4) Copolymer A of vinylidene chloride: acrylonitrile: acrylic acid (96: 3.sat, 5) -11 Copolymer of vinylidene chloride: methyl acrylate: acrylic acid (90:5:5) A-12 Vinylidene chloride: ethyl acrylate: acrylic acid (92:5; 3)
Copolymer A-13 (vinylidene chloride; methyl acrylate: 3-chloro-2-hydroxypropyl acrylate)
(84:9 near) copolymer A-14 vinylidene chloride:
Methyl acrylate N-ethanol acrylamide (8
Copolymer A-15 of vinylidene chloride dimethyl methacrylate: acrylonitrile: acrylic acid (90:2:1) Copolymer A-16 of vinylidene chloride: methyl methacrylate: methylol acrylate: acrylonitrile (90:2:1) :5:4
: Copolymer of I) Also, in terms of adhesion to the substrate, reactive groups (for example, carboxyl group, methylol group, amino group, sulfinic acid group, epoxy group, chloromethyl group, etc.) are added to the side chain.
A copolymer of a heptamer having a vinylsulfonyl group, etc.) is particularly preferred.

The number average molecular weight of the vinylidene chloride copolymer used in the present invention is not particularly limited, but is preferably 200,000 or more, particularly preferably 300,000 or more and 2,000,000 or less.

Crystalline metal oxide particles are preferable as the metal oxide used in the present invention, but those containing oxygen defects and those containing a small amount of foreign atoms that form donors for the metal oxide used are generally used. Specifically, they are particularly preferred because they have high conductivity, and the latter are especially preferred because they do not impart capri to the silver halide emulsion. An example of metal oxide is Z
n○, T! O2, Snow, A11z03, I
nzoz, SiOx, MgO, BaOlMob, ,
V, ○.

etc., or these composite oxides are good, especially ZnO1
Ti○2 and 5nOz are preferred. Examples of containing different atoms include, for example, addition of A1, In, etc. to ZnO;
For SnO, it is effective to add sb, Nb, halogen elements, etc., and for TiO□, it is effective to add Nb, Ta, etc. The amount of these different atoms added is O, O1mo1%~
The range of 30mol% is preferable, but 0.1mol%~
Particularly preferred is 2Qmo1%.

The metal oxide fine particles of the present invention have electrical conductivity, and have a volume resistivity of 10'Ω-cm or less, particularly 105Ω-cm.
It is preferable that it is below.

These oxides are described in JP-A-56-143431, JP-A-56-120519, JP-A-5B-62647, and the like.

Furthermore, as described in Japanese Patent Publication No. 59-6235, a conductive material in which the above metal oxide is attached to other crystalline metal oxide particles or fibrous materials (e.g., titanium oxide) may be used. .

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. Further, in order to minimize the light scattering property, it is very preferable to use conductive particles with a size of 0.5 μm or less, since this makes it possible to form a transparent photosensitive material.

When the conductive material is acicular or fibrous, the length is preferably 30 μm or less and the diameter is 2 μm or less, particularly preferably the length is 25 μm or less and the diameter is 0.5 μm or less, and the length/diameter ratio is is 3 or more.

Weight ratio (A/B) of vinylidene chloride polymer (A) and metal oxide (B) forming the conductive coating layer in the present invention
) is 1/99 to 80/20, preferably 3/
95-60/40, particularly preferably 5/90-55/4
It is 5.

The thickness of the conductive coating layer formed from components (A) and (B) in the present invention can be freely set depending on the application, but after stretching, the thickness is 0.01 to 2 μm, preferably 0.
．． 02-1.5 μm, particularly preferably 0.05-1 μm
It is.

The thickness of the coating layer made of vinylidene chloride polymer (A>, which is another layer in the present invention) is 0 after stretching.
．． 0.01 to 3 μm, preferably 0.02 to 1.5 μm, particularly preferably 0.105 to 1 μm.

In the present invention, the conductive layer consisting of components (A) and (B) and the coating layer consisting of a vinylidene chloride polymer are not particularly specified for the polyester film, and either one may be applied first. The coating may be applied sequentially or simultaneously.

Furthermore, heat-resistant agents, weather-resistant agents, inorganic particles, water-soluble resins, emulsions, etc. may be added to the two types of coating materials within a range that does not impede the effects of the present invention.

For example, it is very preferable to add inorganic fine particles to each of the two types of coating compositions of the present invention and then biaxially stretch them, as this can improve antistatic properties, adhesion, and lubricity without impairing transparency. Examples of the inorganic fine particles to be added include silica, colloidal silica, alumina, alumina sol, kaolin, talc, mica, and calcium carbonate. The a-free fine particles preferably have an average particle size of 0.01 to 10 μm,
More preferably 0.05 to 5 μm, particularly preferably 0.05 μm.
08 to 2 μm, preferably 0.05 to 10 parts by weight based on the solid content in the coating material, and particularly preferably 0.1
~5 parts.

In addition, the two types of coating materials of the present invention contain various organic or inorganic,
A curing agent may also be added. These curing agents may be low-molecular compounds or high-molecular compounds (these may be used alone or in combination).

Examples of low-molecular curing agents include "The Theory to the Photographic Process" by T.H. James (T, 11.
Theory to the Photography
ic Process) J, 4th edition, pages 77-88 are used, and among them, those having vinyl sulfonic acid, aziridine groups, epoxy groups, and triazine rings are preferred, especially those described in JP-A Showa 53-41
221 and JP-A No. 60-225143 are preferred.

A polymer curing agent is a compound having a molecular weight of 2,000 or more and preferably having at least two or more groups in the same molecule that react with a hydrophilic colloid such as gelatin. Examples include aldehyde groups, epoxy groups, active halides (dichlorotriazine, chloromethylstyryl, chloroethylsulfonyl groups, etc.), active vinyl groups, active ester groups, and the like.

Examples of the polymer curing agent used in the present invention include dialdehyde starch, polyacrolein, and U.S. Pat.
Polymers having aldehyde groups, such as the acrolein copolymers described in US Pat. No. 3,623,8
Polymer having epoxy group described in No. 78, Research
Polymers having dichlorotriazine groups described in Disclosure Magazine 17333 (197B) etc. Polymers having active ester groups described in JP-A-56-66841, JP-A-56-142,524, U.S. Pat. No. 161.407, Japanese Unexamined Patent Application Publication No. 1974 = 6503
Issue 3, Research Disclosure Magazine 16725
(1978), etc., or a polymer having a group serving as a precursor thereof is preferable, and in particular, a polymer having an active vinyl group or a group serving as a precursor thereof, as described in JP-A-56-142524, etc., is preferable.
Preferably, the active vinyl group or its precursor group is bonded to the polymer main chain by a long spacer.

Specific examples of the polymer curing agent used in the present invention are described below.

HP -1 + cmz C) I + bs + Cll
□-cm±□.

co c.

NIIC(CHz)zcHzsOJa 0C1lzC
IlzOCOCIIzCIIzSOzCll=CItz
P-4 +CIhCII + qz + Cl1zN1(2 P-5 +cIlzcHsu, 2 O Nl+□ +CIhCII+a NlIcmzNHCOCIlzCIlzSOz(:)l
= Cll2CH-)-.

Nll(JlzNIICOCIIzCIIzSOzCI
I = cmzHP −2 C)13 +011□−CI+±,.

+cH2c+-10 HP-6 +Cl1z CH+q.　+CHz　CH+　+.

HP -3 +cm□-CH+, s +Cth -CH+
zsco c.

NHC(CTo)zcH,sO,Na NHCHJH
COCIl, CIIzSOzC1l=CHzHP -7 L P -(-NHCHCO+ (C1,÷, COOC1l□CHCHzP +cm□-CIl+-*.

-(-C1h-CH+,.

Furthermore, the polymer curing agent that can be used in the present invention is a polymer that already has at least two curing groups in the same molecule to react with hydrophilic colloids such as gelatin, such as the polymers mentioned above. In addition, by using a hardening agent for hydrophilic colloid such as gelatin and a polymer that reacts with the hardening agent to give a polymer having at least two hardening groups in the same molecule, high This term includes substances that create molecular hardening agents.

Next, specific examples of the low molecular curing agent used in the present invention will be shown, but the present invention is not limited thereto.

■4-1 (cm□= Cll5(hcllzcONHcH) z
I -2 (CIIZ = Cll5O2CII□C0NIICI
I□)zcllzCIl□= cmSOzCIhCII
CHzSO□CH=cm゜H I(-4 CIl□= CH3ff□CH, SO□CII=CI+
□CIIZ = CI-3OCl-3OzCIIzOC
1h-5o = CHzClh = Cll5OzC1
bClhCHzSOzctl = Cl1zNa OHC (CHz)zcH0 H Formalin chromium bright bread [(cm□=Cll5O□CI+□±4C]・HzNC
JbCIIgSOJ salt H-12 C'! ＼ /CHO CIIzOI+ In addition, polymers used to make polymer hardeners used in coatings include nucleophilic groups that react with low-molecular hardeners in hydrophilic colloids such as gelatin in the same molecule. Examples of such polymers include a polymer having a primary amino group described in British Patent No. 2.011.912, and a sulfinic acid group described in JP-A-56-4141. Polymers with phenolic hydroxyl as described in U.S. Pat. No. 4,207.109, U.S. Pat. No. 4,215
．． Examples include polymers having active methylene groups described in No. 195.

Specific examples of polymers used to provide the polymer curing agent used in the present invention are shown below.

＋　CHz　　CH+　+.

+　CHz　　CH+　q.

Co CHxNH(
Hz)iNHx NHz+cm□-C1
l + +. +CII□-CII+q.

C) 13 +Chz C) +3 CH-) C) [t N.H.

0J SO□K C.I.

-(-CIl□-C+ +. +CIl□-
CH+q.

co c.

0CHZCLOCOCLCLCOCL NHC(CHs
) zctlzsOJa (The numbers represent molar ratios.) The amount of the polymer used to provide the curing agent and polymer curing agent that can be used in these coatings is as follows: , 0.05 to 30 in weight ratio
parts, preferably 0.5 to 15 parts.

The above coating material is stretched after application, but if the coating composition is within the range of the present invention, the coating film will not crack due to stretching, and will have good adhesion to the polyester film of the base material, antistatic properties, and transparency. A two-wheel stretched polyester film with excellent properties can be obtained.

In particular, in order to significantly exhibit the effects of the present invention, it is best to stretch the coating film with water remaining in it in the process of stretching after coating. Methods such as lowering the temperature and increasing the stretching speed are effective.

The coating concentration is 0.5 to 10% by weight, preferably 0.5 to 10% by weight.
5% by weight, and the stretching temperature is 85-250°C, preferably 95-200°C. The stretching speed is appropriately selected depending on the stretching temperature. For example, when stretching at 85°C, it is 5 to 15 m/min, and when stretching at 135°C, it is 20 m/min.
-70 m/min is a standard.A typical method for producing a biaxially stretched polyester film is shown below, but the present invention is not limited thereto.

Polyester resin is melted at a predetermined temperature, extruded into a sheet onto a cooling drum, and stretched in the longitudinal direction at a predetermined temperature and a predetermined magnification. Either one of the conductive paint consisting of (A) and (B) and the vinylidene chloride polymer paint is applied on the uniaxially stretched polyester film after stretching, and then the other is applied, or both are applied simultaneously. Apply. In this particular case of sequential coating, it is preferable to coat the first layer and dry it at a suitable temperature (preferably 30 to 220 DEG C.) before coating the next layer. At this time, various treatments such as corona discharge treatment, electron beam irradiation treatment, plasma treatment, etc. are performed in air or other gas atmospheres to improve coating properties and adhesion to the substrate. It is preferable.

In the case of sequential coating, it is preferable to apply the above-mentioned treatment before coating the coating material.

For coating, known methods such as gravure coating, reverse coating, barcode coating, and spray coating can be used.

After coating, the uniaxially stretched polyester film is continuously dried appropriately, or while drying, it is stretched perpendicularly to the previous stretching direction and heat treated, or after heat treatment, it is stretched in the longitudinal direction. Re-stretch and heat treat.

The biaxially stretched polyester film produced by the above manufacturing method is
Compared to the case where the coating material of the present invention is applied on a two-wheel stretched heat-set polyester film that has completed normal crystal orientation,
The base polyester film has extremely high adhesion and excellent transparency, and its effects are maintained even after contact with water, acid, or aqueous alkali solutions.

Furthermore, in the present invention, it is possible to further coat other layers on the conductive polyester film obtained above to improve transparency and easy adhesion. For example, gelatin may be used as a binder for forming these layers. , polyvinyl alcohol, poly(meth)acrylic esters, polyvinyl acetates, polystyrenes, cellulose, I! and vinylidene chloride, each of which may be used alone or as a mixture.

Among these, polystyrenes, vinylidene chloride, and gelatin are particularly preferable for adhesion between the layers for providing the hydrophilic colloid layer of the window material on the conductive film of the present invention, and for example, styrene/butadiene (SBR). Mention may be made of polymers vinylidene chloride/ethyl acrylate/itaconic acid. Furthermore, these may be a single layer or may have a layer structure of two or more layers. For example, a 2N structure of a gelatin layer on a tyrene/butadiene layer (at this time, dichloro-hydroxytriazine may be contained in both layers as a hardening agent). ), a 2N structure of vinylidene chloride-aqueous polyester layer/gelatin layer, or a three-layer structure of ethyl acrylate layer/vinylidene chloride layer/gelatin layer, etc. are preferably used. It is even more preferred to pre-treat and activate the film (eg, corona, heat, electron beam, ultraviolet, acid, alkali, etc. treatment) before applying each layer.

Each of these layers may be composed of a single binder, or may be a mixture of two or more kinds of binders, and may further contain other substances (for example, a matting agent, a hardening agent, a surfactant, etc.) depending on the case.

The photosensitive material of the present invention is characterized by having at least one photosensitive silver halide emulsion layer on the biaxially stretched polyester film described above, and in this case, the antistatic layer may be provided on both sides or one side of the support. However, sufficient antistatic properties can be obtained even with only one side. In addition, when the photosensitive silver halide emulsion is provided on only one of the supports,
The antistatic layer is preferably provided on the opposite side (back side).

When coating the photosensitive material layer on the antistatic layer, a coating liquid (generally a hydrophilic colloid liquid) that forms the photosensitive material layer may be applied as it is, but corona treatment, heat treatment, or
Ultraviolet irradiation, flame treatment, electron beam irradiation, acid or alkali treatment, etc. may also be performed.

The sensitive material of the present invention will be described in detail below.

The sensitive material of the present invention is composed of a silver halide emulsion layer, a bank layer, a protective layer, an intermediate layer, an antihalation layer, etc., and these are mainly used as a hydrophilic colloid layer.

In this case, binders for the hydrophilic colloid layer include, for example, proteins such as gelatin, colloidal albumin, and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, and starch derivatives; synthetic hydrophilic colloids. For example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or their i-forms and partially hydrolyzed dispersions, dextran, polyvinyl acetate, polyacrylic acid ester, rosin, etc. Depending on the situation, mixtures of two or more of these colloids may be used.

Among these, gelatin is the most used, and gelatin here refers to so-called lime-processed gelatin, acid-processed gelatin, and enzyme-processed gelatin.

In addition to being able to replace part or all of gelatin with synthetic polymer substances, so-called gelatin derivatives, i.e., amino groups, imino groups, etc. as functional groups contained in the molecule,
A hydroxyl 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 polymer substance are bonded may be used instead.

In the present invention, a fluorine-containing surfactant can also be used 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 material, but it is preferable to use 8WJ! 5, and is particularly preferably the outermost layer.

Preferable fluorine-containing surfactants to be used in combination with the present invention have a fluoro-alkyl group, alkenyl group, or aryl group having 4 or more carbon atoms, and have an anionic group (sulfonic acid (salt), sulfuric acid (salt), salt), carboxylic acid (salt),
Phosphoric acid (salt)), cationic group (amine salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt), betaine group (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt,
Examples include activators having a phosphoammonium salt) or a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group, or sorbitan residue).

These fluorine-containing surfactants are disclosed in JP-A-49-10722, British Patent No. 1.330,356, and JP-A-53-84.
No. 712, No. 54-14224, No. 50-11322
No. 1, U.S. Patent No. 4,335°201, U.S. Patent No. 4,347
, 308, British Patent No. 1.417,915, Japanese Patent Publication No. 52-26687, No. 57-26719, British Patent No. 59-
No. 38573, JP-A-55-149938, JP-A No. 54-
No. 48520, No. 54-14224, No. 5B-200
No. 235, No. 57-146248, No. 5819654
No. 4, British Patent No. 1.439,402, etc.

Preferred specific examples of these are described below.

1 1 Cs F l? S Oy K1 2
CyF+5COONa 1'-3C3H? Cs F + t S Oz N CH2CO○!
-10 CsHriC5FI? SO, 1C) 12CHCH2Osu7+CH!
÷4SOJa Hz CsF+tSOzNCHzCHz"N-CHzCHzS
OzeH H3 ■ C, HT CsF + , SOJ+CHzCHzO+T+CHz+
aSO,lNBC,)1. 0 temporary C. F+7SOJCIIzCIIzO-P ONaN
a CeH +'rO O C CH-S○, Na ■ C1. F z +'COO + CIl□C■2 old mouth ÷ CHzCIICllzO + 4H■ C+zHzs C Io H Z l C8FI7S○2N+C HzC HzO±2,,H ■ zHs Hi C aF + tsO tN + Cll-CIl g
-0-)-! -(-CH zcH to +-rT
-7r(-CH zcllcH 20÷3HC1[.

CH In the present invention, a nonionic surfactant is used, and a nonionic surfactant preferably used in the present invention may also be used, and these compounds are described, for example, in US Pat.

Specific examples of surfactants are shown below.

9th 2.

No. 651, 3.

428.

No. 456, same Compound example 3.

4 5 7.

No. 076, 3 45 4.

No. 625, CIIHz3C○O +C H2C H20+sH 3
.

552.

No. 972, 3.

6 5 5.

No., Special Publication No. 51-9610, Japanese Patent Publication No. 53-29715
No., JP-A-54-89626, Japanese Patent Application No. 7-85764, Japanese Patent Application No. 90909-1987, C I 7 II : l 3 C O O + C I
I z C It z O -)-T-(-C II
z - C II - C It z-h+C If
z C H z O±5] (described in Hiroshi Horiguchi, "New Surfactants" (Sankyo Publishing, 1975), etc.).

■ C + z H 2 S O + C H 2 C H
z O +. H ■ C I 6 H * 2 0 + C H z C I
I t O±+zH ■ C , , 8 3 S O −(− C H , C
H C H , O-)-r+C H t C H
20-). I( CH ■ CH 0+ G Hz CHz O+-T-T-+CHz C
The layer to which the nonionic surfactant used in the present invention is added is not particularly limited as long as it is at least one layer of the photographic material, such as a surface protective layer, an emulsion, etc. A layer, an intermediate layer, a subbing layer, a bank layer, etc. can be mentioned. Among these, the preferable additive layer is a surface protective layer, and it may be added to either the emulsion layer side or the back layer side, but it is more preferable to add it to both surface protective layers. When the surface protective layer is composed of two or more layers, any of these layers may be used, or the surface protective layer may be further overcoated.

The amount of nonionic surfactant used in the present invention may be 0.0001 to Ig per square meter of the photographic material, more preferably 0.0002 to 0.5g.
, particularly preferred is 00003 to 0.2 g. or,
Two or more types of nonionic surfactants of the present invention may be mixed.

In the present invention, another antistatic agent can also be used in combination, and by doing so, a more preferable antistatic effect can be obtained. Such antistatic agents include, for example, U.S. Pat.
No. 3.062785, No. 3,262,807,
No. 3,514.291, No. 3,615,531, No. 3753.716, No. 3.938,999, No. 4.
070-189, German Patent No. 4,147,550, German Patent No. 2,800,466, Japanese Patent Application Publication No. 4891.165,
No. 48-94,433, No. 49-46,733, No. 50-54,612, No. 50-94,053, No. 5
2-129,520, etc., e.g., U.S. Pat. Nos. 3,062,700 and 3,24.
Metal oxides, colloidal silica, etc., barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, colloidal silica, etc. as described in No. 5゜833, No. 3,525,621, etc. Examples include so-called matting agents made of powdered silica and the like.

Also, ethylene glycol, propylene glycol, 1.
l, 1-) Limethylolpropane, etc. JP-A-54-896
Polyol compounds such as those shown in No. 26 can be added to the protective layer or other layers of the present invention.

The present invention is particularly effective in ultra-high contrast sensitive materials containing hydrazine derivatives.

Regarding such a hydrazine derivative-containing carbide 111i material and an image forming method using the same, US Pat. No. 4,224.
No. 401, No. 4,168,977, No. 4,166.
No. 742, No. 4,241,164, No. 4,272.
No. 606, JP-A No. 60-83028, JP-A No. 60-218
No. 642, No. 60258537, No. 61-22373
It is stated in No. 8 etc. As the hydrazine derivative, those represented by the following general formula (Q) are preferred.

General formula (Q) A-N-N-B Y In the formula, A represents an aliphatic group or an aromatic group, and B represents a formyl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, or a carbamoyl group. group, alkoxy or aryloxycarbonyl group, sulfinamoyl group, alkoxysulfonyl group, thioacyl group, thiocarbamoyl group, sulfaniyl group, or heterocyclic group, and X and Y are both hydrogen atoms, or one is a hydrogen atom and the other is It represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.

Representative compounds among the compounds represented by general formula (Q) are shown below.

Q-3) Q-4) Q-2) C,II5USi113Sl+N=NN This effect can also be achieved in a method of obtaining high contrast by processing with a type or MQ type developer. Image forming methods using tetrazolium compounds are described in JP-A-52-18317, JP-A-53-17719, and JP-A-5317720.

The photosensitive material according to the present invention includes ordinary black-and-white silver halide photosensitive materials (for example, black-and-white photosensitive materials for projection, black-and-white photosensitive materials for X-ray, black-and-white photosensitive materials for printing, infrared photosensitive materials, etc.), and conventional multilayer photosensitive materials. Color photosensitive materials (e.g. color reversal film,
(color negative film, color positive film, etc.) and various photosensitive materials. It is particularly effective for silver halide light-sensitive materials for high-temperature rapid processing and high-sensitivity silver halide light-sensitive materials.

The 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 photographic constituent layer of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsification, 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, and glycidol type, higher alkylamines, and quaternary surfactants.
Cationic surfactants such as ammonium salts, pyridine and other heterocycles, phosphoniums or sulfoniums; Anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, phosphoric esters, and amino acids. , aminosulfonic acids, and sulfuric or phosphoric acid esters of aminoalcohols.

Also, in the present invention, lubricating compositions, such as U.S. Pat. No. 3,079,837, U.S. Pat. Modified silicones such as those shown in No. 537 and Japanese Patent Publication No. 52-129520 can be included in the photographic constituent layer.

The photographic light-sensitive material of the present invention has a photographic constituent layer in which U.S. Pat.
No. 411,911, No. 3,411.912, Special Publication No. 4
5-5331 and the like.

Further, the photographic light-sensitive material of the present invention includes U.S. Pat. Nos. 3,411,911, 3,411,912,
The alkyl acrylate latex described in Japanese Patent Publication No. 45-5331 and the like can be included.

The silver halide grains in the emulsion may have a regular crystal shape such as a cube or an 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 various crystalline forms, which may have irregular crystalline forms or may have composite forms of these crystalline forms. Further, tabular grains having a particle diameter of 5 times or more the grain thickness are preferably used in the present invention (for details, refer to IIIEsEARcII
DISCLOSURE Volume 2 2 5 It
em 22534 P, 20-P, 58. January issue, 1983, and JP-A-58-127921, same 5
8-113926).

In the present invention, the photosensitive silver halide emulsion may be a mixture of two or more types of silver halide emulsions. The emulsions to be mixed may differ in grain size, halogen composition, sensitivity, etc. A photosensitive emulsion and a substantially non-photosensitive emulsion (which may or may not be covered on the surface or inside) may be used, or they 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-5812792.
It may be used in different layers as described in Japanese Patent No. 1. 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 (singly or in combination). Typical examples include mucochloric acid, formaldehyde, trimethylolmelamine, glyoxal, 2,3-dihydroxy-14-dioxane, 2,3-dihydroxy-
Aldehyde compounds such as 5-methyl-1,4-dioxane, succinic aldehyde, and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 1°3.5-
triacryloyl-hexahydro-s-triazine,
1,3.5-1-rivinylsulfonylhexahydro-3
-triazine bis(vinylsulfonylmethyl) ether, 3-bis(vinylsulfonylmethyl)propano-
2, active vinyl compounds such as bis(α-vinylsulfonylacetamido)ethane; 2,4-dichloro-6
Hydroxy-S-triazine sodium salt, 2.4-
Active halogen compounds such as dichloro-6-medoxy-s-triazine; 2,4,6-triethyleneimino-S-
Examples include ethyleneimine compounds such as triazine, as well as the above-mentioned polymeric hardeners and low-molecular hardeners.

Types of silver halide used in the silver halide emulsion layer, surface protective layer, etc. of the photographic light-sensitive material of the present invention, manufacturing method, chemical sensitization method, antifoggants, stabilizers, hardeners, plasticizers, lubricants, Coating aids, capping agents, brighteners, spectral sensitizing dyes, dyes,
There are no particular restrictions on color couplers etc. For example, Research Disclosure magazine
Disclosure) Volume 176, pages 22-31 (19
You can refer to the description in ``No. 7, December 2016''.

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

Example 1 ■-1) Preparation of base Polyethylene terephthalate with an intrinsic viscosity of 0.68 was
It was melted at 80°C and extruded onto a cooling drum at about 50°C. Furthermore, after stretching 3.5 times in the longitudinal direction by roll stretching at about 100°C and performing corona discharge treatment in air, a water-based coating agent having the composition shown in Table 1 was applied to the first coating layer and the second coating layer. was applied to both sides at the same time. In addition, each coating agent contains α-
Sulfosuccinate dihexyl soda and p-octylphenoxypoly(polymerization degree 12) oxyethylene ether were each added in an amount of 0.5% by weight based on the solid content.

Table 1 shows the coating thickness after biaxially stretching the coating material with a gravure coater.
Apply as shown below, then apply at 110℃, 10m/
A two-wheel stretched polyester film having a polyester thickness of 18,011 m was produced by stretching the film by 3.5 times in a direction perpendicular to the previous stretching direction under conditions of 10 minutes and heat-treating it at 120°C.

Furthermore, this surface was treated with gelatin (0,15
g/n () and dichlorohydroxytriazine sodium salt (0,006 g/rr+) were coated and dried at 100°C to obtain a photographic support (Base 1-1 to Base 1-19)
. Samples 1-20 and 1-21 were prepared by applying the first coating layer and second coating layer as shown in Table 1 to two-wheel stretched polyethylene terephthalate in advance, and then providing the above-mentioned gelatin coating layer (Base 1). -20~Heas 1-21).

1-2) Structure of dyed layer - -1° extraction method of dyeing layer The following dyes were ball milled by the following method. Water (21,7d) and 6.7% TriLonX-200
"Surfactant aqueous solution (2.65g) (Rohm & H
(sold by AAS) was placed in a 60ml screw cap bottle. A 1.00 g sample of dye was added to this solution. Zirconium oxide (ZrO) beads (4"') (2 mm diameter) were added, the container with a tight lid was placed in the mill, and the contents were milled for 4 days. The container was removed and the contents were
．． It was added to a 5% aqueous gelatin solution (8.0 g). The new mixture was placed on a roll mill for 10 minutes to reduce foam, and the resulting mixture was then filtered to remove the ZrO beads.

Dye C0OH Efu Friendship Surfactant Sodium p-octylphenylethoxyethoxyethanesulfonate and hardener (bis(vinyl-sulfonylmethyl)ether) were added to the above dye-gelatin melt. The melt produced from the latter mixture was then applied to the aforementioned bases 1-1 to 1-21 at a dye coverage of 0.
08g/I, gelatin coating amount 0.4g/rd, surfactant 0.026g/I, and hardener 0.016g/n? It was applied to both sides so that

1-3) Constituent water of emulsion layer! Add 30 g of gelatin, 5 g of potassium bromide, and 0.05 g of potassium iodide into the container and add a silver nitrate aqueous solution (5 g as silver nitrate) and 0.73 g of potassium iodide to the container kept at 75°C while stirring.
An aqueous solution of potassium bromide containing g was added over 1 minute using a double jet method. Furthermore, silver nitrate aqueous solution (14 as silver nitrate)
5 g) and an aqueous potassium bromide solution were added by a double jet method. The addition flow rate at this time was accelerated so that the flow rate at the end of addition was eight times that at the beginning of addition. after this,
0.37 g of potassium iodide aqueous solution was added.

After the addition was completed, soluble salts were removed at 35°C by a sedimentation method, the temperature was raised to 40°C, and 60 g of gelatin was removed.
The pH was adjusted to 6.5. The temperature was raised again to 56°C, and the aggravating dye anhydro-5,5'di-chloro-9-ethyl-3
, 650 mg of 3'-di(3-sulfoprobyl) oxacarbocyanine hydroxide sodium salt was added, and then chemical sensitization using gold and sulfur sensitization was performed.

The obtained emulsion had a hexagonal plate shape with a projected area diameter of 0°85μ.
m, and the average thickness was 0.158 μm.

4-hydroxy-6methyl-1 was added to this emulsion as a stabilizer.
．． 3.3a,7-chitrazaindene and 2.6-bis(hydroxyamino)-4-diethylamino-1,3,5-
Triazine and trimethylolpropane were added.

Furthermore, the following compound was added (350 / I) N (Cz
Hs) z In addition, p-octylphenoxyjethoxyethanesulfonic acid sodium 0.01 g/d1 as a coating aid, dodecylbenzenesulfone 71 salt 0.005 g/m as a thickener, and polybotacium mousstyrene sulfonate 0.0 as a thickener.
3 g/rd, polymer latex (poly [ethyl acrylate/methacrylic acid = 97/33 particles adsorbed with poly [degree of polymerization 10] oxyethylene poly [degree of polymerization 3] oxyglyceryl dodecyl ether [3% by weight of particles]) , average particle diameter - 0.1 μm) 0.4 g/m, sodium polyacrylate (molecular weight 200,000) O, 1 g/n
-7,1,2-bis(vinylsulfonylacetamide)
Ethane 0.04g/n (, trimethylol.

4) Composition of protective layer Mugelatin 1 2g/rd polyacrylamide (molecular weight 45,000) o, 2g/m mudextran (molecular weight 380,000) 0.2g/rd polyacrylate sodium 0.02g/ g Sodium styrene sulfonate O, O] g/n (mucolloidal silica (particle size 0.02, cam) 0.04 g/
+n (degree of polymerization 10) Oxyethylene cetyl ether Q, Q2 g/m poly (degree of polymerization 10) Oxyethylene poly (degree of polymerization 3) Glyceryl-p-octylphenyl ether o, 02 g/mCs 11
? MuCeH+ ,5oZ)l-(-CIIzCIIzO+
-r+CIIz+ 4sOJaO,001g/m 0.0005g/m CI! 3 MuCqH+tCON)1+c112±3N-(JI2C
OO8C,)IT MuCaH+,SO□N+CHz CHz O+TT
+CHx CHC) I z O÷, H0, 005g/m H 0,01g/im Potassium nitrate 0, 05g/nf Mupt-t-octylphenoxyethoxyethoxyethanesulfonic acid sodium salt Ol 02 glof Mu4-hydroxy-6-methyl -1,3,3a, 7 Tetrazaindene O.

Cetyl mpalmitate (dobu) Schirhenzenesulfonic acid Dispersed with soda. Particle size 0.11μm) Mucimethylsiloxane (Geo Cutyru α-sulfocomb Dispersed with sodium citric acid.

Particle size: 0.12 μm) Liquid paraffin (dispersed with dioctyl-alpha-sulfosuccinate soda. Particle size: 0.11 μm) 0.005 g/mm Polymethyl methacrylate fine particles (Average particle size: 3.804 g/n1 005 g/rd o o s g/rtr 0゜μm, 4. 8-2.8μ abundance 80% or more) 0.04g/m Prepare a solution so that the gelatin concentration is 4wt% for each of the above emulsion layer and protective layer. This was the basic formulation for each layer.

The amount of silver coated on each side was 1.9g on the base with the composition shown in Table 1.
/rd and applied to both sides. The layers were arranged in such a way that the dyeing layer, emulsion layer, and protective layer were arranged in order from the side closest to the support.

Samples prepared as shown in Table 1 were evaluated.

In addition, developer, fixer, I went to the street below.

(Developer concentrate) Potassium hydroxide Sodium sulfite Diethylene triamine Pentaacetic acid Carbonate Potassium borate Hydroxynon diethylene glycol 4-Hydroxymethyl-4 Methyl-1-phenyl-3 = Pyrazolidone 5-Methylbenzotriazole Adjust to 11 with water (pH 10゜゜Fixer concentrate〉 Ammonium thiosulfate Sodium sulfite ethylenediaminetetraacetic acid di-and development process (adjusted to 56.6g 00g 6, 7g 16.7g 10g 83.3g 0g 11゜g g 60) 60g 0g Sodium Trihydrate 0.10g Sodium hydroxide 24g Adjust to 12 with water (adjust to pH 5.10 with acetic acid).

Automatic developing machine Second processing developing tank 6
．． 12 35℃ x 10.5 seconds fixing tank 6.5f
35℃ x 9 seconds water washing tank 6.55 20℃ x 7
．． Dry for 5 seconds 50
°C Dry to Dry Processing time: 45 seconds When starting the developing process, each tank was filled with the following processing solution.

Developing tank 2 333 ml of the above developer concentrate, 667 ml of water
- and starter 10- containing 2 g of potassium bromide and 1.8 g of acetic acid were added to bring the pH to 10.15.

Fixing tank 2 250 ml of the above fixer concentrate and 70 ml of water
mZ (1) Static mark test After conditioning an unexposed sample at 25°C and 10% RH for 2 hours, we tested the static mark on various materials in a dark room under the same air conditioning conditions. After rubbing with a rubber roller and a urethane roller to see if
The film was developed with the developer described above, fixed, and washed with water, and the degree of static mark generation was examined.

In Table 1, the degree of static mark occurrence was evaluated in the following four stages.

A: No static marks observed at all, Bt.
Slightly recognized C:
Fairly observed D: Observed on the entire surface (2) Test with dust The sample (20 (to) x 20 cm) before and after development was thoroughly rubbed with gauze under conditions of temperature and humidity of 25°C and 10% RH.
The adhesion of cigarette ash was investigated. Evaluation was performed in the following four stages.

A: No dust was observed at all.

B: A little dust was observed.

C; was significantly observed.

D: - were strongly observed.

(3) Transmittance test Using an unexposed sample that was developed and fixed as described in (1), the total light transmittance was measured.

Sample 1-1 (control) was set as 100, and relative values relative to that were shown in Table 1 as relative transmittance.

Note that the total light transmittance was measured according to ASTM D-1003.

(4) Adhesion test The completed sample was placed in an atmosphere of 25°C and 50% RH for 2 hours.
After leaving it for a week, an adhesion test was conducted using the method described below. The surface tested here is the surface provided with the antistatic layer.

(b) Adhesion test method for dry film On the surface to be tested, make 36 squares by making 7 cuts at 5 as intervals vertically and horizontally. , knit tape) and quickly peel it off in the direction of 180a. In this method, if the unpeeled portion is 90% or more, it is graded A, if it is 60% or more, it is graded B, and if it is less than 60%, it is graded 0. Adhesive strength sufficient for practical use as a photographic material is one that is classified as grade A of the above three-level evaluation.

(b) Wet film adhesion test method At each stage of development, fixation, and water washing, scratch the film at the X mark using an iron pen in the processing solution, and scratch it firmly with the tip of your finger.
Adhesive strength was evaluated during maximum peeling along the x line.

A case where the constituent layer does not peel off after the scratch is removed is graded A, a case where the maximum peeling is within 51 degrees is graded B, and other cases are grade 0.

Adhesive strength sufficient for practical use as a photographic material is one classified as B or higher, preferably grade A, of the above three-level evaluation.

[Metal oxide]

MET I 5no2/Sb (85/15
) (average particle size 0.15 μm) MET-2v2o, (average particle size 0.15 μm) [Comparative polymer] POL-1 poly (ethyl acrylate/butyl acrylate/methacrylic acid) (polymerization molar ratio 75/2015, molecular weight approx. 300,000) POL-2 Sodium polystyrene sulfonate (conductive water-soluble polymer) (molecular weight approximately 400,000) Samples 1-2 to 1-13 having the conductive layer and vinylidene chloride layer of the present invention as seen in Table 1 is superior in terms of static marks, dirt retention, transparency, and adhesion. It is also clear that the object of the present invention can be achieved even if the conductive layer and the vinylidene chloride coating layer are different. Furthermore, it is clear that even in the present invention, better adhesion can be provided by containing a curing agent in each layer.

On the other hand, control sample 1-1, which does not contain the conductive metal oxide of the present invention, was significantly inferior in terms of static marks and dust. On the other hand, comparative sample 1-
14 to 1-19 are vinylidene chloride polymers (A) of the present invention
(Samples 1-14 to 1)
-1.7), which used a conductive, water-soluble polymer instead of a metal oxide, and was particularly poor in terms of adhesion.

Furthermore, when polyethylene terephthalate that had been pre-drawn on two wheels was used (sample 1-20.1-21), the adhesion was extremely poor.

From the above, it is clear that the present invention is significantly superior to conventional techniques, and is the result of many years of research.

Example 2 2-1) Preparation of the base The same coating layer shown in Table 1 of Example 1 was applied on one side of the polyethylene terephthalate, and only the vinylidene chloride polymer with the conductive layer removed was applied on the other side. , and bases 2-1 to 2-2 were prepared in the same manner as in Example 1, except that the thickness of the polyethylene terephthalate after two-wheel stretching was 100 μm.
-21 was created.

2-2) Silver halide emulsion layer formulation In an aqueous gelatin solution kept at 50°C! An aqueous nitrate solution and a mixed aqueous solution of sodium chloride and potassium bromide were simultaneously added at a constant rate for 30 minutes in the presence of 2 x 10-S mol of rhodium chloride per mol to obtain an average particle size of 0.
．． A 2μ silver chlorobromide monodisperse emulsion was prepared. (C7! Composition: 95 mol%) This emulsion was desalted by the flocculation method, and 1+ ng of thiourea dioxide and 0.0 ng of thiourea dioxide per mole of silver were added. 6rN! Add chloroauric acid and heat at 65°C.
The product was aged until the highest performance was achieved.

The following compounds were further added to the emulsion thus obtained.

n-CrzHzs 2 X 10-” mol/A g 1 mol 4 X 10
-'mol/A g 1 mol KBr
20mg/m polystyrene sulfonic acid sodium salt 40■/ba 2.6-
Dichloro-6-hydroxy-1,35-)riazine sodium salt 30 days/day This coating solution was coated at a coating silver amount of 3.5 g/n.

2-2) Emulsion protective layer formulation The following compounds were further added to the protective layer of Example 1. Note that the gelatin content was 1.5 g/m.

Dodecylbenzenesulfonic acid sodium salt 0.05g/Sodium acetate resistant 0.03g/m5-Nitroindazole 13-divinylsulfonyl 2-propatol N-perfluorophthanesulfonyl-N-propylglycinepotadium salt Ethyl acrylate Tratix (average grain Diameter 0,1μ) Q, 015g/m 0゜05g/m 2■/Resistance 2g/n (Bank layer prescription gelatin l1ff C-C= CI+ N\N/C=OHO 03K C□C I N So, to 2゜5 g/m 03Na So, K SO, 40■/d 0J SO, 80mg/m 1.3-Divinylsulfonyl = 2-propanol ethyl acrylate latenox (average particle size 0.1μ) Dihexyl α- Sulfosacnate sodium salt 150mg/I 900mg/m 35■/rd Dodecylbenzenesulfonic acid sodium salt 35■/I2-4)
Back protective layer formulation was prepared in the same manner as in Example 1. In addition, gelatin is 1.0g/
It was set as m.

A sample film was prepared using a conventional method to form a bank layer and a bank layer on the side of the base on which the conductive metal oxide of the present invention or the comparative conductive material was provided. ! A silver halide emulsion layer and an emulsion protective layer were coated on the side not containing other conductive materials.

Table 2 shows the evaluation results of the obtained samples.

・Evaluation method for dimensional changes due to processing (dimensional stability)
Drill two holes with a diameter of 811 at intervals of 25 mm.
1/10001 after being left in a room at ℃30%RH
The distance between the two holes was accurately measured using a pin gauge with m precision. The length at this time is assumed to be XIm. Then, after developing, fixing, washing with water, and drying using an automatic developing machine, the size after 5 minutes is designated as Yll. The dimensional change rate (%) due to treatment is Y-X In the industry, it is considered that there is no practical problem if the dimensional change rate is ±0.01% or less.

The development process was carried out using the FC-660 automatic processor manufactured by Fuji Photo Film Co., Ltd., and the developer and fixer were used by the same company's LD835 and LF-
The treatment was carried out using No. 308 at 38° C. for 20 seconds. The drying temperature at that time was 45°C.

As seen from Table 2, samples 2-1 to 2-1 of the present invention
No. 3 was excellent in all respects of static marks, dust retention, permeability, adhesion and dimensional stability. On the other hand, comparative samples 2-14 to 2-21 were significantly inferior in adhesiveness and dimensional stability.

Note that the samples of the present invention gave excellent images.

Example 3 3-1) Creating a base Create a base 3- with exactly the same content as the base used in Example 2.
1 to 3-21 were created.

A sample of a multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

At this time, the photosensitive layer was formed in the order of the 1st layer to the 16N layer on the side without the base conductive layer, and the bank layer was coated on the conductive layer side of the base in the order of the 1N layer and the 2nd layer.

(Composition of photosensitive layer) The coating amount is the amount expressed in silver g/rd for silver halide and colloidal silver, and the amount expressed in g/rrrt4 for coupler additives and gelatin. The number of moles of the dye is expressed per mole of silver halide in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

U■; Ultraviolet absorber, 5olvH high boiling point organic solvent, Ex
FH dye, ExS; sensitizing dye, ExC; cyan coupler, ExM; magenta coupler ExY; yellow coupler, cpai additive No. 11! (Antihalation layer) Black colloidal silver 0.15 gelatin
2.9V-1 V-2 V-3 olv xF-1 xF-2 2nd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol%, uniform-Agl type, equivalent sphere diameter 0.9V-1 V-2 V-3 olv xF-1 xF-2) 4 μm, coefficient of variation of Ij equivalent diameter 37%, plate-like particles, diameter/W ratio 3.0) Amount applied per coating 0.03 0.06 0.07 0.08 0.01 0, Ol 0.4 0.8 2.3X10-'1.4X10-'2.3X10-'8.0X10-' 0.17 0.03 0.13 Zessian MS-2 ExS-5 ExS-7 ExC-1 ExC-2 ExC- 3 Third layer (medium-sensitivity red-sensitivity emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, core-shell ratio 2:
1 internal high Agl type, equivalent sphere diameter 0.65 μm, coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 2.0) Coated silver! W 0.65 Silver iodobromide emulsion (Agl 4 mol%, uniform Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/W-view ratio 3.0) coating Silver amount 0, 1 1, 0 2 XIO-' 1, 2xlO-'' 2 XIO-' 7 X10-' 0, 31 0, 01 0, 06 Gelatin MS-1 ExS-2 ExS-5 ExS-7 Sn xC- 1 ExC-2 ExC-3 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AglB ratio of 2:l, internal high Ag mol%, core-shell type, equivalent sphere diameter 0.7 μm, sphere Coefficient of variation of equivalent diameter 25%, diameter/thickness ratio 2.5) Application V&Amount Gelatin xS-1 xS-2 xS-5 xS-7 xC-1 xC-4 olv-1 olv-2 pd-7 51st M ( Intermediate N) Gelatin V-4 JV-5 pd-1 Polyethyl acrylate latex olv-1 Platy particles, 0.9 0.8 1.6X10-'1.6X10-'1.6X10"4 6 Xl0-' 0 .07 0.05 0.07 0.20 4.6X10-' 0.6 0.03 0.04 0.1 0.08 0.05 6th layer (low sensitivity green emulsion N) Silver iodobromide emulsion (Ag+ 4 mol%, uniform AgI type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-like particles, diameter/thickness ratio 2.0) Coating amount 0.
18 Gelatin 0,4ExS-
32XIO"'EχS-47X10-'EχS-51XIO-" ExM-50,11 8x M -70,03 ExY-80,01 Solv-10,09 S o l v-40,01 7th layer (Nakauryo green Sensitive emulsion layer) Silver iodobromide emulsion (Ag1 4 mol%, core shell ratio 1:1
surface height Agl type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter/thickness ratio 4.0) Coating 11ffi 0.27 Gelatin 0.6ExS-3
2X10-'ExS-47X10-'ExS-51XIO-' ExM-50,17 ExM-70,04 EχY -80,02 Solv-10,14 Solv-40,02 8th layer C high-sensitivity green-sensitive emulsion layer) Silver bromide emulsion (Ag+ 8.1 mol%, amount ratio 3:
4:2 multilayer structure particle, Ag+ content from inside to 24 mol, 0 mol, 3 mol%, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particle, diameter/thickness ratio 1.6 ) Application iJ! Amount 0.7 Gelatin 0.8E x
S -45,2X10-'ExS-51XIO”' Ex S -80,3 10,25 Solv-20,06 Solv-40,01 Cpd-71XIF' 9th layer (middle layer) Gelatin 0.6Cp d
-10,04 Polyethyl acrylate latex 0,12Sol
v-10,02 10th layer (donor layer for ff1 layer effect on red-sensitive layer) Silver iodobromide emulsion (Ag+ 6 mol%, core shell ratio 2; 1
internal descendant type AII, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.68 Silver iodobromide emulsion (Ag1 4 mol%) , uniform Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.19 Gelatin 1.0ExS-3
6X10-' ExM-100,19 Solv-10,20 11th layer (yellow filter layer) Yellow colloidal silver 0.06 gelatin 0.8Cpd-20
,13 Solv-10,13 Cp d -10,07 Cp d -60,002 8-1 (1,13 12th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag + 4.5 mol%, uniform -Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of 1 sphere equivalent diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount 0.3 Silver iodobromide emulsion (Ag1 3 mol%, uniform - Agl type, equivalent sphere diameter 0.3 μm, coefficient of variation of equivalent sphere diameter 30%, plate-shaped particles, diameter/thickness ratio 7.0) Application 1 ft O, 1
5 Gelatin 1.8ExS-
69X10-' Ex C-10,06 Ex C-40,03 ExY-90,14 ExY-110,89 Solv-10,42 13th N (middle N) Gelatin 0.7E x
Y-'12 0.20Solv
-10,34 14th N (high sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Ag + 10 mol%, internal cylinder Agl type, equivalent sphere diameter 1.0 μm2 coefficient of variation of equivalent sphere diameter 25%, multi-twin plate shape Particles, diameter/thickness ratio 2.0) coating 1 liter
O,5 Gelatin 0.5ExS-
61XIO-' E
Equivalent sphere diameter 0.07 am) Application root l O,12 Gelatin 0.9UV-4
0,11 tJV-50,16 S o l v-50,02 8-10,13 Cpd-50,10 Polyethyl acrylate latex 0.09 No. 16
Layer (second protective layer) Fine grain silver iodobromide emulsion (Ag+ 2 mol%, homogeneous -Agl
Mold, equivalent sphere diameter 0.07 μm) Coated silver amount 0.36 Gelatin polymethyl methacrylate particles (diameter 1.5 μm) Poly(methyl methacrylate/methacrylic acid) (molar ratio 60:40, diameter 2.1 μm) I(- 1 0, 55 0, 1 0, 1 0, 17 zHz CBF ItsOzNcII□C00Ko, oos 0.002 In addition to the above components, each layer contains emulsion stabilizer Cpd-3
(0,07 g/m), surfactant Cpd-4 (0,03
g/m) was added as a coating aid.

(Composition of back layer) O-hack 1st layer, gelatin, α-sulfosuccinic acid dioctyl ester sodium salt, polystyrene sulfonic acid soda, hack 2nd layer, gelatin, polymethyl methacrylate (average molecular weight 3.5 μm), poly(methyl methacrylate) (Mole ratio: 60/40) Average molecular weight: 2.1 μm Sodium p-octylphenoxydiethoxyethanesulfonate, 26-dichloro-4-hydroxy(g/i) Droxy-135 Sodium triazine V-1 0 ■ olv-1 Tricresyl phosphate olv-2 Diptyl phthalate (L), 119 olv-5 Trihexyl phosphate ExF-1 ExS-1 ExS-5 ExS ExS ExS-2 ExS-3 ExS-4 ExS-8 xC- 1 xC-2 (L; 112 saw 5υ: +l1-N (1,; 211 S saw ExC-3 ExC-4 I xM-10 Shil xY-8 xM xM-6 xY-9 xY-11 Cpd-5 Cpd cm゜Cpd-3 Cpd JL3 Cpd-4 Cpd-2 CIIz”CIl SOx C1h C0NHc
mt■ CI+! =CHSow~cmt C0NII cm
xpd-6 The obtained sample was developed using an automatic developing machine according to the method described below.

Processing method step Processing time Processing temperature Replenishment amount Volume color development 3 minutes 15 seconds 38℃ 15m1 2
01 bleaching 6 minutes 30 seconds 38℃ lQmf
401 water washing 2 minutes 10 seconds 35℃ l
Od 201 fixation 4 minutes 20 seconds 38°C
20rnl 3Q1 Washing (2) 1 minute 00 seconds 3
5゛C Stable 1 minute 05 seconds 38゛C Dry 4
Minutes 20 seconds 55°C Replenishment amount per 350°C Next, write down the composition of the processing solution.

(Color developer) 20 composition 101 10In1 ton Mother/& (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethyritine-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Iodine potassium hydroxylamine sulfate 4-(N-ethyl-N β-hydroxyethylamino)-2-methylaniline sulfate and H (bleaching solution) Sodium ferric ethylenediamine tetrasentate 3.0 4.0 30 .0 1.4 1.5 ■ 2.4 4.5 1.01 10.05 Mother liquor (g) 3.2 4.9 30.0 7.2 1, Off1 10.10 Replenisher (g) Sansui Salt 100.0 140.0 Ethylenediaminetetranodic acid disodium salt 10.0 11.0 Ammonium bromide 140.0 180.0 Ammonium nitrate 30.0 40.0 Ammonia water (27% > 6.5d 2.5d water In addition
1.0# 1. (H! pH6,05
,5 (Fixer) Mother liquor (g) Replenisher (g) Ethylenediamine tetranoic acid disodium salt 0.5 1.0 Sodium sulfite 7.0 12.0 Sodium bisulfite 5.0 9.5 Ammonium thiosulfate Water volume Liquid (70%) 170.0m1240.
Add 0ml water 1.011. On
! pH 6,76,6 (washing solution) Common tap water for mother liquor and replenisher was mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH-type anion exchange resin (Amberlite IR-120B manufactured by Rohm and Haas). Water was passed through a mixed bed column packed with sodium chloride isocyanurate 2 (1+r/Il and sodium sulfate 1.5g/Il) to reduce the concentration of calcium and magnesium ions to 3/Il or less. 1 was added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Mother solution (g) Replenishment solution (g) Formalin (37%> 2.(lIn!3.0)
mPolyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) Add ethylenediamine tetranoic acid disodium salt water p) 1 0.3 0.45 0.05 0.08 1.0! 1.01 5.0-8.0 5.0-8.0 The obtained sample was evaluated in the same manner as in Example 2.

The results are shown in Table 3.

Sample 3 using the base of the present invention as shown in Table 3
-2 to 3-13 show excellent performance (static mark occurrence, dust adhesion, transparency, adhesion), while samples 3-14 to 3-21 using the comparison base show dust adhesion. ,
It can be seen that this is accompanied by a significant deterioration in permeability and adhesion.

- From the above, it can be seen that the present invention is significantly superior in all respects to conventional antistatic supports.

Procedural amendment Display of incidents 1999 Patent Application No. 94667 name of invention Silver halide photographic material 3. Person making the amendment Relationship with the incident

Claims (1)

[Claims] In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on at least one side of the support, a vinylidene chloride polymer (A) is provided on at least one side of the polyester film that is the support. and Zn,
Ti, Sn, Al, In, Si, Mg, Ba, Mo, W
, whose main component is V, and whose volume resistivity is 10^7Ω-
Composed of at least one type (B) selected from metal oxides having a size of 1/2 cm or less, the weight ratio of (A)/(B) is 1/99 to 8
After applying a conductive coating layer having a ratio of 0/20 and a coating layer made of a vinylidene chloride polymer (A), the conductive coating layer is stretched in at least one direction, and the thickness of the conductive coating layer is 0.01 to 2 μm and the coating layer is made of vinylidene chloride polymer (A). A silver halide photographic light-sensitive material comprising, as a support, a biaxially oriented polyester film having a vinylidene layer having a thickness of 0.05 to 3 μm.