JPS5939737B2 - photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide photographic material with improved antistatic properties, and particularly to a photographic material with improved antistatic properties without adversely affecting photographic properties.

Photographic materials generally consist of an electrically insulating support and a photographic layer, so during the manufacturing process of the photographic material and during use, it is subject to contact friction or peeling with surfaces of the same or different materials. Electrostatic charges often build up.

This accumulated electrostatic charge causes many problems, but the most serious one is that the photosensitive emulsion layer is exposed to light when the accumulated electrostatic charge is discharged before processing, and the photographic film is processed. When this occurs, dot-like spots or dendritic or feather-like streaks occur. 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 in medical or industrial X-ray film, it will be easily recognized that it will lead to a very dangerous judgment. 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 finished products, separation of the base surface and emulsion surface when winding photographic film is performed, or mechanical parts in automatic X-ray film cameras or fluorescent intensifying screens. This occurs due to contact separation between the It can also occur due to contact with other packaging materials. Static marks on photographic materials induced by such electrostatic charge accumulation become more noticeable as the sensitivity of photographic materials increases and the processing speed increases. Particularly in recent years, static marks are more likely to occur due to the increased sensitivity of photographic materials and the increased exposure to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing. Also, when an undercoat layer is provided on the film support and a hydrophilic colloid layer such as a photosensitive silver halide emulsion layer is coated thereon, static charges may accumulate on the surface of the undercoat layer. However, the uneven electrostatic charge directly manifests itself as uneven coating of the hydrophilic colloid layer, resulting in a serious defect.

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, including the use of various hygroscopic substances, water-soluble inorganic salts, certain surfactants, and polymers. It has been tried.

For example, U.S. Patent Nos. 2,882,157 and 2,972
, No. 535, No. 3,062,785, No. 3,262,
No. 809, No. 3,514,291, No. 3,615,5
31, 3,753,716, 3,938,999, etc., for example, U.S. Pat. , No. 076, No. 3,454,625, No. 3
, 552,972, 3,655,387, etc., for example, U.S. Pat.
No. 62,700, No. 3,245,833, No. 3,52
Zinc oxide, semiconductors, colloidal silica, etc. as described in No. 5,621 are known. However, many of these materials exhibit specificity depending on the type of film support and photographic composition, giving good results with some film supports, photographic emulsions, and other photographic components, but not with others. Vine film supports and photographic components are not only completely useless in preventing static electricity, but may also have an adverse effect on photographic properties. For example, polyethylene oxide compounds are generally known to have an antistatic effect, but often have adverse effects on photographic properties such as increased fog, desensitization, and deterioration of graininess.

As described above, it is very difficult to apply antistatic agents to photographic light-sensitive materials, and the scope of their use is often limited.

A first object of the present invention is to provide an antistatic photographic material.

The second object of the present invention is to reduce the RH at low humidity (25ft). near)
The object of the present invention is to provide a photographic material having low surface resistance and improved antistatic properties.

A third object of the present invention is to provide a photographic light-sensitive material having an undercoat layer that does not cause coating unevenness due to charging phenomena when coating a photosensitive silver halide emulsion layer. These objects are achieved by a photographic material characterized by containing a polymer or copolymer having a repeating unit consisting of a betaine structure represented by the following general formula (1) in an undercoat layer or a backing layer. found that it can be achieved.

General formula (1): Among the repeating units represented by general formula (1), particularly preferred are repeating units represented by the following general formula ().

Examples of comonomers of the general formula () copolymers include acrylic acid, methacrylic acid, and alkyl esters thereof (e.g. methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, propyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, decyl acrylate) , β-cyanoethyl acrylate, β-chloroethyl acrylate, 2-ethoxyethyl acrylate, sulfopropyl methacrylate, etc.),
Vinyl esters (e.g. vinyl acetate, vinyl propionate, vinyl butyrate, etc.), vinyl ethers (e.g. methyl vinyl ether, butyl vinyl ether, oleyl vinyl ether, etc.), vinyl ketones (e.g. methyl vinyl ketone, ethyl vinyl ketone, etc.), styrenes (e.g. styrene) , methylstyrene, dimethylstyrene, 2,4,6-trimethylstyrene, ethylstyrene,
laurylstyrene, chlorostyrene, methoxystyrene, cyanostyrene, chloromethylstyrene, vinylbenzoic acid, styrenesulfonic acid, α-methylstyrene, etc.)
, vinyl heterocyclic compounds (eg, vinylpyridine, vinylpyrrolidone, vinylimidazole, etc.), acrylonitrile, vinyl chloride, vinylidene chloride, ethylene, propylene, butadiene, diisobutylene, isoprene, chloroprene, and the like.

The present invention is not limited to the above copolymerizable monomers, and any copolymer may be used as long as it has the structural unit of the above general formula, but the ratio of the monomers represented by the general formula (1) is It is preferably 50 mol% or more. Next, specific examples of typical polymers or copolymers used in the present invention will be shown. The copolymerization ratio, X, y is an example, and is not limited to this ratio. Compound Example (1) Next, synthesis examples of typical polymers or copolymers having repeating units represented by the general formula () of the present invention will be shown.

Synthesis Example 1 (Synthesis of raw materials for Compound Example (1)) 94.59 (1 mol) of monochloroacetic acid and 350 ml of methanol were placed in a reaction vessel and stirred in ice water. !
is gradually added dropwise so that the temperature within the system does not exceed 30°C.

Next, N-(ma,merdimethyl-3-
A mixed solution of 156.29 (1 mol) of (aminopropyl) acrylamide and 300 ml of methanol is added.

(At this time, as a polymerization inhibitor, phenothiazine 0.59
After that, heat the system so that the temperature in the system reaches about 60°C, and continue stirring for 10 hours.

After the reaction is completed, the generated NaCl is removed and crystallized in a large amount of acetone.

Compounds were identified according to conventional methods. M. R. , elemental analysis,
This was done using infrared absorption spectroscopy. The yield of this reaction is
1459 (approximately 680/)). Synthesis Example 2 (Synthesis of Compound Example (1)) 50 g of the compound shown in Synthesis Example 1 and 150 ml of methanol are added to a reaction vessel, and the mixture is heated and stirred at 60° C. under nitrogen.

To this, AIBN shown by the following formula is added to 20 ml of methanol.
A solution containing 0.29% of (azobisisobutyronitrile) was added dropwise, and stirring was continued for 10 hours.

After the reaction is completed, dialysis is performed to remove unreacted monomers, and lyophilization is performed to obtain a hygroscopic white powder. Yield is 419 (82%
).

Synthesis Example 3 (Synthesis of Compound Example (6)) N,N-dimethylaminoethyl methacrylate 157.
29 (1 mol) and 150 ml of methyl ethyl ketone were placed in a three-necked flask and stirred at -20°C under nitrogen.

To this, β-propiolactone 72.1f9 (1 mol)
A mixed solution of 100 WLI of methyl ethyl ketone was added dropwise. The temperature within this time series should not exceed -10°C. If this reaction solution is stored overnight at -20°C, white crystals are obtained. Yield is 98%. Identification of compounds is
I did it according to the usual law.

The polymerizable betaine monomer thus obtained was synthesized in Synthesis Example (2).
Compound (6) can be obtained as a white powder by polymerization in exactly the same manner as described above. The compound of the present invention is added in the subbing layer or backing layer.

Here, the undercoat layer is the lowest layer on the emulsion side of the support,
This is an intermediate layer for improving the adhesion between the support and the emulsion layer. In addition, the backing layer is a layer on the opposite side of the support from the photosensitive silver halide emulsion layer, and when the backing layer consists of two layers, it can be added to either layer. good. When applying the copolymer used in the present invention to a photographic light-sensitive material, it is dissolved in water, an organic solvent such as methanol, isopropanol, acetone, or a mixed solvent thereof, and then added to a coating solution for a back layer, etc., for dip coating. Air Knife Coat or U.S. Patent 2,681,294
or by the extrusion coating method using a hopper described in US Pat. No. 3,508,947.
Two or more layers may be applied simultaneously by methods such as those described in US Pat. No. 2,941,898 and US Pat.

Further, if necessary, an antistatic liquid containing the compound of the present invention is further coated on the protective layer. The amount of photographic film used per square meter is preferably 0.005 to 5 g, especially 0.005 to 5 g.
It is preferable that it is 01-1.09.

However, it goes without saying that the above range varies depending on the type of photographic film base used, the photograph, the composition, the form, or the coating method.

In addition to the compound represented by the general formula (1), the undercoat layer of the present invention contains gelatin, vinylidene chloride latex, butadiene rubber latex, etc. as a binder, and resorcinol and phenols as swelling agents. It can further contain a gelatin hardening agent, a surfactant, a matting agent, etc.

Here, the gelatin is so-called lime-treated gelatin,
In addition to acid-treated gelatin, it also includes gelatin derivatives.
In addition to the compound represented by the general formula (1), the backing layer of the present invention includes gelatin, cellulose ester polymers, maleic acid polymers, acrylic acid polymers, dyes, colloidal silica, matting agents, surfactants, It can contain a gelatin hardening agent and the like.

Examples of the support used in the photographic material of the present invention include cellulose nitrate film, cellulose acetate film, cellulose acetate butyrate film, cellulose acetate propionate film,
Examples include polystyrene film, polyethylene terephthalate film, polycarbonate film, and laminates thereof.

When the adhesive strength between the support and the photographic emulsion layer is insufficient, the surface of the support may be subjected to conventional pretreatment such as corona discharge, ultraviolet irradiation, flame treatment, etc.

The silver halide emulsion of the photographic light-sensitive material used in the present invention is usually prepared by combining a water-soluble silver salt (for example, silver nitrate) solution and a water-soluble halide salt (for example, potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. It is made by mixing. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used. These silver halide grains are produced according to known and commonly used methods. Of course, it is also useful to use the so-called single jet method, double jet method, controlled double jet method, etc. These photographic emulsions are T. H. James and C. E. K. Written by Meesr
[The Theory of the Photography
icProcess” 3rd edition, published by MacMi11an: P. Chemie Pho by Grafikides
It can be prepared by various methods such as the ammonia method, neutral method, acid method, etc. which are described in books such as "Tographique" and published by Pau Montel and are generally used. The silver halide grains thus prepared were treated with a chemical sensitizer (e.g., sodium thiosulfate, N,N, mertrimethylthiourea, monovalent gold thiocyanate complex, monovalent gold thiosulfate complex, stannous chloride, The sensitivity can be increased without coarsening the particles by heat treatment in the presence of hexamethylenetetramine (such as hexamethylenetetramine). Photographic emulsion contains cyanine as needed.
Spectral sensitization and supersensitization can be performed by using polymethine sensitizing dyes such as merocyanine and carbocyanine alone or in combination, or in combination with styryl dyes and the like. Furthermore, various compounds can be added to the photographic emulsion of the photographic light-sensitive material used in the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage, or processing of the light-sensitive material.

These compounds are 4-hydroxy-6-methyl 1,3,
A large number of compounds have been known for a long time, including 3a,7-tetrazaindene-3-methyl-benzothiazole and 1-phenyl-5-mercaptotetrazole, as well as many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts. There is. Examples of compounds that can be used include T. H.
James and C. E. K. Mees, “The Th.
eoryofthePhotographicProc
ess" 3rd edition (1966), published by MacMilian, citing the original document. When the silver halide photographic emulsion is used as a color photographic light-sensitive material, a coupler may be included in the silver halide emulsion layer.

Such couplers include 4-equivalent diketomethylene yellow couplers and 2-equivalent diketomethylene yellow couplers, such as U.S. Pat. No. 3,277,157, U.S. Pat.
No. 408,194, No. 3,551,155, JP-A No. 4
Compounds described in U.S. Pat. No. 7-26133, U.S. Pat. 437
No. 3,476,560, JP-A-47-26133
Compounds described in U.S. Pat.
, No. 474,293, No. 3,311,476, No. 3,
Compounds described in No. 481,741, etc. are used. In addition, U.S. Patent Nos. 3,227,554, 3,253,924, 3,379,529, and 3
Coupler capable of releasing a development inhibitor described in, for example, No. 617,291 and No. 3,770,436 can also be used.

The silver halide emulsion layer and other layers in the photographic light-sensitive material of the present invention can be hardened with various organic or inorganic hardeners (singly or in combination). Typical examples include mucochloric acid, formaldehyde, trimethylolmelamine, glyoxal, 2,3-dihydroxy-1,
Aldehyde compounds such as 4-dioxane, 2,3,-dihydroxy-5-methyl-1,4-dioxane, succinaldehyde, and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 1,3,5-triacryloylhexahydro -s-triazine, 1,3,5-
Active vinyl compounds such as trivinylsulfonyl-hexahydro-s-triazine bis(vinylsulfonylmethyl)ether, 1,3-bis(vinylsulfonylmethyl)propanol-2, bis(α-vinylsulfonylacetamido)ethane; 2. 4-dichloro-6-hydroxy-s-triazine sodium salt, 2,4-dichloro-
Active halogen compounds such as 6-methoxy-s-triazine; ethyleneimine compounds such as 2,4,6-triethyleneimino-s-triazine; and the like. A surfactant 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 and dispersion, sensitization and other photographic property improvements, and charge sequence adjustment. These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide, glycerin, and glycidol, higher alkylamines, quaternary ammonium salts, pyridine and other heterocycles, phosphonium or Cationic surfactants such as sulfoniums; anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, phosphoric esters, amino acids, aminosulfonic acids,
It is divided into amphoteric surfactants such as sulfuric acid or phosphoric acid esters of amino alcohols. Some examples of surfactant compounds that can be used include U.S. Pat. No. 2,271,623;
No. 2,240,472, No. 2,288,226, No. 2,739,891, No. 3,068,101, No. 3
, No. 158,484, No. 3,201,253, No. 3
, No. 210, 191, No. 3,294,540, No. 3,
No. 415,649, No. 3,441,413, No. 3, 4
No. 42,654, No. 3,475,174, No. 3,54
No. 5,974, No. 3,666,478, No. 3,507
, No. 660, British Patent No. 1,198,450, and Ryohei Oda et al., "Synthesis of Surfactants and Their Applications" (Maki Shoten,
(1964) and A. W. Perry, "Surf S Active Agents" (Interscience Publications, Inc., 1958), J.R.
It is described in books such as "Encyclopedia of Active Agents, Volume 2" (Chemical Publishing Company, 1964) by Sisli.

In the present invention, when a fluorine-containing surfactant is used in combination, it is highly effective in preventing static marks.

Examples of fluorine-based surfactants that can be used in combination include the following compounds: For example, British Patent No. 1,330,356, British Patent No. 1,524,631, U.S. Patent No. 3,666, No. 478, No. 3,589,906,
There are fluorine-containing surfactants described in Japanese Patent Publications No. 52-26687, 49-46733, 51-32322, etc. 〇 Typical examples of compounds include Fluorooctylsulfonyl-N-propylglycine potassium salt, 2-(N-perfluorooctylsulfonyl-N-ethylamino)ethyl phosphate, N-[4-(perfluorononenyloxy)benzyl]-N,N-dimethyl Ammonioacetate, N-[
3-(ma,ma,N'-trimethylammonio)propyl]perfluorooctylsulfonamide iodide,
N-(polyoxyethylenyl)-N-propyl perfluorooctyl sulfamide (C8Fl7SO2N(C3
Examples include H7) (CH2CH2O)NH) and fluorine-containing succinic acid compounds.

In addition, 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. 129520/1988 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, etc., and may also contain silica, strontium sulfate, barium sulfate, polymethyl methacrylate, etc. as matting agents.

By implementing the present invention, failures caused by statics that occur during the manufacturing process and/or during use of photographic light-sensitive materials have been improved.

For example, in the practice of the present invention, contact between the emulsion side and the back side of a photographic material, contact between emulsion side and emulsion side, and contact between the emulsion side and the back side of a photographic light-sensitive material and materials with which photographic light-sensitive materials commonly come into contact, such as rubbers, metals, plastics, and fluorescent enhancers, can be removed. The occurrence of static marks caused by contact with photosensitive paper etc. was significantly reduced.

Regarding the compound represented by general formula (1) of the present invention,
A silver halide dispersant (r) is known in patents for use as a protective colloid together with gelatin, and in patents for incorporating it into photographic emulsions to improve the dimensional stability of coated emulsion films.

They are, for example, U.S. Pat. No. 2,846,417, U.S. Pat.
, 549,605, British Patent No. 786,344, German Patent No. 1,547,679 and Japanese Patent Publication No. 1977-199
51 etc. However, these patents do not mention the use of the compound of the present invention in an undercoat layer or a backing layer, and furthermore, there is no statement that the compound of the present invention is effective in preventing static electricity. The present invention has discovered a photographic light-sensitive material that has excellent antistatic properties and does not cause coating unevenness when coating a hydrophilic colloid layer by using these compounds in an undercoat layer and/or a backing layer. It is. The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto. Example 1 Compounds of the present invention 1, 5, 6, 10, 8 each
9 was dissolved in 10 ml of water and diluted with a mixed solvent of 650 ml of methanol and 350 ml of acetone.

This solution was placed on a cellulose triacetate film for 50 minutes.
It was applied and dried at a ratio of η/M2. Furthermore, a dispersion of 0.39 colloidal silica having a particle size of 0.05 to 3 μm was applied on top of this using a mixed solvent of 300 ml of acetone and 600 ml of methanol. An indirect radiographic emulsion containing 9 wt % gelatin and 9 wt % silver halide (:f) was coated on the opposite side of the film base coated on one side in this manner. Here, sample (1) has no antistatic agent added, and samples (2) to (5) contain compounds 1, 5, 6, 10 of the present invention.
It includes each. The antistatic properties of these samples were investigated using the following method. 2 (a) Measurement of surface resistivity After conditioning the sample at 25°C and 25% RH for 2 hours, the test piece was placed under the same air conditioning conditions with an electrode spacing of 0.14 (Tnl length 10
? between brass electrodes (the part in contact with the test piece is made of stainless steel), and a KEDA RIKEN electrometer (
The surface resistivity of the back surface of the sample was measured for 1 minute using TR-8651).

(Example) Measurement of static mark generation After conditioning the humidity of an unexposed sample under the same conditions as above, a sample was prepared by gluing the emulsion surfaces together with double-sided tape in a dark room under the same air conditioning conditions. After rubbing the sample with a rubber roller, it was developed with the following developer, fixed, and washed with water, and the degree of static mark occurrence was examined.

1 (Developer composition)
Shown in the table.

As is clear from Table 1, by using the compound of the present invention, the surface resistivity of the back layer was significantly lowered, and almost no static marks were observed.

On the other hand, static marks were generated on the entire surface of the sample containing no antistatic agent. Example 2 A back layer and a back protective layer were coated on one side of a cellulose triacetate support, and an antihalation layer, a red sensitive layer, an intermediate layer, a green sensitive layer, a yellow filter layer, a blue sensitive layer and a protective layer were coated on the other side. The samples, which were stacked one on top of the other, were coated and dried according to a conventional method.

The composition of each layer is shown below. (Anti-halation layer) Binder lygelatin 4.49/M2 Hardener: Bis(vinylsulfonylmethyl)ether 59
/1009 Binder coating aid: Sodium dodecylbenzenesulfonate 4η/d Halation prevention component: Black colloidal silver 0.49/Trl (red photosensitive layer) Binder lygelatin 7y/M2 Hardener: 2-hydroxy-4,6- Dichloro-s triazine sodium salt 0.79/1009 Binder and bis(vinylsulfonylmethyl)ether 29/10
09 Binder coating aid: Sodium dodecylbenzenesulfonate 10η/M2 Coated silver amount: 3.1f1/m'' Silver halide composition: Ag 2 mol% and AgBr 98 mol% Fog phase resin 1j: 4-hydroxy-6-methyl -1,3,3a,7-tetrazaindene 0.9g/Ag
lOO9 color former: 1-hydroxy-4-(2-acetylphenyl)azo-N-[4-(2,4-di-tertamylphenoxy)butyl]-2-naphthamide 389/
AglOO9 sensitizing dye: anhydro-5,5'-dichloro-9-ethyl-3,3! -di(3-sulfopropino(
C) Thiacarbocyanine hydroxide pyridinium salt 0.39/AglOOf! (Middle layer) Binder lygelatin 2.69/m” Hardener: Bis(vinylsulfonylmethyl)ether 6g
/100g Binder coating aid: Sodium dodecylbenzenesulfonate 1.2Tn9/I (green photosensitive layer) Binder lygelatin 6.49/M2 Hardener: 2-hydroxy-4,6-dichloro-s triazine sodium salt 0 .79/100f1 binder and bis(vinylsulfonylmethyl)ether 29/1
009 Binder coating aid: Sodium dodecylbenzenesulfonate 9η/I Coated silver amount: 2,29/m” Silver halide composition: AgI 3.3 mol% and AgBr
96.7 mol% Stabilizer: 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene 0.69/Agl
OO9 color former: 1-(2,4,6-trichlorophenyl)3-{3-[(2,4-di-Tert-amylphenoxy)acetazide}-4-(4-methoxyphenyl)
Azo-5-pyrazolone 379/AglOOfl sensitizing dye: anhydro-5,5'-diphenyl-9-ethyl-3
,3'-di(2-sulfoethino(ha)oxacarbocyanine hydroxide pyridinium salt 0.39/AglO
O9 (yellow filter single layer) Binder lygelatin 2.3f1/d Filter component: Yellow colloidal silver 0.7f! /m” Hardener: Bis(vinylsulfonylmethyl)ether 59/1
00f! Binder surfactant: 2-sulfonatosuccinic acid bis(2-ethylhexyl) ester sodium salt 7η/A (blue photosensitive layer) Binder lygelatin 79/A Hardener: 2-hydroxy-4,6-dichloro-s-triazine・Sodium salt 0.79/1009 binder and bis(vinylsulfonylmethyl)ether 29/1
009 Binder coating aid: Sodium dodecylbenzenesulfonate 8Tf19/M2 Coating silver amount: 2.2f! /
Silver halide composition: AgI 3.3 mol% and AgBr
96.7 mol% Stabilizer: 4-hydroxy-6-methyl-
1,3,3a,7-tetrazaindene 0.49/Agl
OO9 color former: 2″-chloro-5″-[2-(2.4-
diTert-amylphenoxy)butyramide]-α(
5.52-dimethyl-2.4-dioxo-3-oxazolidinyl)-α-(4-methoxybenzoyl)acetanilide 459/AglOO9 (protective layer) Binder lygelatin 29/M2 and styrene monoanhydride with an average molecular weight of about 100,000 Maleic acid (1:1) copolymer 0.3g/a Hardener: bis(vinylsulfonylmethyl)
Ether 59/1001 Binder coating aid: Sodium dioctyl sulfosuccinate 5TI19/m" (back layer) Binder lygelatin 6.2f1/M2 Salt: Potassium nitrate 0.19/M° Hardener: Bis(vinylsulfonylmethyl) ether 0 ．．
6g/100g binder (back protective layer) Binder lygelatin 2.2g/immatting agent: polymethyl methacrylate (average particle size 2.5μ) 20η/M2 Hardening agent: bis(vinylsulfonylmethyl)ether 1.29/100f1 binder Coating agent: Sodium dioctyl sulfosuccinate 40W! 9
/a Here, sample (6) consists only of the above composition, and sample (
In addition to the above compositions, 7) to (9) each contained Compounds 1, 3, and 7 of the present invention in the back layer at a ratio of 0.89/I.

The surface resistivities of the back surfaces of these samples were examined in exactly the same manner as in Example 1. The results are shown in Table 2. From Table 2, it can be seen that when the compounds of the present invention are used, the surface specific resistance of the back layer is significantly lowered and is effective in preventing static electricity.

Example 3 An undercoating solution having the following formulation was applied onto a 130 μm thick cellulose triacetate film Jlum and dried.

A liquid having the following formulation was applied to this undercoat layer to form an antistatic layer.
On this antistatic layer, the antihalation layer and the red photosensitive layer described in Example 2 were applied in order from the support using an extrusion method.

The coating unevenness of the emulsion layer due to the charging phenomenon during coating was determined visually using transmitted light, and the results shown in Table 3 were obtained. As is clear from Table 3, the undercoat layer using the compound of the present invention does not cause coating unevenness during emulsion coating. Example 4 On a polyethylene terephthalate film support of about 175μ, 48 mol% butadiene, 47 mol% styrene,
Copolymer 2 consisting of 5 mol% itaconic acid.

5% by weight, 2,4-dichloro-6-hydroxy-1,3
, 5-triazine sulfate, an aqueous solution adjusted to 0.15% by weight, was applied at a rate of 20 ml/day, and dried at 120 C water for 10 minutes.

Here, the sample (self) has no antistatic agent added and (
(au) to (au) are compounds 4 and 9 of the present invention at 1.0, respectively.
It contains % by weight. The surface resistivity of these samples was examined in exactly the same manner as in Example 1. The result is the fourth
Shown in the table. Table 4 shows that when the compound of the present invention is used in the undercoat layer, the surface resistivity is significantly lowered and it is effective in preventing static electricity.

Example 5 The back side of the same photosensitive material as Sample (1) of Example 1 was immersed for 5 seconds in a 1% by weight methanol solution of each of the compounds shown in Table 5, and then dried.

After conditioning these samples at 25° C. and 25% RH for 2 hours, the surface specific resistance was measured under the same air conditioning conditions. The measurement results are shown in Table 5. As is clear from Table 5, even when the compound of the present invention is applied onto the back layer, the surface resistivity is significantly lowered and it is found that it is effective in improving antistatic properties.

Claims (1)

[Scope of Claims] 1. A photographic light-sensitive material characterized in that its undercoat layer or backing layer contains a polymer or copolymer having a repeating unit represented by the following general formula. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, B: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ Mathematical formulas,
Chemical formulas, tables, etc. are available ▼ A: -COO- or -CONH- R_1, R_4: Hydrogen atom or methyl group R_5: Alkyl group with 1 to 3 carbon atoms R_2, R_3: Alkyl group with 1 to 6 carbon atoms p: 2-6
Integer q: an integer of 1 to 4 when R_4 is a hydrogen atom, and 1 when R_4 is a methyl group. D: -COO or -SO_3