JPS62109045A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve antistatistic effect, coatability, photographic characteristics (particularly, sensitivity), and preventing effect for generating contamination, simultaneously, by incorporating both of a F-contg. nonionic surface active agent and a nonionic surface active agent contg. no F to an emulsion layer or one of other constituting layer. CONSTITUTION:In a silver halide photographic sensitive material constituted of a base body and at least one silver halide emulsion layer, a F-contg. nonionic surface active agent and a nonionic surface active agent contg. no F are incorporated into an emulsion layer or at least one of other constituting layers. Preferred F-contg. nonionic surface active agent is one having 6-14C perfluoroalkyl group and a nonionic group comprising substituted or unsubstituted polyoxyethylene group. Preferred nonionic surface active agent contg. no F is one expressed by the following formula. In the formula, R is H atom, 1-4C alkyl group; R7 and R9 are H atom, substituted or unsubstituted alkyl group, etc.; R6 and R8 are substituted or unsubstituted alkyl, etc.; R4 and R5 are H atom, substituted or unsubstituted alkyl, or aryl group; n3 and n4 are, pref., 5-30.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material having good antistatic properties, and particularly to a silver halide photographic material that generates little static electricity on various materials and that does not become static over time. This invention relates to a silver halide photographic material (hereinafter referred to as a "photographic material") that does not change its preventive properties.

(Prior Art) Photographic materials generally consist of an electrically insulating support and a photographic layer, so contact friction or peeling between the surfaces of similar or foreign substances 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 due to the discharge of the accumulated electrostatic charge before processing, and when the photographic film is processed. It causes dot-like spots or dendritic or feather-like streaks on the skin. 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. Or, in the case of color photographic materials, it may ruin memorable memories. This phenomenon becomes apparent only after development, and is one of the most troublesome problems. Also, these accumulated stillness 1! Charges can also cause secondary failures such as dust adhesion to the film surface and inability to apply uniformly.

As mentioned above, such electrostatic charges are often accumulated during the production and use of photographic materials, and for example, during the manufacturing process, there is the contact friction between the photographic film and the roller, or the winding and unwinding of the photographic film. This occurs due to separation of the support surface and emulsion surface during the process. Furthermore, in the finished product, separation of the base surface and emulsion surface occurs when the photographic film is wound and changed, or the mechanical part of the X-ray film in an automatic photographing machine or the fluorescent intensifying screen. This occurs due to separation of the contact between the two.

In color negative films and color reversal films, peeling occurs when rubber, metal, plastic, etc. come into contact with rollers and bars in cameras, bonding machines in photo labs, and automatic processors.

It can also occur due to contact with other packaging materials. Static marks on photographic light-sensitive materials induced by the accumulation of such s-electronic charges become more noticeable as the sensitivity of the photographic light-sensitive materials increases and the processing speed increases.

Especially in recent years, there have been many opportunities for photographic materials to be subjected to harsh handling such as higher sensitivity, high-speed coating, high-speed photography, and high-speed automatic processing, and opportunities for photographic materials to be exposed to lower humidity. Static marks are becoming more likely to occur due to the increase in the number of static marks.

In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic material. However, the antistatic agents that can be used in photographic light-sensitive materials cannot be the same as those commonly used in other fields, and are subject to various restrictions specific to photographic light-sensitive materials. That is, in addition to having excellent antistatic properties, antistatic agents that can be used in photographic light-sensitive materials must not have any adverse effects on the photographic properties of the photographic light-sensitive materials, such as their sensitivity, fog, graininess, and sharpness. It should not have an adverse effect on the film strength of the photosensitive material (i.e., it should not be easily damaged by friction or scratching), and it should not have an adverse effect on the adhesion resistance (i.e., it should not be easily damaged by friction or scratching). (Do not easily stick to the surface of other materials)
Antistatic agents are applied to photographic materials because of the required performance, such as not accelerating the fatigue of processing solutions for photographic materials, not contaminating conveyance rollers, and not reducing the adhesive strength between the constituent layers of photographic materials. There are many restrictions on what you can do.

One way to eliminate problems caused by static electricity is to increase the electrical conductivity of the surface of the photosensitive material so that the accumulated charges can be reduced to nN before they are discharged.
The purpose is to dissipate the charge in a short time.

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

For example, U.S. Patent Nos. 2,882,157 and 3,262
, 807, 3938.999, etc., e.g., U.S. Patent No. 2,982,651.
Surfactants such as those described in US Pat. No. 3, 457.076 and US Pat. Oxides, colloidal silica, etc. are 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.

On the other hand, although it has an extremely excellent antistatic effect, it is often unusable because it adversely affects photographic properties such as sensitivity, fog, graininess, and sharpness of photographic emulsions. For example, 4. Rithelene oxide compounds are generally known to have an antistatic effect, but in order to obtain a good antistatic effect, it is necessary to add a large amount, which may lead to increased fog, desensitization, and grain formation. This often results in adverse effects on photographic properties such as deterioration of image quality. Further, problems such as staining during processing and repellency during application occur. Especially medical direct X
- It has been difficult to establish a technique for effectively imparting antistatic properties without adversely affecting photographic properties in light-sensitive materials such as Ray-sensitive materials in which photographic emulsions are coated on both sides of the support. As described above, it is very difficult to apply antistatic agents to photographic materials, and the scope of their use is often limited.

Another method for eliminating problems caused by static electricity in photographic light-sensitive materials is to reduce the power generation property of the surface of the light-sensitive material, thereby reducing the generation of static electricity due to friction or contact as described above.

For example, British Patent No. 1.33Q356, British Patent No. 1.524
, 631, U.S. Pat. No. 3.66 to 478, U.S. Pat.
9.906, Special Publication No. 52-26687, Japanese Patent Application Publication No. 1973
-46733, 51-32322, 53-84
No. 712, No. 54-14224, U.S. Patent No. 3135
Q642, JP-A-48-52,223, JP-A No. 52-
Attempts have been made to utilize fluorine-containing ionic surfactants such as those shown in Nos. 127,974 and 58-200235 in photographic materials for this purpose.

(Problems to be Solved by the Invention) However, the electrostatic properties of photographic materials containing these fluorine-containing ionic surfactants are generally negatively charged to various materials that come into contact with them; By using a coating agent that has positive charging properties in combination with the rubber roller, Chirurin roller,
Although it is possible to adjust the power generation capacity to a small value for each nylon bar, etc., it is difficult to simultaneously reduce the power generation capacity for all the materials that come into contact with it. For example, when the power generation property is reduced compared to rubber, the dendritic static is
On the other hand, when the power generation with Chirurin is reduced, stain-like static usually occurs due to rubber, etc. located more negatively on the charge series. Moreover, it deteriorates the coating properties, and its power generation properties tend to change during storage after production, making it difficult to use it in practical light-sensitive materials.

Furthermore, the use of fluorine-containing nonionic surfactants is disclosed in JP-A-5O-6L236 and US Pat. No. 4,175,969.

According to these methods, by adding a large amount, it is possible to slightly improve dependence on the other material, but this results in a significant decrease in sensitivity, adhesion between films, and processing stains during development processing. It was difficult to put it into practice.

A first object of the present invention is to provide a photographic material that is antistatic so as to have low power generation properties for various materials.

A second object of the present invention is to provide a photographic material that always has stable charging performance even if the manufacturing conditions change.

A third object of the present invention is to provide a photographic material whose antistatic properties do not change over time after manufacture.

A fourth object of the present invention is to obtain a uniform suspension when coating a photographic coating solution containing various photographic binders such as gelatin or without a binder in a thin film at high speed; To provide a photographic material which can obtain a uniform coating film without causing defects such as "repellency" and "comments".

A fifth object of the present invention is to provide a photographic light-sensitive material which is prevented from being charged and which does not cause contamination of the light-sensitive material during development processing.

A sixth object of the present invention is to provide a photographic material containing a surfactant that does not adversely affect photographic performance.

(Means for Solving the Problems) These objects of the present invention are to provide a photographic light-sensitive material having at least one silver halide emulsion layer on a support. In one layer,
This was achieved by containing both a fluorine-containing nonionic surfactant and a fluorine-free nonionic surfactant.

It was completely unexpected that the combination of a fluorine-containing nonionic surfactant and a non-fluorine nonionic surfactant could simultaneously improve antistatic effect, coating properties, photographic properties (especially sensitivity), and prevention of contamination during processing. It is about.

The fluorine-containing nonionic surfactant used in the present invention is disclosed in JP-A-49-10722 and British Patent No. 1.33 Q 356.
JP-A No. 53-84712, JP-A No. 54-14224, JP-A No. 50-113221, etc. can be used.

Preferred fluorine-containing nonionic surfactants used in the present invention have a fluoroalkyl group having 4 or more carbon atoms, an alkenyl group, or an aryl group, and examples of the nonionic group include substituted or unsubstituted polyoxyethylene groups, polyglyceryl Examples include compounds having a group or a sorbitan residue group.

Particularly preferred is a perfluoroalkyl group, alkenyl group, or aryl group having 6 to 14 carbon atoms, and a substituted or unsubstituted s-lyoxyethylene group (preferably 5 to 50 as an oxyethylene group) as a nonionic group. Examples include fluorine-containing nonionic surfactants.

Preferred specific examples are listed below.

C7F'□5COO+cH2CH20kary-HC1oF
2□C004CH2CH20-)77-Hn+m=11
．． 5 Cl-13 C8F17CH2CH20÷CH2CH2 12.5
H■-12 C9F engineering, O+CH2CH2O guff CH3■-13 ■-14 ■-15 ■-16 The non-fluorine nonionic surfactant used in the present invention has the following general formula Cl-1), Cl-2) or ( Examples include compounds represented by I-3).

General formula (1-x) R□-A+B+n1R General formula CI-2) General formula Cl-3) In the formula, R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, hypoproxyethyl, etc.). ), or alkylcarbonyl having 1 to 5 carbon atoms (eg, acetyl, chloroacetyl, carboxymethylcarbonyl, etc.).

Further, R□ represents a substituted or unsubstituted alkyl group, alkenyl group, or aryl group having 1 to 30 carbon atoms.

A is 10- group, -8- group, -C00- group, -SO□N-
R□. (Here, Rlo represents a hydrogen atom or a substituted or unsubstituted alkyl group.)

B represents an oxyalkylene group.

R2, R3, R7, and R9 represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group, or a sulfamoyl group. .

In the formula, R6 and R8 are substituted or unsubstituted alkyl groups, aryl groups, alkoxy groups, aryloxy groups, halogen groups, acyl groups, amide groups, sulfonamide groups,
Represents a carbamoyl group or a sulfamoyl group. In general formula (T-3), the substituents on the phenyl ring may be asymmetrical.

R4 and R5 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. R4 and R, R6 and R7, and R8 and Ro may be linked to each other to form a substituted or unsubstituted ring. n□, R2, R3 and R4 are average degrees of polymerization of oxyalkylene groups, and are numbers from 2 to 50.

Moreover, m is an average degree of polymerization and is a number from 1.2 to 50.

Preferred examples of the present invention are described below.

B is preferably an oxyalkylene group having 2 to 6 carbon atoms, particularly preferably an oxyethylene group, an oxypropylene group, an oxy(hydroxy)propylene group, an oxybutylene group, or an oxystyrene group.

R□ is preferably an alkyl group, alkenyl group, or alkylaryl group having 4 to 24 carbon atoms, particularly preferably a hexyl group, dodecyl group, instearyl group, oleyl group, t-butylphenyl group, or 2,4-dimethyl group. -t-butylphenyl group, 24-di-7-hentylphenyl group, p
h"7 sylphenyl group, m-4 ntadecaphenyl group, t
-octylphenyl L24-dinonylphenyl group, octylnaphthyl group, etc.

1-2 carbon atoms such as 1-hexyl, t-octyl, nonyl, decyl, dodecyl, trichloromethyl, tribromomethyl, 1-phenylethyl, 2-722-2-i lovir, etc.
0 substituted or unsubstituted alkyl group, phenyl group, substituted or unsubstituted aryl group such as p-chlorophenyl group, -O
A substituted or unsubstituted alkoxy group or aryloxy group, a chlorine atom represented by R□, (where R1□ represents a substituted or unsubstituted alkyl group or aryl group having 1 to 20 carbon atoms. The same applies hereinafter) , a halogen atom such as a bromine atom, an acyl group represented by -COR, □, -NR,CO
An amide group represented by R□, (here KR1□ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The same applies hereinafter), -NR, a sulfonamide group represented by □5O2R□□, or R2 , R3, R7, and Ro may be hydrogen atoms. Among these, R6 and R8 are preferably an alkyl group or a halogen atom, particularly preferably a bulky t-
It is a tertiary alkyl group such as a butyl group, a t-amyl group, a t-octyl group, etc. R7 and R9 are particularly preferably hydrogen atoms. That is, a compound of the general formula Cl-3) synthesized from a 24-disubstituted phenol is particularly preferred.

R4 and R5 are preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, 1-propyl group, n-heptyl group, 1-ethylamyl group, n-undecyl group, trichloromethyl group, tribromomethyl group, etc. Substituted or unsubstituted alkyl group, α-furyl group, phenyl group, naphthyl group, p-chlorophenyl group, p-methoxyphenyl group, m
- Substituted or unsubstituted aryl group such as nitrophenyl group. Further, R4 and R5, R6 and R7, and R8 and R9 may be linked to each other to form a substituted or unsubstituted ring, such as a cyclohexyl ring. Among these, R4
and R5 are particularly preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a furyl group. n□, R2,
R3 and R4 are particularly preferably numbers from 5 to 30. R
3 and R4 may be the same or different.

These compounds are described, for example, in U.S. Patent No. 2,982.651.
No., A42A456, No. 3457.076, No. 3
．． No. 454625, No. 3.552972, No. 3.65
No. 51387, JP 51-9610, JP 53-
No. 29715, Japanese Patent Application Publication No. 1989-89626, Patent Application No. 1983
-85764, Japanese Patent Application No. 57-90909, "New Surfactant" by Hiroshi Horiguchi (Sankyo Publishing, 1975), etc.

Next, specific examples of non-fluorine nonionic surfactants preferably used in the present invention will be shown.

Compound Example II-I C□□H23COO÷CH2CH2O÷
8H[-2C)ic○0+CH2CH2O+15H[-
3C1□H33COO(CH2CH20+, 5HI[-
4C8H□70(-CH2CH20)7Hn-5C□2
H250 (Cd2CH20ji,.HII-6C□6H3
30+CH2CH2O+1□HII-7C engineering, H350
+CH2CH2O+16H■-8C2□H450+CH
2CH2O+25HI[-12C Eng 6H330SoCH2
CH2O arrow□6CH3a+b so-called 15 a+b san 20 n-19C engineering 2H25S+CH2CH2O+□6HCH
2CH2O+CH2CH2O+1□H■-29 ■-30 ■-31 ■-32 ■-33 ■-34 ■-35 ■-36 ■-37 5”ll -t 5”ll ”■-38 ■-41 ■-42 ■-43 ■-44 The fluorine-containing nonionic surfactant and non-fluorine nonionic surfactant of the present invention are added to at least one of the silver halide emulsion layers or other constituent layers of the photographic light-sensitive material.Other configurations The layer is preferably a hydrophilic colloid layer, such as a surface protective layer, a back layer, an intermediate layer, an undercoat layer, etc. The surfactant of the present invention can be added to the surface protective layer, the nozzle layer, etc. Preferably, there are two layers, an intermediate layer, or an undercoat layer.These two surfactants may be present in the same layer or in different layers, but it is preferable that they exist in the same layer.

When the surface protective layer or back layer consists of two layers, either layer may be used, or it may be used by further overcoating the surface protective layer.

When applying the fluorine-containing nonionic surfactant and non-fluorine nonionic surfactant used in the present invention to photographic light-sensitive materials, they can be dissolved in water, an organic solvent such as methanol, inpropatol, acetone, etc., or a mixed solvent thereof. After that, it is added to the coating solution of the surface protective layer or back layer, etc. and coated with dip coating, air knife coating, spraying, or US Patent 2,6.
No. 81,294, the method of extrusion coating using a hopper is used;
a947, 2,941,898, 352552
Two or more layers may be applied simultaneously by methods such as those described in No. 8, or immersed in an antistatic liquid. Further, if necessary, an antistatic liquid (solution alone or containing a binder) containing a fluorine-containing nonionic surfactant and a non-fluorine nonionic surfactant of the present invention is further coated on the protective layer.

The amount of the fluorine-containing nonionic surfactant and non-fluorine nonionic surfactant of the present invention to be used is preferably such that α0001~'toy is present per square meter of the photographic light-sensitive material, and particularly O,OO05~0.31 is preferable. .

The usage ratio (weight ratio) of the fluorine-containing nonionic surfactant and the non-fluorine nonionic surfactant is preferably 1:100.
~100:1, preferably 1:50~20:1.

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

Two or more types of each surfactant of the present invention may be mixed.

Another antistatic agent can also be used in the layer containing the fluorine-containing nonionic surfactant and non-fluorine nonionic surfactant of the present invention or in other layers, and by doing so, a more preferable antistatic effect can be obtained. You can also do it. Such antistatic agents include, for example, U.S. Patent No. G882,157;
Same No. g972,535, No. 3,062,785, Same No. a
No. 262,807, No. 3.514291, No. 3615
No. 531, No. 3753716, No. 39.3a999, No. 07Q1B9, No. 4.147.550, German Patent No. 2.800,466, Japanese Unexamined Patent Publication No. 1987-91,16
No. 5, No. 48-94433, No. 49-4a733,
50-5 Ii 672, 50-94053, 52
-12'4520 etc., polymers such as those described in
For example, US Pat. No. 2;98@651, US Pat. No. 342a45
No. 6, A457; No. 076, No. 3.454625,
Surfactants such as those described in US Pat. No. 3,552,972, US Pat. No. 3,655,387, etc.
．． No. 700, No. 833 on 3.24, 3524%62
Examples include so-called matting agents made of metal oxides, colloidal silica, etc., barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, colloidal silica, powdered silica, etc. as described in No. 1, etc. be able to.

Also, ethylene glycol, flopylene glycol, 1,
1.1-Trimethylolpronone etc. JP-A-54-896
A polyol compound such as that shown in No. 26 can be added to the layer containing the surfactant of the present invention or other layers, and by doing so, a more preferable antistatic effect can also be obtained.

Examples of the support used in the photographic light-sensitive material of the present invention include polyolefins such as polyethylene, polystyrene, cellulose derivatives such as cellulose triacetate, films such as polyethylene terephthalate, or both sides of lighter paper, synthetic paper, or paper. supports consisting of sheets coated with polymeric films and the like.

The support used in the present invention can also be provided with an antihalation layer. For this purpose carbon black or various dyes such as oxonol dyes, azo dyes, aryl tin dyes, styryl dyes, anthraquinone dyes, merocyanine dyes and tri(or di)
Examples include allylmethane dyes.

The photosensitive materials according to the present invention include ordinary black-and-white silver halide photosensitive materials (for example, black-and-white photosensitive materials for photography, black-and-white photosensitive materials for X-ray, black-and-white photosensitive materials for printing, etc.), and ordinary multilayer color photosensitive materials ( Examples include color reversal films, color negative films, color positive films, 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.

Binders for the photographic layer include proteins such as gelatin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, sodium alginate, and starch conductors; synthetic hydrophilic colloids 9 such as polyvinyl alcohol, Textran, and Hozy N. -Vinyl pyrrolyne, polyacrylic acid copolymer,
Polyacrylamide or a conductor and a partial hydrolyzate thereof can also be used in combination. Particularly preferred are gelatin, dextran, and polyacrylamide.

Gelatin referred to herein refers to so-called lime-processed gelatin, acid-processed gelatin and enzyme-processed gelatin.

Other known surfactants may be used alone or in combination in the photographic constituent layer of the present invention. Although they are used as coating aids, they are sometimes applied for other purposes, such as emulsifying and dispersing, improving sensitization and other photographic properties, and reducing power generation.

These surfactants include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide type, glycerin type, and melisidol type, higher alkylamines, and quaternary surfactants.
Cationic surfactants such as anthonium salts, pyridine and other heterocycles, phosphoniums or sulfoniums; Anionic surfactants containing acidic groups such as carboxylic acids, sulfonic acids, phosphoric acids, sulfuric esters, and phosphoric esters; Ampholytic surfactants include amino acids, aminosulfonic acids, and sulfuric or phosphoric acid esters of amino alcohols.

Some examples of surfactant compounds that can be used include U.S. Pat.
No. 8,226, No. 2,739891, No. 306a10
No. 1, No. 3.15a484, No. 3.201, 253, No. 32IQ191, No. 224Q472, No. 3415
．． 649, same mouth L413, same 3442.654, same 447 to 174, same 545974, same 366
No. f14478, No. 3507.660, British Patent No. 1
．． 19a450, as well as Ryohei Oda et al., “Synthesis of surfactants and their applications (Maki Shoten, 1964), and A, W
, ``1-Surf S Active Agents'' by Berry (
Interxience Publications Inc., 1958), J.P.

It is described in the following device: "Encyclopedia Active Agents Vol. 2" (Chemical No. Pritzkan No. 7, 1964).

In addition, in the present invention, lubricating compositions, such as U.S. Pat. No. 3.07'J837, U.S. Pat.
4% No. 970, No. 3,294,537, No. 4047,
Modified silicones such as those shown in No. 958 and JP-A-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. 441, No. 912, Special Publication No. 45-
The polymer latex described in No. 5331 and the like can also contain silica, strontium sulfate, zirium sulfate, polymethyl methacrylate, etc. as a matting agent.

Further, the photographic light-sensitive material of the present invention may contain an alkyl acrylate latex as described in U.S. Pat. No. 411,911, U.S. Pat.

The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention are regular (regular) grains such as cubes and octahedrons.
It may have an irregular crystal shape, such as a spherical shape or a plate shape, or a composite shape of these crystal shapes. Further Hari Search Disclosure 2
The tabular grains described in Vol. 25, No. 22534, pp. 20-58 (1983, 1) may also be used. It may also consist of a mixture of particles of various crystalline forms.

Further, the emulsion used in the present invention is disclosed in U.S. Patent No. 2.99f.
i382, 397,987, 3.70585
As described in No. 8, a mixed emulsion of a light-sensitive silver halide emulsion and an internal silver halide emulsion, or an emulsion that is used in combination in a separate layer, may be used. Here, the patent application 1986-170
It is preferable to further use the mercapto compound described in No. 588 in combination, from the viewpoint of suppressing capri and improving storage stability over time.

The photographic emulsion used in the present invention is B. gelafchides (
"Chimie et Physique Photographic" by P. Glafkides)
(PauIMonte1, 1967), G.F. Duffi
Photographic Emulsion Chemistry (Photographic Emulsion C.
hemistry) J (The Focal Press Th
e Focal Press, 1966), V, L, Zella
``Making and Coating Photography'' by Maki
ng and coatingphotography
c Emul-sion) J (Published by Focal Press, 1964)
It can be prepared using the method described in et al.

In the silver halide emulsion layer of the present invention, a resin dye can be used if necessary. For example, RESEARCHDISCL
O3URE 176 volumes tem 17643 Item 1 can be used. Furthermore, in order to improve the color tone of developed silver, a magenta dye as described in Japanese Patent Application No. 60-127663 may be used.

Types, manufacturing methods, chemical sensitization methods, anti-capri agents, stabilizers, hardeners, plasticizers of silver halogenide used in the silver halogenide emulsion layer, surface protective layer, etc. of the photographic light-sensitive material of the present invention There are no particular restrictions on lubricants, coating aids, matting agents, brighteners, spectral sensitizing dyes, dyes, color couplers, etc.
hDisclosure) Vol. 175, pages 22-31 (December 1978) can be referred to.

(Example) The present invention will be illustrated with the following examples, but the present invention is not limited thereto.Example 1 An emulsion layer and a protective layer are formed on one side of a YH17 polyethylene terephthalate film support of about 175μ. Samples 1-1 to 1-10, which were stacked in this order, were coated and dried according to a conventional method. The various compositions are as follows.

(Emulsion layer: approx. 5μ) Binder: Gelatin 2. ,5117m2 coated silver amount p
51/m ” Silver halide composition; Ag processing L5mOA'J and Ag
Br 9&5 mol '16 Capri inhibitor; 1-phenyl-5-mercap) Terrasil 0.5#/Ag 100N (protective layer; approximately 1μ) Binder; Gelatin L7g/1rL2 Coating agent; P-nonylphenoxybutanesulfonate sodium 7 das of salt/
1rL2 sclerosing agent; 24-dichloro6-human 90 Gycy L45-
Triazine lysium salt 0.4! i/100g gelatin (where sample 1-1 consists only of the above composition), sample 1-
In addition to the above composition, Examples 2 to 1-6 each contained examples of the compounds of the present invention as shown in Table 1 in their protective layers. Samples 1-7 to 1-10 are comparative examples.

After conditioning these unexposed samples at 25°C and 10% RH for 2 hours, we placed the samples in a dark room under the same air conditioning conditions to examine how the static marks would behave against the material. After rubbing with a rubber roller and a nylon roller, it was developed with the following developer, fixed, and washed with water, and the degree of occurrence of static marks was examined.

(Developer composition) Warm water 800
-Sodium tetrapolyphosphate zoI
l Anhydrous sodium sulfite 50,
9 Hyde 90 Quinone 1
0.9 Sodium carbonate (monohydrate)
40.91-phenyl-3-virazolito97
G, 3N potassium bromine
zoI! Add water 10
0 Qa? (pi(1α2)) The antistatic properties of these samples are shown in Table 1.

In the table above, the evaluation of the degree of static mark occurrence is A: No static marks were observed at all B: #
I Slightly recognized C: I
I. Kanashi recognized]) : #
# It was divided into 4 stages, which were recognized on the entire surface.

As is clear from Table 1, the samples (1-2 to 1-6) that were antistatic by using the fluorine-containing nonionic and non-fluorine nonionic surfactants of the present invention in a humidity condition of 10 cm relative humidity. Roller made of two different materials (:
Not only does it have an excellent antistatic effect with virtually no static marks, but it also has good sensitivity and coating repellency. On the other hand, the antistatic properties of the control were significantly inferior.
In samples 1-7 to 1-10 used for comparison, it is impossible to improve static marks on both rubber and nylon materials at the same time. On the other hand, if the static marks on the nylon roller are improved, the static marks will be more severe on the rubber roller, but by using the surfactant of the present invention in combination, the antistatic property can be improved. It can be seen that this is particularly good. It can also be seen that the comparative example is significantly inferior to the present invention in terms of sensitivity and coating repellency.

Example 2 (1) Preparation of silver halide emulsion for upper emulsion layer Formation of silver iodobromide (silver iodide 1.5 mol %) spherical grains with an average grain size of 1 in the presence of cyanmonia by double jet method
．． 0μ), chemically sensitized with chlorauric acid salt and sodium thiosulfate.

After chemical sensitization, Anhiro 4 was added as a spectral sensitizing dye.
5'-dichloro-9-ethyl-3,3'-di(3-sulfopropyl)oxacarbocyanine hydroxide 9.
Sodium salt, potassium iodide, weight average molecular weight (MW)
A coating solution for the upper emulsion layer was prepared by adding polyacrylamide of 6 Q O00, an anti-capri agent, a coating aid, and the like. Silver/
The gelatin ratio is 1.30, and the polyacrylamide/gelatin weight ratio is α15.

(2) Preparation of tabular silver halide grain emulsion Potassium bromide, thioether (HO(CH2)28(CH2)28(CH2)20
H) and gelatin were added and dissolved, and a mixed solution of silver nitrate solution, potassium iodide, and potassium bromide was added by double jet method to the solution maintained at 70'C with stirring.

After the addition was completed, the temperature was lowered to 35°C and soluble salts were removed using the sedimentation method, and then the temperature was raised to 40°C again and gelatin 60°C was added.
I was added and dissolved, and the pm was adjusted to 6.8.

The obtained tabular silver halide grains had an average diameter of 1.25
μ and thickness 0.15 μm 1 average diameter/thickness ratio is 8.33
The amount of silver iodide was 3 mol. Also, pAg at 40℃
was &95.

This emulsion was chemically sensitized using gold and sulfur sensitization. To this chemically sensitized solution, 500 µm of the sensitizing dye anhydro-55'-di-chloro-9-ethyl a3'-di(3-sulfopropyl)oxacarbocyanine hydroxide sodium salt and 200 µm of potassium iodide were added to the solution. Green sensitization was carried out by adding 1 mole of the solution. Furthermore, as stabilizers, 4-hydroxy-6-methyl-L33a, 7-chitrazaiendene and 4
6-bis(hydroxyamino)-4-diethylamine-
La5-triazine was added.

(3) Preparation of coating liquid for surface protective layer Sodium polystyrene sulfonate, polymethyl methacrylate particles (average particle size 3.6μ) as a matting agent,
4-(p-nonylphenoxy)butanesulfonic acid sodium salt (addition amount 101ap/m2), JP-A-58-20
Compound Example-1 described in No. 3435, z4-) An aqueous solution of 10 tisgelatin containing chloro-6-hydroxy-8-triazine sodium salt was prepared and used as a coating solution for a surface protective layer, and used as a control surface protective layer. (Sample 2
-1).

Samples 2-2 to 2-5 have the compound of the present invention added to the surface protective layer. In addition, Samples 2-6 and 2-7 were used as comparative samples.

(4) Preparation of photographic material On an undercoated polyethylene terephthalate film support having a thickness of 180 μm, a tabular silver halide grain-containing emulsion layer, an upper emulsion layer, and a surface protective layer were formed in this order as shown in Table 3. It was coated and dried using a co-extrusion coating method.

The three layers described above were similarly coated on the other side of the support in the same order to produce photographic materials 2-1 to 2-7. - The amounts of silver in the tabular silver halide emulsion layer and the upper emulsion layer were adjusted so that the amount of silver coated on one side of the support was Dmax:=IO.

The amount of gelatin applied to the surface protective layer is 1! It was i/771.

After conditioning these unexposed samples at 25°C and 10% RH for 2 hours, we placed the samples in a dark room under the same air conditioning conditions to examine the static marks on each material. After rubbing with a roller and a nylon roller, development (developer: RD-m manufactured by Fuji Photo Film Co., Ltd.)
), fixing, and washing with water, and the degree of static mark occurrence was examined.

In addition, we also use conveyors (AOT with PDA) that are often used in the market.
-8 film changer (manufactured by Simens-Elema) under the same air conditioning conditions as described above to evaluate the degree of occurrence of static marks.

The results are shown in Table 2.

As is clear from Table 2, the photographic material using both the fluorine-containing nonionic surfactant and the non-fluorine nonionic surfactant of the present invention has a static mark on rollers made of two different materials (rubber and nylon). The present invention is not only good in that it hardly generates static marks and has excellent antistatic properties for different types of materials, but also that static marks were not observed in practical tests using an actual conveyor, indicating that the effects of the present invention are good. is obvious.

On the other hand, it is difficult for the comparative samples to always satisfy the antistatic properties for each material, and static marks occur even in practical tests. The superiority of the antistatic ability of the present invention is noteworthy.

Example 3 ■ Preparation of a photosensitive silver halide emulsion Silver nitrate, potassium bromide, and potassium iodide were mixed with silver nitrate sulfate, potassium bromide, and potassium iodide using the usual ammonia method while keeping the halogen ion concentration in a container containing halogen and gelatin relatively high. Average particle size 1
．． 0μ thick plate-like silver iodobromide emulsion (N = 3.5 mol es
) was prepared and chemically sensitized using chloroauric acid and sodium thiosulfate to obtain a photosensitive silver halide emulsion (2).

■ Preparation of internally fogged silver halide emulsion A silver chlorobromide emulsion with internal light sensitivity and an average grain size of 0.2 μm was prepared in the same manner as in Example ■ in the specification of U.S. Pat. No. 2,592,250. The interior of the emulsion was fogged by irradiation to obtain an emulsion to which 5-alkylamide #2 mercaptoindimidazole was added as a fogging inhibitor.

(2) Preparation of coating sample A sample was prepared by mixing emulsion (2) with Ag at a molar ratio of 4:1. At this time, 4 is added as a stabilizer to the emulsion layer.
3α,7-chitrazaindene was added to -hirroxy6-methyl-,L. The total amount of binder in the emulsion layer is Z5
17 m2 (one side), of which approximately 20% was polymer (polyacrylamide dextran). In addition, a silver chlorobromide emulsion (Br
30% or less) and the surfactant of the present invention as an antistatic material as shown in Table 4, and p- as a coating agent.
Sodium octylphenoxyethoxyethoxyethoxyethanesulfonate (10rn9/rIL2) was used as a matting agent, and polymethyl methacrylate (PMMA) (101n9/rIL2) was used as a matting agent.
rrL2) and Snowtex (10
Q1n9/rrL2) was added. In addition, for color tone improvement, dye emulsion dispersion (so*/m2) dye (the following structure 10,
! i',) Lihexy A/7 Osphae) 10Ii, 59 cc of ethyl acetate, sodium dodecylbenzenesulfonate α5II, and 100 cc of 15% gelatin. ) was added to 3-3.3-8.

The total amount of binder in the protective layer was about 1517 m2, of which about 20% was polymer.

The emulsion and surface protective layer thus prepared were coated on a polyethylene terephthalate support together with a vinyl sulfone hardener and dried to obtain a sample.

Dye; G-CH-CH=CH-G Here, G represents the following.

These unexposed samples were examined in the same manner as in Example 2 to determine the degree of static mark occurrence.

However, the scissor paper aged sample used for the static mark test on the practical conveyor after the scissor paper aged was prepared as follows. Humidify the film at 25°C and 60% RH for 12 hours, sandwich it between scissor paper and heat it to 20 Dragon HII from atmospheric pressure.
It was sealed in a packaging bag under reduced pressure. The samples aged for one week at 25° C. were examined for the degree of static mark occurrence using a practical conveyor.

Processing stain failure was tested and evaluated using the following method.

The coated sample was cut into 30.5 ciX 25.4 (m square) and uniformly exposed so that the optical density after development was 1.3, and then processed using Fuji Photo Film Automated Development!! RU (Developer: Fuji Photo Film). 100 sheets were continuously developed using RD-1 (Fixer: Fuji Photo Film Puji-F, water bath). The degree of staining after treatment was evaluated.

These evaluation results are shown in Table 3.

As is clear from Table 3, Samples 3-2 to 3-5, in which the fluorine-containing nonionic surfactant of the present invention and the non-fluorine nonionic surfactant were used in combination, had significantly more static stability than the control sample 3-1. It can be seen that the mark has been improved. Also, the static mark changes over time and scissor paper is very good.

In comparison, Comparative Samples 3-6 to 3-9, which use only either a fluorine-containing nonionic surfactant or a non-fluorine nonionic surfactant, have significant static marks and are unsatisfactory in terms of antistatic properties. It is enough.

In addition, comparative sample 3 using a large amount of non-fluorine nonionic surfactant
-8 was slightly improved in terms of static marks, but it generated stains during processing and could not be used practically.

On the other hand, the samples of the present invention have no problem with processing stains.

As described above, the present invention is not only excellent in antistatic properties but also excellent in terms of treatment stains.

(Effects of the Invention) According to the present invention, a silver halide photographic material having good antistatic properties, especially a silver halide photographic material that generates little static electricity against various materials and whose antistatic properties do not change over time. A photosensitive material was obtained.

Procedural amendment IBB+December 2, 1960

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, a fluorine-containing nonionic surfactant and a fluorine-free nonionic surfactant are added to the emulsion layer or at least one of the other constituent layers. A silver halide photographic light-sensitive material characterized in that it also contains an agent.