JPS6076742A - Photosensitive silver halide material - Google Patents

Abstract

PURPOSE:To improve the antistatic property by incorporating a nonionic surfactant, an anionic surfactant having a polyoxyethylene group and a fluorine-contg. surfactant having a polyoxyethylene group into a photographic layer. CONSTITUTION:A nonionic surfactant (A) represented by formula I or II (where R1 is 1-30C alkyl, alkenyl or the like; A is O, S or the like; each of R2-R4 is H, alkyl or the like; and each of n1, n2 and m is 2-50), an anionic surfactant (B) having a polyoxyethylene group represented by foumula III (where B is alkyl, alkenyl or the like; D is a water soluble group; and n5 is 1-50) and fluorine- contg. surfactant (C) having a polyoxyethylene group represented by formula IV(where Rf is 1-30C fluoroalkyl, fluoroalkenyl or the like) are incorporated into a silver halide emulsion layer or other hydrophilic colloidal layer to obtain the desired photosensitive silver halide material.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of the Invention) The present invention relates to a silver halide photographic light-sensitive material having good antistatic properties, and particularly relates to a silver halide photographic material having good antistatic properties. contamination, adhesion of water-insoluble substances to the conveyance roller, and troubles caused by the generation of water-insoluble substances (uneven drying, film true photosensitive materials, "photosensitive materials")
This is related to the following.

(Description of Prior Art) Photographic materials generally consist of an electrically insulating support and a photographic layer, so contact friction or peeling occurs between surfaces of the same or different materials during the manufacturing process of the photographic material and during use. Electrostatic charges often accumulate due to exposure to This accumulated static charge causes many problems, but the most serious problem is that the photosensitive emulsion layer is exposed to light due to discharge of the static charge accumulated 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, 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. This phenomenon only became apparent after development.These accumulated electrostatic charges may cause Igx, such as dust adhering to the film surface or uneven coating.
It may also cause further failures.

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. 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 contact separation between the parts.

It also occurs when there is contact with the packaging material. The silence
Static marks in photographic materials induced by the accumulation of IT loads become more pronounced as the sensitivity of photographic materials increases and 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. In order to eliminate these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic light-sensitive 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. In other words, antistatic agents that can be used in photographic materials include
In addition to having excellent anti-soldering performance, it should not have any adverse effect on the photographic properties of the photographic light-sensitive material, such as sensitivity, fog, graininess, sharpness, etc., and should not have any adverse effect on the film strength of the photographic light-sensitive material (i.e. The photosensitive material should not be susceptible to scratches due to friction or scratching), should not have an adverse effect on adhesion resistance (i.e. should not become easily scratched by the surface of the photographic light-sensitive material or with the surface of other substances), Application of antistatic agents to photographic materials requires performance such as not accelerating the fatigue of the processing solution, not contaminating the conveyance rollers, and not reducing the adhesive strength between the +14 and J- of the photographic light-sensitive materials. There are many restrictions on what you can do.

One way to eliminate these problems caused by static electricity is to increase the electrical conductivity of the surface of the photographic material so that the static charge can be dissipated in a short time before the accumulated charge is discharged. .

Therefore, methods of improving the electrical conductivity of the support of photographic light-sensitive materials and the surface layer coated on each spike have been considered, including the use of various hygroscopic substances, water-soluble inorganic salts, certain interfacial occupancy agents, polymers, etc. has been attempted.

Among these, surfactants are important in terms of antistatic ability, and for example, US Pat.
, Jsi issue, same 3. siri, sti issue, same j, a, 2j
, Ari No. 5, West German Patent No. 1. jj, 2. ≠Ot issue,
Same t, z 7. ≠7λ, JP-A-Sho pry-ts, txt
No. 13-/29,623, J Hiro-1j 2.22
No. 3, Dohiroff-/ri.

No. 273, Tokuko Sho ≠ J-J, No. 312, same Kota //
, St, No. 7, same! l-4'A, 7jt, same, betaine and cationic surfactant, or JP-A-Shoj 1f002J, West German Patent No. 1゜4tJ, to2
No., same/l≠22. tit No., Australian Patent No. J
4', 4'4'/issue/lri! The nonionic surfactants described in et al.

However, these materials exhibit specificities depending on the type of film support and photographic composition, giving good results with certain film supports and photographic emulsions and other photographic components, but with poor results with other different films. Supports and photographic components may be of no use in preventing static staining, or, even if antistatic technology is excellent, they may adversely affect the photographic properties of the photographic emulsion, such as sensitivity, fog, graininess, sharp phos, or It has been extremely difficult to apply these substances to photographic materials because they contaminate the processing solution and cause deposits on the rollers.

Furthermore, the antistatic technology using nonionic surfactants is closely related to the coating agents used in combination.

Although progress has certainly been made, no consideration has been given to the contamination of developing processing solutions and the contamination of transport rollers, which is the cause of serious film failures.

For example, it is stated that the ethylene oxide-adducted M@ form of a phenol-formalin condensate shown in Japanese Patent Publication No. Shoji-26io has excellent antistatic properties even when used in combination with a vegetable coating agent. . However, with the method of the patent,
Problems caused by contamination during the development process remain unsolved.

That is, the roller stains, which are thought to be caused by dry deposits on the conveyance rollers, are extremely bad and cause problems in terms of density unevenness in the film.

Furthermore, JP-A No. 1973-J-7/J describes a photographic material containing a specific anionic surfactant and a polyoxyethylene nonionic surfactant, but like the above-mentioned patent, It is not possible to improve film failure due to contamination of the developing processing solution or contamination of the transport roller.

Another known means of improving antistatic performance is to use °Cx fluorosurfactants. This method utilizes the negative chargeability of fluorine groups to reduce the power generation performance of the film, thereby reducing the occurrence of cystic marks. For example, British patent Ht.

26j, Dohiro, 0/3, tFt, Special Public Show 1it-
Hiroshi No. 3130, JP-A-32.223, same! 0-
/ljλj No. 71, No. 71, J4t-1
Examples include No. 11'6.20, No. 11'6.20, No. 2!077, etc.

However, if these methods are followed, charging performance can be improved in some cases, but problems that occur during the development process, such as processing stains (spot-like desilvering defects) caused by processing solution contamination and transport roller There is no solution to the problem of uneven manufacturing due to contamination.

(@Ming's Object) The first object of the present invention is to provide a photosensitive material which is prevented from being charged and which does not cause contamination of the development process U or the roller.

The second object is to provide a photographic material which is free from banding and does not cause contamination of the sensitive material that comes after it during development.

Third, it is an object of the present invention to provide a photographic light-sensitive material that can prevent static electricity without adversely affecting photographic properties such as desensitization.

The second object is to provide a photographic material whose antistatic properties do not change over time after production.

(Structure of the Invention) These objects of the present invention are to provide a silver halogenide photographic photosensitive material having at least one silver halogenide emulsion layer on a support. or other hydrophilic colloid, at least /1ill of nonionic surfactant and at least /at of anionic surfactant having polyoxyethylene groups.
This was achieved by a silver halide photographic light-sensitive material characterized by containing a perfluorine-raising surfactant having a polyoxyethylene group.

Examples of the nonionic surfactant used in the present invention include compounds represented by the following general formula Ll-/), [1-2], or [l-3].

General formula CI-') R1-A + 0H2C1 (20→olH General formula [I-
] General formula (1-J) In the formula, R excludes carbon number/~30 substituted or unsubstituted hei-shin-yutaka Marujanil, &1Zf-1ney71J-44t
"\A is 10- group, -5-3, -COO- group, -N-R
1o group, -CO-N-R□. Group, 1-8O2N-14□. group (here '10 is a hydrogen atom,
Indicates a substituted or unsubstituted alkyl group. ).

(2) 2, R3, 7, and R9 each represent a hydrogen atom, a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen atom, acyl group, amide group, sulfonamide group, carbamoyl group, or sulfamoyl group.

In the formula, kJL 6 and 几8 represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group, halogen group, acyl group, amide group, sulfonamide group, carbamoyl group or sulfamoyl group.

In the general formula (1-3), the substituents on the phenyl ring may be asymmetrical.

R and R represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. fL4 and R5, 几.

and R7 and ■t8 and 几. may be linked to each other to form a substituted or unsubstituted ring.

n 1 , n 2 , na and R4 are the average degree of polymerization of ethylene oxide and are the number of λ to SO.

Moreover, m is an average degree of polymerization, and is a number of 2 to jOO.

Preferred examples of the present invention are described below. R1 is preferably an alkyl group, alkenyl group, or alkylaryl group having v to 21 carbon atoms, particularly preferably a hexyl group, dodecyl group, isostearyl group, oleyl group, t-butylphenyl group, or t-butylphenyl group, -2,≠-
di-t-pentylphenyl group, p-dobufluphenyl 2
1 m-pentadecaffenyl group, t-octylphenyl group, λ, Hiro-dinonylphenyl group, octylnaphthyl group, etc. R2, kL3, kL6, R7, R8 and Rin,
is preferably methyl, ethyl, 1-propyl, t-butyl, t-amyl, t-hexyl, t-octyl, nonyl, tecyl, dodecyl, trichloromethyl, tribromomethyl, l-phenylethyl, cophenyl-copropyl. Substituted or unsubstituted alkyl group having carbon number/~20,
Substituted or unsubstituted aryl group such as phenyl group, p-chlorophenyl group, -014 (herein, □ represents a substituted or unsubstituted alkyl group or aryl group having 1-2゜1 carbon atoms. The same applies hereinafter) a substituted or unsubstituted alkoxy group represented by ), a halo'r7 atom such as a chlorine atom, a bromine atom,
The acyl group represented by -CO''1□, -Nl, is also □C0
1(,1□(Here, R02 is a hydrogen atom or the number of carbon atoms/~,
20 alkyl groups. amide group represented by -N⇠□2so2R□□), and ■t2, 几3, 几7, and 几 may be hydrogen atoms. Among these, R6 and R are preferably an argyl group or a halogen atom, and particularly preferably a bulky tertiary alkyl group such as a butyl group, a t-amyl group, or a t-octyl group. Particularly preferably, RQ is a hydrogen atom, and a compound of the general formula (1-j) synthesized from a ≠-disubstituted phenol is particularly preferred.

1t4, 几 is preferably a hydrogen atom, methyl group, amyl group, n-propyl group, i-propyl group, n-hemethyl group, /-ethylamyl group, n-undecyl group, trichloromethyl group, tribromomethyl group. Substituted or unsubstituted alkyl groups such as groups, α-furyl groups, phenyl groups, naphthyl groups, p-chlorophenyl groups, p-methoxyphenyl groups,
It is a substituted or unsubstituted aryl group such as m-nitrophenyl group. Also, kL4 and R5, R6 and R7, and R8 and R
9 may be connected to each other to form a substituted or unsubstituted ring, such as a cyclohexyl ring. Among these, IL4 and YL5 are particularly preferably a hydrogen atom, an alkyl group having 1 to 1 carbon atoms, a phenyl group, or a furyl group. n
1 , n 2 , n 3 and R4 are particularly preferably j
~30 numbers. R3 and 14 may be the same or different.

These compounds are described, for example, in U.S. Pat.

1.61, 3. L eye, Kou 31, same 3. Hiroj7.0
77, No. 3, 1 Ijlt, tλj No. 3, 532
, No. 972, No. 3, 1.3j, No. 317, Tokuko Shori-
No. 7110, Japanese Patent Publication No. 7110, Japanese Patent Publication No. 7/J, Japanese Patent Publication No. 7/J, Japanese Patent Application No. 57-♂5744', Japanese Patent Application No. 57-♂5744', Written by Hiroshi Horiguchi. It is described in "New Surfactant" (Sankyo Publishing, 1971), etc.

The arrows show specific examples of nonionic surfactants preferably used in the present invention.

Compound example H7C1□1(23COO(CH2CH20+8H1-
,2CHCOOMoCk12CH20+, 5H531 1-J C,7H33COO-(CH2C1-1,,O
+1. Hl-≠ C811□70(-CH2CH20-
)7H1-f C□2)(25(J(-CH2CH20
-), oH" C16H330moCH2CH2O+, 2
HI-7C, 8H350+CH2CH20-), 6H1
-# C2□H450mo CH2CH2O+25Ha +
b = / j i-/l C13H2□CON+CH2CH20-),
2Ha + b = 20 [-/ Ta Cl2H25SMoC1(2C)120+,
6HH3 Cl(2CH20-fCH2CH20+1□HOfCH
2CH20+1□ 0fC1 (2CH20+2oH OfCH2CH20-)2oH OfCH2CH20) 1oH 0mo0H20H20-), □H OmoCH20f(.U+ 1ol-1 1-λriC4H9-t C,H9-t -30 CH-t 04H0 -t9 -31 C5H1□-1C5H1□-1 -32 C1(-t C,H9-t 11 ■-33 C6H13-tC6H13'-t [-J≠ -33 C1□H25C1□H25 1-36 C12H25Cl2H25 -37 C4H0-t C8H, -t -3g 0H-tC8H□7-1 17 1-Jri■-San〇l-Hiroshi α a l-≠2 1-4'J C8H1□-1C8H17-t I-Hiro≠ Ca H1s- i s kl t a-L■-Hiro6 C,H1□-tc5H,1-1 ■-Daza■-≠CHCI( 12251225 -30 C8H□7-1 C8H,7-t ■-!/ CH -1C8H, -t 17 [-jJ CH-tc8H□7-1 17 -13 C12H25Cl2H25 [-, r 弘α -js -jJ C)13C)i3 -17 CH-t c8n,7-t 17 1-jri CH-t c5t-i, -t 11 1-t.

[-,</CH-t C6Hl3-t 13 -J 2 CH-1C5H,□-1 11 -A3 a C1゜1-AhiroCH-t c, u1□-[ 17 1-6! (JC8)117QC8H17 -67- The anionic surfactant having a polyoxyethylene group used in the present invention is represented by general formula i).

General formula (U) ■Mo1AmoCH□Cl□0+. 5B-D type middle box, and A
has the same meaning as the above-mentioned general formula (1-/). B represents a substituted or unsubstituted alkyl group, alkenyl group or aryl group, and D represents a water-soluble group. Further, II 5 is the average degree of polymerization of ethylene oxide, and is the number of /-jO.

As a preferable example of the general formula (U), I(□, A is the same as the general formula ('I-/), and ns is preferably ko~io
and B is preferably an alkylene group having carbon number/-1, particularly preferably a methylene group, an ethylene group,
These include a solopyrene group and a methylene group. D is preferably 1000M, -8OaMs-o-So 3pa, -0-
P-OM, -product 10M.

Here, M represents an inorganic or organic cation, preferably a hydrogen atom group, an alkali metal, an alkaline earth metal, ammonium, or a lower alkylamine.

These compounds are described in U.S. Patent No. 3,0,202,
Same, z, Aoo, t3i- issue, same 2,7/Y.

No. 017, No. 3, 20/Jj No. 2, No. 3. ≠lj, 4≠
No. ri, Tokukai Shoj≠-2123j, Tokuko Shosan〇-23,
7μ7, British Patent No. 1,17g.

No. j44j, same/, 31711. No. 17, U.S. Pat. No. 3, x44t, ior, J, 1. oo, r3
It is described in issue i etc.

Specific examples of the anionic surfactant containing polyoxyethylene of the present invention are shown below.

Compound example It-/C3H1□O+CH2CH2Oga1CH2+
, 803Na11-J Cl2H250eCH2CH2
0f7eCH2+4803Nay -J C□8H35
oecH2CH20u1÷CH2su, 803Naif-
4' C1□H258moCH2CH2Osdc)12as(JaNa1-j -x -7 ■-ta■-10C9H□, 0fCH2CH20+, 1 to 803
-// 1-I2 1- is Cl8H330 (CH2CH20+48
03Na1-/ μ ■-7jC12) I250+CH2CH2O+4CH2
COONa1-/A1-I71Na-1ir The polyoxyethylene-based fluorine-containing surfactant used in the present invention is represented by the following general formula (III).

General formula (ill) Rf -A + CH2CH2O. In the B-E formula, Rf is a carbon number of 7 to 7 which is partially or completely substituted with a fluorine group.
Represents a 3θ substituted or unsubstituted alkyl group, alkenyl group or aryl group. A and B have the same meanings as in general formula (1), and E represents a water-soluble base. Further, n6 is the average degree of polymerization of ethylene oxide, and is the number /~jO.

Preferred examples of the present invention are shown below.几f is preferably an alkyl group or alkylaryl group having a carbon number of μ to /j, particularly preferably )(+CF + CH−1CnF2n +1(CH2)
Examples include n12n22aa4, and n4 represents an integer from θ to l.

Further, n6 is preferably 2 to io. E is preferably 1000M, -8O3M, -0803M.

■ e -N (几) +CH→80, -OH etc. are 11 2
3 can be mentioned. Here, M represents an inorganic or organic cation, preferably a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium, lower alkylamine, or the like.

Further, "11" has the same meaning as the general formula (1--2).

These compounds are described in British Patents Nos. 1 and 2, 3. lry issue,
No. 1,239,391, I &, ECProduct
Research and Development
/(J)(/ritλ,ri)I), /Aj~/Ari, Oil chemistry/2(/ko)(/263)p, As3~tt2, JP-A No. 11-32322, JP-A It is described in Shoj/-1sii2s, Japanese Unexamined Patent Publication No. 11-7742, and the like. Anionic surfactants are particularly preferably used as the fluorine-containing surfactants of the present invention.

Specific examples of the fluorine-containing surfactant of the present invention are shown below.

Compound example) 3 1[-7 C8F17(CH2CH20+t, OH2-i803N
a■-t Hmo CF2+11CH20,000) (2CH2-)-7(
CH2ga5O3H■-2 C7F□5COOSoCH□CH2Oarrow fCH1h803
KCF 80 N(-(J(2CH20+T3S03N
a8 17 2 ■-1i K C, F, MoCH2CH20S Oa N a
■-l! c7F, 5CON(-CH2CH20+-5o3H-
74L Na III −/ 4 111-/l ■ l-13 1l-20 08F, 7moCH2CH2Osu12H1ii-2/ HmoCF ←CI(0soCH2CH20 line, H2102 General formula (1-/), (1- 2], ([--?), 1[)
The amount of surfactant used, which can be expressed as -7: Often, especially 0
1j-co o my is preferred. The method of applying these surfactants of the present invention into a photographic light-sensitive material is to dissolve them in water, an organic solvent such as methanol, ethanol, nasetone, or a mixed solvent of water and the organic solvent, and then apply the surfactants on a support. Light-sensitive emulsion layer, non-light-sensitive supplement 1! UI (e.g. backing layer, antihalation layer, interlayer, protective layer, etc.)
The solution may be contained in the solution, or the surface of the support may be sprayed, coated, or immersed in the solution and dried.

At this time, two or more of each of the nonionic surfactant, anionic surfactant, and fluorine-containing surfactant of the present invention may be mixed. It is also possible to use another anti-static agent in the layer containing the nonionic surfactant, anionic surfactant and fluorine-containing surfactant of the present invention or in other layers, and by doing so, a more favorable antistatic effect can be obtained. It can also be done with respect.

Such antistatic agents include, for example, U.S.
12. /No.37, same 2. ? No. 72,333, 3.06
2,7za No. 5, 3,27. ．． t, No. 107, 3. !
lg, 2ri No. 1, same J, tis, s3i No. 3,
No. 763, 7/, 3. Risr, Tatata issue, Dogu, o
7o, itri issue, dohiro, /hiro 7゜rzo, german patent no. 2. (oo, ≠6 No., JP-A No. 4tr-yl, its No. 44r-pH, lt, No. 33, ≠2-gt, 73
No. 3, same jo-hiro.

No. 472, jO-2 Hiro, No. 053, 5.2-/Kota,! Polymers such as those described in U.S. Pat.
No. t, same 3. ≠! No. 7.076, same 3, gj≠, 6λj
No. 3,132,272, J, tjs, s
Surfactants such as those described in U.S. Pat. No. 3,012,70θ, U.S. Pat.
No. 3. j coj.

So-called mats made of metal oxides, colloidal silica, etc., barium strontium sulfate, polymethyl methacrylate, methyl methacrylate-methacrylic acid copolymer, colloid/lika, powdered silica, etc. as described in No. 1.2l, etc. Agents can be mentioned.

Also, ethylene glycol, fluoropylene glycol, /,
/,/-) Limethylolpropane, etc.
All polyol compounds as shown in 2t can be added to the nonionic, anionic, fluorine-containing, surfactant-containing layer or other layer of the present invention, and by doing so, a more preferable band prevention effect can be obtained. I can do it.

The layer containing the nonionic, anionic, and fluorine-containing surfactant of the present invention includes the emulsion layer and the undercoat # on the same side as the emulsion layer.
) 11i1, an intermediate layer, a surface protective layer, an overcoat layer, a transparent layer on the opposite side to the emulsion layer, etc. Among these, surface layers such as a surface protective layer, an overcoat layer, and a back layer are particularly preferred.

Examples of the support used in the photographic material of the present invention include films such as polyolefins such as polyethylene, polystyrene, cellulose derivatives such as cellulose triacetate, cellulose esters such as polyethylene terephthalate, habalite paper, synthetic paper, and paper. Included are supports made of sheets coated with these polymer films and their analogs.

The support used in the present invention can also be provided with an antinolation layer. Carbon black or various dyes such as oxole dyes, azo dyes, aryl tin dyes, styryl dyes, anthraquinone dyes, merocyanine dyes and tri(or di)allylmethane dyes may be used for this purpose.

The light-sensitive materials according to the present invention include normal black-and-white/silver-genide light-sensitive materials (e.g., black-and-white sensitive materials for photography, black-and-white sensitive materials for X-ray, black-and-white sensitive materials for printing, etc.), and normal multilayer color sensitive materials. Materials, (e.g. color reversal film, color negative film, color positive film, etc.)
, and various photosensitive materials. It is particularly effective for silver halide photosensitive materials for high-temperature, rapid processing and high-sensitivity silver halide photosensitive materials.

Below, the photographic layer of the silver halide photosensitive material according to the present invention will be briefly described.

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 derivatives; synthetic hydrophilic colloids such as polyvinyl alcohol and polyvinylpyrrolidone. , polyacrylic acid copolymer, polyacrylamide or derivatives thereof, partial hydrolysates, etc. can also be used in combination.

Gelatin referred to herein 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 polymeric substances, so-called gelatin conductors, i.e., amino groups, imino groups, etc., as functional groups contained in the molecule,
It is also possible to replace the hydroxyl group or carboxyl group with one treated or modified with a reagent having seven groups capable of reacting with them, or with a graft polymer in which molecular chains of a polymeric substance are bonded.

Silver halogen emulsion of the photographic light-sensitive material of the present invention) Special surface protective layer, etc. Types of silver halogen used, manufacturing method,
Regarding chemical sensitization, antifoggants, stabilizers, hardeners, antistatic agents, plasticizers, lubricants, coating aids, matting agents, brighteners, spectral sensitizing dyes, dyes, color cassillants, etc. There are no particular restrictions; for example, product licensing magazine (Pr.
oduct Licensing) Octopus roll 107~ii
p.o (December 7th) and Research Disclosure magazine.
The description in /76 volume 22-3/ (/71r/April) can be referred to.

In particular, antifoggants and stabilizers include guhydroxy-6-methyl-/, 3,3a,7-tetrazaindene-
3-Methyl-benzothiazole,! -Phenyru! - A large number of compounds including mercaptotetrazole, many heterocyclic compounds, mercury-containing compounds, mercazoto compounds, metal salts, etc., and hardening agents such as mucochloric acid, mucobromic acid, mucophenoxychloric acid, mucophenoxybromic acid, formaldehyde, Dimethylol urea, trimethylol melamine, glyoxal, monomethylglyoxal, co,3-dihydroxy-1. Hiro-dioxane, 2
．． Aldehyde compounds such as 3-dihydroxy-j-methyl-/, μm dioxane, succinic aldehyde, 2゜j-dimethoxytetrahydrofuran, and glutaraldehyde; divinyl sulfone, methylene bismaleimide, 5-
Acetyl-l,3-diacryloyl-hexahydro-S
- triazine, /, 3. j-) lyacryloyl-hexahydro-8-triazine, /, J, t-) ribinylsulfonyl-hexahydro-3-197dinbis(vinylsulfonylmethyl)ether, '+3-bis(vinylsulfonylmethyl)furopanol- λ, an active vinyl compound ij such as bis(α-vinylsulfonylacetamido)ethane, F-dichloro-6-hydroxy-s-triazi/·sodium salt, 2. 'A-dichloro-t-methoxy5-) riazine, 2.4t-dichloro-(booth-7-nilino)-8-1 riazine sodium salt 1.
2. ≠-CycloroA-(-monosulfoethylamino)-
8-) active halogen compounds such as riazine, N,N/-bis(,2-chloroethylcarbamyl)piperazine;
Bis(λ,3-epoxyzolopyl)methylpropylammonium IIp-toluenesulfonate, l,≠-bis(2/,3/-epoxypropyloxy)butane, /,
3. Epoxy compounds such as j-triglycidyl isocyanurate, l,3-diglycidyl-r-(r-acetoxy-β-oxypropyl)in cyanurate; Ko, Hiroshi, A-) lyethyleneimino S-) lyazine, l , 6-
Ethyleneimine compounds such as hexamethylene-N・N'-bisethyleneurea, bis-β-ethyleneiminoethylthioether; /, λ-di(methanesulfonoxy)
Ethane, l.

≠-di(methanesulfonoxy)butane, /・! -ji(
Methanesulfonic acid ester compounds such as methanesulfonoxy)pentane; furthermore, carposide compounds;
Examples include inoxazole compounds; and inorganic compounds such as chromic bread.

Among these hardening agents, compounds having active vinyl groups and/or inorganic compounds can be particularly preferably used.

In addition to the nonionic surfactant, anionic surfactant, and stent-containing surfactant according to the present invention, other known surfactants can be used in the photographic material of the present invention.

Other surfactants that can be used in combination include higher alkylamines, primary ammonium salts, pyridine and other heterocycles, cationic surfactants such as phosphonium or sulfonium; carboxylic acids, sulfo/acids, Anionic surface active r+L containing acidic groups such as phosphoric acid, sulfuric acid ester, phosphoric acid ester, etc. Amino acids, aminosulfone fll'lA
, amino alcohol sulfur! ! Alternatively, amphoteric surfactants such as phosphate esters can be mentioned. Further, a fluorine-based surfactant can also be used in combination.

Further, the photographic light-sensitive material of the present invention includes U.S. Special Edition No. 3I≠ii, R11, No. 3. ≠//ri No. 12, Japanese Patent Publication No. 4 Lj-j 33/, etc., may be included.

Har- in the photographic emulsion used in the photographic light-sensitive material of the present invention
Ij/Tsuru Shicho ヱil+ Everyone ± Ik n shogai subtotal ^ may also have regular crystal bodies, or irregular crystal bodies such as spherical or plate-shaped.
ar) crystal form, or 1 may have a composite form of these crystal forms.

It may also consist of a mixture of particles of various crystalline forms.

These photographic emulsions are P, Chi by Glafkidea.
mie et Physique Photograp
hique (PauJ Monte 1, 1967), G, F.

Photographic Emuls by Duffin
ionChemistry (The Focal P
ress, 1766), V, L, Ze eyes km
Making and Coat by an et al
ing Photographic Emulsion
(The Focal Press-) II, /ri4
i, 141R using the method described in 1999). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt and soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. .

Although the silver halide emulsion can be used as a so-called unripe emulsion without chemical sensitization, it is usually chemically sensitized. For chemical sensitization, the Glafkides or (Akademi
sche Verlagsgesellschaft
.

/91.1) can be used.

That is, a sulfur sensitization method using a compound containing sulfur that can react with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. be able to. As the sulfur sensitizer, thiosulfates, thioureas, thiazoles, rhodanines, and other compounds can be used, and specific examples thereof include U.S. Pat.
2.1110.4 Zari No., J, J7r, F4'7 No. 2
．． 721. Although stannous salts, amines, human didine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used as reduction sensitizers even though they are described in lt1, J, AjA, and RSS, A specific example is U.S. Patent Co., ≠17. IjO, 2. G/P, 27≠ issue, 2
．． j/l, trij issue, 2,5#J, tOW issue, 2,91
No. 3,610, Ko, t9≠, t37.

For noble metal sensitization, in addition to total complex salts, complex salts of metals in group I of the periodic table, such as platinum, iridium, and tsucladium, can be used.
No. 3, J Mamoru 44f, OtO No., British Patent A/za,
It is described in the Oat issue etc.

The photographic emulsions of this invention may be spectrally sensitized with methine dyes and others. The dye used is cyanine color L.
Included are merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes.

For these pigments, any of the nuclei commonly used for cyanine pigments can be used as basic heteronuclear nuclei. Namely, viroline nucleus, oxazinone nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-j-one nucleus, a thiohydantoin nucleus, and a λ-thioxazolidine-J nucleus as a nucleus having a ketomethylene structure.
, 4'-dione nucleus, thiazolidine-2,≠-dione nucleus,
J-J membered heteroartic ring nuclei such as rhodanine nuclei and thiobarbital acid radicals can be applied.

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

(Example) Example 1 (1) Purification of sample: A silver halide emulsion layer having the following composition was coated on an undercoated polyethylene terephthalate film support with a thickness of 1'0μ, and further on A protective layer having the following composition was coated and dried to prepare a black and white silver halide photosensitive material. A nonionic surfactant, an anionic surfactant, and a fluorine-containing surfactant of the present invention or a comparative surfactant were added to the storage layer.

(Emulsion layer) Thickness: approx. jμ Composition and coating value Gelatin λ, ! t/ ;/ m 2 iodobromide scissors (silver iodide i, j molti) jf//m2 1-phenyl-mercaptotetrazole cojMf/1122 (protective layer) Thickness: approx. lμ Composition and coating amount Zera f7 / , 7fl/yn2 2,6-dichloro-4-hydroxy-/, J.

j-) Reazine natrirum salt 10 da/m2 Nonionic surfactant 10 da/m2 Anionic surfactant of the present invention or comparative anionic surfactant, 2j-≠O da/m2 Total fluorine surfactant λ~ iotsu/m'' (2) Method for determining antistatic ability: Antistatic ability was determined by measuring surface resistivity and static mark generation. 0 surface resistivity is measured when the total polar spacing of the specimen is 0./m. 1. Clamp the brass electrode with a length of 10 crs (the part in contact with the test piece is made of stainless steel) and measure 1 stroke with a TkLrtjl type insulation meter made by Takeda Riken.■Static mark generation test is performed on a rubber sheet. In this method, the unexposed photosensitive material was pressed with a rubber roller from above with the surface containing the anti-straightening system facing downward, and then peeled off to generate static marks.

Each measurement condition is that the surface resistivity is measured at 2j0C1λj%RH, and the static mark generation test is performed at COs'CXλ.
I'll do it in jchi 几H. Note that the humidity of the sample test piece was adjusted under the above conditions all day and night.

In order to evaluate the degree of static mark occurrence, each sample was coated with a current 1# of the following composition. The film was developed for 5 minutes at 2°0C using a solution.

Development tL composition N-methyl-p-amine Phenol sulfate Anhydrous sodium sulfite Aoy Hydroquinone Soda carbonate (l water salt) j3f/ Potassium bromide 2jf Add water purple and make it seven.

The evaluation of static marks followed the following j-level criteria.

A: No static marks were observed.

B: Some static marks occur.

C: Static marks occur considerably.

D: Significant static marks occur.

E: Static marks appear on the entire surface.

(3) Photographic property testing method: The sample was exposed to tungsten lamp light through a Fujifilm Co., Ltd. 12 filter 5P-7≠, developed with a developer having the following composition (3j 0C, 130 seconds), fixed, and washed with water. The photographic characteristics were investigated using

Developer composition Warm water r o O11/ Sodium tetrapolyphosphate 2. O1 Anhydrous sodium sulfite 109 Hydroquinone ioy Sodium carbonate (l hydrate) 4tOf l-phenyl-3-pyrazolidone θ, 3I! Add potassium bromide, of water and mix the whole lθ00 1 (4) Low 2 - Measurement of degree of contamination Sample coated with emulsion layer and surface protection J - 30°
fX/7. It was cut into #m square pieces. After uniform exposure so that the optical density after development becomes i, o, an automatic processing machine (having a silicone roller conveyor) (Developer = Fuji Photo Film RD-11jr0C1 Fixing bath = Fuji Photo Film hFuji-F3sOC1 The SO sheet was developed continuously in a water washing bath (consisting of three baths). After thoroughly drying the water-washed squeeze roller, the appearance of streak-like density unevenness at the tip of the j1100 sample was examined.

The degree of roller contamination was evaluated according to the following Hiro stage criteria.

A: No density unevenness was observed.

B: Some am unevenness occurs.

C: Considerable unevenness occurs.

D: Significant density unevenness occurs.

(5) Treatment stain test method A sample coated with an emulsion layer and a surface protective layer was heated at 30°
2t, cut into ≠ 1 corner. The optical density after development is 7.
After uniform exposure to 300 yen, the automatic developing process Isoba U made by Fuji Photo Film (Developing bath = Fuji Photo Film D -
■ss'c, fixing bath Fuji Photo Film Fuji-F
3! 100 sheets were continuously developed in the 3-bath bath (consisting of 3 baths: 'C, water washing bath). The degree of processing contamination was evaluated based on the number of spot-like desilvering defects that occurred on the 100th sheet.

The test results of (2) to (5) above are combined with the general formula % of the present invention.
Regarding the nonionic surfactant represented by the formula [■], the anionic surfactant represented by the general formula [■], the fluorine-containing surfactant represented by the general formula (III), or the comparative compound, the seventh
Shown in the table.

As is clear from Table 1, the photographic material containing the nonionic surfactant, anionic surfactant, and fluorine-containing surfactant having a polyoxyethylene group according to the present invention is as follows:
The surface resistance is sufficiently low and no static marks are observed.
There is almost no decrease in photographic sensitivity, and there are no problems with roller contamination or processing stains.

Preferred embodiments of the invention are as follows.

1. The nonionic surfactant has the general formula CI- as described in the text.
/), (1-2J or (1-j)).

2 The nonionic surfactant has the general formula [l-2] described in the text
] or ([-j)
Photographic material as claimed in F.

1. The nonionic surfactant has the general formula [I-3] described in the text
A photographic material according to the claims characterized in that it is represented by:

! , a photographic light-sensitive material according to claims, characterized in that the anionic surfactant is represented by the general formula (n) described in the text.

B, the nonionic surfactant has the general formula [1-1] and the father is (1-
j), and the anionic surfactant is represented by general formula (II)
A photographic material according to the claims characterized in that it is represented by:

7. A photographic material as claimed in the claims, characterized in that the nonionic surfactant is represented by the general formula CI-j) and the anionic surfactant is represented by the general formula 11).

t. The photographic light-sensitive material according to the claims, wherein the fluorine-containing surfactant is a compound represented by the general formula (lit).

The nonionic surfactant has the general formula [I-2] or CI-
J), and the anionic surfactant is represented by general formula (II)
A photographic light-sensitive material according to the claims, characterized in that the fluorine-containing surfactant is represented by the general formula (III).

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Document, Showa II, Month//Date 1, Incident Indication: Showa SR Special Training #F7.2J' No. 2
, Title of the invention Silver halide photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of the amendment Description 5, Contents of the amendment (No changes) will be submitted.

Procedural amendment 1, case description Showa SR special training 11111ri, 2r
No. 2, Name of the invention Silver halide photographic light-sensitive material 3. Relationship with the case of the person making the amendment Patent applicant Location 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52)
0) Fuji Photo Film Co., Ltd.
06 Tominachi V Shin Film Co., Ltd. Tokyo Head Office, 2-26-30 Nishi-Azabu, Minato-ku, Tokyo Telephone: (406) 2537 L, Subject of amendment ``Detailed Description of the Invention'' column of the specification - Contents of amendment The description in section ``Detailed Description of the Invention J'' of the specification is amended as follows.

l) No. is’ page " 0 (C:H2CHzO+1□ ” ” and correct it.

] First page 1-T-Nol C48g 1 OO ” 1-J, -2 Otsu U4H9 -0 and correct it.

3) No. 77 [■-digit 1”, H, 5C”2H25” [■−≠2 and correct it.

≠) Page 22 [1-ss l-J　-! r ” and correct it.

j) No. ≠ O miller in row "4C112+SOaθ" [CH2→-,5OaOj and correct it.

,! l) 1111-δ' 11(CF2-)-8C020-(c: l12C mouth z+
4 (CIIz+3SOaH" to 11-1ft-"+0'''・cl-1,.(C112CHzU4-・
(C:Hz)・°0°′”1.

Claims (1)

[Claims] In a silver halide photographic material having at least one silver halide emulsion layer on a support, at least one nonionic surfactant and at least one nonionic surfactant are contained in the silver halide emulsion layer or other hydrophilic colloid layer. 1. A silver halide photographic material comprising an anionic surfactant having various polyoxyethylene groups and a fluorine-containing surfactant having at least one polyoxyethylene group.