JPH01280749A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent the stain of the title material caused by a development processing solution, without giving an adverse effect to the photographic characteristic of the photosensitive material by incorporating an anti-static agent and a polymer capable of affording a cation site in the photosensitive silver halide emulsion layer contd. in the photosensitive material. CONSTITUTION:The anti-static agent and the polymer capable of affording the cation site are incorporated in at least one layer of constituting layers, in the photosensitive material contg. at least one layer of photosensitive silver halide emulsions mounted on a supporting body. The anti-static agent is composed of a polyoxyethylene type surface active agent and a fluorine type surface active agent. The polymer capable of affording the cation site is composed of an anion exchange polymer such as an ammonium salt polymer. Thus, the antistatic property of the photosensitive material is improved, without giving the adverse effect to the photographic characteristic, and the photosensitive material which does snot generate the troubles due to the development processing solution and the stain of a roller, is obtd.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a silver halide photographic light-sensitive material having good antistatic properties, which does not adversely affect the photographic properties, and which is free from problems caused by contamination of the processing solution. This invention relates to a silver halide photographic material that does not produce any of the following.

(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. The disadvantage is that electrostatic charges tend to accumulate due to exposure to This accumulated electrostatic charge causes many problems, but the most important one is that the photosensitive emulsion layer becomes sensitized by discharging 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 impairs the commercial value of the photographic film, and in some cases causes the commercial value to be completely lost.

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 during the process. It also occurs when finished products come into contact with packaging materials. Static marks on photographic materials induced by such accumulation of electrostatic charges become more noticeable as the sensitivity of photographic materials increases and processing speed increases. Particularly in recent years, photosensitive materials have become more sensitive and exposed to harsh handling such as high-speed coating, high-speed photography, and high-speed automatic processing, making it more likely that static marks will appear. .

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, antistatic agents that can be used in photographic light-sensitive materials should not only have excellent antistatic properties, but also have no adverse effect on photographic properties such as sensitivity, fog, graininess, and sharpness of the photographic light-sensitive materials. The film strength of the photographic light-sensitive material should not be adversely affected (i.e., it should not become easily damaged by friction or scratching), and the adhesion resistance should not be adversely affected (i.e., the surfaces of the photographic light-sensitive materials should not be exposed to each other or other substances. It is extremely difficult to apply antistatic agents to photographic materials due to the required properties, such as not adhering to the surface of the photosensitive material), not accelerating the fatigue of the processing solution for photographic materials, and not contaminating the conveyance rollers. subject to many restrictions.

One way to eliminate these electrostatic disturbances is to increase the electrical conductivity of the surface of the photographic material so that the electrostatic charges are dissipated before the accumulated charges are discharged.

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

Among these, surfactants are important in terms of antistatic ability; for example, U.S. Pat.
．． No. 251, No. 3,519,561, No. 3,625,
No. 695, West German Patent Box No. 1゜552.408, No. 1
, No. 597,472, JP-A No. 44185826, No. 5
No. 3-129623, 54. -159223, same 4
B-19213, Special Publication No. 46-39312, No. 49
-11567, 51-4.67'55, 55-
Anionic, betaine and cationic surfactants described in Publication No. 14417, etc., or Japanese Patent Publication No. 48-17
No. 882, JP-A No. 52-80023, West German Patent Box 1.
Nonionic surfactants are known, such as those described in Nos. 422,809, 1.422°818, and Australian Patent No. 54,441/1959.

(Problems to be Solved by the Invention) However, these substances exhibit specificity due to differences in the type of film support and photographic composition, and certain film supports, photographic emulsions, and other photographic constituents have specificity. give good results, but other different films, supports, and photographic components may not be of any use in antistatic properties, or may have excellent antistatic properties but may adversely affect the photographic properties or cause problems with processing solutions. or cause contamination of
It has been extremely difficult to apply these substances to photographic materials because they cause deposits on rollers.

Furthermore, antistatic technology using nonionic surfactants and fluorine-containing surfactants is closely related to the coating agents used in combination. In silver halide photographic materials, various surfactants (particularly anionic surfactants) are used as coating aids or for various other purposes. However, some of these surfactants prevent the antistatic agent from distributing on the surface of the photographic material, reducing the antistatic effect. On the other hand, when such a surfactant is used in combination, a large amount of antistatic agent must be used in order to have a sufficient antistatic effect, and this may cause contamination of the developing processing solution and the conveyance roller. It is the cause.

(Objective of the Invention) The first object of the present invention is to provide a photographic light-sensitive material that is antistatic without adversely affecting photographic properties.

The second objective is to provide a photosensitive material that is antistatic and does not cause contamination of the developing solution or rollers.

The third object is to provide a photographic material which is prevented from being charged and which does not cause contamination of the photographic material that comes after it during development.

A fourth object is to provide a photographic material whose antistatic properties do not change over time after manufacture.

(Means for Solving the Problems) These objects of the present invention are to provide a photographic material having at least one light-sensitive silver halide emulsion layer on a support, at least one of the constituent layers of the light-sensitive material. This was achieved by incorporating a polymer which contains an antistatic agent and provides a cation site 1-.

As the antistatic agent used in the present invention, JP-A-60-
No. 80849, No. 6.0-76742 and patent application No. 1983
The polyoxyethylene surfactants and fluorine-containing surfactants described in JP-A-101455 are particularly preferably used.

The polyoxyethylene surfactant used in the present invention has the following general formulas [■-1], (1-2], (1-3).
) or Cl-4).

General formula (T-1) RI-A+CH2CH20-)rrH General formula (1-2) General formula Cl-3) Re Re General formula (1-4) R, -X-Y-B In the formula, R5 is the number of carbon atoms 1 to 30 substituted or unsubstituted alkyl groups, alkenyl groups or aryl groups, A is 10-group,
-3- group, -C00- group, NRIo group, Co
N RI3 groups, SO2N RIG groups (here RIo
represents a hydrogen atom or a substituted or unsubstituted alkyl group. )
represents.

R2, R, , R, , R represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy 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 R11 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.

R4 and R6 represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group. R4 and R, R6 and R7, and R8 and R7 may be linked to each other to form a substituted or unsubstituted ring.

n, -, nz, R3 and R4 are average degrees of polymerization of ethylene oxide and are numbers from 2 to 50.

Moreover, m is an average degree of polymerization and is a number from 2 to 50.

X represents -0-1-CO-1-S-1R 0-N-1 RR -CON-1-soz N-, and R has 1 to 1 carbon atoms.
10 alkyl group or -Y-B. Y is at least +CH2CHz O+- and +CHz CHCR20±
.

H 2 units, a is 5 to 50, preferably 5 to 20, and b is 2 to 20, preferably 2 to 20.
It is 10.

B represents hydrogen, an alkyl group having 8 or less carbon atoms, or a phenyl group. Moreover, the alkyl group, alkenyl group, and aryl group of A in general formula (1) may be further substituted.

Preferred rows of tree stands are listed below. R1 is preferably an alkyl group, an alkenyl group, or an alkylaryl group having a carbon pattern, and particularly preferably a hexyl group, dodecyl tin, instearyl group, oleyl &, t-butylphenyl group, co, ≠- Di-t-butylphenyl-41,2, Hiro-di-t-pentylphenyl tl;, p-dodecylphenyl a, m-pentadecaffeinyl group, t-octylphenyl group, λ, Hiro-dinonylphenyl group, Such as octylnaphthyl group. R2, It 3, It 6, IL 7
, It, and R9 are preferably methyl, ethyl, l-propyl, t-butyl, t-amyl, t-hexyl, t-
Octyl, nonyl, decyl, dodecyl, trichloromethyl, trichloromethyl, l-phenylethyl, λ-phenyl-probyl, etc., with carbon number/~-〇 substitution or no 1
&-substituted alkyl group, p-chlorophenyl, substituted or unsubstituted aryl group, -0R11 (here, R11 is charcoal or unsubstituted alkyl group or aryl group) (hereinafter the same shall apply) substituted or al'Kl-free alkoxyno^, halogen atom such as chlorine atom, bromine atom, cQ tLl 1
An acyl group represented by -NR,2COR11<where R12 represents a hydrogen atom or an alkyl group having a carbon number of /-,20.

The amide group represented by -NRI 2302 R11 is a sulfamoyl pattern, and 112, R3, R7, R
9 may be a hydrated atom. Among these, R6, rL
6Vi is preferably an alkyl group or a logan atom, particularly preferably a bulky t-butyl group.
It is a tertiary alkyl group such as an amyl group or a t-octyl group.

IL7, It is particularly preferably a hydrogen atom. That is, 2. The general formula CT-3, which is synthesized from Hiroshi-disubstituted phenols, is preferred for hemorrhoids.

I (4, R, preferably represents a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an i-propyl group, an n-heptyl group, an ethylamyl group, an n-undecyl group, a trichloromethyl group, a tribromo group) Methyl 4Na+G (body or unsubstituted alkyl group, α-furyl group, phenyl group,
An unsubstituted or unsubstituted aryl group such as naphthyl zG, p-chlorophenyl, W, p-me)xyphenyl group, m-nitrophenyl group, etc. Also R4 and R6, R6 and rt
7 and R8 and R9 are connected to each other and substituted or unsubstituted If
It does not matter if a substituted ring is formed, such as a cyclohexyl ring.

Among these, It4 and R5 are particularly preferably a hydrogen atom, an alkyl side of carbon number/-j, a phenyl group, or a frilled group. n 1 , n 2% n 3 and n4F, particularly preferably V, j to 3Q. It doesn't matter if R3 and R4 are the same or different.

These 11 compounds are listed in US patents and 2t.

4t/No., J, 4(, 2J', 44jA, 3.'tj7.076, 3.≠jμ, 6koo, 3゜ojλ, P7λ, No. 3, 6ta) J, No. 317, Japanese Patent Publication No. 13-2'?7/r, Japanese Patent Application No. 1,2/, No. 77-rj7A
It is described in ``New Surfactants'' by Hiroshi Horiguchi (Sankyo Shuppan/Rei 7/2011), Japanese Patent Application No. 1983, No.

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

1st compound example T-/CxtHzaCOO+CHzCHzO? rH■-2 C1sHaxcOo(-CHzC'HzO月IH-J C1711sacOO+cH2cH20t77H■-弘C5Ht 7(H-CH2CH20廿I(Ct2H25
0+CH2CH2O+-T-5H-A Ci a'(a 30 + CH2(-I(201r
iHC1sl■a so÷CH2CH20-)TTH-
r C22H450 (-CH2CH20 Surname IH ■-2 (-ii ■-/2 ■-/3 i-/ Ko1-/ Yo■-/4 ILa CtaIIz7CON+CH2Cl1zOfri11a
+ b = 20 ■啼♂ ■−77 C12II25S+CH2CI(20+Ti−H■−
10Ct211250+CH-CHzO+T(-CHzCH
zOhl) iCl-1゜■-23 ■-1≠ ■-2j O-G-CH2CH20+T-5H r-,2,< C, U9 i-,27 (-,2J' 0+CHzCHzOiτH 1-.2F C4H9-t C4H9 -t 1-3/ :20 ■-32 ■-33 し6kill 3-t (, atil 3-
t1-J& ■-37 C4Hg-t C8H17L-3t [-37 [-≠O C12H25C12H2S ■-Hiroshi ■-Hiroλ c9H, C9HH1 ■-≠3 (-44Z ■-1/-t C5I(t t -tし5ki11-t■-gut C4L19-t C411g-C41l 5'(42H25(-'12H25 Cat(x 7-t C3H17-t■-!/■-OkoCa1117-t C3H17-CCsHi
x-t C5H11-t Us) 11 1-t1-t C6H1,-t"113-t C5I~■1□-t C3H11J-&J -7g C3H□7-tC5H, -1 1-,< t H3 0C3H170C3H17 -A7 ■ -68 C+ 6Hs:+0+ CthCHzO+rT+CLC
HCLO±, ■■ H ■ -69 ■ -71 H ■ -72 CbH1scHcHzo + CHzCHzO+rr(
-C1hCH(JIzO±311CsHI 7
0H0■ ■ -75 OH ■ -76 0110il 011C1l.

■ -78 ■ -79 CIsH31COO (Cll zcH2o-h-rfC
ll zcH(IJI zo +4 ItOH ■ -80 CISH31COO(CH2CHCH20-)r(-C
I(zcHzo→-tallOH ■ -81 CIS1131COO(CH2C)120 Presentation CH2C
HCH20→Yu CIhCHzOsu, cell+yOH ■ -82 CI21125-3 + CHzC)120-+T-6
-fCH2CHCH20±5HOH a=15 c→-d=5 ■ -84 a+b-20c+d=10 ■ -85 C+282SSO2N(CHzCHzO'+'nr(C
IIzCHCHzO+sHC1l,
OH general formula (I-1), (I-2) of the present invention
) The amount of the nonionic surfactant represented by (I-3) and (1-4) used is 5 to 5 oz per IM of the photographic material.
Qmg is sufficient, and 10 to 300 mg is particularly preferred.

The fluorine-containing compound used in the present invention is a compound containing at least three fluorine atoms, and may be a surfactant or a polymer. These compounds may contain a nonionic, anionic, cationic, or betaine functional group as a paternal aqueous group.

The fluorine-containing compound used in the present invention is, for example, British Patent No. 1,293,189, British Patent No. 1. 259°, 3
Issue 2, US E! ! I Permit No. 3. ! ♂ri, No. 206, same 3
．． tt&, No. 4171, 3,7j≠,? Kohiro issue, same,
3.77j, No. 136, 3. rs0,6 HiroO, JP-A-Sho-4Lgrao, same jA-//≠.

Ri4L Hirono! TO-/61,136, TO-/11-/J
-//No. 27, J-0-j PO2j, zo-//
J, No. 22/, No. l0-m1j, Special Public Sho≠l-≠37
No. 30, J7-1.1t No. 77, patent application Shoj 7-J'
J j J A, same! No. 7-40773, Japanese Unexamined Patent Publication No. 1
3-1'yL7/, No. 2, No. 17-A4'ko λ, I
&ECProduct [(search an
dDevelopmont /(3)(/riA, Z,
F) Oil chemistry Li(12)(/PAj)pA! r3□
= fluorine-containing surfactant described in A6, etc.,
Or JP-A-41-/! l, λλλ issue, same! λ-lko2゜510, special public show≠2-a3. Rco No. 1, owned by the UK
F punishment/, j j 2, ri 7j, same/, 4'ri 7
1λ! No. 6, U.S.A., No. 01, No. 7.

0/l, No. 111, J, 21AO, No. t04, No. 3
．． 67ri, II-11, same j, ! +10.116
No. 3. t32, No. 1341, 'Machikai Akihiro 1-305
'≠Q issue, Tokukaisho! Fluoropolymers described in λ-/2F620, US Patent No. J, 713.7It, etc. are preferably used.

A particularly preferably used fluorine-containing thread compound is a fluorine-containing surfactant, which is represented by the following general formula.

General formula CII) 1tf-A-X where IL f i-j is a partial fluorine ratio or a total fluorine ratio containing at least 3 fluorine atoms, unsubstituted alkyl group, alkenyl group, if 0 or aryl represents a group. 8 represents a divalent linking group, and X represents a water bathing group.

A preferably represents an alkyl group, an aryl group, or an alkylaryl group, and is combined with oxygen, an ester amide group, a sulfonyl group, or a sulfuric acid group! It may be a substituent of ni oII interrupted by A1 & atom, or a linking group without vt substitution.

X is a hydrophilic group, and the arrangement is general formula + B -Oh9B, 3 polyoxyalkylene groups, 10 (here IJ is -C)I2C)x2-1-CI
-12CH2C)i2- or H Average polymerization of lyoxyalkylene groups +t*: W is the number of /~jO. Also, to the nonionic compound represented by ■ (13 represents a substituted or unsubstituted alkyl group or aryl group), a hydrophilic betaine group is Lis Lts /~! Lower alkylene 4mJ is methylene, ethylene, propylene, cutylene, (represents a benzyl group, etc.) ↓ hydrophilic cationic group, R, 16 (wherein, ILL4, ■ (15, ltl, 3 is the above R14
, Yθ is an anion, hydroxyl group, halogen group, sulfate group, carbonate group, peroxygen acid group -
b represents a carboxylic acid group, an organic sulfonic acid group, an organic sulfate group), and preferably a hydrophilic anion group, t is -3O3M, -(1803M.

C00M1 0-A-1 Maru f Temple is mentioned. Here, M is nothing (or an organic cation?S!I, preferably a hydrogen atom, an alkali metal, an alkaline earth metal, diammonium, lower alkylamine, etc.A and Rf are the same as above) It's Hiko.

The following is a series of nine representative fluorine ratios made by Kibaaki.

Compound (Male sequence 1l-7 C7F15COOH H+CF2-) ffcHzcOcNH4f-3 C5F17SO2N 11-μ C3H7 C5F17SO2N-CH2COOK 1[-! H+CFz・-)7COOCHzCHzCHzSOaN
a+1-7CH3 C7F15CON-C)12CH2SO3NaH-(-
CF2-)-8(:H20+CH2CH2O-)-,
-QC-CH-CH2803Xp: Average 3 C3) I7 II -/OC8F 17 So 2N+(,:H2
CH2O)-7;”(-CH2')-7S03Nap:
Average ≠ 3H7 It −/ / C8F I7802N+CH2CH2
0), ('CH2-')'-3SO3Nap: average 7 TI-/-2CI. F 21 CH2CH20+
CH2(,:I□O-箭(C”H2) 7SO3Nap
: Average 6 Na II −/j H+CF! ÷, CH2O+CH, CH
2 liters 7 Hn5.10 ■-/7C8F□7Cn2cH, o+cH, Cn2o2
Hl, I/+2 Ca)ly 1I −/ f C, F17SO2N+CH2CH2O
Fukucho Hn5:ll (-I'(3 H3 CH, CH, OH p: average ≠ CBFl 7G(2Q(200C-CH-803N a
To regret. knee
To 1 song]
To μ−μ− 5t)
clause…
…mi
#The amount of the fluorine-containing compound used in the present invention may generally be from 0.1 to 1 g per 1M of the photographic material, preferably from 0.5 to 309 mg.

The nonionic surfactant and fluorine-containing compound of the present invention may be added to the hydrophilic colloid layer without any particular limitation, but it is preferably the interfacial protective layer or the bank side surface layer.

As the polymer providing cation sites used in the present invention, anion conversion polymers are preferred.

As the anion conversion polymer, various known ammonium salt (or phosphonium salt) polymers can be used. Ammonium salt (or phosphonium salt) polymers are widely known as mordant polymers and antistatic polymers from the following publications.

JP-A-59-1.66.940, U.S. Patent No. 3,958.
995, JP-A-55-142339, JP-A-54-12
6,027, Japanese Patent Publication No. 54-155゜835, Japanese Patent Application Publication No. 1973
-30328, water-dispersed latex described in JP-A-54-92274; polyvinylpyridinium salts described in U.S. Pat. No. 2,548,564, U.S. Pat. 709.690
Water-soluble ammonium salt polymers described in US Pat. No. 3.
898,088.

A preferred anion conversion polymer has the following general formula % where A represents an ethylenically unsaturated monomer unit. R1
a hydrogen atom or a lower alkyl group having 1 to about 6 carbon atoms,
L does not represent a divalent group having 1 to about 12 carbon atoms.

R2, R:l and R4 are each the same or different 1
an alkyl group having ~20 carbon atoms, or 7
represents an aralkyl group or a hydrogen atom having ~20 carbon atoms, and Rt, R's and R4 may be interconnected to form a cyclic structure with Q. Preferably, one or more, more preferably only one, of R2, R3, and R4 is a hydrogen atom from the viewpoint of residual color. Q is N or P, and Xo represents an anion other than iodide ion. X is O~
about 90 mol%, and y is about 10 to 100 mol%.

Examples of ethylenically unsaturated monomers A include olefins (e.g. ethylene, propylene, l-
butene, vinyl chloride, vinylidene chloride, isobutyne, vinyl bromide, etc.), dienes (e.g. butadiene, isoprene, chloroprene, etc.), ethylenically unsaturated esters of fatty acids or aromatic carboxylic acids (e.g. vinyl acetate, acetate-alinope vinyl, etc.) propionate, vinyl butyrate, vinyl benzoate), esters of ethylenically unsaturated acids (e.g. methyl methacrylate, butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate,
Phenyl methacrylate, octyl methacrylate, amyl acrylate, λ-ethyl hequinyl acrylate,
Benzyl acrylate, maleic siphthyl ester,
diethyl fumarate, ethyl crotonate, dibutyl methylene malonate, etc.), styrenes (e.g., styrene, α-methylstyrene, vinyltoluene, chloromethylstyrene, chlorstyrene, dichlorostyrene, bromostyrene, etc.) , unsaturated nitrile (
Examples include acrylonitrile, methacrylaterile, and acrylonitrile. Among these, styrenes and methacrylic esters are preferred from the viewpoint of emulsion polymerizability, hydrophobicity, etc. A may contain two or more of the above monomers.

几 is preferably a hydrogen atom or a methyl group from the viewpoint of polymerization reactivity.

几.

■ U Q -C-N-R5- from the point of m line alkalinity etc.

○ In the formula, 1t5 is alkylene (clear is methylene,
ethylene, trimethylene, tetramethylene, etc.), annelene, aralkylene (alkylene having, for example), Imo. represents a hydrogen atom or il''1t1t2. +1 is/or an integer of co.

Q is preferably N in view of the toxicity of the raw material.

Xe is an anion other than an iodide ion, such as a halogen ion (e.g., chloride ion, bromide ion, etc.), an alkyl sulfur ion (e.g., methyl sulfate ion, ethyl sulfate ion, etc.), an alkyl or aryl sulfone ion (e.g., methanesulfone ion, etc.) acids, ethanesulfonic acid, benzenesulfone m, p-toluenesulfonic acid)
, nitrate 1N ion, acetate ion, sulfate ion, etc.

Among these, chlorine ion, alkyl sulfate ion, aryl sulfone ion, and sulfate ion are particularly preferred.

The alkyl groups and aralkyl groups of R2, R, and I also include substituted alkyl groups and substituted aralkyl groups.

Examples of the alkyl group include unsubstituted alkyl groups, such as methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, hekynyl group, nclohexyl group, 2-ethylhexyl group, dodecyl group, lit ('I?alkyl group) For example, alkylarakyl groups (e.g., methoxybutyl, ethoxyethyl, butquinethyl, vinyloquinethyl, etc.), cyanoalkyl groups (e.g., -anoethyl, 3-cyanozolopyl, etc.), halogenated alkyl M ( For example, l-fluoroethyl group, λ-chloroethyl group, perfluoropropyl group), alkoxycarbonylalkyl group (e.g., ethoxycarbonylmethyl group, etc.), allyl group,
Examples include l-butenyl group and propargyl group.

Examples of the aralkyl group include unsubstituted aralkyl groups, such as benzyl, phenethyl, diphenylmethyl, and naphthylmethyl groups; substituted aralkyl groups, such as alkylaralkyl groups (for example, goomethylbenzyl
．． 2, t-dimethylbenzyl group, ≠-isopropylbenzyl group, Hiro-octylbenzyl group, etc.), alkoxyaralkyl group (for example, Hiro-methquin benzyl group,
Hiro-pentafluoroprobenyloxybenzyl group, Kuethoxybenzyl group, etc.), cyanoalkyl groups (e.g. Hiro-cyanobenzyl group, Ku(4t-cyanophenyl)benzyl group, etc.), halogenated aralkyl groups (e.g. Hiro-cyanobenzyl group, Ku(4t-cyanophenyl)benzyl group, etc.), Chlorobenzyl group, 3-chlorobenzyl%, I
I-y-lomobenzyl group, ≠-(hiro-chlorophenyl)benzyl N, etc.).

The alkyl group preferably has 7 to 72 carbon atoms, and the aralkyl group preferably has 7 to 72 carbon atoms.

几. , 几, and [+4 are interconnected to form a cyclic structure with Q, as shown below.

As an example of an aliphatic heterocycle (representing an atomic group necessary to form a bare ring), for example, 1 also represents four numbers. n is an integer of λ to /λ), )1.1o each represents a hydrogen atom and a lower alkyl group having 7 to 7 carbon atoms. ).

゛・w” The shape TJy represents the atomic group required to make Zen embroidery).

14 represents R9R10 and ■t2. If there are two 1t2, they may be the same or different. ) etc.

Among these ring structures, I.E.J.

Also, ``2g's second IJ[, 2, H, 4, 1 too.
Q and Xθ have the same meanings as in general formula CI).

Of course, the y component may be a mixed component of two or more buildings.

X is preferably from 20 to 0 molar, and y is preferably from μO to 0 molar.

Furthermore, it moves from the desired layer to other layers and into the processing solution,
In order to avoid photographically unfavorable # effects, at least one 11 thyrenically unsaturated group (preferably!~/, t
It is sometimes preferred to copolymerize monomers having ) to form a crosslinked aqueous polymer latex.

The structure of the crosslinked aqueous polymer latex is preferably a structure represented by the following formula (1).

(Pl) t4 In the formula, A and l are also 1. l(2, R3, g4.L, X has the same meaning as in general formula CI). -Formula ([1') y is 10 or 10? Must be F in Morchi, preferably F.
i10~ri! He is in charge of the mole.

ZIdO is between 0 and 0 moles, preferably between 20 and 20 moles.

B is a structural unit obtained by copolymerizing a copolymerizable monomer having at least λ ethylenically unsaturated groups. Examples of B include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, tetramethylene glycol dimethacrylate, pentaerythritol tetramethacrylate, trimethylolpropane trimethacrylate,
Ethylene glycol diacrylate, diethylene glycol diacrylate, neoethylene glycol diacrylate, tetramethylene glycol diacrylate, trimethylolpropane triac IJL/), allyl methacrylate, allyl acrylate, diallylphthale-1
-, methylenebisacrylamide, methylenebismethacrylamide, trivinylclohexane, divinylbenzene, N.

N-bis(vinylbenzyl)-N,N-dimethylammonium chloride, N,N-diethyl-N-(methacryloyloxy/ethyl)-N-(vinylbenzyl)ammonium chloride, IN,N,N/.

N/-tetraethyl-N,N'-bis(bin''1ndyl)-p-xylylene diammonium dichloride, N,N
'-Bis(vinylbenzyl)-tIJ ethylenediammonium dichloride, N, N, N/.

Examples include N'-tetrabutyl-N, N'-bis(vinylbenzyl)-ethylenediammonium dichloride. Among these, divinylbenzene and trivinylnoclohexane are particularly preferred from the viewpoint of hydrophobicity and alkali resistance.

Compound example x:y:z==≠7. jnige7, j:eveningX:y:z='
lj:'13:10 y:z=ri:i5:-go' x:y:z=≠3 Nigej:10 y:z=ri0:10 (]1) ([-7) 6HI3 Cation site The amount of polymer added to provide
The amount is 0.001 g to 3 g, preferably 0.01 g to 2.0 g, as a unit of a monomer containing a cation site, per 1 square meter of the photosensitive material.

The polymer providing cation sites can be added to both the photosensitive layer and the non-photosensitive layer, but it is preferably added with a non-photosensitive layer provided between one photosensitive layer and the support. Among polymers that provide cation sites, those with a high ability to capture anionic surfactants are preferred.

The silver halide grains in the photographic emulsion used in the photographic light-sensitive material of the present invention may have regular crystal bodies such as cubic, octahedral, rhombidodecahedral, and tetradecahedral, and may also have spherical, Irregular (ir
It may have a crystalline form (regu jar) or a composite form of these crystalline forms. Also, Research Disclosure (Research Disc)
tabular grains having an aspect ratio of 5 or more as described in Vol. 225, pp. 20-58 (January 1983).

Further, particles having an epitaxial structure or a multilayer structure in which the inside and the surface of the particle have different compositions (for example, halogen composition) (for example, JP-A-62
-7039).

Further, it is preferable that the average size of the particles is 0.5 μ or more. More preferably, the average size is 0°7μ or more and 5.0
It is less than μ.

The particle size distribution may be wide or narrow. The latter is known as a so-called monodispersed emulsion, and the dispersion coefficient is preferably 20% or less, more preferably 15% or less. Coefficient (standard deviation divided by average grain size) of these photographic emulsions (P,
Glafkides) Chimie et Phyaiq Photographics (Chimie et Phyaiq)
ue Photographique) (Paul Montel), 196
7th year) G.F.Dufin, (G.F.Duf.
fin) Photographic Emulsion Chemistry (Photographic Emulsio)
n Chemistry) (The Focal Press, 19
1966), Bui El Zelikman (V,L.

Making and Coating Photographic Emulsions (Mak
ing and coating photog
rapic Emulsion (The Focal Press), 19
64). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble root salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good.

These photographic emulsions may be any combination of silver chloride, silver bromide, silver iodide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide.

Cadmium salts, zinc salts, lead salts, thallium salts, iridium salts, or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. may be present in the stage of silver halide/grain formation or physical ripening.

Binders for the emulsion layer and other layers of the silver halide photographic material of the present invention include proteins such as gelatin and casein; cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose; sugar derivatives such as agar, dextran sodium alginate, and starch derivatives; Synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N
-Vinylpyrrolidone, polyacrylic acid copolymers, polyacrylamide, or derivatives and partial hydrolysates thereof, etc. can also be used.

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

Further, the photographic material of the present invention may contain an alkyl acrylate latex described in U.S. Pat. No. 3,411,911, U.S. Pat. I can do it.

The emulsion used in the photosensitive silver halide emulsion layer of the present invention is preferably chemically sensitized.

For chemical sensitization, the Glafkid
es) or the book by Zelikman et al. or H, Fr1eser Q
De Grundlagen der Fotografisien
DieG
Rundlagen der Photograp
hischeDProzessemit Silbe
rhalogeniden) Akademische Felleragsgesellschaft (eight kadem ische Ver.
(1968)
The method described in 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. As the reduction sensitizer, stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds, etc. can be used. For noble metal sensitization, in addition to gold prices, complex salts of metals in group I of the periodic table, such as platinum, iridium, and palladium, can be used. □ The light-sensitive material of the present invention can contain various compounds as stabilizers. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptothiI lazole); Mercaptopyridines; the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes;
Many compounds known as stabilizers can be added, such as (especially 4-hydroxy-substituted (1,3,3a,7)tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and the like.

The photographic emulsion layer or other constituent layers of the light-sensitive material of the present invention may contain various additives such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). A surfactant may also be included for this purpose.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic surfactants such as alkylamides or amides, polyethylene oxide adducts of silicones), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Agent; alkyl carboxylate, alkyl sulfonate,
Alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl tauric acid, sulfosuccinate, sulfoalkyl polyoxyethylene alkylphenyl ether, polyoxyethylene Anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups such as alkyl phosphate esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphate esters , amphoteric surfactants such as alkylhetaines, amine oxides; alkylamine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium, imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used. Among these surfactants, JP-A-6
The polyoxyethylene surfactants and fluorine-containing surfactants described in JP 0-80849 and JP 6C1-76742 are particularly preferably used.

The curing agent may be, for example, a polymeric curing agent having diffusion resistance as described in JP-A-56-14-2524, or a subdivision or subdivision curing agent as shown below. Typical examples include divinyl sulfone, methylene bismaleimide, 5-acetyl-1゜3-diacryloyl-hexahydro-8-triazine, 1,3.5-triacryloyl-hexahydro-3-triazine, 1,3 .5-1-
ribinylsulfonyl-hexahydro-8-triazine,
Bis(vinylsulfonylethyl)ether, 1,3-bis(vinylsulfonyl)-2-propatol, 1.3-
Active vinyl compounds such as bis(vinylsulfonylacetylamido)propane; 2,4-dichloro-6-hydroxy-8-triazine sodium salt, 2,4-dichloro-6-nodoxy-S-triazine, 2,4- Dichloro-6-(4-sulfoanilino)-s-triazine sodium salt, 2,4-dichloro-6-(2-sulfoethylamino)-s-triazine, N,N'-bis(2-chloroethylcarbamyl) ) Active halogen compounds such as piperazine can be mentioned.

Particularly preferred among these compounds are compounds having a vinyl sulfone group and active halogen compounds.

The photographic emulsions of this invention are spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, 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. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, pyridine nucleus, oxapurine 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 Imidazole nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

The amount of the sensitizing dye used in the present invention is preferably 1X10-6 to 5X10-3 mol per silver mol.

The photographic emulsion of the present invention may contain a color image-forming coupler, that is, a compound (hereinafter abbreviated as coupler) that reacts with the oxidation product of an aromatic amine (usually a primary amine) developing agent to form a dye. The coupler is preferably a non-diffusible coupler having a hydrophobic group called a ballast group in its molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ion. It may also contain a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler). The coupler may be such that the product of the coupling reaction is colorless.

As the yellow coloring coupler, a known open-chain ketomethylene coupler can be used. Among these, hendiylacetanilide and pivaloylacetanilide compounds are preferred.

As the magenta coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are particularly advantageous.

As the cyan coupler, phenolic compounds, naphthol compounds, etc. can be used.

A dye having absorption in the visible region can be included in the light-sensitive material of the present invention.

Preferably, 80% of the total dye is added to a layer closer to the support than the photosensitive layer.
It is better to include % or more. Preferably, 80% or more of the total dye is contained in the same layer as the polymer providing the cationic dyes 1 to 1.

The protective layer of the silver halide photographic light-sensitive material of the present invention is a layer consisting of a hydrophilic colloid, and the hydrophilic colloid used is one described above.

Further, the protective layer may be a single layer or a multilayer.

Preferably, a pine agent and/or a smoothing agent may be added to the emulsion layer or the protective layer of the silver halide photographic material of the present invention. An example of the cloak agent is polymethyl methacrylate I. Organic compounds such as water-dispersible vinyl polymers such as silver halide, sulfuric acid, etc.
-Inorganic compounds such as barium barium and the like are preferably used. Smoothing agents help prevent adhesion failure similar to matting agents, and are particularly effective in improving the frictional properties of motion picture film related to camera compatibility during shooting or projection; specific examples include liquid paraffin, Waxes such as esters of higher fatty acids, polyfluorinated hydrocarbons or their derivatives, silicones such as polyalkylpolysiloxanes, polyalkylpolysiloxanes, polyalkylarylpolysiloxanes, or their alkylene oxide addition derivatives, etc. is preferably used.

The silver halide photographic material of the present invention may also be provided with an intermediate layer, a filter layer, etc., if necessary.

Typical supports used in the photosensitive material of the present invention include cellulose nylate film, cellulose acetate film, polyvinyl acecool film, polystyrene film, polyethylene terephthalate film, other polyesters, glass, paper, metal, wood, etc. It will be done.

Specific examples of the silver halide photographic material of the present invention include X-ray photosensitive materials, Lithium photosensitive materials, black and white photosensitive materials, color negative photosensitive materials, color reversal photosensitive materials, and color photographic paper.

Preferably, a negative photosensitive material is used.

Particularly preferred is a black and white photographic negative light-sensitive material.

Various other additives may be used in the photographic material of the present invention, if necessary. Examples include development accelerators, optical brighteners, color antifoggants, and ultraviolet absorbers. Specifically, Research Disclosure (RES)
EARCHDISCLO3URE) 176 No. 28
30 (RD-17643, 1978) can be used.

Also, regarding the development processing of the photosensitive material of the present invention, RD-17
643, pages 28 to 30, can be referred to.

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

(Example 1) (1) Preparation of photosensitive silver halide emulsion Potassium bromide, potassium iodide, and silver nitrate were added to an aqueous gelatin solution with vigorous stirring. An average iodine content of 4 mol%) was prepared. Thereafter, it was washed with water by a conventional precipitation method, and then chemically sensitized by a gold and sulfur sensitization method using chloroauric acid and sodium thiosulfate to obtain a photosensitive silver iodobromide emulsion A.

(2) Preparation of coated samples Samples 1 to 1
2 was produced.

(Lowermost layer) Binder: Gelatin Ig/polymer providing bocation sites (listed in Table 1) Additives other than the emulsion in the emulsion layer and the surface protective layer are as follows.

(Emulsion layer) Coated silver amount: 5.5 g/m + Binder: Gelatin 1.6 g/Ag/g Sensitizing dye: ye-1 2.1 mg/Ag/g Coating aid Nidodecylbenzenesulfonic acid sodium salt
0.1 mg/n (Poly p-styrene sulfonic acid potassium salt l m g/m (surface protective layer) Gelatin 0.8 g/mn C
,+sth+C00C+6tl+:+ (n)
50 mg/n (polybotacium p-vinylbenzene sulfone-1.6 mg/polymethyl methacrylate resistant fine particles (average particle size 3/〕m) 0.13 mg/m polyoxyethylene-based and fluorine-containing surfactant agent (listed in Table 1) After applying these samples at a temperature and humidity of 25°C and 65% RH,
It was stored for several days and subjected to evaluation of photographic properties as described below.

Evaluation of static marks After conditioning the humidity of an unexposed sample at 25°C and 310% RH for 2 hours, the sample was placed in a dark room under the same air conditioning conditions to determine the force of the static mark against the material. 8
After rubbing as much as possible with a urethane rubber roller and a nylon rubber roller, development was performed using developer A.

The degree of static mer generation was evaluated in the following four stages.

A: No static marks were observed at all.

B: Slight occurrence of static marks is observed.

C: Significant occurrence of static marks is observed.

D: Static marks are observed on almost the entire surface.

Developer A Metol 3g Anhydrous Sodium Sulfite 100g Hydroquinone
7.5g borax
Add 2g of water to make 1z.

Evaluation of developer and fixer contamination A 35mm x 1.6m sample was exposed to a density of 1.0 using a Macbeth densitometer, and 500 sheets were developed in an automatic processor using newly prepared developer and fixer. . The undissolved bone floating in the developer and fixer was evaluated on the following four scales.

The replenishment amounts of the developer and fixer were 30 cC/sheet and 30 Cc/sheet, respectively.

A: No floating matter was observed.

B: Slightly observed.

C: quite a bit D: Violently The development process is as follows.

Treatment liquid temperature x time Washing with running water
25°C drying
The 50°C results are summarized in Table 1.

As is clear from Table 1, samples 6 to 11 of the present invention are:
It can be seen that it has good antistatic properties and hardly contaminates the fixing solution.

(Example 2) (1) Preparation water of photosensitive silver halide emulsion 17! A container containing 25 g of potassium bromide, 15 g of potassium iodide, 1.9 g of potassium thiocyanate, and 24 g of gelatin was kept at 60°C, and while stirring vigorously, a silver nitrate aqueous solution was prepared using the usual ammonia method. A potassium bromide aqueous solution was added by a double jet method to prepare a relatively amorphous thick plate-like silver iodobromide emulsion with an average grain content of 10 mol % and an average grain size of 1.0 μm. After this, dye A
was added, followed by chemical sensitization using sodium thiosulfate and chloroauric acid to obtain a photosensitive silver iodobromide emulsion (A). Same as (A), except that the amount of potassium iodide in the initial solution was 9 g, the temperature was 40°C, the normal content was 6 mol%, the average particle size was 0.6 μm, the photosensitive silver iodobromide Emulsion (B)
I got it.

Dye A: Preparation of coated sample: Prepared by the manufacturing method described in JP-A-62-115035, the emulsion coated surface was pre-undercoated,
(CI+□)3 on the back! 0-(-CII□CI□O+s It (m-1-n=32) 10mg/mCj2
e 60 mg/n? On a triacetyl cellulose support coated with 143 mg of diacetyl cellulose/5 mg/rd of silicon oxide, the following formulation was coated on the emulsion-coated side to prepare coated samples 12 to 20.

1st layer gelatin 0.6g/rd3.6
mg/m Polybotacium p-vinylbenzenesulfonate 9 mg g/m Second layer gelatin 1.0 g/Compound providing cation sites (listed in Table 2) CI-12CIlzS (hK CH2CH2
26 mg/m CII□CIl in 503. 5O3K CIl□CIl
□ SO, 16 mg/m Hc* o, 11 mg/n (third
Layered gelatin 0.4g/n (polybotacium p-vinylhenzenesulfonate 5mg 4th layer (
Emulsion layer) Emulsion (B) was used.

Coated silver amount 1.36 g/n (gelatin amount 2.0 g/r+(4-hydroxy-6-methyl-1,3,3a).

7-Chitrazaindene 30mg/MCl8H3
SO(CH2CH2O)zsH7m g/rrr Polybotacium p-vinylbenzenesulfonate 5 Q m g/r
dBis-(vinylsulfonylacetamido)ethane
57 mg/rd 5th layer (
Emulsion layer) Emulsion (A) was used.

Coated silver amount 4.2 g/n (gelatin amount 5.5 g/m dextran (
Average molecular weight: 150,000) 1.8 g/ivoriacrylic acid 54 mg/-4-hydroxy-6-methyl-1,3,3a.

7-Chitrazaindene 4.1mg/iC+ o
H3sO (CHzCtlzO) 2511
23 mg/%Cll5CIlzC(CIIzO
H) 3390 mg/n (Polybotacium p
-Vinylbenzene sulfonate 88 mg/rd
6th layer (surface protection layer) Gelatin 0.8g/po 13mg
/n (Polyoxyethylene-based and fluorine-containing surfactants (listed in Table 2) Polybotacium p-vinylbenzenesulfonate 6 mg/rd Polymethyl methacrylate fine particles (average particle size 3 μm) 0.13 mg/H-
CH3 (3) Evaluation of photographic properties The same procedure as in Example 1 was conducted.

The results are summarized in Table 2.

Comparative compound A CH3 C+J□, -Nkichi Cth Cj! - CH3 Comparative Compound B Comparative Compound C CH3 Comparative Compound As is clear from Table 2, samples 12 to 15.2 of the present invention
0-22 It can be seen that it has good antistatic properties and has little developer staining property.

Preferred embodiments of the present invention are as follows.

1. The polymer providing the cationzite has the general formula (II
A photosensitive material according to the claims, characterized in that it is a crosslinkable polymer latex represented by I).

2, the polymer providing the cationic acid 1- has the general formula (I
A photosensitive material according to the claims, characterized in that it is a polymer latex represented by V).

3. - The photosensitive materials of 1 and 2 above, characterized in that in formulas (I) and (TV), only one of R2, R, I and R4 is a hydrogen atom.

4. The photosensitive material as claimed in the claims, wherein the antistatic agent is a polyoxyethylene surfactant or a fluorine-containing surfactant represented by the general formula (1) or (II).

5. The photosensitive material described in 1 to 3 above, wherein the antistatic agent is a polyoxyethylene surfactant or a fluorine-containing surfactant represented by the general formula (1) or (II).

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Claims] In a silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, at least one of the constituent layers contains an antistatic agent and a polymer providing cation sites. A silver halide photographic material characterized by: