JPS58199346A - Method for processing silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To give antistatic properties and to prevent stains due to water droplets, by processing a silver halide photosensitive material with a final processing bath contg. a water-soluble surfactant. CONSTITUTION:The silver halide photosensitive material is subjected to processing of color development, bleaching, fixing, etc., and then, processed with the final processing bath contg. at least one kind of water-soluble surfactant. Said surfactant to be used is exemplified as follows: aliphatic amine, such as formula I , quternally ammonium salts, such as formula II, and such cationic surfactants; alkyl sulfates, such as formula III, higher alkylamidoalkylsulfonates, such as formula IV, and such anionic surfactants; alkylbetains, such as formula Vand such amphoteric surfactants; and anionic surfactants. In addition, said processing with said final bath improves storage stability of a cyan dye.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a mathematical method for silver halide photographic light-sensitive materials, and more particularly to a method for processing silver halide photographic lIA source materials σ that has antistatic performance after processing and is free from water drop stains. .

In general, silver halide photosensitive materials are colored and bleached.

Processes include bleach-fixing, fixing, stabilization, stopping, hardening, fogging, and black-and-white printing. At this time, silver halide photographic materials, especially silver halide photographic materials with plastic films, tend to generate static electricity, which is especially noticeable in winter when the humidity in the air is low or in areas with dry sand silts. It has been observed that static electricity is generated, which causes dust floating in the air to adhere to the area.

In recent years, in order to make cameras more compact and reduce the amount of silver used, SI2-generator photographic materials with plastic films are becoming smaller in size, and film dirt and dust adhesion are a big problem. It is becoming. For this reason, ionene-type cationic polymers such as those described in Japanese Patent Publication No. 55-734, and Japanese Patent Publication No. 50-60
Cellulose diacetate-based materials as described in No.
A method has been proposed in which the alkali metal portion of a long-chain alkylphosphorus ester is deposited on the back of a silver halogenide photographic light-sensitive material as described in No. 572.
Recent ultra-small-volume films made of polyethylene terephthalate paste that are processed by rotation have increased the magnification magnification when printing (a situation that cannot be compensated for by conventionally proposed technologies such as those mentioned above). Furthermore, water droplet stains are becoming a major problem as plastic films become ultra-small.

Therefore, the object of the present invention is to provide a method for processing a silver halide photographic light-sensitive material that is imparted with antistatic properties after processing, and the object of the present invention is to prevent water drop stains on the light-sensitive material after processing. A further object of IIIE3 is to provide a method for processing a silver halide photographic material having a polyethylene terephthalate base, and to impart antistatic properties to the processed photographic material when the silver halide photographic material having a polyethylene terephthalate base is subjected to rotational processing. To provide a method for processing a silver halide photographic light-sensitive material in which water droplet stains are prevented.

As a result of various studies, the present inventors have found that the problem can be solved by treating the silver halide photographic material with a final treatment bath containing at least one water-soluble surfactant.

In the silver halide photographic light-sensitive material according to the present invention, when using the final processing bath of the present invention using a diacylamino cyan coupler represented by the following general formula CI), the storage stability of the cyan dye is also improved. Therefore, in this invention, a cyan coupler of the following general formula CI) is preferable. In the formula, R represents an aryl group such as a phenyl group, a naphthyl group, or a heterocyclic group, and R8 imparts diffusion resistance to the cyan coupler represented by the general formula CI) and the cyan dye formed from the cyan coupler. Represents the pallast group necessary for imparting.

R1 is preferably a naphthyl group or a heterocyclic group (however,
The carbon atom of the dielectric ring group is bonded to the sonoelectric atom of the ureido group. ) or trifluoromethyl, nitro, cyano, -COR, -〇〇0R1-8oR1 represents an aromatic group, and R' represents a water bulk atom, an aliphatic group or an aromatic group. ) is a phenyl group having at least one substituent selected from

Preferred cyan couplers according to the general formula [■] of the present invention are specifically represented by the following general formula (Ia) or [Ib].

General formula (Ia) λ General formula [:Ib] λ In the formula, Y1 trifluoromethyl, nitro, cya, or an alkyl group having 1 to 10 carbon atoms (for example, methyl, butyl, cyclohexyl, benzyl)] or aromatic represents a group (preferably a phenyl group (if fit, phenyl or tolyl)); g'gt represents a water atom or a group represented by R;

Y represents a -valent group, preferably an aliphatic group [preferably an alkyl group having 1 to 10 carbon atoms (e.g. methyl,
tert-butyl, ethoxyethyl, thiazmethyl], aromatic groups [preferably phenyl groups, naphthyl groups (e.g. phenyl, tolyl]), nitrogen atoms (fluorine, chlorine, bromine, etc.), amino groups (ethyl groups), Represents a substituent represented by mino, diethyl (mino) hydroxy, or Yl.

m represents an integer from 1 to 5, and a represents an integer from 0 to 4. More preferably, m + n is 2 or more.

2 represents a nonmetallic atom group necessary to form a heterocyclic group or a naphthyl group, and the heterocyclic group includes a nitrogen atom,
A 5- or 6-membered polycyclic ring containing 1 to 4 N acid atoms or sulfur atoms is preferred.

Examples include furyl group, chenyl group, pyridyl group, quinolyl group, oxacylyl group, tetrazolyl group, benzochirozolyl group, and tetrahydrofuranyl group.

Note that any substituent can be introduced into these rings, for example, alkyl M having a carbon atom number of 1 to 10 (a tip of ethyl i-propyl, l-butyl, octylnato), A!J-44 (phenyl, naphthyl, etc.), halogen IM molecules (77, bromine, etc.), cyano, nido-1 amide group, amide group (e.g. methanesulfonamide, butanesulfone amide group), , P-toluenesulfonamide 1, etc.), sulfamoyl i & (H
(e.g., methylsulfamoyl, phenylsulfamoylnato), sulfonyl groups (e.g., methanesulfonyl, p-toluenecarpamoyl, etc.), oxycarbonyl groups (e.g., ethoxycarbonyl, phenoxycarbonyl, etc.)
, Ryosil M (fFII, tktRose, benzoyl, etc.), heterocyclic groups (eg, pyridyl group, pyrazolyl group, etc.), alkoxy groups, Ryoryloxy groups, Ryosiloxy groups, and the like.

R2 represents an aliphatic group or an aromatic group necessary for imparting diffusion resistance to the cyan coupler represented by the general formula CI) and the cyan dye formed from the cyan coupler, preferably a carbon atom of 124 or so many alkyl groups,
It is a ryyl group or a heterocyclic group. For example, straight-chain or branched alkyl groups (e.g. t-butyl, -monoctyl,
t-octyl, n-dodecyl, etc.), alkenyl groups, cycloalkyl groups, 5- or 6-membered heterocyclic groups, and groups represented by general formula (Ie).

General formula [Ie) In the formula, J is an oxygen atom or a sulfur atom, K is an integer from 0 to 4, I is 0 or 1, and when K is 2 or more, two or more R1s are the same or different. R1
is a linear or branched r-alkyl group having 1 to 20 carbon atoms,
R1 represents a monovalent group, for example, a sluice atom, a rogen atom (preferably chlorobromo), an alkyl group (preferably a linear or branched alkyl group having 1 to 3 carbon atoms (
For example, methyl, t@rt-butyl, tart-pentyl, t@rt-octyl, dodecyl, pentadecyl, benzyl, phenyl)), phenyl), heterocyclic groups (preferably, nitrogen-containing heterocyclic groups) ), an alkoxy group (preferably a linear or branched flucokyloxy group having 1 to 1 carbon atoms (e.g., methoxy, ethoxy, t·rt-butyloxy, octyloxy, decyloxy, dodecyloxy), 1, oryloxy fi(iP
II, phenoxy), hydroxy, syloxy group (preferably an alkylcarbonyloxy group, arylcarbonyloxy group (e.g. acetoxy, benzoyloxy)), carboxy, dicarbonyl group in alcohol (preferably a carbon number from 1 to Straight chain or branched alkyloxycarbonyl group), aryloxycarbonyl group (preferably phenoxycarbonyl), alkylthio group (preferably carbon number 1 to 20), ryosyl group (preferably carbon number 1 to chain or branched fulkylcarbonyl group)
, an acylamino group (preferably a linear or branched alkylcarboamide group having 1 or more carbon atoms, benzenecarboxamide), a sulfonamide group (preferably a linear or branched alkylsulfone esterimide group having 1 or more carbon atoms), benzene sulfonamide group), carbamoyl group (preferably a linear or branched fulkylaminocarponyl group having 1 to 1 carbon atoms, phenylaminocarbonyl group), sulfamoyl group (preferably a linear or branched fulkylaminocarbonyl group having 1 to 1 carbon atoms), alkylaminosulfonyl group, phenylaminosulfonyl group), etc.

X represents a group capable of being eliminated during a coupling reaction with water or an oxidized product of a color developing agent. For example,... rogen atom (e.g., each atom of charcoal, bromine, fluorine, etc.), an oxygen atom or a nitrogen atom directly bonded to the 7-ring position, a T-aryloxy group, a carbamoyloxy group, a carbamoylmethoxy group , afluoxy group, sulfonamide group,
A more specific example is succinimide 1 fathom.

U.S. Patent No. 3,741,563, Japanese Unexamined Patent Publication No. 47-374
25%, Japanese Patent Publication No. 48-36894, Japanese Patent Publication No. 1977-10
No. 135, No. 50-117422, No. 50-1304
No. 41, No. 51-108841, fiil 50-1
No. 20334, No. 52-18315, No. 53-105
Examples include those described in various publications of No. 226 Fathom.

The cyan coupler according to the present invention is disclosed in, for example, U.S. Pat.
It can be easily synthesized by using the methods described in No. 758,308 and JP-A-56-65134.

Preferred compounds of the present invention are described below in specific examples, but the compounds are not limited thereto.

Exemplary compound aHs 01 heavy fleas! The water-soluble surfactants according to the present invention include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants, among which the desired effects of the present invention can be Cationic activators are particularly preferably used because they have a more favorable effect on oxidation.

Next, typical examples of water-soluble surfactants according to the present invention will be listed, but the invention is not limited thereto.

<Cationic activator> /R4 1, aliphatic Tmine or \ represented by the general formula R, -N
R1 ” 5tHtsN) 11・CH, C0OH circle I nium salts CHl CH.

C Maro- OHCI(, Cti, 0H CH.

CH1 CH.

CH.

CH.

CH.

CH.

CH.

C child H.

C,H.

Hm C,K.

Mountain CH island sound CH.

H8 CH1 c,) Is C-mount rubiridinium salts oxyethylene alkylamines 5. The bending anion activator> l, Alkyl carboxylate salts (9M) represented by the general formula R, -C00M'Ctt&sCOONm' C15HsvCOOK 2, Alkyl sulfates represented by the general formula R1-8o, M (example) o CHkl@ @80sN"3, general formula R,
-0804 alkyl sulfate esters (example) oCllI (IIO8osNa'C+sHmiCOOCHsCH(OH)C&O8O
sNm4 Condensate of higher 4 fatty acid and amino acid represented by the general formula Rm-Co-N-mu-COOM (example) ' C1t tbm C0NHCH, CHIC
OONm5, general formula R, -Co -N-A-O8OJ
Luxury shown in! 4 Alkylolated sulfate ester salts of fatty acid esters c Example) LI ClmHllCONHCH1C%Of! !
03NmoCuHnCONH+CH, CI, O÷n C
H*C%08OJa6, general formula R, -C0N-mu-so
, yi Alkylated sulfonic acid salts of higher fatty acid esterimide (example) OCIt Hs@ -CON -CH1CH1
SOgNmCH.

OCIBHll CON-CHtCt1m80sNa
CH, C mountain OH OC1, H,, -CON-CH, Cl, Sod4- o C,, H,, C0N-CI (, SO3Na 薯CH3' CnHst-Co-N-CH1CH180sNmH
11 7, Alkylcarboxylic acid salts of higher alkylsulfonamides represented by the general formula R1-SO, N -A -C00M (example) OCt* Has -SO1NHCH1CTo
COONm8, - General formula Rm-OCO-A -C-C0
0Rs represented by SO,M Hosuccinic acid ester jl (example) OCR10COCHW C-C00CH.

01Na OaNm OCsH+t OCOCHmCH-COOC16Hu 0sNa OC1@Hg0COCH1CH-COOC16HuSO
Drama a 10, Na 0BNm 1 080, M Oil iii acid esters 1 example) o CHH1@OH+CH2%'-COOC
・H1g0SO~a Lioxyethi 1. - To phosphoric acid salts, γ
Rukiru Ryosuru Sulfur*m 12, General formula RO+ CIICHIO+ n BOsM
or xyethylene sulfate (example) o C+s Ha@O+ C11aCH,O+
r* 80. Condensate of Naphthalenesulfonic acid and Polmarine (Amphoteric activator) &C)I C14Has Hs ls C,H.

CH1 4 agent or its salt (example) OCaHty NHCHmCHaNHCHtomiC
H#H-CHmCOOH・HC1OC1,Ichi, -N
HCH, C mountain C00) I3, general formula R, -N+mu-CO
OM), an example of an amphoteric activator represented by) OC□H*i −N + CHsC) facOO
N Koshiki).

In-type amphoteric surfactant or non-ionic surfactant such as Cl, CH, 08OaNa> L Fatty alcohol ethylene oxide represented by the general formula Rs -0+ CH*C 0+aH)' Attachment 710
Object (example) OCu I (me O+ CHICIO+
n HOC1,lm*0-(0%C1p+ Ethylene oxide adduct 3 of 118 alkylphenol, general formula R1-Coo (ClH40+ !l H
An example of a condensate of sulfur-class fatty acids shown by 'Ctti%5COO+C1Hρ+n1H4,
Nonionic activator represented by the general formula R, -NH(CI(NH)CH104m H (example) OC@@HuNH-(CH*C140÷nH
Block copolymer Ha-on activator Rm-&, -1- in the above general formula may be the same or different, but may be an alkyl group having 1 to 30 carbon atoms, which may have a substituent, or a furyl group. Indicates, MU is 2
represents a valent alkyl group. In addition, these surfactants are
, sulfuric acid, nitric acid, acetic acid, etc. may also be used.

The water-soluble surfactant used in the present invention is 0.011
/l - used in the -vertical range of -101/l. This invention &
:Q/・Logenated chain The support for photographic light-sensitive materials is as follows:
Particularly preferred are those made of plastic film.
used. This is because plastic films tend to be easily charged with static electricity.

Furthermore, since it is often used in an enlarged manner, if it adheres due to electrostatic silver scales, it will cause a big problem.The rotation speed of the rotation treatment according to the present invention is 20 to 3000 rpm+,
Preferably it is 50-2500 rpm.

Furthermore, processing methods for the silver halide photographic light-sensitive material according to the present invention include hanging processing II (hanger development processing), roller transport processing, belt conveyance processing, and rotation processing I.
Among them, rotation treatment is preferably used. This is because when the final treatment bath according to the present invention is rotated, more effective effects can be achieved in preventing water droplet unevenness and preventing electrification.

Book Address 114: The final treatment bath refers to a treatment bath at the end of a treatment step, and means, for example, a stable bath, a cleaning bath, a rinsing bath, etc., and preferably a stable bath.

Next, the present invention will be explained more specifically, but it is not limited thereto.

[Example L]

A negative image-forming silver iodobromide emulsion was deposited on a transparent polyethylene terephthalate film at 1.23 g/g/g and gelatin was added at 4. 'll/wl, exemplary cyan coupler (C-4)
A red-sensitive copper halide emulsion layer containing 1.6 x 1 (J-'' mol/-) of di-U-butyl fumerate dissolved in the weight of - 4p gelatin per serving.

A film was produced by applying 1 lII gelatin solution containing 0.2 g of 1.2-bisvinylsulfonyl ethane to a gelatin ratio of 1.39/vl.

The film thus produced was cut into a disk shape with a diameter of 71 cm to prepare a sample for rotational processing.

The above sample for rotational processing was subjected to color development by rotational processing according to the Kishoba process.

Processing process Temperature Processing time Rotation speed (rpm) Color development A℃ 3 minutes 15 seconds 200 standards White
＃6 minutes (capital) seconds 〃Water washing
3 minutes and seconds 〃 Set up 6 minutes and J seconds 〃 Wash with water 〃 3 minutes and 15 seconds 1/Stability 〃 1 minute and 5 seconds 〃 Spin squeeze (fund) ℃ 1 second 2000 seconds Dry 52 to 54℃
Sakura Color Negative Film Processing Agent Tyboo 4 (CNK-4) (manufactured by Konishiroku Photo Industry ■) was used as the JTE solution and the bleaching solution.

Further, as a stabilizing liquid, dust having the following composition was used.

Stable liquid formalin (37-aqueous solution) 5. (117
Konidax (manufactured by Konishiroku Photo Industry ■) 75- Add water to make 1ll.

As shown in Table 1, o and s9/i1 m of the water-soluble surfactant of the present invention were added to the stabilizer solution, respectively, and dust adhesion and water droplet staining due to the electrostatic charge were observed.

*Dust adhesion by XC was measured at Z (℃, humidity [Xl), after the treated sample was collected with a cloth for (a) seconds, 15mX 1.
On a container containing a large amount of 51111 paper, 3.0 cmk-
After I put it on for 1 second, the attached 1,5 l1llX 1.5
I counted the number of pieces of paper. The results are shown in Table 1.

From this, the final stage [111 (here stable ftL) k:
When a water-soluble surfactant is added, there is no water droplet stain.
Furthermore, it can be seen that dust adhesion is also significantly improved.

In particular, the cationic activator is particularly good because there is very little dust adhesion (4P) and there is no water droplet stain.

[Example 2] When the rotation of the rotation process in Experiment 1 was stopped and a similar experiment was conducted, the same effect on dust adhesion was obtained, but some water droplet staining occurred in all cases. From this, when the final treatment bath according to the present invention is rotated.

In particular, it can be seen that the desired effects of the present invention are achieved.

[Example 3] The cyan coupler in the film sample used in Example 1 was
Film samples were prepared in place of those shown in Table 2, and the inner plate was subjected to stepwise exposure for color development. However, if the liquid is stable, this li Meikai active agent is added to O, S11/
One with and one without addition were used.

The sample prepared in this way was heated to ω℃, aita
o* for 7 days, and measured the transmitted red density at the maximum 1°C using Sakura Photoelectric Purity Needle PD Mu-65 (manufactured by Konishiroku Photo Industry ■), and calculated the rate of decrease in color density before and after storage. I asked for it.

From this, it can be seen that when using the cyan coupler according to the present invention and the final processing bath according to the present invention, the preservation property of the dye image is good.

Yoshikane Kuwahara September 1989 2111 1"r j'L 1il-< ,,Y Kazuo Wakasugi Tono 1.
1 Patent Application No. 82751.

2 Name of the invention Processing method for silver halide photographic light-sensitive materials
4'F (127 + Konishiroku Shasei Co., Ltd. Jk Director Nobuhiko Kawamoto Address: East + + r Tokyo 11 Nonaka Sakura-cho HD land) J Nishiroku Shasei 1 Co., Ltd. August 31, 1982 (Delivery date) 6. Statement subject to amendment t" scrap 4

Claims (1)

[Claims] A method for processing a silver halide photographic material, which comprises processing the silver halide photographic material in a final treatment bath containing at least one water-soluble surfactant.