Processing silver halide photographic material with a polymeric defoaming agent
United States Patent [191 Ishihara et al.  
 545] Apr. 29, 1975 221 Filed: Dec.7, 1972 21 Appl.No.:3l2,792  
 [30] Foreign Application Priority Data Dec. 7, l97l Japan 46-98316 [52] US. Cl. 96/50 R; 96/50 PT; 96/63;  
 96/60 R; 96/60 BF; 96/61 R; 96/61 M;  
 [51] Int. Cl. G03c 5/26 [58] Field of Search..... 96/48 R, 66.4, 60 R, 60 BF, 96/6l R, 6l M. 62, 50 R, 50 PT, 63; 252/321 [56] References Cited UNITED STATES PATENTS 2.375.007 5/1945 Larsen et al. 96/664 3.251.782 5/1966 Hanzcl et al. 252/321 Primary ExaminerWon H. Louie, Jr. Attorney, Agent, or Firm-Bierman &amp; Bierman [57] ABSTRACT A light-sensitive photographic material is processed in the presence of a polymer comprising as a polymer component a structural unit of the general formula:  
 c=o OH I l 0--CH2--CHCH2- Q X Wherein R is a hydrogen atom or a methyl group; X&#34; is an anion; and Q* is Where R is a lower alkyl, phenyl or benzyl group; R and R are individually a lower alkyl group; provided that when R is a lower alkyl group, R and R may form together a nitrogen-containing 5-to-6membered heterocyclic nucleus; and A is a group of nonmetal atoms selected from carbon, nitrogen and sulfur. which are necessary to form a 5-to-6-membered heterocyclic nucleus together with N&#39; C-.  
 6 Claims, No Drawings PROCESSING SILVER HALIDE PHOTOGRAPHIC MATERIAL WITH A POLYMERIC DEFOAMING AGENT This invention relates to a method for processing sil- 5 ver halide light-sensitive photographic materials.  
  As is well known, various surface active agents have been used in silver halide light-sensitive photographic materials. When such photographic materials are subjected to development, the surface active agents flow out and accumulate in the processing solutions, with the result that foams are sometimes formed in the said processing solutions to bring about many disadvantages. For example. in a photo finishers plant such as processing laboratory, the development, stopping, hardening, desilvering and fixing, or a combination of such processings, are continuously effected, in most cases, for a long period of time while supplementing the respective processing solutions. In case the processing solutions are vigorously stirred. however, a large number of foams are formed in the processing solutions to bring about such great operational drawbacks that the processing solutions migrate into the adjacent baths, or impurities floating in the processing solutions cannot be removed completely by overflowing operation. Further. in case the foams adhere to the surfaces of the light-sensitive emulsion layers of light-sensitive photographic materials, uneven development, incomplete fixing and incomplete stopping are brought about to cause the so-called uneven processing. As a means for overcoming such drawbacks, there has heretofore been adopted, in general, the procedure that defoaming agents are incorporated into the processing solutions or into the light-sensitive photographic materials to be treated.  
  As the defoaming substances known hitherto. there are many compounds of the silicone, polyglycol and polyester types. However, compounds excellent in defoaming effect are insoluble or poorly soluble in water, in general. When incorporated into processing solutions using water as solvent. therefore. they cannot uniformly disperse therein but adhere to the surfaces of the light-sensitive emulsion layers or agglomerate and precipitate in the processing solutions, whereby the defoaming effects thereof are deteriorated to make it difficult to sufficiently prevent the occurrence of uneven processing and staining and the fluctuation in photographic properties of light-sensitive materials. Further, when incorporated into lightsensitive photographic materials, the compounds incompletely disperse therein and frequently deposit in the gelatin used to affect the photographic properties of the light-sensitive materials. Even when the compounds have been able to be incorporated into the processing solutions, they are not so well dispersible. Thus. it is the actual state that no expected effects can be obtained sufficiently.  
  In view of such actual state as mentioned above, we made extensive studies on deforming agents which are easily soluble in processing solutions, are uniformly dispersible in silver halide light-sensitive photographic materials, can display sufficient defoaming effects, and are not deprived of their defoaming effects with progress of processings. As the result, we have found that homopolymers or copolymers containing as polymer components such unit components of the general formula shown below are excellent defoaming agents having the above-mentioned characteristics, and have accomplished, based on the above finding, a process for treating silver halide light-sensitive photographic materials without causing any drawbacks derived from the foaming of processing solutions, characterized in that the said defoaming agents are incorporated into photographic processing solutions and/or silver halide light-sensitive photographic materials to be treated.  
 General formula:  
 i A o-CH -CH-CH -Q X wherein R is a hydrogen atom or a methyl group; X is an anion; and Q is R 1 2O ll -R or i it,  
 where R is a lower alkyl, phenyl or benzyl group; R and R are individually a lower alkyl group, provided that in case R is a lower alkyl group, R and R may form together a nitrogen-containing 5 to o-membered hetcrocyclic nucleus; and A is a group of non-metal atoms selected from carbon, nitrogen and sulfur atoms which are necessary to form a 5- to o membered heterocyclic nucleus together with N =C. The polymerization degree of such homopolymer or copolymer is found to be within the range of from 20 to 1500.  
  Typical examples of the homopolymers and copolym&#39;ers, which contain as polymer components the unit components having the aforesaid general formula, are enumerated below by way of structural formulas. in which 11,11 and n: are individually an average polymerization degree. and n n is a polymerization molar rano.  
 l l (9 9 OCH2-CH-CH2-N\ Br 5 6 9 I 2] q H -CH -9 c=o OH 2 P I T a CH 0 CH o1 cs n 01 i 2 CH CH 1 2 Il 2 I12 :1  
 1o. -{CH -|CH- C=O OH e? As exemplified above. the defoaming agents used in HESIS EXAMPLE 2 the present invention include not only homopolymers S h i f the exemplified compound (9) but also copolymers with other monomers such as. for A example. acrylamide. N-vinylpyrrolidone. N.N- hlimxture comprlsmg (1 m l of y y dimethylacrylamide. diacetonacrylamide. acrylic acid. &#34;T dcrylne 1 molt?) of Pl&#39; hydrochlomethacrylic acid. methyl acrylate. methyl methacryl- 260 of benzyl h and of hydroquime vinyl acetate and styrene. none was reacted under stirring at room temperature procedures for synthesizing {he above memioned for 8 hours to form a homogeneous solution. This solutypical compounds are explained below with reference was allowed to Stand room temperature for 2 to Synthesis examples. 15 hours. and then charged with acetone to deposit crystals. The crystals were recovered by filtration, washed SYNTHESIS EXAMPLE 1 withacetone and then recrystallized from ethanol to Synthesis f the exemplified compound (6) obtain 185 g. of a monomer of the formula,  
 A mixture comprising 142 g. (1 mole) of glycidyl 40 methacrylate. 96 g. 1 mole) of trimethylamine hydrochloride. 240 g. of benzyl alcohol and 0.1 g. of hydroquinone was reacted with stirring at 60C. for 70 minutes. Thereafter. the reaction mixture was poured into acetone to deposit crystals. The crystals were recovered by filtration and then recrystallized from ethanol to obtain 150 g. of a monomer of the formula.  
  0H OH I 1 g CH =C-COOCH CHCH N(CH C1 m.p. 1.85 C  
 Elementary analysis:  
  C H N C1 Calculated (&#39;71 1: 50.60 8.48 5.90 14.93 Found (71): 49.14 8.60 5.75 15.28  
 Elementary analysis:  
  25.7 Grams (0.1 mole) of the thus obtained monomer and 3.5 g. (0.03 mole) of N-viny1-2-pyrro1idone was dissolved in cc. of methanol. The resulting solution was incorporated with 0.1 g. of azobisisobutyronitrile. and then polymerized at 65C. for 4 hours in a nitrogen atmosphere. The polymerization product was poured into acetone to precipitate a white solid polymer. which was then dried under reduced pressure to obtain 29.0 g. of the exemplified compound (9) having a specific viscosity of 2.35 as measured in a 1 percent aqueous solution at 30C.  
  The above-mentioned homopolymers and copolymers used in the present invention have molecular weights in the range from 5.000 to 200.000. preferably from 10.000 to 50.000. 1n the ease of copolymers. the copolymerization ratio is preferably such that the amount of the unit component of the aforesaid general formula is 30 mole percent or more.  
  The amount of these compounds to be incorporated into processing solutions are preferably in proportion to the amounts of foaming substances accumulated in the processing solutions, as is clear from the application purposes of said compounds. In case the compounds are desired to be incorporated into one of the layers constituting silver halide light-sensitive photographic materials, it is most effective to incorporate the compounds into the outer-most layers, e.g. the protective layer or the outer-most layer on the reverse side, which contact directly with the processing solutions. However, the layers, into which the compounds have been incorporated. may further be coated externally with other layers, so far as the dissolving-out of the compounds is not disturbed.  
  Photographic materials. to which the present process is applicable, include various silver halide lightsensitive materials to be processed according to diffusion transfer method, direct positive method, silver dye bleaching method and stabilization method, in addition to black-white and color negative films, reversal positive films and printing papers which are processed according to ordinary methods. The compounds used in the present invention are incorporated into photographic materials in such a manner that the compound is dissolved in water or an organic solvent or a mixture thereof, and the resulting solution is added to a coating liquid for preparation of a photographic material, thereby incorporating the compound into one of the layers of the photographic material, or the abovementioned solution is directly coated, if necessary after incorporation of a coating aid, on the surface of a photographic material. In this case, the amount of the compound to be incorporated into the said layer of photographic material is to 50 percent by weight based on the weight of gelatin, while the proportion of the compound to be directly coated on the photographic material is 2 mg/m or more, whereby favorable effects can be attained.  
  Processing solutions, to which the present invention is applicable, include various processing solutions such as prehardening solution, developing solution, stopping solution, hardening solution, bleaching solution, and such composite solutions as monobath developing solution and bleach-fix solution. In case the abovementioned compounds are desired to be incorporated into these processing solutions, the compounds may be directly added to the processing solutions or may be incorporated into processing agents to be dissolved.  
  Typical processings, to which the present process is applicable, include any development treatments such as cinefilm development, tank development and spray type development. Further, procedures for agitation of the processing solutions include all such procedures as circulation of the solutions, stirring by means of a stirrer. introduction of nitrogen or air bubbles, jetting of the solutions, vibration or rotation of light-sensitive photographic materials.  
  When the compounds of the present invention are added to the treating solutions in a proportion of 0.005 to 0.5 g. per liter of the processing solutions, the formation of foams bringing about substantial injuries can be sufficiently prevented. Further. an additional advantage that is anti-static effect can be enhanced by use of the present invention.  
  Defoaming abilities of the compounds used in the present invention are explained below with reference to a test example.  
 TEST EXAMPLE Sample developers of the prescriptions (I), (II) and (III) shown in the table below were measured in foaming degree according to shaking method. The samples of the prescriptions (I), (II) and (III) had individually been incorporated with sodium dodecylbenzenesulfonate as a compound corresponding to a foaming surface active agent flowing out ofa silver halide light-sensitive photographic material; the sample of the prescription (II) had additionally been incorporated with the exemplified compound (1) as a defoaming agent; and the sample of the prescription (III) had additionally been incorporated with a high molecular quaternary ammonium salt trimethyl-(vinyloxymethyl)ammonium p-toluenesulfonate (average molecular weight is about 50,000) as a control defoaming compound.  
  Prescription of sample (I) (II) (III) water 800 ml 800 ml 800 ml. Benzyl alcohol 3.8 ml. 3.8 ml. 3.8 ml. Sodium hexamcthaphosphatc 2.0 g. 2.0 g. 2.0 g.  
  Sodium sulfite (anhydrous) 2.0 2.0 2. Sodium carbonate g g 0 (monohydrate) 50.0 g. 50.0 g. 50.0 2. Potassium bromide l.() g. 1.0 g. Mfg. Sodium hydroxide (l7( aqueous solution) 5.5 ml. 5.5 ml. 5.5 ml. 4-Amino-3-methylN- ethyl-N-(methylsulfonamidoethyl)-, 5.0 g. 5.0 g. 5.0 g. aniline 3/2 H 50, monohydrate Surface active agent. sodium dodecylbenzene 0.5 ml. 0.5 ml. 0.5 ml. sulfonate 17: aqueous solution) Compound as defoaming Excmplified Control agent W1 aqueous compound compound solution) (I) 0.5 mlv 0.5 ml. Water to make I liter 1 liter 1 liter Table 1 Time after foaming Average height of b shaking foams (I) (II) (III) 10sec. l8 mm. 0 mm. 9 mm. 30 see. 13 mm. 7 mm. so see. 12 mm. 6 mm.  
 120 see. 12 mm.  
  As is clear from Table l, the sample (ll), which has been incorporated with the exemplified compound 1 is less in foaming degree. and the foams formed in the sample (ll) disappear quickly. Although certain deforming effect is observed in the sample (III), which has been incorporated with the control compound, the effect is lower than that observed in the sample (ll).  
  A sample (I&#39;) identical in composition with the sample (I) except that the amount of the surface active agent was made 1.5 ml.. and a sample (ll) identical in composition with the sample (ll) except that the amount of the surface active agent was made 1.5 ml. and the amount of the exemplified compound (1 was made 0.5 ml.. were individually subjected to the same measurement as above. The results obtained were as set forth in Table 27 Table 2 Time after foaming Average height by shaking of foam (l&#39;) (ll&#39;) I see. 35 mm. 3 mm. see. mm. 2 mm. on see. 31 mm. 0 mm. lZU sec. 30 mm. 0 mm.  
 EXAMPLE 1 Using an automatic developing machine of such a type as to agitate the developer by introduction of nitrogen gas, two silver halide light-sensitive color photographic films were individually treated with each of the developer (1) used in the test example and a developer (Il&#34;) identical in composition with the developer (ll) used in the test example except that 0.5 ml. of a 1 percent aqueous solution of the exemplified compound (3) was used in place of the exemplified compound l In this case. the developers (I) and (II) were individually measured in degree of foaming due to agitation derived from introduction of gas. The method adopted in this case was such that the developer was charged into the same test tube as in the test example, nitrogen gas was continuously introduced into the developer for 30 seconds, and then the averge height of foams formed in the developer was measured after 10. 30 and 60 seconds. The results obtained were as set forth in Table 3.  
 Table 3 Average height of foams Time after stopping of agitation Developer (l) Developer til&#34;) 10 sec. 34 mm. 3 mm. 30 sec. 3] mm. 2 mm. (10 sec. 27 mm, 0 mm.  
 further subjected to the same measurement as above. but the degree of foaming was not different from that measured before incubation. Thus. it was confirmed that the defoaming effect of the developer does not vary with lapse of time. Furthermore. both of the processed color photographic films were entirely identical in photographic properties with each other. and there was observed no influence on the photographic properties due to addition of the exemplified compound (3).  
 EXAMPLE 2 in this example were used two automatic developing machines for silver halide black-white printing papers. A developer of the prescription (lll) shown below was charged into the developer tank of one developing machine. and a stop-fixer of the prescription (1V) shown below was charged into the stop-fixer tank of the same machine. On the other hand, the same developer (III) as above was charged into the developer tank of the other developing machine. and a stopfixer of the prescription (V) shown below was charged into the stopfixer tank of the same machine.  
 Presc ription of developer Water 800 ml. Sodium sulfite 40 g. l-Phenyl-3-pyrazolidone 0.2 g. Hydroquinone 5 g. Sodium carbonate (monohydrate) 30 g. Potassium bromide ().(H g. Benzotriazole (Hll g. Water to make 1 liter Prescription of stop-fixer (l\&#39;) Water bill) ml. ml. Sodium thiosulfate (pentahydrate) ltlt) g. I()() g. Sodium sulfite (anhydrous) l0 g. If) g. Glacial acetic acid 20 ml. 20 ml. Potassium alum [0 g. l() g. Sodium hydroxide 7.5 g. 7.5 g. 17! Aqueous solution of the exemplified compound l.5 ml. Water to make I liter l liter Using these two automatic developing machines, a large number of printing papers were processed according to ordinary procedures, while maintaining the developer and stop-fixers at initial concentrations by supplementation. As the result. the stop-fixer (IV) of the machine using this stop&#39;fixer was vigorously foamed due to the generation of carbon dioxide derived from the decomposition of sodium carbonate in the developer. which had been carried into the stopfixer together with the printing papers. and the thus formed foams migrated into the adjacent developer tank to change the composition of the developer, with the result that the printing papers were deteriorated in development efficiency. In contrast thereto. the stopfixcr incorporated with the exemplified compound (9) was scarcely foamed, and the printing papers could be successfully developed without any injury. At this stage. a part of each fix-developer was taken up and was measured in degree of foaming according to the shaking method adopted in the test example. The results obtained were as set forth in Table 4.  
 Table 4 Average height of foams Time after foaming Stop-fixer (IV) Stop-fixer (V) I sec. l4 mm. 1 mm. 30 see. H) mm. 0mm. 60 see. 9 mm. 0 mm.  
 EXAMPLE 3 In this example were used two automatic developing machines (A) and (B) for silver halide black-white printing papers. The developer (III) used in Example 2 was charged into the developer tank of each developing machine, and the stop-fixer used in Example 2 was charged into the stop-fixer tank thereof. Using these developing machines, a large number of printing papers were processed. That is, the printing papers used in Example 2 were treated with the machine (A), and the same printing papers as above, except that 5 ml/m of a 2 percent aqueous solution of the exemplified compound (5) had been, coated by spraying on the surface of the emulsion layer of each printing paper, followed by drying, were treated with the machine (B). (The light-sensitive materials of the printing papers processed with the machines (A) and (B) were identical in amount with each other.) As the result, the printing papers processed with the developing machine (A) brought about such injuries due to foaming as described in Example I and the development efficiencies of the printing papers were deteriorated, whereas the printing papers processed with the developing machine (B) were less in foaming and brought about no drawbacks in the development. At this stage, a part of each stop-fixer was taken up, like in Example 2, and was measured in foaming degree according to the shaking method shown in Example 1.The results obtained were as set forth in Table 5.  
 Table 5 Average height of foams Time after foaming (A) (B) IO sec. I8 mm. 4 mm. 30 sec. mm. 2 mm. 60 sec. 14 mm. 0 mm.  
 EXAMPLE 4 In this example were used two automatic developing machines (A) and (B) of such a type as shown in Exam- 5 ple l. The developer (I) used in the test example was charged into the developer tank of each developing machine. The developing machine (A) was used to treat the silver halide light-sensitive color photographic film used in Example 1, and the developing machine 10 (B) was used to process the same photographic film as above except that ml/m of a O.l percent methanolacetone (:70) solution of the exemplified compound (6) had been coated on the reverse side of the film, followed by hot air drying. In this case, the developer used in each developing machine was measured in degree of foaming clue to agitation derived from introduction of gas. The method adopted in this case was such that nitrogen gas was continuously introduced into the developer for 30 seconds, and then the average height of foams formed in the developer was measured after 10, 30 and 60 seconds, like in Example I. The results obtained were as set forth in Table 6.  
 55 Table 6 Time after stoppage Average height of foams of agitation (A) (B) 10 sec. 30 mm. 3 mm. to 30 sec. 27 mm. 2 mm. 60 sec. 25 mm. 0 mm.  
  From this example, it is clear that even when coated on the reverse side of photographic film, the exemplified compound (6) can effectively prevent the formation of foams.  
  Furthermore, the exemplified compound (6) did not affect the photographic properties of the developed photographic film.  
  What we claim is: 1. In a method for processing a silver-halide lightsensitive photographic material wherein said lightsensitive photographic material is brought into contact with a processing s olution in the presence of a foam generating material, the improvement which comprises providing as a defoaming agentduring processing an effective amount of a polymer having a polymerization degree of from 20 to I500, said polymer being a homopolymer or a copolymer comprising, as a polymer component, 30 mole percent or more ofa structural unit of the following general formula:  
 wherein R is hydrogen or Xeis an anion; and Q is -N-- R2 01 -N -s 2. A method for processing a silver halide lightsensitive photographic material as claimed in claim 1, wherein said polymer is a homopolymer.  
  3. A method for processing a silver halide lightsensitive photographic material as claimed in claim 1, wherein said polymer is a copolymer comprising as its comonomer unit acrylamide. N-vinylpyrrolidone. N.N- dimethylacrylamide. diacetonacrylamide. acrylic acid.  
  14 methacrylic acid, methyl acrylate. methyl methacrylate. vinyl acetate or styrene.  
  4. A method for processing a silver halide lightsensitive photographic material as claimed in claim 1. wherein said polymer is added to the processing solution before the processing.  
  5. A method for processing a silver halide lightsensitive photographic material as claimed in claim 1, wherein said polymer has been included in one of the layers of said light-sensitive photographic material so that it may be dissolved out during the processing.  
  6. A method for processing a silver halide lightsensitive photographic material as claimed in claim 1. wherein said processing solution is prehardcning solution, developing solution. hardening solution. bleaching solution, stopping solution. fixing solution or the