Patented Dec. 12, 1950 2,533,990

UNITED STATES PATENT OFFICE 2,533,990 SILVER HALDE DEVELOPER COMPOS TIONS CONTAINNG - POLYOXYAL KYLENE ETHERS OF HEXITOL RING DEHYDRATION PRODUCTS Ralph Kingsley Blake, Rochester, N.Y., assignor to E. I. du Pont de Nernours & Company, Wii mington, Del, a corporation of Delaware No Drawing. Application June 10, 1947, Serial No. 753,820 9 Claims. (C. 95-88) 1. 2 This invention relates to photography. More etc.). The alkylene oxide may, however, react particularly, it relates to novel photographic de with several of the hydroxyl groups of the hexi veloper compositions and to processes of devel tans or hexides and introduce several Oxyal oping Silver halide inages therewith. kylene chains. For example, one to four of the An object of this invention is to obtain im hydroxyl groups of the hexitan or one to two of proved silver images. Another object is to pro the hydroxyl groups of the hexide may react and vide improved processes for the development of form a chain or chains of oxyalkylene groups of Silver halide images. A further object is to pro two to 20 or more of such groups. vide improved photographic developer Solutions. The resulting polyoxyalkylene ethers of the A still further object is to provide novel devel O hexitans or hexides may then be reacted with oper compositions which produce enhanced speed a monofunctional etherification agent or esteri and contrast results in the development of sil fication agent to introduce a lipophilic group, wer halide images. Still other objects will be ap e.g., an aliphatic hydrocarbon chain of 8 to 18 parent from the following description of the in or more carbon atoms or the hexitans or hexides vention. 5 may be first esterified or etherified with such It has been found that the inclusion of the agents and the resulting long chain ethers or es polyoxyalkylene ethers of hexitol ring dehydra ters later reacted with an alkylene oxide. Suit tion products in photographic developer Solutions able long chain etherification or esterification re leads to beneficial changes in the effective photo actants include normal alkyl halides of 8 to 20 graphic emulsion speed of exposed silver halide 20 carbon atoms, e. g., n-octylchloride, n-dodecyl emulsion layers and the contrast of the devel bromide, n-tetradecylchloride, n-octadecyl bro oped images. The compounds can be used in mide, and n-hexadecylbromide, or a fatty acid various amounts, e. g., from 0.1 to 2.5 grams of halide of 8 to 20 carbon atoms, e. g., octadecoyl the ethers per liter of developer solution. With chloride, dodecoylchloride, tetradecoyl bromide, most of the ethers, however, the optimum con 25 n-Oley chloride, etc. The introduction of two centration is about 0.5 gram per liter. Oxyalkylene ether groups into the hexitan or The polyoxyalkylene ethers of hexitol ring de hexide is enough to form the products used in hydration products are commercially available. accordance With this invention. It is possible They are essentially non-ionic in character and that the alkyl halides or acid halides react with have been found to have good Wetting and dis- : the hydroxyl group at the end of the oxyalkylene persing properties. They can be made by react chain when etherification with alkylene oxides is ing a hexitol ring dehydration product, such aS effected first. However, if the hexitan or hexide a hexitan or a hexide, with an alkylene oxide, is first esterified or etherified with a long chain e.g., ethylene oxide or propylene oxide, in an monofunctional etherification or esterification amount Sufficient to introduce a plurality of oxy 35 agent, the lipophilic groups become linked to an alkylene groups into the molecule. For instance, acyclic oxygen atom thereof. the reaction may be carried out in a manner sim When hexitols are dehydrated, they generally ilar to that described in British Patent No. 443,559 result in a mixture of ring compounds, namely and United States Patent 2,380,166. In general, hexitans and hexides, which can be separated by the alkylene oxide should be used in an amount 40 fractional crystallization or extraction. For the sufficient to form an ether group on one of the purposes of this invention, the ring dehydration Oxygen atoms of the hydroxyl groups of the hexi products need not be completely separated and tan or hexide and introduce at least two of the mixtures of hexitans and hexides may be uti alkylene groups (-R-O- Wherein R is an al lized to prepare the products used in accordance kylene radical, e.g., ethylene, propylene, butylene, 45 with this invention. 2,538,990 3 4 A class of especially useful products have a than those which normally have short induction structure which is exemplified by the following periods. - hexitans and hexide derivative formulae: The invention will be further illustrated by the (1) O H. following examples. The parts are by weight. - / Y. Eacample I A negative type photographic film bearing a c4 gelatino-silver iodobromide emulsion layer was ()-(CHCH-0)-R exposed to an object. The exposed film was then (2) B divided into parts, one of which was developed in RO-C-C-OH the following developer and one each was devel oped in the respective developing Solutions made He déCH-CH-O-(clich-os-R2. by adding 0.5 gram pf, the respective polyoxy Yo (R. developeralkylene ethers with the of resultshexitans listed and in hexides the following to the (3) H /'s table. In each case the time of development re Ro8 -é, YoH, duired to produce a density of .02 above fog was measured. Theiresults are reported in a relative 20 way as fractions of the control. wherein in the formulae one of the R's is an al N-methyl-p-aminophenol sulfate-grams.- 0.74 kyl radical of 8 to 20 carbonatoms or an acyl Sodium (anhydrous)------do---- 90.4 radical of the formula R-CO- wherein R is of Hydroquinohe ------doll-- 1.0 the same order and the other R's are hydrogen Borax, is------do---- 2.7 and n is 2 to 20 or more. When only one 25 bromide------do---- 0.14 (CH2CH2-O) in Water to:------liter.- 1.0 radical is present then n should be 6 or more. The polyoxyalkylene ethers or hexitol ring de Developer InductionRelative hydration products are useful with a wide variety 30- Period- of photographic developing agents including Ungdified------hydroquinone, chlorohydroquinone, pyrogallol, Modified. With A Modified with paminophenol, - ferrous-oxalate, N-methylap Modified with aminophenol sulfate, 2,4-diaminophenol, N-di Modified with D alkyl phenylenediamines of the formula 5 Modified with E. ElimatelyA" is mannitánimonolaurate 20 oxyethylene groupspolyoxyethylene per molecule divided in?ing 3 Calls...... x::, ...... is proximatelyBissorbitan 209xyethylene, motiolatirate groupSpef polyoxyethylene ether containing ap Cismanitanmonosfearate polyox leculeeneeterCitalingap divided in 3:chais. and their water-soluble salts, where R and R' proximately 20 oxyethylene groupSp ledivided in 3 chiis. - Dissorbitan------Inong-oleate------polyoxyetly lene etercontainingap are the same or different lower alkyl radicals, proximatelyEissorbitan 20 oxyethylenegrolips trioleate polyoxyethylene permolelediyiddin ether editaining 3approxi ghins. e.g.,1,4-diaminonaphthalene, methyl and ethyl, p-aminodiethyltolui1,4-diaminobenzene, mately 20 oxyethylené groups per molecule in one chain. dine, and mixtures of two or more of Such agents, Eacample II etc...... The developers may contain the usual , Strips of photographic paper comprising a e.g., , , potassium baryta, coated paper base bearing ageiatino-silver metabisulfite: alkalies, e.g., Sodium or potassium is iodobromide emulsion layer of a standarden carbonate, sodium hydroxide, borax; Soluble neu st larging type were given a suitable step wedge ex tral salts, e.g., sodium bromide, potassium bro posure simultaneously on a sector wheel Sensi mide; boric acid, formaldehyde, aldehyde-bisul tometer of the intermittent time-scale type. fite complexes, etc., One of the strips was developed for 75 seconds in making the novel developer solutions of this. at 68°F in a developing solution' of the following invention, it is merely necessary to add the poly composition and another in the said developer oxyalkylene ethers of the hexitol ring, dehydra modified by the addition of 0.5 gram of mannitan tion products to the aqueous solution in the same monolaurate polyoxyethylene ether containing an manner that the other ingredients, for example, average of 20 oxyethylene groups per molecule the sulfites and developing agents, are added. 60 divided in 3 chains, with the results indicated The aforesaid ethers readily dissolve or disperse in aqueous solutions. It is usually most con venient to add the aforesaid ethers as a solution. Waterand a and0% byethyl weight alcohol solution are suitablein such solvents is affords a practical means for adding the ethers to ------do---- the developer solution. . . - liter.-- 2.5It grams has beenof a polyoxyalkylenefound that the etheraddition of a of hexitan 0.1 or a hexide or a mixture of such compounds to a ii. developer solution is sufficient to change the in 3, '', 'ry: ... r duction period of development. Induction period feveloper can be defined as the time necessary to produce a density of 0.02 above fog. More can be used if Unmodified... casedesired. of developerThis reduction solutions is whichmore markedare less active Modified--- 2,583,990 5 Eacample III N-methyl-p-aminophenol sulfate--grams--- i. 12 Sodium Sulfite (anhydrous)------do---- 19.0 A perforated motion picture negative type film Hydroquinone ------do---- 4.0 bearing a gelatino-silver iodobromide emulsion Sodium carbonate ------do. -- 26.0 layer is exposed to an object field and divided ------do---- 0.4 into two parts. One of the parts is developed in Water to ------liter-- 1.0 the following solution and the other in the solu g tion modified by the addition of 0.5 gram of Relative mannitan monolaurate polyoxyethylene ether Developer Densities containing an average of 20 oxyethylene groups |Exposuresfor Equal per molecule divided in 3 chains. The develop --al-lam-m-m-m-m-a---mm-a-murm ment in each case is for three minutes and twenty Unmodified------100 Seconds at 68° F. and gives the following results: Modified------109 Sodium Sulfite (anhydrous)------grams-- 90.0 Eacample VI p-Phenylenediamine-hydrochloride--do---- 10.0 5 A photographic film of the kind described in p-Hydroxyphenyl amidoacetic acid--do --- 2.0 Example III was exposed as described therein and Water to ------liter 1.0 separated into two parts which were, respectively, developed for 12 minutes at 68 F. in the solution Relative 20 of the following composition and that modified Developer Resis by the addition of 0.5 of a gram per liter of man Exposures nitan monolaurate polyoxyethylene ether con taining an average of 20 Oxyethylene groups per Unmodified ------100 molecule divided in 3 chains. The results are Modified------200 25 given in the table. N-methyl-p-aminophenol sulfate--grams-- 5.0 Eacample IW Sodium sulfite (desiccated).------do---- 100.0 Sodium metaborate ------do---- 2.0 Strips of positive type motion picture film Sodium thiocyanate------do---- 1.0 bearing a gelatino-silver iodobromide emulsion 30 Potassium bromide------do---- 0.5 layer were given a suitable step wedge exposure Water to------liter.-- 1.0 simultaneously on a Sector wheel sensitometer of the intermittent time-scale type. One of the Relative Densities strips was developed in a solution of the follow Developer for Equal ing composition for three minutes at 68° F. and 35 Exposures the other for the same period in said developer modified by the addition of 0.5 gram per liter of Unmodified------100 mannitan monolaurate polyoxyethylene ether Modified------75 containing an average of 20 oxyethylene groups per molecule divided in 3 chains, with the results 40 listed in the following table: Eacample VII Strips of a standard blue base X-ray film ele Sodium sulfite (anhydrous)------grams-- 40.0 ment bearing a light-Sensitive iodobromide emul N-methyl-p-aminophenol sulfate----do---- 0.3 Sion layer on each Surface were given an X-ray Hydroquinone ------do---. 6.0 45 exposure under an aluminum step wedge of the Sodium carbonate (monohydrated)--do---- 22.5 usual type and strips of a negative type cine film Potassium bromide------do---- 0.9 of the type described in Example III were ex Citric acid------do---- 0.7 posed as described in that example. One strip of Potassium metabisulfite ------do---- i.5 each film was developed in (a) a solution of Water to ------liter-- 1.0 50 ferrous oxalate (made by pouring 750 cc. of 18.5% potassium oxalate into 250 cc. of 18.5% ferrous Sulfate aqueous solution) and (b) such a solution Relative modified by the addition of 0.5 gram per liter of Developer EE mannitan monolaurate polyoxyethylene ether Exposures containing an average of 20 oxyethylene groups Unmodified------100 per molecule divided in 3 chains. The develop Modified.------108 ments were continued for four minutes at 68° F. with the following relative densities for equal expoSures. Eacample V 60 X-ray Cine Strips of a photographic film element bearing Developer Film Film a silver iodobromide emulsion layer wherein the binding agent for the silver halide grains is a 00 00 hydrophilic hydrolyzed ethylene/vinyl acetate co 6. Unmodified.------Modified.------4. 89 polymer prepared after the manner of the similar polymer used in Example II of U. S. P. 2,397,866 Eacample VIII were exposed as in Example II. One film strip was developed in the developer Solution of Ex Strips of a lithographic film element bearing ample II and the other in said solution modified a gelatino-silver halide emulsion layer were given by the addition of Sorbitan monolaurate poly an exposure behind a graduated step wedge in oxyethylene ether containing an average of 20 a sensitometer of the intensity-scale type. Then Oxyethylene groups per molecule divided in 3 the strips were developed in the following de chains for 3 minutes at 68 F. The results are veloper and that developer modified by the addi given in the following table: s tion of 0.1 gram, 0.5 gram, and 2.5 grams per 2,538,990 7 8 liter-of-compound A of Example I for two and How these compounds alter the induction period one-half minutes at 68°F. with the results listed is not known. . It is suspected, however, that ad in the table-below: sorption forces must play, a part as it has been ob Water ------cc. 5000 served that all of the effective compounds...are Sodium sulfite (desiccated).------grams. 300 more or less...strongly-adsorbed to silver...halide Paraformaldehyde ------do --- 75 grains. Potassium metabisulfite------do---- 2.5 What is claimed is: Boric acid, crystals------do---- 7.5 1. The process of developing... a. silver...halide Hydroquinone ------do---- 22.5 image with a developer solution... containing...a Potassium bromide------do---- 1.5 O photographic silver halide developing agent and Coldwater to make------liter.-- 1.0 from 0.1 to 2.5. grams...of a polyoxyalkylene-ether of a hexitol ring. dehydration product per liter of Developer Speed 1 Gamma Fog solution. 2. The process of developing a silver halide;im Plain. 5 age with a developer solution containing a photo 31?o graii) (Example I) per lite .45 .3 .01 ogram of A. (Example) per lite 2.10. 13. 01. graphic silver halide developing-agent and from 2% grains of A(Example'I) per liter 0:1 to 2.5; grams of a polyoxyethylene ether sofia, 195 14.8:01 hexitol ring dehydration product per liter of SO 1 Aspeed figure in which each uritiepresents a full'cathera 'stop. lution. 20 3. The process of developing a silver halide In place of the specific” developing agents de image with an alkaline developer solution con scribed in the above examples, there may be sub taining hydroquinone and from 0.1 to 2.5 grams stituted other developing agents with similar re sults. Likewise other polyoxyalkylene ethers of of a polyoxyethylene ether of a hexitan per liter ring dehydration products as disclosed-above can of Solution. 25 4. The process of developing a silver halide ilarbe substituted resultS. for those in the examples with sim image with an alkaline developer solution con In the...above examples:ther quantity of oxy taining hydroquinone and from 0.1 to 2.5 grams ethylene-groups is approximate... The invention, of a polyoxyethylene'ether "of mannitan mono however, is not limited-to-the-specific polyoxy larate per liter of Solution. alkylene ether. derivatives-described in the:ex 30 5. An aqueous developer: Solution containingsa, samples...but, on the contrary, any of such deriva photographic: Silverhalide developing-agent and -tives having the characteristics prescribed above from 0.1:..to 2.5 grams of a polyoxyalkylene ether may be substituted in like manner. Thus manni of a hexitol ring dehydration product per;literi of tanmono-, di-, and tri-oleates, -Stearates, -pal solution. imitates, -margarates, etc., containing from 2 to 20 35 -6. An aqueous;alkaline; developerSolution. Coal oxyalkylene-groups which are distributed in from taining hydroquinone and 0.1 to 2.5 grams, ofia, 1 to 3 chains are useful. Similarly the corre polyoxyethylene ether-of-a-hexitol ring dehydra sponding mannides containing one of said fatty tion-product per liter of solution. w acid-groups and a similar amount of oxyalkylene 7. An aqueous alkaline developer-solution-con groups per molecule. Other-suitable compounds 40 taining hydroquinone-and:0.1 to 2.5 grams of a including the mannide'etheresters, e. g., the pal polyoxyethylene ether of a hexitan per-liter...of imitates, margarates, Stearates.oleates, which Solution. ... ." contain from 2 to 20.7 oxyalkyleneé groups: i and 8. An aqueous alkaline developer Solution con especiallyoxyethylene groups: staining hydroquinone and 0.1 to 2.5-grams, of a 45 polyoxyethylene ether of a hexide per liter: of solution. which are distributed in from 1 to.3 chains. Man 9. An aqueous alkaline developer solution-con initan, mannide, Sorbitan and Sorbide, decyl, do taining hydroquinone and 0.1 to 2.5 grams of a ° decyl, tetradecyl, hexadecyland octadecyl ethers polyoxyethylene ether of mannitan monolatrate containing the Sarne number of oxyalkylene, 50 per liter of Solution. "especially oxyethylene' groups:... are... also useful, The compounds are:"useful in Siraiple; and infixed RALPH. KINGSLEY BAKE... . 'silver halides emulsions of various-types including REFERENCES CITED ...those containing silver chloride, only and those The following references are of record in the containing one or more other light-sensitive silver 55 file of this patent: halides, e.g., Silver-bromide and Silveriodide. It is not known Why, the above "ethers' confer UNITED STATES PATENTS beneficial results in the development of silver Number Name Date, . halide images. The compounds alter the inditle tion period of development. Perhaps in doing so, 6) 2,363,493 Baldsiefen. ------Nov. 28, 1944 latent image centers which were not previously 2,377,375 Russell------June 5, 1945 developable are made developable. In some cases 2,419,9752,400,532 Blake et al. ------May 21, 1946 they are apparentlyrrendered less developable, Trivellietal. ------. May 6, 1947