US3514293A - Photographic surfactant compositions - Google Patents

Description

, U'.s. Cl. 96-1145 cidol.

I presence of certain coating aids.

Patented May 26, 1970 1 NoDrawing. Continuation-impart of application Ser. No. r 515,179, Dec. 20, 1965. This application Nov. 26, 1968,

Ser. No. 779,236

Int. Cl. G03c 1/38 17 Claims ABSTRACT OF THE DISCLOSURE This invention relates to compositions which are used in layers of photographic elements or element combinations,

said compositions comprising a hydrophilic colloid and an alkylphenoxypoly-(hydroxypropylene oxide) having from about 3 to about 15 hydroxypropylene units. In one aspect of this invention, the alkylphenoxypoly(hydroxypropylene oxide) is a compoundhaving the formula:

K wherein R represents an alkyl group having from about 6- units of hydroxypropylene oxide said polyether group comprising n-propylene and isopropylene moieties. In another aspect, the composition comprises a hydrophilic colloid and the reaction product of an alkylphenol and a gly- This is a continuation-in-part application of, Ser. No. 515,179 filed Dec. 20, 1965, and now abandoned.

This invention relates to hydrophilic colloid layers, photographic elements and element combinations containing those layers and to aqueous hydrophilic colloid coating compositions, all of which are characterized by the Many image-recording systems use imageforming materials comprising a support'such as glass, metal, paper or plastic, overcoated with one or more layers comprising hydro philic colloidal materials such as gelatin. Silver. salt ""s'eri'sitized"photographic materials, for example, usually contain one ormore aqueaus gelatin coatings on film base ,or paper. The layer containing the silver salt is frequency l .coated in combination with several other gelatin layers which serve, for example, as carriers for reflective pigments, antihalation dyes or filter dyes, or as undercoatings to improve adhesion, overcoatings to impart abrasion resistance, and the like.

In' the coating of such hydrophilic Ebndia layers, particularly those containing gelatin, it has been customary toemploy surface-active agents as coating aidsto improve f the quality and uniformty of the layers and the ease and reproducibility of their application. The surfactants used :often influence other oharacteristics'than the coating performance, e.g., surface roughness, permeability to processing solutions, and the like.

Saponin, a material prepared from quillaia bark, has ueen widely used for this purpose. Being of natural origin, saponin varies in composition according to the source, the method of extracton, and the like, and commercial saponin may include impurties which produce undesirable effects in photographic materials. Saponin has been a reasonably effective coating aid in many applications; however, newer coating procedures which involve increased coating speeds, the application of liquid coating compositons to set (but undried) underlayers and/ or the coating of a plurality of layers, have increased the requirements of a satisfactory coating aid and saponin and many other prior art coating aids have been inadequate. Synthetic surfactants have been widely used in recent years in an effort to provide specific requirements in particular coating operations, but a great number of these have been found Wanting in one or more particulars when used in recent coating procedures. ing aids which are photographically inert, but which im- An object of my invention is to provide new and improved hydrophilic colloid coating compositions;

Another object of my nvention is to provide photographic hydrophilic colloid layers containing certain coating ads which are photographically inert, but which impart to said layers good surface characteristics such as a high degree of surface roughness, excellent developer rewettability, lack of repellencies and improved permeability by processing solutions;

A further object of my invention is to provide gelatinsilver halide photographic emulsions containing a certain coating aid which facilitates coating upon a support;

A still further object of my invention is to provide photographic elements containing at least one layer of hydrophilic colloid, for example, gelatin which has excellent characteristics;

Other objects of my invention will appear herein.

I have found that alkylphenoxypoly(hydroxypropylene oxides) can be used'very effectively in hydrophilic colloid coating compositions used in making photographic elements. These materials, when incorporated in photographic hydrophilic colloid coating compostions and hydrophilic colloid coatings, increase the ease and efiiciency of the coating process and provide a favorably high degree of surface roughness and excellent developer rewettability on coated layers having few or no repellencies, without adversely affecting the photographic properties of the final product. The coating aids of our invention are compatible with both aoidand lime-processed gelatin as well as a 'wide variety of photographic emulsion addenda such as hardeners, antifoggants, mordants, couplers, antistatic agents and the like.

The alkylphenoxypoly(hydroxypropylene oxides) of this invention are generally of the formula:

atoms, and is preferably in the para position; R represents a hydrogen atom or an alkyl group having from about 1 to 18 carbon atoms and preferably from 6-14 carbon atoms; and Q represents a polyether group comprising from 3 to 15 hydroxypropylene oxide units and preferably consists of at least 8 units which can be interconnected by ether linkages through an oxygen atom on any of the three carbon atoms of the propylene unit, such as to form isopropylene and n-propylene moieties in the group.

The alkylphenoxypoly(hydroxypropylene oxides) can be formed by reacting the alkylphenol with hydroxy compounds according to the procedures normally used to prepare polyglycerol-type compounds. However, the compounds and procedures used in the reaction will, of course, affect the degree of branching and precise structural composition of the product. Since the glycerols, glycerides, glycidols and related compounds required to produce the poly(hydroxypropylene oxide) groups have three possible reaction sites, a high degree of random branching in the molecule is likely to occur, especially when several units are formed in the chain during the reaction as, for example, as when the reaction is continued to form more than 6 units of glycidol. In instances where the alkyphenoxy compound contains upwards of 6 and preferably at least 8 reacted glycidol units, the compound contains sufficient hydroxy and methylol groups to impart improved water solubility and to provide optimum physical and coating characteristics in certain preferred embodiments.

In one preferred embodiment of this invention, an alkylphenoxypolyglycidol is used in coating hydrophilic colloid layers of photographic elements. These compounds are made by reacting the alkylphenol with a glycidol at a temperature above about 100 C. A typical procedure for reacting glycidols is set forth in Belgian Pat. 652,862 granted Sept. 9, 1964.

Typical surface-active agents which are commercially available and which are very useful in my invention include Surfactant 3G (Olin Mathieson Chemical Corp.) which is essentially a para-isononylphenoxypolyglycidol containing an average of 3.3 moles of reacted glycidol; Surfactant 6G (Olin Mathieson Chemical Corp.) which is essentially a para-isononylphenoxypolyglycidol containing an average of above 6 glycidol units; and Surfactant 10G (Olin Mathieson Chemical Corp.) which is essentially a para-isononylphenoxypolyglycidol containing about 10 glycidol units.

The coating aids of this invention are useful in aqueous coating compositions containing hydrophilic colloid. They are useful in coating mixtures of gelatin with other hydrophilic colloid materials which may act, for example, as gel extenders, and to reduce the modulus of elasticity, increase covering power, and the like. Polymers such as copoly(ethyl acrylate-acrylic acid) in monomer ratios of 3:1 to :1 and copoly(buty1 acrylateacrylic acid) in monomer ratios of 5 :1 to 9:1 are sometimes useful as gelatin extenders. Covering power of emulsions is sometimes increased by incorporating in gelatin-sliver halide photographic emulsions such colloids as copolymers of acrylic acid and N-substituted acrylamide as described in French Pat. 1,328,889 and the like.

The utility of surface-active agents in accordance with my invention is not limited to coatings and coating procedures involving photo-sensitive silver halide-gelatin compositions. They can also be used in coating hydrophilic colloid layers which are used in photographic elements or element combinations to be used in conjunction with a photographic element containing a siliver halide layer, such as carrier layers for reflective pigments, antihalation dyes, filter dyes, mordants and the like, receiving layers for diffusion transfer, and undercoatings and overcoatings which impart characteristics such as improved adhesion and improved resistance to abrasion. The coat mg aids denoted as useful in my invention impart to 4 various hydrophilic colloid layers increased permeability to processing solutions.

It has been further found that the coating aids denoted as useful in my invention can be used in admixture with other surface-active agents such as anionic surfac tants, e.g., alkylaryloxyalkylene ether sulfonates, maleopimarates, alkyl sulfates, and amphoteric surface-active agents such as N-alkyl-beta-aminopropionates, acylalkyltaurines, etc.

The coating aids of this invention are also useful in controlling the incidence of longitudinal coating streaks and other defects which occur in the preparation of photographic layers. The reduction of the incidence of coating streaks has been correlated with the increased stainless steel spread values imposed upon hydrophilic colloid solutions by the addition of a coating aid. Stainless steel spread values are obtained by measuring the area over which a sample of a hydrophilic colloid solution will spread on a stainless steel plate. The greater the stainless steel spread values, the more effective is the coating aid in suppressing longitudinal coating streaks.

It is shown in the following examples that the coating aids utilized in my invention effectively control the incidence of coating streaks.

The use of coating compositions in accordance with my invention renders the coating of hydrophilic colloid layers in making photographic products adaptable to modern high-speed coating techniques. For example, they operate well in the coating of multilayer photographic elements by the techniques described in British Pats. 855,849 and 929,905, and US. Pat. 2,761,791 of Russell.

To illustrate the practice of this invention a number of coatings were prepared by the application to barytacoated photographic paper base of a silver halide-gelatin photographic emulsion and a clear gelatin overcoat by a multilayer coating technique. The concentration of the surfactant, the developer spread, the coeflicient of friction and the number of repellencies per unit area are recorded in the following tables. Developer Spread is determined by delivering in a standard manner 1 cc. of developer solution to a surface of photographically sensitized paper carrying a clear gelatin overcoat and measuring the area which develops in a period of 30 seconds. This test indicates how effectively an emulsion will wet. A developer spread of 4.0 cm. or more is desirable.

EXAMPLE 1 Coating of emulsion and overcoat layers on paper using, as a coating aid therein, a material of the structure:

(011930 clam-GO wherein Q represents a poly(hydroxypropylene oxide) group contaimng approximately 10 units of glycidol.

The following table shows the structures of similar compounds which operate in our invention. In this table x is given as an approximate average value for the number of units of glycidol in the poly(hydroxypropylene oxide) chain represented by Q.

YIIXBIZELIF? EXAMPLE 3 1 Coating of emulsion and overcoat layers to paper using,

3 a I M as a coating aid, Surfactant 66. R V V ...P0slti0n romnccmcwnm r (cmnocmewm): g

-- n :s I P "1: H J V 8 11 F OaHu H 0 l CaHu P CaHin o 0101111 P --CH3 0 5 0 11,, I? O1H1 0 12 Co n CH: H o

EXAMPLE 2 Surfactant concentration Coating of emulsion and overcoat layers. papeusing, as a coating aid, Surfactant 6G sold by Qhn'Mathte; son Chemical Corp.

. Wet Develop- Coefli- Repelleneies (7.5 it?) Wet emulovercoat, er spread, cient of sion g./1b. glib. cm. friction Brlght Dull 0.5 16.60 0.45 None None 0.5 16.60 0.47 None --None 0.5 16.60 0. 47 4 2 0.5... 0.5 10.50 0.50 4 14 i 0.0... 1.0 16.60 0.49 2 2 1 0.26 ,1.0 16.60 0.49 Non None 0.5. 1.0 16.60 0.48 None 1 None 1.0- 1.0 16.60 0.53 None 'None Surfactant 0.0. 2 0 1s. 60 0. 51 None 7 None 0011081102010 0.5. 2.0 12.33 53 Nom gone 1.0- 2.0 1 .5 7 one Wet Develop- Coefiiweemulovercoat, Bowed, w 3:3: Z13 123 31%? 5332 5333 sion g./lb. g./lb. omJ frletion Bright ML 4 16.60 N 3 N 2 2.0. 4.0 i 16. 60 one one 8-; -33 8 :2 4.0. 4. 0 16.60 0. 41 None None 5 0 0 37 010.- 2 V 1 f 0.' 5 10.50 0 s9 None The following examples illustrate the eifectiveness of the compounds of my invention when used in combination with other surface-active agents as coating aids.

. E L Coating of emulsion and overcoat layers to paper using, e following data lndlcate that at concentratwns as coating aids, mixtures of sodium maleopimarate and boxe...eaa..aratnl. .l f 419 5111155151: 106, sold by Olin Mathieson Chemical Corp., layer, satisfactory coatings are obtained. a in various proportions by weight.

Surfactant concentration 7 Ratio by Coefli- Repellencies welght; of Wet Wet Developer oient (7.5 it?) sodium maleoemu1., overcoat, spread of 3 .punarate/lOG gJlb. g./1b cm 2 friction Bright Duh 0. 0 0. 5 4. 15 0. 48 None None 13 0. 5 4. 15 0. 52 1 2 .25 0.5 14.52 0.53 None None 5 0. 5 4.52" 0. 52 None None .0 ..9-, 4. 52 0.54 H None 13 0.5 72' 0.52- 1 25 0.5- 5.72 0.51 7 None 0.5 0.5] 10.20 0.52. f 1. 1 0.0 r 0.5 --,5.'31 0.54 1 0. 13 0. 5 11. 00 0. 54 1 0. 25 0. 5 14. 50 0. 52 None 0,5... M ..0.5 16 ..60 None 0. 0 0. 5 5. 72. 0. 51 one None 0.13 0. 5 16.60 .0. 52 None None 0.25 0.5 16.60" .j 0.52 None None 5 r 05 .16. 1 .0. 49 None None ..0 0;.5 v; 9.08. .053 None None .13 0.5 16.60 0.50 None. None ..25 0. F 16.60. 0.52 None j None I v 0.5 ..0.5 16.60 0. 51 v None None 0.0 0.5 16.60 ;0. 51 None 1 "None 0.13 0.5 16. 60 .0.49 None .None .0. 25 0.5 16.60 0.49 None 'None 0.5 ,0.5 16. 60 0. 48 None None -.9. i 9-0. 13 1.9.5. lIQ 1. .-.-.N

7 EXAMPLE 5 Coating of emulsion and overcoat layers to paper using, as coating aids, mixtures of Aerosol OT (the dioctyl ester of sodium sulfosuccinic acid, a surface-active agent sold 8 EXAMPLE 7 Coating of emulsion and overcoat layers to paper using, as coating aids, mixtures of sodium lauryl sulfate and Surfactant 6G. I

Surfactant concentration Repellencies Wet Wet Developer Coetfi- (7.5 it?) emul., overcoat, spread, cient oi Coating aid g./lb g./lb cm. friction Bright Dull Sodium lauryl 5111- 0. 0. 16, 60 0. 32 None None late/6G ratio by 0. 13 0.5 16. 60 0. 31 None None wt. 1/1. 0. 0. 5 16. 60 0. 34 None None 0. 5 0. 5 16. 6O 0. 37 None None 0. O 0. 0 4. 52 0. 44 None None by American Cyanamid Company) 1 and Surfactant 106 in various proportions by weight.

Concentration Repellencies Developer Coeifi- (7.5 (H) Ratio by weight Wet emul., Wet overspread, cient of of IOG/Aerosol OT g./lb. coat g./1b. cm. friction Bright Dull 0. 0 0. 5 7. 07 0. 54 None None 0. 13 0.5 16. 60 0. 53 None Mone 0. 25 0. 5 16. 60 0. 46 None None 0. 5 0. 5 16. 60 0. 48 None None 0. 0 0. 5 16. 60 0. 48 None None 0. 13 0. 5 16. 60 0. 47 None None 0. 25 0. 5 16. 60 0. 51 None None 0. 5 0. 5 16.760 0. 46 None None 0. 0 0. 5 16. 60 0. 45 None None 0. 13 0. 5 16. 6O 0. 47 None None 0. 25 0. 5 16. 60 0. 49 None None 0. 5 0. 5 16. 60 0. 45 None None 0. 0 0. 5 16, 60 0. 48 None None 0. 13 0. 5 16. 60 0. 46 None None 0, 25 0. 5 16. 60 0. 46 None None 0. 5 0. 5 16. 60 0. 43 None None 0. 0 0. 5 9. 08 0. 42 None None 0. 13 0. 5 16. 60 0. 43 None None 0. 25 0. 6 16. 60 0. 42 None None 0. 5 0. 5 16. 60 0. None None 0. 0 0. 5 6. 16 0. 38 None None 0. 13 0. 5 8. 04 0. 31 None None 0. 25 0. 5 16. 60 0. 35 None None 0. 5 0. 5 16. 60 0. 36 None 1 0. 0 0. 0 3. 80 None None I Aerosol 0'1 is bis (2-ethy1hexyl) sodium sulfosuceinate and has the structure:

CH -COOCHiCHWHihOH, EXAMPLE 8 Coating of emulsion and overcoat layers to paper using, aS-CH-C OOCHWHw niC a as coating aids, mixtures of sodium lauryl sulfate and Surfactant 3G.

Surfactant concentration Re ellencies Wet Wet Developer Coefli- 7.5 it!) emul., overcoat, spread, cient Coating aid g./1b. g./lb. cm. friction Bright Dull Sodium lauryl 5111- 0. 0 0. 5 16. 0. 36 None None fate/3G ratio by 0. 13 0. 5 16. 60 0. 36 None None wt. 1/1. 0. 25 0. 5 16. 60 0. 37 None None 0. 5 0. 5 16. 60 0. 38 None None 0. 0 0. 0 4. 52 0. 44 None None EXAMPLE 6 Coating of emulsion and overcoat layers to paper using, as coating aids, mixtures of sodium lauryl sulfate (Duponol C sold by DuPont Company) as Surfactant 10G.

Surfactant concentration Repeliencies Wet Wet Developer Coefli- (7.5 it!) emul., overcoat, spread, cient Coating aid gJlb g./lb. cm I trietion Bright Dull Sodium lauryl sul- 0.0 0. 5 16. 60 0. 35 None Myriad fate/10G ratio 0. 13 0. 5 16.60 0. 34 None None by wt. 1/1. 0.25 0. 5 16. 60 0. 33 None None 0. 5 0. 5 16. 60 0. 33 None None 0. 0 0. 0 4. 52 0. 44 None None 3,514,293 t 1o The coating aids employed in the practice of this invention can be used in various kinds of silver halide photographic emulsions. In addition to being useful in EXAMPLE 9; Coating of emulsion and overcoat layers to paper using sodium lauryl sulfate as a coating aid. 7

Surtaetant concentration Repeliencies Wet Wet Developer Coefli- (7.5 it!) emul., overcoat, spread, cient Coating aid g./ib. g./lb. cmJ triction Bright Dull Sodium lauryl 0.0 0.5 None None sulfate. 0.13 0.5 "6.16 0.27 None None 0.25 0.5 6. 60 0.24 None None 0.5 0.5 6.16 0.24 None None 0.0 :0 4.52 0.44 None None The following examples illustrate the high stainlessi orthochromatic, panchromatic and infrared-sensitive steel spread values obtainedfor gelatin solutions when a mixtureof Surfactant G and Aerosol OT is added-to the solutions. The stainlessiste'el spread" values a'rcdetermined by deliveringtoa warm stainless steel plate one cubic centimeter of a gelatin solution, cooling the plate,

Stainless steel s read values forl solutions ofjli rne processed gelatin containing, as coating'aids, mixtures, in various ratios by weight, of Surfactant 110G and Aerosol A blank sample of the same gelatin solution testsd as above gave a stainless steel spread of 3.8 cmF.

EXAMPLE 11 Stainless steel spread values for solutions of low-grade, acid-processed pig gelatin containing, as coating aids, mixtures, in various ratios by weight, of Surfactant 106 and Aerosol OT.

Stainless steel spread (cm!) at various emulsions, they are also useful in X-ray and other nonoptically sensitized emulsions. They can be used in sulfur and gold sensitized silver halide emulsions. Emulsions 1 containing various types of silver salts can be used such as silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide, silver bromoiodide or silver chloroiodide. The coating aids employed in the practice of this invention can be used to coat hydrophilic colloid layers in elements intended for color photography, for example, silver halide emulsions containing color-forming couplers or emulsions to be devel- OTC" generating materials.

. 1... iii". if The coating aids of the invention can be employed to Stainlessstellspread-(c1113) atvarlous ratios L"130 C0311 hYdi'OphiliC COllOid layers containing mordants, piggg t ggg ifig gg m. r Surfactant IOG/Aerosol 0'1 ments, such as titanium dioxide, zinc oxide, silica parof emulsion a lo o q 91 1 4 1,; 7 3v :r/ .;3/7 ticles, manganese dioxide, absorbing dyes and the like. 0.07 L M3 27, 5 Photographic layers coated according to this invention 0.13 5193 6273 6161* i 183' 7:97' can be used in diifusion transfer processes which utilize 8223::::::::::::::::::: $333 315? 2:33 3:33 3:?3 di a nondsveloped Silver halide in the nondeveloped silver halide in the non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer. Such processes are described in Rott, U.S. Pat. 2,352,014, Land, U.S. Pat. 2,543,181, and Yackel et a1., U.S. Pat. 3,020,- 155. The silver halide emulsions described herein can also be used in color transfer processes which utilize the dilfusion transfer of an imagewise distribution of developer, coupler or dye from a light-sensitive layer to a second layer while the two layers are in close proximity to one another. Color transfer processes of this type are de- Corcentrzgzion of ratios of surfactant 10G/aerosol OT b d Y U S P 2 856 1 eoa ng iii in scri e 1n utzy, at. ,142; Land et a., U.S.

emulsm 9/1 4/1 7/3 Pat. 2,983,606, Whitmore et al., British Pats. 904,364 and 2.23 3. 5 23 -23 23 840,731; and Whitmore et al., U.S. application Ser. No. 6157 71 17 7123 7177 7.80 s. 20 392,47 6. 77 7- 70 37 73 The invention has been described in considerable detail A blank sample of the same gelatin solution tested as above gave a stainless steel spread of 3.9 cm?.

The coating aids of this invention can the used with any of the conventional hyd'rophilic water-permeable binding materials employed in the preparation of photographic silver halide emulsions and elements, as exemplified by gelatin, colloidal albumin, cellulose derivatives, synthetic resins such as polyvinyl compounds, e.g., acrylamide polymers and the like, as well as mixtures with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be etfected within the spirit and scope of the invention as described hereinabove and in the appended claims.

I claim:

1. An aqueous coating composition comprising an aqueous dispersion of a hydrophilic colloid and a silver halide containing therein a compound having the formula:

R of these materials.

The coating aids of this invention can be used to coat hydrophilic colloids on a wide variety of supports. The 5 hydrophilic colloid layers can be coated on one or both sides of the support, if desired. Typical supports are cellulose nitrate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, and related films or resinous materials, as well as glass, paper, metal and the like. Supports such as paper, which are coated with alpha-olefin polymers, particularly polymers of alpha-olefins containing two or more carbon atoms, as exemplified by polyethylene, polypropylene, ethylenebutene copolymers and the like, can also be employed.

wherein R represents an alkyl group having from about 6-18 carbon atoms, R represents a hydrogen atom or an alkyl group having from 1 to 18 carbon atoms and Q represents a polyether group comprising from about 3 to 15 units of hydroxypropylene oxide said polyether group comprising n-propylene and isopropylene moieties.

2. The composition according to claim 1 wherein said R is an isononyl group in the para position of said phenoxy.

3. The composition according to claim 1 wherein Q consists of at least 8 hydroxypropylene units.

4. The composition according to claim 1 wherein R is a hydrogen atom.

5. The composition according to claim 1 wherein said hydrophilic colloid is a gelatin.

6. An aqueous coating composition comprising an aqueous dispersion of a hydrophilic colloid and a silver halide containing therein an alkylphenoxypo1y(hydroxypropylene oxide) having a polyether group from about 3 to 15 hydroxypropylene oxide units said polyether group comprising n-propylene and isopropylene moieties and the said alkyl of the alkyl-phenoxy group contains at least 6 carbon atoms.

7. A composition according to claim 6 wherein said alkylphenoxypoly(hydroxypropylene oxide) is prepared by reacting an alkylphenol with glycidol.

8. A composition according to claim 7 wherein said alkylphenoxypolyglycidol contains at least 8 units of reacted glycidol.

9. A composition according to claim 6 containing an anionic surface-active agent in combination with said alkylphenoxypoly(hydroxypropylene oxide).

10. A composition according to claim 6 wherein said anionic surface-active agent is sodium maleopimarate.

11. A composition according to claim 9 wherein said anionic surface-active agent is sodium lauryl sulfate.

12. A composition according to claim 9 wherein said anionic surface-active agent is bis(2-ethylhexyl)sodium sulfosuccinate.

13. A photographic element combination comprising (1) a support, (2) at least one layer containing a silver halide and (3) at least one layer containing a hydrophilic colloid and a compound having the formula:

12 wherein R represents an alkyl group having from 6 to 18 carbon atoms, R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms and Q represents a polyether group comprising from 3 to about units of hydroxypropylene oxide, said polyether group comprising n-propylene and isopropylene moieties.

14. A photographic element combination according to claim 13 wherein said alkylphenoxypoly(hydroxypropylene oxide) is prepared by reacting an alkylphenol with glycidol.

15. A photographic element combination according to claim 14 wherein said alkylphenoxypolyglycidol consists of an alkylphenol reacted with at least 8 units of a glycidol. 16. A photographic element combination according to claim 13 wherein said hydrophilic colloid is a gelatin.

17. A photographic element according to claim 13 wherein said silver halide-containing layer and said alkylphenoxypoly(hydroxypropylene oxide) containing layer are coated on the same support.

References Cited UNITED STATES PATENTS 2,089,569 8/1937 Orthner et al 260-406 2,213,477 9/1940 Steindorlf et a1 260-613 2,752,246 6/1956 Weaver 96-114 3,201,252 8/1965 Knox et al 96114.5 3,415,649 12/1968 Nishio et al 96114.5

FOREIGN PATENTS 652,862 9/1964 Belgium.

NORMAN G. TORCHIN, Primary Examiner M. F. KELLEY, Assistant Examiner @2353? UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3 1 Dated y 26 1 97 Patent No.

Inventofls) illiam J. Knox, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

I.- In Column 1 line 52 (page 1 line 1 1 of application) "frequency" should read --frequently-- In Column 2, line 21 delete entire line.

In Column 2, line 2;, (page 2, line 10 of application), "nvention" should read --invention---.

In Column l line 36, (page 6, line 18 of application) "concentration" should read ---concentrations--.

In Column 9, line 37, (page 1 3, line 12 of 1 application), "tested" should read -tested--.

Claim 10, line 1 (Claim 10 of application) "Claim 6" should read ---Claim 9--.

3151166. am sealed this 29th day of February 1972.

(SEAL) Attest EDWARD M.FLETCHER, JR. ROBERT OTTSCHALK Attesting Officer Commissioner of Patents