US3564576A - Gelatin coating compositions containing a mixture of sodium maleopimarate and a sucrose ester of an aliphatic acid - Google Patents

Abstract

COATING PROCESS AND COMPOSITIONS OF MATTER COATED THEREBY COMPRISING GELATIN AND CONTAINING THEREIN, AS A COATING AID, A MIXTURE OF SODIUM MALEOPIMARATE AND A SUCROSE ESTER OF AN ALIPHATIC ACID ARE DISCLOSED. SAID PROCESSES AND COATING COMPOSITIONS FIND PARTICULARLY GOOD USAGE IN PHOTOGRAPHIC LAYERS, EMULSIONS AND ELEMENTS.

Description

GELATIN COATING COMPOSITIONS CONTAIN- ING A MIXTURE OF SODIUM MALEOPIMARATE AND A SUCROSE ESTER OF AN ALIPHATIC ACID William J. Knox, Jr., Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Continuation-impart of application Ser. No. 365,180, May 5, 1964. This application Sept. 11, 1964, Ser. No. 395,949

Int. Cl. G03c ]/38 US. Cl. 96-1145 11 Claims ABSTRACT OF THE DISCLOSURE Coating processes and compositions of matter coated thereby comprising gelatin and containing therein, as a coating aid, a mixture of sodium maleopimarate and a sucrose ester of an aliphatic acid are disclosed. Said processes and coating compositions find particularly good usage in photographic layers, emulsions and elements.

This application is a continuation-in-part of application Ser. No. 365,180, filed May 5, 1964.

This invention relates to gelatin coating compositions particularly for use in the manufacture of photographic products, involving the use of sucrose esters of fatty acids of 8-18 carbon atoms (or their mixtures with sodium maleopimarate) as coating aids therein.

In the application of gelatin layers to a surface particularly in the making of photographic products, it is usually desirable to include in the composition a coating aid to facilitate the aplication of the composition Onto a surface. Saponin has been widely used for this purpose but being a natural material it varies in uniformity and effectiveness and is subject to contamination when obtaining it from its source.

Various coating aids have been mentioned in the prior art, many of which are unusually effective for some particular use. However, the surfactants heretofore suggested as coating aids often leave something to be desired, hence, those which have been suggested heretofore cannot be considered as of universal application in the laying down of gelatin layers.

Sodium maleopimarate has been suggested as a coating aid in Knox and Fowler US. Pat. No. 2,823,123. However, this material when used alone does not impart to the final product a rewettability sufficient for most mechanical processing. This deficiency has heretofore been overcome by using saponin therewith. This does not achieve the goal of complete elimination of saponin from coating operations.

One object of my invention is to provide gelatin coating compositions adapted for use in photographic products. Another object of my invention is to provide gelatin coating compositions containing certain sucrose esters of fatty acids as coating aids. A further object of my invention is to provide a coating aid for gelatin which makes United States Patent possible the simultaneous application onto a support of gelatin-silver halide photographic emulsion layers and gelatin overcoatings without any substantial amount of defects in the products obtained. A still further object of my invention is to provide gelatin layers, containing coating aid, characterized by excellent rewettability without excessive reduction of surface friction. Other objects of my invention will appear herein.

My invention is directed to gelatin coating compositions either aqueous solutions of gelatin or photographic emulsions, the latter ordinarily being composed of an aqueous solution of gelatin containing as the light sensitive material a silver halide, which compositions contain as a coating aid therein a sucrose ester of a fatty acid of 8-18 carbon atoms with or without the addition of sodium maleopimarate. The compositions may contain other added materials such as dyes, hardeners, antifoggants, stabilizers, plasticizers, pigments or the like.

The coating aid is employed in a proportion which is effective in imparting good coating properties to the gelatin composition. Ordinarily a proportion of coating aid of from 0.1% to 10% based on the dry weight of the gelatin composition is effective, however, the coating aid in accordance with my invention improves the coating properties of the gelatin composition when present in almost any proportion. When sodium maleopimarate is used in conjunction with the sucrose ester as the coating aid, the proportion of the two materials may vary greatly from as much as nine parts of sodium maleopimarate to one part of sucrose ester through equal parts to a predominating proportion in the coating aid of the sucrose ester.

The sucrose esters which are useful as coating aids in gelatin compositions are the sucrose esters of fatty acids, =both saturated and unsaturated, having 8 or more, but more particularly 12-18, carbon atoms. For example, the monolaurate, the monomyristate, the monooleate, etc. of sucrose have shown usefulness in gelatin compositions in accordance with my invention.

Coating aids in accordance with the invention have shown themselves to be especially useful in gelatin compositions to be employed in multilayer coating techniques as described in US. Pat. No. 2,761,791 of Russell. This coating method is especially useful in the manufacture of photographic film and photographic paper by application to a support of one or more light sensitive e'mulsions and/or subcoatings, protective coatings, light filtering layers, overcoatings and the like applied simultaneously whereby a distinct layer relationship and desired thickness of each layer is obtained. These compositions are useful in the making of products in either black and white or color photography or for similar situations in which gelatin coatings are applied to a support such as paper, film base such as of the' cellulose ester or polyethylene terephthalate type or to some other supporting material.

In one example of the invention a silver halide photographic emulsion using gelatin as the vehicle was prepared and sucrose monolaurate was added as the coating aid. Also prepared were plain gelatin compositions and layers of both, the emulsion and the gelatin composition (as an overcoating over the emulsion) were applied simultaneously. The concentrations of the sucrose monolaurate in the emulsion and in the overcoating were varied in accordance with the proportions given in the accompanying table. The coating was applied in the manner described in Russell US. Pat. No. 2,761,791, the coating having been carried out at a speed of 60 ft. per minute and at a temperature of 95 F. It appeared that the presence of the sucrose monolaurate aided in the coating operation and better repellency values were obtained than where that material was not present. The coatings were made at the proportions specified and the repellency occurrences for the most part remained fairly low particularly where the proportions of coating aid in both layers were somewhat commensurate. The products obtained in this operation sometimes had a low coefficient of friction which in some cases tended to cause difficulty in handling. In other runs sodium maleopimarate was also present as part of the coating aid and the slipperiness was reduced when that feature was considered to be of some importance.

TABLE II Surfactant concentration, wet Repellenemulsion cies,

Blank Q gt (control)- Gelatin-silver halide photographic emulsions were supplied with sucrose monomyristate as a coating aid and those emulsions and gelatin overcoating layers containing sucrose monomyristate were applied in a hopper coating TABLE 1 procedure to paper by the method described in the Russell i ggf ggg 5 patent referred to. The coating was applied to the support at the rate of 60 ft. per minute, the temperature being l g Repellencies 05 F. The proportions of surfactant and data concern- (g./lb.) (g./1b.) 7.5 it! mg the products are shown 111 the above table.

0 13 (113 0 In some cases it has been thought desirable to add 0 0.15 0 sodium maleopimarate as a portion of the coating aid. 8: Myriag For example, a silver halide gelatin emulsion and a clear 0.13 0.25 1 gelatin overcoat were applied by a multilayer technique 13g 83g? to paper by the method described in the Russell patent 1. 0 0.25 Myriad referred to above. The runs resulting were divided into 81 3;; g examples using various proportions for the coating aid. 1.5 0.2 0 The proportions of the maleopimarate (SMP) to 0. 3 1 5 sucrose monomyristate (SMM) the concentrations of sur- 0- 5 1 -0 0 factant used in the emulsion and in the overcoat and the 1 :8 3 results obtained by measuring various physical properties were as follows:

Surfactant concentration Developer Repel- In emulsion, In 800, spread Coetlicient lencies SMPzSMM ratio g./lb. ./1b. (0111. of friction (7.5 It!) 0. 0 0. 5 5. 31 0. 53 None 1 0.13 0.5 5.72 0.54 Nono 0. 25 0. 5 0. e2 0. 52 I 0. 0. 5 1e. 0. 45 None 0. 0 0. 5 5. 72 0. 47 None 4 0. 13 0. 5 13. 20 0. 46 None 0. 25 0. 5 16. 60 0. 42 None 0.50 0.5 16 60 0.43 None 0. 0 0. 5 5. 31 0. 45 N one T3 0. 13 O. 6 13. 90 0. 37 None 0.25 0. 5 16 00 0 37 None 0.50 o. 5 16.60 0 40 None 0. 0 0. 5 16.00 0 30 None M 0.13 0.5 16. 60 0 33 None 0. 25 0. 5 10. 60 0 20 None 0. 50 0. 5 10. 00 0 32 None 1 Simultaneous overcoat.

2 Small.

As a further example of coating with a gelatin composition in which sucrose monolaurate has been incorporated as a coating aid, that material was incorporated into photographic emulsion in the proportions indicated. The concentration of the sucrose monolaurate in the wet emulsion and the repellencies of the coated products ob- 7 made involving the simultaneous application to paper ing as a coating aid therein a mixture of sodium maleopimarate and sucrose monococoate.

5. A composition of matter comprising gelatin containing as a coating aid therein a mixture of sodium maleopimarate and sucrose monolaurate.

6. A gelatin-silver halide photographic emulsion containing as a coating aid therein a mixture of sodium maleopimarate and a sucrose aliphatic acid ester.

7. The composition of matter according to claim 1 in which the proportions of said sodium maleopimarate SMP AND SUCROSE MONOCOCOAIE AS THE COATING AID Surfactant concentration Developer Repel- In emulsion, In SOC., spread Coefficient lencies SMP/ester ratio g./1b. g./1b. (cmfl) of friction (7.5 it.)

0. 0 0. 5 4. 90 0. 48 None 9 1 0.13 0. 5 4.15 0.44 None 0. 25 0.5 7.07 0.51 None 0. 50 0. 5 10. 0. 47 None 0. 0 0. 5 4. 52 0. 48 None 4 1 0. l3 0. 5 10. 70 0.45 None 0. 0. 5 13. 90 0. 43 None 0. 50 0. 5 16. 60 0. 43 None 0. 0 0. 5 6. 16 0. 47 1 7 3 0. l3 0. 5 15. 2O 0. 42 None 0. 25 0. 5 16. 60 0. 41 None 0. 50 0.5 16. 60 0. None 0. CI 0.5 6. 16 0.39 None 1 1 0. 13 O. 5 16. 60 0.36 None 0 25 0. 5 16. 60 0.34 None 0. 0. 5 16. 0.35 1 0. 0 0. 5 16. 60 0. 31 None 3 7 0.13 0.5 16.60 0. 29 None r 0. 25 0. 5 16. 6O 0. 28 None SMP AND SUCROSE MONOOLEATE AS THE COATING AID Surfactant concentration Developer Repel- In emulsion, In 800., spread Coefliclent lencies S MP/ester ratio g./lb. g./lb. (cm?) of friction (7.5 ft.)

0. 0 0. 5 6. 16 0. 54 2 0. 13 0. 5 6. 16 0. 54 1 0. 25 0.5 5. 31 0.50 0 0. 50 0. 5 13. 20 0. 51 5 0. 0 O. 5 5. 72 0. 44 1 0. 13 0.5 16. 60 0.42 None 0. 25 0. 5 16. 60 0. 49 None 0. 50 0. 5 16. 60 0. 43 None 0. 0 0. 5 9. 62 0. 38 None 0. 13 0.5 06.60 0.38 None 0. 25 0. 5 16. 60 0. 38 None 0. 50 0. 5 16. 60 0. 38 None 0. 0 0. 5 16. 60 0. 30 None 0. l3 0. 5 16. 60 0.30 None O. 25 0. 5 16. 60 0. 27 None 0. 50 0. 5 16. 60 0. 29 None 0. 0 0. 5 16. 60 0. 28 None 0. 13 0.5 16. 60 0. 25

' 0. 25 0. 5 16. 60 0. 26 None 0. 50 0. 5 16. 60 0. 24 None The invention has been described in considerable detail with particular reference to certain preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove, and as defined in the appended claims.

I claim:

1. A composition of matter comprising gelatin containing as a coating aid therein a mixture of sodium maleopimarate and a sucrose ester of an aliphatic acid of 8-18 carbon atoms.

2. A composition of matter comprising gelatin containing as a coating aid therein a mixture of sodium maleopimarate and sucrose monomyristate.

3. A composition of matter comprising gelatin containing as a coating aid therein a mixture of sodium maleopimarate and sucrose monooleate.

4. A composition of matter comprising gelatin containand sucrose ester mixture are sufficient to impart to said gelatin a developer spread of not less than about 5.72

60 cm. and a coeflicient of friction of greater than about 65 and an aliphatic monocarboxylic acid ester.

9. In a process of coating a photographic silver halidecontaining element comprising a support and at least one layer comprising gelatin, the improvement comprising adding to said layer a mixture of sodium maleopimarate and a sucrose ester of an aliphatic monocarboxylic acid.

10. The process of claim 9 in which said mixture comprises a sucrose ester of said acid having more than 8 carbon atoms.

11. The processof claim 9 in which said mixture is comprised of proportions of sodium maleopimarate and said ester sufiicient to impart to said gelatin, a developer spread of not less than about 5.72 cm. and a coefficient of friction of greater than about 0.29.

References Cited UNITED STATES PATENTS 8 OTHER REFERENCES Hopkins et al., Journal of the American Pharmaceutical Association, vol. 49, pp. 220-4 (1960).

Osipow, Journal Society Cosmetic Chemists, vol. 7, pp. 5 249-55 (1956).

Merck Index, Sixth Edition, p. 454, Merck and Company, Rahway, NJ. (1952).

Harris 16791 Knox er a1 96. 94 J. TRAVIS BROWN, Primary Examiner 167 91 US. Cl. X.R.

Hagge 61', al. 9694