US3169870A - Photographic gelatin layers containing the salts of various alkyl and alkenyl succinamates as coating aids - Google Patents

Description

Jersey No. Drawing. Filed Dec. 4, 1961, Ser. No. 156,97 3 Claims. (Cl. 9694) v This invention relates to improved gelatin coating compositions containing certain -succinamates as coa ting aids and their. application to base and paper.

In the photographic industry it is frequently desirable to apply two or more gelatin layers tofilm base or paper.

This may be conveniently accomplished by successive coating or by multiple coating as described in U.S. Patent 2,761,791. That patent discloses a method 'of applying Unitcd States Patent 0 a plurality of separate coatings to the surface of a moving Y 7 web simultaneously while still maintaining a distinct layer relationship between the coatings after deposition. Essentially, this method involves continuously forming each fluid composition into a layer of given thickness, bringing these layers into surface Contact prior to the time they are applied to the surface ofthe web and directing them while in combined relation to the point of where they are applied simultaneously tofthe web in the desired orientatioii with no noticeable mixing-or contamination at the interface of the layers. Apparatus for thesimultaneous applicationof multiple coatings is described in U.S. Patents 2,761,417 and 2,761,418; The term successive coating refersto coating a gelatin layer on a support and, before that coating has dried, applying. another gelatin layer thereover. This method of coating a plurality of gelatin layers on a support is also referred to as wet-onwet coating. g

Gelatin coatings applied simultaneously in accordance with the method described .in' the above-identified patent but without the use of a coating aid, are unsatisfactory :in several respects. Crescent-shaped uncoated areas (repellencies) probably attributable to oil impurities in the gelatin are found in the coating. These defects may be about the size of a pinhead with streaks running down from the points of the crescent in a direction opposite to that of the coating. In addition, longitudinal pencil-line streaks and double-edge comets may appear in the coating. Accordingly, a number of coating aids have been tested, some of which have been found toproduce blemishfree coatings. However; the coatings produced with these coating aids when dried have been generally considered unsatisfactory because of surface slickness or inadequate rewettability. Handling problems result from surface slickness while inadequate rewettability causes processin difiiculties.

A number of coating aids have beensuggested to facilitate single-layergelatin coatings. saponin which; when employed in single-layer coatings,

'efiectively suppresses repellencies and yields dried coatings with satisfactory developer wettability and adequate surface roughness. However, in the simultaneous appli:

cation of two or'more gelatin layers to a base or paper,

saponin is ineffective to prevent pencil-line streaks and double-edged comets. Saponin is a naturally occurring substance which varies in quality and composition from A notable example is Ice batch to batch which may. cause an increasein fog or a change in phot'ographic sensitivity. H ence, various synthetic coating aids have been'propos'ed for single-layer inadequate rewettabilityor defects in the coating itself, 3

such as pencil-line streaks or double-edged comets.

We have now found a class of compoundswhich may be employed as coating aids in single-layer gelatin coatings, or simultaneous gelatin coatingoperations to produce blemish-free coatings which, when dried, possess the necessary surface roughness and rewettability. I

One object of our invention is to provide improved gelatincoating compositionscontaining certain succinamates as coating aids. Another objectof our invention. is to provide a plurality of coating compositions which may be simultaneously applied to a base or paper to produce substantially blemish-free coatings having adequate surface roughness and rewettability. Still other objects of our invention will appear herein.

We have now found that by incorporating certain succinamates as coating aids in gelatin coating compositions,

improved single-layer coatings areobtained. We have also found that these succinamate's may be incorporated into a plurality of gelatin coating compositions which J may be coated successively or simultaneously onto film base or paper. The succinamates which: we have found to be useful are indicated in the following formula:

thegroup consisting of alkyl and alkenyl radicals con- (x being 2-5 and y being 1-4, the sum of x and y being 3-9) and--C(CHOH) (CH ),,CH (n being 0 to 3),

R where R is selected from the group consisting of CH CH OH and CH CH CH OH, is selected from,

the group consisting of CH CH OH,

- '-CH CH CH OH, -CH (CHOH) CH OH andthe alkyl radicals containing 2 to 5 carbon atoms and, M is a salt forming radical such asNa, K, NH

Patented Feb. 16, 196.5

and

, description of i above.

coating aids yl or alkenyl sucin the presence of in protein c'oat the dodecenyl radical is a mixture of branched monoole- V fins formed by tetramerizing propene) with a compound selected from the group consisting of 2,2 iminodiethanol;

N-methylglucamine; and l- 2-( 2'-hydroXy) ethOxy-Zeththecoating aids thusproduced are indicated below.

s ntan .A i

I cannonsoi ronnononnonzon I, on oo'oNa' I and a i i on,

onzoononnononnomon ang, HCOONa uineanoN oH 0H omi on o oio'isra V ongoonionlonzonjz I GXZHM COON Q ou' naorrooNn orig n(001120 95 11 ihoniooona ornco is a highly branched monoolefin radical. .-As indicated above, various other alkyl and alkenyl substituted sucjcinarnates may be employed in accordance with this in vention. Representative examples include the followingz' a tetramethylbutylsuccinamic acid, .SOClilIIIl salt; a V

branchedchain-dodecylsuccinamic acid, sodium salt; a

Branched-chain tridecylsuccinamic acid, sodium salt; a

branched-chain 'p'entadecylsuccinamic acid, sodium salt; a

branched-chainhexadecylsuccinamic acid, sodium salti a branched-chain nonenylsuccinamic acid, sodium salt;

- a branched-chain dodecenylsuccin'amic acid, sodium salt;

a branched-chain pentad'ec'enylsnccinamic. acid, sodium salt;,and,, a branched chain hexadecenylsuccinamic acid,

sodium salt. In each of the foregoing compounds, the alkyl or alkenyl radical contains not less thantwo points.

'fof branching. Of-course, the substituents attached to the nitrogen atom in these compounds conform to the general the succinamates of our invention given v The coating materials containing our agent may be of various compositions; However, for general explanation, I

reference Will be made to proteinaceous coating compositions of a photographic nature. Such coatings are illustrated by. gelatin containing various sensitive components to in somedetail inasmuch as it concerns our preferred embodiment and also presents'more problems than certainother coating compositions. That is, whilein the art many kinds of surface-active agents have been added to coating compositions and do facilitate their, 'coating,never,-"

,theless such agents would not be suitable in compositions such as thephotographic coatings under-description since such agents may injure the light-sensitive photographic 15. in appears unnecessary.

fit uanooazonna fly The dodecenyl radical of'the above compounds coni tains not less than two points Tofbranching, and generally application. Y z

mateiials Hence, "it is thought that sho present, our invention would likewise have utility and A sfju'st mentioned, or a medium such as.

or bromide. The emulsionmay likewise contain dyes 1 and'various other materials. Inasmuch as: a description .The structurallformulas of" usual conventional base materials. ticular reference is made to a paper base. A' description rial of this typewould preterahly be usediin the present invention.

ofemulsion coatings is found inthe publication Fonda mentals of Photographic Theory .by;T. H. James and.

George C. Higgins, published in 3. John W. .Wiley & Sons, Inc, Chapter Z, further detailed description here- The. base, to'be coated composed of ,any :ot the of photographicjpaper is found in Kodak DataBool-z, 5th Edition, Kodak-Papers, pages? and4. A basemate- The over-all coating procedures which may be utilized comprise any otfthe standard procedures employed in'the 7 industry. Chief amongfthese'. are the extrusion hopper coatings from which the coating rneltin a single layer coating is'delivered, at a measured rate, orvarious coating melts in a multilayer coating are. delivered simultaneously,

each at a measured rate, to the support so as to give dried.

:- coatings with layers of the desired. thickness in accordanc-e With thel jnethod outlined in US. Patent 2,761,791, A with apparatus-disclosed in U.S. Patent 2,761,417, or

2,761,418. r V r In practicing our invention; the coating composition which it is desired to apply to a film base or paperis prepared in the usual manner. However, at sometime before a the actual coatingoperation thereiis' incorporated into the coatingcompositiona surface-active agent of thepresent invention. 'This'incorporatiodmay be accomplished*ad-- vantag eouslyinthe following "manner: A 2.5% aqueous solution ot the coating aid may be prepared; An amount equal to 0.0410 1.0 gram ,(dry weight) of coating aid 7 from a consideration of the severalspecifie examples which'follow. In these examples a single pelloid coating was applied to-a film base, using the preferre'd coating aids per 454 g. oficoating solution'fis added to'thegelatin- .silver'halide emulsion at any point after the emulsionis in a liquid state, either.before,"during, o ft th lion Of other materials; 1

f A further understanding ot our invention will be had referred to above at a concentration of 0.22 gram per "such as silver salts. This type of composition is referred I j number of uncoated spots. 1 lar coating experiment in 454 g. of wet coating melt, The resultsare shown in the following t'able: v V I Table I 7 p Repellenoies Longitudinal Surfactant on 25 sq. ft. Mottle" .Streaks 'ofQoating, a o VerySllghtr 0' D0. (l .Do.

21- SlightJ 1 In the abovetable, by RepellenciesTiye referto the The Control involved a sirni which no, surfactant'was used;

.A series of experiments were conducted in which a' gelatinrsilver. halide photographic emulsion and, its clear gelatin overcoat were appliedsimultaneously to a paper support using a hopper technique and coating aids in accordance with our invention in each layer. The results are 'shownin thefollowing table:

vving that the present invention functions an environment of lighth sensitive photographic,coatings, it will be apparent 7 that even Where the problem of photographicsensitivityis not photographic'coatings are comprised V gelatin which contains light-sensitive v material comprising a silver salt such as jsilverlchloride In this. invention par- I 53 Table II Concentration of Surfactant, g.

Developer Coeflficient Repel- Surfactant Spread, lencies Per 454 g. Per 454 g. .cm. Friction 2 Emulsion Clear Gelatin 0.13 g 0. 5 8. 55 0.497 None. 0. 25 0. 5 12. G 0. 497 D0. 0. 0. 5 15. 90- 0. 497 Do. 0. 13 0. 5 r 6. 60' 0. 408 None. 0.25 0.5 13. 90 0. 442 D0. 0.5 0.5 4). 08 0. 408 Do. 0.13 0. 5 8.04 0. 276 None 0.25 0.5 9.08 0.276 Do. 0.5 0.5 11. 90 0.276 Do.

One cc. of developer solution is deliveredto a surface of a paper support coated with a photographic emulsion and a clear gelatin coat thereover, and the area which develops in about 30 seconds was measured. This test indicates how effectively an emulsion containing a coating aid of our invention will wet. A developer spread of 4.0 cm. or more is desirable.

2 Two sheets of a paper support were coated with a gelatin-silver halide photographic emulsion and a clear gelatin coating thereover, and one sheet was placed upon the other so that the uncoated side of one paper support was against the coated side of the other paper support.- The coeflicient of friction was measured to determine the sliclrness of gelatin coatings containing the coating aids of this invention. Difliculties occur instacking coated sheets when the coet'dcient of friction is less than about .25.

, 3 The number of uncoated spots on 7.5 sq. ft. of coating.

The occurrence of pencil-line streaks is a persistent defeet in coatings achieved by the simultaneous application of two gelatin layers to a film base or paper. The ability of a coating aid to reduce the incidence of pencil-line in different concentrations, to determine their ability to control pencil-line streaks in simultaneously applied gelatin coatings. The results are shown in Table III.

Table III Surfactant Surfactant Concentration, Saponin grams per pound ill HO one of R and R being H, the other being selected from the group consisting of the alkyl and the alkenyl radicals containing 8-16 carbon atomshaving at least two points of branching; R is selected from the group consisting of --H, CH --CH CH OH and -CH CH CH O-H; R where R is selected from the group consisting of H 6 and -CH is selected from the CH (CHOH) .zCHzOH; U

(x beings-s, y being 1-4,.the"sum-of x and y-being. 3-9 and --C(CH OH) (CH CH n being"0-3);'

. 2. A photographic element comprisin'g a flexible photographic base, a light-sensitive coating thereon containing a gelatin silver halide emulsion, and a clear gelatin coating thereover, at least one of the latter two coatings containing as a coating aid a compound having the folone of R and R being H, the other being selected from the group consisting of the alkyl and the .alkenyl radicals containing 8-16 carbon atoms having at least two points of branching R is selected from the group consisting of H, -CH3, and R where R is selected from the group consisting of H and -CH is selected from the group consisting of --CH (CHOH) CH OH,

(x being 2-5, y being 1-4, the sum of x and ybeing 3-9 and -C(CH2O I-I)2(CH2),1C,H3' (n being 0 3 R4, where R3 is selected from the group consisting'of -CH CH OH and CH CH CH O-H, is selected from",

the group consisting of CH CH OH,

CH (CHOH) CH OH and the alkyl'radicals containing 2 to 5 carbon atoms; and, M is a salt forming sub stituten't, which coating aid provides fthe photographic element with good surface roughness to prevent slippage when sheets of the photographic element are stacked upon one another, and imparts good rewettability characteristics to facilitate development of the photographic element. 1

.3. A gelatin-silver halide emulsion containing as a coating aid a compound having the following formula:

H 0 R, R1( 3- I T R4 m- O0M I I I one of R and R being H, the other being selected from the group consisting of the alkyl and the alkenyl radicals containing 8-16 carbon atoms having at least two points of branching; R is selected from the group consisting R where R is selected from the group consisting of H and -CH is selected from the group consisting of CH (CHOH) CH OH,

(x being 2-5, y being 1-4, the sum of x and y being group consisting of

Claims (1)

1. 3. A GELATIN-SILVER HALIDE EMULSION CONTAINING AS A COATING AID A COMPOUND HAVING THE FOLLOWING FORMULA: