US2110496A

US2110496A - Subbing photographic film

Info

Publication number: US2110496A
Application number: US65873A
Authority: US
Inventors: George S Babcock
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1936-02-26
Filing date: 1936-02-26
Publication date: 1938-03-08
Anticipated expiration: 1955-03-08

Description

March 8, 1938. s, BABCOCK 2,110,496

SUBBING PHOTOGRAPHIC FILM Filed Feb. 26, 1956 IIYDROLYZED CELLULOSE ACETATE AND RESIN CELLULOSE ORGANKZ DERIVATIVE SUPPORT EMUL8ION GELATIN AND CELLULOSE ESTER GELATIN-RESIN-CELLULOSE ESTER MIXTURE GELATIN YZED CELLULOSE ACETATE AND RESIN ORGANIC DERIVATIVE SUPPORT BY W 1 fw/W' 68 M I/M'zZ ATTORNEYS.

20 such treatment. I with a'layer of gelatin, resin, and a cellulose 20 30 ments of the fire underwriters. a synthetic resin. The hydrolyzed ester is one 30 Patented Mar. s, 1938 2,110,496

UNITED-f STATES-PATENT OFFICE -c I SUB I S IiNG rno'ioonarnlc FILM George SQ BabcockQ Rochester, N. Yaassig nor, by

mesne assignments, toEa'stman, Kodak Company, Jersey 'City, N. J 's-corporation ot'New ',Jfil'sgy'. y- ,.g.-j 4 1 v ppn a i6 e uary-26,1936, Serial No. 65,873 v 10 was. (01. 95-4 v This invention relates to photographic mawill appear from the following description of my terials, and, moreparticularly, to methodsi'fo'r invention? I v applying light sensitive emulsions to cellulose I have found that a layer of a cellulose ororganic ester film supports. 1 ganic ester may be applied to a cellulose organic It is well known that a gelatind-silver halide ester film base to which it would' not ordinarily 5 emulsion cannot be applied directly to a cellulose" adhere by mixing with it a synthetic resin, such organic derivative film 'support'A number of as acetone soluble glyceryl' phthalate. I have intermediate or' sublayersfinust be applied bealso found that the subbing properties of a celtween the support and the emulsion and each of lulose organic ester which ordinarily adheres to these layers must adhere to the layer adjoining the film base may, be-improved by mixing it it. The degree of adhesion of the layers must be with gelatin and a synthetic resin in proper properly controlled in order to avoid the formaamounts. 7 tion of a product which is brittle or in which In the accompanying drawing which illustrates the layers peel from the support. If the adhesion in enlarged sectional views three types of film is too great, the film is brittle and the layers crack made according to my invention, Fig. 1 shows a 15 when the film is bent. If the adhesion is too film in which a cellulose organic derivative supslight the layers are likely to peel or strip from port is coated with a layer of hydrolyzed cellulose the support when the film is treated in the deacetate and resin; Fig. 2 shows a film in which veloping or fixingbaths or when it is dried after a cellulose acetate propionate support is coated One method of avoiding these undesirable re organic ester; and Fig. .3 shows a film similar to suits in a photographic film is to coat the cellulose thatof Fig. 1 in which both sides of the support organic derivative support with a layer, of anare subbed and sensitized. other ester, such as cellulose nitrate, to which According to the preferred form of my inventhe gelatin or other 'subcoating layers may be tion a film support of-a cellulose organic ester,

made to adhere. This method, however, has the which may be cellulose acetate or cellulose acedisadvantage that it introduces an inflammable tate propionate, is coated in any suitable manmaterial into the film and produces a product her with a mixture of a hydrolyzed cellulose which, in many cases, does not meet the requireester, such as hydrolyzed cellulose acetate, and

In t e D O app of G y, e which has been hydrolyzed to such an extent that No. 1, filed Ja y 1935, a method has it is not compatible with the ester of which the b n p op s d for subbing cellulose organic ester support is made andwould not adhere to it. The film base and avoiding the use Of cellulose nitrate resin may be any suitable synthetic resin, p05- layers which Co p i pp y example, sessing adhering qualities for the base such as 35 a Cellulose acet Dropionate film 198558116065" acetonesoluble glyptal or polymerized vinyl ace- Siv ly hy olyzed layers of'cellulose acetate pr0 tate. This subcoat is followed by the usual gelap one of the more hydrolyzed layers thus tin layer and the sensitized emulsion layer. The applied is of a Compositmn to which a gelatin following examples illustrate several methods of 40 bing solution can be made to adhere, whereas the producing a fil according to my invention 40 gelatin layer would not adhere to a less hydrolyzed ester. This method requires the application of Example 1 at least three undercoating or sublayers to the support. A film: base of cellulose acetate propionate Itisan object of the present invention to'overwhich has been slightly hydrolyzed and has a 45 come the above mentioned prior art dimculties propionyl content of,16% and an acetyl conand to provide'a method for reducing the number tent of 29%,"is lead through an immersion type of sublayers required to afiix a gelatinemulsion hopper containing the following solution of celto a cellulose organic derivative film base. Anlulose' acetatehydrolyzed to such an extent that other object is to provide a subbing method which its precipitation valuexis about 69%: 5o

avoids the use of cellulosenitrate or other in.- y Y Grams. flammable material in a photographic film. A' Cellulose acetate; -l. 6- further object is to provide a subbing method Ethyl alcoho1 40" which does not result in a brittle productvor one Acetone 160 having loosely adhering layers. Other objects Glyce'ryl-'-phthalateresin'(Glyptal) rr 3 55" This solution is coated. at a linear speed of approximately three feet per minute. The film is then-lead through an appropriate drying appara- -tus which is maintained at a temperature. of

approximately 120-300 1"., where the solvent is evaporated from the surface of the material. The resin and ester coated material is then carried through a second immersion hopper containing a gelatin solution of approximately the following composition which is coated directly on the resin and ester layer:

. Grams Gela in 1.2 Acetic a 7 0.12 Acetone '70 Water m Ethyl alcohol 22.6

The gelatin coated material is then dried at appropriate temperatures after which the usual gelatin silver halide emulsion is applied upon the gel surface by known technic. thuscompleting the film.

Example I! A film base of, cellulose acetate, which has been hydrolyzed to such an extent that its precipitation value is about 90%, is lead through an immersion type hopper containing the fol lowing cellulose acetate and resin, solution in which the cellulose acetate has been hydrolyzed to such an extent that its precipitation value c is about 69%: l

' l Grams Hydrolyzed cellulose acetate '6 Ethyl alcohol 1 4O Acetone a 158 .Glycerylephtha-lateresin." 2

This coating is dried and followed by the gelatin solution and gelatino-silver halide emulsion as described the preceding example. I

ample m 'A fully esterifiedcellulose acetate propionate film base which a precipitation value of -96% is lead through an immersion hopper as described in the preceding examples and' is coated with the following resin and hydrolyzed cellulose acetate solution in which the cellulose acetate has a precipitation value of about 69% Grams Hydrolyzed cellulose acetate I 6 Ethyl alcohol 40 Acetone 156 Glyceryl-phthalate resin 1 1 complished by the presence of the resin in the.

coating, since withoutthe resin, the film showed objectionable brittleness. This coating is dried in the usual way and is followed by asub of gela-, tin and cellulose ester, and the gelatino-silver halide emulsion.- The following examplesillustrate a method ofmaking a film according to this modification ofmyinvention:

' Cellulose acetate propionate 5 This coating is dried in an appropriate manner Example IV I A film base of a cellulose acetate propionaie hydrolyzed to such an extent that the propionyl content is 16% and the acetyl content 29% is coated with a solution of cellulose acetate pro- 5 Gelatin a5 Cellulose acetate propionate 12 Glycerylfphthalate resin 8 This coating is dried and is followed by a solution of gelatin and cellulose acetate propionate of the same composition as that used in the first coating and applied from any suitable solvent. The solid content of this coating is as follows:

Percent Gelatin 06 and is followed by theusual gelatino-siiver halide emulsion, which is coated by known technic to complete the film.

E'mmple V A film base of cellulose acetate propionate having a composition similar to that described in the preceding example is coated with a solution of hydrolyzed cellulose acetate having an apparent acetyl content of 39%, mixed with gelatin 'and a synthetic resin. The solid content of this solution is approximately as follows:

7 Per cent Gelatin 93 Cellulise acetate propionate 4 Glyceryl-phthalate resin 3 Cellulose acetate propionate 15 This coating is dried in an appropriate manner andcoated with the usual gelatino-silver halide emulsion.

'My invention will now be described by reference to the accompanying drawing. As illustrated therein Fig. 1 shows a film made according to the preferred embodiment of my invention in which i0 is a film support of a cellulose organic derivative and is coated with a layer ii ofa synthetic resin and a hydrolyzed cellulose ester such as hydrolyzed cellulose acetate which is in compatible'withthe ester of which the support is made, but compatible with the resin with which it is mixed. This layer is dried as described in thepreceding examples-and is followed by a gelatin layer I2 and an emulsion layer l3.

InFig. 2 which illustrates afilml romeo a- A cording to .thesecond fmodification of invention inwhich a support .of cellulose acetate .propionate is coatedwgwith a layer ll of gelatin. synthetic resin, and a cellulose ester which is a compatible with the ester'of which the support is made; This is followed by a layer II (if-gelatin 1 a'nd' -a cellulose ester and on top of this is coated the usual gelatin layer l3. The -film shown in Fig. 31s a duplitized or double-coated film having a cellulose organic X-ray photography.

My invention is applicabletethe -subbing b: any type of cellulose organic ester film base, such as a, fully esterified or hydrolyzed mixed ester,

' for example, cellulose acetate propionate or cellulose acetate butyrate, or, a simple ester, such as hydrolyzed cellulose acetate. The esters used in the subbing layers may also be, of any composition which meets the requirements of compatibility or lack of compatibility as described above.

Among the artificial resins which may be used according to my invention, a great many materials are available. These include the polyvinyl esters, such as polymerized vinyl acetate which is known, for example, under the trade name Gelva, the preparation oi! which is described in the U. S. Patents No. 1,241,738; No. 1,586,803 and No. 1,710,825. A further type of resin which may be used is the polyvinyl acetal type. These resins are condensation products' of partially or completely hydrolyzed polyvinyl acetate and an aldehyde such as formaldehyde, acetaldehyde, or butyraldehyde and are known as polyvinyl acetals. They are sold under various trade names such as Formvar, and Alvar, the preparation of which is described in Br. Patent 351,082 and in U. S. Patents Nos. 1,955,068 and 1,990,399. A still further typeof resin whiclLI may use are the alkyd resins, which are condensation products of a poly-basic acid and a polyhydroxy alcohol. An example of this type of resin is "Glyptal, which is a condensation product of glycerin and phthalic acid or phthalic anhydride. A still further type of resin is the group known as the Santolites which are condensation products of formaldehyde with aromatic sulfonamides.

Ihave referred to the precipitation value of I a number of cellulose esters in the description of my invention. Precipitation value is the customary test which is used to determine the degree to which a cellulose organic ester has been bydrolyzed. It is carried out as follows for testing a cellulose acetate:

Five grams of thedry cellulose ester are accurately weighed and placed in a wide mouth 12 oz. bottle. To this are added 10000. of acetone (commercial grade of 99% orv better), the mixture is stirred until homogeneous. (The bottle should be closed during the stirring with a rubber stopper fitted with a shaft for the stirrer.) To this dope is added slowly from a pipette and with thorough stirring, 150 cc. of a mixture consisting of 2 parts of distilled water and 1 part acetone by volume. keep the solvents and mixtures at 20 C. wherever volumes are being measured. 1

At the end of the addition of the acetone water mixture, a mixture is obtained containing" 40% water by volume (neglectingcontraction).

in which is suspended the precipitated ester. This is allowed to stand for 12 hours at 2071C. At the end of this time precipitation has reached equilibrium and proceeds no further, and during the same time settling of the precipitate occurs.

25 cc. of the clearest portion (supernatent solu- Care should be taken to the support, .a gelatin layer, and a light-sensitive emulsion layer.

tion) are removed with a pipette. This 25 cc. is centrifuged in stoppered bottles at high speed until the liquid is perfectly clear. Exactly 5 cc. of the clear liquid are removed with a pipette and evaporated to dryness on a tarred watch glass. It W is the weight of the residue in grams the precipitation value which equals the per cent .ester precipitated,

properties when subjected to the usual tests which are described for example in my prior application Serial No. 27,409, filed June 19, 1935. The degree of adhesion of the sub layers according to my present invention is controlled by the composition of the cellulose ester and by the proportion or ester to resin. It is not necessary to rely on the strength oi. the solvent and its action on the film base in order to obtain layers which adhere in suificient degree to the base. A further advantage in the use of a cellulose ester layer directly over the film base is that it seals in the plasticizer which is ordinarily contained in the film base, and therefore results in a better surface to which to apply the following gelatin-containing subbing solutions.

I claim:-'

1. A photographic element comprising a cellulose organic ester support, and in order thereon, a layer comprising a mixture of a. synthetic resin selected from the group consisting of polyvinyl resins and alkyd resins and a hydrolyzed cellulose organic ester, a, gelatin layer, and an emulsion layer.

2. A photographic element comprising a cellulose organicester support, and in order thereon, a layer comprising a mixture of a synthetic resin selected from the group consisting of polyvinyl resins and alkyd resins and a hydrolyzed cellulose organic ester which is incompatible with the support, a gelatin layer, and an emulsion layer.

3'. A photographic element comprising a cellulose organic ester support, and in order thereon, a layer comprising a mixture of a synthetic resin selected from the group consisting of polyvinyl resins and alkyd resins and a hydrolyzed cellulose organic ester, a gelatin layer, and a light-sensitive emulsion layer.

4. A photographic element comprising a cellulose organic ester support, and in order thereon, a, layer comprising a mixture of a, synthetic resin selected from the group consisting of polyvinyl resins and alkyd resins and a hydrolyzed cellulose organic ester which is incompatible with 5. A photographic element comprisingza cellulose organic ester support, and in order'there- -on, a layer comprising a mixture of asynthetic resin selected from the group consisting of polyvinyl resins and. alkyd resins and a hydrolyzed 1 cellulose organic ester, a gelatin layer, and a gelatino-silver halide emulsion layer.

' 6. A photographic elementcomprising a cellulose organic ester support, and in order therevinyl resins andy'alkyd resins and a hydrolyaed' on, a layer comprising a; mixture of a-synthetic resin selected i'rom the group consisting of poly cellulose organic ester which ls-incompatible with the support, a gelatin layer, and halide emulsion layer.

7. A photographic element comprising a fully esterifled cellulose organic ester support, and in order thereon, a layer comprising a mixture 10! a synthetic resin selectsdiirom the group consisting of polyvinyl resins and alkyd resins and a hydrolyzed" cellulose organic ester which is inf compatible with the support, a gelatin layer, and j a gelatino-sllverhalideemulsion layer.

8. A photographic element comprising acellulose organic mixed ester support, and in order thereon,, a layer, comprising a mixture 01' asynthetic resinfselected from the group consisting of polyvinyl resins and alkyd resins and, a hy- 20 drolynedcellulose organic ester which is incoma gelatino-silver patible with the support. a gelatin layer, and a i gelatino-silver halide emulsion layer.

9. A photographic element comprising a 0G1? lulose acetate propionate support, .and-in order thereon, a layer comprising a mixture of a synthetic resin from the group conlilting or polyvinyl resins :and alkyd resins and a by:

cellulose omnic'ester which i'sj incompatible with the who; a gelatin layer, anda geiatino-silver halide emulsion layer. p 10. A photographic element comprising accllulose organicmixed eater-support, and in' order thereon a layu' comprising a mixture or a synthetie resin selected from'the group consistins o! P lyvinyl resins and alkyd resins anda hydrolysed cellulose acetate propionate which is incompatible with the support. a gelatin layer,and a gelatino-silver halide emulsion layer.