US2600831A - Light-sensitive silver halide photographic elements - Google Patents

Description

June 17, 1952 W. D. BALDSIEFEN LIGHT-SENSITIVE SILVER HALIDE PHOTOGRAPHIC ELEMENTS Filed July 26, 1949 GELATIN SILVER HALIDE CELLULOSE ACETATE BASE NON-HALATION DYE GELATIN AND No-p-TER.- OCTYL-PHENOXY ET OXY ETHYL SULFONATEv rra GELATIN AND Na.- -TER-OCTYL-PHEOXY ETHxY ETHYL SULFONA GELATIN SILVER HALIDE CELLULOSE ACETATE BASE GELATIN AND Nu- -TER-ocTYI.- PHENoxY ETHoxY ETHYL s LFoNATE i., GELATIN sILvER HAUDE m,4!'f cELLULosE AcETATE BASE GELATm SILVER HALIDE F G. 3.

wIlWlWWIllllI/B GELATIN SILVER HALIDE CONTAINING Nc1p-TER.OCTYLPHENOXY ETHOXY ETHYL SULFONATE CELLULOSE FILM BASE GELATIN SILVER HALIDE CELLULOSE ACETATE BASE NON-HALATION DYE, GELATIN, GLYOXAL AN NGpTER.OCTYL-PHENOXY ETHOXY ETHYL SULFONATE I IN1 LEYTOR. WALTER DEWEY ALDs/EFEN A TTORNE Y Patented June 17, 1952 UNITED STATES Meur oFFIcE LIGHT-SENSITIVE SILVER HALIDE PHOTO- GRAPHIC ELEMENTS ware Application .luly 26, 1949, Serial No. 106,962

(Cl.A 95-8) 6 Claims. 1

The invention relates to photographic elements, an outer Water-permeable layer or stratum of which has improved surfacev characteristics. More particularly','it relates to photographic films and paperswhich have an outer light-sensitive, anti-abrasion and/or non-halation layer" which has improved'surface characteristics and other usefulpro'perties. It also relates to a process of coating vphotographic films and papers.

lhotographic films and papers are generally manufactured in the form ofcontinuous sheets orv webs which are provided with various coatings from predominantly aqueous "solutions The coatings are dried .byv passing the coated web through a chamber maintained'at an elevated temperature. This is generally 'accomplished by festooning so that the length of thev chamber can be kept'within reasonable limits.4 'The coatings which generally consist'of a Water-permeable oolloid which serves as a binding agentfor the silver halides, anti-'hallation dyes or pigments, etc., are quite smooth and when the film or` paperis vagain "passed through the drying chamber With the coated surface'in contact With the festoonin'gsupports, tend to slip with damage to the coated sheet or web. Saponiu is generally used in the coating solutions in 'order to facilitate the spreading of the coatings, but it is not always uniform in properties and what is more serious Washes out during photographic processing operations which causes ."waterspots which are caused by non-*wetting by Vsubsequent processing baths. Thesew'ater spots which are present in negative lms, etc., serious- 1y. aifect the quality of the resulting positive prints. Various surface active wetting agents have been proposed to facilitate spreading of gelatin silver halide layers,"'antihalation layers and the like but they render the surfaces smooth so'that slipping on the festooning supports becomes a real problem.V

An object of this invention is to improve the art ofY coating continuous lengths of photographic films and papers. A further object is'to provide coatings for photographic elements which have improved noni-Slipping "surface characteristics. A still further Yoltject'is to provide photographic elements with Water-permeable coatings Which have good uniform rewetting characteristics. Still other objects will be apparent from the following' detailed description of the invention.

' It has been found that improved photographic films and papers can'be made byincorporating in an outer water-permeable colloid light-sensitive silver halide layer, a Water-permeable colloid anti-abrasion layer on a water-permeable backing or anti-halation layer or in a plurality of such layers a salt of an alkyl-substituted aryloxy alkylene ether sulfonate of the general formula:

i. where R is an alkyl radical of 4 to l2 carbon atoms, 'n is a cardinal number from 1 to 2 and M is an alkali metal or ammonium.`V R may be straight chain or branched chanbutyl, amyl, hexyl, heptyl, octyl, nonyl or decyl. The radical n is preferably 1 and R p-tertiary octyl.

- layer in question.

A coating solution for a non-halation backing layer was prepared by dissolving 400 grams of gelatin and 15 grams of nigrosine (Colour Index No. 865) in sufficient water to'make 10 liters. To this solution there was added 5 grams of sodium p-tertiary-octyl phenoxy ethoxy ethyl sulfonate of the'formulai (E Hg (IZIIS @appara-50-oHToHz-o-CHZ-onrsoNa om om This material Was then coated onto a cellulose acetate film baseV l las shwnin l'g'igl 1 `ofthe drawing to form non-'halation' layer 2` which was dried in the manner knownV to thea'rt. A'gelatino-silver halide emulsion layer 3l 4was 'then coated from'an aqueous dispersionon 'the bpposite surface of the support.` During` this latter operation no difficulty was'encountered with the film slipping from the festooning "supports,V due to slipperiness of the` non-halation l'ais'fer'.'Y Example II A gelatine-silver halide emulsion layer 5 was coated cinto a Vcellulose acctate'iil'm base d" as Shown in Fig. 2 of the drawing and dr'jicl.n 'ro 10,000 grams of an anti-abrasion overcoating solution containing 200 grainsof 'hard gelatin dissolved in 9,800 gramsv gf Water, there tvgsfdded 2 grams of sodium p-tertiary octylphenoxy ethoxy ethyl sulfonate having the formula given in Example I and the resulting solution was coated onto the silver halide emulsion layer to form antiabrasion layer 6 and dried. A sample of this material was then exposed 'and processed in a developing bath containing 2 grams of metol, 5 grams of hydroquinone, 100 grams of sodium sulfite and 6 grams of borax dissolved in sufficient water to make a total volume of the solution 1 liter. It Was observed that the material could be rapidly plunged into the solution without the formation of air bubbles on the emulsion surface, and that the solution wet said surface completely, thus obviating the formation of Water-spots in the processed material.

Example III A continuous length of photographic fllm prepared as in Example II was coated on the back side with another gelatino-silver halide emulsion layer, and passed through a drying chamber. This film is shown in Fig. 3 of the drawing and consists of cellulose acetate film base 4 which has superimposed on one surface gelatin silver halide emulsion layer 5 on which is superimposed gelatin layer 6 containing sodium p-tertiary, octyl phenoxy ethoxy ethyl sulfonate and on the reverse side of the film base is gelatin silver halide layer 1. During this latter coating operation no difficulty was encountered because of slippage of the material during its travel in festoons through the drying.

Example IV To 10,000 grams of a gelatino-silver halide emulsion containing approximately 1600 grams of solids there was added 8 grams of sodium p-tertiary octylphenoxyethoxyethyl sulfonate having the formula set forth in Example I; the emulsion Was then coated on a cellulose film base 8 as shown in Fig. 4 of the drawing in the manner known in the art to form layer 9. It was observed that the emulsion coated smoothly and with uniform adherence to the base. It was found that the emulsion surface was wetted instantly during the processing operations, and that no spots were visible when the processed lm was finally dried.

Emample V A continuous length of cellulose acetate lm base 2 as shown in Fig. 5 of the drawing was coated on its back surface with an aqueous solution made by dissolving 400 grams of gelatin, grams of nigrosin in sufiiciet water to make 10 liters of solution. To this solution there was added 1.2 grams of glyoxal and 5 grams of sodium p-tertiary-octyl-phenoxy ethoxy ethyl sulfonate having the formula set forth in Example I and resulting layer I was dried in a tunnel provided with festooning supports. The front surface of the lm base was then coated with a sliver iodo bromide emulsion layer 3 from asolution of the type described in Example II and dried in like manner. The film had the advantage that the surfaces did not slip on the festooning supports. In addition, the sodium p-tertiary octylphenoxy ethoxy ethyl sulfonate did not wash out during processing and resulted in negative pictures which were free from water spots. The glyoxal, moreover, prevented reticulation of layer I' during processing.

The above coatings were made under conditions that no actinic light exposed the light-sensitive silver halide coatings.

,4 In place of the specific anti-halation dye of the foregoing examples there may be substituted one or more other dyes or pigments or colloidal silver. The particular dye or dyes, etc., used depends on the characteristics of the emulsion. The anti-halation material should be absorptive of light of wavelengths to which the emulsion is sensitive. Suitable additional dyes include:

Auramine (C. I. 655) Helianthin (C. I. 142, 146) Brilliant yellow S (C. I'. 144) Chrysoin (C. I. 148) Acid blue black (C. I. 246) Rhodamine (C. I. 749, '750, '751, '146, 753, 761, r163) Fuchsin (C. I. 677) Safranine G (C. I. 841) Ponceau 6R (186) Crocein scarlet (C. I. 277, 251, 286, 252, 291, 183) Azorubin (C. I. 179) Safranine O (C. I. 841) Ponceau 2R (C. I. 79)

Spirit soluble nigrosine (C. I. 864) Metanil yellow (C. I. 138) Acid magenta O (C. I. 692) The C. I. numbers in the foregoing table refer to Colour Index numbers, the Colour Index being the Society of Dyers and Colourists Colour Index, edited by F. M. Rowe, published by the society, Bradford, Yorkshire, England.

Similarly in place of gelatin as the waterpermeable colloid other such materials may be used. Among such materials are albumin, casein, agar agar, polyvinyl alcohol, hydrolyzed ethylene/vinyl acetate copolymers, polydioxolanes, etc.

The, invention is not limited to the use of cellulose acetate film base as stated above, but can be used with practically any type of transparent film or paper e. g., baryta or resin coated paper; or film composed of polyamides, cellulose nitrate, polyvinyl acetals, cellulose propionate, cellulose mixed esters, cellulose ethers, vinyl chloride and copolymers, styrene, acrylonitrile and copolymers, polyesters, vinyl acetate and copolymers, vinyl fluoride and copolymers, polyvinyl alcohol; transparentized paper, etc.

Sensitizing dyes and other emulsion adjuvants may be added to the above emulsion layers without their function being affected by the alkyl substituted aryloxy alkylene ether sulfonates. This is particularly advantageous in the case of the so-called duplicoated photographic elements, where an emulsion layer may be sensitized to one portion of the spectrum, while the emulsion layer on the opposite side of a film base may be sensitized to another portion of the spectrum, or may not be especiallysensitized at all. The agents of Formula I are included in at least one, and preferably both of the emulsion layers, to facilitate coating and subsequent processing. The principal advantage of the invention, however, is that it allows the manufacture of such a double coated element, without the danger of waste caused by the element slipping off from the festooning supports on to the floor of the drying tunnels.

A further advantage over saponin is that uniform results can be obtained. The former being a naturally occurring material often varies in properties.

As many Widely different embodiments of this invention can be made without departing from the spirit and scope thereof, it is to be understood that the invention is not to be limited except as defined by the claims.

What is claimed is:

1. A photographic element comprising a support and a light-sensitive silver halide emulsion layer said element having at least one waterpermeable outer layer which contains a small amount of a compound of the formula:

3. A photographic element comprising a transparent flexible lm base bearing a light-sensitive colloid silver halide emulsion layer, a waterpermeable colloid anti-abrasion layer on said emulsion layer and a layer of a water-permeable colloid containing an anti-halation material on the reverse surface of the base at least one of the latter two layers containing a small amount of a compound of the formula:

Q (o-om-cHm-o-oHz-CHZ-som wherein R is an alkyl radical of 4 to 12 carbon atoms. n is a cardinal number from 1 to 2 and M is a member taken from the group consisting of alkali metals and ammonium.

4. A photographic element comprising a transparent exible film base bearing a light-sensitive colloid silver halide emulsion layer, a waterpermeable colloid anti-abrasion layer on said emulsion layer and a layer of a water-permeable colloid containing an anti-halation material on the reverse surface of the base at least one of the latter two layers containing a small amount of a compound of the formula:

CH; CH: CHV-CHT- O-CHg-CHz-O-CHVCHz-SOaNa OH: Ha

5. A photographic element comprising a transparent flexible film base bearing a gelatino silver iodo bromide emulsion layer on one surface, a gelatin anti-abrasion layer on said emulsion layer and a layer of gelatin containing an anti-halation material on the reverse surface of the base each of the two latter layers containing a small amount of a compound of the formula:

and a small amount of glyoxal.

6. An element as set forth in claim 5 wherein the anti-halation material is acid Magenta O.

WALTER DEWEY BALDSIEFEN.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,946,635 Murray et a1 Feb. 13, 1934 2,115,192 Bruson Apr. 26, 1938 2,118,059 Slack et al. May 24, 1938 2,143,759 Bruson Jan. 10, 1939 2,287,807 Kendall June 30, 1942 2,400,532 Blake May 21, 1946

Claims (1)

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT AND A LIGHT-SENSITIVE SILVER HALIDE EMULSION LAYER SAID ELEMENT HAVING AT LEAST ONE WATERPERMEABLE OUTER LAYER WHICH CONTAINS A SMALL AMOUNT OF A COMPOUND OF THE FORMULA:

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