US2694639A

US2694639A - Light-sensitive metal base photographic element

Info

Publication number: US2694639A
Application number: US231632A
Authority: US
Inventors: Gale F Nadeau; Clemens B Starck; Carl F Smith
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1951-06-14
Filing date: 1951-06-14
Publication date: 1954-11-16
Anticipated expiration: 1971-11-16

Description

Nov. 16, 1954 G. F. NADEAU ErAL 2,694,639

LIGHT-SENSITIVE METAL BASE PHOTOGRAPHIC ELEMENT Filed June 14, 1951 14 GELA r//v EMULS/olv 13 GELA TIN F19. 1 ,z Pom/Nn Acer/1TE- CELLULOSE NITRATE ,o cAReoxYLATEo coPoLYMER RESIN-POLYvl/VYL ACETATE- TITANIUM ox/DE METAL SUPPORT Ta foLYv/NYL ALCOHOL EMULS/olv 1716 PoLYv/NYL ALcoHoL Fg- 2 '5E- \HYDROLYZED POLYVNYL ACETATE 9\\\\\\\\\\\\\\\\\`\\\\ CELL ULOSE NITRATE l0 '9 TA /oN F193 l? HYDRO/.HE D 10 CELLULOSE ACETATE Gale ENade au Clemens. Sieg/'0k Carl E Smzh JNVENToRs BYO-al' 2,694,639 Patented Nov. 16, 1954 LIGHT-SENSITIVE METAL BASE PHOTOGRAPHIC ELEMENT Gale F. Nadeau, Clemens B. Starck, and Carl F. Smith,

Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application June 14, 1951, Serial No. 231,632

Claims. (Cl. 95-8) This invention relates to light-sensitive photographic elements and more particularly to such elements having a metallic base or support.

In the art of photography, it is well known that the conventional hydrophilic colloid-silver halide emulsion layers require a support such as cellulose ester, resin, paper, metal, etc. Many patents directed to means for adhering the emulsions to such supports have been granted mainly in the field of adhering emulsions to cellulose ester and resin supports.

The prior art would indicate that relatively few problems have arisen when the emulsion is to be adhered to metallic supports. However, we have discovered that in order to obtain optimum adherence and quality in metalbased sensitive elements, it is essential to provide certain adhesive or subbing layers for obtaining the desired adherence of the emulsion to the metal support. This is particularly true when the sensitive elements are to be subjected to abnormal atmospheric conditions such as high temperature and low relative humidity, with conditions are manifest by the formation of fissures in the emulsion layer.

Accordingly, the primary object of our invention is to provide subbing layers for adhering hydrophilic colloid-silver halide emulsion layers to metal supports. Other objects will become apparent from consideration of the following description of our invention.

In general, the objects of our invention are accomplished by providing a metal base or support, such as aluminum, steel, copper, brass, etc., particularly in the form of thin sheets, with two thin subbing layers, the rst comprising a mixture of a light-colored inert filler material, a resinous copolymer, and preferably, but not necessarily, polyvinyl acetate, the second layer being a mixture of polyvinyl acetate and cellulose nitrate. Thus provided with a subbed metal-based element, the desired hydrophilic colloid-silver halide emulsion layer may then be adhered thereto by means of one or more additional organic colloid subbing layers containing polymeric units in common with the colloid vehicle comprising the particular hydrophilic organic colloid-silver halide emulsion y vehicle under consideration.

In the drawings:

Fig. l shows in greatly enlarged cross-sectional view the appearance of metal-based photographic element carrying a gelatino-silver halide emulsion layer adhered to the metal base by means of the subbing layers of the invention.

Fig. 2 is a similar View of a metal-based element carrying a polyvinyl alcohol-silver halide emulsion layer adhered to the base by means of the novel subbing layers.

Fig. 3 is a similar view of a metal-base lm utilizing the subbing layers of the invention for causing adherence of a cellulose acetate-silver halide emulsion to the metal support.

The following examples illustrate preferred methods for adhering hydrophilic organic-colloid-silver halide emulsion layers to metal supports:

Example 1 Per cent Acetone Butyl acetate In this subbing composition the solvents may be replaced by a comparable amount of methylene chloride, but the indicated solvent combination is preferred. In the composition the ratio of the two resins may be varied somewhat, but approximately equal parts by Weight of the two resins are preferred. However, as perviously mentioned, this composition can include only the solid ingredients: resinous copolymer and filler material. The polyvinyl acetate is not an essential ingredient, serving only asa modifier or plasticizer. The essence of the invention is the use of the copolymer'and tiller material as the first subbing layer 11 in conjunction with the second subbing layer 12 of polyvinyl acetate and cellulose nitrate to be described hereinafter. The filler material, titanium oxide, can be varied within reason, a range of from about 25 to 75 per cent by weight of the resins of the filler material being most efficacious. The filler material, titanium oxide, is representative of a class of light-colored inert materials such as barium sulfate, calcium carbonate, zinc oxide, etc., essential to successful operation of our invention. That is, it has been found that while useful products can be made when the filler material is omitted from the subbing formula, the filler material, when used in conjunction with the resinous vehicle, not only provides a white or light-colored background for silver images developed on the metal support, but, which is more important, prevents ow of the subbing layers during drying and shrinking of the emulsion, thus preventing the emulsion from showing shrinkage cracks or skidding. In the formula the viscosity of the particular polyvinyl acetate used is not especially critical as it appears only to alter the viscosity of the subbing composition.

The resinous copolymer indicated in the subbing formula is a carboxylated copolymer of a mixture of vinyl chloride, vinyl acetate, and an ,-ethylenically unsaturated dicarboxylic acid, such as fumarie or maleic acid, preferably one containing about 86 per cent by weight of vinyl chloride groups, about 13 per cent by weight of vinyl acetate groups, and about l per cent by weight of maleic acid groups. In the various iigures of the drawings is shown the position of the subbing layer 11 atlig'tnedi to the metal support 10 by the method just de- SCIl e The first subbing layer 11 s then coated with the second thin subbing layer from the following representative composition:

Per cent Cellulose nitrate 3 Polyvinyl acetate 0.5 Titanium oxide 2.5 Acetone 40 Ethylene glycol monomethyl ether 10 Methyl alcohol 44 In the various figures of the drawings this subbing layer is represented by layer 12.

ln the subbing formula immediately above, the ller material may be omitted, but its presence tends to improve the appearance of the coating. The type of cellulose nitrate used is not especially critical, but it is preferable to use the well known low to medium viscosity highly alcohol-soluble varietyl containing about ll per cent nitrogen. The proportions of polyvinyl acetate and cellulose nitrate in the formula may be varied somewhat, the preferred proportions being from about six to twelve parts of cellulose nitrate per part of polyvinyl acetate.

As pointed out above, the metal support, now having been provided with the two subbing layers of the invention, can be sensitized with a variety of organic hydrophilic colloid-silver halide emulsions. This is accomplished by utilizing a third intervening subbing layer having approximately the same chemical and physical characteristics as the colloid vehicle of the emulsion layer.

Accordingly, 'agelatino silver halide emulsion is applied to the element provided with

subbing layers

11 and 12 as follows:

A third thin subbing'layer 13 was applied to the surface -of sub-hing vlayer u12 `from the composition:

Per cent Gelatin 1.2 Methyl alcohol `87.8 Water '10 Glacial acetic acid 1.0

in whichthe :gelatin concentration maybe varied as desired, for example, between l and 2 per vcent `concentration. Following this, la gelatine-silver halide 'emulsion layer 14 of vthe conventional type was A'coated 'over subbing layer .13. The result was a dilm of .good flexibility free of the .mentioned defects. As will be apparent, suitable antihalation materials, for example, dyes, may :be incorporated into the sensitive llm as desired.

Example 2 Per cent Hydrolyzed polyvinyl acetate .1.5 Cellulose nitrate. `0.5 Ethylene -glycol monomethyl ether l5 Methyl alcohol 75 Water 8 In .this formula the .ratio Vo'f partially r`hydrolyzed polyvinyl `acetate to cellulose nitrate can be varied somewhat, for example, within'the range'of 4from about two to six parts per'part of cellulose nitrate. The hydrolyzed polyvinyl yacetate used :in the "above formula 'contained 37.9% vinyl acetate groups by weight, the remainder being vinyl alcohol groups. While a hydrolyzed polyvinyl acetate of this analysis is preferred, other hydrolyzed polyvinyl acetates varying as much as 10 per cent .in vinyl alcohol `group content can tbe used for .the samepurpo'se.

Per cent Polyvinyl alcohol 1.5 Methyl alcohol '40 Zirconium nitrate (based on weight of lpolyvinyl alcohol) Water 54 Following application .of subbing layer 16, a polyvinyl alcohol-silver halide emulsion layer I7 is coated in a well known manner to provide the Vfinished productshown in Fig. 2 of the drawings.

Example 3 The pre-subbed element prepared as described in Bxample 1 and having subbing

layers

11 and 12 of thefinvention on the metal support v10, layer .11 preferably containing the modifier resin polyvinyl acetate, "is fcoated as shown in Fig. 3 with a subbing layer 18 from the composition .Per cent Hydrolyzed cellulose ester 1-3 Water 10 Ethylene glycol monomethyl ether l5 Methyl alcohol 74 The .hydrolyzed cellulose ester used in the above lcornposition is selected from hydrolyzed cellulose esters containing from about 19 to 33% acyl groups, and preferably consists of hydrolyzed cellulose acetate containing about 27% acetyl. Hydrolyzed cellulose esters' described iu the Salo U. S. Patent 2,110,491 granted March 8, 1938, are suitable for this composition and for the Vcolloid vehicle of the silver halide emulsion layer 19 which is subsequently applied over layer 18. 'The cellulose ester emulsion layer can be applied from solvent systems selected from those disclosed in the 'patent mentioned.

We claim:

l. A light-sensitive photographic element comprising a metal support, adhered directly thereto, a first layer of a mixture of a light-colored inert filler material and a resinous copolymer of a mixture of vinyl chloride, vinyl 4 acetate and an ,-ethylenically unsaturated dicarboxylic acid, 'said 'layer -'being l'substantially free 'of polymerizable material adhered directly to said first layer a second layer of a mixture of polyvinyl acetate and cellulose nitrate, and a hydrophilic organic colloid-silver halide emulsion layer adhered to said second layer.

2. A light-sensitive photographic element comprising a metal support, adhered directly thereto, a'first layer of a mixture of a light-colored 4inert filler material, polyvinyl acetate and a resinous copolymer of vinyl chloride, vinyl acetate `and an rogt-ethylenically unsaturated dicarboxylic acid, said layer being substantially free of p'olymerizable material, .adhered directly to said first .layer a second layer of a mixture of polyvinyl acetate and cellulose nitrate, and a hydrophilic colloid-silver halide emulsion layer adhered to .said second layer.

3. A light-sensitive photographic element comprising a metal support, adhered directly thereto, a first layer of amxture ofa light-colored inert filler material, 'polyvinyl acetate and .a resinous `copolymer containing about 86% by weight of vinyl chloride groups, about 13% by weight of 'vinyl acetate groups, 'and about 1% by weight of maleic acid groups, said layer being substantially free of polymerizable material, adhered directly to said first layer 'a second llayer of a mixture 'of polyvinyl acetate and cellulose nitrate, and a hydrophilic 4organic colloid-silver halide emulsion layer adhered to said second layer.

4. A light-sensitive photographic element comprising 'a metal support, adhered directly thereto, a first layer of a mixture of a light-colored Yinert filler material, polyvinyl acetate and a resinous 4copolymer containing about 86% by weight of vinyl chloride groups, about 13% by weight of Vinyl acetate groups, and labout 1% by weight of vmaleic acid groups, lsaid layer being substantially free of `polymerizable material, adhered directly to ysaid first layer aisecond layer of a ymixture of polyvinyl acetate vand cellulose nitrate, and a gelatine-silver halide emulsion adhered Eto said 'second layer by means of a gelatin layer.

5. .A ,light-'sensitive .photographic yelement comprising a metal support, adhered directly thereto, a yfirst layer o'f a mixture of a light-colored :inert filler material, polyvinyl acetate and a resinous copolymer containing about 86% by weight of vinyl chloride groups', about 13% yby weight of vinyl acetate groups, and about 1% by weight of maleic acid groups, said layer being substantially free of -polymerizable material, adhered directly to said first layer a second layer of a mixture of polyvinyl acetate and cellulose nitrate and a polyvinyl alcohol-silver halide emulsion layer adhered to said second layer by means of a layer of partially hydrolyzed polyvinyl acetate.

6. A light-sensitive photographic element comprising a metal support, adhered directly thereto, a first layer of a mixture of a light-colored inert filler material, polyvinyl acetate and a resinous copolymer containing about 86% by weight of vinyl chloride groups, about 13% by weight of vinyl acetate groups, and about 1% by weight of maleic acid groups, said layer being substantially free of polymerizable material, adhered directly to said first layer a second .layer of a mixture of polyvinyl acetate and cellulose nitrate, and a hydrophilic cellulose organic acid ester-silver halide emulsion layer adhered to said second layer by means of a hydrophilic cellulose ester layer.

7. A light-sensitive photographic element comprising a metal support, adhered directly thereto, a first layer of va mixture of approximately equal parts by weight of polyvinyl acetate and a resinous copolymer containing about 86% by weight of vinyl chloride groups, about 13% by weight of vinyl acetate groups and about 1% by weight of maleic acid groups together with from about 25-75% by weight of resin of a light-colored inert filler material, 'said layer being substantially free of polymerizable material, adhered directly to said first layer a second layer of a mixture of from about 6 to l2 parts of cellulose nitrate per part of polyvinyl acetate, and a gelatino-silver halide emulsion layer adhered to said second layer by means of a gelatin layer.

8. A light-sensitive photographic element comprising an aluminum support, adhered directly thereto, a first layer of a mixture of approximately equal parts by weight of polyvinyl acetate and a resinous copolymer containing about 86% by weight of vinyl chloride groups, about 13% Vby weight of vinyl acetate groups and about 1% by weight of maleic acid groups, together with from about 25-75% by weight of resin of a light-colored inert filler material, said Alayer -beingsubstantially free of polymerizable material, adhered directly to said rst layer a second layer of a mixture of from about 6 to 12 parts of cellulose nitrate per part of polyvinyl acetate, and a gelatino-silver halide emulsion layer adhered to said second layer by means of a gelatin layer.

9. A light-sensitive photographic element comprising a metal support, adhered directly thereto, a rst layer of a mixture of approximately equal parts by weight of polyvinyl acetate and a resinous copolymer containing about 86% by weight of vinyl chloride groups, about 13% by weight of vinyl acetate groups and about;1% by weight of maleic acid groups together with from about 25-75% by weight of resin of a light-colored inert filler material, said layer being substantially free of polymerizable material, adhered directly to said rst layer a second layer of a mixture of from about 6 to 12 parts of cellulose nitrate per part of polyvinyl acetate, a third layer of a mixture of from about 2 to 6 parts of partially hydrolyzed polyvinyl acetate per part cellulose nitrate adhered directly to said second layer, and a polyvinyl alcohol-silver halide emulsion layer adhered to said third layer by means of a layer of polyvinyl alcohol.

10. A light-sensitive photographic element comprising a metal support, adhered directly thereto, a rst layer of a mixture of approximately equal parts by weight of poly- 25 vinyl acetate and a resinous copolymer containing about 86% by weight of vinyl chloride groups, about 13% by weight of vinyl acetate groups and about 1% by weight of maleic acid groups together with from about 25-75% by weight of resin of a light-colored inert ller material, said layer being substantially free of polymerizable material, adhered directly to said first layer a second layer of a mixture of from about 6 to 12 parts of cellulose nitrate per part of polyvinyl acetate, and a hydrophilic cellulose organic acid ester-silver halide emulsion layer adhered to said second layer by means of a layer of hydrolyzed cellulose organic acid ester of approximately 19 to 33% acyl content. i

References Cited in the tile of this patent UNITED STATES PATENTS Number Name Date 2,362,580 Nadeau et al Nov. 14, 1944 2,398,056 Staud Apr. 9, 1946 2,411,590 Powell Nov. 26, 1946 2,483,465 Johnson Oct. 4, 1949 2,527,263 Hart Oct. 24, 1950 2,569,954 Ruebensaal Oct. 2, 1951 FOREIGN PATENTS Number Country Date 600,039 Great Britain Mar. 30, 1948

Claims

1. A LIGHT-SENSITIVE PHOTOGRAPHIC ELEMENT COMPRISING A METAL SUPPORT, ADHERED DIRECTLY THERETO, A FIRST LAYER OF A MIXTURE OF A LIGHT-COLORED INERT FILLER MATERIAL AND A RESINOUS COPOLYMER OF A MIXTURE OF VINYL CHLORIDE, VINYL ACETATE AND AN A,B-ETHYLENICALLY UNSATURATED DICARBOXYLIC ACID, SAID LAYER BEING SUBSTANTIALLY FREE OF POLYMERIZABLE MATERIAL ADHERED DIRECTLY TO SAID FIRST LAYER A SECOND LAYER OF A MIXTURE OF POLYVINYL ACETATE AND CELLULOSE NITRATE, AND A HYDROPHILIC ORGANIC COLLOID-SILVER HALIDE EMULSION LAYER ADHERED TO SAID SECOND LAYER.