US 2528395 A
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DIAZOTYPE DRY STRIP FILM Filed Dec. 31, 1946 INVENTOR f1 TTORNEYS Patented Oct. 31, 1950 DIAZTYPE DRY STRIP FILM `Sam Charles Slifkin, Binghamton, N. Y., assigner to General Aniline & Film Corporation, New York, N.v Y., a lcorporation of Delaware Application December 31, 1946, Serial No. 719,399
This invention relates to light-sensitive diazotype layers. More particularly, it relates to such layers on a plastic strip nlm base.
AIn the photographic and reproduction nelds it is often necessaryV to. produce prints which can be transferred` to a'support which latter cannot itself be readily sensitized for photo reproduction purposes. For example, such a case would exist Where it is desired to. permanently afnx a label notice or trade-mark design onto a metal surface of a machine. It has hitherto been possible to do this only by preparing a stock of designs in advance of their use. Such stock designs have been prepared Aby printing on metal plates suitable for mechanical or adhesive attachment to the surface of the machine or other surface where it is desired to display thedesign or by printing on stripping nlm or other type ytransfers also capable of being adhesively anixed to the desired surface. All of these known means for ailixing` or transferring a designto a selected surface are subject to problems of stocking the prepared designs. Any changesy which havel to be made or additions which have to be incorporated into the design introduce additional problems since new stocks have to be accumulated and the cost of old stocks, on the other hand, has to be absorbed.
It has now been discovered that a stripping nlm can be prepared containing` a diazo photo sensitized layer by means of which the design of a trade-mark label, notice or the like can be conveniently reproduced from a master original. Such reproductions can be made immediately before use, thus the design can be kept up to date as corrections or additions can be made on the master original. If it becomes necessary to make major changes in the design onlythe master original need be replaced. The said master original can be made on any transparent or semi-v transparent material such as tracing cloth, plastic nlm, transparentized paper, a stencil design or any similar material wherein the design is opaque to ultraviolet and other actinic light and Ythe background is transmissive of suchlight.
The new strip nlm is prepared by anxing a plastic nlm to a non-absorbent or poorlyfabsorbent support by means of a pressure sensitive adhesive. A composite nlm on support having the form pictured in the accompanying drawing results. This composite is thenphoto-sensitized 4 Claims. (Cl. 95-9) on the plastic nlm side by a diazotype sensitizing solution. This is accomplished by the bead dip method of applying diazotype coatings to plastic nlm surfaces or by spraying or otherwise applying an excess of the sensitizing solution and doctoring off the excess with a doctor blade.
In the preferred bead dip method of coating, the composite strip nlm is drawn across a vessel containing the diazotype coating solution with the plastic nlm side of the composite in continuous contact with the meniscus of the coating solution. The coating solution will contain a solvent or plasticizerfor the plastic nlm material. During the period of Contact of the plastic nlm surface with the meniscus of the coating solution, this solvent or plasticizer will act on the nlm surface to produce a swelling or softening of the nlm. The lm is thereby rendered susceptible to penetration and impregnation with the sensitizing Components of the diazctype coating solution and is simultaneously impregnated with such components. The plastic nlm employedl is preferably cellulose acetate although other cellulose ester nlms such as cellulose butyrate, cellulose propionate or mixtures of such cellulose esters may be used. Other types of plastic nlm such as cellulose ethers, such as cellulose ethyl ether, vinylv yethers and superpolyamides may be used also.
The particular solvent or plasticizer employed in the coating solution to aid the impregnation or penetration of the nlm surface by the lightsensitive components will depend upon' the nlm material employed. Examples of typical volatile organic substances which function as swelling agents when used on the commonly known nlm materials listed above include ethyl alcohol, methyl alcohol, butanol, ethyl lactate, isopropanol, formic and acetic acids, acetone, diacetone alcohol, ethylmethyl ketone and methyl glycol. Softeners or plasticizers which may be used include tricresyl phosphate, tri-phenyl phosphate, tri-acetin and di-chlorhydrin.
The swelling medium or solvent for the plastic nlm may be employed singly, in combination with a Yknown solvent such as water, benzene or toluene or it may be formed from a plurality of the swelling agents or solvents depending upon the nature of the plasticizer and the composition of the plastic nlm. Manifestly,rthere is no set rule for determining the proportions of the' respective ingredients of the swelling medium. However, I have found that a mixture of water and alcohol is particularly effective for this purpose and I prefer to use this mixture in a proportion of two to one by volume.
The adhesive which is used for aixing the plastic film to the non-absorbent base may be any pressure sensitive adhesive of the resin type such as rubber latex, polyvinyl alcohol, vinyl ether resins and polyisobutynol and the support or base material may be any non-absorbent or poorly absorbent material which is preferably sufciently flexible to permit rolling and passage through a printing and developing machine of the type commonly used in exposing and developing diazotypes. Examples of such material are glassine paper, lacquered paper, cellophane, cellulose ester and cellulose ether and film base materials such as those given as examples for the sensitized lm of the composite strip lm.
In the coating solution which is used for sensitizing the strip lm any combination of diazoand azo components which is suitable for 'the preparation of two-component diazotype layers and which wil1 produce the shade desired for the final image may be employed. Diazo compounds which are suitable for such two-component diazotype layers are known to be those which are derived from 1,2 and 2,1-aminonaphthols,p1,4 aminonaphthols and aromatic p-diamines of the benzene series, particularly p-phenylene diamines which are N-mono or di-substituted on one of the amino groups. Examples of such diazo compounds which are commonly used in the production of diazotype images are the diazo derivatives of p-amino N methylaniline; p amino-N-dimethylaniline; p-amino-N-ethylaniline, p-amino-N-diethylaniline, p-amino-N-hydroxyethyl aniline; p-amino N ethyl-N-hydroxyethyl aniline; 4-amino-2-methoxy-l-cyclohexyl aniline; 1-amino-4-(dibrom 26 benzyl)- aminobenzene; p-amino-N-diethyl-m-toluidine; 1amino 3 methyl -4- ethylaminobenzene; 3- aminocarbazole; 1-amino-2-naphthol-4-sulfonic acid and 2-amino-l-hydroxy-3,6naphthalene disulfonic acid.
As examples of suitable azo coupling components, there may be mentioned the sodium salt of 2-amino-S-naphthol-S-disulfonic acid, 2,3- dihydroxynaphthalene or its 6-sulfonic acid derivative, -naphthol-B-disulfonic acid, 2,7-dihydroxynaphthalene, 1,7aminonaphthol,2 -hydroxy-S-biguanide, lamino8-naphthol-3,6di sulfonic acid, l-naphthol-Ll-sulfonic acid, 1- naphthol-3,8disulfonic acid, phloroglucinol, mhydroxyphenyl-urea, acetoacetanilide, 'I -hydroxy- 1,2-naphthimidazole, 7-hydroxynaphthalene-1- biguanide and acetoacetcyclohexyl-amide After the plastic film surface of the strip film composite has been sensitized with the diazotype coating solution, it is dried and stored for use. It may be used to apply a diazotype image to many types of surfaces such as the metal surfaces of machines mentioned above, glass, tile, wood, plaster, or anywhere that an adhesive-back strip film may be applied. In using it, the sensitized surface of the film is exposed to actinic light in the same manner as any diazotype surface under the picture or design to be reproduced. After so exposing the sensitized surface, the image is developed by treatment with ammonia fumes. The strip'film containing the developed image of the design is then stripped 01T of its support and refastened to the desired surface vby means of the adhesive remaining on the underside of thev stripped lm. In another manner of using this diazotype sensitized strip lm, the sensitized plastic film may be stripped from its support, applied to a sheet of metal, wood, or other such surface, and then exposed under the original of the desired pattern and developed by contacting the exposed surface with ammonia fumes. By this method, a dimensionally correct phototemplate may be made which can be subsequently stripped from the metal or wood surface when the necessary work has been completed.
The following examples are given as illustrative of typical coating solutions which may be employed for impregnating the cellulose acetate or other plastic surfaces of the strip lm composite with a diazotype light-sensitized layer. It is understood that the invention is not in any way limited to the materials or proportions given in these examples. The proportions are by weight unless otherwise specified.
Example 1 A composite strip film comprising a cellulose acetate lm adhesively afxed to a glassine support by means of a polyvinyl alcohol adhesive is drawn across the surface of a diazotype coating solution containing the following ingredients:
Water cubic centimeters 100 Isopropanol do- 50 Formic acid grams 3 Citric acid do 3 Phosphoric acid cubic centimeters 1 y Phenylmethyl-pyrazolone grams 1 ZnCl2 salt of lp-diazo-N--ethyl-N-hydroxyethyl aniline grams 7 The surface of the cellulose acetate film is kept in contact with the meniscus of this solution by drawing the strip film across the surface of the coating solution in the form of a curve tangential to the surface of the coating solution. The coated lm is then dried, exposed to light under an original design, and developed by drawing the film through an atmosphere of ammonia fumes. The thus treated film containing vthe developed image of the original is then stripped olf the glassine support and fastened to a desired surface which may be paper, metal, glass or other like surface. The image of the design is reproduced in a red color.
Example 2 A strip film made by adhesively afxing a cellulose butyrate film to a glassine base by means of an adhesive polyisobutanol is sensitized on the exposed surface of the cellulose butyrate film by means of the following Adiazotype coating solution:
Water cubic centimeters Ethyl alcohol do 50 Citric acid grams 10 Thiourea do 4 Formic acid do 3 2,3-dihydroxynaphthalene do 0.5 ZnClz salt of l-diazo-3-methyl-4-diethylaminobenzene grams 7 This coating solution is sprayed onto the surface of the strip lm which is then dried, exposed to light under an original design, and developed in the same manner as in the case of Example 1. The strip film containing the developed image is then stripped off the glassine support and ref fastened by means of the adhesive contained on the under-side of the cellulose butyrate rllm onto a metal surface. The azo dye image of the original design is developed in a deep blue shade.
Example 3 A strip nlm composite made up by adhesiveiy ailxng a sheet of cellulose propionate film onto a glassine support by means oi a Vinylether resin adhesive is sensitized bythe following diazotype coating solution.
Water cubic centimeters 100 Ethyl alcohol do 50 Citric acid grams Thiourea do 4 Form acid cubic centimeters" 10 ZnClz grams 3 Phenylmethyl pyrazolone do 0.5 ZnClZ of p-diazo-diethyl aniline do 8 This coating solution is doctored onto the exposed surface of cellulose propionate lm by means of a trough and doctor blade in accordance with the method generally employed in coating of diazotype papers. The film is then dried, exposed to actinic light under an original pattern and de- Veloped by contacting it with ammonia fumes in the same manner as in the case of Example l. The image is developed in a red shade and the strip lm bearing this image is stripped ofi of the glassine support and refastencd to a metal base by means ofthe adhesive retained on the unsen sitized side of the cellulose propionate lm.
It is understood that any of the diazo compounds orl azo components listed above, or any other diazo compounds or azo components known to the art for use in diazotype layers, may be subas may be necessary for the production of a sta-y ble diazotype layer may be substituted for those speciically mentioned in the examples. Furthermore, any of the swelling agents, plasticizers, and
solvents for the cellulose esters, cellulose ethers details herein described, except as dened in the appended claims.
1. A composition of matter comprising a plastic nlm of the class consisting of cellulose acetate, cellulose butyrate, and cellulose propionate, sensitized on one side with a diazotype layer containing a light-sensitive diazo compound of a pphenylenediamine and an azo dye coupling component, said iilm being afxed on its other side to a glassine support by a pressure-sensitive adhesive of the class consisting of polyvinyl alcohol, polyisobutanol, and vinyl ether resin.
2. A composition of matter comprising a cellulose acetate plastic lm sensitized on one side with a .diazotype layer containing a light-sensitive diazo compound of a p-phenylenediamine and an azo dye coupling component, said lm being ali'lxed on its other side to a glassine support by polyvinyl alcohol adhesive.
3. A composition of matter comprising Ya cellulose butyrate plastic lm sensitized on one side with a diazotype layer containing a light-sensitive diazo compound of a p-phenylenediamine and an azo dye coupling component, said nlm being afxed on its other side to a glassine support A by polyisobutanol adhesive.
or other type of plastic lm commonly used for 1 that purpose may be used in place of the alcohols specically mentioned in these examples to the extent thatthey are compatible in the light-sensitive solution and do not create interfering side reactions.
Since it is obvious that various changes may be made in the coating solution, the method of applying the coating Solution to the carrier and in the production of the strip lm carrier without departing from the nature and spirit of the invention, the invention is not limited to the specc 4. A composition of matter comprising a cellulose propionate plastic nlm sensitized on one side with a diazotype layer containing a light-sensitive diazo compound of a p-phenylenediamine and an azo dye coupling component, `said filmbeing afxed on its other side to a glassine support by vinyl ether resin adhesive.
SAM CHARLES SLIFKIN.
REFERENCES CITED The ioliowing references are of record in the le of this patent: