Патент USA US2403533код для вставки
July 9, 1946- F. J. KASZUBA 2,403,533 NONSTATIC PHOTOGRAPHIC FILM Filed Aug. 1s, 1945 @j 3 / [Mms/olv „9 / GMAT/NE Juas/NG ¿A yff? \ fìnv/ 5,455 INVENTOR HP0/wf .I /1//15205/1 ATTO R N EY Patented July 9, 1946 2,403,533 UNITED STATES PATENT oFFlcE 2,403,533 NONSTATIC PHOTOGRAPHIC FILM Frank J. Kaszuba, Binghamton, N. Y., assigner to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware Application August 18, 1943, Serial No. 499,037 ’ 10 Claims. (Cl. 95-9) l 2 The present invention relates to the manufac ture of anti-static articles and is particularly directed to the production of sheets or ñlms hav hydride condensation products, casein sheets. ing anti-static properties valuable for use as gelatin and the like. ' The non-static material which I employ is, as stated, the intermolecular polycondensatlon photographic films. product of a dibasic acid or anhydride and a One of the principal objects of this invention is hydroxy amine. The dibasic acid may be either to provide moulded articles which have proper an aromatic acid such as phthalic acid or an ties which prevent defects and avoid diiiiculties hydride, a saturated aliphatic acid, succinic or caused by the accumulation of static electricity adipic acid or their anhydrides, or an unsatu on such articles. Additional objects will be ap 10 rated aliphatic acid such as maleic or fumarie parent from the detailed description which acid or their anhydrides, The hydroxy amine may be either a monohydric or polyhydric sub follows: In the accompanying drawing Figs. 1, 2, 3 and stance; suitable monohydric amino alcohols are 4 are diagrammatic sections of three speciñc Z-amino, y2 methyl, 1 propanol and 2 amino, 1 embodiments of the present invention as applied 15 butanol. Suitable polyhydroxy amines are 2 to photographic iilm. It is well known that amino, 2 methyl, 1,3 propandîol and tris (hydroxy sheets or ñlms and- other moulded articles manu methyl) amino methane. It should be under factured from electrifiable highly polymeric stood that the foregoing polybasic acids and hy droxy amines are speciiically mentioned merely colloids such as cellulose derivatives, polyvinyl compounds, albumen derivatives such as gelatin 20 as illustrative of suitable compounds and that the broad class of polybasic organic acids and and casein, easily become charged with static hydroxy amines are operative for the present electricity. This property is frequently quite invention. troublesome. For instance, in the case of photo The non-static resin may be prepared by mix graphic films, the photographic emulsion layer is liable to so-called static markings which are 25 ing in suitable lproportions a dibasic organic acid and a hydroxy amine and heating until esteri capable of development and thus spoil the film. ñcation, amidation and imidation reactions It is also undesirable in very thin films of elec take place. The proportions of the ingredients trifiable highly polymeric colloids such as poly may be Varied Within fairly Wide limits. Thus vinyl chloride or acetyl cellulose which are used in the manufacture of cigarette tips and numer 30 I have found that suitable non-static resins may ous uses in the textile field. When these articles receive static charges they tenaciously adhere to non-conductors and can be removed there from without injury only with greatest difficulty. I have discovered that moulded articles of electri?iable highly polymeric colloids may be made non-static by incorporating in such ma be produced when the molar proportions are in the range of 1 to 3 mols of the hydroxy amine to 3 to 1 mols of the polybasic organic acid. These resins per se do not form a part of the present invention, their preparation is not there fore described in complete detail here. Suitable methods for their preparation are disclosed in the literature, thus, Xthe preparation of several terials a relatively minor amount of resin of the resins falling Within the class which are em type obtained as the intermolecular polycon ployed in accordance with the present invention densation product of a dibasic organic acid or 40 is disclosed in the Journal of American Chem anhydride and a hydroxy amine. This anti istry Society, vol. 6l, page 3381 (1939), and the static resin may either be incorporated in direct methods therein described are applicable gen admixture with the electriflable highly polymeric erally to producing resins of this class. colloid or may be applied to one or both surfaces thereof as a separate layer. It should be noted that the resins obtained by reacting a monohydroxy amine with a dibasic acid or by reacting a polyhydroxy amine with phthalic acid are thermoplastic rather than Many materials used for the production of ñlms and sheets are electriñable highly poly merio colloids and are rendered non-static in thermosetting. These thermoplastic resins are accordance with the present invention. Typical 50 frequently desirable since they do not require the examples of such electrifiable highly polymeric rigid control in preparation which is necessary colloids are: cellulose derivatives, as cellulose in -the case of the thermosetting types of resins. acetate and cellulose nitrate, regenerated cellu They are also frequently preferable from the lose and the like, polyvinyl compounds such as use standpoint since the thermoplastic resins are esters (polyvinyl chloride) polyvinyl alcohol, an 55 not affected adversely in numerous process steps 2,403,538 4 to which the moulded article in which they are densation product of 2 amino, 2 methyl. 1,3-pro incorporated are subjected, such as drying steps pandiol and phthalic anhydride. This gelatin and the like. subbing solution was employed for coating photo The accompanying drawing shows the inven graphic ñlms in the usual manner on both sides tion applied to a photographic film. In Figure of the film and producing X-ray films as illus I the support I is made from an electrifiable high trated in Fig. II and on only one side of the film polymeric colloid. for instance, cellulose acetate as illustrated in Fig. I. The films were subse with the addition of a minor amount of the quently coated with a photographic emulsion in intermolecular polymeric product of a dibasic the usual manner and all the films were found acid and a hydroxy amine. It should be noted 10 to have excellent anti-static properties. Similar that the non-static resins of the type employed films were produced using the intermolecular in accordance with the present invention are polycondensation product of 2 amino, 1 butanol among the few resins which are compatible with and maleic anhydride and the films obtained were cellulose acetate. The support I bears a con found to have excellent anti-static properties. ventional gelatin subbing layer 2 and a light 15 sensitive layer I such as a gelatino-silver halide emulsion. , . Example 3.--The intermolecular polycondensa tion product of 2 amino, 2 methyl, 1,3 propandiol and maleic anhydride was incorporated in a cel In another embodiment of the present inven tion illustrated in Figure II the support I is made from an electrifiable high polymeric ccllcid, for the same manner. instance, cellulose acetate which may or may not vsolution and photographic emulsion in the known be impregnated with a minor amount of a non static resin oi the type employed in the present invention. This support I is coated on both sides lulose acetate iilm dope and the mixture cast in The thus obtained film base was coated' with conventional gelatin subbing manner and the photographic iilm which was similar to the film illustrated in Fig. I thus ob tained was found to have excellent anti-static with a gelatin subbing layer 2 in which is in 25 properties. corporated a minor amount, generally about 12% It should be understood that the foregoing ex of the solids content of a non-static resin, a con amples are illustrative only of the present inven ventional gelatino-silver halide emulsion light tion and this invention is not limited to such ex sensitive layer 3 is supported on the subbing layer amples. Other resins which I have employed and 2. It should be noted that the resins employed 30 which impart excellent anti-static properties to in the present invention are among the few that photographic films are the intermolecular poly are compatible with gelatin subbing layers comv monly used in photographic films and thus the present invention is particularly valuable for the production of X-ray films in which, in accordance 35 with conventional practice, both sides of the film are coated with a light sensitive layer and a gelatin subbing layer. condensation product of tris (hydroxy methyl) amino methane and phthalic anhydride, also the intermolecular polyccndensation product of 2 amino, 2 methyl, 1 propanol and adipic acid. As indicated above, various modifications may be made `in the present invention. Specifically, the anti-static resin may be incorporated in the In the form a film illustrated in Fig. III the film finished photographic film in several manners. It base I which may be cellulose acetate is coated on 40 may be admixed directly with the film base, it may one side with a gelatin subbing layer 2 to which in be applied in admixture with a conventional turn has been applied a conventional gelatine gelatin subbing layer, or in admixture with a layer silver halide emulsion light sensitive layer 3, on applied for some special purpose, for instance, an the other side of the iilm base has been applied anti-halation layer or it may be applied as a sep an anti-static layer 4 of the intermolecular poly 45 arate layer or it may be applied in any combina condensation product of a polybasic organic acid tion of these manners. Generally, I prefer to in and a hydroxy amine. corporate the anti-static resin in either the film Another possible form of film embodied in the base dope, or in the conventional gelatin subbing present invention is illustrated in Fig. IV. As layer, since by so doing the iinished photographic shown there the film base I is coated on one side 50 film will be anti-static, but a separate processing with a conventional gelatin subbing layer 2, which step to impart such non-static properties thereto in turn is coated with an anti-static layer 4 of the is unnecessary. Various other modifications will intermolecular polycondensation product of a pol be apparent to those skilled in the art. ybasic organic acid and a hydroxy amine. A con As heretofore stated the anti-static resins em ventiona1 gelatino-silver halide emulsion light 55 ployed in accordance with the present invention sensitive layer 3 is applied to the anti-static are not claimed as novel per se and it should be layer 4. understood that these resins may be modified in The following examples illustrate the present various ways by suitable treatment. Thus their invention: molecular Weight may be increased and con Example 1.-The intermolecular polycondensa 60 sequently their melting point raised by distillation tion product obtained by reacting molar propor in a high vacuum or by distillation of a solution tions of 2 amino, 2 methyl, 1,3 propandiol and cf the resins in a high boiling, water imiscible phthalic anhydride was dissolved in a suitable solvent (an acetone-methanol mixture) so as to solvent (e. g. isophorone). The chemical groups may be modified, for instance, by acylation of any form a 0.2% solution of the resin. This solution 65 free ---OH, _NH2 or ---NH groups or by ester iflcation of free carboxyl groups. If the amino film of cellulose acetate. and the film was subse groups are removed the product becomes more quently coated on its other side with a conven soluble in alkali while if the hydroxyl groups are tional gelatin subbing layer and with a photo removed the amino group is more active. Like graphic emulsion. 'I'he film which is similar to 70 wise, mixtures of several polybasic acids and/or that illustrated in Fig.'IV was found to have ex amino alcohols or diols may be employed. The was applied in known manner to one side of a cellent anti-static properties. Example 2.-A gelatin subbing solution con taining about .7 gm. of gelatin- per 100 cc. was mixed with 0.1 gm. of the intermolecular polycon degree of polymerization may be controlled by in corporating minor amounts of mono functional acids, alcohols or amines. Also by employing an unsaturated dibasic acid the double bond may be 2,403,533 5 combined with l,various agents to >impart speciai 6 of the intermoleoular polycondensation product properties to the product. Thus the sulfonic acid - of an organic polybasic acid and a hydroxy pri groups may bej introduced by treatment with mary mono amine and a layer of a photosensitlve sodium sulñte orj bisulñte oran amino derivative emulsion thereon. may be obtained` by~treatment with liquid am 6. An anti-static laminated photographic ñlnr monia. -By such treatment the water solubility 6 which comprises a base of an electriflable highly7 and 'conductibility ofthe non-static resin maybe polymeric colloid, a. layer of a photosensitive increased or modified.. , ` emulsion thereon, and a layer of the intermolec‘n ular polycondensation product of phthalic acid 1. An anti-static laminated photographic ñlm which comprises a base of an electriñable highly and a primary mono amino diol. polymeric ` colloid, a layer of a. photosensitive which comprises a base of a cellulose ester con taining as an anti-static agent a minor amount of emulsion thereon, and a layer of the intermolec ular polycondensation product of an organic poly basic acid and a hydroxy primary mono amine. 2. An anti-static laminated photographic ñlm which comprises a base of an electriñable highly 7. An anti-static laminated photographic illm the intermolecular polycondensation product of phthalic acid and a primary mono amino diol and a layer of a photosensitive emulsion thereon. 8. An anti-static photographic iilm which com polymeric colloid, a snubbing layer of l gelatin prises a base of an electriñable highly polymeric emulsion containing as an anti-static agent a colloid, a photosensitive emulsion, and an anti minor amount ofthe intermolecular polyconden 20 static agent comprising a minor amount of an sation product of an organic polybasic acid and a intermolecular polycondensation product of an hydroxy primary mono amine and a layer of a organic polybasic acid and a. hydroxy mono photosensitive emulsion thereon. l 3. An anti-static laminated photographic iilm amine. 9. An anti-static photographic ñlm which com which comprises a base of a cellulose ester, a layer 25 prises a base of an electrifiable highly polymeric of a photosensitive'emulsion thereon, and a layer colloid, a photosensitive emulsion, and an anti of the intermolecular polycondensation product static agent comprising a minor amount of the of an organic polybasic acid and a hydroxy pri intermolecular polycondensation product of an mary mono almine. organic polybasic acid and a hydroxy primary 4. An anti-static laminated photographic film 30 mono-amine. which comprises a base of a cellulose acetate oon 10. An anti-static laminated photographic film taining as an anti-static agent a minor amount of the intermolecular polycondensation product which comprises a 'base of an electriñable highly polymeric colloid containing as an anti-static agent a minor amount of an intermolecular poly of an organic polybasic acid and a hydroxy pri mary mono amine and a layer of a photosensitive 35 condensation product of an organic polybasic acid emulsion thereon. and a hydroxy primary mono-amine and a layer 5. An anti-static laminated photographic ñhn which comprises a base of a cellulose ester con taining as an anti-static agent a minor amount of a photosensitive emulsion thereon. FRANK J . KASZUBA.