|Publication number||US3645733 A|
|Publication date||Feb 29, 1972|
|Filing date||Mar 27, 1969|
|Priority date||Mar 27, 1968|
|Also published as||DE1915273A1|
|Publication number||US 3645733 A, US 3645733A, US-A-3645733, US3645733 A, US3645733A|
|Inventors||Brinckman Eric Maria, Meeussen Louis Achilles|
|Original Assignee||Agfa Gevaert Nv|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (4), Referenced by (25), Classifications (11)|
|External Links: USPTO, USPTO Assignment, Espacenet|
Attorney-William J. Daniel United States Patent Brinckman et al.
[ Feb. 29, 1972  SUBTITLING OF PROCESSED PHOTOGRAPHIC MATERIALS  Inventors: Eric Maria Brinckman; Louis Achilles Meeussen, both of Mortsel, Belgium  Assignee: Gevaert-Agfa N.V., Mortsel, Belgium  Filed: Mar, 27, 1969 211 App]. No.: 810,959
 Foreign Application Priority Data Mar. 27, 1968 Great Britain ..l4,779/68  US. Cl ..96/36, 96/43, 250/65.1, 96/1 15 R  lint. Cl. ..G03e 5/00, G030 5/04  Field of Search ..96/36, 43, 44, 115, 27; 250/65.l
 References Cited UNITED STATES PATENTS 1,769,599 7/1930 Neidich ..96/36 2,051,603 8/1936 l-Iruska ...96/43 2,915,581 12/1959 Pajes ..96/43 FOREIGN PATENTS OR APPLICATIONS 754,990 8/ 1956 Great Britain ..96/ 36 Primary ExaminerNorman G. Torchin Assistant Examiner-John Winkelman [5 7] ABSTRACT Graphic information, such as a subtitle, is recorded on a recording material, such as a motion picture film, by means of an externally applied surface layer of an organic film-forming polymer adapted to undergo a differential increase in solubility in an appropriate solvent as a result of imagewise heating so that, by contacting the differentially heated and thereby solubilized surface layer with the appropriate solvent, the relatively more soluble areas can be selectively removed, leaving the underlying areas of the recording material exposed. Heating can be effected directly within the surface layer by uniformly distributing throughout the polymer forming the same finely divided pigment or dye which, when exposed to a radiation image such as from a copying light, preferably a flashlight, absorbs such radiation and converts the same directly into heat. Where'sufficient pigment or dye is present as to impart opacity to the surface layer, preferably an optical density of at least one, the graphic information can be formed by selective removal of the nonimage areas of the surface layer leaving an opaque relief image thereof to constitute the graphic information. Alternatively, the recording material with the partially removed surface layer thereon can be contacted with a liquid effectively bleaching the colorant material, i.e., the metallic silver or dye image, therein or, in the case of motion picture film, carrying a developed silver halide emulsion layer disintegrating the binder of that layer, or contains a dye which penetrates the exposed regions of the recording material.
19 Claims, 1 Drawing Figure SUBTITLING OF PROCESSED PHOTOGRAPHIC MATERIALS I The present invention relates to a method for recording and reproducing graphic information on processed photographic material, more particularly to subtitling of motion pictures.
Various methods for subtitling processed silver halide black-and-white or color movies are known.
According to such known techniques a side part or the bottom part of photographic images producedby silver halide black-and-white or color photography is provided with text.
According to one technique of subtitling the emulsion layer is removed at the areas corresponding with the text characters, e.g., by tearing out. For this purpose printing blocks carrying the text in relief are pressed against the previously wetted emulsion layer and then separated therefrom, thus tearing out the emulsion down to the support in correspondence with the relief. However, such procedure is rather cumbersome and incurs the risk of bad reproduceability and damage to the film. Too strongly hardened an emulsion cannot be torn out as deeply as the support, so that the text is not reproduced in a sufficiently white tone.
According to another technique, the emulsion side of a processed film is covered with a wax layer, which in accordance with the text markings, is pressed back by means of metal letterpress dies to allow the binder of the emulsion, image silver or image dye(s) to be attacked locally. Subsequently the remaining parts of the wax layer are dissolved away. The manufacture of metal letterpress dies with minute characters needs great care, and the successive pressing steps wherein the emulsion layer is made free for local attack cannot be carried out at a high rate and without loss of sharpness of the characters. Moreover, the need to remove the remaining parts of the wax layer with an organic solvent, e.g., naphtha, makes that technique less attractive.
According to another technique, described in the U.K. Pat. No. 754,990, a varnish layer, which is resistant to an etching liquid containing an alkali metal of alkaline-earth metal hypochlorite, is applied to the image-containing emulsion and is then covered itself by a light-sensitive emulsion layer. The light-sensitive top layer is first exposed by light transmitted through a support bearing transparent characters of the subtitles, and then developed. Subsequently, the gelatin of the emulsion layer is degraded at the image areas containing silver, e.g., by means of a commonly used oxidizing solution containing dichromate. The varnish layer is then dissolved away at the areas, where the gelatin-containing top emulsion layer was removed. Subsequently the image silver or image dye in the subjacent emulsion layer(s) is etched or bleached away by means of an aqueous hypochlorite solution.
' Alternatively, the top emulsion layer can be exposed to light transmitted through a support bearing the subtitles as an opaque text, then be treated in a tanning-developing bath and washed away at the unhardened areas, whereupon the above procedure of imagewise removing the varnish and etching the emulsion layer is applied.
Obviously, the application of a varnish layer and a light-sensitive emulsion layer to a processed silver halide material is extremely time consuming. The coating of a light-sensitive silver halide emulsion can only be effected in the dark and the emulsion requires special care in its preparation. Furthermore, the cumbrous processing impedes the practical realization of this technique.
It has been found now that graphic information can be recorded simply and adequately on photographic materials containing black-and-white or color images, e.g., motion pictures, by the steps of:
l. applying to the image side of a processed photographic black-and-white or color material an overlayer, which by the action of heat becomes more permeable for and/or removable by an appropriate treating liquid,
2. and inforrnationwise heating said overlayer so that the information is recorded in terms of a difference in permeability for and/or removability by an appropriate treating liquid of different portions of said overlayer.
By the term appropriate treating liquid" is meant a liquid, which selectively permeates, degrades or dissolves the heated portions of said overlayer. The selective removal may be helped by a soft rubbing of the overlayer while wetting it with the treating liquid.
The selection of an appropriate treating liquid can be carried out by tests in which heated and nonheated portions of an overlayer of the composition in view are contacted by a liquid to be tested and in which, after a few minutes, the amount of the composition dissolved and/or softened or of the liquid penetrated into (penetration depth) each of the portions, is determined. 1
The inforrnationwise change in the overlayer effected by the inforrnationwise heating enables a developed record of the information to be formed by treating the photographic material nondifferentially with a treating liquid which penetrates or removes portions of the overlayer which have been rendered permeable or soluble, or which have been rendered more penneable or more soluble, by the treating liquid. Depending on the composition of the photographic material and/or the overlayer, and of the treating liquid, the visible record may be formed by parts of the overlayer itself, or such record may be formed by virtue of a physical and/or chemical change effected in an underlying layer, e.g., a silver halide layer, by the treating liquid. The image areas forming the developed record may be of higher or lower optical density than the surrounding areas.
A development involving physical and/or chemical attack of portions of the photographic material, e.g., portions of a developed silver halide emulsion layer, may be achieved by using as treating liquid, a liquid which has the property of etching, degrading, dissolving, bleaching, discoloring or coloring some or all of the ingredients of the photographic material, e.g., so that in the areas where such liquid penetrates to the photographic material, the optical density of an imagewise exposed and developed silver halide emulsion layer is increased or decreased. The liquid will only exert its influence on those portions of the photographic material which are not shielded by the portions of the overlayer which are still impermeable or only slightly permeable by the treating liquid. After the desired action by the treating liquid has taken place, the overlayer, or if portions of the overlayer have already been removed by the treating liquid, then the still remaining portions of the overlayer, can be removed from the photographic material.
In general, positive motion pictures are subtitled by reducing the optical density of the photographic material in correspondence with the graphic information to be reproduced. This can be achieved by using a treating liquid by which the silver metal particles constituting the silver image of a developed silver halide layer are bleached or etched away. Alternatively, the dyes of a positive color print obtained in developed silver halide color material can be bleached, degraded, and washed away in accordance with the subtitle to be produced. The binder of the recording layer, e.g., a proteinaceous binding agent, such as gelatin contained in common silver halide recording materials, can be degraded with liquids comprising hydrogen peroxide or alkali metal hypochlorites (ref. P. GlatkidesPhotographic Chemistry Vol. lI-Fountain Press London, pp. 668-669).
Subtitle indicia of higher optical density than the surrounding areas can of course also be produced by the action of a treating liquid which affects the portions of the photographic material from which the covering portions of the overlayer have been removed or which are covered by portions of such overlayer which have been rendered permeable or more permeable to the treating liquid by the inforrnationwise heating step. Thus, a treating liquid can be used which is a dye solution. According to another technique, subtitle indicia of higher optical density than the surrounding areas can be formed by portions of the overlayer itself. Thus, the composition of the overlayer may be such that this layer is an opaque colored or black layer and the latent record of the heat pattern can be developed just by using a treating liquid which washes away the portions of the overlayer which are sufficiently soluble in or permeably by the treating liquid, i.e., the portions of such overlayer which have been heated.
The formation of a subtitle in the form of dark or opaque markings is of special interest in the subtitling of negative or duplicating negative motion pictures, which are used to print release prints.
Opaque graphic markings can be formed by introducing a silver salt or silver salt complex into the photographic material in areas where the overlayer has'been removed or rendered permeable or more permeable and by reducing the said salt or complex to silver metal or by introducing colorless color couplers, which react with ingredients absorbed in one or more layers of the material. A color reaction can be catalyzed by a catalyst either present in said layer(s) or in an aqueous treating liquid. It is equally possible to produce colored or opaque image markings by introducing through the openings or permeabilized portions of the overlayer a dye solution containing a dye or a mixture of dyes absorbing light of a part or the whole visible spectrum. In order to prevent lateral diffusion, said dye(s) are preferably used in combination with mordanting agents, e.g., those known from the imbibition printing process, wherein acid dyes are applied. Suitable dyes and mordanting agents are described, e.g., in the UK. Pat. No. 830,189, and the U.S. Pat. No. 3,234,025.
Suitable compositions for preparing a heat-sensitive overlayer or surface layer of use according to the present invention are described in the U.S. Pat. Ser. No. 763,354, filed Sept. 27, 1968 the content of which should be read in conjunction herewith, and is deemed to form part of the present disclosure.
Compositions and compounds which are suited for producing an overlayer of use according to the present invention are described hereinafter in Table l TABLE 1 1. galactomannan, which is a glucoside having the following structural units:
CHaOH H l*" O :1.
2. cationic hydroxypropyl starch (the viscosity of a 5 percent solution in water at 25 C. is preferably 5 P);
3. hydroxypropylmethylcellulose preferably having a DS methoxyl 1.7-1.8; DS hydroxypropoxyl 0.1-0.2; the viscosi ty of a 2 percent solution in water at 20 C. is preferably 45 P. DS Degree of Substitution);
4. cellulose acetate butyrate preferably having a DS acetate 0.4-0.5; DS butyrate 2.4; the viscosity of a 20 percent solution in acetone at 20 C. is preferably 17 P;
5. melamine-formaldehyde resins, methylol-melamine resins,
gallic acid, barbituric acid, 2,4-dihydroxybenzoic acid, pamino-salicylic acid, stearic acid, itaconic acid, mandelic acid, succinic acid, methacrylic acid and polyacrylic acid;
6. anionic water-soluble urea-formaldehyde resins, which after coating are hardened (preferably weakly) by a moderate nondifferential heat-treatment or simply by keeping the coated recording layer for some weeks at room temperature prior to recording;
7. a resorcinol-formaldehyde resin soluble in ethanol or in a mixture of ethanol and water, and which becomes soluble in pure water by heating;
8. a composition containing a water-soluble polyvinyl alcohol mixed with a hardening agent containing (a) reactive carbonyl group(s), e.g., formaldehyde or l,4-dichloro-2,3-butanedione; 9. a composition containing a water-insoluble polymer comprising a basic nitrogen-containing heterocyclic nucleus, e.g., a poly( 1 ,2-dihydro-2,2,4trimethylquinoline) (see for such type of polymer the U.S. Pat. No. 2,718,517 and also our UK. Pat. application No. 4276/68) and an organic or inorganic compound with acidic character, e.g., hydrogen chloride, acetic acid or a polymer or copolymer of an afiethylenically unsaturated compound containing a carboxylic or sulphonic acid group, e.g., polyacrylic acid, polystyrene sulphonic acid, copoly(methacrylic acid/styrene), copoly(acrylic acid/N- vinylpyrrolidone), copoly(acrylic acid/acrylamide), copoly(methacrylic acid/methyl methacrylate), or methacrylic acid, the compound having an acidic character being preferably used in a weight ratio of 20-500 percent in respect of the poly( l,2-dihydro-2,2,4-trimethyl-quinoline), more preferably in a weight ratio of 50-300 percent;
10. a water-soluble polymer or copolymer of an a, fi-ethylenically unsaturated compound containing one or more carboxylic acid groups, e.g., polyacrylic acid, in admixture with a reactive compound forming a product with said polymeric compound, which product is less soluble in water than said polymeric compound and that on heating is dissociated again resulting in an increase of the solubility in water of the composition. Suitable reactive compounds for that purpose are cobalt naphthenate and 2,4-dihydroxy benaophenone;
l 1. alginic acid ester, e.g., 2-hydroxypropyl alginate;
12. novolak type resins e.g., a monohydroxybenzene-fonnaldehyde novolak such as phenol-formaldehyde, cresol-formaldehyde, p-tert.butylphenol-formaldehyde or mixed monohydroxybenzene homologue-formaldehyde novolak resins;
l3. polymers including copolymers containing azo groups linked through a carbon atom to a nitrile group, preferably polymers comprising groups of the following structure:
The preparation of polymers containing such groups is described in Makromol. Chem. 103 (I967) p. 301-303. Typical representatives are polyesters and polyarnides containing the following structural group in their recurring units:
R represents a lower alkyl group, and
Y a bivalent hydrocarbon radical preferably an alkylene radical of less than four carbon atoms.
Useful good results are obtained with a polyester or a polyamide having the following recurring units respectively:
L Ha H3 14. poly(N-vinylpyrrolidone);
l5. crude and/or bleached shellac optionally in admixture with a peroxide compound, e.g., cumene hydroperoxide;
16. poly-l ,2-dihydro-2,2,4-trimethyl-quinoline;
17. poly(N-vinylpyrrolidone) in admixture with a melamineformaldehyde resin containing methylol groups;
18. a composition containing polyvinyl alcohol or a partially hydrolyzed polyvinyl acetate mainly containing vinyl alcohol latex undergoes an increase in solubility in a C C alkanol byheating;
21. a copoly(styrene/acrylate ester) applied from alatex, preferably a copoly(styrene/ethyl acrylate) (20/80);
22. a composition containing a copoly(butadiene/styrene) and an ortho-quinone-diazide compound, e.g., as described in the U.K. Pat. No. 1,116,737, e.g., 2,2-bis(2-bromo-6-diazo-2,4- cyclohexadiene-4-yl-l-one)-propane and the ortho-quinonediazide compounds splitting off an acid on heating as described in the Belgian Pat. No. 674,218; 23. a composition containing a phenol-formaldehyde resin and a peroxide compound, e.g., cumene hydroperoxide.
By the term Novolak" according to British Standard 1755-1951 has to be understood soluble, fusible, synthetic resins produced from a phenol and an aldehyde, having no methylol groups in the molecule and therefore incapable of condensing with other novolak molecules on heating without the addition of hardening agents."
Information about the preparation and structure of novolaks can be found in C. Ellis, The Chemistry of Synthetic Resins, Vol; 1 (1935) Reinhold publishing Corporation, New York, pp. 303309 and in Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band XlV/2 Makromolekulare Stoffe, Teil' 2, p. 201 seq.
Overlayers containing the compounds or compositions listed in the above Table l undergo an increase in solubility in an appropriate solvent upon a proper intensive heating. Thus the compound or compositions 1 to 11 show an increase in solubility in water; the compounds 12 to 15 an increase in solubility in an alkaline aqueous medium, e.g., an aqueous solution having a pH 12, and in the case of the compound 13 also arise in solubility in an ether-type solvent, e.g., ethylene glycol or the monomethyl ether of diethylene glycol and in the case of the compound 15 also a rise in solubility in a C -C alkanol; the compounds 16 to 20 a rise in solubility in a C -C alkanol, e.g., ethanol and the compound 20 also a rise in solubility in a lower ketone containing C,C carbon chains linked to the carbonyl group, e.g., acetone, as does compound 21', the compositions 22 and 23 an increase in solubility in chlorinated aliphatic hydrocarbons, e.g., methylene chloride and carbon tetrachloride.
In order to make the overlayer sufficiently insoluble in the processing liquid, e.g., an aqueous etching liquid for silver metal, it is necessary in particular cases, i.e., in the case of the above-mentioned melamine resins, to dry the applied layer nondifferentially for a certain time at a temperature between 50 and 130 C., e.g., for 5 hours at C.'or for 5 minutes at C. The optimal processing time and temperature should be detennined experimentally, since too strong and too lengthy a heating causes an irreversible insolubility in water,
which by a rather short high-intensive heating cannot be an nulled anymore.
The overlayer may comprise suitable ingredients such as pigments, e.g., carbon particles or metal particles, reinforcing or filling agents, and unreactive inorganic solids of small size including glass, mica'Qsilica, bentonite, etc. Preferably, these ingredients are used in a weight ratio in respect of the above selected polymers not surpassing 20 percent.
The heated portions'of the recording layer containing the compounds or compositions l to 11 described above in Table 1 can be removed more adequately when containing a certain amount of water-soluble compounds, with the proviso, however, that the selectively of the washing away is not substantially disturbed. Such compounds are, e.g., polyacrylic acid, polyacrylamide, poly(N-vinylpyrrolidone) and polyoxyethylene resins.
- The application of heat to the overlayer in correspondence with the graphic information to be reproduced can be achieved in different ways. Thus, it is possible to heat the overlayer by bringing it in contact with image markings of an original containing the graphic information to be reproduced and simultaneously exposing said markings to infrared or highintensity visible radiation, which is absorbed bysaid markings When using metal letterpress dies, the heating may be can ried out by means of a high frequency alternating current passing through the parts of the overlayer brought into contact 'with the conductive relief parts of the die. In this case the backing of the processed recording material stands in contact with an electrode and the overlayer contains a sufficient amount of high-frequency heatable material, e.g., iron particles.
Selective internal heating of the overlayer used according to the present invention is, however, preferably realized by exposing-an overlayer, containing infrared and/or visible lightabsorbing substance(s) converting absorbed light into heat, to infrared radiation and/or visible light modulated a'ccording to the pattern to be reproduced.
Some specific examples of substances absorbing visible light and infrared radiation and converting said light or radiation into heat are, i.e., finely divided carbon particles, e.g., carbon black and heavy metals in finely divided state, e.g., silver, bismuth, lead, iron, cobalt, and nickel, oxides and sulphides of these metals, e.g., manganese dioxide, magnetic iron oxide (Fe O chromium (ll) oxide, cobalt sulphide, nickel sulphide, lead sulphide, and pigments and dyes such as Prussian blue (C.1. Pigment Blue 27), chlorinated copper phthalocyanine (CI. Pigment Green 7) or indigo (C.l. Vat Blue 1). The particle size of these substances preferably does not exceed 0.1 41..
Methods and apparatus by which the recording material can be exposed to an original when using the heat-generating property of said substances are described in the published Dutch Pat. applications Nos. 6,606,719, 6,414,226, 6,506,548, 6,607,637 and 6,608,504.
1f the overlayer contains substance(s), which abs0rb(s) copying light (infrared radiation and/or visible light) and convert(s) it into heat, a contact exposure of high intensity and short duration (preferably less than 10 sec.) is preferably applied. The original, is, e.g., a negative transparency of the text 7 fuse into the surface layer, which is heated-only internally by the light absorbed in the light-absorbing substances contained therein. Preferably the concentration of said light-absorbing substances is such that at least 50 percent of the light to which the overlayer is exposed is absorbed.
Suitable radiation sources producing copying light that can be converted into heat necessary for imagewise increasing the permeability, the solubility and/or swellability of the surface layer containing light-absorbing substances, which convert the copying light into heat, are so-called flash lamps. Good results are obtained with xenon gas discharge lamps with an exposure time of 10 to seconds. Details on a copying device containing such a discharge lamp can be found in the Belgian Pat. No. 664,868. I
- If the emitted energy is focused onto a relatively small heatsensitive area, e.g., having the size of an image (one picture) of a motion picture film, a gas discharge lamp with a relatively low-energy output can be used. For instance, for copying a text on 18 mm. X 24 mm. motion picture image a flash lamp with an energy output of 40 watt.sec. will suffice. According to the type of thermopermeabilizable substance heat-sensitive surface layers having an optical density of at least 1, resulting from the presence in the recording layer of light-absorbing substances converting absorbed light into heat, require a light energy of .at least 0.1 watt.sec/sq.cm. to realize a detectable image differentiation. In most cases, an exposure of 0.5-1.0 watt. sec./sq.cm. yields satisfactory results.
The exposure may of course be carried out progressively or intermittently, e.g. with (a) flash lamp(s) yielding an overlapping intermittent exposure. Successive overlapping exposures are not harmful since no further change in the image differentiation is obtained thereby. As an example of progressive exposure the transparent text original can be scanned, e.g., with a high-intensity light beam, e.g., a laser beam, which rapidly linewise scans the original, or it can be exposed progressively through a slit, wherein, e.g., copying light is focused from a tubelike radiation source.
Self-evidently, the heat-sensitive surface layer before or during the production of the imagewise heat differentiation can be subjected to an overall heating to a certain temperature below the temperature at which a substantial increase in permeability, solubility and/or swellability to a selected treating liquid takes place. In this way less imagewise supplied heat energy is required to produce the desired increase in permeability, solubility and/or swellability.
After production of the imagewise differentiation in permeability, solubility and/or swellability for an appropriate treatingliquid, the surface layer is brought into contact with the selected liquid and, e.g., softly rubbed with a foamed rubber sponge, to remove selectively the heated portions. When a transparent subtitle has to be produced, the binder of the emulsion layer, e.g., gelatin, can be disintegrated and the image silver and/or the dyes present in the processed silver halide emulsion layer(s) can be removed, e.g., by means of an aqueous solution of an hypochlorite of an alkali or alkaline earth metal.
Subtitling of a silver image picture can also proceed by bleaching the silver without affecting the gelatin binder by using a conventional bleaching bath and a subsequent'fixing bath, or by using a combined bleaching-fixing solution.
In order to illustrate the subtitling process of a motion picture film according to the invention, a diagrammatic section of a processing unit suited for continuous subtitling is represented in the accompanying drawing. In said diagram the motion picture film l, e.g., a positive black-and-white or a color film, is unwound from a takoff roll 2 and by means of the 1 guiding rollers 3, 4 and 5 introduced into a coating tray 6,
wherein the emulsion side of the film l is coated with a composition 7, which on drying in the ventilated drying channel'8 yields a heat-sensitive surface coating of the type described hereinbefore.
The motion picture film coated with its heat-sensitive surface layeris exposed with a flash lamp 9 through a transparent negative image 10 of the text to be reproduced. A smooth flat backing plate ll serves for securing a close adjustment with the diapositive. After the exposure the motion picture film is introduced by the guiding rollers 12 and 13 into the washing bath 15 containing a selected treating liquid 16 for removing the heated portions of the surface layer and containing etching substances, e.g., sodium hypochlorite, for removing the silver or dye occasionally together with the binder of the emulsion layer(s) in the areas corresponding with the removed portions of the heat-sensitive surface layer. The removal of the residual portions (the unexposed portions of the surface layer) proceeds by washing and rubbing in a rinsing bath 19 contain- 1 ing the guiding rollers 17 and 18 and wherein a solvent 20 continuously streams through and wherein a rubbing roller 21 rotates in rubbing contact with the surface layer in opposite direction to the motion direction of the film. Subsequently, the film is dried in a drying channel 22 and wound up on a takeup roller 23.
' Depending on the type of overlayer it can be necessary to use a separate bath for the treating liquid and etching or bleaching solution. The selective removal of the overlayer can be speeded up by rubbing the overlayer in wet state, e.g., in an apparatus described in the published Dutch Pat. application No. 6,807,686.
For subtitling negative pictures with an opaque subtitle as already described above as a first technique, an opaque overlayer can be applied, which is heated in correspondence with the nonirnage parts of a subtitle to be reproduced, and the heated portions of the overlayer removed leaving in that'way an opaque relief pattern of the opaque overlayer representing the desired subtitle information.
Compositions for preparing an opaque or colored overlayer which can be selectively removed in the heated portions by an aqueous treating liquid are the compositions mentioned under the numbers 1 to 11 of Table 1. Using such compositions and the technique of opaque subtitling described above no etching step and washing step for integral removal of the overlayer has to be applied.
Although not strictly necessary, e".g., when using a colorless overlayer, it is preferred, after the subtitle has been formed, to remove the resist portions of the overlayer entirely. This can be accomplished by dissolving the said portions, e.g., with the solvent or solvent mixture, from which the overlayer has been coated.
The following examples illustrate the present invention.
EXAMPLE l The silver image-containing emulsion layer of an exposed and developed silver halide photographic material was coated at a rate of 25 g. per sq.m. with a covering layer prepared by ball milling the following ingredients for 12 hours:
cresol-formaldehyde resin, type Novolalt (softening range -l05 C.) 200 g. carbon black 15 g. ethanol L130 cc.
water 280 cc. Javelle water, comprising approxi mately I20 g. of active chlorine and 4 g. of sodium hydroxide per liter cc. l N sodium hydroxide 20 cc.
The parts of the covering layer and the subjacent silver image containing emulsion layer, which correspond with the light-struck areas, where then removed by rubbing with a plug of wadding. The material was then dipped again for sec. in the abovegdescribed etching bath. Finally the whole covering layer was removed by treating with a plug of wadding soaked with ethanol and rinsed with water.
EXAMPLE 2 A color developed Gevacolor (registered trade name) 16- mm. film was provided with the covering layer described in Example 1. The material was exposed for 0.008 sec. by means of a flash lamp, receiving an energy output of 1.03 watt.sec/sq.cm. The exposed material was then dipped first, for 60 sec. in a 0.6 percent solution of sodium hydroxide in water and subsequently dipped for 40 sec. in a solution of Javelle water containing approximately 30 g. of active chlorine and 1 g. of sodium hydroxide per liter. The covering layer was then removed with ethanol. Finally, the material was rinsed with water.
As a result of the imagewise degrading of the gelatin, a relief image of the subtitle was produced on the film.
EXAMPLE 3 A developed duplicating negative motion picture film was covered at a rate of 40 g. per sq.m. with a heatsensitive layer prepared by ball-milling the following ingredients for 12 hours:
ethanol L640 cc. poly( l ,2-dihydro-2,2,4-trimethylquinoline) 45 g. polyacrylic acid 100 3. carbon black 45 g.
2 g. 1 cc.
water Carbidschwarz E (C.l. 30,235) 25% solution of ammonia in water Next the dipped material was rinsed with water and the rest of the covering layer removed by means of a plug of wadding soaked with a 5 percent solution of acetic acid in water.
Finally after rinsing with water and drying a negative motion picture film containing on the emulsion side in the picture frames a blueblack reproduction of a subtitle was obtained.
EXAMPLE 4 A developed duplicating negative motion picture film was provided at a rate of 32 g. per sq.m. with a heat-sensitive covering layer containing the following ingredients:
PAREZ RESIN 68 (a 80% by weight aqueous dispersion ofa dimethyltrimethylolmclamine-forrnaldehyde resin sold by American Cyanarnid Comp.. New York, N.Y.. U.S.A.) I00 3.
poly(N-vinylpyrrolidone) 4 8- water 7l6 cc. ascorbic acid 8- aqueous carbon black dispersion con taining per l00 g. :53 g. ofcarbon.
23 g. of water, l8 g. of ethylene glycol and 6 g. of nonylphenyl poly(ethylcne oxide),-,, l00 g. isooctylphenyl poly(ethylene 0xide) 10% in water 70 cc.
After drying of the coated layer at 90 C., the material was exposed for 0.008 sec. through a transparent positive image of a subtitle by means of a flash lamp, receiving an energy output of 0.80 watt.sec./sq.cm.
The exposed parts of the covering layer were then removed by rubbing with a plug of wadding soaked with water.
The the negative images of the motion picture film a black reproduction of the subtitle was superposed.
EXAMPLE 5 A novolak consisting of the copolycondensate of equal molar parts of phenol and p-tert.butylphenol was prepared as follows.
ln the three-necked flask of 2 l. equipped with a strong stirrer, a reflux condenser and a thermometer, a solution was prepared by mixing:
demineralised water 300 cc. anhydrous oxalic acid 10 g. freshly distilled phenol 94 g. p-tert.butylphenol ISO 3. 37.5% aqueous solution of formaldehyde I26 cc.
The mixture was allowed to react and refluxed for 3 hr. with stirring at ll5l20 C. Then 20 cc. of concentrated hydrochloric acid (d=l.l9) were added, whereupon the mixture was refluxed for further 4 hr.
From the obtained pasty melt the water was decanted. The resin was washed thrice with 500 cc. of boiling water, and then dehydrated under reduced pressure till a temperature of l45l50 C. was reached. The liquid resin was poured into a cooled metal dish, wherein it could easily be pulverized.
Softening point: 1 15120 C.
50 g. of this novolak were ball-milled for 8 hrs. with 5 g. of carbon black in 450 g. of isopropanol. The fine dispersion obtained was then applied to the emulsion side of a developed positive silver image motion picture film in a proportion of 50 g. per sq.m. After drying, the covering layer thus formed was exposed for 0.004 sec. through a negative transparency of the subtitle to be reproduced by means of a flash lamp, receiving an energy output of 0.77 watt.sec./sq.cm. Thereupon the film was first dipped in 0.6 aqueous sodium hydroxide solution for 20 sec., shortly rinsed with pure water and finally for 25 sec. dipped into a solution of Javelle water containing per litre about 30 g. of active chlorine and l g. of sodium hydroxide. The film was then again rinsed shortly in pure water and the covering layer eliminated with ethanol. After drying, as a result of imagewise degradation of gelatin, a transparent pattern and a relief print of the subtitle to be reproduced were obtained in the emulsion layer of the film.
EXAMPLE 6 Example 5 was repeated, but after exposure the coated positive motion picture film was treated as follows:
dipping in 0.6 percent aqueous solution of sodium hydroxide for 20 sec.;
shortly rinsing in water;
dipping in the bleaching-fixing bath of the following composition for 25 sec.:
iron(lll)chelate of the monosodium salt of ethylenediaminetetraacetic acid 60 g. anhydrous sodium carbonate 5 g. potassium bromide 30 g. potassium thiocyanate l0 g. sodium thiosulphate-S-water I40 g. demineralised water to L000 cc.
shortly rinsing in water elimination of the covering layer by means of ethanol rinsing in water and drying.
By imagewise eliminating the silver from the emulsion'layer, a transparent copy was obtained of the subtitle to be reproduced.
1. A method of recording graphic information on a recording material already containing an image, comprising the steps of: coating the image side of said material with a composition consisting essentially of an organic film-forming polymer which upon heating undergoes an increase in solubility in a correspondingly selected solvent and uniformly distributed finely divided particles of a pigment or dye capable of absorb: ing copying light and converting the same to heat; exposing said image side of said material to an image of copying light for less than about 0.1 sec., said light being of such intensity as to produce in said surface layer by the absorption and conversion thereof by said finely divided particles sufficient heat to cause the heated areas of said surface layer to undergo said change in solubility; and contacting said exposed surface layer with said selected solvent to substantially remove said heated areas of said surface layer while leaving the unheated areas essentially intact.
2. A method of recording as in claim 1 wherein said material is a black-and-white or color photographic material, the image of which is formed by means of at least one light-sensitive silver halide emulsion layer,
3. A method according to claim 1 wherein said organic filmforming polymer undergoes an increase in solubility in water in response to heating and is selected from the group consisting of:
a cationic hydroxypropyl-starch;
a cellulose acetate butyrate;
a melamine-formaldehyde resin, a methylol-melamine resin;
or an etherified methylol-melamine resin of the watersoluble type, which resins are partially hardened after coating;
an anionic water-soluble urea-formaldehyde resin, which is partially hardened after coating;
a resorcinal-formaldehyde resin soluble in ethanol or in mixture of water and ethanol; and which becomes soluble in water by heating;
a composition containing a water-soluble polyvinyl alcohol mixed with a hardening agent containing reactive carbonyl groups;
a composition containing a poly( l,2-dihydro-2,2,4-
trimethylquinoline) and an acidic compound;
a water-soluble polymer or copolymer of an a, B-ethylenically unsaturated compound containing at least one carboxylic acid group and in admixture therewith cobalt naphthenate or dihydroxy benzophenone forming a product with said unsaturated compounds that is less soluble in water than the a, B-ethylenically unsaturated compound and that on heating dissociates resulting in an increase of the solubility in water of the composition; and
an aiginic acid ester.
4. A method according to claim 1 wherein said organic filmforrning polymer undergoes an increase in solubility in an alkaline aqueous medium in response to heating and is selected from the group consisting of:
a novalak-type resin;
a polymer containing an azogroup linked through a carbon atom to a nitrile group;
poly( N-vinylpyrrolidone); and
crude and/or bleached natural shellac.
5. A method according to claim 1 wherein said organic filmfonning polymer undergoes an increase in solubility in a C -C alkanol in response to heating and is selected from the group consisting of:
a composition containing poly(N-vinylpyrrolidone) and a melamine-formaldehyde resin having methylol groups;
a composition containing polyvinyl alcohol or a partially hydrolized polyvinyl acetate mainly containing vinyl alcohol units, mixed with a quinone-diazide compound and an aldehyde or latent aldehyde splitting off formaldehyde on heating; and
a copoly(styrene/N-vinylpyrrolidone) applied from a latex.
6. A method according to claim 1 wherein said organic filmfon'ning polymer undergoes an increase in solubility in a lower ketone containing up to 4 carbon atoms linked to the carbonyl group in response to heating and is selected from the group consisting of:
a copoly(styrene/N-vinylpyrrolidone) applied from a latex and a copoly( styrene/ acrylate ester). 7. A method according to claim 1 wherein said organic filrnforming polymer undergoes an increase in solubility in a chlorinated aliphatic hydrocarbon solvent in response to heat ing and is selected from the group consisting of:
a composition containing a copoly(butadiene/styrene) and an o-quinone-diazide compound which decomposes to form an acid when heated; and a composition containing a phenol-formaldehyde resin and a peroxide compound; is imagewise heated in the areas corresponding with the graphic information to be recorded, and
is treated with a suitable treating liquid, by means of which the heated portions of the surface layer are removed and/or permeated.
8. A method according to claim 1, wherein the said surface layer is irradiated for a period less than about 0.01 second and with an energy of at least 0.1 watt.sec./sq.cm.
9. A method according to claim 8, wherein said copying light contains visible and infrared light.
10. A method according to claim 1, wherein the recording is a black-and-white or a color motion picture film and the graphic information to be recorded is a subtitle.
11. A method according to claim 10, wherein the film contains positive images in a developed silver halide emulsion layer and the surface layer is exposed through a negative image of a subtitle before treatment with said liquid.
12. A method according to claim 11, wherein the surface layer during or after its treatment with the selected liquid is contacted with an aqueous liquid, which has an etching or bleaching effect on the metallic silver or a bleaching effect on dye forming the image in the developed emulsion layer.
13. A method according to claim 11, wherein the surface layer during or after its treatment with the selected liquid is contacted with an aqueous liquid, which disintegrates the binder of a developed silver halide emulsion layer.
14. A method according to claim 13, wherein the aqueous liquid for disintegrating the developed silver halide emulsion layer contains a hypochlorite of an alkaline or an alkaline earth metal.
15. A method according to claim 10, wherein the film contains negative images and the surface layer is exposed through a negative image of a subtitle before treatment with said liquid.
16. A method according to claim 15, wherein the surface layer during or after its treatment with said liquid is treated with an aqueous liquid, which produces a coloration in an underlying layer.
17. A method according to claim 10, wherein the blackand-white or color motion picture film contains negative images and said surface layer contains sufficient pigment or dye as to be generally opaque and is exposed to a positive copying light image of said subtitle so that the areas of the surface layer that correspond to the nonimage parts of the subtitle undergo said increase in solubility and are removed when the layer is contacted with said liquid, thereby leaving an opaque pigmented or dyed relief pattern representing the subtitle on the film.
18. The method of claim 17 wherein said dye or pigment is present in sufficient amount to impart to the surface layer an optical density of at least 1.
19. A method for applying graphic information to a recording or reproduction material already containing an image according to claim 1, comprising the steps of: (1) coating the image layer side of said material with a surface layer essentially consisting of a phenol-formaldehyde, cresol-formaldehyde, p-tert.butylphenol-formaldehyde or mixed monohydroxybenzene homologueformaldehyde novolak mixed with a finely divided infrared and/or visible light-absorbing substance or mixture of substances converting absorbed light into heat; (2) image-wise irradiating said surface layer with infrared and/or visible light of a sufficient energy to increase its solubility in an aqueous alkaline medium, and (3) treating the imagewise exposed surface layer with an aqueous alkaline liquid selectively removing thereby the exposed portions of the surface layer.
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|U.S. Classification||430/325, 430/270.1|
|International Classification||B41M5/36, G03F7/26, B41M5/26, G03C11/02, G03C11/00|
|Cooperative Classification||B41M5/368, G03C11/02|
|European Classification||B41M5/36S, G03C11/02|