US2458905A - Photographic process for converting black and white or monochrome pictures into multicolor pictures - Google Patents

Description

Patented Jan. 11, 1949 PHOTOGRAPHIC PROCESS FOR CONVER'I- mo BLACK AND WHITE on MONO- CHROME PICTURES INTO 'MULTICOLORR PICTURES Harold C. Harsh, Richard M. .Hafig'andFrank 'J.

Kasz'uba, Binghamton, N. Y., assignors to Gen eral Aniline & Film Corporation; New York, N.Y.,' acorporation of Delaware No Drawing. Original, application August 31,. 1944, Serial No.,552,210. Divided and this ap-' plication. May 18, 1946, Serial No. 670,850

s Claims.

This invention relates to color photography and more particularly to a process of converting black and white or monochrome drawings into colored drawings.

In preparing colored drawings from an original black line or monochrome drawing, the process employed is to copy or photograph a black and white or monochrome drawing on a photographic film. After development, washing and drying'of the exposed film, the negative is laid on a glass illuminated from below and dye coating solutions 1 applied to the transparent lines and areas of the negative which are to appear in color in thefinished print. The colors'of the'dye' solutions em'- ployed are complementary to the colors "desired in the final print. To obtain'in the final print, a line or area of any color, for example, green, the line or area in the negative is dyed with'a color complementary to green, namely, magenta. The system may be best understood by reference to the following table:

Color desired in finished reproduc- Color of dye applied tolllm tron negative Rail...

gyan (Blue-Green) No dye needed. The negative is left nncolored.

A photographic paper consisting of three emulsions coated on a support, each emulsion layer sensitive to light of one of the colors, red, green and blue, and each layer containing a color form ing compound, is exposed in a printing frame in I contact with the emulsion surf aceiof the'colored print composed of lines or areas which are complernentar to the colored lines or negative.

The development of the above process has been areas of the attended with difiiculties' connected with the ap- 2.. plication of the dyecoatingcompositions to the transparent lines'or areas of the negative which are to appear in color in the finished print. The aqueousor alcohol-solutions of the dyes previouslyused are not satisfactory forcoloringthe negatives since they aredifilcult to apply in sufiicient density 'with' reasonable speed. Furthermore, crystallization of the dye takes placeupon drying. These dye solutions also have a'tendency to ru n after application into-uneven areasresultingin the formation ofareas of unequal density so that uneven-color linesor areas are obtained in the finished print; I

It is arr-object of the-present inventionto overcome'these and other undesirable characteristics and disadvantages, and to provide improved dye coating compositions, whereby colored negativesof' desirable characteristic ,are obtained.

A further object is to provide a simplifiedproc ess of convertingblack andwhite or'rnonochrome drawings into multicolorphotographs.

Other objectsand advantages of this invention will lee-apparent 'byrefe'rence to the rollowing specification, in'which its-preferred details and embodiments are described.

According to the presentinvention theabove objects'are accomplished-by the preparation and use of'dye coating compositions ofthe following general composition Water soluble dyegrams 1-10 5-2 5% Aqueous" solution of hydrophilic 1 polymer cc .50- Water soluble aliphatic polyhydric alcohol containing ,at. least two carbon atoms gram 0:5-1 Wettingagent nu s do 0.5-1

In the above general composition any commercially availablewater soluble dye may be employed. The nature of the dye is immaterial so long as it is watersolubleand givesthe desired colorimetric'result; Ingeneral, the most satisfactory water soluble dyes are'found in the group of dyes'classified under 'th'eusua'l constitutional headings; which-are grouped in'the following list:

, Acridine dyes; e: g: Acridine Orange R I.

Eriochrome Phosphine R (C. I. #157), etc., nitro dyes, e. gI,' 'Victoria Yellow (C; I. #8), Naphthol Yellow (C. I. #10), Amido Yellow (C. I. #11), etc., oxazine dyes, e. g. Brilliant Blue CC (C. I. #876) Chromazurine E (C. I. #879) etc., pyrazolone dyes, e. g., Fast LightYellow (C. I. #636), Kiton Fast Yellow 3G (C. I. #645) Pyrazolorange G (C. I. #653), etc., stilbene'dyes, e.jg., Chlorazol Yellow GX (C. I. #620), Cotton Orange 6305 (C. I. #625), Direct Fast Orange BGL. (C. I. #633), etc., thiazine dyes, e..g;, Genthianine (C. I. #921), Methylene Azure (C. I. #923), Indoohromogen S (C. I, #930), and triphenyl methane dyes, e. g., Turquiso Blue G (C. I. #661), Acid Green (C. I. #669) Xylene Blue AS (C. I, #673) and the like.

The above dyes were selected because of their brilliancy of color. The preferred dyes from the above group, however, are those which effectively transmit a sharply isolated spectral band while eliminating undesirable transmissions of a secondary spectral band. Thus, for example, the red dye which maybe a mixture of Anthraquinone Rubine and Tartrazine, transmits freely in the red wave length beyond 600 m and is substantially opaque to the spectral region below 600 mg. The green dye. which may be a mixture of Anthraquinone Blue SE and Tartrazine N transmits freely in the green wave length between 500. and 600 my and issubstantially opaque. to other spectral regions. The blue dye which may be a mixture of Anthraquinone BlueSE and Fast Acid VioletB transmits freely in the blue wave length between 400 and 500 my and is substantially opaque to the longer wave lengths of the spectrum. The orange dye such as Pyrazolorange G transmitsabove 500111;.0 and is substantially opaque to the shorter wave lengths of the spectrum. The magenta dye such as Anthraquinone Rubine transmits freely two bands, one in the blue region of 400-500 m and the other band in the red region above 600 m and is opaque to the green region of the spectrum. The cyan dye such as Anthraquinone Blue SE transmits freely in the blue and green region between 400 and 600 me and is likewise opaque to the longer wave lengths of the spectrum. The actual selection of the preferred dyes is made bycolorimetric methods which are well known to the art and need notbedis'cussed herein, or by actually preparing the dye coating'composition, coloring a negative and printing it out on color paper.

The cyan dyes suitable for forming red lines or areas in the finished print are, for example, Anthraquinone Blue SE (Schultz #861), Brilliant Alizarin Viridine F (Schultz #854) and Alizarin Cyanine Green F (Schultz #865).

The yellow dyes suitable for formingthe blue linesor areas in they finished print are, for example, Pyrazolorange G (Schultz #747), Stilbene Yellow 3 GA (C. I..#622), Milling Yellow (Schultz #230), Erie Yellow Y (C. I. #365), Solantine Yellow FF (CL I. #814), Naphthol Yellow S (Schultz #7) and Tartrazine N (Schultz #23). The magenta dyes suitable for forming'th green lines or areas in the finished print are, for example, Brilliant Congo G (Schultz #369), Geranine GL, Erie Pink 23 (C. I. #128), Rose Bengal .N (Schultz #595), Brilliant Purpurine 4B (Schultz #368) and Brilliant Crocein B (Schultz #227).

Several red dyesmay be obtained by blendin magenta dyes with yellow dyes. Suitable greens may be obtained by blending cyan dyes, with yellow dyes. Suitable blue-violets may be obtained by blending cyan dyes with violet or magenta dyes. Similarly, the hue of the single dyes, yellow, magenta and cyan, may be adjusted to the requirements of the color paper by blending two dyes together.

The amount of dye employed in each coating composition will depend upon the amount of hydrophilic polymer used and the depth of shade required. The amount employed may range from 1 to 10 grams per cc. of the aqueous hydrophilic polymer. The desirable proportions, however, are in the range of 3 to 5 grams per 100 cc. of aqueous hydrophilic polymer.

The aqueous solution of hydrophilic polymer referred to in the above general composition acts both as a carrying and binding medium for the dyes. Suitable materials of this type are any of the natural gums and synthetic resins (polymers) which have an affinity for water and aqueous media. The hydrophile radical of these gums and resins consists of hydroxy groups or carboxy groups, or both, and imparts to the gum or polymer molecule of which it is a member, a tendency to .be wetted by water and aqueous media. As typical illustrations of water swellable and water soluble hydrophilic gums and polymers may be mentioned gum acacia, gum grindelia, gum tragacanth, Irish moss, polyvinyl alcohol, water soluble polyvinyl acetals, sodium salt of cellulose glycolate, sodium salt of carboxy ethyl cellulose, and Elastolac, a resin obtained by the intermolecular polycondensation of aleuritic acid CH2(OH) .(CI-I2) 5.CHOH.CHOH.(CH2) v.COOH

These hydrophilic gum materials are well known in the art, and as for the polyvinyl alcohol, water soluble polyvinyl acetals, and the sodium salts of the polymeric celluloses, suitable methods for their preparation have been described in the literature.

The water soluble aliphatic polyhydric alcohols which act as spreading agents for the dye carrying medium (dye and aqueous hydrophilic polymer) contain at least 2 carbon atoms and are either liquid per se or if solid are soluble in water. As suitable polyhydric alcohols may be mentioned, ethylene glycol, trimethylene glycol, propylene glycol, glycol di-glycolate, glycerol, i-erythritol, di-arabitol, xylitol', rhamnitol, dulcitol, d-mannitol and d-sorbitol. The principal function of these polyhydric alcohols is to assist in spreading the dye carrying medium evenly over the negative and to prevent cracking thereof after application to the negative upon drying.

Suitable wetting agents that are employed in dispersing the dye in the dye carrying and binding medium, and at the same time preventing the partial precipitation or sedimentation of the dye in solution are, alkylated mono sodium benzenesulfonate, di-hexyl ester of sodium sulfosuccinate, sodium salt of an alkylnaphthalene sulfonic acid, sodium salt of tetrahydronaphthalene sulfonic acid, calcium glycerin phosphate, alkylphenyl polyethylene glycol, oleic acid ester of hydroxyethane sulfonic acid and sulfonated higher molecular weight primary or secondary aliphatic, aromatic and cyclo-aliphatic oarboxy acids. It is to be noted, however, that any commercially available wetting agent may be employed. The nature of the wetting agent is immaterial so long as it possesses wetting, dispersing and emulsifying properties, and its aqueous solutions are colorless or only slightly tinted.

;glass. The; film- 1negative-ev and'z glassie. we

the additioii= of water.- Tnpreparih the dye coatii'ig co'mposition; "a paste iisxnifid o'f heedye by mixing it with a- -smairquantity or aqueous solution of thehydrephi lio p" ter'ia untiltlie-dye-is wette'i The remaindemoI th 'aq'uec'ms soluitioii o'f 'the -hydrop'hilic polymer material is then addedand brougl'it -td ule de sired volume; after whichrthe requisite; quantity of a water-soluble aliphatic polyhydric alcohol and wetting agent-is added: i The following examples are illustrative of; the

manner in which compositions of this invention 1 are prepared- EXAMPLE I sme ma-er dye-- we e: ew 9? A specific example of employing the above dye coating ,compos'itiqns in the preparat on; of i-a colored filmnegative' for color printin'gj-isthe renewin l F A drawing of aneIectricaI jcircuit .in. ,india ink i was copied on. a high" contrast pliotcigraphic film so'as tdbbtjain" high densities ahdflba'n... lte lines. After exposure, thfilm wasdvelopdi'n the usual developing solution, fixed: washed and dried: The dried negative was thenv temporarily r cemented, emulsion downwards, on a placed; on "a light tableau-a reasonablyle .tion;; The light-table'wasifittediwith daylight fluorescent tubes win order to. obtain: desirable color quality 'for' judgment "of. color d' 'nsitiesl The filmnegative was-thenicleanedfiwitheacloth moistened withrethyl alcohol inorderto repair-e itfor even dyeing, I e M The above cblue violetr yellowand magentaijdye coatingccompositions were then: 'appliedi: evenly over the white' :linesof the negative iwhichi arei-a to appear as, yellow, blue; and. green respectivelyvin the: final print; The-rdy'e coating solution were apoliedjby meansr-of ia'rssma-ll aspottingz btusherthe sharp needlei pointof "which? was cut roff; so as tozconflnextheidye substantially toathe linebeing colore'dgi'z that: :is; without substantially toverlape pin'gsitheriwhite'line or forming areas, of excess dyel adjoining: the: white: line.-. One application with the brush" r fully -charged-with each of. the

dyes. to; the lines I being;'-c01or.ed,-. was adequate. to

and even.v :The colored negative wasuthen con- 7 tactlprinted' on; .a. threev superimposed; emulsion layer; photographic. zacolor paper, emulsion to emulsion: imra; printing. frame, six ieet'from. a SO-Watt frosted mazda lamp. The exposuretime was approximatelyxloz seconds; The; exposed colors-paperwas :then developed-in 'a developer 'Ofllth'G foll'owing composition:

Water to make. Y lit er l Aftervbleac'hing; fixing; washing and i drying, the resulting vprinti :showedino; uneyeness in the colored lines. All the colored lines-weretsmooth andvof- .pure colorrg" -:Thephotographic,multilayer element (color paper) or othertprintingimaterialused-in carrying :out'the'qprooess. deseribedin. the present invention "consists-ref- .aneintegralhtripack; emulsion coated :oneither-the usual-paper base; or a clear cellulose acetatenor nitrate-:film base-{or :in' some cases an opaqueiswhitefilmrbase- Each; of the emulsion layers is sensitlzedlgto one of the primary colors ofa-ligl'it; namely blue, .grteen a-nd red: The top layerais ?blue:--.sensitiv:e=- ,v A filter layer, yellow in color andblue'absorbing; lies underzthe top layer.

Below this filter layer dies a; green sensitive emulsiomlayer; andibelow this a red sensitive; emulsion layer. Each of the three silver halideiemulsion layers contain dye-forming compounds which .H-HitGE dHPiHgLthG development ,ofwa silver image inlan aromaticiamine developing agent to form a-dye with thei oxidation product of the developing agent-.i-(As-lsilver.is also formed. during develop ment it must be-removed after .color development byatreatmenti ina-'- bleach, gfollowed bya bath of sodiumnthiosulfate; as;-is -welltknown- ,to the art. A yellow dye is formed :in the=blue sensitive emulsion; a magenta dye is formed in the greenisensitive emulsion; and a cyan .dye is formed in the red sensitive emulsion; The combinations ofthese three printinggprimaries yield red green, .blue and blackjlines. Suitable methodsfor the preparation" of multicolor emulsion layers have been described in'.th'e'literature relating to color photography, and are; therefore, not described here. .atTheidye coating-compositions of the presentinveritionr a're-noti limited to the coloring of a black and white film 'negativegiven above; such being merelycillustrativeof the-manner of employing the dye coating compositions of this invention.

r Insteadr-of coating-black and white negatives,

that-dye coating compositions of' the present invention may be employed for making colored transparencies from black and white or blue print drawings. In this process, a thin and fiat transparent medium such as paper, organic ester of cellulose, superpolyamide, polyester, or synthetic resin, is superimposed over a black and white or blue print drawing, and the various lines or areas which are to appear in color are inked or coated. with the dye coating compositions. After drying the transparency, it is then; removed from the original drawing and printed on color paper as hereinbefore described. The dyecoating compositions may also be employed'fcr retouching or repairing damaged areas of colored photographs such as transparencies or paper prints. The various dye coating compositions may be mixed on a piece of opal glass with a small brush to match the prevailing color of the area surrounding the blemish. The dye is then applied with the brush to the blemish. On drying,'the dye will assume the surface characteristics of the gelatine image-bearing layer, and the repaired or retouched area will not be readily detectable. 1 i

By the term hydrophilic polymer as used hereinabove and in the appended claims, we intend to designate water s'wellable or water soluble natural gums which yield on hydrolysis a mixture of aldohexoses and hexuronic acids. This term likewise designates the synthetic resins (polymers), the character of which manifests itself by the presence of hydroxy or carboxy hydrophil e radicals which impart to the polymer molecule, of which either one or bothof said radicals is a member, a tendency to be wetted by water and i aqueous media.

This application is a division of our co-pending application Serial No. 552,210, filed onAugust 31, 1944, now Patent No. 2,447,462, of August 1'7, 1948.

While we have herein disclosed'the preferred embodiments of our invention, we do not thereby desire or intend to limit ourselves solely to the specific examples, since it will berea dily'apparent to those skilled in the art, that the precise proportions ofthe materials utilized may be varied and other materials having equivalent chemical or physical properties may be employed if desired without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the apfpended claims.

We claim:- '1. The processof producing subtractively colcred photographic prints which comprises photographing a monochrome image onto a photo-" graphic light-sensitive silver-halide emulsion, developing the exposed emulsion'to a'negative,

coloring certain portions of the negative which are to appear in color in said subtractively'colored print with a dispersion consisting'ofz' Water-soluble organic dye "grams--. T 1-10 5-25% Aqueous solution of. hydrophilic polymer cc 50-100 Water soluble aliphatic polyhydric alcohol containing at least two carbon. atoms "gram .,0.'5-1 Wetting agent do 0.5-1

said water soluble organic dyein said dispersion being of a color, complementary to that which from that of said first dispersion andcomplementary to that'which is to represent the. .c0rresponding colored portion of said print, printing-the resulting coloredpnegative onto a photographic, multi-layer, light-sensitive emulsion,-the layers of which are selectively sensitized to the red, green, and blue regions of the spectrum, each layer containing a color former-capable of yielding a dye image complementary in color to that for which it issensitized and developing the exposedlayers .by color forming development. into a subtractivelycolored print. I

- 2. The processes defined inclaim 1 in which portions of the negative which correspondto portions of the, print-to-be colored red are colored with a dispersion consisting of: I 1

anth a mone Blue S E (Schultz #861) grams; j 3.0

Fast Acid Violet B (Schultz #580) do I 1.5

Polyvinyl alcohol 15% so1ution cc 100 gram 1 3. The processes defined inclaim 1 in which portions of .the negative which correspond to portions ofthe print to be colored blue are colcred with a dispersion consisting of Pyrazolorange G (Schultz #fi'linegramsn 2 Sodium salt'of, cellulose glycolate 20 solution-r. cc d-Sorbitol40% solution grams 1.5 Sodium salt of tetrahydronaphthalene sulfonic acid gram 0.5

4. The process as defined in claim 1 in which portions of the negative which correspond to'portions of the print to be colored green are colored with a dispersion consisting of:

Brilliant CongoGKS chuItZ #369) grams 1.5

Sodium saltsof carboxyethyl cellulose 10% solution cc 50 d-Mannitol 40% solution grams 1.5 Sodium salt of isopropylnaphthalene sulfonic acid 1 "gram" 0.5

5. A metho d of producing subtractively colcred photographic prints which comprises coloring certain portions of'a transparent sheet material which are to appear in color with a dispersionconsisting of:

said Water soluble organic dye said dispersion being of a color complementary to that'whiclr is to represent the corresponding colored portion in said print and coloring other portions of said transparent sheet material with a dispersion as F aforesaid in whichthe'water soluble organic dye isof a color difierent from that of said first dispersion and complementary to that which is to represent the corresponding colored portion of said'printprinting the resulting colored sheet material onto a photographic, multi-layer, lightsensitive emulsion, the layers of which are selectively sensitized to the red, green, and blue regions of the spectrum, each layer containing a color former capable of yielding adye image complementary in color to that for which'it is sensitized .and developing the 'exposedlayers by color forming development into a subtractively colored print.

6. The method as defined in claim 5 in which portions of the sheet material which correspond to portions of the print to be colored red are 001- ored with a dispersion consisting of:

Anthraquinone Blue SE (Schultz #861) grams" Fast Acid Violet B (Schultz #580) do Polyvinyl alcohol 15% solution cc Glycerin gram Sodium salt of sulfonated ethyloleate 8. The method as defined in claim 5 in which portions of the sheet material which correspond portions of the print to be colored green are colored with a dispersion consisting of 7. The method as defined in claim 5 in which portions of the sheet material which correspond to portions of the print to be colored blue colored with a dispersion consisting of:

Pyrazolorange G (Schultz #747) grams Sodium salt of cellulose glycolate 20% solution cc d-Sorbitol 40% solution grams Sodium salt of tetrahydronaphthalene sulionic acid gram RICHARD M. HAFF'. FRANK J. KASZUBA.

are REFERENCES CITED 2 The following references are of. record in the file of this patent:

5o 20' FOREIGN PATENTS 1.5 Number Country Date 5 486,848 Great Britain June '7, 1938 Certificate of Correction Patent No. 2,458,905. January 11, 1949.

HAROLD O. HARSH ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 5, line 31, Example I, for oleate grams 7 read oleate -7 -grams- 1 and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 23rd day of August, A. D. 1949.

THOMAS F. MURPHY,

Assistant Commissioner of Patents.