US3499758A - Color oscillograph recording paper - Google Patents

Color oscillograph recording paper Download PDF

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Publication number
US3499758A
US3499758A US462063A US3499758DA US3499758A US 3499758 A US3499758 A US 3499758A US 462063 A US462063 A US 462063A US 3499758D A US3499758D A US 3499758DA US 3499758 A US3499758 A US 3499758A
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United States
Prior art keywords
color
paper
silver
color former
coating
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Expired - Lifetime
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US462063A
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English (en)
Inventor
Carl E Johnson
Dewey M Dumers
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GAF Corp
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GAF Corp
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/3003Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/30Hardeners

Definitions

  • This invention relates to color oscillograph recording materials and, more particularly, to photosensitive recording paper having utility for recording oscillograph traces in at least three colors.
  • Photosensitive papers adapted for light recording, for example, oscillograph, recordings are known. Such materials are both of the print-out type and the developingout type.
  • the print-out type of material requires no development step and may or may not be fixed. Such materials are generally much slower than the materials used in developing-out processes and have poor image permanency.
  • the developing-out type as the name implies, requires that the exposed material be chemically developed, fixed and washed in order to provide a stable visible image on said material. It is this second type of printing material with which the present invention is concerned.
  • An object of this invention is to provide a new recording material for use in oscillograph recording which will improve trace separation and readout.
  • Another object of this invention is to provide a simplified system of processing such papers for development employing a minimum number of solutions.
  • Another object of this invention is to provide a color system which closely approximates the handling procedures used with conventional black and white oscillograph papers.
  • Still another object is a procedure which does not require a bleach step to remove image silver as required in conventional color systems.
  • a photographic material comprising a flexible support bearing on at least one surface thereof (a) an undercoat comprising a silver chlorobromide emulsion layer having a low blue sensitivity, being practically insensitive to light having a wave length of 460 microns and above before optical sensitization, being sensitized to the green region of the spectrum ice and containing a colorless color former fast to diffusion capable of reacting with the oxidation products of an aromatic p-amino-developing agent to form a magenta dye image; (b) a separating layer comprising a hardened gelatin layer; (c) an outer coating comprising a silver bromoiodide emulsion layer having a high sensitivity to the blue light without containing an optical sensitizing dye, but containing a color former capable of forming a cyan dye image upon color development; and (d) a hardened gelatin surface layer.
  • photographic paper and recording paper are used throughout the specification and claims to include photosensitive emulsions disposed in any suitable support such as paper, film or other usable medium. It is preferred, however, to employ a paper such as 45-90 grams/ square meter Document Paper rag) without baryta coat or other surface or a paper similar thereto.
  • the invention contemplates conventional photographic recording techniques in exposing the photosensitive emulsions to light in an oscillograph recorder.
  • the recorder is necessarily provided with suitable colored filters in front of galvanometers used in conjunction therewith.
  • the conventional photographic recording techniques generally referred to as oscillography, involves the exposure of an entire roll of a record paper to the information to be recorded with subsequent and separate chemical development of the roll thus exposed. In this procedure a record roll of approximately 250400 feet in length is entirely exposed before its removal from the oscillographic recorder and its subsequent development by conventional means.
  • the color formers employed herein are those which are well known in the photographic art.
  • the term color former is use throughout the specification and claims to define an essentially colorless compound fast to diffusion which is capable of reacting with the oxidation products of an aromatic p-amino developing agent, particularly of the N,N-disubstituted p-phenylenediamine series as exemplified by N,N- diethylamino aniline, N,N-di (B hydroxyethyl)-aniline and the like, to produce dyes of the azomethine, quinoneimine, indoaniline and phenazine (azine) series.
  • color formers are well known to persons skilled in the art and described in the patent literature, for instance in United States Patents 2,500,487; 2,547,307; 2,829,975 and others.
  • Illustrative of the color formers which are usable in accordance with this invention are compounds such as: 1-octadecyl-2-(2',1-hydroxynaphthyl) benzimid azole-S- sulfonic acid as a cyan color former; 1-(4-phenoxy-3'- sulphophenyl)-3-stearyl-5-pyrazole as a magenta color former; and 2-(4-benzolylacetaminophenyl)-l-octadecylbenzimidazole-S-sulfonic acid as a yellow color former.
  • the quantity of color former used per unit of silver halide is selected in such a. way that sufficient density of the trace is achieved upon exposure and developing so as to provide proper readout.
  • the ratio of color former to silver halide per silver halide emulsion layer be about 10 millimols of color former to about 2 to 20 grams of silve halide.
  • the invention contemplates the use of a sensitizing dye capable of sensitizing in the green region of the spectrum. If desired, the blue sensitivity of the blue sensitive layer can be further increase-d by the use of a sensitizing dye for the blue. It is preferred that these dyes
  • the emulsions may contain the usual coating finals such as those proposed to retard or prevent fog in light-sensitive silver halide emulsions. These compounds are commonly referred to as antifoggants or stabilizers and are, in many instances, heterocyclic compounds with a plurality of nitrogen atoms or with a mercapto group in their molecule.
  • Certain other adjuvants normally incorporated into silver halide photographic emulsions such as wetting agents, may also be employed.
  • aqueous gelatin dispersions and gelatin silver halide emulsions employed herein with a hardening agent in order to reduce the tendency of the layers to soften, melt or reticulate during processing, particularly at temperatures which are higher than the temperature of 68 F. (20 C.) previously specified for the processing of photographic materials.
  • a hardening agent in order to reduce the tendency of the layers to soften, melt or reticulate during processing, particularly at temperatures which are higher than the temperature of 68 F. (20 C.) previously specified for the processing of photographic materials.
  • Compounds which have been used for the hardening of gelatin and gelatin emulsion layers include formaldehyde, hydroxyaldehydes, glyoxal and its derivatives, triacrylformal, as well as mixtures of such aliphatic aldehydes with an aromatic hydroxy compound such as phenol, or resorcylic aldehyde.
  • Other con ventional hardeners also applicable include alum, chromal
  • Suitable supports for the novel silver halide emulsions and elements of this invention include the flexible supports used in the prior art for oscillographic recordings. These supports may be transparent but, in general, a photographic grade flexible paper is selected. In this regard, 55 g./m. of Document Paper (100% rag) without a baryta coating or other surface coating is especially preferred. However, there can be used any other flexible material suitable for coating with a photographic colloid silver halide emulsion.
  • EXAMPLE I An improved recording paper was prepared by adding to 1000 grams of a low blue sensitive chlorobromide emulsion the following ingredients: 120 cc. of a 1:2000 solution containing a sensitizing dye for the green; 0.5 gram of an antifoggant; 30 cc. of a solution of an ammonium salt of a sulfate ester of an alkyl phenoxypolyoxyethylene ethanol which serves as a coating aid; 1.2 grams of a triacrylformal hardener; and grams of a magenta color former having the formula:
  • the material with the two silver halide layers was exposed using a commercially available oscillograph (manufactured by the Midwestern Instruments Corp.) employing a tungsten light source under the following conditions:
  • the lamp voltage was set at 12 volts and paper travel rate was adjusted at 2.5 inches/ second.
  • signal generators were used to apply a sine wave of 20 cycles/second to each galvanometer and the amplitude was varied to give a trace deflection of from 1 to 4 inches.
  • the resulting exposed material was then placed in a standard automatic oscillogram processor as manufactured by Consolidated Electrodynamics Corp. and processed at a rate of about 4 feet/minute.
  • processor apparatus 4 tanks were utilized, each being maintained at a temperature of about F., with the following tank arrangement as to contents:
  • Tank No. Tank contents 1 Color developer. 2 Do. 3 Fixer.
  • Color developer Ingredient Amount, grams Sodium pyrophosphate 1.0 Sodium sulfite (anhydrous) 4.0
  • Fixer Ingredient Amount, grams HYPO (sodium thiosulfate, anhydrous- 130.0 Water up to 1 liter.
  • the resulting processed paper showed four distinct and separate traces, namely, cyan, magenta, deep blue and purple.
  • the magenta trace was produced by the light from galvanometer A which was fitted with the yellow filter.
  • the cyan trace was produced by the light from galvanometer B which was fitted with the magenta filter.
  • the deep blue trace was produced by the light from galvanometer C which was fitted with the pale magenta color-correction filter and the purple trace by the light from galvanometer D, which was not fitted with a filter.
  • the filters selected to produce the various desired colored trace lines are determined by the speed of the sensitive material as related to the light source intensity and the color temperature.
  • the above filters were selected for use with a tungsten light source.
  • other filters may be needed especially to balance the so-called white light trace.
  • Nonlimiting examples of the filters which may be suitably employed are as follows:
  • Color trace Filter type Magenta Wratten Nos. 12, 15, 16, 56, 57, 8, 61, 74. Cyan Wratten Nos. 32, 34, 47B, 48, 49. Blue to bluish magenta Neutral density or pale magenta color correction or pale yellow color correction filters.
  • EXAMPLE 2 A recording paper was prepared in a manner similar to that of Example 1 exceptfor changes in the color formers employed. Thus, the paper was prepared by adding to 1000 grams of a low blue sensitive chlorobromide emulsion the following ingredients: 120 cc. of a sensitizing dye for the green, 0.5 gram of an antifoggant; 30 cc. of a solution of the ammonium salt of a sulfate ester of an alkyl phenoxypolyoxyethylene ethanol which serves as a wetting agent; 1.2 grams of triacrylformal hardener; and 10 grams of the magenta color former employed in Example 1, and 5 grams of a yellow color former having the formula:
  • a layer was coated prepared from a high-speed bromoiodide emulsion containing 0.5 gram of an antifoggant; 30 cc. of the above wetting agent solution; 1.2 grams of a formaldehyde hardener and 10 grams of the cyan color former employed in Example 1 and 5 grams of the yellow color former employed in Example 1.
  • the processing technique employed offers several advantages.
  • the availability of two developer and fixer tanks makes it possible to extend not only the developing time and fixing time but also the useful life of the processing solutions.
  • the omission of the bleaching step results in color pictures which contain a warm tone silver deposit.
  • the presence of the silver deposit makes it possible to reproduce the oscillograph recording on diazotype materials.
  • a multicolor recording paper for recording oscillograph traces in at least three colors which comprises a flexible support bearing on at least one surface thereof in the following order: (a) a hardened silver chlorobromide emulsion substantially insensitive to light of a wave length of 460 microns and above, being optically sensitized to the green and containing a color former capable of forming a magenta dye image upon color development, (b) a hardened gelatin intersurface layer, (c) a hardened silver bromoiodide emulsion coating having blue sensitivity and containing a color former capable of forming a cyan dye image upon color development, and (d) as an outer surface layer a hardened gelatin layer, each of said emulsion layers being coated to a silver coating weight of 0.4 to 0.8 gram silver per square meter.
  • a multicolored image which comprises exposing with a plurality of selectively filtered colored lights, a multicolor recording paper for recording oscillograph traces in at least three colors which comprises a flexible support bearing on at least one surface thereof in the following order: (a) a hardened silver chlorobromide emulsion substantially insensitive to light of a wave length of 460 microns and above, being optically sensitized to the green and containing a color former capable of forming a magenta dye image upon color development, (b) a hardened gelatin intersurface layer, (c) a hardened silver bromoiodide emulsion coating having blue sensitivity and containing a color former capable of forming a cyan dye image upon color development, and (d) as an outer surface layer a hardened gelatin layer, each of said emulsion layers being coated to a silver coating Weight of 0.4 to 0.8 gram silver per square meter, developing the imagewise exposed recording material with a developer solution comprising an aromatic amino developing agent and fixing

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Color Printing (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US462063A 1965-06-07 1965-06-07 Color oscillograph recording paper Expired - Lifetime US3499758A (en)

Applications Claiming Priority (1)

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US46206365A 1965-06-07 1965-06-07

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US (1) US3499758A (xx)
DE (2) DE1952682U (xx)
GB (1) GB1140039A (xx)
NL (1) NL6607644A (xx)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3226234A (en) * 1961-10-28 1965-12-28 Agfa Ag Hardening photographic layers containing proteins
US3265503A (en) * 1962-06-27 1966-08-09 Eastman Kodak Co Photographic recording element
US3372030A (en) * 1962-12-14 1968-03-05 Pavelle Corp Method of shortening the processing time of color photography

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3226234A (en) * 1961-10-28 1965-12-28 Agfa Ag Hardening photographic layers containing proteins
US3265503A (en) * 1962-06-27 1966-08-09 Eastman Kodak Co Photographic recording element
US3372030A (en) * 1962-12-14 1968-03-05 Pavelle Corp Method of shortening the processing time of color photography

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Publication number Publication date
GB1140039A (en) 1969-01-15
NL6607644A (xx) 1966-12-08
DE1952682U (de) 1966-12-29
DE1547908A1 (de) 1970-01-08

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