US3220859A - Data processing materials - Google Patents

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Publication number
US3220859A
US3220859A US70544A US7054460A US3220859A US 3220859 A US3220859 A US 3220859A US 70544 A US70544 A US 70544A US 7054460 A US7054460 A US 7054460A US 3220859 A US3220859 A US 3220859A
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US
United States
Prior art keywords
acid
carrier
composition
thermally
sulfo
Prior art date
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Expired - Lifetime
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US70544A
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English (en)
Inventor
Berman Elliot
Charles H C Pian
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northrop Grumman Guidance and Electronics Co Inc
Original Assignee
Itek Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to NL259126D priority Critical patent/NL259126A/xx
Application filed by Itek Corp filed Critical Itek Corp
Priority to US70544A priority patent/US3220859A/en
Priority to GB42631/60A priority patent/GB959402A/en
Priority to FR847202A priority patent/FR1282715A/fr
Priority to US217837A priority patent/US3238047A/en
Application granted granted Critical
Publication of US3220859A publication Critical patent/US3220859A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03B—APPARATUS OR ARRANGEMENTS FOR TAKING PHOTOGRAPHS OR FOR PROJECTING OR VIEWING THEM; APPARATUS OR ARRANGEMENTS EMPLOYING ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ACCESSORIES THEREFOR
    • G03B27/00—Photographic printing apparatus
    • G03B27/02—Exposure apparatus for contact printing
    • G03B27/14—Details
    • G03B27/30—Details adapted to be combined with processing apparatus
    • G03B27/306—Heat development
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron

Definitions

  • the present inventions and discoveries in their broadest aspects relate to data processing and to improved media, including improved materials for rapid economical reception, reproduction, recording and storing data such ras coded and uncoded intelligence, documents, records, images and the like. More particularly, our invention and discoveries relate to novel materials for thermally responsive reception, recording land storage of such information to sensitize carrier materials adapted to be marked in accordance with the therrnographic techniques, and to combinations of such compositions and carriers as articles of manufacture.
  • Such carrier materials may be paper, cloth, cellulosic compositions for example, or other suitable web or sheetlike materials.
  • the materials of the present invention are improvements over the iixable, thermal responsive materials disclosed in co-pending U.S. application Serial No. 860,008 of Leonard E. Ravich dated December 16,
  • the present invention includes improvements in reducing thermal responsiveness of such materials after image formation by solvent rinsing or volatilization of the residual background compounds.
  • thermographic papers and the like except for those disclosed in said Ravich applications, have certain varying and differing disadvantages and undesirable limitations.
  • a few of these disadvantages are that the image formed, when the sheet is exposed to heat, may be blurred, of poor or non-uniform color intensity and/or provide poor contrast with the copy sheet; moreover, exposure of the sheet may require heating for an undesirably long time period.
  • Such sheets in some instances are sensitized by compounds in a wax layer which is relatively expensive to manufacture, and result in poor image resolution, which may be subsequently obscured by exposure of the sheet to further heat or radiation.
  • the present invention also provides permanently iixable information carriers falling within the purview of the said Ravich disclosures with improvement of the quality of the sensitizing materials and images produced, obviates the abovementioned disadvantages of prior copy papers, and has the following general advantageous properties: inexpensive system; aqueous or common solvent solution for simplified manufacture; paper support or carrier not adversely affected; good stability under normal storage conditions; stable to ultraviolet radiation, eg., sunlight, for a prolonged duration; will not smudge; print is of archival quality; good sensitivity, i.e it does not require a high temperature (120 C.), or a relatively long time at a specific temperature, or heating over a Wide range of temperature to produce a visible change of sufficient in- 3,220,859 Patented Nov.
  • Reflex reproduction as herein referred to is effected by placing a radiation transmissive, thermally sensitive carrier material in surface contact with the image on the graphic original to be reproduced between said image and va radiation source which transmits radiation through the carrier to the iamge.
  • the radiation passes through the sensitized material, is :absorbed by and increases the temperature of the marking areas of the original image sufficiently above the background or spacing area temperatures to reproduce the marking areas rapidly on the thermally sensitive carrier as a result of heat-conductive pressure contact, such for example as that disclosed in U.S. Patent No. 2,740,895 and 2,740,896 to Mi-ller; 2,891,165 to Kuhrmeyer; and 2,813,043 to Clark.
  • temperatures of the marking areas of the master are selectively raised above the spacing or background areas sufiiciently by irradiation or other suit-able means and immediately thereafter brought into contact with the copy carrier in a manner to reproduce a positive image by thermal foramtion of the marking areas.
  • the copy materials of the present invention may be utilized in either a direct, reiex, or any other thermally responsive marking processes. Use thereof in a reex process is limited however, to a radiation tnansmissive carrier material.
  • the background areas are rendered incapable of forming an limage when exposed to certain conditions after the desired image has been formed by thermographic process.
  • Another object of the present invention is to provide sensitizing processing media compositions for thermally responsive graphic data processing media which provide permanent images and which may be iixed after image formation, i.e., the thermal responsiveness reduced by either a solvent rinse or volatilization.
  • Another object of the present invention is to provide solutions of sensitizing compositions that may be veasily and quickly applied to a carrier.
  • Still another object of the invention is to provide thermally sensitive carriers on which any one of a variety of differently colored images Imay be formed on a light background.
  • a further object of the invention is to provide a sensitized thermographic carrier inherently capable of reproducing a large amount of detail.
  • Still another object of the invention tis to provide thermally responsive gnaphic data processing media having the foregoing advantages and which may be produced at low cost.
  • FIGURE 1 is a table of examples of sensitizing compositions in accord with the present invention.
  • colorless compositions are normally utilized consisting of a base ingredient such as an acid and a color forming additive, as alpha-sulfo-palmitic acid and pyrogallol, to make a carrier heat sensitive and useful for thermally responsive marking processes.
  • a base ingredient such as an acid and a color forming additive, as alpha-sulfo-palmitic acid and pyrogallol
  • Such a composition may be simply prepared by dissolving the chosen base ingredient and additive in a solvent, such as water, acetone, alcohol, etc., then impregnating or coating the carrier with the solution and drying the copy carrier at any convenient temperature below that at which the now thermally sensitive carrier will change color.
  • a solvent such as water, acetone, alcohol, etc.
  • one may add quantities of certain materials such as carboxylic acids, as shown in detail hereinafter, to enhance the stability of the composition.
  • the table of FIGURE 1 illustrates examples, read horizontally from a particular example number, of compositions formulated in accord with the present invention.
  • the upper figure in each box of the table indicates the preferred relative amount of the particular ingredient in the example while the preferred range is indicated in the lower half of the box below the dotted line.
  • gredients are broken up into general groupings classified as base ingredients, color forming additives, and solvents.
  • the base ingredient, boron triuoride-diphenol complex also acts as a color forming agent.
  • compositions having uoboric acid as a base ingredient are all desensitizable by volatilization which occurs after the image has been formed on the carrier by exposing the carrier to a temperature condition sufficient to permit volatilization of the composition of the carrier i but insuicient to cause a color change in the background areas thereof.
  • phloroglucinol as a color forming additive several other compounds give effective results such as, for example, sucrose, sorbitol, polyvinyl alcohol, A-naphthol, B-naphthol, 3-hydroxy-2-naphthoic acid, o-aminophenol, tartaric acid, pyrogallol and resorcinol.
  • the base ingredient is a sulfo-aliphatic acid, alpha-sulfo-palmitic acid and alphasulfo-stearic acid being given as illustrative examples of this class.
  • a carrier may be impregnated therewith by any convenient method.
  • the carrier may be coated with the solution by any known method. While a white carrier has been found to be particularly effective, carriers of other colors may be used. Even practically transparent papers, such as the glassine papers, make very satisfactory carriers which may, in turn, be used, e.g., as masters for copying systems such as the known diazo or photographic reproduction systems.
  • the impregnated, or coated, carrier is then dried, again by a convenient method.
  • rapid and complete drying is easily accomplished at room temperature under a partial vacuum.
  • the way in which drying is accomplished is not essential
  • the into the invention it being necessary only that the application of excessive heat be avoided to prevent discoloration of the now sensitized carrier.
  • the sensitized carrier becomes ready for use. Since the alpha-sulfo-palmitie acid and the pyrogallol in or on the carrier are colorless, no visible change will have taken place.
  • the prepared carrier When it is desired to use the prepared carrier in a reflex copy process for example, it is simply assembled with the master to be copied and the two put through conventional reproduction apparatus such as that designated by the trademarks Masterfax or Thermofax In such apparatus, when the master to be copied irradiated through the carrier by infrared radiations, a reflex copy is produced. It will be found that a colored copy of the image on the master is formed on the carrier. It will be imiediately apparent that the character of the original image will affect the copy, it being assumed that the original image is capable of thermographic reproduction. It is also apparent that the character of the carrier itself will affect the speed at which an image may be copied in that paper of different compositions and thickness transmit infrared radiations and conductive heat differently.
  • the amount of solvent in the present compositions is not critical since it merely serves as a means of applying a dissolved composition to a copy carrier, and is thereafter removed as by drying.
  • organic acids with a color forming additive the following example illustrated as Example l in FIGURE 1 of the drawing has been found satisfactory.
  • Example 1 Preferred Alpha-sulfo-palmitic acid g 1 Pyrogallol ..g 0.55 Acetone rnl-- 20 TABLE 1 [Base compound, alphasullopalmitic acid, 1 g.)
  • Phloroglucinol .55 g..- Brown Light tan. Phloroglucinol, .38 g Brown Almost colorless.
  • carboxylic acids such as citric acid
  • tartaric acid may also be substituted for the tartaric acid as stabilizers without any apparent difference in result.
  • compositions containing alpha-sulfo-palmitic acid other sulfo-aliphatic acids also are operative to thermally sensitize carriers for graphic data indication production.
  • alpha-sulfostearic acid in molar ratios of 1:1 through 5:1 with pyrogallol or phloroglucinol as the color forming additive and tartaric or citric acid as the stabilizer coated on or in a sheet from a suitable solvent, gives images with high contrast in a thermographic reflex process.
  • the manner in which any of these compositions is prepared is the same as previously outlined in connection with alpha-sulfo-palmitic acid containing compositions.
  • the materials are soluble in many known solvents; the materials have a low order of toxicity; none of the systems are pressure sensitive; none leave any residues in the reproducing apparatus during the copying process; a rst surface image is formed when the carrier is impregnated with the materials; the carrier may be used as a master in other reproduction systems; and the materials may be easily and cheaply applied to the carrier by known coating or impregnating methods.
  • the carrier may be xed, i.e., the sensitized background may be desensitized by application of a solvent rinse such as Water to the carrier.
  • thermally sensitive composition contain a sulfonic acid as a constituent part thereof before any image may be formed.
  • Other compositions may be used with the carrier to form a desired image in apparatus such as the Thermofax machine.
  • many of the acid salts of amines will react with zinc fluoroborate at elevated temperatures to form an image.
  • Example 9 is exemplary of such a composition.
  • the components for this example may be prepared by making two solutions, as follows:
  • an image may also be generated in the carrier by the thermal decomposition of the boron trifluoride-diphenol complex.
  • a satisfactory composition may be prepared simply by dissolving 10 parts by volume of the boron trifluoride-diphenol complex in 40 parts by volume of acetone or other suitable solvent.
  • Example 12 is exemplary of such a composition. Since the boron triuoride-diphenol complex is a liquid at room temperature, it may be applied without a solvent. However, it is easier to impregnate the carrier with the aid of a solvent.
  • sensitizing compositions apart from the sulfonic acid and fluoboric acid types utilize a 40% zinc fluoroborate solution (60% water by Weight) with a solvent and color forming additive such as benzidine dihydrochloride or with a like amount of 2-amino-S-diethylaminotoluene monohydrochloride.
  • Example 10 is illustrative of cornpositions of this type.
  • a thermally sensitive composition for producing a sensitized carrier for use in thermally responsive marking processes said composition forming color in response to heat and consisting essentially of a thermally responsive ingredient selected from the group consisting of (a) the boron triuoride-diphenol complex and (b) thermally responsive mixtures of a thermally sensitive acid reagent selected from the group consisting of a-sulfo palmitic acid, a-sulfo stearic acid, 4,4'diphenyl disulfonic acid, m-benzene disulfonic acid, fluoboric acid, and zinc uoborate in combination with effective amounts of a reagent forming color in the presence of said acid reagent under the influence of heat and selected from the group consisting of pyrogallol, phloroglucinol, resourcinol, a-naphthol, -naphthol, 3-hydroxy-2-naphthoic acid, N,Ndiethyl-
  • composition as in claim 1 which additionally contains a solvent for said ingredients facilitating their application to a carrier.
  • composition as in claim 1 which additionally contains a carboxylic acid stabilizer selected from the group consisting of tartaric and citric acids.
  • thermoly responsive ingredients are an a-sulfo aliphatic carboxylic acid and a phenol.
  • a thermally sensitive color-forming composition for producing a sensitized carrier for use in thermally responsive marking processes, said composition comprising as its essential thermally responsive color-forming ingredients -sulfo-palmitic acid and 3hydroxy2naphthoic acid.
  • a thermally sensitive color-forming composition for producing a sensitized carrier for use in thermally responsive marking processes, said composition comprising as its essential thermally responsive color-forming ingredients m-sulfo-palmitic acid and pyrogallol.
  • a thermally sensitive color-forming composition for producing a sensitized carrier for use in thermally responsive marking processes, said composition comprising as its essential thermally responsive color-forming ingredients a-sulfo-stearic acid and phloroglucinol.
  • a thermally sensitive color-forming composition for producing a sensitized carrier for use in thermally' responsive marking processes, said composition comprising as its essential thermally responsive color-forming ingredients a-sulfo-palmitic acid and phloroglucinol, said composition additionally containing tartaric acid as a stabilizer, and a solvent for the ingredients facilitating their application to a carrier.
  • a thermally sensitive recording medium consisting essentially of a carrier and a thermally sensitive composition thereon, said composition forming color in response to heat and consisting essentially of a thermally responsive ingredient selected from the group consisting of (a) the boron trifluoride-diphenol complex and (b) thermally responsive mixtures of a thermally sensitive acid reagent selected from the group consisting of a-sulfo palmitic acid, -sulfo stearic acid, 4,4diphenyl disulfonic acid,

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
US70544A 1960-11-21 1960-11-21 Data processing materials Expired - Lifetime US3220859A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NL259126D NL259126A (en, 2012) 1960-11-21
US70544A US3220859A (en) 1960-11-21 1960-11-21 Data processing materials
GB42631/60A GB959402A (en) 1960-11-21 1960-12-12 Thermographic copying process and apparatus therefor
FR847202A FR1282715A (fr) 1960-11-21 1960-12-16 Systèmes et matières pour le traitement de données
US217837A US3238047A (en) 1960-11-21 1962-08-20 Data processing media

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7084160A 1960-11-21 1960-11-21
US70544A US3220859A (en) 1960-11-21 1960-11-21 Data processing materials
US217837A US3238047A (en) 1960-11-21 1962-08-20 Data processing media

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US3220859A true US3220859A (en) 1965-11-30

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US217837A Expired - Lifetime US3238047A (en) 1960-11-21 1962-08-20 Data processing media

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3432327A (en) * 1964-03-13 1969-03-11 Pilot Pen Co Ltd Pressure sensitive copying sheet and the production thereof
DE1571819A1 (de) * 1965-06-22 1970-04-02 Agfa Gevaert Ag Thermographisches Verfahren zur Herstellung waermebestaendiger Kopien
JPS5274406A (en) * 1975-12-05 1977-06-22 Dainippon Toryo Kk Ink for ink jet recording

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2748024A (en) * 1952-05-13 1956-05-29 Dick Co Ab Transfer sheet for use in a hectograph duplicating process
US2795504A (en) * 1952-10-25 1957-06-11 Dick Co Ab Compositions for use in the manufacture of elements in reproduction
US2813042A (en) * 1952-10-02 1957-11-12 Dick Co Ab Method of preparing a sensitized thermographic copy sheet and resultant sheet
US2859351A (en) * 1951-02-02 1958-11-04 Minnesota Mining & Mfg Method of making permanent facsimile copies
US2967784A (en) * 1958-05-02 1961-01-10 Columbia Ribbon Carbon Mfg Thermographic copying paper
US2980551A (en) * 1959-02-13 1961-04-18 Minnesota Mining & Mfg Method of making a heat-sensitive copysheet and resultant article
US3102812A (en) * 1960-11-16 1963-09-03 Gen Aniline & Film Corp Stabilizers for one-component diazotype materials
US3108872A (en) * 1961-09-27 1963-10-29 Photo-thermolytical vesicular

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA552743A (en) * 1958-02-04 Minnesota Mining And Manufacturing Company Method of using heat-sensitive copying-paper
US1763291A (en) * 1927-08-29 1930-06-10 United States Gypsum Co Process of chemical printing
US1693735A (en) * 1927-11-17 1928-12-04 Clarence W Bickford And Mary B Method of decorating glass surfaces
US2637657A (en) * 1946-06-10 1953-05-05 Product Dev Lab Inc Thermosensitive papers and compositions therefor
US2625494A (en) * 1948-05-05 1953-01-13 Morrison Montford Heat-sensitive recording element
US2864720A (en) * 1954-10-29 1958-12-16 Ditto Inc Transfer sheet coated with a composition containing a salt and a hydrotrope
BE576280A (en, 2012) * 1958-03-08

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2859351A (en) * 1951-02-02 1958-11-04 Minnesota Mining & Mfg Method of making permanent facsimile copies
US2748024A (en) * 1952-05-13 1956-05-29 Dick Co Ab Transfer sheet for use in a hectograph duplicating process
US2813042A (en) * 1952-10-02 1957-11-12 Dick Co Ab Method of preparing a sensitized thermographic copy sheet and resultant sheet
US2795504A (en) * 1952-10-25 1957-06-11 Dick Co Ab Compositions for use in the manufacture of elements in reproduction
US2967784A (en) * 1958-05-02 1961-01-10 Columbia Ribbon Carbon Mfg Thermographic copying paper
US2980551A (en) * 1959-02-13 1961-04-18 Minnesota Mining & Mfg Method of making a heat-sensitive copysheet and resultant article
US3102812A (en) * 1960-11-16 1963-09-03 Gen Aniline & Film Corp Stabilizers for one-component diazotype materials
US3108872A (en) * 1961-09-27 1963-10-29 Photo-thermolytical vesicular

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GB959402A (en) 1964-06-03
US3238047A (en) 1966-03-01
NL259126A (en, 2012)

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