Classifications

• • 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
  • B41M5/10—Duplicating or marking methods; Sheet materials for use therein by using carbon paper or the like
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/914—Transfer or decalcomania
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils
  • Y10T428/265—1 mil or less
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/3188—Next to cellulosic
  • Y10T428/31895—Paper or wood
  • Y10T428/31906—Ester, halide or nitrile of addition polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
  • Y10T428/31913—Monoolefin polymer
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31909—Next to second addition polymer from unsaturated monomers
  • Y10T428/31928—Ester, halide or nitrile of addition polymer

Definitions

• aqueous dispersion containing as essential dispersed matter 4.5 to 14% by weight of aliphatic saturated polycarboxylic acid of a molecular weight ranging from 1,000 to 20,000 and an acid number in the range of to 150, which acid comprises a main chain of carbon atoms, the terminal groups of which are free from carboxylic groups, and the carboxyl groups are bonded to the main chain as branches; the top layer is then dried at a temperature below the fusion point of the said carboxylic acid.
• This invention relates to transcriptive materials for making copies without the use of carbon paper; and to process for manufacturing such materials.
• transcriptive material which serve, when written upon, to make simultaneously one or several copies without the use of carbon paper.
• a conventional transcriptive material consists, for example, of a flexible sheet such as a paper sheet, as carrier, which bears on one side thereof a color layer for transmitting to a copy sheet the writing which is being applied to the color-free side of the carrier.
• the color layer may be of varying composition and comprise, e.g., pigment as well as binders and/or fillers.
• the carrier to which the writing to be transcribed, is applied under pressure, for instance, by means of a writing device such as the letters of a type-writer, may consist of common writing paper, type-writer paper, or like writing material.
• Transcriptive sheet materials which permit the making of copies without use of carbon paper have been known in the art under such names as manifolding sheet, copying paper, transfer sheet, transcript material and others.
• a flexible sheet carrier one surface of which is adapted for being written upon with a writing tool exerting a pressure thereupon, which pressure is of a magnitude as is generated when writing by hand with a ball-pen or pencil, lor by a manual or electric typewriter.
• Flexible sheet carriers suitable for use in the transcriptive material according to the invention are sheets of paper, woven or non-woven fibrous materials of cellulosic or other material, foils and films of synthetic polymeric resin or the like materials, but also other sheets of organic or inorganic substances of such surface texture that the color layer can satisfactorily adhere thereto.
• At least a portion of one surface of said sheet carrier bears a color layer consisting essentially of a mixture of a colored pigment and a high-molecular-weight organic binding agent which is free from waxy, oily and fatty components, in particular, polyvinylacetate, which layer is of such hardness and fastness to rubbing that no pigment rubs off or migrates therefrom directly into cellulosic material of a writing sheet placed thereunder when the carrier is subjected to the normal pressure exercized by writing on its uncoated surface.
• a color layer consisting essentially of a mixture of a colored pigment and a high-molecular-weight organic binding agent which is free from waxy, oily and fatty components, in particular, polyvinylacetate, which layer is of such hardness and fastness to rubbing that no pigment rubs off or migrates therefrom directly into cellulosic material of a writing sheet placed thereunder when the carrier is subjected to the normal pressure exercized by writing on its uncoated surface.
• Colored pigments suitable for preparing the color layer of the inventive transcriptt materials are e.g. the following dyestuffs denominated in accordance with the Colour Index 2. Edition, 1956: CI. Pigment Black 11, Cl. Pigment Blue 15 or 29, Cl. Vat Blue 1 or 14 (as pigments), C.I. Pigment Green 15, C.I. Pigment Orange 2 or 19 or 20, CI. Pigment Red 3 or 48 or 49 or 54 or 63, CI. Pigment Violet 4 or 5, CI. Vat Violet 1 (as pigment), CI. Pigment Yellow 1 or 23 or 31 or 34, Cl. No. 16185 in the form of Amaranth Maroon Lake.
• a top layer which consists essentially of a deposit obtained from an aqueous dispersion of 4.5 to 14% by weight of aliphatic saturated polycarboxylic acid of a medium molecular weight ranging from 1,000 to 20,000 and an acid number of 10 to 150, which acid comprises a main chain of carbon atoms the terminal groups of which are preferably free from carboxyl groups, and the carboxyl groups are bonded directly to said main chain as branches or to aliphatic side chains of, preferably from 1 to 4 carbon atoms which are in turn linked to the said main chain of carbon atoms.
• the saturated aliphatic polycarboxylic acids have, within the limits defined hereinbefore, for example, medium molecular weights of from 1,000 to 4,000 in the case of acid members ranging from 100 to 150, or medium molecular weights of 15,000 to 20,000 in the case of acid numbers of 10 to 30, 1
• carboxyl groups of these polycarboxylic acids used in the preparation of the top layer of the transcriptive material according to the invention may be bonded directly to the main carbon chain of the polymeric acid substance; or they may be present therein as substituents of short aliphatic, preferably alkyl side chains, preferably of the above-defined number of carbon atoms, which are in turns linked to the aforesaid rnain carbon chains; such side chains are preferablyCH COOH or --CH CH --COOH groups.
• transcriptive sheet materials according to the invention the top layer of which is prepared using aliphatic saturated polycarboxylic acids in which a portion of the carboxylic acid radicals has been esterfied to such a degree that the polymers possess saponification numbers in the range of from 30 to and acid numbers of from 10 to 140, i.e., the polycarboxylic acids contain simultaneously esterified and free carboxylic acid radicals.
• Esterification of the carboxylic acid groups can range from 1% up to 80% of the total of carboxylic acid radicals present and can be carried out with aliphatic alcohols, preferably with alkanols of from 1 to 20 carbon atoms, as alcoholic ester component.
• High-molecular-weight polycarboxylic acids of the above described special structure are of excellent dispersibility and especially good adherence to cellulose and to cellulosic writing materials.
• the esterified products are produced in a manner known per se, by esterification with methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, glycerol, propylene glycol, mannital, pentaerythritol and the like or by reaction of free carboxylic acid groups of the polymer or starting materials therefor with ethylene oxide or propylene oxide.
• An advantageous embodiment of the invention comprises a top layer of the novel transcriptive material in which the carboxyl groups of the saturated aliphatic polycarboxylic acids of a medium molecular weight of 1,000 to 20,000 have been esterified with a mixture of monoaud/or polyhydric alkanols, whereby the saponification number of the polymeric product ranges from 30 to 70 and the acid number from 10 to 150.
• polycarboxylic acids are produced in a well-known manner, for instance, by oxidation of branched polyethylenes or polypropylenes or by copolymerization of mixtures of ethylene and propylene, with unsaturated monoor di-carboxylic acids.
• Substances of such a kind suitable for preparing the top layer of the incentive transcriptive material are e.g. OA-Wachs LK 5012 and Emulsion LK 5022 produced by the Badische Anilinu. Soda- Fabrik A.G., Ludwigshafen, A-C Polyethylene 629 produced by the Allied Chemical Corporation, New York, and the special types E10, E13, E14, HDE and LVE 01f Epolene--waxes produced by the Eastman Chemical Products, Inc., Kingsport, Tenn.
• OA-Wachs LK 5012 and Emulsion LK 5022 produced by the Badische Anilinu. Soda- Fabrik A.G., Ludwigshafen, A-C Polyethylene 629 produced by the Allied Chemical Corporation, New York
• E10, E13, E14, HDE and LVE 01f Epolene--waxes produced by the Eastman Chemical Products, Inc., Kingsport, Tenn.
• polymeric products have several advantageous properties; they are particularly suited for the formation of aqueous dispersions, in which form they are used in the preparation of the top layer of the novel transcriptive material, which top layer imparts the transcriptive property to the said material. It is a further advantage of the said polymeric products that they are produced in the form of aqueous polymeric dispersions which can directly form such top layer.
• the polymeric carboxylic acids described hereinbefore can also be used in mixture with high-molecular-weight substances which also contain polar groups in their molecules; carboxylic acid groups, carboxylic acid amide, carboxylic acid ester and polyether groups have been found to be especially advantageous polar groups.
• the following mixtures are suitable for use in the formation of the top layer according to the invention:
• polymeric substances of such a kind containing polar groups and suitable to be mixed with the polycarboxylic 4 acids according to the invention may be used e.g. the special types D, 200D, 300D, "-1250D, 1300B, 1400B, 1450B of Lutofan or the special types 1D, 4D, 14D, 40D, 300D, 350D, 400D, 450D, 500D, 550D, 6001) of Acronal, both type groups produced by the Badische Anilinu. Soda-Fabrik A.G., Ludwigshafen, and KP Wachs or KSE-Wachs, both produced by the Farb- Maschinene Hoechst A.G., Frankfurt-Hoechst.
• polycarboxylic acids which form the essential constituents of the above described top layer e.g. polyethylene and polypropylene derivatives, are preferably present in such mixtures as the major portion thereof, in amounts of at least 60% by weight of the mixture.
• the high-molecular polycarboxylic acids can be used in mixture with esters of polyacrylic acid and alkanols having 1 to 10 carbon atoms, in the form of aqueous dispersions.
• the color pigment layer is of a thickness corresponding to 2 to 4 grams per square meter of carrier surface, while the top layer of polycarboxylic acid is preferably of a thickness of 0.5 to 3 grams per square meter of carrier surface.
• the transcriptive material according to the invention permits production of Well-readable manual or typed transcripts on common, untreated writing or printing papers.
• the copy of the writing thus produced on the latter type of paper has a dry, non-Waxy touch and does not rub off or smear.
• the above-described transcriptive material according to the invention is excellently suited for the production of text copies on a high number of superimposed sheets, the backs of which are provided with the above-described color layer and top layer according to the invention.
• a set of such papers can, for instance, be fastened together in pad-form.
• novel transcript paper is produced by the process according to the invention which comprises:
• aliphatic polycarboxylic acid or a mixture of such acid with the other substances described hereinbefore offers great advantages over the use of organic solvents, e.g. chlorinated hydrocarbons which have hitherto been used to apply top coatings of this kind. Handling of the aqueous dispersions is safer and healthier than that of the conventional organic solutions. Moreover the preparation and use of these aqueous dispersions is much more economical.
• the manufacture of the transcriptive material according to the invention is carried out by first applying to a carrier of the type described, a solution or dispersion of the pigment dyes and the above-defined binding agent, e.g. polyvinyl acetate.
• a carrier of the type described e.g. polyvinyl acetate.
• Well-known application techniques such as application with a brush or a roller, pouring, printing, or draw-down with a doctor blade or: air-knife can be employed.
• the color layer is thus formed on the carrier preferably in a thickness of 2 to 4 grams per square meter and dried in a hot air current.
• the pigment layer is then coated with the top layer by applying thereto the aqueous dispersion of the abovedescribed saturated aliphatic polycarboxylic acids with or without an admixture of other high-molecular-weight organic materials containing polar groups as defined hereinbefore, in such amounts that after drying there remains a thin layer, not exceeding 3 grams per square meter of the surface of the pigment layer; conventional application techniques using measuring and metering apparatus are employed.
• application can be carried out by means of rollers with the aid of doctor blades adjusted to meter the amount of top layer-forming dispersion applied, or by means of rotary printing, immersion, application with a brush, pouring on or spraying on of the said dispersion, or in a similar known manner.
• the top layer is then dried in a hot air current having a temperature of 45 to 55 C.
• a hot air current having a temperature of 45 to 55 C.
• the polymeric particles of the dispersion might melt and coalesce, which is to be avoided, since the color-transfer power of the top layer would suffer.
• drying of the top layer must be effected immediately and rapidly in order to prevent undue penetration of the top layer constituents into the color layer below the same. Drying with infrared radiation is more rapid than with a hot air current.
• the web should be passed through the hot air-drying chamber at a speed of 50 to 70, preferably about 60 meters per minute, or through an infrared irradiation zone more rapidly, e.g. at 80 to 120, and preferably at about 100 meters per minute.
• a typical transcript sheet produced by the method according to the invention bears a color layer of a thickness of 4 to 6 microns and a top layer of 2 to 4 microns.
• the invention is further illustrated by the following nonlimitative examples in which all temperatures are given in degrees centigrade and all parts and percentages are by weight unless expressly stated ottherwise.
• Example 1 A mixture serving for the production of a color layer is produced by mixing the following components together and grinding them in a ball mill:
• the resulting dispersion is then applied by a printing roller onto a web of cellulose paper in an amount of 40 grams per square meter of the web, excess is removed and the layer is then dried at 50 C., so as to leave a color layer of 2 grams per square meter on the paper web.
• the thickness of this color layer is about 0.005 mm.
• the resulting paper coated with the color layer is not yet suited for writing through to obtain copies on other paper sheets.
• the resulting dispersion is applied with a roller onto the color layer of the paper web, produced as described above under (a) and the web is moved immediately at a speed of about 60 meters per minute through a drying chamber in which it is dried in a stream of hot air having a temperature of 50-55.
• the resulting transcriptive paper web is cut into sheets and is now ready for use.
• a sharply delineated copy of the written text is produced on the untreated writing paper.
• the copy text does not smear and is very resistance to rubbing. It does not stain the fingers of a person handling the copy, as is the case frequently with copies prepared with known transcriptive paper.
• Example 2 15 parts of the alizarine-aluminum lake used in Example 1, and 4.0 parts of silica are intimately mixed with 2.5 parts of ethyl cellulose dissolved in 78.5 parts of ethanol, the whole is ground in a 'ball mill to produce a fine dispersion.
• the mixture is then applied to one side of a cellulose paper web and dried in the same manner as described in Example 1.
• Example 3 (a) A color layer is produced on a web of writing paper by the procedure and with the mixture described in step (a) of Example 1.
• the resulting transcriptive paper possesses good qualities similar to those of the paper produced in Example 1.
• Example 4 (a) A color layer is produced on a web of writing paper by the same procedure and with the same mixture as described in step (a) of Example 1.
• Example 2 35 parts by weight of an aqueous dispersion of polyoarboxylic acid as used in Example 1. 44 parts of an aqueous dispersion containing about 10% of montan wax ester (commercially available as KPE wax), 2.5 parts of an aqueous dispersion containing about 50% of vinylchloride-acrylic acid copolymerizate (commercially available as Lutofan 200 D), 2.5 parts of an aqueous dispersion containing about 50% of a co-polymerizate of different acrylic acid ester (commercially available as Acronal 500 D), and 16 parts of water are mixed intimately with each other, and the resulting dispersion is used as described in Example 1 for the production of a top layer on the color layer obtained in step (a) of this example.
• montan wax ester commercially available as KPE wax
• 2.5 parts of an aqueous dispersion containing about 50% of vinylchloride-acrylic acid copolymerizate commercially available as Lutofan 200 D
• the resulting transcriptive paper possesses good qualities similar to those of the paper produced in Example 1.
• Example 5 (a) A color layer is produced on a web of writing paper by the same procedure and with the same mixture as described in step (a) of Example 1.
• Emulsion LK 5022 produced by the Badische Anilinu. Soda- Fabrik A.G., Ludwigshafen, i.e. an aqueous dispersion containing 40% of a polycarboxylic acid having an acid number of 20-30, a saponification number of 5 0-60 and a molecular weight of 20,000 and the same content of emulsifier and dispersion-stabilizer as in the dispersion of Example 1, and 75 parts of water are mixed with each other and then applied in the same manner and in the same amount onto the color layer formed according to step (a) of this example, as is described under step (b) of Example 1.
• Example 6 (a) A color layer is produced on a web of writing paper by the same procedure and with the same mixture as described in step (a) of Example 1.
• the resulting transcriptive paper possesses good qualities similar to those of the paper produced in Example 1.
• a process for the manufacture of transcriptive materials producing a positive copy of writing on an underlying surface without the use of carbon paper or the like which process comprises:
• polycarboxylic acid is of a molecular weight of 15,000 to 20,000 and has an acid number in the range of 10 to 30.
• a .water-dispersible polymerizate selected from the group consisting of vinyl homopolymerizate, vinyl chloride-acrylic acid copolymerizate, vinyl chlorideacrylic acid-vinyl ester copolymerizate, acrylic acid amide polymerizate, methacrylic acid polymerizate, methacrylic acid ester polymerizate, montan wax containing carboxyl groups and montan wax containing esterified carboxyl groups.
• a transcriptive material producing a positive copy of the writing of an underlying surface without the use of carbon paper or the like which material comprises a flexible sheet carrier at least a portion of one surface of which bears a color layer consisting essentially of a mixture of a colored pigment and a high-molecularweight binding agent free from waxy, oily and fatty components, and a top layer covering said color layer and consisting essentially of a deposit obtained from an aqueous dispersion of 4.5 to 14% by 'weight of aliphatic saturated polycarboxylic acid of a medium molecular weight ranging from 1,000 to 20,000 and an acid number of 10 to 150, which acid comprises a main chain of carbon atoms the terminal groups of which are free from carboxyl groups, and the carboxyl groups are bonded to said main chain as aliphatic saturated branches of from 1 to 4 carbon atoms, said acids being the product of the oxidation of branched polyethylene or polypropylene or the copolymerization product of mixtures of ethylene or propylene

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• Duplication Or Marking (AREA)
• Paper (AREA)
• Color Printing (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=7404807

Family Applications (1)

Country Status (3)

Cited By (3)

Families Citing this family (1)

Citations (2)

• 1963
  • 1963-09-12 DE DER36101A patent/DE1240098B/de active Pending
• 1964
  • 1964-09-11 GB GB37233/64A patent/GB1092953A/en not_active Expired
• 1967
  • 1967-11-01 US US679944A patent/US3468692A/en not_active Expired - Lifetime

Patent Citations (2)

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