US3484264A - Method of making transfer sheet - Google Patents

Method of making transfer sheet Download PDF

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US3484264A
US3484264A US679591A US3484264DA US3484264A US 3484264 A US3484264 A US 3484264A US 679591 A US679591 A US 679591A US 3484264D A US3484264D A US 3484264DA US 3484264 A US3484264 A US 3484264A
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Prior art keywords
pigment
transfer layer
sheet
pigments
parts
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Eugen Strauss
Wilhelm Koreska
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Kores Manufacturing Corp
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Kores Manufacturing Corp
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3669—Treatment with low-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • 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

Definitions

  • the present invention relates to a copy sheet and a method of making the same and, more particularly, the present invention is concerned with a copy sheet which can be inscribed or imprinted, for instance by typewriter, under simultaneous production of one or more copies without interposing carbon papers between the individual sheets.
  • Such transfer layer may cover the entire back face of the carrier sheet or only a portion thereof.
  • Sets of such copy papers are known for making several copies of bills, statements or the like without inserting a carbon paper or the like between the sheets on which the hand or machine-written notices are to be formed.
  • Such papers generally include a transfer layer applied to the back face of the carrier sheet on the front face of which the original writing will be formed, for instance by typing. By superposing the back face of such sheet upon the front face of a similar sheet, and writing or forming impressions on the front face of the first sheet, a copy of such impressions is obtained on the front face of the underlying sheet.
  • copy sheets were developed which have at the back face of the top sheet a transfer layer and on the front face of the underlying sheet a special take-up layer which is adapted to receive the pressure- 3,484,264 Patented Dec. 16, 1969 ice exposed portions of the transfer layer of the superposed sheet.
  • the transfer layer is so composed in this case that it will riot smear on contact, even if such contact is under a certain degree of pressure, as long as the contacting surface is not of substantially the composition of the take-up layer.
  • the carrier sheet must be passed twice through the coating machinery and this will result in an increase in production costs and reduction of the output.
  • the take-up layer consists completely of wax-like materials and this Wax-like coating closes the pores of the underlying carrier sheet so that the absorptive capacity of such carrier sheet, for instance a paper sheet is lost.
  • direct imprinting, for'instance by means of a typewriter, or writing with ink or with a ball point pen on the take-up layer-coated paper is made difficult or impossible due to the fact that the surface of the sheet formed by a coating of the take-up layer is a poor acceptor for printing ink or writing liquid.
  • the sheets are to be imprinted as is the case in many instances when sets of bills and the like forms are to be produced, special care must be taken or special printing inks must be used in order to obtain satisfactory imprints on the take-up layer-covered surface of the various sheets.
  • the transfer layer which is preferably used according to the present invention is such that by application of pressure to a transfer layer coated carrier sheet, the pressure exposed portions of the sheet will be transferred to the contacting surface of conventional paper and the like without requiring any special treatment or coating of accepting sheet.
  • the transfer layer has incorporated therein a dark pigment of higher specific gravity and a light pigment of lower specific gravity, preferably so that the specific gravity of the dark pigment is greater and the specific gravity of the lighter pigment is smaller than the specific gravity of the binding or dispersing agent in liquid condition.
  • a dark pigment of higher specific gravity preferably so that the specific gravity of the dark pigment is greater and the specific gravity of the lighter pigment is smaller than the specific gravity of the binding or dispersing agent in liquid condition.
  • a transfer layer is formed of a flowable mixture which includes two different pigments which, generally, will be of different colors and, in any event, will be so chosen that one of the pigments will be held in dispersion in the mixture only as long as the mixture includes a first liquid, whereas the other of the pigments will be held in dispersion in the mixture even after removal of the first liquid therefrom.
  • the first pigment will precipitate and, for instance by sedimentation will settle on or in the immediate vicinity of a substrate, whereas the second pigmentupon subsequent drying of, for instance a coating formed of the initial mix-. ture-will settle superposed upon the first settled pigment.
  • the initial mixture contains additional constituents required to form a pigment-containing coating which may act as a transfer layer.
  • a pigment-containing coating which may act as a transfer layer.
  • the latter may be of the type which by pressure may be transferred to an untreated copy sheet, or may be of the type-for instance as more fully described in US. Patent 3,169,880-- which requires a specially treated receiving or copy sheet.
  • the above-described first and second liquids are organic solvents, and the entire pigments-containing mixture is substantially anhydrous.
  • FIG. 1 is a cross-sectional elevational view of a copy paper according to the present invention during processing of the same, after the flowable coating of transfer material has been applied to the carrier sheet but prior to drying of the transfer layer;
  • FIG. 2 is a cross-sectional elevational view of the completed copy paper
  • FIG. 3 is an exploded view of a three sheet assembly utilizing the copy paper according to the present invention.
  • a uniform dispersion of a first pigment and of a second pigment in a homogeneous flowable mixture including a first liquid, a second liquid and a substance which is adapted to form a pressure sensitive transfer layer is applied to a carrier sheet so as to form on the upper face of the carrier sheet a coating of the pigment dispersion in the mixture, the first pigment being held in dispersion in the mixture only in the presence of the first liquid, and the second pigment being held in dispersion in the presence of the second liquid, and the first liquid hav ing a significantly lower boiling point than the second liquid, and successively evaporating the first and second liquid from the thus formed coating so as to successively precipitate first the first pigment and thereafter the second pigment and thereby forming a transfer sheet comprising the carrier sheet and a transfer layer having the first pigment distributed substantially adjacent the carrier sheet and the second pigment adjacent to the free face of the transfer layer, which covers one face of the carrier sheet.
  • the present invention also includes a copy paper or the like, comprising a carrier sheet provided on one face thereof with a transfer layer adapted upon application of pressure thereto to be transferred to a contacting take-up sheet, the transfer layer having a pigment of a first color distributed through the portion thereof adjacent to the carrier sheet and having a pigment of a second color distributed through the portion thereof adjacent to the free outer face of the transfer layer, so that the face of the copy paper formed by the transfer layer will be substantially of the first color and, upon transfer of portions of the transfer layer from said copy sheet onto a take-up sheet, the free face of the transfer layer portions on the take-up sheet will be substantially of the first color.
  • the method of the present invention is not limited t the use of specific binding agents and it is also not necessary to use magnetic or magnetizable pigments, although such pigments may be used. Magnetizable or magnetic pigments will be used primarily when the copies formed of the pressure exposed portions of the transfer layer are to be used in data processing devices.
  • the copy papers of the present invention are particularly suited for this purpose due to the fact that very sharp and well defined copies can be produced therefrom.
  • the fiowable coating when applied has dispersed therein dark and light pigments in a substantially uniform distribution.
  • the carrier sheet is indicated by reference numeral 1, the flowable coating by reference numeral 2, the light colored pigments by reference numeral 4, and the dark colored pigments by reference numeral 3.
  • the dry transfer layer is indicated in FIG. 2 by reference numeral 5.
  • FIG. 3 shows the result of form; ing an impression of exerting pressure on a portion of the uncoated upper face of the top sheet. It is accomplished thereby that portions of the transfer layer 5 of the upper and intermediate copy sheets will be transferred to the carrier layer 1 of the intermediate copy sheet and to a plain paper sheet 7 forming the bottom sheet.
  • the transferred portions of the transfer layers 5 of the two copy sheets, i.e., the top sheet and the intermediate sheet, are indicated by reference numerals 6, and it will be immediately apparent that the upper face of the transferred portions is of dark color due to the accumulation of dark pigment in the vicinity of the upper face of the transferred portion.
  • a typewriter key 8 is shown as the source of pressure causing the transfer of selected portions of the transfer sheets.
  • Copy sheets when used according to the present invention and as illustrated in FIG. 2, include a flexible carrier sheet 1, which may consist of paper or film of a synthetic polymer, and at least one pressure sensitive layer 5 which includes two substances of different color.
  • the pressure sensitive material which forms the transfer layer is so treated according to the present invention that the lighter one of the two differently colored constituents of the transfer layer will concentrate in the zone of the free upper surface of the copy sheet and thus will mask the substance of darker color which is concentrated in the vicinity or adjacent to the carrier sheet and thus interposedbetween'the carrier sheet and the outer portion of the transfer layer which contains at least most of the substance such as pigments of lighter color. It is achieved thereby that-provided that the pigment is of substantially the same color as the carrier sheet-the copy sheet of the present invention will be of substantially the same color or color tone at the face formed by the carrier sheet and at the face formed by the transfer layer.
  • the separation of the two differently colored substances, particularly of lighter and darker pigments within the transfer layer is achieved according to the present invention by utilizing for producing the transfer layer the darker and lighter pigments in combination with liquids in which the constituents of the transfer layer other than the pigments are soluble or dispersable and which possess different characteristics with respect to their ability to form dispersions of the darker and lighter pigments.
  • the forces which hold a specific pigment in suspension within a specific vehicle such as a liquid, for instance an organic solvent, may be identified as surface forces.
  • pigments including hydrophilic or polar groups will remain in dispersion in solvents including polar groups, and, in a similar manner, solvents or liquids of a non-polar type will be capable of forming stable suspensions of pigments having hydrophobic characteristics.
  • the present invention can be carried out by utilizing two differently colored pigments which differ in their hydrophilic or hydrophobic characteristics, in combination with at least two liquids or solvents which also differ in their hydrophilic or hydrophobic characteristics, whereby the wax-like constituents or binding agents are maintained in solution or dispersion in the mixture of the two solvents. If then the solvent or dispersing liquid which possesses hydrophilic characteristics similar to that of the darker colored pigment and/or dyestuffs is removed, the darker pigment or the like will be precipitated since, in the absence of the solvent of compatible hydrophilic characteristics, i.e. in the presence of only the second solvent, which differs in its hydrophilic character istics or is hydrophobic, the darker pigments cannot be maintained in suspension.
  • the residual solvent or dispersing agent is removed and thereby the lighter pigment and/or dyestuffs which were maintained in suspension by the last-removed solvent, will also precipitate superposed upon the portion of the transfer layer which contains the first precipitated darker pigment.
  • the transfer layer-forming mass contains at least two pig ments, namely one which is light or white and one which is dark or black. These two pigments differ greatly in their hydrophilic or hydrophobic characteristics. These different characteristics can be obtained either by choosing ab initio a hydrophilic and a hydrophobic pigment, or by specially treating pigments which initially do not have different characteristics in this respect, in order to give these pigments a desired degree of hydrophilic or hydrophobic characteristics.
  • such treatment may consist in an intensive grinding of the pigments with suitable additives, or in a precipitating of the pigments together with hydrophilic or hydrophobic materials.
  • Pigments which in one or the other way have been treated soas to have hydrophilic or hydrophobic characteristics are well known to those skilled in the art and commercially available. They serve generally for facilitating dispersion of these pigments in different solvents or vehicles.
  • the degree of hydrophobic characteristics of carbon black which frequently is utilized as a dark pigment is too low to permit separating the two different pigments with the desired speed.
  • the hydrophobic characteristics of pigments such as carbon black can be increased by treating the carbon black for instance with pyrene, fluoranthene, 1,2-benzopyrene, 3,4- benzopyrene, benzoperylene, coronene; oils such as castor oil, cotton oil; ricinoleic acid, naphthenic acid or octoic acid.
  • the pigments may be endowed with hydrophilic characteristics by treatment with amides, alcohols, glycols, glycerol, pentaerythritol and the like.
  • Another essential feature of the present invention is the use of a mixture of vehicles or liquids or solvents, preferably organic solvents.
  • the solvents which are suitable for the purpose of the present invention must be capable of dissolving or at least dispersing the transfer layerforming wax-like or binder constituents, or at least must not cause precipitation of binder solutions even if the concentration thereof is subsequently changed, for instance during the drying of the coating on the paper or the like support.
  • Such solvent mixture will comprise at least two solvents, one having hydrophilic and one having hydrophobic characteristics and, furthermore, the two solvents will preferably have significantly different boiling points so that the solvent of lower boiling point can be selectively removed by heating to a temperature which is still considerably below the boiling point of the other solvent.
  • the mixture may also consist of more than two solvents, for instance of a mixture of several hydrophilic solvents and a mixture of several hydrophobic solvents.
  • the transfer layer may comprise the following constituents particularly if the transfer sheet is to be used in combination with a copy sheet which has not been specially treated:
  • a wax-like material which may consist of natural and synthetic, saturated and unsaturated fatty acids and fatty acid derivatives, for instance their esters and lactones; fatty alcohols and their derivatives; natural and synthetic waxes.
  • the wax-like material will achieve transfer of pressure exposed portions of the transfer layer onto a substrate, such as a paper which has not been specially treated for receiving portions of the transfer layer. Due to the presence of the wax-like material, the tranfser layer will be accepted upon exertion of pressure by a paper or the like which does not carry a special take-up layer.
  • the wax-like material will form between 10 and 70% by weight and most preferably between and by weight based on the dry weight of the entire transfer layer.
  • the waxy material is dissolved or dispersed in the above described mixture of solvents, namely two solvents or solvent mixtures which differ from each other by their hydrophilic or hydrophobic characteristics and the boiling points of which are sufficiently far apart so that upon drying of a coating of the dispersion on a carrier sheet the major portion of one of the solvents or solvent mixtures will evaporate before the other solvent or solvent mixture starts to be volatilized to a significant extent.
  • solvents or solvent mixtures there should also be a sufficiently large difference between the specific heat of evaporation of the two solvents or solvent mixtures.
  • a mixture of at least one dark or black and one white or light pigment is introduced into the above described solution of the wax-like material in the two solvents by methods which are known per se such as stirring, grinding, dispersion and the like. If the darker pigment has hydrophobic characteristics and the lighter pigment has hydrophilic characteristics, the hydrophobic solvent or solvent mixture must volatilize prior to or at lower temperature than the hydrophilic solvent or solvent mixture. However, if a dark pigment of hydrophilic characteristics is chosen and a lighter pigment of hydrophobic characteristics, then the boiling point of the hydrophilic solvent or solvent mixture must be below that of the hydrophobic solvent or solvent mixture.
  • the dark or black pigment preferably will be present in an amount equal to between 3 and 40% by weight of the dry transfer layer and most preferably between 9 and 15%.
  • the ratio between dark and light pigment depends on the relative hiding power of the individual pigments. Generally, a ratio of 1:1.5 to 1:2.5 should be maintained, however, these ratios may be exceeded in both directions.
  • the amount of the light pigment based on the dry weight of the entire transfer layer preferably will be between 25 and 80% and most preferably between and (4)
  • the transfer layer may also include one or more resins or synthetic polymers in order to cause firmer binding of the layer and to control the intensity of the copy formed by transfer of portions of the transfer layer. For this purpose, a great number of synthetic and natural materials may be used which are well known to those skilled in the art and which will be so chosen as to achieve the results desired in any given case.
  • binding agents or binders The great number of different materials which may be successfully used as binding agents or binders is indicated in the examples further below and includes for instance polystyrene, polycarbonate, polychloroprene, styrene-butadiene copolymers, polyvinylacetate, polyvinylacetal, copolymers of polyvinylacetate and polyvinylchloride and many others.
  • binding agents may be varied within wide limits by the introduction of primary or secondary softeners and for this purpose all of the generally used conventional softeners may be employed.
  • polymers and softeners By specific combinations of polymers and softeners, a wide variety of characteristics of the transfer layer can be achieved in a manner which is known to those skilled in the art and not subject of the present invention.
  • the transfer layer may additionally include fixing agents or lubricating agents which alone or jointly with the binding agents may contribute to forming an abrasion resistant transfer layer which will not give off color upon manual contact.
  • fixing agents or lubricating agents which alone or jointly with the binding agents may contribute to forming an abrasion resistant transfer layer which will not give off color upon manual contact.
  • metal soaps of saturated or unsaturated fatty acids may be used as such lubricants.
  • the thus obtained transfer layer-forming fiowable mass is then applied by means of conventional devices and in a conventional manner to a carrier material or substrate such as paper, a polymer foil or another suitable flexible carrier so as to form a coating of the fiowable mass on the carrier sheet.
  • the hydrophilic solvent or solvent mixture will start to be volatilized, and during the passage of still liquid hydrophilic solvent through the cross section of the coating towards the free face thereof, the hydrophilic light pigment particles will be carriedalong towards the free surface zone of the coating, since the entire hydrophilic solvent content of the drying coating has to move towards the free surface of the layer until all of the solvent is vaporized.
  • a concentration of light or white pigment will take place whereas simultaneously the portion of the coating which is directly adjacent the carrier sheet will be impoverished with respect to light or white pigment.
  • separation into two layers will take place, namely a lighter, free surface layer portion and a darker lower transfer layer portion which is interposed between the surface portion and the carrier sheet.
  • the other constituents of the transfer layer such as wax-like material, binder, lubricant or fixing agent are not affected by this removal of the solvents since they remain in solution or dispersion until the solvents have been vaporized, and no precipitation takes place.
  • these other constituents of the transfer layer i.e. the entire transfer layer with the exception of the pigments will remain homogeneously distributed and thereby it is assured that neither the transfer sheet carrying the transfer layer, nor transferred portions of the transfer layer, i.e. copies made therefrom, will smear or give up color upon manual contact.
  • the same effect of obtaining separation into two layers of different pigment composition is achieved by choosing a dark pigment having hydrophilic properties and a light pigment having hydrophobic properties in combination with a hydrophilic solvent or solvent mixture which will more easily vaporize than the hydrophobic solvent or solvent mixture.
  • a copy sheet produced in this manner has at the surface formed by the transfer layer a white or light color and nevertheless, upon forming a copy thereof by transfer of portions of the transfer layer, will give dark copies. During handling of such sheet no color will be released and no soiling :will take place upon manipulation Without undue pressure.
  • the light color of both faces of the coy sheet, ie the face formed by the carrier sheet and the face formed by the transfer layer is also esthetically desirable.
  • Example I Sixty parts by weight cyclohexane, ten parts by weight methanol, ten parts by weight microcrystalline wax having a melting point of 63-65 C. (Microwax 63, Quaker State Oil Refining Corp), ten parts by weight zinc oxide and five parts by weight kaolin are jointly ground for three hours in a ball mill together with a paste formed previously on a 3-roll grinder of two parts by weight of carbon black (Furnex Columbian Carbon Co.) and three parts by weight of polyglycol E 300 (Dow Co.). The thus formed fiowable mass is applied to a suitable sheet material by means of a doctor blade arrangement and a device which includes an arrangement for evaporating the solvent content of the fiowable mass.
  • a doctor blade arrangement and a device which includes an arrangement for evaporating the solvent content of the fiowable mass.
  • Example II Forty-one parts by weight toluene, ten parts by weight acetone, ten parts by weight ethanol, ten parts by weight spermaceti wax (Archer Daniels Midland), two parts by weight hydrophilic carbon black (Colloidex No. 3, Columbian Carbon Co.) and fifteen parts by weight lithopone are ground for one hour in a ball mill. Thereafter, a solution of two parts by weight acrylic resin (Lucite 44, E. I. du Pont de Nemours) in ten parts by weight chloroform are added, thoroughly mixed and the thus formed fiowable coating material is then applied as described in Example I.
  • acrylic resin Luciite 44, E. I. du Pont de Nemours
  • Example III Forty parts by weight xylene, twenty parts by weight isopropanol, ten parts by weight stearyl alcohol (Aldol 62, Archer Daniels Midland), four parts by weight cadmium stearate (Chem. Werke Baerlocher, Germany), eight parts by weight magnetic pigment (Magnetpigment No. 345, BASF eighteen parts by weight titanium white (Tioxide R-H-D, British Titan Products) are jointly ground in a ball mill for two hours and thereafter applied to a carrier sheet as described in Example I.
  • Example IV First, two parts by weight carbon black (Statex B 12, Columbian Carbon Co.) are ground on a 3-roll grinder together with three parts by weight sorbitol (Merck Co.), by being passed three times through the grinder in order to be very finely ground. The thus formed carbon black paste is then ground for one hour in a ball mill together with 65 parts by weight benzene, 5 parts by weight methanol, ten parts by weight stearic acid (Hydrofol acid 150, Archer Daniels Midland), five parts by weight calcium palmitate Baerlocher Maschinene, Germany) and ten parts by Weight of lithopone. The thus obtained coating material is then ready to be applied to a paper sheet or other flexible support to form upon evaporation of the solvents the copy sheet of the present invention.
  • sorbitol Merck Co.
  • Example V Fifteen parts by weight ethanol, forty parts by weight xylene, eight parts by weight hydrogenated castor oil (Castor Wax, Baker Caster Oil Co.), fifteen parts by weight titanium white, five parts by weight calcium carbonate and four parts by weight mercury sulfide are ground in a ball mill for one hour. Thereafter, a solution of three parts by weight ketone resin (Kunstharz AW 2, BASF, Germany), in ten parts by weight of xylene is added, thoroughly mixed and the thus formed mass applied to the carrier sheet by means of doctor blades.
  • ketone resin Kerone resin
  • Example VI Two parts by weight of carbon black (Spezialschwarz IV, Degussa) are finely ground on a 3-roll refiner together with two parts by weight diglucol-stearate (Atlas Goldschrnidt Ges.). Ten parts by weight of methanol, fifty parts by weight trichloroethylene, ten parts by weight 12 hydroxy-stearic acid (Hydrofol acid 200, Archer Daniels Midland) ten parts by weight lithopone, nine parts by Weight kaolin, seven parts by weight titanium white, and the above described carbon black paste are then ground in a ball mill for one hour and the thus formed coating mass is applied as described in Example I.
  • carbon black Spezialschwarz IV, Degussa
  • Pigments having hydrophobic characteristics include most types of carbon black, preferably carbon black which had been ground with oil prior to use for the present purpose. Such pigments are commercially available under various trade names such as Furnex (Columbian Carbon Co.), CK (Degussa), Printex (Degussa), Corax L and Corax B (Degussa).
  • Hydrophilic pigments include Aquablak (Columbian Carbon Co.), Special Black IV (Degussa), Corax 6 and Corax 7 (Degussa), Pigmosol dye stuffs of BASF such as Litholechtgruen NCR, Paliogen RT, Eisenrot G, Litholcharlach NCR, Paliogen GN, Pigmentgruen B, Farbuss 3, Titanweiss, Spin Black A, B and C (Degussa), and materials such as kaolin, lithopone and titanium white.
  • Aquablak Cold Carbon Co.
  • Special Black IV (Degussa)
  • Corax 6 and Corax 7 Degussa
  • Pigmosol dye stuffs of BASF such as Litholechtgruen NCR, Paliogen RT, Eisenrot G, Litholcharlach NCR, Paliogen GN, Pigmentgruen B, Farbuss 3, Titanweiss, Spin Black A, B and C (Degussa), and materials such as kaolin, lithopone and titanium white.
  • Organic solvents having hydrophobic characteristics include ketones, aromatic hydrocarbons such as benzene, toluene, xylene and decahydronaphthalene, aliphatic hydrocarbons such as hexene, heptene and octane, substituted hydrocarbons such as chloroform, trichloroethylene, methylene chloride and chlorobenzene, ether and polyethers such as diethyl ether and various glycol ether solvents commercially available under the trade name Poly-Solv (Olin Mathieson Chemical Corp.,) and nitrohydrocarbons.
  • aromatic hydrocarbons such as benzene, toluene, xylene and decahydronaphthalene
  • aliphatic hydrocarbons such as hexene, heptene and octane
  • substituted hydrocarbons such as chloroform, trichloroethylene, methylene chloride and chlorobenzene
  • Organic solvents having hydrophilic characteristics include aliphatic alcohols such as methanol, ethanol and isopropanol, glycols, acetone and dioxane.
  • Wax-like materials which may form part of the transfer layer include fatty acids and derivatives thereof such as ketocarboxy fatty acids, hydrogenated fatty acids, dicarboxy fatty acids and alkyl derivatives thereof, hydroxy fatty acids (particularly dito hexa-hydroxy), l2-hydroxy-stearic acid and alkyl esters thereof, saturated fatty acid lactones, fatty acid alkyl esters, mono-, diand triesters of fatty acids with glycerol and sorbitol, mono-fatty acids, nitro-fatty acids, polyoxyethylene fatty acids, glycols and polyglycols, for instance the products commercially available under the trade name Carbowax (Union Carbide Corporation).
  • fatty acids and derivatives thereof such as ketocarboxy fatty acids, hydrogenated fatty acids, dicarboxy fatty acids and alkyl derivatives thereof, hydroxy fatty acids (particularly dito hexa-hydroxy), l2-hydroxy-stearic acid and alkyl esters thereof, saturated fatty acid
  • Suitable wax like materials also include aliphatic alcohols and derivatives thereof, saturated alcohols as well as unsaturated alcohols, and esters thereof, 12-hydroxystearin alcohol, also waxes which are at least partially soluble in the solvents used in a given case, such as natural waxes, saturated and unsaturated hydrocarbon waxes, chlorinated and nitrated hydrocarbon waxes, cycloparafiins, ketones and hydroxy-ketones fatty acid amines, stearamide, oxidized hydrocarbon waxes, hydrogenated oils and many others.
  • Resins and synthetic polymers which may be incorporated in the transfer layer as binder material include also polyvinyl acetate, mixed polymerizates with polyvinyl acetate, colophonium, polymethylacrylate, polymethylmetacrylate, polycarbonate, polystyrene, polychloroprene, copolymers of styrene and butadiene, synthetic cellulose resins such as methyl, ethyl-, benzyl-, carboxymethyland nitrocellulose, coumarone resins and coumaronephenol resins.
  • the transfer layer may also contain a softener, for instance, castor oil, dibutylphthalate, dioctylphthalate, diamylphthalate, tricresylphosphate, cyclohexyl-p-toluene sulfonamide, dioctylsebacate, dibutylstearate, tri'butylphosphate, ricinoleic acid and many other softeners which are effective with respect to the particular binder material used in a given case.
  • a softener for instance, castor oil, dibutylphthalate, dioctylphthalate, diamylphthalate, tricresylphosphate, cyclohexyl-p-toluene sulfonamide, dioctylsebacate, dibutylstearate, tri'butylphosphate, ricinoleic acid and many other softeners which are effective with respect to the particular binder material used in
  • the white or lighter pigment irrespective of whether it has hydrophobic or hydrophilic characteristics preferably should be present in a larger proportion than the dark or black pigment.
  • the ratio of light to dark pigment may vary greatly from about equal proportions of light and dark pigment to ratios of one part of dark pigment to about 50 parts of light pigment.
  • the two pigments-containing transfer layer will be of the type'(apart from the selective pigment distribution) more fully described in US. Patent 3,169,880.
  • Such transfer layer may be formed, for instance on a carrier sheet, of a flowable mixture including the two different liquids and the two different pigments as described above, and also including a resinous substance selected from the group consisting of polyvinyl acetate, mixed polymerizates of polyvinyl acetate, colophonium, polymethylacrylate, polymethylmethacrylate, polycarbonates, polystyrene, polychloroprene, styrene-butadiene copolymers, synthetic cellulose resins, cumarone resin and cumarone-phenol resins, of an effective amount of at least one plasticizer for said resinous substance, of at least one organic fixing agent in an amount of between about 15-90% of the weight of said resinous substance and selected from the group consisting of tannic acid, phthalic acid
  • the coating which is applied to the carrier sheet to form thereon, after removal of the solvents, the transfer layer generally will comprise the following constituents:
  • One or more resins or synthetic polymers in order to cause binding of the layer and to control the intensity of the copy formed by transfer of portions of the transfer layer.
  • synthetic and natural materials may be used which are well known to those skilled in the art and which will be so chosen as to achieve the results desired in any given case.
  • the great number of different materials which may be successfully used as binding material or binder is indicated in the examples and includes, for instance polystyrene, polycarbonate, polychloroprene, styrene-butadiene-copolymers, polyvinylacetate, polyvinylacetal, copolymers of polyvinylacetate and polyvinylchloride and many others.
  • binding agents may be varied within wide limits by the introduction of primary or secondary plasticizers and for this purpose all of the generally used conventional plasticizers may be employed.
  • plasticizers By specific combinations of polymers and plasticizers, a wide variety of characteristics ofthe transfer layer can be achieved in a manner which is, known to those skilled in the art and not subject to the present invention.
  • the binder is dissolved or dispersed in the above described mixture of solvents, namely two solvents or solvent mixtures which differ from each other by their hydrophobic characteristics and the boiling points of which are sufficiently far apart so that upon drying of a coating of the dispersion on a carrier sheet the major portion of one of the solvents or solvent mixtures will evaporate before the other solvent or solvent mixture starts to be volatilized to a significant extent.
  • solvents or solvent mixtures which differ from each other by their hydrophobic characteristics and the boiling points of which are sufficiently far apart
  • a mixture of at least one dark or black and one light or white pigment is introduced into the above described solution of binder mataerial in the two solvents by methods which are known per se as stirring, grinding, dispersion and the like. If the darker pigment has hydrophobic characteristics, the hydrophobic solvent or solvent mixture must volatilize prior to or at lower temperature than the hydrophilic solvent or solvent mixture.
  • the boiling point of the hydrophilic solvent orsolvent mixture must be below that of the hydrophobic solvent or solvent mixture.
  • the dark or black pigment preferably will be present in an amount equal to between 3 and 40% by weight of the dry transfer layer and most preferably between 9 and 15%.
  • the ratio between dark and light pigment depends on the relative hiding power of the individual pigments; Generally, a ratio of 1:15 to 1:25 should be maintained; however, these ratios may be exceeded in both directions.
  • the amount of the light pigment based on the dry weight of the entire transfer layer preferably will be between 25 and and most preferably between 55 and 65%.
  • the transfer layer may additionally include fixing agents or lubricating agents which jointly with the binding agents may contribute to forming an abrasion resistant transfer layer which will not give off color upon manual contact.
  • fixing agents or lubricating agents which jointly with the binding agents may contribute to forming an abrasion resistant transfer layer which will not give off color upon manual contact.
  • metal soaps of saturated or unsaturated fatty acids may be used as such lubricants.
  • transfer layer-forming flowable mass is then applied by means of conventional devices and in a conventional manner to a carrier sheet or substrate such as paper, a polymer foil or another suitable flexible carrier so as to form a coating of the flowable mass on the carrier sheet.
  • a carrier sheet or substrate such as paper, a polymer foil or another suitable flexible carrier
  • hydrophilic pigments may be made hydrophobic by kneading equal amounts of channel black and of a 10 percent solution of pyrene in toluene in a closed indirectly heatable vessel. After one hour the toluene is vaporized and the residual treated channel black is usable as hydrophobic pigment for instance with titanium white as the hydrophilic pigment.
  • carbon black may be treated with an equal amount of an 8 percent solution of naphtenic acid in benzene, or a 10 percent solution of 3-4 benzopyrene in toluene.
  • I-lydrophilic properties of a pigment may be improved for instance by kneading equal proportions of rutile-type titanium white containing aluminium zinc and silicon with a 3 percent aqueous solution of chlorinated starch followed by evaporation of water.
  • titanium white 15 may be treated with a 3 percent solution of glycerol in ethanol followed by evaporation of ethanol, or by treating with a 3 percent solution of pentaerythritol in aqueous ethanol.
  • treated hydrophilic titanium white may be used in combination with carbon black made hydrophobic as described above.
  • a complete coating composition may be formed of an 8 percent solution of polyvinyl acetate in 90 percent ethanol as binder and including primary and secondary softeners such as 4 parts ricinoleic acid, 4 parts castor oil, 8 parts ethyl-hexyl-sebacate for 45 parts of solution. 5 parts hydrophobically treated channel black and 26 parts hydrophilically treated titanium White are ground and dispersed into the above mixture. 8 parts methylglycol are introduced for stepwise evaporation of solvents. Since in this case the black pigment is hydrophobic, ethanol must be evaporated prior to water so that the channel black will be first precipitated and the titanium white will form the upper layer.
  • primary and secondary softeners such as 4 parts ricinoleic acid, 4 parts castor oil, 8 parts ethyl-hexyl-sebacate for 45 parts of solution. 5 parts hydrophobically treated channel black and 26 parts hydrophilically treated titanium White are ground and dispersed into the above mixture. 8 parts methylglycol are introduced
  • the coating composition may be formed of a mixture of 3.6 parts polyvinyl acetate of medium polymerization degree, 20 parts 94 percent ethanol, 4 parts water and 17.4 parts acetone into which are introduced 8 parts dibutylphthalate, 4 parts amylphthalate, 4 parts castor oil, 5 parts carbon black, 5 parts kaolin, 21 parts hydrophilically treated titanium white and 8 parts isopropanol.
  • a method of forming a transfer sheet comprising the steps of uniformly dispersing a first pigment and a second pigment of a different color than said first pigment in a homogeneous fiowable mixture including a first and a second liquid and a substance which is soluble in said liquids and which is adapted to form a pressure sensitive layer, said first pigment being held in dispersion only in the presence of said first liquid and precipitating in the absence of said first liquid, and said second pigment being held in dispersion only in the presence of said second liquid and precipitating in the absence of said second liquid, said first liquid having a significantly lower boiling point than said second liquid, one of said pigments and the corresponding liquid having hydrophilic characteristics, and the other of said pigments and the other of said liquids having hydrophobic characteristics; applying said uniform dispersion to a carrier sheet so as to form on one face of said carrier sheet a coating of said pigment dispersion in said mixture; and successively evaporating said first and said second liquid from said coating so as to successively precipitate in the indicated sequence said first
  • said waxlike material is selected from the group consisting of saturated and unsaturated fatty acids and derivatives thereof, fatty alcohols and derivatives thereof, and natural and synthetic waxes.
  • binder material is selected from the group consisting of polystyrene, polycarbonate, polychloroprene, styrene-butadiene copoly-mers, polyvinylacetate, polyvinylacetal, copolymers of polyvinylacetate and polyvinylchloride, and polymethylmethacrylate.
  • said flowable mxiture includes a resinous substance selected from the group consisting of polyvinyl acetate, mixed polymerizates of polyvinyl acetate, colophonium, polymethylacrylate, polymethylmethacrylate, polycarbonates, polystyrene, polychloroprene, styrene-butadiene copolyrners, synthetic cellulose resins, cumarone resin and cumaronephenol resins, an effective amount of at least one plasticizer for said resinous substance, and at least one organic fixing agent in an amount of between about 15-90% of the weight of said resinous substance and selected from the group consisting of tannic acid, phthalic acid, gallic acid, digallic acid, salicylic acid, phenyl salicylate, 4-butylphenyl-salicylate, 5-chloro-Z-hydroxy-benzophenone, 2,4- dibenzoyl-resorcin, phenol and pyrogallic
  • a resinous substance selected from

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Color Printing (AREA)
  • Medicinal Preparation (AREA)
  • Fats And Perfumes (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Paints Or Removers (AREA)
  • Decoration By Transfer Pictures (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
US679591A 1966-09-12 1967-10-18 Method of making transfer sheet Expired - Lifetime US3484264A (en)

Applications Claiming Priority (2)

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US57857966A 1966-09-12 1966-09-12
US67959167A 1967-10-18 1967-10-18

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US (1) US3484264A (enrdf_load_stackoverflow)
BE (1) BE700187A (enrdf_load_stackoverflow)
CH (1) CH456333A (enrdf_load_stackoverflow)
DE (1) DE1561752A1 (enrdf_load_stackoverflow)
FR (1) FR1549261A (enrdf_load_stackoverflow)
GB (2) GB1175065A (enrdf_load_stackoverflow)
NL (1) NL6708722A (enrdf_load_stackoverflow)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819397A (en) * 1969-09-16 1974-06-25 G Ehrhardt Method of forming improved pressure sensitive transfer media
US3946138A (en) * 1974-04-01 1976-03-23 Monarch Marking Systems, Inc. Compositions and methods relating to transfer processes
US3957495A (en) * 1973-05-26 1976-05-18 Pilot Man-Nen-Hitsu Kabushiki Kaisha Solid writing material
FR2407080A1 (fr) * 1977-10-25 1979-05-25 Minnesota Mining & Mfg Element pour former des images graphiques
US4533596A (en) * 1983-06-28 1985-08-06 Ncr Corporation Thermal magnetic transfer ribbon

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3520308A1 (de) * 1985-06-07 1986-12-11 Pelikan Ag, 3000 Hannover Verfahren zur herstellung eines thermofarbbandes fuer den thermotransferdruck und das danach erhaeltliche thermofarbband
IN168779B (enrdf_load_stackoverflow) * 1986-03-24 1991-06-01 Cabot Corp

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB906187A (en) * 1959-03-02 1962-09-19 Ancar A G Improvements in duplicating papers
US3111422A (en) * 1961-04-27 1963-11-19 Columbia Ribbon & Carbon Methods for preparing pressure-sensitive transfer elements
US3337361A (en) * 1964-01-06 1967-08-22 Kee Lox Mfg Company Process of making pressure sensitive transfer sheet
US3382088A (en) * 1963-02-12 1968-05-07 Noda Ryuzo Method of manufacturing self-copying sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB906187A (en) * 1959-03-02 1962-09-19 Ancar A G Improvements in duplicating papers
US3111422A (en) * 1961-04-27 1963-11-19 Columbia Ribbon & Carbon Methods for preparing pressure-sensitive transfer elements
US3382088A (en) * 1963-02-12 1968-05-07 Noda Ryuzo Method of manufacturing self-copying sheet
US3337361A (en) * 1964-01-06 1967-08-22 Kee Lox Mfg Company Process of making pressure sensitive transfer sheet

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819397A (en) * 1969-09-16 1974-06-25 G Ehrhardt Method of forming improved pressure sensitive transfer media
US3957495A (en) * 1973-05-26 1976-05-18 Pilot Man-Nen-Hitsu Kabushiki Kaisha Solid writing material
US3946138A (en) * 1974-04-01 1976-03-23 Monarch Marking Systems, Inc. Compositions and methods relating to transfer processes
US4069179A (en) * 1974-04-01 1978-01-17 Monarch Marking Systems Compositions and methods relating to transfer processes
FR2407080A1 (fr) * 1977-10-25 1979-05-25 Minnesota Mining & Mfg Element pour former des images graphiques
US4533596A (en) * 1983-06-28 1985-08-06 Ncr Corporation Thermal magnetic transfer ribbon

Also Published As

Publication number Publication date
GB1175065A (en) 1969-12-23
DE1803698A1 (de) 1971-06-09
FR1549261A (enrdf_load_stackoverflow) 1968-12-13
NL6708722A (enrdf_load_stackoverflow) 1968-03-13
BE700187A (enrdf_load_stackoverflow) 1967-12-01
GB1241187A (en) 1971-07-28
CH456333A (de) 1968-07-15
DE1561752A1 (de) 1970-03-12

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