US3684544A - Process for making a dry transfer material - Google Patents

Process for making a dry transfer material Download PDF

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Publication number
US3684544A
US3684544A US797505A US3684544DA US3684544A US 3684544 A US3684544 A US 3684544A US 797505 A US797505 A US 797505A US 3684544D A US3684544D A US 3684544DA US 3684544 A US3684544 A US 3684544A
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United States
Prior art keywords
adhesive
ink
layer
signs
powder
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Expired - Lifetime
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US797505A
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English (en)
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Jean Gustave Jules Piron
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
    • B41M3/12—Transfer pictures or the like, e.g. decalcomanias
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B44—DECORATIVE ARTS
    • B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
    • B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
    • B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
    • B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
    • B44C1/17—Dry transfer
    • B44C1/1733—Decalcomanias applied under pressure only, e.g. provided with a pressure sensitive adhesive
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259—Silicic material

Definitions

  • a dry transfer material comprising a support, ink signs and a pressure-sensitive adhesive layer covering both the ink signs and the parts of the support without ink signs
  • the adhesive layer has on its free surface a layer of fine solid particles such that the adhesive cannot act unless a sufficient pressure is applied during a sufficient period of time to allow the adhesive to pass through the particle layer and to cause the ink signs to be transferred to adhere to a receptor surface.
  • the ink signs contain a non-volatile liquid material capable of oozing into the adhesive layer so as to reduce the viscosity of the latter.
  • the present invention relates to a dry transfer material i.e. a material for effecting under dry conditions the transfer of one or more ink signs or indicia from a support carrying .the same to a receptor surface. It also relates to a process for making such a dry transfer material.
  • ink signs as used herein is intended to mean any figure or part of ligure, for example, drawing, letter, numeral, punctuation mark printed or applied in any other -way onto a support.
  • the prior art discloses dry transfer material for making dry decalcomania pictures with transfer materials comprising very tacky adhesives, similar to those used in the adhesive tape industry.
  • Dry transfer assemblies are also known wherein the adhesive has a slight tacky touch.
  • These types of adhesives generally are made of waxes or waxy materials mixed with pressure-sensitive adhesives which-allow the ink signs to slide on the receptor surface and to be adjusted thereon. However, their adhesive power is reduced by the waxy materials.
  • the present invention has for its object a dry transfer material having the advantages of the known systems without the drawbacks of the latter.
  • the ink signs should be easily slidable and adjustable on the receptor sheet without any reduction of property such as the adhesive power of the pressure-sensitive adhesive.
  • the free surface of the adhesive layer has a layer of solid particles joined side by side to one another, in such a way that the free surface of the adhesive layer substantially has no adhesiveness, said particles having a maximum size of 50 millimicrons, a specific gravity below 3 and a refractive index below 1.7, whereby the adhesive cannot pass through said layer of particles, wet the latter and reach the receptor surface unless a suicient pressure is applied onto the face of the supporting sheet opposed to that face which carries the signs and the adhesive layer, and the ink signs contain a non volatile liquid material capable of oozing into the adhesive layer so as to reduce the viscosity of the latter and to facilitate the dispersion of said particles in the adhesive layer when said pressure is applied.
  • This invention also relates to a process for making a dry transfer material for dry transferring ink signs to a receptor surface, in which process ink signs and a pressuresensitive adhesive layer are successively applied onto a supporting sheet.
  • an adhesive which comprises a volatile fraction and a non volatile fraction and contains solid particles of a maximum size of 50 millimicrons, a specific gravity below 3 and a refractive index below 1.7, the said solid particles being dragged towards the free surface of the adhesive layer under the action of the volatile fraction during the evaporation of the latter so as to form a layer of solid nontacky particles joined side by side to one another at said surface, and with the ink of said signs, a liquid non volatile material is incorporated, said material being capable of oozing into the adhesive layer so as to reduce the viscosity of the latter.
  • the supporting sheet comprises, at least at the surface thereof carrying the ink signs, a hydrocarbon polymer such as polyethylene or polystyrene having a critical surface tension below 37 dynes/cm.
  • a hydrocarbon polymer such as polyethylene or polystyrene having a critical surface tension below 37 dynes/cm.
  • a supporting sheet is passed through an apparatus which modifies the surface polarity thereof by ion bombarding the same in high voltage alternating electric fields, an apparatus of the ⁇ EL-type, available from the German firm DEMES, may be used therefor.
  • a good spreading or coating of ink is obtained on said supports as well as a weak adhesion allowing the ink film to be well separated or stripped as a result of the tractive force of the pressure-sensitive adhesive by using inks or varnishes whose surface layer is formed by evalporation of the solvents and whose binder comprises linear thermoplastic resins.
  • polyvinyl butyral, nitrocellulose, ethylcellulose are quite suitable. These resins are normally plastied according to the known principles for imparting to the dry ink film good resilient characteristics.
  • the ink contains in addition, according to the present invention, a non volatile liquid material adapted for oozing into the adhesive layer which will cover the ink sign, so as to lower the viscosity thereof.
  • This liquid non volatile material preferably has a molecular weight below 600. It should be inert with regard to the polymer of the ink and incapable of forming solvates therewith so that it may esaily ooze out of the molecular chains.
  • oozing non volatile materials include di(2ethylhexyl) azelate, butyl stearate, triethyl phosphate, vegetable and mineral oils.
  • the ink sign When the ink sign is made of several superimposed layers of different colours, it is not necessary to incorporate the exuding material or uidity agent with all layers. Only the last layer in contact with the adhesive should contain said exuding material. The last layer, or the sole layer when the ink sign only comprises one layer, preferably has a thickness of at least 7 microns.
  • the fluidity agent in the form of an exuding material also is a plasticizer with respect to the pressure-sensitive adhesive which improves the adhesion properties of the adhesive.
  • a plasticizer with respect to the pressure-sensitive adhesive which improves the adhesion properties of the adhesive.
  • butyl stearate and ricinus oil are plasticizers of polyvinylethylether.
  • ink formulae may be used according to the present invention.
  • Ink Formula l Parts by weight Nitrocellulose 1/2 second 100 Rosin ester l Dioctyl phtalate 40 Butyl alcohol 50 yIsopropylglycol 344 Ethylglycol acetate 208 Butyl stearate 12 Ricinus oil (castor oil)
  • Ink Formula 2 Parts by weight Polyvinyl butyral 100 Dioctyl phtalate 8 Isopropyl alcohol 60 Butylglycol 40 Di(2ethylhexy1) azelate l0 These formulae give transparent ink lms. In order to obtain coloured lms, one adds the necessary pigments thereto.
  • Pressure-sensitive adhesives have been known for a long time. They comprise a cohesion agent which may be a natural or synthetic elastomer or a high molecular weight polymer, and a thermoplastic compatible material giving adhesion and adhesive power, which may be a tacky resin or a low molecular weight polymer.
  • Such adhesives ordinarily used in the manufacture of adhesive tapes have a tractive power greater than the adhesion power of the ink on the provisional support. They give a very good adhesion of ink on the receptor surface and may be used according to the present invention. Examples of adhesive formulae are given hereinafter.
  • Adhesive Formula l Parts by weight Polyvinylethylether, molecular weight above Cit terpene) adhesion agent 50 Hexane 600 Naphtha solvent 5
  • Adhesive Formula 3 Parts by Weight High molecular weight isobutyl polyvinylether,
  • cohesion agent 45 Low molecular weight isobutyl polyvinylether
  • adhesion agent 40 Gum ester 5 Ethylene glycol Heptane t 200 Xylene l0 lt is seen that the adhesive of the above formulae contain as a non volatile fraction at least one polyvinyl alkyl ether or a natural or synthetic rubber, while, their volatile fraction comprises at least one liquid aliphatic or aromatic hydrocarbon.
  • the superficial adhesive effect is eliminated by causing the so-called flooding or horizontal fioatation of a very thin layer of very ne powder at the exposed surface of the adhesive.
  • said powder layer should isolate the adhesive mass from any direct contact with the receptor surface without reducing in any way the properties of the underlying adhesive mass. If the powder remains embedded within the adhesive, the supercial adhesive elect will remain unless the amount of powder is such that a reduction of superlicial adhesive elect will be the result of a corresponding reduction of the adhesive properties of the whole adhesive mass, which would be contrary to the aimed object.
  • the powder in order to provide a good fioatation, should meet the particles size and density requirements indicated above, namely:
  • particle size maximum 50 millimicrons particle specific gravity: below 3.
  • the refractive index of the powder material be below: 1.7 and it is important that the powder be transluscent.
  • synthetic silica specic gravity 2.4; refractive index synthetic silicates such as calcium silicate: specific gravity 2.60; refractive index 1.53
  • Atloatation phenomenon concerning powder particles in adhesive is much analogous to what occurs in a pigment mixture in paint and varnish.
  • the process conditions in connection with the adhesive according to the present invention are given hereinafter: lst--The pressure-sensitive adhesive is applied onto the provisional support and the ink signs by a process such as silk screen which makes it possible to deposit a layer whose thickness is not below 20 microns before evaporation of the solvents.
  • the thickness of the adhesive layer should be equal to or greater than Imicrons after evaporation of the solvent. Therefore,
  • the ratio of the Weight of the volatile fraction to the weight of the non volatile fraction should be at least of 3:1.
  • 2d-One obtains under the best circumstances the disappearance of the superficial adhesive effect when the ratio of the weight of the powder to the weight of the volatile fraction 'is at least of 1:45.
  • 3d-One obtains under the best circumstances the reappearance of transparency and superficial adhesive effect under a pressure when the ratio of the weight of the powder to the weight of the non volatile fraction p is at most of 2:5.
  • the pressure necessary for transferring the ink sign depends upon the latter ratio as well as on modifications of the rheological properties of the adhesive due to the migration of the fluidity agent.
  • the adhesive In order to cause migration of the fluidity vagent in the adhesive, it has been found sufficient for the adhesive to contain volatile materials without true solvating action on the ink polymer, so as to cause a slight swelling in the surface area of the ink lm.
  • a contact of very short duration was necessary to bring about the migration of stearate in an adhesive containing aliphatic solvents such as benzine or ⁇ aromatic solvents such as toluene.
  • the migration of ink fluidity agent into the adhesive above the ink sign modifies the rheological properties of the adhesive at that place in Vsuch a way that the adhesive covering the ink signs answers more easily when subjected to a pressure applied on the back of the provisional support, slides between the particles of powder, nets the latter and reaches the receptor surface to make the ink sign adhere thereto.
  • the adhesive mass located out of the ink sign has a higher threshold of deformation and goes a little, if any, through the layer of powder.
  • the modification of the rheological properties of the adhesive above the sign also has for its effect to facilitate the shearing of the adhesive on the edge of the ink sign.
  • dry transfer material According to the intended use of the dry transfer material and the requirements of the user, it is possible, by increasing the concentration of the powder in the given limits and lby varying the percentage of fluidity agent migrating into the adhesive, to make dry transfer materials iby transferring perfectly an ink sign at a pressure between 50 and 350 g./mrn.2.
  • the powder particles contained in the adhesive have a relatively high capacity of absorbing oil and similar materials, in direct relation with their fineness.
  • the particles are indeed wetted by the low molecular weight phase of the adhesive.
  • the result thereof is a reduction of adhesive power of the adhesive.
  • a plasticizer such as tricresyl phosphate, ricinus oil, methyl abietate.
  • the weight of added plasticizer is at least equal to twice the weight of powder mixed with the adhesive.
  • the superficial adhesive properties appear under the effect of a pressure. It is thus necessary that said transfer assembly be protected before use by means of a protecting sheet having anti-adhesive properties.
  • a silicone-treated paper sheet is used according to the present invention. The superficial adhesive action of the adhesive having disappeared the protecting sheet cannot even slightly adhere to the adhesive.
  • the protecting sheet In order to avoid that the protecting sheet slides or be shifted during handling preceding use of the transfer material, it is necessary that the protecting sheet be attached to the support or carrier by means of pressuresensitive adhesive tapes applied on at least one side of the support sheet as disclosed in Belgian Pat. No. 614,- 782, or by sewing, soldering or clipping.
  • reference numeral 1 designates the provisional support sheet made, for example of polystyrene, on which an ink sign 2 is printed.
  • the support or carrier sheet 1 and the ink sign 2 are covered with an adhesive layer 3.
  • the ink of sign 2 contains a non volatile oozing material 4 such as described above, concentrated at the ⁇ upper surface of the sign and having exuded into the adhesive layer 3 when the latter has been brought into contact with ink sign 2.
  • the adhesive layer 3 has on its free surface, a layer 5 made of one or more strata of side by side placed particles of silica powder such as described above, said layer being formed by floatation of a silica powder contained within the adhesive, upon evaporation of the volatile fraction 0f the adhesive, after the latter has been applied onto the provisional support sheet 1 and the ink sign 2.
  • the non volatile exuding material 4 modifies the properties of the adhesive 3 above the ink sign 2, in such a way that under the action of a sufficient pressure, the adhesive located above the ink sign 2 may pass more easily than the ⁇ adhesive located out of the ink sign, through the particles layer 5, wet the latter and reach a (not shown) receptor surface so as to make the ink sign 2 adhere selectively to said receptor surface.
  • the latter After printing of the ink signs and before applying an adhesive onto the polystyrene sheet, the latter is passed through an apparatus of the EL-l type, available from the German firm DEMES, in order to modify by an ion bombarding in high tension alternating electric fields the polarity characteristics of that face of said sheet which will receive the ink signs, so as to provide a better bonding of the adhesive to the polystyrene.
  • an apparatus of the EL-l type available from the German firm DEMES
  • a pressure-sensitive adhesive of the polyvinylether type according to adhesive Formula 1 given above is applied as a 24 micron layer, said adhesive containing, per 445 parts by Weight of adhesive, 100 parts by weight of a non volatile fraction in the form of polyvinylether and 300 parts by weight of a volatile fraction, the latter comprising a mixture of toluene, benzine( 100/ 140) and heptane in the proportions indicated above in adhesive Formula 1.
  • the adhesive contains, in addition, parts by Weight of pyrogenated silica powder having a particle size between 5 and 20 millimicrons, a specific gravity of about 2.4 and a refractive index of about 1.5.
  • the adhesive contains, also according to the present invention, about 30 parts by Weight of ricinus oil as a plasticizer. 1
  • the superficial adhesive characteristic of the adhesive in the provisional support-ink sign-adhesive material according to the present invention is caused to appear or revealed by rubbing by means of a hard tool.
  • the optical densities in white light respectively of the control adhesive, the revealed adhesive and the not revealed adhesive are measured using an optical densitometer, with the following results:
  • the difference of transmitted light between revealed and not revealed adhesives indicates the formation of a very thin layer of powder obtained by floatation.
  • the almost identical values for the control adhesive and the revealed adhesive show that the powder concentration did not appreciably influence the transparency.
  • the superficial adhesive effect of the control adhesive is seen to be identical with that of the revealed adhesive Using a dynamometer, it is seen that a pressure of 220 g./mm.2 should be applied during seconds to provide a transfer of the ink sign and that under such pressure and during that time, the adhesive molecules overlapping the ink sign do not reach the receptor surface.
  • a process for making a dry transfer material comprising (a) providing a light-transmitting support sheer which has a surface of synthetic polymeric material with a critical surface tension less than 37 dynes/cm., (b) placing on said surface ink signs which contain, a nonvolatile liquid of molecular weight below 600 capable of diffusing from said signs through the surface thereof opposed to their surface of contact with said support sheet, said liquid being a plasticizer for pressure-sensitive adhesive (c) covering said surface of said support sheet with a pressure-sensitive adhesive layer having in itself great adhesiveness once it is dried, the adhesive of said adhesive layer being applied as a composition comprising a volatile fraction of at least one member selected from the group consisting of aliphatic liquid hydrocarbons and aromatic liquid hydrocarbon and a non-volatile fraction of at least one member selected from the group consisting of polyvinylalkylether, natural rubber, and synthetic rubber in a Weight ratio of at least 3:1, said adhesive composition also containing solid particles of silica having a size between 5 and 2O millimi
  • nonvolatile diffusing liquid is selected from a group consisting of di(2ethylhexyl) azelate, butyl stearate, triethyl phosphate castor oil and whereas said plasticizer contained in the adhesive is selected from a group 1consisting of tricresyl phosphate, castor oil and methyl abieate, and after applying ink signs and before applying the adhesive layer,
  • ROBERT F. BURNETT Primary Examiner R. J. ROCHE, Assistant Examiner U.S. Cl. X.R. ll7-l5, 138 UA, 33; 156-240

Landscapes

  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Decoration By Transfer Pictures (AREA)
  • Color Printing (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Printing Methods (AREA)
US797505A 1968-06-21 1969-02-07 Process for making a dry transfer material Expired - Lifetime US3684544A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE60041 1968-06-21

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US3684544A true US3684544A (en) 1972-08-15

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US797505A Expired - Lifetime US3684544A (en) 1968-06-21 1969-02-07 Process for making a dry transfer material

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US (1) US3684544A (es)
BR (1) BR6906612D0 (es)
CH (1) CH489373A (es)
DE (2) DE6911299U (es)
ES (1) ES364358A1 (es)
FR (1) FR2011351A1 (es)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900633A (en) * 1972-03-28 1975-08-19 Jean Gustave Jules Piron Patterned transfer sheet
US3936559A (en) * 1971-02-19 1976-02-03 Columbia Ribbon And Carbon Manufacturing Co., Inc. Pressure-sensitive transfer elements
US4034843A (en) * 1974-11-22 1977-07-12 Columbia Ribbon And Carbon Manufacturing Co., Inc. Split correction ribbon and method
US4082593A (en) * 1975-06-25 1978-04-04 Irvin Bros. (Fleet Works) Limited Printing on the sides of paper pads
US4219596A (en) * 1977-11-07 1980-08-26 Avery International Corporation Matrix free thin labels
US4253899A (en) * 1979-03-08 1981-03-03 Avery International Corporation Method of making matrix free thin labels
US4454179A (en) * 1982-05-10 1984-06-12 Minnesota Mining And Manufacturing Company Dry transfer article
US4640727A (en) * 1985-01-28 1987-02-03 Minnesota Mining And Manufacturing Company Graphic design article
US4716052A (en) * 1986-01-21 1987-12-29 The D. L. Auld Company Method of making pressure sensitive adhesive tag or label stock
US4919994A (en) * 1986-04-01 1990-04-24 Minnesota Mining And Manufacturing Company Dry transfer graphics article and methods of preparation and use thereof
US4985260A (en) * 1988-05-06 1991-01-15 Vitas Niaura Food body with surface color indicia

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3936559A (en) * 1971-02-19 1976-02-03 Columbia Ribbon And Carbon Manufacturing Co., Inc. Pressure-sensitive transfer elements
US3900633A (en) * 1972-03-28 1975-08-19 Jean Gustave Jules Piron Patterned transfer sheet
US4034843A (en) * 1974-11-22 1977-07-12 Columbia Ribbon And Carbon Manufacturing Co., Inc. Split correction ribbon and method
US4082593A (en) * 1975-06-25 1978-04-04 Irvin Bros. (Fleet Works) Limited Printing on the sides of paper pads
US4219596A (en) * 1977-11-07 1980-08-26 Avery International Corporation Matrix free thin labels
US4253899A (en) * 1979-03-08 1981-03-03 Avery International Corporation Method of making matrix free thin labels
US4454179A (en) * 1982-05-10 1984-06-12 Minnesota Mining And Manufacturing Company Dry transfer article
US4640727A (en) * 1985-01-28 1987-02-03 Minnesota Mining And Manufacturing Company Graphic design article
US4716052A (en) * 1986-01-21 1987-12-29 The D. L. Auld Company Method of making pressure sensitive adhesive tag or label stock
US4919994A (en) * 1986-04-01 1990-04-24 Minnesota Mining And Manufacturing Company Dry transfer graphics article and methods of preparation and use thereof
US4999076A (en) * 1986-04-01 1991-03-12 Minnesota Mining And Manufacturing Company Dry transfer graphics article method of preparation
US4985260A (en) * 1988-05-06 1991-01-15 Vitas Niaura Food body with surface color indicia

Also Published As

Publication number Publication date
DE1914273B2 (de) 1973-08-02
CH489373A (fr) 1970-04-30
ES364358A1 (es) 1970-12-16
DE1914273A1 (de) 1970-03-05
BR6906612D0 (pt) 1973-01-18
FR2011351A1 (es) 1970-02-27
DE1914273C3 (de) 1974-04-04
DE6911299U (de) 1969-10-30

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