EP0555398B1 - Method of forming a coated sheet which wicks away oil and product thereof - Google Patents

Method of forming a coated sheet which wicks away oil and product thereof Download PDF

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Publication number
EP0555398B1
EP0555398B1 EP92901236A EP92901236A EP0555398B1 EP 0555398 B1 EP0555398 B1 EP 0555398B1 EP 92901236 A EP92901236 A EP 92901236A EP 92901236 A EP92901236 A EP 92901236A EP 0555398 B1 EP0555398 B1 EP 0555398B1
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EP
European Patent Office
Prior art keywords
oil
coating
membrane
substrate
recited
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP92901236A
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German (de)
English (en)
French (fr)
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EP0555398A1 (en
Inventor
John J. Fitch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissha Medical Technologies
Original Assignee
Van Leer Metallized Products USA Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US07/608,049 external-priority patent/US5173363A/en
Application filed by Van Leer Metallized Products USA Ltd filed Critical Van Leer Metallized Products USA Ltd
Publication of EP0555398A1 publication Critical patent/EP0555398A1/en
Application granted granted Critical
Publication of EP0555398B1 publication Critical patent/EP0555398B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/502—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording characterised by structural details, e.g. multilayer materials
    • B41M5/504—Backcoats
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • This invention relates to the decoration of sheeting, and more particularly to the decoration of materials such as standard, light weight, cellulosic sheets (paper).
  • This invention also relates to the embossment of sheets or films, and more particularly to the wicking away of oil from the decorative surface of sheets or films.
  • Cellulosic sheets are normally decorated by imprinting. To achieve certain special effects, the imprinting requires special inks and relatively complex printing procedures. In addition, some decorative effects can not be realized by imprinting.
  • One very desirable decorative effect is the iridescent visual effect created by a diffraction grating. This striking visual effect, attributed to Sir John Barton, Director of the British Royal Mint (circa 1770), occurs when ambient light is diffracted into its color components by reflection from a diffraction grating.
  • a diffraction grating is formed when closely and regularly spaced grooves (5,000 to 11,000 grooves per cm.) are embossed on a reflective surface.
  • this diffraction grating technology has been employed in the formation of two-dimensional holographic images which create the illusion of a three-dimensional image to an observer.
  • This holographic image technology can form very attractive displays.
  • the economics of forming holographic images is significantly dependent upon economies of scale, the concept of using holographic images to discourage counterfeiting has found wide application.
  • thermoplastic films have been embossed by heat softening the surface of the film and then passing them through embossing rollers which impart the diffraction grating or holographic image onto the softened surface. In this way, sheets of effectively unlimited length can be decorated with the diffraction grating or holographic image on a surface.
  • the decorated surface of polymers is normally sufficiently reflective that the optical effect of the diffraction grating occurs without further processing, because the incident light is reflected by the facets of the decorated surface.
  • the term diffraction grating includes holographic images that are based on diffraction grating technology.
  • a decorated sheet of this type is known from WO-A-89/03760.
  • the decorated surface is coated with a protected transparent polymeric layer to keep the skin oil out of the grooves in the decorated surface, it has been found that the presence of the decorated layer itself will destroy the iridescent optical effect.
  • the present invention provides for embossing the coating of a substrate, such as paper sheeting.
  • the coating is a thermosensitive material which has discernable thermoplastic properties.
  • thermoplastic as used hereinafter, shall be construed to include such materials.
  • thermoplastic material advantageously is supplied with the coating of thermoplastic material.
  • the thermoplastic coating is typically applied in a water base or other suitable liquid by gravure, or reverse roll methods.
  • the actual formation of the coating would begin by spreading a pre-membrane composition, formed of a dispersion of polymer spheres in evaporable liquid onto the oil-absorbing paper substrate. Subsequently, the pre-membrane-covered substrate would be heated to evaporate the liquid and cause the polymer particles to fuse together.
  • the resulting coating is a porous membrane capable of absorbing oil which is deposited on the coating surface and wicking the oil to the oil-absorbing paper substrate. Because the membrane is thermoplastic, it can be embossed to form a diffraction grating or holographic image. This must be done without destroying the porosity of the membrane; best oil wicking characteristics have been observed when the membrane has a cracked or crazed surface after embossing.
  • the resulting optical effect or image will not be destroyed by oil which is deposited on the surface of the coating, because that oil will be wicked away from the surface and deposited in the underlying oil-absorbing paper substrate. Furthermore, ink adheres well to the decorative surface and, when lightly applied, does not interfere with the decorative effect produced by the embossment.
  • the preferred pre-membrane coating composition is an aqueous dispersion of spheres of an oleophilic polymer such as a styrene polymer. Applicant has observed that dispersions of substantially uniform particle size are preferred, and that generally larger particle sizes yield improved oil wicking characteristics. The most preferred dispersion comprises 0.5 micron diameter spheres of styrene/acrylic copolymer.
  • the coating composition would also typically include a primer, a plasticizer, an emulsifier, a dispersant, pigment, and a defoamer. The plasticizer would be present in a minimum quantity, sufficient to provide adhesion of the membrane to the substrate, but insufficient to cause the membrane to have blocking qualities.
  • Standard paper sheeting 10 is provided with a thermoplastic pre-membrane coating 11, for example, by pouring the liquid pre-membrane mixture from a feed box 12 onto the upper surface 13 of the paper sheeting 10.
  • the thermoplastic coating 11 may also be applied in a solvent or water-base using gravure, or reverse roll methods, represented schematically by the feed box 12.
  • Paper sheeting 10 thickness usually varies from about 40 microns to about 100 microns.
  • the coating weight of thermoplastic coating 11 should be sufficient to accept and retain the microembossed image; rougher papers require thicker thermoplastic coatings. On the other hand, higher coating weights tend to increase curl of the paper sheeting.
  • the preferred range for the coating weight of thermoplastic coating 11 has been determined to be about 3-20 grams per square meter.
  • the paper sheeting would provide both the strength for the final product and the oil absorbing property, which, as will be seen, draws oil through the coating. It would be possible to form the substrate from a first, very strong layer (e.g., polymeric film), and a second oil-absorbing paper layer between the first layer and the coating.
  • oil absorbing substrates may be employed in the invention in lieu of paper, such as, for example, nonwoven fabrics.
  • the coated substrate is outer layer of the coating 11 to evaporate the liquid carrier and to fuse or sinter the coating into a porous membrane.
  • additional heating can be employed.
  • an infrared heater which can be disposed away from the surface that is being softened. Such a heater is operated at heater surface temperatures of about 1,000°F.
  • thermoplastic (thermally deformable) coating 11 should be heated to well above its softening temperature.
  • a practical limit to the heating of coating 11 is about 230°C (450°F). Above that temperature, the paper substrate begins to degrade.
  • coating 11 should be heated to a temperature typically between about 120°C to 177°C (250°F to 350°F), which range represents a preferred range for most thermoplastic coatings to be coalesced and embossed in the process of the present invention.
  • the pre-membrane mixture is coalesced.
  • the coalescing process involves the evaporation of any water (or other liquid carrier) still present in the mixture after the coating operation and the fusing of the thermoplastic particles which are a primary component of the pre-membrane mixture.
  • the resulting coating is a porous membrane firmly attached to the substrate.
  • the resulting laminate After the softened thermoplastic layer has been coalesced to a porous membrane, the resulting laminate would normally be fed directly to the embossing step. However, it would be possible to allow the resulting laminate to be cooled down and stored so that the embossing step might take place at some later time.
  • an embossing arrangement is employed for decoration .
  • the arrangement uses a heated platen 32, an embossing roll 31, and a pressure nip roll 33.
  • the embossing roller 31 is a conventional embossing master which has the desired embossing pattern on its surface. This pattern is produced on the roller or rollers by engraving, embossing with a hard material, or mounting patterned plastic films or metal foils on to the surface of the roller 31.
  • the embossing roller 31 contacts the softened plastic surface 11, the embossing pattern is transferred to the coating 11 on the paper. Simultaneously, the contact with the relatively cooler roller cools the coating. This cooling action prevents flow of the coating after it is removed from the embossing roller. The result is a decorated, polymer coated paper.
  • the temperature of the embossing master (embossing roller 31) must be below the softening temperature of the thermoplastic coating 11.
  • the embossing master's (roller 31) preferred temperature in the process of the present invention is between about 66°C (150°F) to about 93°C (208°F) which is below the temperature of the thermoplastic coating 11. It has been determined that, in the context of the present process, this generally places the preferred web temperature between about 100°C (212°F) and 200°C (392°F).
  • a take-off roller 34 has been added to allow longer contact between the thermoplastic coating 11 and the embossing roll 31.
  • the longer contact time allows better cooling of the embossed surface to facilitate easy parting of the web from the embossing roll and to prevent possible re-flow of the coating and loss of the embossed pattern.
  • the pressure nip roller 33 may be metal or may be surfaced with a resilient material such as rubber.
  • the force applied between the pressure nip roller 33 and the embossing roller 31 should range from about 50 lbs. per lineal inch (PLI) to about 1,000 PLI along the length of the contact between the two rollers.
  • the force applied between the pressure nip roller 33 and the embossing roller 31 may advantageously be 50-300 PLI, but is more preferably between about 100-200 PLI.
  • the surface of the embossing roller should be hard and distortion resistant so that the embossing pattern is preserved during the embossing step.
  • the opposing roller i.e., nip roller 33
  • nip roller 33 should be firm, but also somewhat resilient. This allows nip roller 33 to apply a nearly uniform distributed pressure to the back of the sheeting being embossed. It has been determined that nip roller 33 can be quite firm, typically with a Shore A durometer hardness (ASTM D-412) reading of about 70-80, or even somewhat higher, and yet not so hard as to interfere with attainment of a uniformly distributed pressure on the back of the sheeting being embossed.
  • the contact (dwell) time wherein the embossing roller 31 and nip roller 33 contact the sheeting to achieve embossing is generally in the range of about 8 milliseconds (E.G., 300 ft./min. for a 1/2 inch wide contact area) to about 0.2 millisecond (e.g., 300 ft./min. for a 1/8 inch wide contact area).
  • embossing can be achieved by the embossing. If the diffraction pattern is not to be continuous, a matte background can be provided by suitable modification of the embossing roller. Alternatively, the embossing pattern can, in parts, be filled in with coating material, such as ink or clear lacquer, in those areas where no embossed decoration is desired.
  • coating material such as ink or clear lacquer
  • FIG. 5 shows an enlarged cross-sectional view of the substrate 10 which is a paper sheet with a coating 11 of pre-membrane mixture, prior to the fusing of the pre-membrane mixture 11.
  • FIG. 5 shows the thermoplastic spheroids 37, 38, 39, and 40 which make up the primary component of the pre-membrane mixture 11. The spheroids form the coating 11 on the substrate 10 prior to fusing of the coating.
  • FIG. 5 is figurative in that it shows the interface between the upper surface 13 of the substrate 10 and the lower layer of the uncured coating 11.
  • the spheres would be piled up more than forty spheres deep on the substrate so that the coating is about 20 microns thick.
  • FIG. 6 shows a cross-sectional view of the laminate after the coating 11 has been fused to form a porous membrane.
  • the spheroids present in FIG. 5 are fused together in such a way that pores 46, 47, 48 and 49 are formed between the spheroids which pores pass from the upper surface 14 of the coating 11 to the lower surface 15 of the coating 11.
  • the lower surface of the coating 11 is, of course, in contact with the upper surface 13 of the substrate 10.
  • the microporous membrane coating after fusing, would be about 20 microns thick (top to bottom) and about 100 microns between pores.
  • the pores are about five microns wide and form a mud-crack-like interconnected three-dimensional network which connects the coating surface to the substrate.
  • the pores are shown as capillaries which run from the top to the bottom of the coating, but it should be understood that the pore structure may be more complicated, e.g., a series of interconnecting cracks.
  • Applicant has observed that the final surface texture depends upon the choice of polymer particle dispersion (see Example 1, below) as well as the drying and embossing conditions. Longer drying times, and higher embossing temperatures, both tend to increase the time required for wicking oil. In general, a cracked or crazed surface provides superior oil wicking properties.
  • FIG. 7 shows an enlarged cross-sectional view of the laminate of the present invention after the embossing of the upper or decorative surface of the coating 11 has been accomplished.
  • the embossing is shown as grooves 51.
  • the grooves are one micron peak-to-peak and one-half micron deep.
  • FIG. 8 shows an enlarged cross-sectional view of the laminate of the present invention with a drop of human skin oil 50 deposited on the upper surface 14 of the coating 11.
  • the oil has penetrated the grooves 51 in the embossed surface and, because the index of refraction of the oil and of the thermoplastic from which the coating 11 is formed are not vastly different, the visual effect of the grooves beneath the oil is effectively extinguished.
  • FIG. 9 shows an enlarged cross-sectional view of the laminate of the present invention in which the oil has wetted and been attracted to the internal surface of the pore 46 so that the oil is drawn down into the pore and toward the substrate 10.
  • FIG. 10 shows an enlarged cross-sectional view of the laminate of the present invention in which the oil 50 has been effectively wicked away from the upper surface of the coating 11, along the pore 46 and completely absorbed by the substrate 10. The result is that the oil which previously disturbed the visual effect on the upper surface of the coating has been completely eliminated from the upper surface of the coating. Applicant has observed a typical transmission rate of between about one half minute and three minutes for finger oil to pass from the surface to the oil absorbing substrate.
  • the key element of the present invention is the microporous coating which is adapted to absorb, into its pores, any oil which is deposited on its decorative or embossed surface.
  • the polymer from which the membrane is formed must form pores which have pore surfaces which are oleophilic, that is, they must attract or be wetted by human skin oil.
  • the membrane would be formed by the fusion of thermoplastic polymeric particles of uniform size into the membrane skin populated with pores or microcracks capable of absorbing oil. As seen in Example 1, below, a particle diameter of about 0.5 microns is preferred.
  • the microporous coating has the ability to also transmit gasses, but repel water (hydrophobic). This might also have utility (with or without surface embossing) as a selective membrane in packaging produce by allowing respiration while preventing dehydration.
  • the pre-membrane mixture consists of uniform 0.5 micron diameter polystyrene spheroids dispersed in water with a plasticizer, colored pigment dispersions (if desired for appearance) and certain other processing aids.
  • this coating is applied to the paper substrate and dried at 130°C (266°F), the polystyrene particles fuse together, leaving a clear film containing interconnecting microcracks. These cracks are capable of wicking away any surface oils into the membrane and thereafter into the paper substrate below.
  • the coating can be stored after fusing or thermally embossed immediately after fusing.
  • the pre-membrane mixture of the present invention would typically involve the following ingredients.
  • the plasticizer should be charged with the emulsifying agent.
  • the binder is then added to the plasticizer under gentle agitation.
  • Half of the defoamer should be added to the mix, followed by the dispersing agent.
  • the pigment dispersion can be slowly added to the mix, followed by the balance of the defoamer.
  • Formulation E with appropriate choice of color pigment, provides the best combination of properties. It can be fused by heating to 110°C (230°F) to form a very effective membrane.
  • the preferred paper is high-wet-strength, clay-coated paper.
  • the dispersions and latices of Table 1 were used without additives or modifiers to evaluate the properties of the polymers themselves in producing microembossed coated paper.
  • the dispersions were coated on 35 grams per sq. meter Sibille Stenay clay-coated stock (One Newbury St., Peabody, Massachusetts 01960), using a #12 wire-wound rod.
  • the samples were dried in a 130°C oven for twenty seconds, then embossed at 120°C using a diffraction embossed metallized mylar master. The quality of embossing was evaluated in terms of release of the master from the embossed coating.
  • the embossed coated papers were tested for oil wicking by smearing skin oil across the surface and measuring the time for the diffraction pattern to reappear. Adhesion of the coating to the paper was determined using 3M MAGIC tape (Minnesota Mining & Mfg. Co.) applied with finger pressure and pulled up quickly. The embossed surfaces were photographed at X200 magnification to show their void structure.
  • ADCOTE 61JH61A is a styrene/acrylic copolymer dispersion of Morton Chemical Co., Chicago, Illinois.
  • 37R345 is a high molecular weight ethylene interpolymer dispersion from Morton Chemical Co.
  • UNOCAL 3512 is an acrylic polymer dispersion from B. F. Goodrich Chemical Co., Cleveland, Ohio.
  • Ethylene Vinyl Acetate CoPolymer emulsion (Polybond x34-21/Morton) 7. Acrylic ester CoPolymer emulsion (Hycar 26315/Goodrich) 8. Acrylic emulsion (Rhoplex LC-40/Rohm & Haas) 9. Polyurethane acqueous dispersion (Neores R-960/ici) 10. Ethylene Vinyl Chloride Latex (Airflex 4514/Air Products) 11. Styrene acrylic CoPolymer emulsion (Nacrylic 78-6334/National) 12. Acrylic ester CoPolymer emulsion (Hycar 26084/Goodrich) 13.
  • the oil absorbing coated sheets of the invention may be employed in applications (e.g., commercial paper) in which security against counterfeiting is desired. This technique may also be used to produce tamper evident packaging, by using a fragile substrate which would indicate tampering.

Landscapes

  • Laminated Bodies (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Cleaning Implements For Floors, Carpets, Furniture, Walls, And The Like (AREA)
  • Stereophonic System (AREA)
  • Developing Agents For Electrophotography (AREA)
  • Stringed Musical Instruments (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Paper (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Holo Graphy (AREA)
  • Thermotherapy And Cooling Therapy Devices (AREA)
EP92901236A 1990-11-01 1991-11-01 Method of forming a coated sheet which wicks away oil and product thereof Expired - Lifetime EP0555398B1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US07/608,049 US5173363A (en) 1990-11-01 1990-11-01 Coating sheet which wicks away oil
US608049 1990-11-01
US77614891A 1991-10-15 1991-10-15
US776148 1991-10-15
PCT/US1991/008168 WO1992007723A1 (en) 1990-11-01 1991-11-01 Method of forming a coated sheet which wicks away oil and product thereof

Publications (2)

Publication Number Publication Date
EP0555398A1 EP0555398A1 (en) 1993-08-18
EP0555398B1 true EP0555398B1 (en) 1994-09-07

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ID=27085651

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92901236A Expired - Lifetime EP0555398B1 (en) 1990-11-01 1991-11-01 Method of forming a coated sheet which wicks away oil and product thereof

Country Status (12)

Country Link
EP (1) EP0555398B1 (es)
JP (1) JPH06502818A (es)
AT (1) ATE111031T1 (es)
AU (1) AU651162B2 (es)
BR (1) BR9107019A (es)
CA (1) CA2095337A1 (es)
DE (1) DE69103905T2 (es)
DK (1) DK0555398T3 (es)
ES (1) ES2059208T3 (es)
FI (1) FI931974A (es)
NO (1) NO931589L (es)
WO (1) WO1992007723A1 (es)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0755332B1 (en) * 1994-04-14 1997-10-08 Sihl GmbH Recording material
EP0940427A1 (en) 1998-03-06 1999-09-08 Imation Corp. Method of preparing a microporous film, and image accepting member
WO1999055537A1 (en) * 1998-04-29 1999-11-04 3M Innovative Properties Company Receptor sheet for inkjet printing having an embossed surface
GB2345653A (en) * 1999-01-12 2000-07-19 Ici Plc Receiver medium for ink jet printing
EP1189757B1 (en) 1999-06-01 2003-07-30 3M Innovative Properties Company Optically transmissive microembossed receptor media
CN1167553C (zh) 1999-06-01 2004-09-22 3M创新有限公司 喷墨打印介质及其制备方法
GB0115814D0 (en) * 2001-06-28 2001-08-22 Arjo Wiggins Fine Papers Ltd Production of holographic images
JP4218941B2 (ja) 2003-02-25 2009-02-04 日東電工株式会社 光学部材、その製造方法、粘着型光学部材および画像表示装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989003760A1 (en) * 1987-10-26 1989-05-05 Dennison Manufacturing Company Embossing of coated sheets
JPH089269B2 (ja) * 1989-05-23 1996-01-31 新王子製紙株式会社 感熱記録材料

Also Published As

Publication number Publication date
FI931974A (fi) 1993-06-29
WO1992007723A1 (en) 1992-05-14
NO931589D0 (no) 1993-04-30
ATE111031T1 (de) 1994-09-15
JPH06502818A (ja) 1994-03-31
DK0555398T3 (da) 1995-01-09
CA2095337A1 (en) 1992-05-02
AU9057591A (en) 1992-05-26
EP0555398A1 (en) 1993-08-18
DE69103905T2 (de) 1995-02-23
DE69103905D1 (de) 1994-10-13
FI931974A0 (fi) 1993-04-30
BR9107019A (pt) 1993-08-17
ES2059208T3 (es) 1994-11-01
AU651162B2 (en) 1994-07-14
NO931589L (no) 1993-06-10

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