US3922457A - Dry wipe writing system and ink therefor - Google Patents

Dry wipe writing system and ink therefor Download PDF

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Publication number
US3922457A
US3922457A US42610573A US3922457A US 3922457 A US3922457 A US 3922457A US 42610573 A US42610573 A US 42610573A US 3922457 A US3922457 A US 3922457A
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United States
Prior art keywords
sheet
resin
group
coloring material
dry
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Inventor
George Derrick Barnwell
Reginald Charles Peter
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STRATABORD Ltd
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STRATABORD Ltd
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Priority to GB562773*[A priority Critical patent/GB1442996A/en
Priority claimed from GB562773*[A external-priority patent/GB1442996A/en
Application filed by STRATABORD Ltd filed Critical STRATABORD Ltd
Priority to US42610573 priority patent/US3922457A/en
Priority to FR7345781A priority patent/FR2211352B3/fr
Priority to JP469174A priority patent/JPS4996822A/ja
Priority to DE2363887A priority patent/DE2363887A1/en
Application granted granted Critical
Publication of US3922457A publication Critical patent/US3922457A/en
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B43—WRITING OR DRAWING IMPLEMENTS; BUREAU ACCESSORIES
    • B43L—ARTICLES FOR WRITING OR DRAWING UPON; WRITING OR DRAWING AIDS; ACCESSORIES FOR WRITING OR DRAWING
    • B43L1/00—Repeatedly-usable boards or tablets for writing or drawing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/402—Coloured
    • B32B2307/4023—Coloured on the layer surface, e.g. ink
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2432/00—Cleaning articles, e.g. mops, wipes
    • 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
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24893—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material
    • Y10T428/24901—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including particulate material including coloring matter
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
    • Y10T428/31544—Addition polymer is perhalogenated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31725—Of polyamide
    • Y10T428/31739—Nylon type
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31942—Of aldehyde or ketone condensation product

Definitions

  • a drywipe system comprising a sheet of polymeric material which is a homopolymer or copolymer of at least one perfluorinated olefine and a support for the sheet, the sheet being capable of receiving a resin bodied solvent ink to form a dry-wipe image.
  • the invention is based on the observation that contrary to expectation it is possible to write on these fluorocarbon polymers using a resin bodied solvent ink without break up of the ink and furthermore that after the ink has dried it may readily be rubbed off.
  • the fluorocarbon polymer used for the sheet is preferably polytetrafluoroethylene (PTFE), fluoroethylene propylene (FEP) or, most preferably ethylene tetrafluoroethylene copolymer (EFTE).
  • PTFE polytetrafluoroethylene
  • FEP fluoroethylene propylene
  • EFTE ethylene tetrafluoroethylene copolymer
  • the FEP is a thermoplastic copolymer of tetrafluoroethylene and hexafluoropropylene and is available from du Pont.
  • the EFTE is also a thermoplastic copolymer but of ethylene and tetrafluoroethylene, and again is available from du Pont.
  • the PTFE is preferably a type of smoothed PTFE supplied by Fluorplast Ltd., of Stoke-on-Trent, Staffordshire, England.
  • PTFE, FEP AND EFTE are all generally translucent in appearance and will therefore show the colour of, or any designs or guide lines or indicia generally, with which the support may be provided.
  • the writing surface of the material may be evenly embossed to cut down reflectance; this embossing also has the effect of masking skive marks and increasing scratch resistance.
  • the support may be of any desired material which will allow one to write on the sheet and then to rub the writing off. Although a rigid support is preferred, supports with some flexibility may also be used.
  • Preferred rigid supports include metal, sheets, suchas steel, which are preferably provided with a coloured coating by dipping, spraying or like process, the coating preferably being white in colour.
  • the sheet of polymeric material may be attached to the support in a semipermanent manner for example by use of springs or clips or a like mechanism or may be permanently bonded using an adhesive.
  • a suitable adhesive is a high-tack adhesive.
  • the polymeric material can be provided with a layer of a high-tack adhesive which is covered with a release paper such as silicone coated paper, which may be removed before boriding.
  • the polymeric sheet can then be adhered to any desired support.
  • the polymeric sheet may be first applied to a flexible backing sheet. e.g. a polyvinyl chloride foil and the other side of the backing sheet can be coated with adhesive and, if desired, provided with a release paper.
  • This assembly of the polymeric m ate-- rial and backing sheet can then beadhered toany desired support.
  • Thebacking sheet may be translucent or 2 opaque and can, if desired, be printed in any desired way.
  • the sheet of polymeric material can be formed on the backing sheet or support by spraying or otherwise applying the polymer to the backing sheet or support.
  • the polymeric sheet and support is preferably applied to a sheet of blockboard, chipboard or like material, with the use of impact adhesive, and edged with a suitable trim. In this manner articles such as blackboards and display boards generally may be made.
  • the ink to be used should be a resin bodied solvent ink.
  • the ink comprises a solvent and dispersed or dissolved therein a colouring material which may either be a dyestuff or a pigment.
  • resin bodied solvent ink as used herein means an ink containing dyestuff and/or pigment dissolved or dispersed in a solvent and resin which causes the dyestuff or pigment to adhere to substrates to which it is applied.
  • Preferred inks which may be used according to the invention are resin bodied solvent inks, in which the solvent is a water miscible organic solvent, and the constitution of the ink is such that on application to a smooth, non-absorbent surface, such as PTFE, FEP or EFTE it dries to deposit an amorphous, non adherent, granular and brittle film which may be readily dusted off the surface.
  • a smooth, non-absorbent surface such as PTFE, FEP or EFTE it dries to deposit an amorphous, non adherent, granular and brittle film which may be readily dusted off the surface.
  • a method of writing on a surface to give a drywipe image which comprises applying in any desired configuration a resin bodied solvent ink to a supported sheet of polymeric material which is a homopolymer or copolymer of at least one perfluorinated olefine.
  • the invention also provides a dry-wipe writing system which comprises a sheet of polymeric material which is a homopolymer or copolymer of at least one perfluorinated olefine, the sheet being provided with a support and a resin bodied solvent ink which will, on application to the sheet, form a dry-wipe image.
  • resin bodied solvent inks may also be used for writing on smooth surfaces other than fluorocarbon polymers as specified such surfaces including for example, glass, porcelain, enamel and similar surfaces.
  • the water miscible organic solvent is preferably an alcohol or an alcohol-ether.
  • water soluble alcohols include ethyl alcohol and industrial methylated spirits as well as glycols, such as ethylene glycol and glycol derivatives in particular ethers thereof such as the monoethyl ether of ethylene glycol (Cellosolve) and the monomethyl ether of ethylene glycol.
  • inks There are two major preferred classes of inks, one containing dyestuffs and the other containing pigments as the colouring materials.
  • the resin in the dyestuff-containing ink is preferably a phenol-formaldehyde Novolac resin.
  • Suitable Novolac resins include, for example, Alvonol PN430 sold by the Albert Resin Co. (Reinhold-Albert Gmbl-l) of "Wiesbaden-Biebrich, Germany.
  • Other resin materials which may be used include alkoxy-alkylated nylon such as Tresin 30.
  • the dye used in the ink is preferably of the metal complex type; particularly suitable are those of the copper of chromium complex type.
  • the dyestuff-containing ink preferably contains an inorganic salt which is soluble in the solvent used.
  • Calcium chloride which is alcohol soluble is suitableltis preferred that the salt, like CaCl be hygroscopic but this is not essential.
  • the ink according to the invention may contain water but only in a minor proportion (2 to Preferred ratios of the components of the dyestuffcontaining ink are as follows:
  • a preferred type of pigment for use in the inks is one in which the pigment particles are already resin coated this means that addition of further resin to promote adherence is not always necessary.
  • Such pigments are available under the Hoesta tradename from Farbwerke Hoescht. These pigments are already coated with a vinyl resin.
  • the solvent used preferably has at least some solvent action on the vinyl resin.
  • a particularly preferred mixture of solvents is of butyl acetate, ethyl acetate and methyl isobutyl ketone.
  • a barrier system is preferably used to prevent too strong an adherence of the pigment to the fluorocarbon polymers; such systems include mixtures of fatty acid alcohols and esters. Plasticisers are also preferably used.
  • the dry-wipe surface of thePTFE, FEP or EFTE and the ink combine to form a dry-wipe system of outstanding properties.
  • this material with an adhesive coating is to be stored before further processing there is applied to the adhesive a conventional silicone coated release paper. Otherwise the PTFE sheet is applied to a sheet of steel coated with a Colorcoat coating (Colorcoat is supplied by The British Steel Corporation) with the adhesive in contact to form the laminate which for final use is preferably adhered to a sheet of blockboard, chipboard, hardboard'or like material with the use of impact adhesive and edged with a suitable trim. Any desired permanent markings may be printed on the coated steel before the PTFE is bonded to it.
  • EXAMPLE 2 (Dyestuff based) Alvonol PN 430" Resin (Albert Resin Co.) 4 grns Calcium Chloride (CaCl,) 2 gms -continued Zapon Fiery Red 3* 2 gms. Industrial Methylated Spirits mls. Chromium complex dyestuff sold by B.A.S.F. (Badische Anilin & Sodal'abrik). Ludwigshal'en. Germany.
  • EXAMPLE 3 (Dyestuff based) Alvonol PN 430" Resin 4 gms. Crystalline Sodium Acetate (non-hygroscopic) 1 gm. Zapon Fast Blue FLE** 4 gms. 98% industrial Methylated Spirits I00 mls.
  • EXAMPLE 4 Hoesta print Black L 5.5 gms. Paraplex G 53 1.0 gms. Barrier system* 5.5 gms. Ethyl acetate 6.7 mls. Butyl acetate 26.8 mls. Methyl isobutyl ketone 6.7 mls. 50:50 mixture of Alfoil I216 and Estol 653.
  • EXAMPLE 5 (Pigment based) Hoesta print Green 00 5.0 gms. Paraplex G 53 L0 gms. Ethyl acetate 6.7 mls. Butyl acetate 26.8 mls. Methyl isobutyl ketone 6.7 mls.
  • lf'this material with an adhesive coating is to be stored before further processing there is applied to the adhesive a conventional silicone coated release paper. Otherwise the FEP sheet is applied to a sheet of steel coated with a Colorcoat coating with the adhesive in contact to form the laminate which for final use is preferably adhered to a sheet of blockboard, chipboard, hardboard or like material with the use of impactadhesive and edged with a suitable trim. Any desired permanent markings may be printed on the coated steel before the FEP is bonded to it.
  • the FEP surface of the above material can readily be written upon using the inks referred to in Examples 2 to 5.
  • the adhesive a conventional silicone coated release paper. Otherwise the TEFZEL sheet is applied to a sheet of steel coated with a Colorcoat coating with the adhesive in contact to form the laminate which for final use is preferably adhered to a sheet of blockboard, chipboard, hardboard or like material with the use of impact adhesive and edged with a suitable trim. Any desired permanent markings may be printed on the coated steel before the TEFZEL is bonded to it.
  • TEFZEL surface of the above material can readily be written upon using the inks referred to in Examples 2 to 5.
  • Paraplex G53 is a polyester plasticiser available from Messrs. Rohm and Haas; Estol 653 is glycerol monooleate and Alfoil 1216 is a mixture of higher fatty alcohols available from Messrs. Conoco.
  • a dry-wipe writing system comprising a writing surface which is a sheet of a polyfluorocarbon polymer selected from the group consisting of polytetrafluoroethylene, fluoroethylene propylene copolymer and ethylenetetrafluoroethylene copolymer; a support to which the said sheet is laminated; and a resin-bodied solvent ink on the said writing surface in any desired configuration, the resin-bodied solvent ink comprising a volatile, organic solvent, a coloring material which is selected from the group consisting of dyestuffs, in combination with an inorganic salt, and pigments, and a resin selected from the group consisting of phenol-formaldehyde novolacs, alkoxy-alkylated nylons and vinyl resins, which, together with the coloring material, forms, when dry, an amorphous, granular, brittle film wipably removably adherent-to the writing surface.
  • a writing surface which is a sheet of a polyfluorocarbon polymer
  • a method of writing on a surface to give a dry-wipe image comprising applying to a writing surface which is a sheet of a polyfluorocarbon polymer selected from the group consisting of polytetrafluoroethylene, fluoroethylene propylene copolymer and ethylenetetrafluoroethylene copolymer which is laminated to a support, in any desired configuration a resin-bodied solvent ink comprising a volatile organic solvent, a coloring material which is selected from the group consisting of dyestuffs, in combination with an inorganic salt, and pigments, and a resin selected from the group consisting of phenol-formaldehyde novolacs, alkoxy-alkylated nylons and vinyl resins, which, together with the coloring material, forms, when dry, an amorphous, granular, brittle film wipably removably adherent to the writing surface.
  • a writing surface which is a sheet of a polyfluorocarbon polymer selected from the group consisting of poly
  • the solvent is selected from the group consisting of alcohols, ethers, esters and ketones.

Abstract

This invention provides a dry-wipe writing system, particularly useful in the education field. The system comprises a writing surface formed from a polyfluorocarbon polymer laminated to a support, and a resin-bodied solvent ink on the writing surface in any desired configuration, the resin-bodied solvent ink comprising a volatile, organic solvent, a coloring material selected from the group consisting of dyestuffs and pigments, and a resin.

Description

United States Patent [191 Barnwell et al.
[ 5] Nov. 25, 1975 DRY WIPE WRITING SYSTEM AND INK THEREFOR [75] Inventors: George Derrick Barnwell,
Harrogate; Reginald Charles Peter, Uxbridge, both of England [73] Assignee: Stratabord Limited, Harrogate,
England [22] Filed: Dec. 19, 1973 [21] Appl. No.: 426,105
[52] U.S. Cl. 428/207; 35/66; 106/32.5; 427/256; 428/421; 428/422; 428/474;
[51] Int. Cl. B32B 3/10 [58] Field of Search 117/37 R, 38, 138.8 UF, 117/161 UG; 161/97, 189, 146,88, 87;
[56] References Cited UNITED STATES PATENTS 3,304,221 2/1967 Eggleton 117/37 R 12/1970 Frech 35/66 2/1971 Liberman et a1. 117/38 Primary ExaminerThomas J. Herbert, Jr. Assistant Examiner-Bruce H. Hess Attorney, Agent, or FirmWilliam R. Liberman ABSTRACT 13 Claims, N0 Drawings DRY WIPE WRITING SYSTEM AND INK THEREFOR This invention relates to a new dry-wipe writing system of particular application in education and in other fields where it is desired to write indicia, such as letters and figures, on a display sheet and to be able to rub off the indicia simply by dry-wiping e.g. with a dry duster or cloth. It also relates to an ink of particular utility in the new dry-wipe system.
It is an object of the invention to provide a new drywipe system on which indicia can readily be written and removed at will by dry-wiping.
According to the invention there is provided a drywipe system comprising a sheet of polymeric material which is a homopolymer or copolymer of at least one perfluorinated olefine and a support for the sheet, the sheet being capable of receiving a resin bodied solvent ink to form a dry-wipe image.
The invention is based on the observation that contrary to expectation it is possible to write on these fluorocarbon polymers using a resin bodied solvent ink without break up of the ink and furthermore that after the ink has dried it may readily be rubbed off.
The fluorocarbon polymer used for the sheet is preferably polytetrafluoroethylene (PTFE), fluoroethylene propylene (FEP) or, most preferably ethylene tetrafluoroethylene copolymer (EFTE).
The FEP is a thermoplastic copolymer of tetrafluoroethylene and hexafluoropropylene and is available from du Pont.
The EFTE is also a thermoplastic copolymer but of ethylene and tetrafluoroethylene, and again is available from du Pont.
The PTFE is preferably a type of smoothed PTFE supplied by Fluorplast Ltd., of Stoke-on-Trent, Staffordshire, England. PTFE, FEP AND EFTE are all generally translucent in appearance and will therefore show the colour of, or any designs or guide lines or indicia generally, with which the support may be provided. The writing surface of the material may be evenly embossed to cut down reflectance; this embossing also has the effect of masking skive marks and increasing scratch resistance. The support may be of any desired material which will allow one to write on the sheet and then to rub the writing off. Although a rigid support is preferred, supports with some flexibility may also be used. Preferred rigid supports include metal, sheets, suchas steel, which are preferably provided with a coloured coating by dipping, spraying or like process, the coating preferably being white in colour.
The sheet of polymeric material may be attached to the support in a semipermanent manner for example by use of springs or clips or a like mechanism or may be permanently bonded using an adhesive. A suitable adhesive is a high-tack adhesive. For ease of assembly the polymeric material can be provided with a layer of a high-tack adhesive which is covered with a release paper such as silicone coated paper, which may be removed before boriding. I
The polymeric sheet can then be adhered to any desired support. However the polymeric sheet may be first applied to a flexible backing sheet. e.g. a polyvinyl chloride foil and the other side of the backing sheet can be coated with adhesive and, if desired, provided with a release paper. This assembly of the polymeric m ate-- rial and backing sheet can then beadhered toany desired support. Thebacking sheet may be translucent or 2 opaque and can, if desired, be printed in any desired way.
The sheet of polymeric material can be formed on the backing sheet or support by spraying or otherwise applying the polymer to the backing sheet or support.
For permanent use the polymeric sheet and support is preferably applied to a sheet of blockboard, chipboard or like material, with the use of impact adhesive, and edged with a suitable trim. In this manner articles such as blackboards and display boards generally may be made.
The ink to be used should be a resin bodied solvent ink. This means that the ink comprises a solvent and dispersed or dissolved therein a colouring material which may either be a dyestuff or a pigment.
Clearly if such a simple ink were used the colouring material would simply tend to fall off the surface to which it had been applied. Thus the ink also must contain resin which causes the colouring material to adhere to the surface to which it has been applied when the solvent has evaporated. The term resin bodied solvent ink as used herein means an ink containing dyestuff and/or pigment dissolved or dispersed in a solvent and resin which causes the dyestuff or pigment to adhere to substrates to which it is applied.
Preferred inks which may be used according to the invention are resin bodied solvent inks, in which the solvent is a water miscible organic solvent, and the constitution of the ink is such that on application to a smooth, non-absorbent surface, such as PTFE, FEP or EFTE it dries to deposit an amorphous, non adherent, granular and brittle film which may be readily dusted off the surface.
According to an aspect of the invention there is provided a method of writing on a surface to give a drywipe image which comprises applying in any desired configuration a resin bodied solvent ink to a supported sheet of polymeric material which is a homopolymer or copolymer of at least one perfluorinated olefine.
The invention also provides a dry-wipe writing system which comprises a sheet of polymeric material which is a homopolymer or copolymer of at least one perfluorinated olefine, the sheet being provided with a support and a resin bodied solvent ink which will, on application to the sheet, form a dry-wipe image.
The suitability of any particular ink for forming a drywipe image on EFTE, PTFE or FEP can be determined by a simple test, that is by application to a sheet of the polymer. I
These resin bodied solvent inks may also be used for writing on smooth surfaces other than fluorocarbon polymers as specified such surfaces including for example, glass, porcelain, enamel and similar surfaces.
The water miscible organic solvent is preferably an alcohol or an alcohol-ether. Examples of water soluble alcohols include ethyl alcohol and industrial methylated spirits as well as glycols, such as ethylene glycol and glycol derivatives in particular ethers thereof such as the monoethyl ether of ethylene glycol (Cellosolve) and the monomethyl ether of ethylene glycol.
There are two major preferred classes of inks, one containing dyestuffs and the other containing pigments as the colouring materials.
The resin in the dyestuff-containing ink is preferably a phenol-formaldehyde Novolac resin. Suitable Novolac resins include, for example, Alvonol PN430 sold by the Albert Resin Co. (Reinhold-Albert Gmbl-l) of "Wiesbaden-Biebrich, Germany. Other resin materials which may be used include alkoxy-alkylated nylon such as Tresin 30.
The dye used in the ink is preferably of the metal complex type; particularly suitable are those of the copper of chromium complex type.
The dyestuff-containing ink preferably contains an inorganic salt which is soluble in the solvent used. Calcium chloride which is alcohol soluble is suitableltis preferred that the salt, like CaCl be hygroscopic but this is not essential.
The ink according to the invention may contain water but only in a minor proportion (2 to Preferred ratios of the components of the dyestuffcontaining ink are as follows:
A preferred type of pigment for use in the inks is one in which the pigment particles are already resin coated this means that addition of further resin to promote adherence is not always necessary. Such pigments are available under the Hoesta tradename from Farbwerke Hoescht. These pigments are already coated with a vinyl resin. The solvent used preferably has at least some solvent action on the vinyl resin. A particularly preferred mixture of solvents is of butyl acetate, ethyl acetate and methyl isobutyl ketone. In the inks containing pigments a barrier system is preferably used to prevent too strong an adherence of the pigment to the fluorocarbon polymers; such systems include mixtures of fatty acid alcohols and esters. Plasticisers are also preferably used.
The dry-wipe surface of thePTFE, FEP or EFTE and the ink combine to form a dry-wipe system of outstanding properties.
The invention is illustrated by the following Examples:
EXAMPLE 1 A dry-wipe system was made up as follows.
To a sheet of smoothed PTFE obtained from Fluorplast Ltd., there is applied a layer of high-tack adhesive.
If this material with an adhesive coating is to be stored before further processing there is applied to the adhesive a conventional silicone coated release paper. Otherwise the PTFE sheet is applied to a sheet of steel coated with a Colorcoat coating (Colorcoat is supplied by The British Steel Corporation) with the adhesive in contact to form the laminate which for final use is preferably adhered to a sheet of blockboard, chipboard, hardboard'or like material with the use of impact adhesive and edged with a suitable trim. Any desired permanent markings may be printed on the coated steel before the PTFE is bonded to it.
. The PTFE surface of the above material can readily be written upon using the inks referred to herein, representative inks being as follows:
EXAMPLE 2 (Dyestuff based) Alvonol PN 430" Resin (Albert Resin Co.) 4 grns Calcium Chloride (CaCl,) 2 gms -continued Zapon Fiery Red 3* 2 gms. Industrial Methylated Spirits mls. Chromium complex dyestuff sold by B.A.S.F. (Badische Anilin & Sodal'abrik). Ludwigshal'en. Germany.
EXAMPLE 3 (Dyestuff based) Alvonol PN 430" Resin 4 gms. Crystalline Sodium Acetate (non-hygroscopic) 1 gm. Zapon Fast Blue FLE** 4 gms. 98% industrial Methylated Spirits I00 mls.
"Copper complex dyestuffsold by B.A.S.F. (Badische Anilin & Sodafahrik). Ludwigshafen. Germany.
EXAMPLE 4 (Pigment based) Hoesta print Black L 5.5 gms. Paraplex G 53 1.0 gms. Barrier system* 5.5 gms. Ethyl acetate 6.7 mls. Butyl acetate 26.8 mls. Methyl isobutyl ketone 6.7 mls. 50:50 mixture of Alfoil I216 and Estol 653.
EXAMPLE 5 (Pigment based) Hoesta print Green 00 5.0 gms. Paraplex G 53 L0 gms. Ethyl acetate 6.7 mls. Butyl acetate 26.8 mls. Methyl isobutyl ketone 6.7 mls.
EXAMPLE 6 A dry-wipe system was made up as follows.
To a sheet of PEP (du Pont) there is applied a layer of a high-tack adhesive.
lf'this material with an adhesive coating is to be stored before further processing there is applied to the adhesive a conventional silicone coated release paper. Otherwise the FEP sheet is applied to a sheet of steel coated with a Colorcoat coating with the adhesive in contact to form the laminate which for final use is preferably adhered to a sheet of blockboard, chipboard, hardboard or like material with the use of impactadhesive and edged with a suitable trim. Any desired permanent markings may be printed on the coated steel before the FEP is bonded to it.
The FEP surface of the above material can readily be written upon using the inks referred to in Examples 2 to 5.
EXAMPLE 7 A dry-wipe system was made up as follows.
To a sheet of EFTE (sold bu du Pont as TEFZEL") there is applied a layer of a high-tack'adhesive.
If this material with an adhesive coating is to be stored before further processing there is applied to the adhesive a conventional silicone coated release paper. Otherwise the TEFZEL sheet is applied to a sheet of steel coated with a Colorcoat coating with the adhesive in contact to form the laminate which for final use is preferably adhered to a sheet of blockboard, chipboard, hardboard or like material with the use of impact adhesive and edged with a suitable trim. Any desired permanent markings may be printed on the coated steel before the TEFZEL is bonded to it.
The TEFZEL surface of the above material can readily be written upon using the inks referred to in Examples 2 to 5.
In Examples 4 and 5 Paraplex G53 is a polyester plasticiser available from Messrs. Rohm and Haas; Estol 653 is glycerol monooleate and Alfoil 1216 is a mixture of higher fatty alcohols available from Messrs. Conoco.
What is claimed is:
1. A dry-wipe writing system comprising a writing surface which is a sheet of a polyfluorocarbon polymer selected from the group consisting of polytetrafluoroethylene, fluoroethylene propylene copolymer and ethylenetetrafluoroethylene copolymer; a support to which the said sheet is laminated; and a resin-bodied solvent ink on the said writing surface in any desired configuration, the resin-bodied solvent ink comprising a volatile, organic solvent, a coloring material which is selected from the group consisting of dyestuffs, in combination with an inorganic salt, and pigments, and a resin selected from the group consisting of phenol-formaldehyde novolacs, alkoxy-alkylated nylons and vinyl resins, which, together with the coloring material, forms, when dry, an amorphous, granular, brittle film wipably removably adherent-to the writing surface.
2. The system of claim 1 wherein the said writing surface is a sheet of ethylenetetrafluoroethylene copolymer which is adhered to a rigid support by high tack adhesive.
3. The system of claim 2 wherein the said support is white in colour.
4. The system of claim 1 wherein thesolvent is selected from the group consisting of alcohols, ethers, esters and ketones.
5. The system of claim 4 wherein the coloring material is a dyestuff of the metal complex type.
6. The dry-wipe writing system of claim 1 wherein the coloring material is a pigment.
7. A method of writing on a surface to give a dry-wipe image comprising applying to a writing surface which is a sheet of a polyfluorocarbon polymer selected from the group consisting of polytetrafluoroethylene, fluoroethylene propylene copolymer and ethylenetetrafluoroethylene copolymer which is laminated to a support, in any desired configuration a resin-bodied solvent ink comprising a volatile organic solvent, a coloring material which is selected from the group consisting of dyestuffs, in combination with an inorganic salt, and pigments, and a resin selected from the group consisting of phenol-formaldehyde novolacs, alkoxy-alkylated nylons and vinyl resins, which, together with the coloring material, forms, when dry, an amorphous, granular, brittle film wipably removably adherent to the writing surface.
8. The method of claim 7 wherein the sheet of polyfluorocarbon polymer is of ethylenetetrafluoroethylene copolymer.
9. The method of claim 7 wherein the said sheet has been adhered to a rigid support by a high tack adhesive.
10. The method of claim 9 wherein the said support is white in colour.
11. The method of claim 7 wherein the solvent is selected from the group consisting of alcohols, ethers, esters and ketones.
12. The system of claim 7 wherein the coloring material is a dyestuff of the metal complex type.
13. The method of claim 7 wherein the coloring material is a pigment.

Claims (13)

1. A DRY-WIPE WRITING SYSTEM COMPRISING A WRITING SURFACE WHICH IS A SHEET OF A POLYFLUOROCARBON POLYMER SELECTED FROM THE GROUP CONSISTING OF POLYTETRAFLUOROETHYLENE, FLUOROETHYLENE PROPYLENE COPOLYMER AND ETHYLENETETRAFLUOROETHYLENE COPOLYMER; A SUPPORT TO WHICH THE SAID SHEET IS LAMINATED; AND A RESIN-BODIED SOLVENT INK ON THE SAID WRITING SURFACE IN ANY DESIRED CONFIGURATION, THE RESIN-BODIED SOLVENT INK COMPRISING A VOLATILE, ORGANIC SOLVENT, A COLORING MATERIAL WHICH IS SELECTED FROM THE GROUP CONSISTING OF DYESTUFFS, IN COMBINATION WITH AN INORGANIC SALT, AND PIGMENTS, AND A RESIN SELECTED FROM THE GROUP CONSISTING OF PHENOL-FORMALDEHYDE NOVOLACS, ALKOXY-ALKYLATED NYLONS AN VINYL RESINS, WHICH, TOGETHER WITH THE COLORING MATERIAL, FORMS, WHEN DRY, AN AMORPHOUS, GRANULAR, BRITTLE FILM WIPABLY REMOVABLY ADHERENT TO THE WRITIN SURFACE.
2. The system of claim 1 wherein the said writing surface is a sheet of ethylenetetrafluoroethylene copolymer which is adhered to a rigid support by high tack adhesive.
3. The system of claim 2 wherein the said support is white in colour.
4. The system of claim 1 wherein the solvent is selected from the group consisting of alcohols, ethers, esters and ketones.
5. The system of claim 4 wherein the coloring material is a dyestuff of the metal complex type.
6. The dry-wipe writing system of claim 1 wherein the coloring material is a pigment.
7. A method of writing on a surface to give a dry-wipe image comprising applying to a writing surface which is a sheet of a polyfluorocarbon polymer selected from the group consisting of polytetrafluoroethylene, fluoroethylene propylene copolymer and ethylenetetrafluoroethylene copolymer which is laminated to a supPort, in any desired configuration a resin-bodied solvent ink comprising a volatile organic solvent, a coloring material which is selected from the group consisting of dyestuffs, in combination with an inorganic salt, and pigments, and a resin selected from the group consisting of phenol-formaldehyde novolacs, alkoxy-alkylated nylons and vinyl resins, which, together with the coloring material, forms, when dry, an amorphous, granular, brittle film wipably removably adherent to the writing surface.
8. The method of claim 7 wherein the sheet of polyfluorocarbon polymer is of ethylenetetrafluoroethylene copolymer.
9. The method of claim 7 wherein the said sheet has been adhered to a rigid support by a high tack adhesive.
10. The method of claim 9 wherein the said support is white in colour.
11. The method of claim 7 wherein the solvent is selected from the group consisting of alcohols, ethers, esters and ketones.
12. The system of claim 7 wherein the coloring material is a dyestuff of the metal complex type.
13. The method of claim 7 wherein the coloring material is a pigment.
US42610573 1972-12-22 1973-12-19 Dry wipe writing system and ink therefor Expired - Lifetime US3922457A (en)

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GB562773*[A GB1442996A (en) 1972-12-22 1973-02-05 Dry-wipe writing system
US42610573 US3922457A (en) 1972-12-22 1973-12-19 Dry wipe writing system and ink therefor
FR7345781A FR2211352B3 (en) 1972-12-22 1973-12-20
JP469174A JPS4996822A (en) 1972-12-22 1973-12-21
DE2363887A DE2363887A1 (en) 1972-12-22 1973-12-21 DRY ERASABLE WRITING SYSTEM

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GB357073 1973-01-24
GB562773*[A GB1442996A (en) 1972-12-22 1973-02-05 Dry-wipe writing system
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US4120608A (en) * 1975-08-22 1978-10-17 E. I. Du Pont De Nemours And Company Heat-stable polymer coating composition with antioxidant
US4122226A (en) * 1974-09-27 1978-10-24 E. I. Du Pont De Nemours And Company Heat-stable polymer coating composition with oxidation catalyst
FR2480680A1 (en) * 1980-04-21 1981-10-23 Levy Daniel MAGNETIC PRESSURE ERASER BLOCK, MAKING A MARKER
WO1984001328A1 (en) * 1982-09-29 1984-04-12 Sanford Res Co Writing board and method for manufacturing thereof
EP0142257A2 (en) * 1983-10-17 1985-05-22 Anthony Martin Tengs Article of wearing apparel with an erasable writing surface
EP0227115A1 (en) * 1985-12-25 1987-07-01 Mitsubishi Petrochemical Co., Ltd. Writing screen
US4978568A (en) * 1988-08-08 1990-12-18 Hach Associates, Inc. Flexible writing surface
US5203913A (en) * 1990-02-13 1993-04-20 Sakura Color Products Corporation Erasable aqueous ink composition
US6251500B1 (en) 1999-02-01 2001-06-26 Rjf International Corporation Write-on/wipe off wall covering
US20010051280A1 (en) * 1998-03-05 2001-12-13 Omnova Solutions Inc. Easily cleanable polymer laminates
US6383651B1 (en) 1998-03-05 2002-05-07 Omnova Solutions Inc. Polyester with partially fluorinated side chains
US6403760B1 (en) 1999-12-28 2002-06-11 Omnova Solutions Inc. Monohydric polyfluorooxetane polymer and radiation curable coatings containing a monofunctional polyfluorooxetane polymer
US6423418B1 (en) 1998-03-05 2002-07-23 Omnova Solutions Inc. Easily cleanable polymer laminates
US6465566B2 (en) 2000-07-06 2002-10-15 Omnova Solutions Inc. Anionic waterborne polyurethane dispersions containing polyfluorooxetanes
US6465565B1 (en) 2000-07-06 2002-10-15 Omnova Solutions, Inc. Anionic waterborne polyurethane dispersions containing polyfluorooxetanes
US6579966B1 (en) 1998-03-05 2003-06-17 Omnova Solutions Inc. Cured polyesters containing fluorinated side chains
US20030158367A1 (en) * 1999-06-28 2003-08-21 Omnova Solutions Inc. Radiation curable coating containing polyfluorooxetane
US6660828B2 (en) 2001-05-14 2003-12-09 Omnova Solutions Inc. Fluorinated short carbon atom side chain and polar group containing polymer, and flow, or leveling, or wetting agents thereof
US20040018345A1 (en) * 2002-07-26 2004-01-29 Athorn-Telep Yvonne K. Dry-erase ink marking media
US20040081844A1 (en) * 2002-08-30 2004-04-29 Vivek Bharti Method of making erasable articles and articles therefrom
US6805048B2 (en) 2002-08-30 2004-10-19 3M Innovative Properties Company Method of marking a substrate using an electret stencil
US20040224164A1 (en) * 1998-03-05 2004-11-11 Wright Joe A. Fluorinated polymer and amine resin compositions and products formed therefrom
US6927276B2 (en) 1999-12-28 2005-08-09 Omnova Solutions Inc. Monohydric polyfluorooxetane oligomers, polymers, and copolymers and coating containing the same
US20060003307A1 (en) * 2004-07-02 2006-01-05 3M Innovative Properties Company Dry erase article
US7022801B2 (en) 2001-05-14 2006-04-04 Omnova Solutions Inc. Polymeric surfactants derived from cyclic monomers having pendant fluorinated carbon groups
US20080053610A1 (en) * 2006-08-31 2008-03-06 Schneider Robert W Dry erase writing board and method
US20150135415A1 (en) * 2011-01-04 2015-05-21 Robert Oppenheim Helmet with a Writing Surface, Markers, and Stencil Kit

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DE2512734B2 (en) * 1975-03-22 1979-02-08 Schwan Stabilo Schwanhaeusser Ink for writing on writing boards
JPS59179011U (en) * 1983-05-17 1984-11-30 日本カイザー株式会社 Floor slab using precast concrete board
JPH0579501A (en) * 1991-09-20 1993-03-30 Tokai Rubber Ind Ltd Manufacture of accumulator

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US3549463A (en) * 1968-06-21 1970-12-22 Riegel Paper Corp Universal graphic display material having an embossed polyvinyl fluoride surface layer
US3563782A (en) * 1969-07-31 1971-02-16 Gamco Inc Writing surface and ink composition for marking thereon

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Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4122226A (en) * 1974-09-27 1978-10-24 E. I. Du Pont De Nemours And Company Heat-stable polymer coating composition with oxidation catalyst
US4120608A (en) * 1975-08-22 1978-10-17 E. I. Du Pont De Nemours And Company Heat-stable polymer coating composition with antioxidant
FR2480680A1 (en) * 1980-04-21 1981-10-23 Levy Daniel MAGNETIC PRESSURE ERASER BLOCK, MAKING A MARKER
WO1984001328A1 (en) * 1982-09-29 1984-04-12 Sanford Res Co Writing board and method for manufacturing thereof
EP0142257A2 (en) * 1983-10-17 1985-05-22 Anthony Martin Tengs Article of wearing apparel with an erasable writing surface
EP0142257A3 (en) * 1983-10-17 1985-06-19 Anthony Martin Tengs Article of wearing apparel with an erasable writing surface
US4627110A (en) * 1983-10-17 1986-12-09 Tengs Anthony M Article of wearing apparel with an erasable writing surface
EP0227115A1 (en) * 1985-12-25 1987-07-01 Mitsubishi Petrochemical Co., Ltd. Writing screen
US4746576A (en) * 1985-12-25 1988-05-24 Mitsubishi Petrochemical Company Limited Writing screen
US4978568A (en) * 1988-08-08 1990-12-18 Hach Associates, Inc. Flexible writing surface
US5203913A (en) * 1990-02-13 1993-04-20 Sakura Color Products Corporation Erasable aqueous ink composition
US20010051280A1 (en) * 1998-03-05 2001-12-13 Omnova Solutions Inc. Easily cleanable polymer laminates
US6383651B1 (en) 1998-03-05 2002-05-07 Omnova Solutions Inc. Polyester with partially fluorinated side chains
US7846507B2 (en) 1998-03-05 2010-12-07 Omnova Solutions Inc. Method of making an easily cleanable polymer laminate
US6423418B1 (en) 1998-03-05 2002-07-23 Omnova Solutions Inc. Easily cleanable polymer laminates
US7320829B2 (en) 1998-03-05 2008-01-22 Omnova Solutions Inc. Fluorinated polymer and amine resin compositions and products formed therefrom
US20050048213A1 (en) * 1998-03-05 2005-03-03 Callicott Marten S. Method of making an easily cleanable polymer laminate
US6579966B1 (en) 1998-03-05 2003-06-17 Omnova Solutions Inc. Cured polyesters containing fluorinated side chains
US20040224164A1 (en) * 1998-03-05 2004-11-11 Wright Joe A. Fluorinated polymer and amine resin compositions and products formed therefrom
US6686051B1 (en) 1998-03-05 2004-02-03 Omnova Solutions Inc. Cured polyesters containing fluorinated side chains
US6251500B1 (en) 1999-02-01 2001-06-26 Rjf International Corporation Write-on/wipe off wall covering
EP1163118A2 (en) 1999-02-01 2001-12-19 Rjf International Corporation Write-on/wipe-off wall covering
US6673889B1 (en) 1999-06-28 2004-01-06 Omnova Solutions Inc. Radiation curable coating containing polyfuorooxetane
US20030158367A1 (en) * 1999-06-28 2003-08-21 Omnova Solutions Inc. Radiation curable coating containing polyfluorooxetane
US6927276B2 (en) 1999-12-28 2005-08-09 Omnova Solutions Inc. Monohydric polyfluorooxetane oligomers, polymers, and copolymers and coating containing the same
US6403760B1 (en) 1999-12-28 2002-06-11 Omnova Solutions Inc. Monohydric polyfluorooxetane polymer and radiation curable coatings containing a monofunctional polyfluorooxetane polymer
US6727344B2 (en) 1999-12-28 2004-04-27 Omnova Solutions Inc. Monohydric polyfluorooxetane polymer and radiation curable coatings containing a monofunctional polyfluorooxetane polymer
US6972317B2 (en) 1999-12-28 2005-12-06 Omnova Solutions Inc. Monohydric polyfluorooxetane polymer and radiation curable coatings containing a monofunctional polyfluorooxetane polymer
US6962966B2 (en) 1999-12-28 2005-11-08 Omnova Solutions Inc. Monohydric polyfluorooxetane oligomers, polymers, and copolymers and coatings containing the same
US6465566B2 (en) 2000-07-06 2002-10-15 Omnova Solutions Inc. Anionic waterborne polyurethane dispersions containing polyfluorooxetanes
US6465565B1 (en) 2000-07-06 2002-10-15 Omnova Solutions, Inc. Anionic waterborne polyurethane dispersions containing polyfluorooxetanes
US6660828B2 (en) 2001-05-14 2003-12-09 Omnova Solutions Inc. Fluorinated short carbon atom side chain and polar group containing polymer, and flow, or leveling, or wetting agents thereof
US7022801B2 (en) 2001-05-14 2006-04-04 Omnova Solutions Inc. Polymeric surfactants derived from cyclic monomers having pendant fluorinated carbon groups
US7087710B2 (en) 2001-05-14 2006-08-08 Omnova Solutions Inc. Polymeric surfactants derived from cyclic monomers having pendant fluorinated carbon groups
US20040018345A1 (en) * 2002-07-26 2004-01-29 Athorn-Telep Yvonne K. Dry-erase ink marking media
US6805048B2 (en) 2002-08-30 2004-10-19 3M Innovative Properties Company Method of marking a substrate using an electret stencil
US20040081844A1 (en) * 2002-08-30 2004-04-29 Vivek Bharti Method of making erasable articles and articles therefrom
US20060003307A1 (en) * 2004-07-02 2006-01-05 3M Innovative Properties Company Dry erase article
WO2006014239A3 (en) * 2004-07-02 2006-08-24 3M Innovative Properties Co Dry erase article
US7399184B2 (en) 2004-07-02 2008-07-15 3M Innovative Properties Company Dry erase article
WO2006014239A2 (en) * 2004-07-02 2006-02-09 3M Innovative Properties Company Dry erase article
US20080053610A1 (en) * 2006-08-31 2008-03-06 Schneider Robert W Dry erase writing board and method
US7713375B2 (en) 2006-08-31 2010-05-11 Avery Dennison Corporation Dry erase writing board and method
US20100178476A1 (en) * 2006-08-31 2010-07-15 Avery Dennison Corporation Dry erase writing board and method
US20150135415A1 (en) * 2011-01-04 2015-05-21 Robert Oppenheim Helmet with a Writing Surface, Markers, and Stencil Kit

Also Published As

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DE2363887A1 (en) 1974-06-27
FR2211352B3 (en) 1976-10-15
FR2211352A1 (en) 1974-07-19
JPS4996822A (en) 1974-09-13

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