Stock material or miscellaneous articles – Composite – Of metal
Reexamination Certificate
1999-02-04
2002-07-23
Chen, Vivian (Department: 1773)
Stock material or miscellaneous articles
Composite
Of metal
C428S482000, C428S483000, C525S437000, C525S438000, C525S441000, C525S443000, C525S444000, C525S444500, C528S299000, C528S300000, C528S402000
Reexamination Certificate
active
06423418
ABSTRACT:
FIELD OF INVENTION
This invention relates to laminates having improved stain resistance due to the incorporation of a polymer having repeat units from an oxetane monomer having pendant fluorinated groups into a stain resistant surface layer. The stain resistant layer can also be adhered to a variety of substrates including polyesters, paper, polyolefins etc. The coatings exhibit dry erase characteristics when dry erase markers are used.
BACKGROUND OF INVENTION
U.S. Pat. No. 4,603,074 sets forth a polyester-amino resin composition that can form a stain resistant layer on plasticized polyvinyl chloride substrates. While this coating was very good with respect to stain resistance and abrasion resistance, it would be desirable to have further increases in cleanability without using solvents, while maintaining stain resistance and abrasion resistance.
A variety of polymeric coatings and surface treatments for natural and synthetic materials have been developed to enhance the dirt and stain release characteristics. Some of the more effective ones to date allow for reapplication of the anti-soil treatment after cleaning (such as with carpets) or in tents.
Dry erase boards and ink or marker pens are popular replacements for chalkboards. A variety of relatively nonporous writing surfaces have been developed along with special dry erase markers that are specially designed to leave strong well defined continuous marks that can be erased with a dry cloth or eraser. U.S. Pat. Nos. 3,834,823; 3,922,457; 3,949,132; 4,746,576; 4,988,123 and 5,324,764; disclose such technology and are herein incorporated by reference for their teachings on dry erase systems.
U.S. Pat. No. 5,650,483 describes the preparation of oxetane monomers useful to form oxetane polymers with pendant fluorinated chains. The oxetane polymers were characterized as having low surface energy, high hydrophobicity, and a low coefficient of friction. That patent is incorporated by reference herein for its teachings on how to prepare the oxetane monomers and polymers. In the reference the oxetane polymers could be formulated with isocyanates to form crosslinked compositions. Additional patents issued on variations of the oxetane monomers and polymers. These were U.S. Pat. Nos. 5,654,450; 5,663,289; 5,668,250, and 5,668,251 also incorporated herein by reference.
SUMMARY OF INVENTION
According to the present invention, an improved stain and abrasion resistant polymeric layer was developed by incorporating a minor amount of a hydroxyl terminated polymer having repeat units from an oxetane monomer having pendant fluorinated groups thereon into a polyester-amino resin composition. The hydroxyl terminated polymer may have other repeat units such as derived from the ring opening polymerization of cyclic ethers including tetrahydrofuran and/or more conventional ring opening polymerization of oxetane or epoxy monomers. Excellent stain release and abrasion release are observed with as little as 0.1, 0.2 or 0.5 to 10 or 15 parts by weight of repeat units from the oxetane monomer with pendant fluorocarbon groups based on 100 parts of polyester resin and amino resin in the dry coating. The coating may be as thin as 0.1 to 2 or 4 mil (thousandths of an inch) thick. One preferred embodiment is a layer of a flexible vinyl chloride polymer coated with said polyester-amino resin composition in solvent and heated to cure and adhere the resin to the vinyl chloride polymer layer with removal of the solvent. This provides the flexible vinyl chloride polymer layer with a coating which is stain resistant or which can readily be cleaned (either dry or with solvent) without significant abrasion to remove stains.
The vinyl chloride layer may be a vinyl chloride polymer, which is a plastisol coated and fused or is a plasticized vinyl chloride polymer composition which has been calendered or extruded. The vinyl chloride may be applied to a backing, substrate or support. In either case the polyvinyl chloride layer (about 1 to 30 or 100 mils thick) can be printed one or more times. The printed layer can be embossed, before and/or after printing, and finally coated with a layer of a solution of a said polyester-amino resin composition and cured to provide the vinyl chloride polymer layer with an outer stain resistant layer about 0.1 to 2 or 4 mils or more thick.
DISCUSSION OF DETAILS AND PREFERRED EMBODIMENTS
The reactive polyester-amino resin for use as the outer or top coating on a substrate is prepared from a solution of a reactive polyester (alkyd resin) and an amino resin in a solvent (such as methyl ethyl ketone, water, alcohols, or combination thereof) containing a catalyst such as p-toluene sulfonic acid and is applied at a temperature desirably of at least about 150, 200, 250, or 400° F. or more (66, 93, 121, or 204° C.) to cause curing or cross-linking of the polyester resin and the amino resin. The reactive polyester-amino resin composition may be applied to a substrate (e.g. vinyl chloride polymer, polyester, cellulosic, polyolefin composition) directly or with an intermediate tie layer. The substrate may be with or without a backing or substrate, with or without the printing and with or without the embossing. A preferred embodiment includes the catalyzed reactive polyester-amino resin solution being applied over a tie layer to an embossed and printed compounded and plasticized vinyl chloride polymer composition carried on a suitable backing or substrate. Such vinyl chloride polymer based substrates are readily available from wallcovering manufacturers.
The polyester resins (alkyd resins) are made by a condensation polymerization reaction, usually with heat in the presence of a catalyst, or a mixture of a polybasic acid and a polyhydic alcohol. Fatty monobasic oils or fatty acids, monohydroxy alcohols and anhydrides may be present. The polyester contains active hydrogen atoms, e.g., carboxylic acid groups and/or hydroxyl groups for reaction with the amino resin. Example of some acids to use to form the alkyd resin or reactive polyester are adipic acid, azelaic acid, sebacic acid, terephthalic acid, phthalic anhydride, and so forth. Examples of some polybasic alcohols include ethylene glycol, propylene glycol, diethylene
3
glycol, dipropylene glycol, glycerine, butylene glycol, 2,2-dimethyl-1,3-propanediol, trimethylol propane, 1,4-cyclohexanedimethanol, pentaerythritol, trimethylolethane and the like. Mixtures of the polyols and polycarboxylic acids can be used. An example of a suitable reactive polyester is the condensation product of trimethylol propane, 2,2-dimethyl-1,3-propanediol, 1,4-cyclohexanedimethanol, phthalic anhydride and adipic acid. Mixtures of these reactive polyester or alkyd resins can be used. Alkyd resins are well known as shown by the “Encyclopedia of Polymer Science and Technology,” Vol. 1, 1964, John Wiley & Sons, Inc., pages 663-734; “Alkyd Resins,” Martens, Reinhold Publishing Corporation, New York, 1961 and “Alkyd Resin Technology,” Patton, Interscience Publishers, a division of John Wiley and Sons, New York, 1962. Some unsaturated polybasic acids and unsaturated polyols may be used in the condensation reaction but are generally undesirable. The reactive polyester (alkyd resin) is usually added to the amino resin while dissolved or suspended in a solvent, e.g. such as a mixture of polyester in a ketone and an alkyl acetate at about 60-80% solids or a mixture of polyester in alkyl alcohols and alkylene glycol alkyl ethers.
Alternatively to using a separate polyester and hydroxyl terminated polymer including repeat units from an oxetane monomer having a pendant pendant —CH
2
—O—(CH
2
)
n
—Rf one can react said hydroxyl terminated polymer into the polyester thus replacing two components with a single component. The hydroxyl terminated polymer is more completely bound into the network as a result of prereacting the polyester forming components with the hydroxyl terminated polymer and is therefore less likely to be removed from the coating by wear or cleaning. In the claims the polyester including the repeat units derived from
Callicott Marten S.
Gottschalk Daniel C.
Hyde David L.
Kausch Charles M.
Medsker Robert E.
Chen Vivian
Hudak Daniel J.
Omnova Solutions Inc.
Rywalski Robert F.
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