Stock material or miscellaneous articles – Composite – Of polyamidoester
Reexamination Certificate
1999-10-28
2001-01-30
Yoon, Tae (Department: 1714)
Stock material or miscellaneous articles
Composite
Of polyamidoester
C428S482000, C428S483000, C428S904000
Reexamination Certificate
active
06180243
ABSTRACT:
FIELD OF INVENTION
A vinyl chloride polymer layer is coated with the reaction product of a polyester resin and an amino resin to provide a laminate with improved stain resistance. The coating is distinguished from prior coatings in that it uses water and other relatively non-hazardous solvents.
BACKGROUND OF INVENTION
Plasticized vinyl chloride polymers are widely used as wallcoverings, upholstery material and related uses. The plasticizer in the vinyl chloride polymers (PVC) make them soft and pliable. However the plasticizers also make it easier to abrade (scuff) the PVC and to stain or discolor the PVC. Thus it is desirable to coat plasticized PVC compositions (wallpaper and upholstery materials) with a scuff resistant and stain resistant coating.
U.S. Pat. 4,603,074 to GenCorp discloses a reaction product of a polyester and an amino resin as a flexible stain resistant layer for PVC laminates. However Example I of the patent illustrated that the coating included about 43 wt. % methyl ethyl ketone. It would be desirable to have a coating with similar properties but that is free of certain solvents considered harmful to the environment.
SUMMARY OF INVENTION
According to the present invention, a layer of a plasticized flexible vinyl chloride polymer is coated with a water based polyester-amino resin composition and heated to cure and adhere the resin to the vinyl chloride polymer (PVC) layer with removal of the solvent. This provides a flexible vinyl chloride polymer layer with a coating which is stain resistant and which can readily be cleaned to remove stains. Prior to the discovery of this coating, it was generally accepted theory by those skilled in the art that an organic solvent based coating was necessary to provide the required stain barrier and abrasion resistance.
A vinyl chloride polymer plastisol can be coated and fused or a plasticized vinyl chloride polymer composition can be calendered or extruded to form the PVC layer. They may be applied to a substrate or support. In either case the vinyl chloride polymer layer (about 1 to 30 or 100 mils thick, thicker coatings are usually expanded PVC) can be printed one or more times. The PVC layer can be embossed, before and/or after printing, or embossed after the application of coating. After the optional printing step, the PVC layer can be coated with a layer of water based polyester-amino resin composition and cured to provide the vinyl chloride polymer layer with an outer stain resistant layer about 0.1 to 2 mils thick. The water-based solvent comprising water, isopropanol and propylene glycol n-propyl ether facilitates compliance with the federal Clean Air Act and its amendments as compared to solvent based coatings including methyl ethyl ketone and methyl isobutyl ketone.
DISCUSSION OF DETAILS AND PREFERRED EMBODIMENTS
The vinyl chloride polymer (PVC) can be an emulsion (plastisol grade) or a suspension grade vinyl chloride polymer. Vinyl chloride polymer and polyvinyl chloride are alternate ways to refer to a polymer made by the polymerization of vinyl chloride monomer. The vinyl chloride polymer can be homopolyvinyl chloride (preferred) or a copolymer of a major amount by weight (e.g. at least 90 wt. %) of repeat units from vinyl chloride and a minor amount by weight of repeat units from a co-polymerizable monomer preferably selected from the group consisting of vinyl acetate, vinylidene chloride and maleic ester. Bulk and solution vinyl chloride polymers. also, may be used. Mixtures of vinyl chloride polymers can be used. Vinyl chloride polymers and copolymers are well known. In this connection please see “Vinyl and Related Polymers,” Schildknecht, John Wiley & Sons, Inc., New York, 1959; Sarvetnick, “Polyvinyl Chloride,” Van Nostrand Reinhold Company, New York 1969; Sarvetnick, “Plastisols and Organosols,” Van Nostrand Reinhold Company, New York, 1972 and “Modern Plastics Encyclopedia 1980-1981,” October, 1980, Volume 57, No. 10A, McGraw-Hill Inc., New York.
The amount of plasticizer used to plasticize the vinyl chloride polymer to make it flexible may vary from about 20 or 30 to about 100 parts by weight parts per 100 parts by weight of total vinyl chloride polymer resin more desirably from about 20 or 30 to about 50 or 60 parts by weight for wallcovering applications and preferably from about 60 to about 100 parts by weight for upholstery type applications per 100 parts by weight of total vinyl chloride polymer resin. Generally any conventional PVC plasticizer can be used. Examples of plasticizers which may be used are butyl octyl phthalate, dioctyl phthalate, hexyl decyl phthalate, dihexyl phthalate, diisooctyl phthalate, dicapryl adipate, dioctyl sebacate, trioctyl trimellitate, triisooctyl trimellitate, triusononyl trimellitate, isodecyl diphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, polymeric plasticizers, epoxidized soybean oil, octyl epoxy tallate, isooctyl epoxy tallate and so forth. Mixtures of plasticizers may be used.
Other conventional vinyl chloride polymer compounding ingredients are desirably incorporated in the vinyl chloride polymer compositions. Examples of such ingredients are the silicas such as precipitated silica, fumed colloidal silica, calcium silicate and the like; calcium carbonate; ultra violet light absorbers; fungicides; carbon black; barytes; barium-cadmium-zinc stabilizers; barium-cadmium stabilizers; tin stabilizers; dibasic lead phosphite; Sb
2
O
3
; zinc borate and so forth and mixtures of the same. TiO
2
, red iron oxide, phthalocyanine blue or green or other color pigments can be used. The pigments and the other dry additives preferably are dispersed or dissolved in one or more plasticizers before adding to the plasticized vinyl chloride polymer compositions. These compounding ingredients are used in effective amounts to control color, mildew, stabilization, viscosity and so forth of the plasticized vinyl chloride polymer.
The vinyl chloride polymer composition may contain suitable blowing or foaming agents such as sodium bicarbonate, and the organic agents like 1,1-azobisformamide, 4,4-oxybis (benzene sulfonylhydrazide), p-toluenesulfonyl hydrazide and so forth to form a cellular or foamed vinyl chloride polymer composition layer or sheet on fusing. The blowing agents may require an activator. Such blowing agents are well known.
Vinyl chloride polymer blending or extender resins, also, can be used in the compositions in a minor amount by weight as compared to the vinyl chloride polymer composition.
The ingredients forming the vinyl chloride polymer composition may be charged to and mixed together in any one of several mixing devices such as a Ross Planetary mixer, Hobart dough type mixer, Banbury, 2-roll rubber mill, Nauta mixer and ribbon blender and so forth.
The vinyl chloride polymer composition can be formed into layers or films which can be unsupported or supported (preferred). Where a vinyl chloride polymer plastisol composition is used, it may be cast on a release surface and heated to fuse it to form a film. Where a plasticized suspension grade vinyl chloride polymer composition is used, it can be calendered or extruded and fused to form a film. Temperatures may vary from about 200 to about 400° F. (93 to 204° C.). However, it is preferred in many embodiments that the compounded vinyl chloride polymer composition be supported or have a backing. In the case of the supported vinyl chloride polymer composition, the substrate can be a woven fabric (drill, scrim, cheese-cloth, and so forth), a knit fabric, a non-woven fabric, paper, etc. The fabric can be made of cotton, cellulose, nylon, polyester, aramid, polyolefin, rayon or acrylic fibers or cords or mixtures of the same. It may be necessary in some instances to treat the fabric with an adhesive coating or dip to adhere or to adhere better the fabric to the vinyl chloride polymer composition.
The vinyl chloride polymer composition film or layer, supported or unsupported, is preferably printed on the surface of the vinyl chloride polymer, opposite the backing if any, with a suitable vinyl chloride
Callicott Marten S.
Davis Richard W.
Gottschalk Daniel C.
Johnson Jay A.
Pate Joseph L.
Hudak Daniel J.
OMNOVA Solutions Inc.
Rywalski Robert F.
Yoon Tae
LandOfFree
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