CA1127022A - Methods for bonding dissimilar synthetic polymeric materials and the products involved in and resulting from such products - Google Patents
Methods for bonding dissimilar synthetic polymeric materials and the products involved in and resulting from such productsInfo
- Publication number
- CA1127022A CA1127022A CA336,072A CA336072A CA1127022A CA 1127022 A CA1127022 A CA 1127022A CA 336072 A CA336072 A CA 336072A CA 1127022 A CA1127022 A CA 1127022A
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- Prior art keywords
- acrylated
- synthetic polymeric
- polyurethane
- vinyl resin
- polyurethanes
- Prior art date
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Abstract
METHODS FOR BONDING DISSIMILAR SYNTHETIC POLYMERIC MATERIALS
AND THE PRODUCTS INVOLVED IN AND RESULTING FROM SUCH METHODS
ABSTRACT OF THE DISCLOSURE
A method of improving the bond between dissililar polymeric ma-terials, such as, for example, a vinyl resin material and a poly-urethane or acrylated polyurethane resin material, which com-prises: including in the vinyl resin material an acrylate or an acrylated urethane; providing in the polyurethane or acrylated polyurethane resin material an organic peroxide or other UV or thermal activated free radical initiators; bringing the vinyl resin material and the polyurethane or acrylated polyurethane resin material into contact; and exposing the vinyl resin mater-ial and the polyurethane or acrylated polyurethane resin mater-ial, while in contact, to curing conditions in the presence of said organic peroxide or other UV or thermal activated free rad-ical initiators, whereby there is sufficient chemical inter-reaction between these resin materials as to create a strong and permanent primary chemical bond therebetween, in addition to any secondary bonds, such as hydrogen bonds and/or van der Waals forces. The present invention also relates to the products in-volved in and resulting from such methods.
AND THE PRODUCTS INVOLVED IN AND RESULTING FROM SUCH METHODS
ABSTRACT OF THE DISCLOSURE
A method of improving the bond between dissililar polymeric ma-terials, such as, for example, a vinyl resin material and a poly-urethane or acrylated polyurethane resin material, which com-prises: including in the vinyl resin material an acrylate or an acrylated urethane; providing in the polyurethane or acrylated polyurethane resin material an organic peroxide or other UV or thermal activated free radical initiators; bringing the vinyl resin material and the polyurethane or acrylated polyurethane resin material into contact; and exposing the vinyl resin mater-ial and the polyurethane or acrylated polyurethane resin mater-ial, while in contact, to curing conditions in the presence of said organic peroxide or other UV or thermal activated free rad-ical initiators, whereby there is sufficient chemical inter-reaction between these resin materials as to create a strong and permanent primary chemical bond therebetween, in addition to any secondary bonds, such as hydrogen bonds and/or van der Waals forces. The present invention also relates to the products in-volved in and resulting from such methods.
Description
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THE F~ELD OF TH~ INVENTION
The present inven-tion relates to me-thods of making mul-ti-layered products, and more particularly multi-layered sheet materials, such as resilient Eloor coverings, which comprise a vinyl resin layer and a polyure-thane or acrylated pol~urethane resin layer, wherein it is necessary that such layers be adhered and bonded togethex in a strong and perma-nent bond that resists delamination very well~
BACKGROUND OF T~E IN~ENTION
It is well known in the manufacture of multi-layered products, such as resilient floor, wall, or ceiling coverings, or resilient desk, table, or counter tops, and the like, that it is often necessary to bond together two or more layers of dissimilar synthetic polymeric materials and that it is often dif~icult ~o obtain a strong and permanent bond r between such dissimilar synthetic polymeric ma-terials that will successfully resist delamination of the layers.
Such difficulties often are believed to arise in the bonding of such dissimilar synthetic polymeric materials because of differences in surface energies~ For e~amplè, if atoms from two dissimilar synthetic polymeric materials cannot get close enough to each other, perhaps because of large dissimilarities or disparities in polarityr van der Waals forces cannot be adequately taken advantage of to create strong and permanent bonding that will resist delamin-ation very well. Nor is it belieYed that hydrogen bonding can be adequately taken advantage of in such situations. Many proposals have been made hitherto to overcome such difficulties and to improve the bond between such ~issimilar synthetic ~ - 1 - '` ~
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polymeric materials but none has been found to be completely satisfactoxy to date.
The present .invention will be described wi-th particular reference to the bonding o~ dissimilar synthetic polymeric materials, such as, ~or e~ample, v:inyl resin materials and polyurethane or acrylated ~olyurethane resin materials but it is to be appreciated that the principles of the present invention are equally applicable to other equi-valent dissimilar synthetic polymeric materials. In the same way, the present invention will be described with particular reference to multi-layered decorative sheet materials such as resilient floor coverings, utilizing such dissimilar synthetic polymeric materials but, again, it is to be appreciated that the principles of the present invention are equally applicable to other multi-layered products util-izing such dissimilar synthetic polymeric materials or layers.
In the manufacture of resilient floor coverings, normally a base layer or substrate is laid out in a substan-tially flat, horizontal condition. Such a base layer or substrate is customarily a felted or matted fibrous sheet of overlapping, intertwined fibers and/or filaments, usually o~
asbestos or of natural or syn-thetic or man-made fibers of cellulosic origin, althouyh many other forms of sheets, films, or textile materials and many other fibers and/or ~ilaments may be used.
Upon this substantially fla-t, horizontal base layer or substra-te is then applied a substantially uniform base layer of a liquid or semi-liquid resinous composition con-taining a synthetic polymeric material, usually an ungelled b/ - 2 -~.
THE F~ELD OF TH~ INVENTION
The present inven-tion relates to me-thods of making mul-ti-layered products, and more particularly multi-layered sheet materials, such as resilient Eloor coverings, which comprise a vinyl resin layer and a polyure-thane or acrylated pol~urethane resin layer, wherein it is necessary that such layers be adhered and bonded togethex in a strong and perma-nent bond that resists delamination very well~
BACKGROUND OF T~E IN~ENTION
It is well known in the manufacture of multi-layered products, such as resilient floor, wall, or ceiling coverings, or resilient desk, table, or counter tops, and the like, that it is often necessary to bond together two or more layers of dissimilar synthetic polymeric materials and that it is often dif~icult ~o obtain a strong and permanent bond r between such dissimilar synthetic polymeric ma-terials that will successfully resist delamination of the layers.
Such difficulties often are believed to arise in the bonding of such dissimilar synthetic polymeric materials because of differences in surface energies~ For e~amplè, if atoms from two dissimilar synthetic polymeric materials cannot get close enough to each other, perhaps because of large dissimilarities or disparities in polarityr van der Waals forces cannot be adequately taken advantage of to create strong and permanent bonding that will resist delamin-ation very well. Nor is it belieYed that hydrogen bonding can be adequately taken advantage of in such situations. Many proposals have been made hitherto to overcome such difficulties and to improve the bond between such ~issimilar synthetic ~ - 1 - '` ~
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polymeric materials but none has been found to be completely satisfactoxy to date.
The present .invention will be described wi-th particular reference to the bonding o~ dissimilar synthetic polymeric materials, such as, ~or e~ample, v:inyl resin materials and polyurethane or acrylated ~olyurethane resin materials but it is to be appreciated that the principles of the present invention are equally applicable to other equi-valent dissimilar synthetic polymeric materials. In the same way, the present invention will be described with particular reference to multi-layered decorative sheet materials such as resilient floor coverings, utilizing such dissimilar synthetic polymeric materials but, again, it is to be appreciated that the principles of the present invention are equally applicable to other multi-layered products util-izing such dissimilar synthetic polymeric materials or layers.
In the manufacture of resilient floor coverings, normally a base layer or substrate is laid out in a substan-tially flat, horizontal condition. Such a base layer or substrate is customarily a felted or matted fibrous sheet of overlapping, intertwined fibers and/or filaments, usually o~
asbestos or of natural or syn-thetic or man-made fibers of cellulosic origin, althouyh many other forms of sheets, films, or textile materials and many other fibers and/or ~ilaments may be used.
Upon this substantially fla-t, horizontal base layer or substra-te is then applied a substantially uniform base layer of a liquid or semi-liquid resinous composition con-taining a synthetic polymeric material, usually an ungelled b/ - 2 -~.
2:2 polyvinyl chloride plastisol, and usually containing a blowing or foaming agent. This liquid or semi-liquid plasti-sol composi~ion is subsequently heated and yelled at an ele-vated temperature to a relatively firm condition.
This relatively firm, gelled polyvinyl chloride plastisol may then be printed with a decorative multi-colored pat-tern or design in which certain predetermined areas may contain a blowing or foaminy inhibitor which subsequently modifies the action of the blowing or foaming agent in those certain predetermined areas.
A substantially uniform wear layer of a clear liquid or semi-liquid resinous composition, containing usually another polyvinyl chloride plastisol but normally not containing any blowing or foaming agent is then applied as a wear resistant top coating to the surface of the gelled, printed base layer of polyvinyl chloride plastisol and is subsequently gelled and firmed thereon either as a separate operation or jointly in connection with a fusion and blowing or foaming operation of the base layer of polyvinyl chloride plastisol.
Thus far, there is relatively little or no diffi-culty in creating a strong and permanent bond or adhesion between the base layer o~ polyvinyl chloride plastisol and the wear layer which is also of polyvinyl chloride plastisol.
Such layers just naturally bond together immediately upon contact, followed by the subsequent heatingO
It is then frequently desired to provide a top surface coating on top of the surface of the polyvinyl chloride wear layer and such top surface coating is often b/ ~ _ 3 _ 1~27~2Z
desired t~ be a polyurethane or acrylated polyurethane resin coating because of their superior physical and chemical properties and characteristics. However, in manyinstances, it is found that the bond or adhesion be-tween the vinyl resin materi.al of -the wear layer anc1 the polyurethane or acrylated polyurethane resin material of the top surface layer is not as strong or as permanent, as desi.red, and does not resist délamination as well as de-sired. It is believed that such is due to the fact that the wear layer material and the top surface coating mater-ial are dissimilar synthetic polymeric materials.
PURPOSES AND OBJECTS OF THE INVENTION
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It i5 therefore a principal purpose and object of the present invention to provide for methods of improving the adhesive bond between such dissimilar synthetic poly-meric materials, and particularly between a vinyl resin : material and a polyurethane or acrylated polyurethane material, whereby a strong and permanent bond or adhesion is created between such dissimilar synthetic polymeric materials.
BRIEF SUMMARY OF THE INVENTION
. _ It has been found that such principal purpose and object, as well as other principal purposes and ob~ects which will become clear from a further reading and understanding of this disclosure, may be achieved by forming a layer or material comprising: tl) a vinyl resin; t2) one or more plasticizers for the vinyl resin; and (3~ an acrylate o.r an acrylated urethane; providing a polyurethane or acry-lated polyurethane resin layer or material containing an ,' ~
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organic peroxide or other UV or thermal activated free radical initiators; bringing the vinyl resin layer or material and the polyurethane or acrylated polyurethane resin layer or material in-to con-tact; and exposiny the ~inyl resin layer or material and the contactiny poly-urethane or acrylated polyurethane ~ayer or material to curing conditions in the presence of the organic peroxide ,or other UV or thermally activated free radical inikiakor, whereby there is sufficient chemical'interreacti'on,! between the ~inyl resin layer or material and the polyurethane or acrylated polyurethane resin layer or material as to create a strong and permanent primary chemical bond there-between, in addition to any secondary bonds, such as hyd-rogen bonds and/or van der Waals forces.
DESCRIPTION OF PREFERRED AND TYPICAL E~BODIMENTS
T~E BA:SE LAYER OR SUBSTRATE
The specific base layer or substrate which is used to iliustrate the preferred and typical embodiments of the present invention does not relate to the essence thereof and no detailed description is deemed necessary. It is customarily and conventionally a felted or matted fibrous sheet of overlapping, intertwined fibers and/or filaments, usually of asbesto's or of cellulosic origin, although many other'f~r~s of sheets, films, or fabrics and many other fibers and/or filaments may be used, such as is described in United States Patents 3,293,094 and 3,293,103.
THE BASE SYNTHETIC POLYMERIC MATERIAL OR LAYER
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The specific base synthetic polymeric material or , layer which is used to illustrate the preferred and typi-cal embodiments of the present invention does not relate 5 _ -mab/
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to the essence thereof and it should be sufficient to state that it may be potentially foamable or non-foamable and that, al-though a polyvinyl chloride plastisol i5 preferred and typical, many other synthetic resins are als~ of use, not only as p~as-tisols but also as o.rg~no~
sols or as aqueous :Latices (aquasols or hydras~ls).
THE VINYL ~ESIN WEAR LAYER
The specific vlnyl resin which is used in the pre-paration of the vinyl resin wear layer does not relate to the essence of the present invention. Although a poly-vinyl chloride plastisol is the preferred embodiment, many other vinyl resins are also of use, such as a vinyl chloride~vinyl acetate copolymer, a vinyl chloride-vinyli-dene chloride copolymer, or copolymers of vinyl chloride with other vinyl esters such as vinyl butyrate, vinyl propionate, or even alkyl substituted vinyl esters. As usual, plastisols are preferred but organosols and aqueous latices are also of use. Substantlally anybasic vinyl resin wear layer formulation will suffice, such as those disciosed in the previously cited United States Patents, with the modification that there be included in the for-mulation from about 10 percent by weight to about 30 per-cent by weight, and preferably from about 15 percent to abou-t 30 percent by weight of an acrylate or an acrylated urethane, or mixtures thereof.
THE ACRYLATES
Specific examples of suitable acrylates which are to be included in the,wear layer formulation include the following as illustrative but not limitative: methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acry-mab/
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la-te, allyl acrylate, hexyl acryla-te, 2-ethylhexyl acrylate, butoxye-thyl acrylate, isodecyl acrylate, be.nzyl acryla-te, cyclohe~yl acrylate, 1,3-butylene ~lycol acrylate, 1,3-butylene glycol diacrylate, 1,4-bu-tanediol diacryla-te, d.iethylene glycol diacrylate, 1,6-hexanediol di.acrylate, 2,2-dimethylpropane-1,3~diacrylate, propylene glycol 200 diacrylate, tetraethylene glycol diacrylate, trimeth~lol-propane triacrylate, pentaerythritol triacrylate, penta-erythritol tetraacrylate, allyl methacrylate, tetra-hydrofurfuryl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol di-methacrylate, polyethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane tri-~` methacrylate, pentaerythritol tetramethacrylate, etc TH~ ACRYLATED POLYURETHANES
The acrylated polyurethanes-which are to be in-; cluded in the vinyl resin ~ear layer may be prepared by several different conventional methods, preferred and typical methods involving the use of three basic react-ants, namely: a polyisocyanate, usually a diisocyanate;
a polyfunctional compound such as a polyol, polyamine, ; etc.; and a hydroxyalkyl acrylate.
For example, a W reacti~e acrylated urethane ollgomer or polymer may be synthesized, for example, from two basic reactants, the first being a conventional iso-cyanate-function terminated polyurethane (the reaction product of a stoichiometric excess of a polyisocyanate (including di-, tri- and tetra-isocyanates and mi.xtures mab/
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thereof) with a polyfunctional compound, such as polyols, includin~ diols, triols, tetrols, and mixtures thereof, as well as ether-type polyols, ester-type polyols, poly-amines hydroxyamines, polymercaptans, hydro~ymercapt~ns, and mixtures thereof) and the other reactank beiny a hydroxya:lkyl acrylate, whereby an essentially polyurethane structure having terminal acrylate func-tlonality is ob~
tained.
THE POLYISOCYANATES
The polyisocyanates used in preparing the conven-tional isocyanate-function terminated polyurethane used in carrying out the principles of the present invention in-clude: 4,4'-methylen~-~is-cyclohexyl . diisocyanate, hexa-methylene-1,6-diisocyanate, tetramethylene-1,4-diisocy-anate, cyclohexane-l,~-diisocyanate, 2,2,4-trimethyl-1,6-'~ hexane diisocyanate, trimethyl hexamethylene diisocyanate,-dimer acid diisocyanate, trimer of hexamethylene diisocy-.
anate, ethylene diisocyanate, ethylidene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 4,4'-me.thylene bis-(phenylisocyanate), naphthylene-1,5-diisocy-anate,,4,4'-biphenylene diisocyanate, furfurlidene dii-socyanate, butane-1,4-diisocyanate, isophorone diisocyanate, pentane-1,5-diisocyanate, etc.
THE POLYFUNCTIONAL COMPOUND
The polyfunctional compounds which are employed to react with any of the above-listed polyisocyanates or mi~-tures thereof may be selected from a large group of suit-able chemical compounds of which the following are illus-trative but not limitative:
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Diols such as e-thylene glycol, propylene glycol, butylene glycol, trime-thylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, neo-pentyl glycol, etc.: tri.ols such as glycerol, 1,1,1-tri~ethylol propane, l,l,l-tr.i.methylol ethane, 1,2,3-butanetriol, 1,~,4-butanetriol, 1,2,3-pentanetriol, :L,2,3-hexanetriol, 1,2,~-hexanetriol, 1,2,5-hexanetriol, 1,2,~-hexanetriol, 2,3,4-hexanetriol, 1,3,6-hexanetriol, etc.:
tetrols such as erythritol, pentaerythritol, etc: ether~
type polyols which are adduct products o~ the above polyols with alkylene oxides having from 2 to 5 carbon atoms, such as ethylene oxide, propylene oxide, trimethylene oxide, 1,2-butylene oxide, isobutylene oxide, 1,4-tetramethylene oxide, pentamethylene oxide, and mixtures thereof, and e:specially diethylene glycol, trie~hylene glycol, tetra-ethylene glycol, pentaethylene glycol, and higher mole-cular weight poly.alkylene glycols having the general for-mula HO~CnH2n)XOH, etc: ester-type polyols which are con-densation products of the above polyols with polycarboxy-lic acids such as oxalic, ~alonic, succinic, glutaric, . pinelic, suberic, azelaic, sebacic, fumaric, phthalic, isophthalic, terephthalic, mellitic, etc.: polyamines such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, diethylene diamine, triethylene diamine, tetraethylene diamine, tetraethylene pentamine, isophorone diamine, piperazine, etc.: poly mercaptans such as ethylene dimercaptans, 1,3-propanedithiol, 1,4-butanedithiol, 2,2-dimercaptodiethyl ether, glycol dimer-capto acetate, glycerol dimercapto propionate, trimethylol-g _ ~ mab/
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propane tri(3-mercapto propionate) etc.: hydroxyamines such as monoethanolamine, diethanolamine, 3-aminopropanol-l, 4-aminobutanol-l, etc.: hydroxymercaptans such as l-thioglycerol, 2--thioglycerol, 2-mercapkoethanol, 2,3-dimercapto propanol-l, etc.
THE HYDROXYALK~L ACR~LATES
- Examples of preferred and typical hy~roxyalkyl acrylates include: hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and mixtures thereof. If desired, the hydroxyalkyl acrylates may be replaced h~
hydroxyalkyl methacrylates or by hydroxyalkyl-containing vinyl compounds to yield essentially polyurethane structures having terminal methacrylate or vinyl functionality. ~xam-ples of preferred and typical hydroxymethacrylates are:
hydroxyethyl methacrylate, hydroxymethyl methacrylate, r hydroxypropyl methacrylate, and mi~tures thereof. Examples of preferred and typical hydroxyalkyl-containing v1nyl com-pounds include: B-hydroxyethyl vinyl ether, B hydroxyethyl sulfide, etc.
The acrylated polyurethane resins may also be made by other conventional methods disclosed in the pr1or art, such as those disclosed in United States Patent ~,100,318 which issued on ~uly 11, 1978.
The thickness of the substantially uniformly applied vinyl resin wear layer is the range of from about 0.001 inch to about 0.030 inch, and preferably from about 0.005 inch to about 0.025 inch.
The vinyl resin wear layer containing the added acrylates or the acrylated polyurethanes, or mixtures thereof is then passed through a heated oven maintained at mab/
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an elevated temperature of about 250F. to about 460F. and preferably from about 270F. to about 450F. for a period of time of from about 1 1/2 minu-tes to abou-t 10 minutes and pre~
ferably rom ~bout 2 minu-tes to about 8 minutes whereupon the vinyl resin in the wear layer gels and fuses and the vinyl re~in in the base synthetic polymeric plastisol layer fuses, ac-companied by the blowing and foaminy thereo~.
THE TOP SURFACE COATING
The polyurethane or the UV curable acrylated poly-urethane resin which is used in the formulation of the top sur-face coating that is applied to the vinyl resin wear layer does not relate to the essence of the present invention. The poly-urethane resin may be any conventional polyurethane resin and the UV curable polyurethane resin may be the same as that pre-viously included in the vinyl resin wear layer.or it may be a different UV curable acrylated polyurethane. .However, regard-less of which resin is used and regardless of the precise method of its manufacture-or the precise components which enter its formulation, there must be from about 0~5 percent to about 20 percent by weight of free available isocyanate thèrein, and preferably from about 2 percent to about 10 percent by weight, based on the total weight of the top surface layer.formulation.
Additionally, there is included in the top surface layer formulation from about 0.5 percent by weight to about 20 percent by weight, and preferably- ~rom about 2 percent by weight to about 10 percent by weight of a free radical polymerization initiator r or catalyst, such as an organic peroxide, such per-centages being based on the total weight of the top surface layer formulation.
THE FREE RADICAL POLYMERIZATION INITIATOR
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Specific free radical polymeriæation initiators, or catalys-ts, notc~b.ly organic peroxides, useful for the appliccation of -the principles of the presen-t inventlon include the follcwing, as illus-trative but not limitative:
di-t-butyl peroxide, 2,5-dime-thyl~Z,5-bis(t~butylperoxy) hexane, 2,5-dinethyl-2,5-bis(t-butylperoxy)hexyne-3, di-t~amyl peroxide, t-butyl-2-hydroxye-thyl peroxide, a,a'-bis(t-butylperox~)diisopropyl benzene, benzoyl peroxide, diisobutyryl peroxide, 2,4-dichlorobenzcyl peroxide, diisononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, aoetyl peroxide, succinic acid peroxide, bis-p-chlorobenzoyl peroxide, 2,5-dihydroperoxy-2,5-dimethylhexane, cumene hydroperoxide, -t-butyl hydroperoxide,p-methc~ne hydroperoxide, dilsopropylbenzene hydroperoxide, 1,1,3,3-tetranethyl butyl hydroperoxide, dicu~yl peroxide, di(n-propyl) peroxy dicarbonate, diisopropyl peroxydicarbonate, di(sec-butyl)peroxy-dicarbonate, di(2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydi-carbonate, dicetyl peroxydic æbonate, bis(4-t-butylcyclohexyl)peroxydi-carbonate, t-butylperoxy isopropyl monocarbonate, 2,2-azobis(isobutyroni-trile), l,l-bis(t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl peroxy-acetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyI perox~t pivalate, t-butyl peroxyneodecanoate, t-butyl peroxymaleic acid, di-t-butyl diperoxyph-thalate, 2,5-dimethyl-2,5-bis(benzoylperoxy) hexane, 2,3-dimethyl-bis(octanoylperoxy)hexane, t-butyl peroctoate, t-butyl perbenzoate, acetylcyclohexyl sufonyl peroxide, acetyl sec-heptyl sulfonyl peroxide, 2-t-butylazo-2-cyano-4-methoxy-4-methyl pentane, 2-t-butylazo-2-cyano-4-methyl pentane, 2-t-butylazo-2-cyanopropane, methyl ethyl ketone peroxide, 2,4-pentanedione peroxide, cyclohexanone peroxide, etc.
It is to be noted tha-t, if the free radical polymerization initiator, or catalyst, or organic peroxide, is a powdered material, SU~I as lauroyl peroxide, for example~ it should be dissolved in a small mab/
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amoun-t of a suitable solvent, such as vinyl acetate, for exa~le, prior -to actual use. If the free radical polymerization ini-tia-tor, or catalyst, or organic per.oxide, is a liqlid, it may be used direct.ly .in that forrn.
The thickness of the applied top coa-ting layer is norrnally in the range of from about 1 mil to about 15 mils, depen~:iny upon the future re~uirements or the product being made.
Curing conditions for acryla-ted polyurethane re.sins differ from those normally employed for more conventional polyurethane .resins, in that the acrylated polyurethane resin is cured by being passed through an actinic radiation source, such as, for example, an ultraviolet lam~
ping..unit oYen. Radiation curing by electron beam, gamma and x-ray treatment, and other suitable sources may be employed. ~l-traviolet radiation is the preferred and typical source. In the presence of photo-initiators, such radiation induces a photc-chemical reaction which produ oes free radicals which are capable of inducing ~ polyrnerization.
Sour oe s of ultraviolet radiati~on may be mercury vapor arc lamps, plasma arcs, pulsed xenon lamps and carbon arcs. Mercury vapor lamps are pre-ferred and typical for most cases. Special wavelengths of light which are most effective will vary, aepending primarily upon the particular acrylated polyurethane coating used and the particular photo-sensitizer employed. In some instances, combinations of conventional thermal and radiation curing conditions may be used.
During the actinic radiation curing conditionsr polymerization of the acrylated polyurethanernaterialstakes place~ along wi-th polyfneri~
zation of other resinous materials which are present, and with sufficient chemical inter-reaction between the acrylates or acrylated polyurethanes in the vinyl resin wear layer and the polyurethanes and acrylated poly-urethanes in the top surface layer as initiated by ~he free radical poly-merization initiator or the organic peroxide in the top coating layer.
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As a result, there is created a strong and permanent primary chemical bond between the vinyl resin wear layer and the polyurethane or acrylated polyurethane resin layer which is additioI~al to any existiny secondary bonds, such as hydrogen bonds or van der Waals forces. Such a strong and permanent bond is capc~ble oE resisting delamina-tion forces very well.
The inven-tion will be further described in greater de-tail by the followiny specific working examples. Althou(Jh these examples may describe in very particuLar detail some of the more specific features of the present invention, they are given primarily for purposes of illus-tration and the invention in its broader aspects is not to be considered as limited thereto.
.- ' EX~LE 1 , m e base layer or substrate comprises a relatively flat, 0.040 inch thick fibrous sheet of felted or matted asbestos fibers with an acrylic smoothing or leveling coating thereon. The asbestos fiber sheet is coated with a substantially uniform coating to a thickness ~wet) of about 0.015 inch with the following potentially foamable polyvinyl chloride plastisol composition: -Parts - Polyvinyl chloride, l~w mol, wt., general purpose dis-persion resin, inh.vis. 0.99 (ASTM D-1243-661 30.2 Polyvinyl chloride, med. mol wt., dispersion grade resin, inherent viscosity 1.0 8 2 Polyvinyl chloride, med. mol. wt., blending resin, inherent viscosity 0.9 17.1 ~nhydrous alumin silicate filler 6.9 Alkyl benzyl phthalate plasticizers 24.7 Polydodecyl benzene 7.4 Azodicarbonamide 1.1 Accelerator~stabilizer 0.4 Titanium dioxide 2.5 mab/
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Dioctyl ph-thalate 1.5 Wetting agent 0.03 (Parts by weigh-t) Gel:Ling and firrning of the potentially foamable polyvinyl chloride plastisol is accamplished in an oven a-tmosphere which is main-tained at an elevated temperature oE about 300E. for a period o~ tir~ of ~bout
This relatively firm, gelled polyvinyl chloride plastisol may then be printed with a decorative multi-colored pat-tern or design in which certain predetermined areas may contain a blowing or foaminy inhibitor which subsequently modifies the action of the blowing or foaming agent in those certain predetermined areas.
A substantially uniform wear layer of a clear liquid or semi-liquid resinous composition, containing usually another polyvinyl chloride plastisol but normally not containing any blowing or foaming agent is then applied as a wear resistant top coating to the surface of the gelled, printed base layer of polyvinyl chloride plastisol and is subsequently gelled and firmed thereon either as a separate operation or jointly in connection with a fusion and blowing or foaming operation of the base layer of polyvinyl chloride plastisol.
Thus far, there is relatively little or no diffi-culty in creating a strong and permanent bond or adhesion between the base layer o~ polyvinyl chloride plastisol and the wear layer which is also of polyvinyl chloride plastisol.
Such layers just naturally bond together immediately upon contact, followed by the subsequent heatingO
It is then frequently desired to provide a top surface coating on top of the surface of the polyvinyl chloride wear layer and such top surface coating is often b/ ~ _ 3 _ 1~27~2Z
desired t~ be a polyurethane or acrylated polyurethane resin coating because of their superior physical and chemical properties and characteristics. However, in manyinstances, it is found that the bond or adhesion be-tween the vinyl resin materi.al of -the wear layer anc1 the polyurethane or acrylated polyurethane resin material of the top surface layer is not as strong or as permanent, as desi.red, and does not resist délamination as well as de-sired. It is believed that such is due to the fact that the wear layer material and the top surface coating mater-ial are dissimilar synthetic polymeric materials.
PURPOSES AND OBJECTS OF THE INVENTION
. _ .
It i5 therefore a principal purpose and object of the present invention to provide for methods of improving the adhesive bond between such dissimilar synthetic poly-meric materials, and particularly between a vinyl resin : material and a polyurethane or acrylated polyurethane material, whereby a strong and permanent bond or adhesion is created between such dissimilar synthetic polymeric materials.
BRIEF SUMMARY OF THE INVENTION
. _ It has been found that such principal purpose and object, as well as other principal purposes and ob~ects which will become clear from a further reading and understanding of this disclosure, may be achieved by forming a layer or material comprising: tl) a vinyl resin; t2) one or more plasticizers for the vinyl resin; and (3~ an acrylate o.r an acrylated urethane; providing a polyurethane or acry-lated polyurethane resin layer or material containing an ,' ~
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~;27~
organic peroxide or other UV or thermal activated free radical initiators; bringing the vinyl resin layer or material and the polyurethane or acrylated polyurethane resin layer or material in-to con-tact; and exposiny the ~inyl resin layer or material and the contactiny poly-urethane or acrylated polyurethane ~ayer or material to curing conditions in the presence of the organic peroxide ,or other UV or thermally activated free radical inikiakor, whereby there is sufficient chemical'interreacti'on,! between the ~inyl resin layer or material and the polyurethane or acrylated polyurethane resin layer or material as to create a strong and permanent primary chemical bond there-between, in addition to any secondary bonds, such as hyd-rogen bonds and/or van der Waals forces.
DESCRIPTION OF PREFERRED AND TYPICAL E~BODIMENTS
T~E BA:SE LAYER OR SUBSTRATE
The specific base layer or substrate which is used to iliustrate the preferred and typical embodiments of the present invention does not relate to the essence thereof and no detailed description is deemed necessary. It is customarily and conventionally a felted or matted fibrous sheet of overlapping, intertwined fibers and/or filaments, usually of asbesto's or of cellulosic origin, although many other'f~r~s of sheets, films, or fabrics and many other fibers and/or filaments may be used, such as is described in United States Patents 3,293,094 and 3,293,103.
THE BASE SYNTHETIC POLYMERIC MATERIAL OR LAYER
.
The specific base synthetic polymeric material or , layer which is used to illustrate the preferred and typi-cal embodiments of the present invention does not relate 5 _ -mab/
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to the essence thereof and it should be sufficient to state that it may be potentially foamable or non-foamable and that, al-though a polyvinyl chloride plastisol i5 preferred and typical, many other synthetic resins are als~ of use, not only as p~as-tisols but also as o.rg~no~
sols or as aqueous :Latices (aquasols or hydras~ls).
THE VINYL ~ESIN WEAR LAYER
The specific vlnyl resin which is used in the pre-paration of the vinyl resin wear layer does not relate to the essence of the present invention. Although a poly-vinyl chloride plastisol is the preferred embodiment, many other vinyl resins are also of use, such as a vinyl chloride~vinyl acetate copolymer, a vinyl chloride-vinyli-dene chloride copolymer, or copolymers of vinyl chloride with other vinyl esters such as vinyl butyrate, vinyl propionate, or even alkyl substituted vinyl esters. As usual, plastisols are preferred but organosols and aqueous latices are also of use. Substantlally anybasic vinyl resin wear layer formulation will suffice, such as those disciosed in the previously cited United States Patents, with the modification that there be included in the for-mulation from about 10 percent by weight to about 30 per-cent by weight, and preferably from about 15 percent to abou-t 30 percent by weight of an acrylate or an acrylated urethane, or mixtures thereof.
THE ACRYLATES
Specific examples of suitable acrylates which are to be included in the,wear layer formulation include the following as illustrative but not limitative: methyl acrylate, ethyl acrylate, butyl acrylate, isobutyl acry-mab/
~;27~2'Z
la-te, allyl acrylate, hexyl acryla-te, 2-ethylhexyl acrylate, butoxye-thyl acrylate, isodecyl acrylate, be.nzyl acryla-te, cyclohe~yl acrylate, 1,3-butylene ~lycol acrylate, 1,3-butylene glycol diacrylate, 1,4-bu-tanediol diacryla-te, d.iethylene glycol diacrylate, 1,6-hexanediol di.acrylate, 2,2-dimethylpropane-1,3~diacrylate, propylene glycol 200 diacrylate, tetraethylene glycol diacrylate, trimeth~lol-propane triacrylate, pentaerythritol triacrylate, penta-erythritol tetraacrylate, allyl methacrylate, tetra-hydrofurfuryl methacrylate, cyclohexyl methacrylate, n-hexyl methacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol di-methacrylate, polyethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane tri-~` methacrylate, pentaerythritol tetramethacrylate, etc TH~ ACRYLATED POLYURETHANES
The acrylated polyurethanes-which are to be in-; cluded in the vinyl resin ~ear layer may be prepared by several different conventional methods, preferred and typical methods involving the use of three basic react-ants, namely: a polyisocyanate, usually a diisocyanate;
a polyfunctional compound such as a polyol, polyamine, ; etc.; and a hydroxyalkyl acrylate.
For example, a W reacti~e acrylated urethane ollgomer or polymer may be synthesized, for example, from two basic reactants, the first being a conventional iso-cyanate-function terminated polyurethane (the reaction product of a stoichiometric excess of a polyisocyanate (including di-, tri- and tetra-isocyanates and mi.xtures mab/
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thereof) with a polyfunctional compound, such as polyols, includin~ diols, triols, tetrols, and mixtures thereof, as well as ether-type polyols, ester-type polyols, poly-amines hydroxyamines, polymercaptans, hydro~ymercapt~ns, and mixtures thereof) and the other reactank beiny a hydroxya:lkyl acrylate, whereby an essentially polyurethane structure having terminal acrylate func-tlonality is ob~
tained.
THE POLYISOCYANATES
The polyisocyanates used in preparing the conven-tional isocyanate-function terminated polyurethane used in carrying out the principles of the present invention in-clude: 4,4'-methylen~-~is-cyclohexyl . diisocyanate, hexa-methylene-1,6-diisocyanate, tetramethylene-1,4-diisocy-anate, cyclohexane-l,~-diisocyanate, 2,2,4-trimethyl-1,6-'~ hexane diisocyanate, trimethyl hexamethylene diisocyanate,-dimer acid diisocyanate, trimer of hexamethylene diisocy-.
anate, ethylene diisocyanate, ethylidene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 4,4'-me.thylene bis-(phenylisocyanate), naphthylene-1,5-diisocy-anate,,4,4'-biphenylene diisocyanate, furfurlidene dii-socyanate, butane-1,4-diisocyanate, isophorone diisocyanate, pentane-1,5-diisocyanate, etc.
THE POLYFUNCTIONAL COMPOUND
The polyfunctional compounds which are employed to react with any of the above-listed polyisocyanates or mi~-tures thereof may be selected from a large group of suit-able chemical compounds of which the following are illus-trative but not limitative:
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Diols such as e-thylene glycol, propylene glycol, butylene glycol, trime-thylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, neo-pentyl glycol, etc.: tri.ols such as glycerol, 1,1,1-tri~ethylol propane, l,l,l-tr.i.methylol ethane, 1,2,3-butanetriol, 1,~,4-butanetriol, 1,2,3-pentanetriol, :L,2,3-hexanetriol, 1,2,~-hexanetriol, 1,2,5-hexanetriol, 1,2,~-hexanetriol, 2,3,4-hexanetriol, 1,3,6-hexanetriol, etc.:
tetrols such as erythritol, pentaerythritol, etc: ether~
type polyols which are adduct products o~ the above polyols with alkylene oxides having from 2 to 5 carbon atoms, such as ethylene oxide, propylene oxide, trimethylene oxide, 1,2-butylene oxide, isobutylene oxide, 1,4-tetramethylene oxide, pentamethylene oxide, and mixtures thereof, and e:specially diethylene glycol, trie~hylene glycol, tetra-ethylene glycol, pentaethylene glycol, and higher mole-cular weight poly.alkylene glycols having the general for-mula HO~CnH2n)XOH, etc: ester-type polyols which are con-densation products of the above polyols with polycarboxy-lic acids such as oxalic, ~alonic, succinic, glutaric, . pinelic, suberic, azelaic, sebacic, fumaric, phthalic, isophthalic, terephthalic, mellitic, etc.: polyamines such as ethylene diamine, propylene diamine, trimethylene diamine, tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, diethylene diamine, triethylene diamine, tetraethylene diamine, tetraethylene pentamine, isophorone diamine, piperazine, etc.: poly mercaptans such as ethylene dimercaptans, 1,3-propanedithiol, 1,4-butanedithiol, 2,2-dimercaptodiethyl ether, glycol dimer-capto acetate, glycerol dimercapto propionate, trimethylol-g _ ~ mab/
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propane tri(3-mercapto propionate) etc.: hydroxyamines such as monoethanolamine, diethanolamine, 3-aminopropanol-l, 4-aminobutanol-l, etc.: hydroxymercaptans such as l-thioglycerol, 2--thioglycerol, 2-mercapkoethanol, 2,3-dimercapto propanol-l, etc.
THE HYDROXYALK~L ACR~LATES
- Examples of preferred and typical hy~roxyalkyl acrylates include: hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, and mixtures thereof. If desired, the hydroxyalkyl acrylates may be replaced h~
hydroxyalkyl methacrylates or by hydroxyalkyl-containing vinyl compounds to yield essentially polyurethane structures having terminal methacrylate or vinyl functionality. ~xam-ples of preferred and typical hydroxymethacrylates are:
hydroxyethyl methacrylate, hydroxymethyl methacrylate, r hydroxypropyl methacrylate, and mi~tures thereof. Examples of preferred and typical hydroxyalkyl-containing v1nyl com-pounds include: B-hydroxyethyl vinyl ether, B hydroxyethyl sulfide, etc.
The acrylated polyurethane resins may also be made by other conventional methods disclosed in the pr1or art, such as those disclosed in United States Patent ~,100,318 which issued on ~uly 11, 1978.
The thickness of the substantially uniformly applied vinyl resin wear layer is the range of from about 0.001 inch to about 0.030 inch, and preferably from about 0.005 inch to about 0.025 inch.
The vinyl resin wear layer containing the added acrylates or the acrylated polyurethanes, or mixtures thereof is then passed through a heated oven maintained at mab/
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an elevated temperature of about 250F. to about 460F. and preferably from about 270F. to about 450F. for a period of time of from about 1 1/2 minu-tes to abou-t 10 minutes and pre~
ferably rom ~bout 2 minu-tes to about 8 minutes whereupon the vinyl resin in the wear layer gels and fuses and the vinyl re~in in the base synthetic polymeric plastisol layer fuses, ac-companied by the blowing and foaminy thereo~.
THE TOP SURFACE COATING
The polyurethane or the UV curable acrylated poly-urethane resin which is used in the formulation of the top sur-face coating that is applied to the vinyl resin wear layer does not relate to the essence of the present invention. The poly-urethane resin may be any conventional polyurethane resin and the UV curable polyurethane resin may be the same as that pre-viously included in the vinyl resin wear layer.or it may be a different UV curable acrylated polyurethane. .However, regard-less of which resin is used and regardless of the precise method of its manufacture-or the precise components which enter its formulation, there must be from about 0~5 percent to about 20 percent by weight of free available isocyanate thèrein, and preferably from about 2 percent to about 10 percent by weight, based on the total weight of the top surface layer.formulation.
Additionally, there is included in the top surface layer formulation from about 0.5 percent by weight to about 20 percent by weight, and preferably- ~rom about 2 percent by weight to about 10 percent by weight of a free radical polymerization initiator r or catalyst, such as an organic peroxide, such per-centages being based on the total weight of the top surface layer formulation.
THE FREE RADICAL POLYMERIZATION INITIATOR
m~h ~
Specific free radical polymeriæation initiators, or catalys-ts, notc~b.ly organic peroxides, useful for the appliccation of -the principles of the presen-t inventlon include the follcwing, as illus-trative but not limitative:
di-t-butyl peroxide, 2,5-dime-thyl~Z,5-bis(t~butylperoxy) hexane, 2,5-dinethyl-2,5-bis(t-butylperoxy)hexyne-3, di-t~amyl peroxide, t-butyl-2-hydroxye-thyl peroxide, a,a'-bis(t-butylperox~)diisopropyl benzene, benzoyl peroxide, diisobutyryl peroxide, 2,4-dichlorobenzcyl peroxide, diisononanoyl peroxide, decanoyl peroxide, lauroyl peroxide, aoetyl peroxide, succinic acid peroxide, bis-p-chlorobenzoyl peroxide, 2,5-dihydroperoxy-2,5-dimethylhexane, cumene hydroperoxide, -t-butyl hydroperoxide,p-methc~ne hydroperoxide, dilsopropylbenzene hydroperoxide, 1,1,3,3-tetranethyl butyl hydroperoxide, dicu~yl peroxide, di(n-propyl) peroxy dicarbonate, diisopropyl peroxydicarbonate, di(sec-butyl)peroxy-dicarbonate, di(2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydi-carbonate, dicetyl peroxydic æbonate, bis(4-t-butylcyclohexyl)peroxydi-carbonate, t-butylperoxy isopropyl monocarbonate, 2,2-azobis(isobutyroni-trile), l,l-bis(t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl peroxy-acetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-butyI perox~t pivalate, t-butyl peroxyneodecanoate, t-butyl peroxymaleic acid, di-t-butyl diperoxyph-thalate, 2,5-dimethyl-2,5-bis(benzoylperoxy) hexane, 2,3-dimethyl-bis(octanoylperoxy)hexane, t-butyl peroctoate, t-butyl perbenzoate, acetylcyclohexyl sufonyl peroxide, acetyl sec-heptyl sulfonyl peroxide, 2-t-butylazo-2-cyano-4-methoxy-4-methyl pentane, 2-t-butylazo-2-cyano-4-methyl pentane, 2-t-butylazo-2-cyanopropane, methyl ethyl ketone peroxide, 2,4-pentanedione peroxide, cyclohexanone peroxide, etc.
It is to be noted tha-t, if the free radical polymerization initiator, or catalyst, or organic peroxide, is a powdered material, SU~I as lauroyl peroxide, for example~ it should be dissolved in a small mab/
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amoun-t of a suitable solvent, such as vinyl acetate, for exa~le, prior -to actual use. If the free radical polymerization ini-tia-tor, or catalyst, or organic per.oxide, is a liqlid, it may be used direct.ly .in that forrn.
The thickness of the applied top coa-ting layer is norrnally in the range of from about 1 mil to about 15 mils, depen~:iny upon the future re~uirements or the product being made.
Curing conditions for acryla-ted polyurethane re.sins differ from those normally employed for more conventional polyurethane .resins, in that the acrylated polyurethane resin is cured by being passed through an actinic radiation source, such as, for example, an ultraviolet lam~
ping..unit oYen. Radiation curing by electron beam, gamma and x-ray treatment, and other suitable sources may be employed. ~l-traviolet radiation is the preferred and typical source. In the presence of photo-initiators, such radiation induces a photc-chemical reaction which produ oes free radicals which are capable of inducing ~ polyrnerization.
Sour oe s of ultraviolet radiati~on may be mercury vapor arc lamps, plasma arcs, pulsed xenon lamps and carbon arcs. Mercury vapor lamps are pre-ferred and typical for most cases. Special wavelengths of light which are most effective will vary, aepending primarily upon the particular acrylated polyurethane coating used and the particular photo-sensitizer employed. In some instances, combinations of conventional thermal and radiation curing conditions may be used.
During the actinic radiation curing conditionsr polymerization of the acrylated polyurethanernaterialstakes place~ along wi-th polyfneri~
zation of other resinous materials which are present, and with sufficient chemical inter-reaction between the acrylates or acrylated polyurethanes in the vinyl resin wear layer and the polyurethanes and acrylated poly-urethanes in the top surface layer as initiated by ~he free radical poly-merization initiator or the organic peroxide in the top coating layer.
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As a result, there is created a strong and permanent primary chemical bond between the vinyl resin wear layer and the polyurethane or acrylated polyurethane resin layer which is additioI~al to any existiny secondary bonds, such as hydrogen bonds or van der Waals forces. Such a strong and permanent bond is capc~ble oE resisting delamina-tion forces very well.
The inven-tion will be further described in greater de-tail by the followiny specific working examples. Althou(Jh these examples may describe in very particuLar detail some of the more specific features of the present invention, they are given primarily for purposes of illus-tration and the invention in its broader aspects is not to be considered as limited thereto.
.- ' EX~LE 1 , m e base layer or substrate comprises a relatively flat, 0.040 inch thick fibrous sheet of felted or matted asbestos fibers with an acrylic smoothing or leveling coating thereon. The asbestos fiber sheet is coated with a substantially uniform coating to a thickness ~wet) of about 0.015 inch with the following potentially foamable polyvinyl chloride plastisol composition: -Parts - Polyvinyl chloride, l~w mol, wt., general purpose dis-persion resin, inh.vis. 0.99 (ASTM D-1243-661 30.2 Polyvinyl chloride, med. mol wt., dispersion grade resin, inherent viscosity 1.0 8 2 Polyvinyl chloride, med. mol. wt., blending resin, inherent viscosity 0.9 17.1 ~nhydrous alumin silicate filler 6.9 Alkyl benzyl phthalate plasticizers 24.7 Polydodecyl benzene 7.4 Azodicarbonamide 1.1 Accelerator~stabilizer 0.4 Titanium dioxide 2.5 mab/
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Dioctyl ph-thalate 1.5 Wetting agent 0.03 (Parts by weigh-t) Gel:Ling and firrning of the potentially foamable polyvinyl chloride plastisol is accamplished in an oven a-tmosphere which is main-tained at an elevated temperature oE about 300E. for a period o~ tir~ of ~bout
3 n ~ utes. The te~,perature is not that elevated as to activate or de~orn-pose the blcwing or foaming agent which is present.
The gelled, firmed potentially foamable polyvinyl ehloride plastisol is the~ printed with a mul;ticolored decorative pattern or design using (1) a conventional or standard printing ink camposition and (2) an inhioitor-containing printing ink cGr~position, as follows:
Printing ink cc~,position (1):
Parts - Solution grade copolymer of vinyl chloride (90 parts) and vinyl acetate (10 parts) 15 ,~ Methyl ethyl ketone 85 Pigment or colorant, as desired Printing ink composition (2):
Parts Solution grade copolymer of vinyl chloride (90 parts) and vinyl acetate (10 parts) 12 Met~yl ethyl ketone 68 Trimellitic ar~ydride 20 Pigment or colorant! as desired m e printed, gelled and firmed potentially foamable polyvinyl chloride plastisol is then allcwed to air-dry and a polyvinyl chloride plastisol wear layer is substantially uni~ormly applied thereto to a wet thickness of about 0.015 inch depth and having the follewing formulation by weight:
Parts Polyvinyl chloride,-dispersion grade, high rnol. wt.89.36 Polyvinyl chloride, blending r~sin, inherent viscosity r~lb/
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0.86 (ASTM ~-12~3-66) 10.64 Butyl benzyl phthala-te plasticizer 7.5 2,2,4--trimethyL-1,3-pentanediol diisobutyrate 7.5 Polyethylene y:Lycol dimethacrylate 30.0 Epoxy plas-ticizer 5.0 Ba-Zn stabilizer 3.0 Toner 0.21 W absorber 0.32 Gelling and firming of the polyvinyl chloride plastisol wear layer takes place at an elevated temperature of about 300F. for a period of time of about 3 minutes, followed by fusing, blowing or foaming at a more elevated temperature of about 430DF. for a period of about 1 minute and 40 seconds.
The base synthetic polymeric l~yer and the wear layer having cooled, they are subsequently pre-warmed to an elevated temperature of about 260F. before being substantially uniformly coated with a W curable acrylated urethane top surface coating having the follcwing composition by weight:
Parts Lauroyl peroxide 5 20 AcLylated urethane resin ' 60 Polyether polyol 650 10 Vinyl acetate 30 Isobutyl ether of benzoin photoinitiator 3%
Dibutyl tin dilaurate 0.5%
The curing of the W curable acrylated urethane resin top coating takes place by passage through an ultraviolet unit having a length of about 3 feet (2 lamp parallel unit, 12 inches long, 200 watts each lamp, medium pressure, mercury lampj and a nitrogen atmosphere at a rate of about 10 feet per minute.
The adhesion or bond between the vinyl resin wear layer and the ~ - 16 ~
- m~h/ ` --, ~ .
acryla-ted polyurethc~ne resin top corating layer is tes-ted and is found to be strong and permanent and capable of resisting dela~ination very well. The results are generally comparable to the results ob-tained in repeated tests.
EX~MPLE II
m e procedures decribed in Example I æ e ~ollowed substantial~y as set forth -therein with the excep-tion tha-t the formulation of the vinyl resin wear layer is changed to the follcwing:
Parts Polyvinyl chloride, dispersion grade, high mol. w-t. 89.36 Polyvinyl chloride, blending resin, inh. vis. 0.86 10.63 Butyl benzyl phthalate plasticizer 7.S
2,2,4-trimethyl-1,3-pentanediol diisobutyrate 15.0 Polyethylene glycol dimethacrylate 22.5 Epoxy plasticizer 5.0 Ba-Zn stabilizer 3.0 Toner ; 0.21 W absorber - - 0.32 m e adhesion or bond between the vinyl resin layer and -the acryl-ated polyurethane resin top coating layer is tested and is found to be strong and permanent and to resist delaminàtion ~ery well. The results are generally comparable to the results of Example I.
EX~MPLE III
The procedures described in Example Iare follcwed substantiall~
as set ~orth therein with thè exception that the formulation of the vinyl resin wear layer is changed to the follcwing composition by weight:
Parts Polyvinyl chloride, dispersion grade, high mol. wt. 89.36 Polyvinyl chloride, blending resin, inh. vis. 0.86 10.63 Epoxy plc~sticizer 5.0 Ba-Zn stabilizer 3.0 Trimethylol propane trimethacrylate 45.0 ' ' , I
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, ~1~27~Z2 Butyl ben~yl phthalate plasticizer 6.0 Toner 0.21 W absorber 0.32 Ihe adhesion or bond between the vinyl resin wear l~yer and the acrylated polyurethane resin top coating layer is tes-ted and is found to be excellent and capab:le of resisting deLamination very well. 'l~e resul-t~
are generally comparable to those of Examp:Le I.
_ _ _ The procedures described in Example I are followed substantially as set forth therein with the exception that the lauroyl peroxide in the W curable acrylated polyurethane resin top coating layer is replaced by 10 parts of t-butylperoxy isopropyl monocarbonate as the free radical polymerization initiator.
The results are generally comparable to the results obtained in Example I. The adhesion of the bond between the vinyl resin layer and the acrylated polyurethane top surface coating is tested and is found to be excellent and to resist delamination very well.
EXAMPLE V
The procedures of Example I are follcwed substantially as set forth therein with the exception that the lauroyl peroxide is replaced by dicu~lyl peroxide as the free radical polymerization initiator.
The results of this Example are found to be generally comparable to the results obtained in Example I. Ihe bond or adhesion between the vinyl resin layer and the acrylated polyurethane layer is tested and is found to be excellent and well capable of resisting dek~mination.
F~ PIE VI
The procedures described in Example I are follcwed substan-tially as set forth therein with the exception that the polyethylene glycol dimethacrylate in the wear layer formulà-tion is replaced by an equal amount of methoxy polyethylene glycol 300 mono-acrylate.
.
:
.
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l~e results of this example are yenerally c~lparable to -the results ob-tained in Example X. m e bond or adhesion between the vinyl resin wear layer and the acrylated polyurethane resin layer is tested and found to be excellent.
EXPMPLE VII
The procedures described ln Example I are ~ollcwed substanti~ll*
as set forth therein with the exception -~hat the polyet~lene ylycol dimethacrylate in the vinyl resin wear layer is replaced by an acrylic urethane prep æed by reactiny 4,4'-methylene-biscyclohexyl diisocyanate and Teraco ~ 650 polytetrame-thylene e-ther glycolr and hydroxye-thyl methacrylate.
I'he results of this Example æe generally comparable to the re-sults obtained in Example I. The bond or adhesion between the vinyl resin wear layer and the acrylated polyurethane resin layer is tested and is found to be excellent and to resist delamination very well.
. EXAMPLE VIII
The procedures described in Example I æe followed substan-tially as set forth therein with the exception that the polyethylene ; glycol dimethacrylate is replaced by an acrylated polyurethane resin derived from reacting 4,4'-methylene-bis-cyclohexyl diisocyanate, Pluraco ~ 450 polyoxyaIkylene polyol based on pentaerythritol, and hydroxy ethyl methacrylate.
The results of this Example are yenerally co~parable to the results of Example I. Ihe bond between t~e vinyl resin wear layer and the acrylated polyurethane resin layer is tested and found to be excel-lent and well capable of resisting delamination.
EXAMPLE IX
~he procedures described in Example I are followed substan-tially as set forth therein with the exception that the polyethylene glycol dimethacrylate is replaced by an acrylated polyurethane resin mab/
.
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derived by reacting isophorone diisocyana~e, Teracol 550 polytetra-methylene ether g1ycol, and hyclroxyethyl methacrylate.
rlhe results of this Example are cJenerally cc~mparable to the res~lts obtained in Exclrple I. r~he bond or adhesion between the vinyl resin wear layer and -the acrylated polyur~-thane res:in layer i~ ~ested and is found to be excellent and well capable of resis-tiny delamination.
E~MPLE X
...
The procedures described in Exa~ple VII are follcwed substan-tially as set forth therein with the excep-tion that the hydroxye-thyl methacrylate used in the formation of the acrylated polyurethane for the ~inyl resin wear layer is replaced by hyclroxyethyl acrylate.
The results of this Example are generally comparable to the results obtained in Example VII. The bond or adhesion between the vinyl resin wear layer and the acrylated polyurethane resin top coatiny layer is tested and is found to be excellent and well capable of resis-~iny dela~ination.
. .
T~e procedures described in Example ~II are follcwed substan-tially as set forth therein with the exception that the hydroxyethyl methacrylate used in the form~llation of the acrylated polyu~ethane fQr - the ~inyl resin wear layer ;s replaced by hydroxypropyl acrylate.
e results of this Example æ e generally comparable to the results obtained in Exclmple VII. The bond or adhesion between the vinyl - resin wear layer and the acrylated polyurethane top coating layer is tested and is found to be excellent and well capable of resisting delamination.
... ... ..
EX~MPLE XII
The procedures set forth in Example I are follcwed substan~
tially as described therein with the added definition that the acrylated m~b/
' ~
z urethane resin used in the top swrface coatincJ is th~ reaction prodw-t of: (XIIa) 4,4'-methylene-bis-cyclohexyl diisocyanate, polyte-tra-methylene ether glycol, and hyc1ro~yethyl acryla-te: (XIIb) 4,4'-methylene-bis-cyclohexyl diisocyanate, polyoxyaIkylene polyol basecl on pen-taerythri-tol, and hydroxyethyl me-thacrylate: (XIIc) isophorone di-isocyana-te, polytetramethylene ether glycol, and hyclroxymethacrylate:
(XIId) isophorone diisocyanate, polyoxyalkylel1e polyol base~ on pent~~
erythritol, and hyclroxyethyl methacrylate: ~XIIe) 4,~'-meth~lene-bis-cyclohexyl diisocyanate, polytetrameth~lene ether glycol, and h~dro~y-methyl acrylate: (XIIf) 4,4'-methylene-bis-cyclohexyl diisocyanate, polytetramethylene ether glycol, and hydroxypropyl methacrylate.
The results of these Examples are all generally co~parable to the results obtained in EXample I. The bond or adhesion between the Yinyl resin wear layer and the acrylated polyurethane resin top surface coating layer is strong and permanent and is capable of resisting de-lamination very well.
- EXAMPLE'XIII
The procedures of Example I are followed substantially as set forth therein with the exception that a different top surface coating layer is used which is formulated as follcws: a conventional' polyurethane resin is prepared from an aliphatic diisocyanate (hexa-methylene dii~socyanate) as the NCO source; the reacting polyhydrox~
groups are provided for a ~QXture of polyols, the polyols (both polyester polyol types and polyether polyol types, with the polyester forming the ~ajor proportion and the polyethers forming the nur.or proportion), and the catalyst being a ~xture of tetrakis-2 hydroxypropyl ethylene diamine, a tertiary amine, and dibutyl tin dilaurate. Five percent by weight of lauroyl peroxide is included as the orgam c peroxide.
The conventional polyurethane resin top surface coating layer ~b/ .
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is applied to the vinyl resin wear layer and is subseq~lently heated in an oven at an elevated temperature of about 385F~ for a period of time of about 2 minutes and 45 seconcls. Fusion *akes place, along with the blowing and Eoaming of the polyvinyl chloride base synthetic polymeric layer con-taining the blowing or foaming agent.
rrhe results of this Example are generally ccmparable ~o the results obtained in Example I. rrhe bond or adhesion between the vinyl resin wear layer and the polyurethane resin top surface coating layer is tested and is f,ound to be s-trong and permanent and capable of resisting delamination very well.
Although several specific working Examples,of the inventiye concept have been described in particularity, the invention in its broader aspects should not be construed as limited thereto but should be considered as including various other equivalen-t features as set forth and encompassed by the appended claims. Any suitable changes, modifications and variations may be made without departing f,,rom the scope and the spirit of such appended claims.
~/
.
The gelled, firmed potentially foamable polyvinyl ehloride plastisol is the~ printed with a mul;ticolored decorative pattern or design using (1) a conventional or standard printing ink camposition and (2) an inhioitor-containing printing ink cGr~position, as follows:
Printing ink cc~,position (1):
Parts - Solution grade copolymer of vinyl chloride (90 parts) and vinyl acetate (10 parts) 15 ,~ Methyl ethyl ketone 85 Pigment or colorant, as desired Printing ink composition (2):
Parts Solution grade copolymer of vinyl chloride (90 parts) and vinyl acetate (10 parts) 12 Met~yl ethyl ketone 68 Trimellitic ar~ydride 20 Pigment or colorant! as desired m e printed, gelled and firmed potentially foamable polyvinyl chloride plastisol is then allcwed to air-dry and a polyvinyl chloride plastisol wear layer is substantially uni~ormly applied thereto to a wet thickness of about 0.015 inch depth and having the follewing formulation by weight:
Parts Polyvinyl chloride,-dispersion grade, high rnol. wt.89.36 Polyvinyl chloride, blending r~sin, inherent viscosity r~lb/
~7~Z
0.86 (ASTM ~-12~3-66) 10.64 Butyl benzyl phthala-te plasticizer 7.5 2,2,4--trimethyL-1,3-pentanediol diisobutyrate 7.5 Polyethylene y:Lycol dimethacrylate 30.0 Epoxy plas-ticizer 5.0 Ba-Zn stabilizer 3.0 Toner 0.21 W absorber 0.32 Gelling and firming of the polyvinyl chloride plastisol wear layer takes place at an elevated temperature of about 300F. for a period of time of about 3 minutes, followed by fusing, blowing or foaming at a more elevated temperature of about 430DF. for a period of about 1 minute and 40 seconds.
The base synthetic polymeric l~yer and the wear layer having cooled, they are subsequently pre-warmed to an elevated temperature of about 260F. before being substantially uniformly coated with a W curable acrylated urethane top surface coating having the follcwing composition by weight:
Parts Lauroyl peroxide 5 20 AcLylated urethane resin ' 60 Polyether polyol 650 10 Vinyl acetate 30 Isobutyl ether of benzoin photoinitiator 3%
Dibutyl tin dilaurate 0.5%
The curing of the W curable acrylated urethane resin top coating takes place by passage through an ultraviolet unit having a length of about 3 feet (2 lamp parallel unit, 12 inches long, 200 watts each lamp, medium pressure, mercury lampj and a nitrogen atmosphere at a rate of about 10 feet per minute.
The adhesion or bond between the vinyl resin wear layer and the ~ - 16 ~
- m~h/ ` --, ~ .
acryla-ted polyurethc~ne resin top corating layer is tes-ted and is found to be strong and permanent and capable of resisting dela~ination very well. The results are generally comparable to the results ob-tained in repeated tests.
EX~MPLE II
m e procedures decribed in Example I æ e ~ollowed substantial~y as set forth -therein with the excep-tion tha-t the formulation of the vinyl resin wear layer is changed to the follcwing:
Parts Polyvinyl chloride, dispersion grade, high mol. w-t. 89.36 Polyvinyl chloride, blending resin, inh. vis. 0.86 10.63 Butyl benzyl phthalate plasticizer 7.S
2,2,4-trimethyl-1,3-pentanediol diisobutyrate 15.0 Polyethylene glycol dimethacrylate 22.5 Epoxy plasticizer 5.0 Ba-Zn stabilizer 3.0 Toner ; 0.21 W absorber - - 0.32 m e adhesion or bond between the vinyl resin layer and -the acryl-ated polyurethane resin top coating layer is tested and is found to be strong and permanent and to resist delaminàtion ~ery well. The results are generally comparable to the results of Example I.
EX~MPLE III
The procedures described in Example Iare follcwed substantiall~
as set ~orth therein with thè exception that the formulation of the vinyl resin wear layer is changed to the follcwing composition by weight:
Parts Polyvinyl chloride, dispersion grade, high mol. wt. 89.36 Polyvinyl chloride, blending resin, inh. vis. 0.86 10.63 Epoxy plc~sticizer 5.0 Ba-Zn stabilizer 3.0 Trimethylol propane trimethacrylate 45.0 ' ' , I
mab/
, ~1~27~Z2 Butyl ben~yl phthalate plasticizer 6.0 Toner 0.21 W absorber 0.32 Ihe adhesion or bond between the vinyl resin wear l~yer and the acrylated polyurethane resin top coating layer is tes-ted and is found to be excellent and capab:le of resisting deLamination very well. 'l~e resul-t~
are generally comparable to those of Examp:Le I.
_ _ _ The procedures described in Example I are followed substantially as set forth therein with the exception that the lauroyl peroxide in the W curable acrylated polyurethane resin top coating layer is replaced by 10 parts of t-butylperoxy isopropyl monocarbonate as the free radical polymerization initiator.
The results are generally comparable to the results obtained in Example I. The adhesion of the bond between the vinyl resin layer and the acrylated polyurethane top surface coating is tested and is found to be excellent and to resist delamination very well.
EXAMPLE V
The procedures of Example I are follcwed substantially as set forth therein with the exception that the lauroyl peroxide is replaced by dicu~lyl peroxide as the free radical polymerization initiator.
The results of this Example are found to be generally comparable to the results obtained in Example I. Ihe bond or adhesion between the vinyl resin layer and the acrylated polyurethane layer is tested and is found to be excellent and well capable of resisting dek~mination.
F~ PIE VI
The procedures described in Example I are follcwed substan-tially as set forth therein with the exception that the polyethylene glycol dimethacrylate in the wear layer formulà-tion is replaced by an equal amount of methoxy polyethylene glycol 300 mono-acrylate.
.
:
.
~27~
l~e results of this example are yenerally c~lparable to -the results ob-tained in Example X. m e bond or adhesion between the vinyl resin wear layer and the acrylated polyurethane resin layer is tested and found to be excellent.
EXPMPLE VII
The procedures described ln Example I are ~ollcwed substanti~ll*
as set forth therein with the exception -~hat the polyet~lene ylycol dimethacrylate in the vinyl resin wear layer is replaced by an acrylic urethane prep æed by reactiny 4,4'-methylene-biscyclohexyl diisocyanate and Teraco ~ 650 polytetrame-thylene e-ther glycolr and hydroxye-thyl methacrylate.
I'he results of this Example æe generally comparable to the re-sults obtained in Example I. The bond or adhesion between the vinyl resin wear layer and the acrylated polyurethane resin layer is tested and is found to be excellent and to resist delamination very well.
. EXAMPLE VIII
The procedures described in Example I æe followed substan-tially as set forth therein with the exception that the polyethylene ; glycol dimethacrylate is replaced by an acrylated polyurethane resin derived from reacting 4,4'-methylene-bis-cyclohexyl diisocyanate, Pluraco ~ 450 polyoxyaIkylene polyol based on pentaerythritol, and hydroxy ethyl methacrylate.
The results of this Example are yenerally co~parable to the results of Example I. Ihe bond between t~e vinyl resin wear layer and the acrylated polyurethane resin layer is tested and found to be excel-lent and well capable of resisting delamination.
EXAMPLE IX
~he procedures described in Example I are followed substan-tially as set forth therein with the exception that the polyethylene glycol dimethacrylate is replaced by an acrylated polyurethane resin mab/
.
7~
derived by reacting isophorone diisocyana~e, Teracol 550 polytetra-methylene ether g1ycol, and hyclroxyethyl methacrylate.
rlhe results of this Example are cJenerally cc~mparable to the res~lts obtained in Exclrple I. r~he bond or adhesion between the vinyl resin wear layer and -the acrylated polyur~-thane res:in layer i~ ~ested and is found to be excellent and well capable of resis-tiny delamination.
E~MPLE X
...
The procedures described in Exa~ple VII are follcwed substan-tially as set forth therein with the excep-tion that the hydroxye-thyl methacrylate used in the formation of the acrylated polyurethane for the ~inyl resin wear layer is replaced by hyclroxyethyl acrylate.
The results of this Example are generally comparable to the results obtained in Example VII. The bond or adhesion between the vinyl resin wear layer and the acrylated polyurethane resin top coatiny layer is tested and is found to be excellent and well capable of resis-~iny dela~ination.
. .
T~e procedures described in Example ~II are follcwed substan-tially as set forth therein with the exception that the hydroxyethyl methacrylate used in the form~llation of the acrylated polyu~ethane fQr - the ~inyl resin wear layer ;s replaced by hydroxypropyl acrylate.
e results of this Example æ e generally comparable to the results obtained in Exclmple VII. The bond or adhesion between the vinyl - resin wear layer and the acrylated polyurethane top coating layer is tested and is found to be excellent and well capable of resisting delamination.
... ... ..
EX~MPLE XII
The procedures set forth in Example I are follcwed substan~
tially as described therein with the added definition that the acrylated m~b/
' ~
z urethane resin used in the top swrface coatincJ is th~ reaction prodw-t of: (XIIa) 4,4'-methylene-bis-cyclohexyl diisocyanate, polyte-tra-methylene ether glycol, and hyc1ro~yethyl acryla-te: (XIIb) 4,4'-methylene-bis-cyclohexyl diisocyanate, polyoxyaIkylene polyol basecl on pen-taerythri-tol, and hydroxyethyl me-thacrylate: (XIIc) isophorone di-isocyana-te, polytetramethylene ether glycol, and hyclroxymethacrylate:
(XIId) isophorone diisocyanate, polyoxyalkylel1e polyol base~ on pent~~
erythritol, and hyclroxyethyl methacrylate: ~XIIe) 4,~'-meth~lene-bis-cyclohexyl diisocyanate, polytetrameth~lene ether glycol, and h~dro~y-methyl acrylate: (XIIf) 4,4'-methylene-bis-cyclohexyl diisocyanate, polytetramethylene ether glycol, and hydroxypropyl methacrylate.
The results of these Examples are all generally co~parable to the results obtained in EXample I. The bond or adhesion between the Yinyl resin wear layer and the acrylated polyurethane resin top surface coating layer is strong and permanent and is capable of resisting de-lamination very well.
- EXAMPLE'XIII
The procedures of Example I are followed substantially as set forth therein with the exception that a different top surface coating layer is used which is formulated as follcws: a conventional' polyurethane resin is prepared from an aliphatic diisocyanate (hexa-methylene dii~socyanate) as the NCO source; the reacting polyhydrox~
groups are provided for a ~QXture of polyols, the polyols (both polyester polyol types and polyether polyol types, with the polyester forming the ~ajor proportion and the polyethers forming the nur.or proportion), and the catalyst being a ~xture of tetrakis-2 hydroxypropyl ethylene diamine, a tertiary amine, and dibutyl tin dilaurate. Five percent by weight of lauroyl peroxide is included as the orgam c peroxide.
The conventional polyurethane resin top surface coating layer ~b/ .
~,12'~f~Z
is applied to the vinyl resin wear layer and is subseq~lently heated in an oven at an elevated temperature of about 385F~ for a period of time of about 2 minutes and 45 seconcls. Fusion *akes place, along with the blowing and Eoaming of the polyvinyl chloride base synthetic polymeric layer con-taining the blowing or foaming agent.
rrhe results of this Example are generally ccmparable ~o the results obtained in Example I. rrhe bond or adhesion between the vinyl resin wear layer and the polyurethane resin top surface coating layer is tested and is f,ound to be s-trong and permanent and capable of resisting delamination very well.
Although several specific working Examples,of the inventiye concept have been described in particularity, the invention in its broader aspects should not be construed as limited thereto but should be considered as including various other equivalen-t features as set forth and encompassed by the appended claims. Any suitable changes, modifications and variations may be made without departing f,,rom the scope and the spirit of such appended claims.
~/
.
Claims (16)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A multi-layered construction of dissimilar synthetic polymeric materials comprising:
a first synthetic polymeric material containing a vinyl resin, at least one plasticizer for said vinyl resin, and from about 10 to about 30% by weight of a member of the group consisting of acrylates, acrylated polyurethanes and mixtures thereof; and a second synthetic polymeric material containing a member of the group consisting of polyurethanes and acrylated polyurethanes and a free radical polymerization initiator capable of initiating a polymerization reaction between said acrylates and/or acrylated polyurethanes and said polyurethanes or acrylated polyurethanes, said second synthetic polymeric material containing from about 0.5% to about 20% by weight of free available isocyanate.
a first synthetic polymeric material containing a vinyl resin, at least one plasticizer for said vinyl resin, and from about 10 to about 30% by weight of a member of the group consisting of acrylates, acrylated polyurethanes and mixtures thereof; and a second synthetic polymeric material containing a member of the group consisting of polyurethanes and acrylated polyurethanes and a free radical polymerization initiator capable of initiating a polymerization reaction between said acrylates and/or acrylated polyurethanes and said polyurethanes or acrylated polyurethanes, said second synthetic polymeric material containing from about 0.5% to about 20% by weight of free available isocyanate.
2. A multi-layered construction as defined in claim 1 wherein said free radical polymerization initiator is an organic peroxide.
3. A multi-layered construction as defined in claim 1 wherein said free radical polymerization initiator is lauroyl peroxide.
4. A multi-layered construction as defined in claim 1 wherein said free radical polymerization initiator is t-butylperoxy isopropyl monocarbonate.
5. A multi-layered construction as defined in claim 1 wherein said polyurethane in said second synthetic polymeric material is a reaction product of a diisocyanate and a polyol.
6. A multi-layered construction as defined in claim 1 wherein said acrylated polyurethane in said second synthetic polymeric material is a reaction product of a diisocyanate, a polyol, and a hydroxyalkyl acrylate.
7. A multi-layered construction as defined in claim 1 wherein said vinyl resin in said first synthetic polymeric material is polyvinyl chloride.
8. A multi-layered construction as defined in claim 1 wherein said acrylate in said first synthetic polymeric material is trimethylolpropane trimethylacrylate.
9. A multi-layered construction as defined in claim 1 wherein said acrylate in said first synthetic polymeric material is methoxy polyethylene glycol mono-acrylate.
10. A multi-layered construction as defined in claim 1 wherein said acrylated polyurethane in said first synthetic polymeric material is a reaction product of a diisocyanate, a polyol, and a hydroxyalkyl methacrylate.
11. A multi-layered construction as defined in claim 1 wherein said acrylated polyurethane in said first synthetic polymeric material is a reaction product of a diisocyanate, a polyol, and a hydroxyalkyl acrylate.
12. A multi-layered construction of dissimilar synthetic polymeric materials comprising.
a first synthetic polymeric material containing a vinyl resin, at least one plasticizer for said vinyl resin and from about 10 to about 30% by weight of a member of the group consisting of acrylates, acrylated polyurethanes and mixtures thereof; and a second synthetic polymeric material containing a member of the group consisting of polyurethanes and acrylated polyurethanes, said synthetic polymeric materials being bonded in a strong and permanent primary chemical bond therebetween by a reaction product of a polymerization involving acrylates or acrylated polyurethanes and polyurethanes or acrylated poly-urethanes.
a first synthetic polymeric material containing a vinyl resin, at least one plasticizer for said vinyl resin and from about 10 to about 30% by weight of a member of the group consisting of acrylates, acrylated polyurethanes and mixtures thereof; and a second synthetic polymeric material containing a member of the group consisting of polyurethanes and acrylated polyurethanes, said synthetic polymeric materials being bonded in a strong and permanent primary chemical bond therebetween by a reaction product of a polymerization involving acrylates or acrylated polyurethanes and polyurethanes or acrylated poly-urethanes.
13. A method of improving the bond between a vinyl resin material and a member of the group consisting of polyurethane and acrylated polyurethane resin materials, said polyurethane resin materials containing from about 0.5% to about 20% by weight of free available isocyanate, which comprises:
including from about 10 to about 30% by weight of a member of the group consisting of acrylates, acrylated polyurethanes and mixtures thereof in said vinyl resin material;
providing a free radical polymerization initiator in said polyurethane or acrylated polyurethane resin material;
bringing said vinyl resin material and said poly-urethane or acrylated polyurethane resin material into contact;
and exposing said vinyl resin material and said poly-urethane or acrylated polyurethane rosin material to curing conditions, whereby there is sufficient chemical inter-reaction between said resin materials as to create a strong and permanent primary chemical bond therebetween, in addition to any hydrogen bonds or van der Waals forces.
including from about 10 to about 30% by weight of a member of the group consisting of acrylates, acrylated polyurethanes and mixtures thereof in said vinyl resin material;
providing a free radical polymerization initiator in said polyurethane or acrylated polyurethane resin material;
bringing said vinyl resin material and said poly-urethane or acrylated polyurethane resin material into contact;
and exposing said vinyl resin material and said poly-urethane or acrylated polyurethane rosin material to curing conditions, whereby there is sufficient chemical inter-reaction between said resin materials as to create a strong and permanent primary chemical bond therebetween, in addition to any hydrogen bonds or van der Waals forces.
14. A method as defined in claim 13 wherein a polyurethane resin material is used and curing conditions take place at elevated temperatures of from about 260°F. to about 410°F. for a period of time of from about 1 minute to about 8 minutes.
15. A method as defined in claim 13 wherein an acrylated resin material is used and curing conditions take place at elevated temperatures by means of radiation curing techniques.
16. A method as defined in claim 13 wherein an acrylated resin material is used and curing conditions take place by means of mercury vapor arc radiation curing.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US2310679A | 1979-03-23 | 1979-03-23 | |
| US23,106 | 1979-03-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1127022A true CA1127022A (en) | 1982-07-06 |
Family
ID=21813162
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA336,072A Expired CA1127022A (en) | 1979-03-23 | 1979-09-21 | Methods for bonding dissimilar synthetic polymeric materials and the products involved in and resulting from such products |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1127022A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5643677A (en) * | 1989-09-15 | 1997-07-01 | Armstrong World Industries, Inc. | Aminoplast/polyurethane wear layer for PVC support surface |
| US6440500B1 (en) | 1999-07-28 | 2002-08-27 | Armstrong World Industries, Inc. | Method for manufacturing a surface covering product having a controlled gloss surface coated wearlayer |
| US6572932B2 (en) | 1999-07-28 | 2003-06-03 | Awi Licensing Company | Process for providing a gloss controlled, abrasion resistant coating on surface covering products |
| US6908585B2 (en) | 2000-11-15 | 2005-06-21 | Awi Licensing Company | Pigmented radiation cured wear layer |
-
1979
- 1979-09-21 CA CA336,072A patent/CA1127022A/en not_active Expired
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5643677A (en) * | 1989-09-15 | 1997-07-01 | Armstrong World Industries, Inc. | Aminoplast/polyurethane wear layer for PVC support surface |
| US6440500B1 (en) | 1999-07-28 | 2002-08-27 | Armstrong World Industries, Inc. | Method for manufacturing a surface covering product having a controlled gloss surface coated wearlayer |
| US6569500B1 (en) | 1999-07-28 | 2003-05-27 | Awi Licensing Company | Method for controlling gloss level |
| US6572932B2 (en) | 1999-07-28 | 2003-06-03 | Awi Licensing Company | Process for providing a gloss controlled, abrasion resistant coating on surface covering products |
| US6908585B2 (en) | 2000-11-15 | 2005-06-21 | Awi Licensing Company | Pigmented radiation cured wear layer |
| US6908663B1 (en) | 2000-11-15 | 2005-06-21 | Awi Licensing Company | Pigmented radiation cured wear layer |
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