CA1125588A - Methods for bonding dissimilar synthetic polymeric materials and the products involved in and resulting from such methods - Google Patents

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 dissimilar synthetic polymeric materials, such as, for example, a vinyl resin mater-ial and a polyurethane or acrylated polyurethane resin material which comprises; including in the vinyl resin material a chem-ical compound possessing hydroxy, carboxy, amido, amino, imino, mercapto, or like functions containing reactive hydrogen; pro-viding free, available isocyanate in the polyurethane or acryl-ated polyurethane resin material; bringing the vinyl resin material and the polyurethane or acrylated polyurethane resin material into contact: and exposing the vinyl resin material and the polyurethane or acrylated polyurethane resin material, while in contact, to curing conditions, whereby there is suf-ficient chemical inter-reaction between these resin materials as to create a strong and permanent primary chemical bond there-between, in addition to any secondary bonds, such as hydrogen bonds and/or van der Waals forces. The present invention also relates to the products involved in and resulting from such methods.

Description

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METHODS ~OR BONDINC DISSIMILAR SYNT~TIC POLYMERIC MATERIAIfS
AND THE PPi~ODUCTS INVOLVED IN AND RES~LTING FROM SUCH iMETHODS

THE FIELD OF THE INVENTION
The present in~irention relate~ to methods of maXing multi-layered products, and more particularly multi-layersd sheet materisls, such as resilient floor coveringg, T~hich comprise a vinyl resin layer and a polyurethane or acrylated polyurethane resin layer, wherein it is necessary that such layers be adhered together in a strong and permanent bond which resists delamination very well.
BACKGROUND OF TH~ INVENTION
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 nec-essary to bond together two or more layers o$ dissimilar syn-thetic polymeric materials and that it is orten difficult to obtain a strong and permanent bond between such dissimilar syn-thetic materials.
Such difficulties often are believed to arise in the bonding Or such dissimilar synthetic polymeric materials because o$ the differences in surface energies. Yor example, if atoms from two dissimilar synthetic polymeric materials cannot grat close enough to each other, perhaps becaus~a of l~rge dissimilarities or disparities in polarity, van der Waals forces cannot be ade-.. .
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quately taken advantage of to create strong permanent bonding.~'or ~s it believed that hydrogen bonding can be adequately taken advi,~taee of in such s1tuations. Many proposals have been made to overcome such d1fficulties and to improve the bond between such dissimilar synthetic polymeric materials but none has beeD
found to be completely satisfActory to date.
The present invention will be described with partlcular refer-ence to the bonding of dissimilar synthetic polymeric materials, such as, for example, vinyl resins and polyurethane or acrylated polyurethane resins but it is to be appreciated that the prin-ciples of the present invention are equally applicable to other equivalent synthetic polymeric materials. In the same way, the present invention will be described with specific reference to multi-layered products, such as, for example, resilient floor co~erings utilizing dissi~ilar synthetic polymeric materials but again, it i8 to be appreciated that the principles of the pres-ent invention are equally applicable to other mult~-layered products which also utilize dissimilar synthetic polymeric mater-ials.

In the manufacture of resilient floor covering6, normally a relatively flat base layer or gub6trate i6 laid out in substan- ., tially horizontal conditlon. Such a base layer or substrate i8 customarily a felted or matted fibrous sheet of overlapping, in-tertwined fibers and/or filament6, ui-i3ually of asbestos or of natural, synthetic or man-made cellulosic origin, although many other forms of sheets and filmg or textile materials or fabrics may be used.

Upon this substantially flat, horizontal base layer or subst~ate is then applied a substantially uniform base layer of a liquid or semi-liquid resinous composition which contains a synthetic polymeric material, usually an ungelled polyvinyl chloride plastisol, usually containing a blowing or roaming agent. This ~u ~ ,; ? ~ h ~ r~ ,~ t Z5S~8 liquid or semi-liquid plastisol composition is subsequently Eelled at an elevated temperature to a relatively fir~ condi-tion by procedures which are conventional and well known in the art. This relatively firm, ~elled plastisol may then be printed with a decorative, multi-colored pattern or design in ~hich certain predetermined areag contain a blowing or foaming inhibitor which subsequently modifies the action of the blowing or foaming agent in those certain predetermined areas. Several different printing ink compositions may be used.
A substantially uniform wear layer usually of a clear liquid or semi-liquid resinous compo8ition and usually containing another ungelled polyvinyl chloride plasti901 composition but genera}ly not containing any blowing or foaming agent is then applied as a wear resistant coating to the surface of 'the base layer of printed, firmed and gelled polyvinyl chloride plastisol and is subsequently gelled and firmed thereon, either as a separate operation or in a joint operation operation with a subsequent ~using and blov~ing and foaming operation of the base layer of polyvinyl chloride plastisol. Thus far, there is relatively very little difficulty in creating a strong, permanent bond or adhesion between the bage layer of polyvinyl chloride plastisol and the wear layer, which is also a polyvinyl chloride plastisolO
It is then frequently desired to provide a top surface coating to the surface of the polyvinyl chloride wear layer'and it is often desir'ed that such top surface coating be a polyurethane or acrylated polyurethane resin, primarily because of their superior physical and chemical properties and characteristics.
However, in many in6tances, it is found that the adheqion or " bond between the vinyl resin wear layer and the polyurethane.or acrylated polyurethane resin top surface coating is not as strong or as permanent, as desired or required. It is believed that such lack of strength and of permanency or lack of suit-able resistence to delamination i8 due to the fact that the wear layer and the top surface coating are dissimilar ~ynthetic polymeric materials.

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P~RPO~tEj AND OBJECTS OF THE INVENTION
It is therefore a principal purpose and object Or the present invention to provide for methods of improving the bond b~tween dlssimilar synthetic polymeric materlals, and particularly be-tween a vinyl resin material and a polyurethane or acrylate,d polyurethane resin material, whereby a strong, permanent ~
created between such materials which will resist delamination very well.

BRIEF SUM,u~RY OF THE INV7~NTION
It has been found that such principal purpose and ob~ect, as well as other princlpal purposes and objects which will become clear from a further reading and understanding of thls dis-closure, may be achieved by forming a layer comprising a vinyl resin, one or more plasticizers for the vinyl resin, and a chem-ical compound possessing a hydroxy, carboxy, amido, amino, imino, mercapto, or like functions containing reactive hydrogen providing apolyurethane or acrylated polyurethane resin which contains free, available isocyanate~ bringing the vlnyl resin layer and the polyurethane or acrylated polyurethane resin into .
contact~ and exposing the vinyl resin layer and the polyurethane or acrylated polyurethane resin, while in contact, to c~ring conditions, whereby there is sufficient chemical inter-reaction between the vinyl resin layer and the polyurethane or acrylated polyurethane resin as to provide a strong and permanent bond therebet~een, in addition to any secondary bonds such as hydro-gen bonds and van der Waals forces, the strong and permanent bonds comprising primary chemical bonds well capable of resist-ing delamination.

1~2~5 DESCRIPTION OF PREFERRED AND TYPICAL E~.80DIMENTS
THE BASE LAYER OR SUBSTRATE
The specific ba3e layer or substrate which is used to illustrate the preferred and typical embodiments of the present invention does not relate to the essence of the inventive concept and no specific or detaili3d description thereof i9 deemed necessary.
It is custo~arily and conventionally 8 felted or matted fibrou~
sheet of overlapping, intermingled fibers and/or filaments, usually of asbestos or of cellulosic origin, although many other forms of sheet, films, or fabrics, and many other fibers and/or fi/laime~nlts may be used~ such as degcribed in United State~ Patents 3,293,094 and 3,29t,1 8 to Nairn et al.

T~æ BASE SYNTHF.TIC POLY~ERIC LAYER
The specific base synthetic polymeric layer which is used to lllustrate the present lnvention does not relate to the essence thereof and it is sufficient to state that it may be any poten-tially foamable or non-foamable resinous composition and that, although a plastisol of polyvinyl chloride is preferred and is typical, many other synthetic resins are also of use, not only as plastisols but also as organosols or as aqueous latices.

Typical of the plasticizers which are used in the formation of the preferred and typical polyvinyl chloride plastisols are dioctyl phthalate, butyl benzyl phthalate, dibutyl sebacate, and many others citcd in the previously mentioned United St2tes Patents,.

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THE YINYL RESIN WEAR LAYFR
The specific vinyl regln which iE~ used in thc preparatlon of the wear layer does not relate to the esgence of the present inven-tion Although a polyvinyl chloride homopolymer in the form Or a plastisol is the preferred and typical embodiment, many other vinyl resins are of uge, guch a8 a vinyl chloride-vinyl acetate copolymer, a vinyl chloride-vinylidene chloride copolymer, or copolymers of vinyl chloride with other vinyl esters, such as vinyl butyrate, vinyl propionat~c,, or alkyl su~stituted vinyl esters, and the like. Other 6ynthetic polymers are also of use.
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Subatantially any vinyl resin wear layer will E;uffice, such aEt those disclosed in the prevlously cited Unlted States Patents, with the modification that there also be included in the formu-lation from about 0.5 percent to about 2b percent by weight, and preferably from about 3 percent to about 10 percent by weight, of a chemical compound possessing hydroxy, carboxy, a~ido, amino, imino, mercapto, or like functions which contain reactive hydrogen, such percentages being based on the total weight of the vinyl resin wear layer formulation.
Specific examples of such chemical compounds containing react-ive hydrogen include, as illustrative but not limitative, the ~ollowingt Diols E;uch as ethylene glycol, propylene glycol, butylene gly-col, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, etc.~ triols such as glycerol, l,l,l-trimethylol propane, l,l,l-trimethylol ethane,`1,2,3-butanetriol, 1,2,4-butanetriol, 1,2,3-pentane-triol, 1,2,3-hexanetriol, 1,2,4-hexanetriol, 1,2,5-hexanetriol, 1,2,6-hexanetriol, 2,3,4-hexanetriol, 1,3,6-hexanetriol, etc.
tetrols such as erythritol, pentaerythrotol, etc.l as well as various mixtures of such polyols in varying proportions.

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Ether-type polyols whlch are adduct product of the above polyols with alkylene oxides havlng from 2 to 5 carbon atoms, ~uch as ethylene o~ide, propylene oxide, trimethylene oxlde, 1,2-butyl-ene oxlde, isobutylene oxide, 1,4-tetramethYlene oxide, penta-methylene oxlde, and mixtureg thereof, and especially diethyl-ene glycol, triethylene glycol, tetraethylene glycol, penta-ethylene glycol, and higher molecular weight polyalkylene gly-cols having the general chemical formulas HO(CnH2n)xOH, etc.
Ester-type polyols which are condengation products of the above polyols with polycarboxylic acid~ such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, mellitic acid, etc.

Polyamines such as.ethylene diamine, propylene diamine, tri-methylene diamine, tetramethylene diamine, pentamethylene di-amine, hexamethylene diamine, diethylene diamine, triethylene diamine, tetraethylene diamine, tetraethylene pentamine, iso-phorone diamine, piperazine, etc.
Polymercaptans such as ethylene dimercaptan, 1,3-propanedithiol, 1,4-butanedithiol, 2;2-dimercapto diethylether, glycol dimer-capto acetate, glycerol dimercapto propionate, trimethylolpro-pane, tri-(3-mercapto propionate), etc.
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Hydroxyamines such as monoethanolamine, diethanolamine, 3-amino-propanol-1, 4-amino butanol-l, etc.
Hydroxy.mercaptans such as l-thioglycerol, 2-mercapto ethanol, O

2,3-dimercapto propanol-l, etc..

It i8 to be noted that these chemical compounds possess at least two reactive hydrogens and that such reactive hydrogens are attached to different atoms, that is to say that they are at-tached to different sites.

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The vinyl resin wear layer formulation, including one or more plasticizers for the vinyl resin, such as listcd previously in the above cited United State~ Patents, together with fillers, stabilizers, antioxldantg, etc., a~ desired or required, and containing the chemlcal compounds having the reactive hydrogen is cast or farmed on the surrace of the baGe synthetic polymer-ic gelled and firmed plastigol layer of polyvinyl chloride to a substantially uniform thicknegs of from about 2 mils to about 30 mils or more. The vinyl regin wear layer 18 then gelled, either in a separate operation at an elevated temperature of from about 240 F. to about 430 F. for a period of time of from about 1 minute to about 4 minutes, whereby it beco~es firm, or combined with a fusion operation, along with the blowing and the foaming operation for the base gynthetic polymeric layer at an elevated temperature which is higher than the gelling or firming operation and is in the range of from about 270 F. to about 450 F. for a period of time of from about 2 minuteg to about 10 minutes, and preferably from about 3 minuteg to about 8 minutes.

THE TOP COATING
The specific polyurethane or acrylated polyurethane resin which is used in the formuiation of the top surface coating which i6 to be applied to or formed on the vinyl resin wear layer does not relate to the essence of the present invention. The poly-urethane may be a conventional polyurethane resin, or it may be a modified or acrylated polyurethane resln.
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CONVENTIONAL POLYURETHANES
., Conventional polyurethane resins are polymerization reactlon -products of any of the previously listed polyols, polyamines, polymercaptans, etc., with any of the following aliphatic, aromatic, cycloaliphatic, or heterocyclic polyisocyanates l~Z55 4,4-methylene-bi~-cyclohexyl di~socyanate tetramethylene-1,4-diieocyanate trlmethyl hexamethylene diisocyanate trimer of he~amethylene diisocyanate 2,4-tolylene dii 8 ocyanate p-phenylene d3isocyanate 4,4'-methylene-bis(phenylisocyanate) 4,4'-biphenylene dii 8 ocyanate butane-1,4-diisocyanate pentane-1,5-diisocyanate hexamethylene-1,6-diisocyanate cyclohexane diisocyanate dimer acid diisocyanate ethylene diisocyanate 2,6-tolylene diisocyanate m-phenylene diisocyanate naphthylene-1,5-diisocyanate furfurylidene diisocyanate isophorone diisocyanate xylene diisocyanate --In the formula~ion of the conventionai polyurethane resin topcoating composition, the proportion6 of the polyisocyanate and the reacting polyol, polyamine, polymercaptan, etc. must be 80 selected that there is provided from about 0.5% to about 10% by weight of free available isocyanate, and preferably from about 2~ to about 5% by weight, based on the total weight of the poly-urethane rPsln top coating formulation.
Conventional polyurethane resins are normally cured by conven-tional thermal processing in ovens or other suitable heating apparatus at elevzted temperatures of from about 150 F. toabout 450 F. and preferably from about 260 ~. to about 410 F. for a period of time of from about 1 minute to about 8 minutes, and preferably from about 3 minute~ to about 5 minutes.

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MODIFIED OR ACRYLATED POLYURETHA
~odified polyurethanes, such as acrylated p31yurethanes, may be prepared by several different methods, one preferred and typl-cal method using three basic componentsl (1) a UV reactive pol-ymerl (2) a diluent system composed of multifunctional acrylate acrylate ester6 (and occasionally monofunctional acrylic e~t-er~)l and (3) a photoiniator system.

The UV reactive polymer may be initially synthesized, for ex-ample, from a conventional isocyanate-function terminated poly-urethane by reaction with a hydroxyalkyl acrylate to form an essenti~lly polyurethane structure having termlnal acrylate functionality If desired, the hydroxyalkyl acrylate may be replaced by hydroxyalkyl methacrylates, or by other hydroxy-containing vinyl compounds, guch as vinyl esterg, vinyl ethers, vinyl sulfides, etc., to yield essentially polyurethane struc-tures ha~ing terminal methacrylate functionality or vinyl functionality. The acrylate functionality is normally pre-ferred. Examples of preferred or typical hydroxyalkyl acryl^
ates are~ hydroxyethyl acrylate, hydroxymethyl acrylate, hyd-roxypropyl acrylate, etc. Examples of preferred and typical hydroxyalkyl methacrylates are~ hydroxyethyl methacrylate, hydroxymethyl methacrylate, hydroxypropyl methacrylate, etc.
Examples of other preferred and typical hydroxy-containing vinyl compounds are~ B-hydroxyethyl vinyl ether, ~-hydroxyethyl vinyl sulfide, etc.
The diluent system is composed of multifunctional acrylate esters ~and occasionally monofunctional acrylic ester6) such as~
pentaerythritol triacrylate, trimethylolpropane triacrylate, 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, poly-ethylene glycol (200) dimethacrylate, pentaerythritol tetra-acrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol di-acrylate, neopentyl glycol diacrylate, etc. If monofunctional monomers are to be included along ~ith the multifunctional com-pounds, -the following illustrative examples of such monomers .
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may be used~ methyl acrylate, ethyl acrylate, butyl acrylate, hexyl acrylate, isobutyl acrylate, benzyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, buto~yethyl acrylate, isodecyl acrylate, glycidyl acrylate, vinyl acetate, etc.

The photoinitiator may be selected from a lHrge group of known photoinitiators of which the following are illustrative but not limitativel brnzoin and its alkyl ethers such as methyl or iso-butyl ether of benzoin, benzophenone and its derivatives such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methox~ benzophenone, used singly or in combination with amine compounds such as dimethyl-aminoethanol, N,N-dimethylaniline. triphenylphosphine, etc., di-methoxyphenyl acetophenone, diethoxy acetophenone, etc., xan-thone, thioxanthone, anthraquinone, flavone, benzil, polycyclic aromatic ketones, etc. Such photoinitiators are used in amounts of from about 0.5g to about 20~ by weight, and preferably from about 1% to about 5% by weight, based on the total weight of the ultraviolet curable formulation.
, The acrylated polyurethane resin top surface coating may be pre-pared by other conventional methods ~ell kno~t~n in the art, such as, ~or example, those methods disclosed in United ~tates Patent 4,100,318 but, again, must be so formulated as to possess from about 0.5% to about 10% by weight of free, available isocyanate, and preferably from about 2~ to about 5% by weight, based on the total weight of the acrylated polyurethane resin top surface coating formulation. Thi8, of course, is provided for in the original synthesis of the isocyanate-function terminated poly-urethane resin by employing an excess of the diisocyanate over the reacting polyol, polyamine, polymercaptan, etc.
Curing conditions for the modified or acrylated polyurethane resins differs from those employed for the more conventional polyurethane resins. in that the modified or acrylated polyure-thane resins are cured by passed through an actinic radiation source, such as an ultraviolet lamping unit. Radiation curing by electron beam, gam~a and x-ray treatment, and other suitable ~"~ ; r -' - 7v~

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radlatlon sources may be employed but must be used at relatively low energy levels, inasmuch as they are essentially examples of very high energy irradiation techniques leading to extremely rapid polymerization. Ultra violet radiation is the preferred and typical i,ource. In the presence of photoinitiators, such radiation sources induce a photochemical reaction whlch produces free radicals capable of inducing polymerization. Sources of ultraviolet radiation may be mercury vapor arc lamp3, plasms arcs, pulsed xenon lamps and carbon arcs. Mercury vapor arc lamps are preferred and typical, preferably at medium pressure rather than high pressure or low pressure. Specific wavelrtngths of light which are most effective will vary, depending primarily upon the particular polyurethane top coating formulation used and the particular photo-sensitizer employed. It is also to be appreciated that, in some instances, combinations of thermal curing and radiation curing conditions may be used.
During the curing conditions to which the polyurethane or the acrylated polyurethane resins, whether conventional or modifiad or acryl~ted, is exposed, there iB sufficient chemical inter-reaction between the reactive hydrogens in the vinyl reEin wear layer and the free, available isocyanate in the top surface coating as to create a strong and permanent primary chemical bond between the two layers of dissimilar synthetic polymeric materials. Such, of course, is additional to any existing sec-ondary bonds or forces, such as hydrogen bonds or van der Waals forces.
The present invention will be further described with particu-lar refercnce to tXe following specific working examples, where-in there are disclosed preferred and typical embodiments Of the present invention. However, it is to be pointed out that such specific examples are primaril illustrative and not limitative of the broader principles of the inventive concept and that other specific materials, chemicals, processes, etc., may be employed without departing from the scope and the sp~rit of the appended claims.
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EXAMPLE I
The base layer or substr~te comprises a relatively flat, 0.040 inch thick fibrous shcet of felted, matted asbestos fibers with an acrylic resin smoothing and leveling coating thereon. The asbestos fibro~s sheet is coated substantially uniformly to wet thickness depth of about 0.015 inch with the followLng foi~m-able polyvinyl chloride plastisol composition as the base syn-thetic polymeric layerl Parts Polyvinyl chloride, low mol. wt. general purpose, dispersion resin, inherent viscosity 0.99 (AST~; 1243-66 30.2 Polyvinyl chloride, med. mol. wt. dispersion grade, inherent viscosity 1.0 ~ 8.2 Polyvinyl chloride, med. mol. wt. blending resin, inherent viscosity 0.9 17.1 --Anhydrous alumina silicate filler 6.9 Alkyl benzyl phthalate plasticizers 24.7 Polydodecyl benzene 7.4 Azodicarbonamide blowing agent 1.1 Accelerator/stabilizer 0.4 Titanium dioxide 2.5 Dioctyl phthalate 1.5 Wetting agent -3 (parts oy weight) ' Gelling and firming of the potentially foamable ployvinyl chlor-ide plastisol is accomplished in a heated oven atmosphere main-tained at an elevated temperature of about 300 F. for a period of time of about 3 minutes. This temperature is not that ele-vated as to activate or decompose the azodicarbonamide blowi~g agent in the polyvinyl chloride plastisol base synthetic poly-meric layer as to cause blowing or foaming thereof.

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The gelled, firmed potentially foamable polyvinyl chloride plastisoL is then printed with a multicolored decorative design or pattern, using (1) a conventional or standard printing ink composition and (2) an inhibitor-containing printing ink compo-sition, having the following compositions, respectively:
Parts Solution grade vinyl chloride-vinyl acetate copolymer (90 parts: 10 parts) 15 Methyl ethyl ketone 85 Pigment or colorant, as needed or required Parts Solution grade vinyl chloride-vinyl acetate copolymer (90 parts: 10 parts) 12 Methyl ethyl ketone 68 Trimellitic anhydride blowing inhibitor 20 Pigment or colorant, as needed or required The printed, gelled, potentially foamable polyvinyl chloride plastisol is then allowed to air-dry and a polyvinyl chloride plastisol wear layer is substantially informly applied thereto to a wet thickness depth of about 0.015 inch. The wear layer has the following composition by weight:
Parts ;
Polyvinyl chloride, dispersion grade, high mol. wt. 89.4 Polyvinyl chloridè, blending resin, inh. VlS . O . 9 10 . 6 Butyl benzyl phthalate plasticizer 28. 9 2,2,4-trimethyl-1,3-pentanediol diisobutyrate6 . 9 Plasticizer (Santicizer* - 587) (dodecyl benzene) 9.3 - Epoxy plasticizer (Paraplex* G-62) (epoxide soybean oil) 5.0 *Trademark sd/y`~ -14-l~Z~
Ba-Zn stabilizer 7.0 Toner 0.21 UV absorber 0.31 Oxyester T 1136 (V) linear polyester with hydroxy groups, hydroxyl value 107 mg. KOH/g., acid value less than 2 mg KOHtg (Veba Chemie AG) 20.0 B Sdti' ~ -14A-~ l~zsse.~ ~ ' ' Gelllng and firmine of the applied poly~inyl chloride plastl801 wear layer takes place at an elevated tempe~ature in a hcate~
oven at about 300 F. for a-period of time of about 3 minutes, followed by a fusing of the polyvlnyl chlorlde layer~, and a blowine and foaming of the base gynthetic polymeric layer at an elevated temperature of about 430 F. for a period of tlme of about ons minute and forty seconds.

The polyvinyl chloride wear layer is then coated substantially uniformly to a wet thicknesg depth of about 1~ mils with the following acrylated polyurethane top coating compoaition which contains 1.93~ free available NC0.
Parts Acrylated urethane oligo~er 80 Tetraethylene glycol diacrylate 10 ~-vinyl pyrrolidone 15 To this formulation is added 3~ Vicure-10 (isobutyl ether o~
benzoin) photoinitiator.
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The curing of the applied polyurethane resin top coating t~ke~
place by passage through an ultraviolet unlt having a length of about 3 feet (2 lamp parallel unit, 12 inches long, 200 watts .
each lamp, medium pressure, mercury lamp) and a nitrogen atmos-phere at a rate of about 10 feet per minute.
The bond between the vinyl wear layer and the scrylated polyure-thane top surface coating is tested and is found to be strong and permanent and capable of reslstlng delamination very well. Primary chemical bonds exist between the dissimilar synthetic polymeric layers. ' 1~' ; ~ ~`

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EXAMPLE II - .
The procedures described in Example I artt followed substantially as set forth therein with the exception that the Oxyester T 1136 (V) in the wear layer is replaced by 15 parts by weight of Oxy-ester V 2922 (V), a highly branched polyester with hydroxyl groups, hydroxyl value 275 mg ~OH/g and an acld value less than 2 mg KOX/g (Veba Chemie AG). The bond between the vinyl resln wear layer and the acrylated polyurethane top surface coating is tested and is found to be strong and permanent and to re~ist delzmination very well. Primary chemical bonds exist between the dissimilar synthetic polymeric layers.

EXA~'PLE III
The procedures described in Example I are followed substantially as set forth therein with the exception that the Oxye~ter T 1136 -~
(V) in the wear layer is replaced by 20 parts by weight of OAY-ester B 926 (V), a hydroxyl-terminated polyester with slightly branched chains, hydroxyl value 91 mg KO ~g, acid value less than 2 mg KOX/g (Veba Chemie AG) The bond between the vinyl resin wear layer and the acrylated polyurethane top surface layer i5 tested and is found to be strong, permanent and to resist de-lamination very weil. Primary chemical bonds exist between the dissimilar synthetic polymeric layers.
EXAI~IPLES IV and V
The procedures described in Example I are followed substantially as set forth therein with the exception that the amount of Oxy-ester T 1136 (V) isl increase~l from 20 parts to 25 parts (Example IV)~ and decreased to 15 parts (Example V). The results of these Examples are found to be generally comparable to the results of Example I. The bond between the dissimilar synthetic polymeric layer3 is found to be strong and permanent and to resist delam-ination very well.

EXA~,PLE VI
The procedures de~cr~bed in Example I are followed sub3tantiOlly as set forth therein with the exceptlon that the Oxyester T 1136 B (v) ls replaced by an equivalent amount of Teracol~650, a poly-tetramethylene polyether glycol, molecular weight 650, hydroxyl number 1~3, acid number 0.05 max.

The results of this ExOmple are found to be generally comparable to the results obtained in Exemple I. The bond between the vinyl resin layer and the acrylated polyurethane re3in layer is tested and iB found to be Otrong and permenent and to resist de- -lamination very well. Primary chemical bonds exist between the t~o dissimilar synthetic polymeric layers.

EXAMPLE VII
- The procedures described in Example I are followed substantially as set forth therein with the exception that the Oxyester T 1136 (V) in the wear layer is replaced by an equivalent amount Or Pluracol~PeP 450, a polyether tetrol, molecular weight 400, hyd-roxyl number 560, acid number 0.05 maximum.
The results of this Example are found to be generally comparable to the results obtained in Example I. The bond between the vinyl resin WQar layer and the acrylated polyurethane top sur-face coating i8 tested and i6 found to be strong and permanent and to resist delamination very well. Primary chemical bonds exist between the two dissimilar ~ynthetic synthetic polymeric layers.
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The procedures described ln Example I are followed substantially as set forth therein with the exception that the acrylated poly-urethane top coating composition has the following formulationr Grams Acrylated urethane oligomer 80 Tetraethylene glycol diacrylate 10 2-ethylhexyl acrylate 15 Vicure-10 (isobutyl ether of b~nzoin) photoinitiator 3 (Free available ~C0 = 1.93~) The results Or this Example are generally comparable to the re-sults of Example I. The bond between the dissimilar synthetic polymeric materials is strong and permanent. Delamination is found to be resisted successfully.

EXAMPLE IX
The procedures described in Example I are followed substantially as set forth therein with the exception that the acrylated poly-urethane top coating composition has the following composition Crams Acrylated urethane oligomer 80 1,6-hexanediol diacrylate 10 2-ethylhexyl acrylate 8 Vinyl acetate 7 Vicure-10 (isobutyl ether of benzoin) photoinitiator 3 (Free available NC0 = 1.9~
The results of this Example are generally comparable to the re-sults of Example I. The bond between the dissimilar synthetic polyrneric materials is strone and permanent. Delamination i9 resisted very well.
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EXAl.iPLE X
The procedures descrlbed in Example I are foLlowed 6ubstantially as r3et forth therein with the added deflnltion that the acryl-ated urethane oligomer in thc top coating composition is derived ~i from Hylene~W methylene-bls(4-cyclohexylisocyanate),Teracolkk650 polytetramethylene ether glycol, and hydroxyethyl methacrylate.
The results are satisfactory and are generally comparable to the results obtained in Example I. (Yree, available NC0 = 2~) EXAMPLE XI
.
The procedures described in Example I are followed substantially as set forth therein with the added definition that the acryl-ated urethane oli~omer in the top coating composition iB derived from Hylene~W ~ethylene-bis(4-cyclohexylisocyanate), Teracol~650 polytetramethylene ether glycol, and hydroxyethyl acrylate. The rçsults are satisfactory and are generally co~parable to the re-sults obtained in Example I. (Free, available NC0 = 3~) EXA~PLE XII .¦
The procedures described in Example I are followed substantially as set forth therein with the added definition that the acryl-ated urethane oligomer in the top coating compositi~l is dlerived from Hylene~W methylene-bis(4-cyclohexylisocyanate), Plur~ 50 Tetrol polyoxyalkylene polyol based on pentaerythritol, and hydroxypropyl acrylate. The results are satisfactory and are ~enerally comparable to the results obtained in Exarrlple I.
(Frae, available NC0 = 4%) All free, available NC0 percentages cited in this Exat~ple and in all other Examples refer to the free, available NC0 in the top surface coating composition.
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EXAMPLE XIII
The procedures descrlbed ln Example I are followed substantially as set forth therein with the exception that the acrylated poly-urethane top coating composition i3 replaced by a conventional polyurethane top coating composition wherein the polyurethane is derived from Hylene W methylene-bis(4-cyclohexylisocyanQte) and Teracol 650 polytetramethylene ether glycol. Curing takes place at an elevated temperature of about 385 F. for 2 minutes and 45 seconds. The results are satisfactory and are generally con-parable to the results obtained in ~xample I. (Free, available NC0 = 2%) EXA~.PLE XIV
-The procedures described in Example I are followed sybstantially as set forth therein with the exception that the acrylated poly-urethane top coating composition is replaced by a conventional p~lyurethane top coating composition wherein the polyurethane i5 derived from isophorone diisocyanate (3-isoc~anatomethyl-3,5,5-trimethylcyclohexyl isocyanate~ and Pluraco~r650 Tetrol polyoxy-alkylene polyol based on pentaerythritol. Curing takes place at about 385 F. for 2 minutes and 45 seconds. The results are satisfactory and are generally comparable to the results obtained in Example I. (Free, available NC0 = 5%) EXAMPLE XV
The procedures described in Example X are followed substantially as set forth therein with the exception that the Hylene~
methylene-bis(4-cyclohexylisocyanate) in the top coating formu-lation is replaced by trimethyl hexamethylene diisocyanate. The results are satisfactory and are generally comparable to the re-sults obtained in Example X. (Free available NC0 = 2%) e n~t~rk r _ ~ r ~,, ~ ~

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Although several specific wor~ing Ex~mples of the inventive con-cept have been described ln particularity. the ~ame should not be conr~strued as limitative of the invention but aF merely illustra-ting specific materials and procedure6 which are preferred and typical. Other materialg and procedures may be used, as well as other equivalent featureg and agpect~i. without departing from the scope and the sp~rit of the appended claims.

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
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 and at least one plasticizer for said vinyl resin, and a second synthetic polymeric material containing a member of the group consisting of polyurethanes and acrylated polyurethane compositions, said synthetic polymeric materials being bonded in a strong and permanent primary chemical bond therebetween by a reaction product of a first synthetic polymeric material containing a vinyl resin, at least one plasticizer for said vinyl resin and from about 0.5% by weight to about 20% by weight of a chemical compound containing reactive hydrogen, and a second synthetic polymeric material containing a member of the group consisting of a polyurethane or acrylated poly-urethane composition and from about 0.5% by weight to about 10% by weight of free available isocyanate capable of reacting with said chemical compound containing reactive hydrogren in said first synthetic polymeric material.

2. A multi-layered construction as defined in claim 1 wherein said vinyl resin is polyvinyl chloride.

3. A multi-layered construction as defined in claim 1 wherein said chemical compound containing reactive hydrogen is a polyhydroxy compound.

4. A multi-layered construction as defined in claim 1 wherein said polyurethane is the reaction product of methylene-bis (4-cyclohexylisocyanate) and polytetramethylene ether glycol.

5. A multi-layerd construction as defined in claim 1 wherein said polyurethane is the reaction product of trimethyl hexamethylene diisocyanate and polytetramethylene ether glycol.

6. A multi-layered construction as defined in claim 1 wherein said polyurethane is the reaction product of isophorone diisocyanate and a tetrol polyoxyalkylene polyol based on penta-erythritol.

7. A multi-layered construction as defined in claim 1 wherein said chemical compound containing reactive hydrogen is a polyester-type polyol.

8. A multi-layered construction as defined in claim 1 wherein said chemical compound containing reactive hydrogen is a polyether-type polyol.

9. 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 which comprises:
including from about 0.5% by weight to about 20% by weight of a chemical compound containing reactive hydrogen in said vinyl resin material; providing from about 0.5% by weight to about 10%
by weight of free, available isocyanate in said polyurethane and acrylated polyurethane resin materials, bringing said vinyl resin material and said polyurethane and acrylated polyurethane resin materials into contact; and exposing said vinyl resin material and said polyurethane and acrylated polyurethane resin materials 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.

10. A method as defined in claim 9 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.

11. A method as defined in claim 9 wherein an acrylated polyurethane resin material is used and curing conditions take place by means of radiation curing.

12. A method as defined in claim 11 wherein an acrylated polyurethane resin material is used and curing conditions take place by means of mercury vapor arc radiation curing.