CA1155623A - Polyurethane polymerization processes and products - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A method of bringing about a heat-controlled polyurethane polymerization reaction between polyols and polyisocyanates which comprises, forming a foamable or non-foamable plastisol layer comprising a synthetic resin and a plasticizer therefor, firming the surface of the foamable or non-foamable plastisol layer, forming on the surface of the foamable or non-foamable plastisol layer a non-foamable plastisol wear layer comprising a synthetic resin, a plasticizer for the synthetic resin, and a polyurethane polymerization catalyst not having any polymeriz-ing effect on the synthetic resin but capable of bringing about a polyurethane polymerization reaction between polyols and polyisocyanates; firming the surface of the non-foamable plast-isol wear layer; forming on the surface of the non-foamable plastisol wear layer a top coating layer comprising unreacted polyols and unreacted polyisocyanates but essentially no poly-urethane polymerization catalyst, nor any reacted polyols nor any reacted polyisocyanates nor any polyurethane polymers or prepolymers; and heating the non-foamable plastisol wear layer and the top coating layer whereby the polyurethane polymeriza-tion catalyst in the non-foamable plastisol wear layer is be-lieved to migrate therefrom to enter the top coating layer com-prising the polyols and polyisocyanates to bring about a poly-urethane polymerizarion reaction therein. The products which exist during and subsequent to such polyurethane polymerization reaction are also included within the scope and the spirit of the present inventive concept.

Description

POLYURETH~NE POLYMERIZ~TION PROCESSES AND PRODUC~S
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THE FIELD OF THE INVENTION
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The present invention relate~ to heat-controlled polyurethane polymerization reactions or processes and to the products exi~ting during and re~ultin~ from 6uch reactions or proce~ses.
;
More particularly, the pre6ent in~ention relates to one-part, one shot, low viscos~ty, 100~ solids or non-volatile6, poly-urethane polymerization reactions or processes uithout employ-ing volatile organic golvents, nor requiring any prior pre-polymer formation, and being eggentially heat-controllable at wlll, E~en more particularly, the present inven~ion i8 con-cerned with polyurethane polymerization reactions or processe~
essentially utilizing raw materials only and involving one or more polyhydroxy compound~ or polyols with one or ~ore polyiso-cyanates in the presence of one or more polyurethane polymeri-zation cataly6ts.

THE B~C~ROUND OF THE INVENTION

In the commercial and industrial production of polyurethane polymerization product6 from polyols and polyisocyanates, the polymerization reaction often proceeds at a fairly rapid rate, once thè polyol6 and poly~socyanate~ are contacted by a suitable polyurethane polymerization catalyst, or otherwise exposed to suitable polymerization conditions. Quite often, æuch reaction rates are extremely rapid and do not allow for sufficient or adequate handling or proce6sing time for the polyurethane ; polymer to be formed and then carefully and properly ~inished or applied, particularly when it i8 in the form o~ a relati~ely-thin layer or coating to be applied to a suitable sub~trate. In other terms, the "pot life" of the polyurethane polymerization product being formed is too short.

.

In some ca~e~, a liquid prepoly~er iB formed, u~ually by react-ing an inadequate or in~u~ficient 8toichiometric amount of the polyol component with a stoichiometric exce~s of the polyi60-cyanste component, in the presence of a suitable polyurethane polymeri~ation catalygt. Such a liquid prepclymer can be sub-sequently mixed with additional polyol, shortly berore being applied to the de6ired subgtrate, and the polymerization re-action completed and the resulting polyurethane poly~er cured, as desired or required. Or, alternati~ely, additional polyol need not be aaded to the prepolymer but the polyurethane polymerization reaction completed and cured through reaction with moisture in the atmosphere by a moisture-curing proce6s.
Other processes involving the uge of amines are also known for the formation of polyurethane polymerization products.

However, regardlesg of whether the aboYe-described procedures or other procedures are used in the polymerization and curing of polyurethane polymers, if there is a shut-down or a delay in the commercial or industrial production line, the polymerization reaction ~hich continues during such shut-down or delay may pro-ceed too far during such time, or may be so completed that any further processing or other handling may not be feasible. For example, the viscosity of the polyurethane polymerization reaction mixture may increase to such a high level during such shut-down or delay that the pot-life time may be decreased to such an extent that suf~icient further working or handling pro-cedures are not possible. ~s one consequence, substantial quantitie8 of the partially reacted or partially cured poly-urethane polymerization products may have to be diRcarded.

. 1155623 And, even if there iB no ~hut-down or delay in the manufacturing cycle, the vi~cosity of the polyurethane polymerization reaction ~ixture containing prepolymerg i8 not alwayg a con~tant, as time progresses, but actually increases, while it awaits delivery from a source of ~upply to the point of actual delivery and applicat~on to a substrate, whereby ~iscosity variables ~ntro- ~
duce handling difficultieg during such application to the sub-8 trate.

The u~e of ~olatile solventg, normally of an organic nature, is therefore frequently resorted to, in order to control and to bring the viscosity of the prepolymer-containing mixture to within utilizable levelg, uhich, of course, introduces addi-tional ~ariables and handling difficulties into the manufac-turing process.

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PURPOSES AND OBJECTS OF T~E IN~ENTION

It i8 thererore a principal purpose and obaect of the present invention to provide for a one-shot, one part, low viscosity, 100% solids or non-volatiles process or method for polymerizing polyhydroxy compounds or polyols with polyisocyanates, wherein such compounds may be brought together and mixed and then held, if de~ired or neceæsary, for a considerable period oi time, or perhaps indefinitely, without entering into any polymerization or any other che~ical reaction, and then, subsequently, at a de-sired future time, to be applied as a thin layer or coating to a desired substrate and to be capable of remaining a~ a thin layer or coating on the desired substrate for a considerable period of time, if de~ired or neces~ary, ~ubstantially without any fear of a premature or oYerly-rapid polymerization or other chemical re-action, whereby sufficient and adequate time (pot-life) i~ pro-vided for proper or necessary handling, processing or finishing.

. . _ -`- 1 155623 ~nd then, at a desired or required sub6equ~nt time which iB con-trollably selected, and when all the nece~sary and reguired handling, processlng and finishing have been completed, to have - the polyurethane polymerization ~tart, under controlled time and temperature conditiong, to proceed promptly in a matter of a relatively short period of time through a curing period to a commercially acceptable tack-free condition.

It will ~mmediately be realized that one of the benefits of such a controlled polymerization and curing process i8 the reduction to an absolute minimum, or perhaps the ~irtually complet~ elim-ination, of any 1088 or forced discarding or dispo6al Or any reaction material~.

;BRIEF SUMMURY OF THE INVENTION

It has been found that such purposes and ob~ects, as well as any other purpose~ and ob~ects of the present invention which ~ill become clear from a further reading and under~tanding of this disclosure, may be accomplished by a method or proces~ oY bring-ing about a heat-controlled polyurethane polymerization reaction between one or more polyols and one or more polyisocyanates which comprises~ forming a foamable or non-foamable plastisol layer comprising a synthetic resin and a plasticizer therefor~
gelling or firming the surface of the foamable or non-foamable plastisol layer~ rorming on the firmed or gelled surface of the foamable or non-foamable plastisol layer a non-foamable plasti-sol wear layer comprising a 6ynthetic resin, a pla~ticizer for the synthetic re~in, and a polyurethane polymerization catalyst not having any poly~erizing effect on the synthetic resin but capable of bringing about a polyurethane polymerizatio~ reaction between polyols and polyisocyanatecs gelling or firming the surface of the non-foamable plastisol wear layerl forming on the firmed or gelled 6urface of the non-foamable pla8ti801 wear layer a top coating layer comprising polyols and polyisocyanate8 .. . . .. ~

1 155~3 but essentially no polyurethane polymer~zation cataly~ts, nor any polyols reacted with any polyisocyanates, nor any poly-urethane polymer~ or prepolymers or any polymerization product~
of polyols and polyisocyanateg~ and heating the non-foamable plastisol wear layer and the top coat~ng layer, whereby the polyurethane polymerization catalyst in the non-foamable plastisol wear layer is believed to migrate therefrom to enter the top coating layer comprising the polyols and polyisocyanates to bring about a pol~urethane polymerization reaction therein.
The products ~hich exist during and subsequent to ~uch polyure-thane poly~erization reaction are also included within the scope and the spirit of the present inventive concept.

BRIEF DESCRIPTION OF THE DRAWINGS
-In the rollowing specification and accompanying self-explanatory drawings, there are described and illustrated pre~erred and typ- -ical embodiments of the present invention but it i8 to be appre-ciated that the broader aRpects and features of the present in-vention are not to be construed as limited or restricted to such preferred and typical embodiments as are ~pecifically described and illustrated herein, but to include various other similar and equivalent embodiments, as are determined by the scope and the spirit of the appended cla~ms.

Referring to the accompanying self-explanatory drawings, FIGURE 1 iæ a fragmentary, diagrammatic, elevational, cro~s-sectional view of one embodiment of the present invention showing a fibrous backing layer, a non-foama~le or foamable plastisol layer thereon~ a non-foamable plastissl wear layer thereon~ and a top coating layer~

FIG. 2 is a fragmentary, diagra~matic, elevational, cros~-sectional view of the embodiment of Figure 1 but showing the effects of including a blowing or foaming agent in the plastisol layer on the fibroug backing layer, subsequent ~o expo~ure to a blowing and foaming processl FIG. 3 is a frag~entary, diagrammatic, elevational, cro~3-~ectional view of the embodiment Or Figures 1 and 2 but showing the effect~ of including blowing or foaming inhibiting agents in ~elec~ed areas of the pla~ti801 layer~ and ~IG. 4 is a fragmentary, diagrammatic, elevational, cros8-sectional view of a simpler and legs comprehensive embodiment of the principles of the pre~ent inventive concept.

These Figure6 have not been drawn precisely or accurately to the same scale. Some portions and some dimensions have ~een drawn to a larger scale, wherea~ certain other portions and certain other dimensions have been drawn to a smaller Rcale . Thi~ has been done primarily merely to ~ring out more clearly so~e Or the finer detail~ o$ the ~maller portions and to accentuate ~ome of the details of the more important portions. It is believed that sush will lead to a more facile and clearer under~tanding of the principles of the pre~ent in~entive concept.

__ _ . _ _ .. . _ . _ ~__ _ . .. . . , = ~ _ __ _ .. _ . .. = . ... . .

: 1155623 GENER~L DESCRIPTION OF THE INVENTION

With ~peeific reference to Figure 1 of the drawing~, there ie ~hown therein a resinou~ polymer sheet material 10 compriEing a fibrous backing sheet ~aterial or substrate 12 upon which ha8 been depo6ited and adhered a resinous polymer composition layer 14, on top of which has been deposited and adhered another relatively ~lat, resinous poly~er composition wear layer 16, : and on top of all these layer~ i8 a top coating 18.

THE ~ACKING SHEET MATERI~

A relatively flat, backing web or gheet material may be used, ~f ~o desired or required, a~ the fibrous backing sheet material or substrate lZ, the most commom in the industry being a fibrous, felted asbesto~ or cellulo~ic 6heet. Many other types and forms of fibrous backing sheet materials are, Or course, utili~able ~ithin the ~cope and spirit of the present invention and many of these materials are described in the prior art, ~uch as in U.S.
Patent 3,293,094, Such ribrou~ backing sheet materials do not relate to the essence of the present in~ention and may be omitted if 80 desired.

THE RESINOUS POLYMER COMPOSITION LAYER
-The resinous polymer compo~ition layer 14 may comprise a potent- -ially foamable or non-foamable resinous polymer composition which may be made by well-kno~n conventional and standard methods and techniques and may contain one or more synthetic resins, pref-erably a polymer, copolymer, homopolymer, or terpolymer Or vinyl chloride, as the main constituent.

1 ~55S23 Although polyvinyl chloride is the preferred and typical resin, many other synthetic resins are equally applicable. The spec-ific synthetic resins which are used do not relate to the es-sence of the present invention and many other suitable resins are set forth in the previously cited U. S. Patent.

Of particular use are the copolymers of vinyl chloride with vinylidene chloride or with esters such as vinyl acetate, vinyl propionate, vinyl butyrate, or alkyl substituted vinyl esters.
The copolymers of vinyl chloride with various acrylic compounds, such as acrylic acid and metharcylic acid and the esters thereof, are also of use. Other resins such as polystrene, substituted polystyrenes, polyolefins such as polyethylene and polypropylene, acrylates and methacrylates, polyamides, polyesters, etc., are also applicable to the principles of the present invention.

Also, although such resins are preferably used as plastisols in the form of a dispersion or suspension of the resin in a plast-cizer therefor, aquasols or aqueous latices and organosols are of use in which the dispersing or suspending medium is water or an organic solvent.

A few preferred and typical plasticizers used in the formulation of such plastisols are dibutyl sebacate, dioctyl sebacate, butyl benzyl sebacate, dibenzyl sebacate, dioctyl adipate, didecyl adipate, dibutyl phthalate, dicapryl phthalate, dioctyl phthal-ate, dibutoxy ethyl phthalate, butyl benzyl phthalate, dibenzyl phthalate, di(2-ethylhexyl) phthalate, alkyl aryl modified phthalate esters, alkyl aryl hydrocarbons, tricresyl phosphate, octyl diphenyl phosphate, dipropylene glycol dibenzoate, dibasic acid glycol ester, epoxidized soya oil, epoxidized tall oil esters, and many other primary and secondary plasticizers.

g ~ther constituents of the resinous polymer composition include:
a blowing or foaming agent, such as azodicarbonamide, if a blowing or foaming procedure is desLred; various accelerators, initiators, or catalysts such as diabasic lead acetate, dibasic lead phosphate, etc.; various heat and light s~abilizers such as dibasic lead phosphite, phenyl phthalate, etc.; UV absorbers;
colorants such as dyes and pigments, particularly titanium di-oxide; solvents and diluents such as methyl ethyl ketone.
methyl isobutyl ketone, dodecyl benzene, etc.; fillers such as clay, limestone, etc.; viscosity improvers; anti-oxidants;
bacteriostats and bacteriocides; etc.

The specific nature and the particular physical properties and characteristics of the various constituents of the resinous polymer composition do not relate to the essence of the present inventive concept and further specific elaboration of such add-itives is believed unnecessary and not required. All of these constituents are well known and conventional in the industry and many are set forth in the previously cited U. S. Patent.

The thickness of the resinous polymer composition, as it is applied to the backing sheet material and is still wet, is in the range of from about 0.005 inch to about 0.060 inch.

After the resinous polymer composition has been applied to the backing sheet material, it is then heated in an oven or other suitable heating apparatus maintained at an elevated temperature of from about 240 F. to about 450 F., and preferably from about 260 F. to about 410 F., for a period of time of from about 1 minute to about 5 minutes, whereby it gels and becomes firm. The temperature and the time are interdependent and the higher the temperature, the shorter the time~ and vice versa.
The elevated temperature, however, is not that high as to act-ivate or decompose any blowing or foaming agent which may be in-cluded in the formulation of the resinous polymer composition as to cause blowing or foaming at this time.
.

THE PRINTING OF THE GELLED RESINOUS POLY~ER COMPOSITION

The gelled and firmed resinoug polymer composition i~ then printed or coated with a printing ink composition containing a colorant such as a dye or a pigment, if a de~ign or a pattern i8 desired or required to appear in the final product. The print- ~
ing composition may al~o contain resins, plasticizers, stabili-zers, anti-oxidants, blowing or foaming inhibitors in selected area6, ctc. Drying pf the applied print~ng ink CompoBition i8 accomplished by air-drying, or by conventional heating and drying procedureg. Preferred and typical printing ink composi-tlons are to be noted in the previou~ly cited U. S. Patent~

.
THE WEAR L~YER

The relatively flat, re~inoug polymer composition wear layer 16 has an average thickness of from about 0.002 inch to about 0.025 inch and is applled subgt~ntially uniformly to the surface o~ the printed, gelled and firmed reginous polymer compo6ition 14. The wear layer 16, in normal practice, i8 u6ually a çlear, unpig-mented resinous polymer compositîon and its basic purpose is customarily to give to the resilient floor co~ering improved wearing qualities. Many of the constituents of the previously described non-foamable resinouæ poly~er compositions are also present in the formulation of the wear layer 16, notably th~
polyvinyl chloride polymers, or the other previou~ly mentioned polymers, as well as plasticizers! ~tabilizers, etc. Blowing or foaming agents and pigments or dyes are normally omitted.
Typical formulations of pre~erred and typical wear layer~ 16 are to Oe found in the previously cited U. S. Patent.

Additionally, there is lncluded in the wear layers 16 of the pre~ent resinous polymer compositions 14 substantially uniformly throughout a polyurethane polymerization catalyst which does not possess any polyurethane polymerizing, or any oth~r chemica~ or phy~ical effects on the particular synthetic resin or blend of . . s 11556~3 synthetic resins in the wear layer 16 but i8 capable, ho~ever, sf brlnging about ~ polyurethane polymerization o~ ~uitable polyhydroxy compound~ or polyols ~ith 8uitable polyi~ocyanates, when and if brought into contact therewith wnder the proper polymerizing condition~.
-THE POLYURETH~NE POLYMERIZATION C~T~LYSTS

The particular polyurethane polymerization catalyst which i8included substQntially uniformly in the wear layer 16 doe~ not relate to the es~ence of the present invention and many cata-lyst~ u~eful for such purpo6e are well known in the indu~try.
Organo-metallic compound8, particularly of zinc, lead and tin~
zinc soaps~ and suitable tertiary amines are among the most frequently used. Preferred and typical polyurethane polymer-ization catalysts include~ dibutyl tin dilaurate, dibutyl tin di-2-ethylhexoate, dibutyl tin diacetate, dibutyl tin oxide, tetramethyl tin, dibutyl tin maleate, dimethyl dioctyl tin, stannous octoate, lead octoate, ~inc octoate, zinc 2-ethyl hexa~
anoate, lead naphthenate, copper naphthenate, N-methyl diethan-olamine, N,N-dimethyl ethanolamine, N-methyl morpholine, diethyl cyclohe~ylamine, triethylamine, etc.

Such polyurethane polymsrization catalyst~ are normally present in the wear layer 16 in the range of rrom about 0.007% to about 10% by weight, and preferably from about 0.07% to about 2% by ~eight, ~ased on the total weight of the wear layer 16.

After the wear layer 16 has been applied to the printed, gelled and firmed resinou~ polymer composition 14, it i8 then heated in an oven or other suitable heating apparatus ~aintained a~ an el-evated temperature of fro~ about 240 F. to about 450 F., and preferably from about 260 F. to about 410 F. for a period of time of from about 1 minuts to about 5 minutes, whereby it gels and become~ rirm. ~gain, the temperature and the time ar~ inter-dependent and no blowing or foaming take place at this time.

_ . . ..

. 11~5623 If desired, the preceding gelling and firming process may be combined with a fusing and blowing or foaming process by heatlng to a higher temperatur~, the specific temperatures of each pro- -cess being dependent upon the chemical and physical properti~s and characteristic~ of the reginous polymer composition 14 and the wear layer 16, the ~pecific synthetic resins therein, and the nature of the blowing or foaming agent employed. Under normal conditiong, fuging and blowing or foaming may taks place by exposure to ele~ated temperatures of from about 2~0 F. to about 460 F. and pr~ferably from about 270 F. to about 420 F~
for periods of time of ~rom about 2 minutes to about 10 minutes.

The resulting product is shown in Figure 2, wherein there i8 illu~trated a blown resinous polymer sheet material 20 comprising a fibrous backing sheet material or substrate 22 upon which has been deposited and adhered a blown resinou~ polymer composition layer 24, on top of which hag been deposited and adhered another relati~ely flat, reginous polymer composition wear layer 26, and a top coating 28 to be de~cribed more fully hereinafter.

And, if blowing or foaming inhibitorg were used in order to mod-ify the blowing or foaming effects, the re~ulting product is shown in Figure 3, wherein there is illustrated a blo~n and em-bossed resinous polymer sheet material 30 comprising a fibrous backing sheet material or substrate 32 upon which has been depos-ited and adhered a blown re~inous polymer composition layer 34, on top of which has been deposited and adhered another relatively rlat, but no~ embossed, resinou~ polymer composition wear layer 36, and a top coating 38 comprising lands or higher portion~ 37 and mortar~ or lower portions 39, which will be descr~bed in greater detail hereinafter.

.. _ , , . _ _ _ _ _ . , ~ ......... . ~ ,,, . _, _, . _ .. , , .. ..... . _ _ _,. "

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` ` 1155623 THE TOP COATING

The top coating 28 or 38 which is applied to the firmed and gelled or fused surface of the wear layer 26 or 36 comprises a sub6tantially uniform mixture of polyols and polyisocyanates~
additives, such as surfactantsl and other constituents, as de-sired or required. It is to be observed particularly that such polyols and polyisocyanates are not reacted with each other to any extent at this time prior to their application to the firmed and gelled or fused surface of the wear layer 26 or 36 and that, consequently, there are no polyurethane polymers or prepolymers present in such mixture. Additionally, it is to be noted that there are no polyurethane polymerization catalysts present and that such uniform mixture is applied as a top coating 28 or 38 to the firmed and gelled or fused surface of the wear layer 26 or 36 which, as a result of such firming, gelling or fusing, is not that porous or permeable that the top coating 28 or 38 read-ily penetrates thereinto. Therefore, there is substantially no interaction or chemical reaction to speak of at the time of ap-plication or for a considerable period of time thereafter.

The particular proportions of the polyols and the polyisocyan-ates in the top coating 28 or 38 do not relate to the essence of the present invention but, normally, the NCO/OH ratio is in the stoichiometric range of from about 1/1, or 1.01/1 which repre-sents an excess of NCO, up to a stoichiometric ratio of about

2,1, with preferred ranges of from aboutl.O5:1 to about 1.711.
.
The thickness of the top coating mixture will vary according to the future use of the product and is normally in the range of from about 4 mil to about 15 mils.

THE POLYHYDROXY COMPOUNDS OR POLYOLS
. . _ The polyhydroxy compounds or polyols may be selected from a very - wide variety of diols, triols, tetrols, or various other polyols, or mixtures thereof, from various sources.

, .

THE DIOLS

The diols used in carryin~ out the principles of the present in-ventive concept may be selected from a large group of diols or glycols, or derivatives thereof, such as polyether diols, poly-ester diols, etc. Illustrative of such suitable diols but not limitative thereof are the following-ethylene glycoldiethylene glycol triethylene glycol tetraethylene glycol pentaethylene glycol propylene glycol trimethylene glycol tetramethylene glycol pentamethylene glycol hexamethylene glycol neopentyl glycol The polyether glycols aFe condensation products of one or more of the above-identified glycols, or mixtures thereof, with an alkylene oxide having from 2 to ~ carbon atoms, such as ethylene oxide, propylene oxide, trimethylene oxide, 1,2-butylene oxide, isobutylene oxide, 1,4-tetramethylene oxide, pentamethylene oxide, or mixtures thereof. Also of use are the polyester glycols which are condensation products of one or more of the above-identified glycols, or mixtures thereof, with various saturated or unsaturated, aliphatic or aromatic dibasic acids, or mixtures of such acids.

THE TRIOLS

... ... .. . . .. , ., .. , .. _ _ _ _ The triols or trihydroxy-containing compounds used in carrying out the principles of the present inventive concept may be se-lected from a large group of triols, or derivatives, or con-densation products thereof, such as polyether triols, polyester triols, etc. Illustrative but not limitative of such triols are the ~ollowing-glyceroll,l,l-trimethylol propane l,l,l-trimethylol ethane 1,2,3-butanetriol 1,2,4-butanetriol 1,2,3-pentanetriol 1,2,3-hexanetriol 1,2,4-hexanetriol 1,2,~-hexanetriol 1,2,6-hexanetriol 2,3,4-hexanetriol 1,3,6-hexanetriol The derivatives and the condensation products of such triols are formed by chemical procedures analogous to the chemical proced-ures used in deriving analogous derivatives and condensation products of the diols, as described previously hereinbefore.

' ' -` 11S5623 THE TETRO~S

The tetrols or tetrahydroxy-containing compounds used in carrying out the principles of the present inventive concept may be se-lected from the following polyols, or derivatives thereof, or condensation products thereof, as previously described. These polyols are, of course, illustrative but not limitative.

erythritol pentaerythritol OTHER POLYOLS
, Polyols of higher functionality than four are also generally of use in the application of the principles of the present inventive concept. Polyhydroxy-containing compounds including pentols, such as adonitol and arabitol, for example, and hexitols, such as dulcitol, mannitol and sorbitol, for example, are also of use.
These, of course, may be used as is, or in the form of deriva-tives thereof, or condensation products thereof with various alkylene oxides, as previously described herei~. "RUCOFLEX"
(Hooker) R-102, a highly branched, low molecular weight of 700, ester polyol, having a hydroxyl number of 400, and a functional-ity of five is a specific example o~ such a polyol of higher functionality.

Caprolactone polyols are also generally of application within the broader scope of the present invention. Such caprolactone polyols are based on or derived from hydroxy carboxylic acids and are used as is, or as polymerization products thereof with various alkylene oxides, or as other derivatives thereof. 0f particular application are caprolactone polyols PCP-0300 and PCP-0301 (Union Carbide) which are liquid caprolactone polyols having low viscositi~s, are trifunctional, have melting points of 20 or less, with molecular weights between about 300 and 540, and hydroxyl numbers, that is, mg. KO ~ g. o~ between about 560 and 310, respectively.

Other polyhydroxy-containing compounds are also of use within the broader scope of the present inventive concept, provided they a~e capable of furnishing the necessary hydroxyl for re-action with the isocyanate in the formation of the polyurethane polymer, Typical of such other polyhydroxy-containing compounds are the poly(hydroxyalkyl) derivatives of such compounds as the alkylenepolyamines t or the various polyether polyols with amine.
One specific example of such a group is "QUADROL'~ (BASF-Wyan-dotte) which is N,N,N',N'-tetra-kis (2-hydroxypropyl) ethylene-diamine, a colorless viscous liquid having a functionality of four, a molecular weight of 292, a hydroxyl number of 770, and a boiling point of 190 C. (1 mm).

THE POLYIS0CYANA~ES

, _ . _ ... .. . . ~ _ . .. _ ., The polyisocyanates used in carrying out the principles of the present invention are selected from a large group of aliphatic, aromatic, cycloaliphatic, and heterocyclic polyisocyanates.
They include the following, which are illustrati~e but not limitative.

4,4'-methylene-bis-cyclohexyl diisocyanate hexamethylene-1,6-diisocyanate -tetramethylene-1,4-diisocyanate cyclohexane-1,4-diisocyanate 1,4-cyclohexylene diisocyanate 2,2,4-trimethyl-1,6-hexane diisocyanate trimethyl hexamethylene diisocyanate dimer acid diisocyanate trimer of hexamethylene diisocyanate ethylene diisocyanate ethylidene diisocyanate 2,4-tolylene diisocyanate 2,6-tolylene diisocyanate p-phenylene diisocyanate m-phenylene diisocyanate 4,4'-methylene bis(phenylisocyanate) naphthylene-1,5-diisocyanate 4,4'-biphenylene diisocyanate furfurylidene diisocyanate butane-1,4-diisocyanate isophorone diisocyanate The top coating 28 or 38, comprising polyols and polyisocyantes, after being formulated and mixed, comprises a stable mixture which does not undergo any polyurethane or other poly~erization, or chemical reaction, or viscosity or other physical change, over a long period of time, extending into weeks or even months, and hence the formulated and mixed top coating 28 or 38 may be stored, as desired or required, or held in readiness, for use substantially indefinitely.

Additionally, such a top coating 28 or 38, comprising polyols and polyisocyanates, even after being applied at room tempera-tures to the firmed surface of the wear layer 26 or 36 contain-ing the polyurethane polymerization catalyst, does not readily or rapidly undergo any polyurethane polymerization or chemical reaction, or change in viscosity or other physical change, for a considerable period of time, extending into many hours, or even days, and hence sufficient time is provided in case of a line shut-down, or other delay in the manufacturing process.

It is believed that the gelling or fusing processes which firm the surface of the wear~layer 26 or 36 prevent any ready or rapid interaction or reaction between the polyols and polyisocyanates in the top coating 28 or 38 and the polyurethane polymerization catalyst in the wear layer 26 or 36. And then, subsequen~ly, when sufficient heat is applied to the wear layer 26 or 36, it is believed that the polyurethane polymerization catalyst therein migrates therefrom to enter the top coating 28 or 38 to bring about a polyurethane polymerization reaction between the polyols and the polyisocyantes therein.

Such subsequent sufficient heating is applied to the top coating - 28 or 38 and to the wear layer 26 or 36 during heating at ele-vated temperatures of from about 250 F. to about 460 F., and preferably from about 2?0 ~. to about 420 F., for periods of time of from about 2 minutes to about 10 minutes during which time curing of the polyurethane polymer takes place.

` 115562`3 ~o ~lthough the pre~ent invention has been specirically described in great particularity with reference to i~B application to resilient floor coverings or 8imilar product~ comprising a fibrous backing 6heet material or 8ubstrate~ a re~inous polymer composition layer~ a wear layer~ and a top coating, a~ shown in Figures 1 - 3, the principles of the present invention ar~
equally applicable to ~impler or more complex products and constructions.

simpler construction i8 shown in Figure 4, wherein there i~
illustrated a relati~ely flat, re~inous polymer sheet material 40 comprising a relatively flat, fibrous backing Rheet material 42,lwhich may be omitted, if 80 desired~ a resinous polymer composition layer 44~ and a top coating 48.

The fibrous backing sheet material or ~ubstrate 42 is similar to the previously de~cribed fibrous backing sheet material or substrate 12 of Figure l but, ag indicated hereinbefore, may be omitted, if 90 de6ired.

The resinous polymer composition layer 44 i8 substantially iden-tical to the previously described resinous polymer compos~tion layer 14 of Figure 1, with one ~ery important additional ingred-ient included substantially uniformly therein in the ~ame range of concentrations as de~ined previously. Such additional in-gredient comprises one or more poly~rethane polymerization cata-lysts, such a6 was included in the wear layer 16 of Figure 1.
Such polyurethane polymerization cataly~ts have no polyurethane polymerization eirects or any other chemical or physical errccts on the particular synthetic resin or blend Or resins included in the resinous polymer composition layer 44 but are capable o*
bringing about a polyurethane polymerization of suitable pol~-hydroxy compounds or polyols with suitable polyisocyanates, when and if they are brought together under the proper polymeri-zing conditions.
-`~ . , 115~623 The surface of the re~inoug polymer composition layer 44 i8gelled and firmed, ag previously described, and may be fused and blown or foamed, a8 de~cribed previou~ly, such as shown in Figure 2, ir ~ blow~ng or foaming agent, ~uch ae azodicarbon-amide, i8 included in the original formulation.

Ths top coating 48, containlng gimilar polyhydroxy compounds or polyol~ and similar polyi80cyanate8, a8 mentioned previously, i8 applied to the firmed surface of the resinous polymer ¢om-position 44, as de~cribed previou81y~ in connection with Fig-ures 1 - 3. The top coiting 48, prior to itB application to the firmed 6urface of the reæinous poly~er composition layer 44, i8 a very stable mixture and does not undergo any chemical or physical changes for long periods of time extending into weeks or monthg. The top coating 48, even after application to the resinous polymer composition layer 44 containing the poly-urethane polymeri~stion catalysts, does not readily or rapidly undergo any polyurethane polymerization or chemical or physi-cal change, such as a change in vi~cosity, for a considerable period of time extending into many hours, or even days. Hence, ~uificient time is pro~ided in case of a line shut-down or a delay in the manufacturing process.

Gelling or firmi~g of the various resinous polymer composition layers, or fusing and blo~ing or foaming, or curing o~ the poly-urethane polymer, takes place within the pre~iously mentioned temperature and time limits in ovens or other suitable heating apparatus.

- ` ~ 1 155623 The present invention will be further described with particular reference to the following specific examples wherein there are disclosed preferred and typical embodiments of the present in-vention However, it is to be pointed out that such specific examples are primarily illustrative of the principles of the present invention and that the specific materials, chemicals, patterns, designs, and other particular aspects described should not be construed as limitative of the broader aspects of the present invention, except as defined and limited by the scope and the spirit of the attached claims.

1 1 5 ~62 3 2~

EX~MPLE I

The relatively flat, ribroug, backing gheet mater~al i8 an O.030 inch thick felt sheet of asbestos fibers ~mpregnated with 5% of a urea-formaldehye res~n and 25% of a copolymer o~
butadiene and acrylonitrile. The re8in-impregnated asbestos fiber shest is heated and the re8in iB cured. In addition, the asbegtog f~ber 8heet ig coated with a 8iZ~ of one-halr methyl methacrylate and one-half butyl acrylate in an amount equal to 0,025 poun~s per ~quare yard, followed by a drying o~ the size coat.

The potentially foa~able pla8ti~01 coating composition which i8 applied ~ub~tantially uniformly to the surface of th~
backing sheet material hag an average thickness of about 0.015 inch (as applied and Etill wet) and has the ~ollowing formu-lations Parts Polyvinyl chloride, disper~ion grade, speci$ie vi~C08ity 0 . 6 5 Polyvinyl chloride, dispersion grade, ~pecific viscosit~ 0.4 5 Butyl benzyl phthalate plasticizer 52 ~lkyl aryl hydrocarbon secondary plasticizer 18 ~zodicarbonamide blo~ing agent 3 Dibasic lead phosphite 6tabilizer-accelerator 2 Titanium dioxide pigment 5 The potentially foa~able plastisol coating compo~ition ~s heated and gelled to a firm condition in an oven maintained at an elevated temperature of about 300 F. ~he exposure time for the heating and gelling iB about thre~ minutes.

The gelled plasti~ol i8 then printed in the desired pattern or design by printing inks haYing the ~ollowing formulations by weights -``` . 1155623 Parte Vinyl chloride-vinyl acetate copolymer 8.5 Methyl ethyl ketone 51.5 Titsnium dioxide pig~ent (55%) 25,0 -Trimellitlc anhydride inhibitor 15.0 Parts V~nyl chloride-~inyl acetate copolymer 13.5 Methyl ethyl ketone 61.5 Pigment 25.0 No inhibitor -The applied printing ink compo~itions are heated and dried.

~ wear layer composition having the following formulation by weight i8 then applied to the gelled, printed, dried plasti~ol substantially uniformly to an average thickness of about 0.010 inch (as applied and still wet) Part~
Polyvinyl chloride, di~ersion grade, specific viscosity 0.5 95.0 Polyvinyl chloride, suspension grade. ~pecific viscosity 0.35 5-~lkyl aryl modified phthalate ester plasticizer 38~0 Epoxidized tall oil ester secondary plasticiz~r 5.0 2,2,4-trimethyl-1,3-pentanediol diisobutyrate 7.
Stabilizer 3 Viscosity control agent 1.2 Dibutyl tin dilaurate 0.11 (0.07~ by weight o~ total formulation) The wear layer composition iB heated and gelled to a firm con-dition in an oven ~aintained at an ele~ated temperature of about 300 F. The exposure ti~e i8 about three minutes in the oven.

1 155~23 The heated, gelled product ig then heated in a fusion oven maintained at an elevated temperature of about 385 ~. for a period of exposure time of about 2 mnutes and 45 seconds.
Fu6ion of the polyvinyl chloride re~ins takes place, along with the decomposition or acti~ation of the azodicarbonamide blowing or ~oaming agent and the plagti~ol composition iB blown or foamed and embo~sed in accordance with the printed pattern or de~ign containing designated area~ ~ith trimellitic anhydride inhibitor therein and other degignsted areas not containin~ any inhibitor.

The fused and blown or foamed, embo~sed product ~8 then coated to a thicknes~ of about 1-1/2 mils by means o~ an applicator with a top coating having th~ following formulationt Grams "Hylene~ W (DuPont) methylene-bis(4-cyclohexylisocYan-ate), molO wt. 264, 31.8% min. NC0 content 85.8 UTeracol 650 (DuPont) polytetramethylene ether glycol mol, wt, 650, hydroxyl ~umber 174 9.8 "Pluracol" PeP 650 ~B~SF Wyandotte) polyoxyalkylene polyether tetrol, mol. wt. 600, hydroxyl number 374 69.0 Q43667 reactive silicone wetting agent (Dow Corning3 mol. wt. 2400, hydroxyl nu~ber 47 0.12 The top coating i8 prepared as follo~s~

The methylene-bis(4-cyclohexylisocyanate) i8 premixed with the reactive silicone wetting agent at room temperature and the -glycol and tetrol are 810wly added thereto, with thorough mixing, again at room temperature. No reaction Or the diiso-cyanate and th~ glycol and tetrol take place and there i8 no rormation Or any polyurethane polymer or prepolymer. The ~ixed materialg have a Broo~rield visco~ity Or 125 ce~tipoises, as 1 155~23.

determined with a # 1 spindle at 20 r.p.m. at 77 F. (25 C.).
~t no time prior to the application of the top coating to the fused and blown or foamed, embo~ged product ~ the temperature of the mixture of diisocyanate, glycol and tetrol allowed to exceed lsO~F. t66 C,), The top coating, arter application to the fused and blown or foamed, embo~sed product, i8 heated and dried in an oven main-tained at an eleYated temperature of about 300 F, Th~ time o~ e~posure to the elevated temperature i8 about 5 minutes.
Polymerlzation of the diisocyanate and the glycol and tetrol takes place during this time, due to migration o~ the d~butyl tin dilaurate catalyst fro~ thc polyvinyl chloride wear layer.
Curing of the polyurethane polymer iB also acco~pli~hsd prior to removal from the heated oven.

The re&ulting polyurethane polymer top coating i8 found to po~sess good resistance to abra6ion and to sol~ent and chemical attac~, good flexibility and impact resistance, good toughnes~, good high gloss rstention, good surface text~re, good weather-ability, and iB con8idered eminently commercially accsptable.

EX~MPLE 2 The procedure~ described ~n Example 1 ar~ followed substantially a~ ~et forth therein with the exception that the top coating has the followin~ formulationt Grams Hylene W (DuPont) methylene-bis(4-cyclohexylisOcyan- -ate), mol. wt. 264, 31.8~ min. NC0 content - ~S.8 "Terecol~ 1000 (DuPont) polytetramethylene ether gl~col mol. wt. 1000, hydroxyl number 113 25.0 . .

~Pluracol~ PeP 650 (BASF Wyandotte) polyo~yal~ylene polyether tetrol, ~ol. ~t. 600, hydroxyl number 374 67.5 Wetting a~ent 0.25 , In addition, there iB no dibutyl tin dilaurate polyurethan~
polymerization cataly~t in the pla~tl601 wear layer.

~t the end of 5 minutes of heating in a fusion oven at 300 F., the surrace o~ the top coating iB still wet and very tacky.
This iB due to the absence of any polyurethane poly~erization ca~alyst in the plasti~ol ~ear layer and the lack Or polymeri-zation of the polyol6 and the polyi~ocyanates in the top coating layer.

1 15~623 .

The procedures described in Example 1 are followed substantially as set forth therein, with the exception that 0.2 grams of dibutyl tin dilaurate polyurethane polymerization catalyst is included in the initial original preparation of the diisocyan-ate-diol-tetrol top coating mixture which is subsequently ap-plied to the surface of the fused and blown or foamed embossed product. Two separate samples are run individually and the pot life is very undesirably reduced in each case to 30 minutes, presumably due to the presence of the dibutyl tin dilaurate polyurethane polymerization catalyst in the diisocyanate-diol-tetrol top coating mixture and the concomitant polymerization and formation of polyurethane polymer or prepolymer therein, prior to its application to the fused polyvinyl chloride wear layer.
This is.to be compared to the results obtained by application of the principles of the present invention wherein pot times of at least 24 hours (1440 minutes) are obtained in all samples wherein the diisocyanate-diol-tetrol top coating mixture does not include any polyurethane polymerization catalyst, nor any polyurethane polymer or prepolymer prior to application to the fused, em-bossed polyvinyl chloride wear layer.

-The procedures described in Example 1 are followed substantially as set forth therein, with the e~ception that the applicator so functions that a 1~ mil thick top coating mixture is applied to most of the surface of the fused poly~inyl choloride wear layer, except for a narrow ~ inch wide strip in the length-wise machine-direction approximately 18 inches from the trimming edge. Such narrow ~ inch wide strip receives a top c~ating mixture which is 13.8 mils thick. It subsequently shows no tackiness after the normal curing operation, passes cross-hatch adhesion, and is equal to low film thickness in strain resistance.

.

1 155&23 ,., EX~MPLE 5 The procedures described in Example 1 are followed ~ubstantially a~ set forth therein with the exception that the amount of the dibutyl tin dilaurate polyurethane polymerization cataly~t is increased to 0.14% by ~eight Or the total formulation.

The results obtained in thi~ Example 5 are generally comparable to the re~ults obtained in Example 1. The resulting products are generally similar and the principles of the pre~ent inve~- :
ti~e concept are equally applicable. The polyurethanc polymer top coating exhibits generally comparable characteri~tics and properties.

1155~23 EXAMPLES 6-ll The procedureg de~cribed in Example 2 are follo~ed substantially as ~t ~orth therein with the exc~pti3n that the follow~ng amounts of dibutyl tin dilaura~c polyurethane polymerization catalyst are included ln the pla~tisol wear layer~ ~

Example 6 0.007 Exampie 7 0.014%

Exa~pl~ ô 0.021%

Example 9 0.028 -- , Example lO 0.035 Example ll 0.043%

Tack ~as ~easured after 5 minutes of heating at 300 ~. with the follo~ing results, all of ~hich are considered satisfactory and acceptable commerc1allyl - ;

Exa.mpl~ 6 Slight Example 7 Very slight Example 8 Slight trace Example 9 Trace - Example lO None Example ll Non~
-`~ 115~623 The procedures de~cribed in Example 1 are ~ollowed substantially as ~et forth therein with the exception that the ~Hylene~W
methylene-b~s(4-cyclohexylisocyanate) is replaced by 72,2 grams of isophorone dii~ocyanate ~3-isocyanatomethyl-3,5,5-trimethYl- -cyclohe~yl-isocyanate).

The re6ults obtained in this Example 12 are generally comparable to the re~ults obtsined in Example 1. The resul~ing product~
are generally sim~lar and the principles of the present inven-tive concept are equally applicable hereto. The top coating exhibits generally comparable properties and characteristics.

The procedures described in Exampls 1 are followed sub~tantially as set forth therein with the except~on that the "Hylene~ W
methylene-bis(4-cyclohexylisocyanate iB replaced by 68.3 grams Or 2~4~4-trimethyl-hexamethylene diisocyanate. The polyure-thane polymerization proceed~ in generally comparable fashion.
The results obtained in this Exanple 13 are generally comparable to the result~ obtained in Example 1. The resulting products are generally similar and the principles of the present inven-tive concept are equally applicable hereto. The polyurethan~
polymer top coating exhibits generally comparablo characteristics and properties.

-~2 EX~MPLE 14 Th~ procedures descr~bed in Exampl~ 1 ar~ followed substantially as ~et forth therein, with the exception that the procedures are stopped ~u6t a~ter the ~iigocyanate-diol-tetrol top coating mix-ture ha~ been ~ixed and prepared and just prior to its applica- -tion to the ~used polyvinyl chloride wear layer containing the polyurethane polymerization catalyst.

A portion of th~ diisocyanate-diol-tetrol top coating mixture i8 set aside at room temperature for further obser~ation and evalu-ation. At the end of three weekg, the Brookfield ~isc06ity iB `
still found to be 125 centipo~ges, as deter~ined ~ith a # 1 spindle at 20 rpm at 77 ~ (25 C.) Thus, there i8 no sub-stantial change in t~e vi6cosity of the top coatingl there ~8 presumably no substantial polymerization or for~ation o~ any polyurethane polymer or prepolymerl and the diisocyanate-diol-tetrol top coating mixture i8 therefore con~idered to have an indefinte ~pot life. The manu~acturing procedures are then resumed for the 6et-aside portion and no difriculties are en-countered.

EX~NPLE 15 The procedures described in Example 1 are follo~ed substantially 8S Bet forth therein, wit~ the exception that the procedure~ are stopped ju~t after the diisocyanate-diol-tetrol top coating mlx- -ture i8 applied to the fused polyvinyl chloride wear layer con-taining the polyurethane polymerization catalyst. This i8 done to simulate a ~shut-down" or delay in the manufacturing cycle.
The simulated "~hut-down~ i8 allowed to exist fo~ 24 hour~ (or 1440 minute~) and the procedures arc th~n res~me~. No di~ri-culties are encountered in the further proce~sing cycle, thu~
indicating a contact "pot life" of ~t leagt 24 hours (1440 ~in-utes) . . . ~

EX~MPLES 16 - 17 _, The procedures de~cribed in Example 1 are follo~ed substantially as set forth therein, with the exceptlons that the amounts of the wetting agent ihcluded in thc diisocyanate-diol=tetrol top coating mixture are in Example 16 increased from 0.1~ grams to 0.50 grams and in Example 17 decreascd from 0.12 grams to 0.03 grams.

The resulting obtained ln these Examples 16 and 17 are gener-ally comparable to the results obtained in Example 1. The re-~ulting products are generally similar to the product of Example 1, there are no material difference~ in the procedur¢s employed, aad the principles o~ the present inventi~e concept are equally applicable hereto.

EXAMP~ES 18 - 45 The procedure~ described in Example 1 are rollowed substantially as set forth therein, with the exception that the formulation Or the polyisocyanate-polyol top coating mixture is changed, as in-dicated in the rollowing Table. ~li values are lndica~ed a6 parts by weight, unle~s 6pecifically indicated otherwise.

~ ~ .

"Hylene" W diisocyanate 85.8 85.8 85.8 85.8 85.8 "Teracol" 650 diol 22.8 16.2 b "TeracolÇ~ 1000 diol 10 c "Teracol~ 2000 diol d ~D
"Pluracol" 410 diol 18.0 . e "VoronolR 2103 diol 6 f "~oronol~ 2070 triol g "Pluracol~ PeP 450 tetrol h "Pluracol~ PeP 550 tetrol 54.0 52.0 56.2 "Pluracol~ PeP 650 tetrol 71.0 69.o "Polymeg" 1000 diol k "Polymeg~ 650 diol PPG-1025 diol m PPG-1225 diol n PP~-425 diol . _ _ _ _ _ _ a 69.0 69.0 69.085.869.o 77.0 69.077.0 69.0 b 22,8 9.89.8 c 10`
d e 18,0 f 6.0 6.0 6.o g . .

i ~2.0 54.0 ~ 71.0~9.069.0 69.o 6g.069.0 69.0 -m n ~

11556`23 '`

32 33 34 35 36 3~ 38 39 40 ., , . I
85.885,8 85.8 85.885,869.0 85.8 94.0 105.6 a ;

9.8 9.~ 9.8 0 ' :

,., ' ,, g h ~' 54.0 i 67.5 67.5 6~.5 69.~ 69.0 69.0 69.0 69.0 ~

25.0 k 22.8 25.0 30.0 n 8 5 8.5 0 .

1 155~23 a 114.0 132.0 85.8 85.8 85.8 b 9.8 9.8 c 25.0 d 50.0 e f g 120,0 h . 44.o 69 . 0 69 . 067 . 5 k , m n ~- 1155623 .

Ih~ procedures described in Example 1 are ~ollowed sub~tantially as set forth thereln, ~ith the exception that, instead Or firm-ing the surface of the appl~ed polyvinyl chlor.ide resin wear lay~r by ~1) a gelling step, follo~ed by (2) a fusion and blow- -ing or foaming step prior to the application of the polyi~ocyan-ate-polyol top coat~ng ~ixture, only a gelling step i~ used to.
firm the surface of the applied polyvinyl chloride resin wear layer prior to the application of the polyi~ocyanate-polyol top coating mixture.

.
In these examples, the applied polyvinyl chloride resin wear layer containing the dibutyl tin dilaurate polyurethane polym- 1 erization catalyst i8 heated and gelled to a firm consistency, a~ is previously obtained in Exampl~ 1, in an oven maintained at . -~
an elevated temperature of about 300 F. The exposure ti~e for the gelling operation i8 about 3 minutes in the oven.

The polyisocyanate-polyo~ ~op coating mixture i8 then applied .
substantially uniformly~to a depth of about 1~ mils on the sur-face of the gelled, firmed polyvinyl chloride resin ~ear layer.
and fusion, blowing or foaming, and curing take place at an el-evated temperatur~ of about 385 F. for about 3 minute~.

Polymerization of the dii~ocyanate and the diol and ~etrol ta~e place during this time, apparently due to migration of the di-butyl tim dilaurate polyurethane polymerizatio~ catalyst ~ro~
the poly~inyl chloride resin wear layer into the top coating layer, Curing of the polyurethane polymer is also acco~pli6hed prior to removal from the heated o~en.
.
The resulting polyurethane polymer ~op coating iB ~ound to be ~ell resistant to abrasion and to solvent and che~ical attac~, to have good fle~ib~lity and i~pact re3istance, good toughness, good high gloss retention, good surface texture, good ~eath~r-ability, and is considered e~inently com~ercially acceptablc.

S~23 The formulationc for the polyisocyanate-polyol top coating mi~-tures used in the~e Examples are as followst A UHylen~ W di~60cyanate 85.8 85.8 "Pluracol~ PeP 650 tetrol67-5 , Teracol 1000 diol 25,0 Pluracol~PeP 550 tetrol 56.o ~Pluracol~ 410 diol 10.0 The procedures described in Example 1 are rollowed substantially as described therein, w~th the exception that only 85 gra~s of the me~ylene-bis(4-cyclohexyli~oeyanate) i8 used and the only polyol included i~ 215 grams of Lexore~ XP-148-20, a cross-linked, aliphatic, hydroxy-$erminated polyester polyol having a functionality of 3.4.

The r2sults obtained in thi~ Example are generally co~parable to the results obtained in Example 1. The resulting .products are generally ~imilar and the top coating exhib~t~ gen~rally comparable properties and character~stics.

5 5~2 3 _ _ _ , _ The procedures described in Example 1 are followed substantially as set forth therein with the exception that the top coating has the following formulationl Example 49 Example 50 Grams Grams Hylene~W (DuPont) methylene-bis-(cyclo-hexylisocyanate), mol. wt. 264, minimum NC0 content - 31.8% 85.8 132.0 Terecol 1000 (DuPont) polytetrametnylene-ether glycol, mol. wt. 1000. hydroxyl number 113 25.0 25.0 Pluracol PeP 650 (BASF Wyandotte) polyoxy-alkylene polyether tetrol, mol. wt. 600, hydroxyl number 374 67.$ 67.5 Wetting Agent 0.25 0.25 Xylene 331.5 436.0 Percent Solids (~non-volatiles) 35% 35~

The results obtained in these Examp~es are generally comparable to the results obtained in Example 1. The resulting products are generally similar and the principles of the present inventive concept are equally applicable. The polyurethane polymer top coatings exhibit generally comparable characteristics and prop-erties.

' As used herein, "Tereco~' polyether glycols are polytetra-methylene ether gl~cols, the numerical suffix indicating the approximate molecular weight; "Pluracol" polyether tetrols are -polyols based on pentaerythritol, the numerlcal suffix indica-ting the approximate molecular weight; "Voronols'' are polyether glycols, "Voronol~' 2103 being a diol having a molecular weight of about 300 and "Voronol~ 2070 being a triol having a molecu-lar weight of about 700; "Polymeg~ (Quaker Oates) polyether glycols are polytetramethylene ether glycols, the numerical suffix indicating the approximate molecular weight; PPG poly-ether glycols are polypropylene glycols, the numérical suffix indicating the approximate molecular weight; "Lexorez~ polyols are polyester polyols of various functionalities and various molecular weights.

Although many specific examples of the invention have been des-cribed, the same should not be construed as limiting the invention to the specific features and/or materials mentioned therein.
The inventive concept is considered to include various other equivalent features and/or materials and is not to be limited, except as defined by the scope and the spirit of the attached claims. It is to be understood that any suitable modifications, changes and variations may be made without departing from the spirit and the scope of the broader aspects of the present in-ventive concept.

Claims (11)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. In a resinous polymer sheet material comprising:
a first layer having a thickness of from about 0.005 inch to about 0.060 inch, of a potentially foamable resinous polymer composition of synthetic resin, a plasticizer for said synthetic resin, and a blowing or foaming agent, and a fibrous backing sheet material substrate on one surface of said first layer, a second layer of a printing ink composition on the opposite surface of said first layer in the form of a predetermined design or pattern; a third layer covering said printed design, having a thickness of from about 0.002 inch to about 0.025 inch comprising a synthetic resin and a plasticizer for said synthetic resin, and a fourth top coating layer covering said third layer having a thickness of from about 1/4 mil to about 15 mils and comprising substantially uniformly therein monomeric polyols and monomeric polyisocyanates and substantially completely free of (1) polymerization products or other reaction products of said monomeric polyols and said monomeric polyisocyanates, and (2) polyurethane polymers or prepolymers, said monomeric polyols and said monomeric polyisocyanates being capable of entering into a polyurethane polymerization reaction only if contacted by a polyurethane polymerization catalyst, the improve-ment which comprises including in said third layer a polyurethane polymerization catalyst not having any polyurethane polymerizing effect on said synthetic resin but capable of bringing about a polyurethane polymerization reaction between monomeric polyols and monomeric polyisocyanates in said fourth layer if brought into contact therewith under suitable temperature conditions;

and being capable, under suitable temperature conditions, of migrating from said third wear layer into and completely through said fourth top coating layer, bringing about a polyurethane polymerization reaction in all parts of said fourth top coating layer, whereby the reaction product after heating loses its wetness and tackiness and develops good resistance to abrasion and to solvent and chemical attack, good flexibility and impact resistance, good toughness, high gloss retention, good surface texture and good weatherability.

2. A resinous polymer sheet material as defined in claim 1, wherein said synthetic resin in said first and third layers is a polyvinyl chloride resin.

3. A resinous polymer sheet material as defined in claim 1, wherein said monomeric polyols comprise polyether polyols.

4. A resinous polymer sheet material as defined in claim 1, wherein said monomeric polyols comprise polyester polyols.

5. A resinous polymer sheet material as defined in claim 1, wherein said monomeric polyols comprise diols.

6. A resinous polymer sheet material as defined in claim 1, wherein said monomeric polyols comprise triols.

7. A resinous polymer sheet material as defined in claim 1, wherein said monomeric polyols comprise tetrols.

8. A resinous polymer sheet material as defined in claim 1, wherein said monomeric polyisocyanates comprise methylene-bis(4-cyclohexylisocyanate).

9. A resinous polymer sheet material as defined in claim 1, wherein said monomeric polyisocyanates comprise 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanate.

10. A resinous polymer sheet material as defined in claim 1, wherein said monomeric polyisocyanates comprise 2,4,4-trimethyl hexamethylene diisocyanate.

11. A resinous polymer sheet material as defined in claim 1, wherein said substrate comprises a fibrous backing sheet material of felted asbestos fibers.