Note: Descriptions are shown in the official language in which they were submitted.
1 155623
POLYURETH~NE POLYMERIZ~TION PROCESSES AND PRODUC~S
.
THE FIELD OF THE INVENTION
.
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.
.
1 155623
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.
.
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~
1 155623
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.
55623
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.
.
1155623
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
12
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.
.. _ , , . _ _ _ _ _ . , ~ ......... . ~ ,,, . _, _, . _ .. , , .. ..... . _ _ _,. "
, .
` ` 1155623
13
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.
, .
1 155623
14
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
... ... .. . . .. , ., .. , .. _ _ _ _
1 155623
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
16
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.
2 3
17
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
, _
. _ ... .. . . ~ _ . .. _ .,
1155623
18
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
-- 1155623
19
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
21
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
22
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
24
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.
26
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.
1 155623
27
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
.
28
EXAMPLE 3
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.
EXAMPLE 4
-
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
,.,
29
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
31
EXAMPLE 12
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.
EXAMPLE 13
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.
- 1155623
-
~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)
. . . ~
1 1 55623
33
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.
~ ~ .
55623
8 19 20 21 22
"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
1 1 55623
23 24 2526 27 28 29 3 31
. _ _ _ _ _ _
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 '`
36
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
37
41 42 43 44 45
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
38
.
EXAMPLES 46 - 47
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
39
The formulationc for the polyisocyanate-polyol top coating mi~-
tures used in the~e Examples are as followst
46 47
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
EXAMPLE 48
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
EXAMPLES 49 AND 50
_ _ _ , _
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.
'
41
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.
