Note: Descriptions are shown in the official language in which they were submitted.
~12'7~
THE F~ELD OF TH~ INVENTION
The present inven-tion relates to me-thods of making
mul-ti-layered products, and more particularly multi-layered
sheet materials, such as resilient Eloor coverings, which
comprise a vinyl resin layer and a polyure-thane or acrylated
pol~urethane resin layer, wherein it is necessary that such
layers be adhered and bonded togethex in a strong and perma-
nent bond that resists delamination very well~
BACKGROUND OF T~E IN~ENTION
It is well known in the manufacture of multi-
layered products, such as resilient floor, wall, or ceiling
coverings, or resilient desk, table, or counter tops, and the
like, that it is often necessary to bond together two or more
layers of dissimilar synthetic polymeric materials and that
it is often dif~icult ~o obtain a strong and permanent bond
r
between such dissimilar synthetic polymeric ma-terials that
will successfully resist delamination of the layers.
Such difficulties often are believed to arise in
the bonding of such dissimilar synthetic polymeric materials
because of differences in surface energies~ For e~amplè,
if atoms from two dissimilar synthetic polymeric materials
cannot get close enough to each other, perhaps because of
large dissimilarities or disparities in polarityr van der
Waals forces cannot be adequately taken advantage of to
create strong and permanent bonding that will resist delamin-
ation very well. Nor is it belieYed that hydrogen bonding can
be adequately taken advantage of in such situations. Many
proposals have been made hitherto to overcome such difficulties
and to improve the bond between such ~issimilar synthetic
~ - 1 - '` ~
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polymeric materials but none has been found to be completely
satisfactoxy to date.
The present .invention will be described wi-th
particular reference to the bonding o~ dissimilar synthetic
polymeric materials, such as, ~or e~ample, v:inyl resin
materials and polyurethane or acrylated ~olyurethane resin
materials but it is to be appreciated that the principles of
the present invention are equally applicable to other equi-
valent dissimilar synthetic polymeric materials. In the
same way, the present invention will be described with
particular reference to multi-layered decorative sheet
materials such as resilient floor coverings, utilizing such
dissimilar synthetic polymeric materials but, again, it is
to be appreciated that the principles of the present invention
are equally applicable to other multi-layered products util-
izing such dissimilar synthetic polymeric materials or layers.
In the manufacture of resilient floor coverings,
normally a base layer or substrate is laid out in a substan-
tially flat, horizontal condition. Such a base layer or
substrate is customarily a felted or matted fibrous sheet of
overlapping, intertwined fibers and/or filaments, usually o~
asbestos or of natural or syn-thetic or man-made fibers of
cellulosic origin, althouyh many other forms of sheets, films,
or textile materials and many other fibers and/or ~ilaments
may be used.
Upon this substantially fla-t, horizontal base layer
or substra-te is then applied a substantially uniform base
layer of a liquid or semi-liquid resinous composition con-
taining a synthetic polymeric material, usually an ungelled
b/ - 2 -
~.
2:2
polyvinyl chloride plastisol, and usually containing a
blowing or foaming agent. This liquid or semi-liquid plasti-
sol composi~ion is subsequently heated and yelled at an ele-
vated temperature to a relatively firm condition.
This relatively firm, gelled polyvinyl chloride
plastisol may then be printed with a decorative multi-
colored pat-tern or design in which certain predetermined
areas may contain a blowing or foaminy inhibitor which
subsequently modifies the action of the blowing or foaming
agent in those certain predetermined areas.
A substantially uniform wear layer of a clear
liquid or semi-liquid resinous composition, containing
usually another polyvinyl chloride plastisol but normally
not containing any blowing or foaming agent is then applied
as a wear resistant top coating to the surface of the gelled,
printed base layer of polyvinyl chloride plastisol and is
subsequently gelled and firmed thereon either as a separate
operation or jointly in connection with a fusion and blowing
or foaming operation of the base layer of polyvinyl chloride
plastisol.
Thus far, there is relatively little or no diffi-
culty in creating a strong and permanent bond or adhesion
between the base layer o~ polyvinyl chloride plastisol and
the wear layer which is also of polyvinyl chloride plastisol.
Such layers just naturally bond together immediately upon
contact, followed by the subsequent heatingO
It is then frequently desired to provide a top
surface coating on top of the surface of the polyvinyl
chloride wear layer and such top surface coating is often
b/ ~ _ 3 _
1~27~2Z
desired t~ be a polyurethane or acrylated polyurethane
resin coating because of their superior physical and
chemical properties and characteristics. However, in
manyinstances, it is found that the bond or adhesion be-
tween the vinyl resin materi.al of -the wear layer anc1 the
polyurethane or acrylated polyurethane resin material of
the top surface layer is not as strong or as permanent, as
desi.red, and does not resist délamination as well as de-
sired. It is believed that such is due to the fact that
the wear layer material and the top surface coating mater-
ial are dissimilar synthetic polymeric materials.
PURPOSES AND OBJECTS OF THE INVENTION
. _ .
It i5 therefore a principal purpose and object of
the present invention to provide for methods of improving
the adhesive bond between such dissimilar synthetic poly-
meric materials, and particularly between a vinyl resin
: material and a polyurethane or acrylated polyurethane
material, whereby a strong and permanent bond or adhesion
is created between such dissimilar synthetic polymeric
materials.
BRIEF SUMMARY OF THE INVENTION
. _
It has been found that such principal purpose and
object, as well as other principal purposes and ob~ects which
will become clear from a further reading and understanding
of this disclosure, may be achieved by forming a layer or
material comprising: tl) a vinyl resin; t2) one or more
plasticizers for the vinyl resin; and (3~ an acrylate o.r
an acrylated urethane; providing a polyurethane or acry-
lated polyurethane resin layer or material containing an
,' ~
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,
' ~
~;27~
organic peroxide or other UV or thermal activated free
radical initiators; bringing the vinyl resin layer or
material and the polyurethane or acrylated polyurethane
resin layer or material in-to con-tact; and exposiny the
~inyl resin layer or material and the contactiny poly-
urethane or acrylated polyurethane ~ayer or material to
curing conditions in the presence of the organic peroxide
,or other UV or thermally activated free radical inikiakor,
whereby there is sufficient chemical'interreacti'on,! between
the ~inyl resin layer or material and the polyurethane or
acrylated polyurethane resin layer or material as to
create a strong and permanent primary chemical bond there-
between, in addition to any secondary bonds, such as hyd-
rogen bonds and/or van der Waals forces.
DESCRIPTION OF PREFERRED AND TYPICAL E~BODIMENTS
T~E BA:SE LAYER OR SUBSTRATE
The specific base layer or substrate which is used
to iliustrate the preferred and typical embodiments of the
present invention does not relate to the essence thereof
and no detailed description is deemed necessary. It is
customarily and conventionally a felted or matted fibrous
sheet of overlapping, intertwined fibers and/or filaments,
usually of asbesto's or of cellulosic origin, although
many other'f~r~s of sheets, films, or fabrics and many other
fibers and/or filaments may be used, such as is described
in United States Patents 3,293,094 and 3,293,103.
THE BASE SYNTHETIC POLYMERIC MATERIAL OR LAYER
.
The specific base synthetic polymeric material or
, layer which is used to illustrate the preferred and typi-
cal embodiments of the present invention does not relate
5 _ -
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-- ~lZ~ P2Z
to the essence thereof and it should be sufficient to
state that it may be potentially foamable or non-foamable
and that, al-though a polyvinyl chloride plastisol i5
preferred and typical, many other synthetic resins are
als~ of use, not only as p~as-tisols but also as o.rg~no~
sols or as aqueous :Latices (aquasols or hydras~ls).
THE VINYL ~ESIN WEAR LAYER
The specific vlnyl resin which is used in the pre-
paration of the vinyl resin wear layer does not relate to
the essence of the present invention. Although a poly-
vinyl chloride plastisol is the preferred embodiment,
many other vinyl resins are also of use, such as a vinyl
chloride~vinyl acetate copolymer, a vinyl chloride-vinyli-
dene chloride copolymer, or copolymers of vinyl chloride
with other vinyl esters such as vinyl butyrate, vinyl
propionate, or even alkyl substituted vinyl esters. As
usual, plastisols are preferred but organosols and aqueous
latices are also of use. Substantlally anybasic vinyl
resin wear layer formulation will suffice, such as those
disciosed in the previously cited United States Patents,
with the modification that there be included in the for-
mulation from about 10 percent by weight to about 30 per-
cent by weight, and preferably from about 15 percent to
abou-t 30 percent by weight of an acrylate or an acrylated
urethane, or mixtures thereof.
THE ACRYLATES
Specific examples of suitable acrylates which are
to be included in the,wear layer formulation include the
following as illustrative but not limitative: methyl
acrylate, ethyl acrylate, butyl acrylate, isobutyl acry-
-- 6 --
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~;27~2'Z
la-te, allyl acrylate, hexyl acryla-te, 2-ethylhexyl acrylate,
butoxye-thyl acrylate, isodecyl acrylate, be.nzyl acryla-te,
cyclohe~yl acrylate, 1,3-butylene ~lycol acrylate, 1,3-
butylene glycol diacrylate, 1,4-bu-tanediol diacryla-te,
d.iethylene glycol diacrylate, 1,6-hexanediol di.acrylate,
2,2-dimethylpropane-1,3~diacrylate, propylene glycol 200
diacrylate, tetraethylene glycol diacrylate, trimeth~lol-
propane triacrylate, pentaerythritol triacrylate, penta-
erythritol tetraacrylate, allyl methacrylate, tetra-
hydrofurfuryl methacrylate, cyclohexyl methacrylate, n-
hexyl methacrylate, triethylene glycol dimethacrylate,
ethylene glycol dimethacrylate, tetraethylene glycol di-
methacrylate, polyethylene glycol dimethacrylate, diethylene
glycol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,3-
butylene glycol dimethacrylate, trimethylolpropane tri-
~` methacrylate, pentaerythritol tetramethacrylate, etc
TH~ ACRYLATED POLYURETHANES
The acrylated polyurethanes-which are to be in-
; cluded in the vinyl resin ~ear layer may be prepared by
several different conventional methods, preferred and
typical methods involving the use of three basic react-
ants, namely: a polyisocyanate, usually a diisocyanate;
a polyfunctional compound such as a polyol, polyamine,
; etc.; and a hydroxyalkyl acrylate.
For example, a W reacti~e acrylated urethane
ollgomer or polymer may be synthesized, for example, from
two basic reactants, the first being a conventional iso-
cyanate-function terminated polyurethane (the reaction
product of a stoichiometric excess of a polyisocyanate
(including di-, tri- and tetra-isocyanates and mi.xtures
- 7 -
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thereof) with a polyfunctional compound, such as polyols,
includin~ diols, triols, tetrols, and mixtures thereof,
as well as ether-type polyols, ester-type polyols, poly-
amines hydroxyamines, polymercaptans, hydro~ymercapt~ns,
and mixtures thereof) and the other reactank beiny a
hydroxya:lkyl acrylate, whereby an essentially polyurethane
structure having terminal acrylate func-tlonality is ob~
tained.
THE POLYISOCYANATES
The polyisocyanates used in preparing the conven-
tional isocyanate-function terminated polyurethane used in
carrying out the principles of the present invention in-
clude: 4,4'-methylen~-~is-cyclohexyl . diisocyanate, hexa-
methylene-1,6-diisocyanate, tetramethylene-1,4-diisocy-
anate, cyclohexane-l,~-diisocyanate, 2,2,4-trimethyl-1,6-
'~ hexane diisocyanate, trimethyl hexamethylene diisocyanate,-dimer acid diisocyanate, trimer of hexamethylene diisocy-.
anate, ethylene diisocyanate, ethylidene diisocyanate,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-
phenylene diisocyanate, m-phenylene diisocyanate, 4,4'-
me.thylene bis-(phenylisocyanate), naphthylene-1,5-diisocy-
anate,,4,4'-biphenylene diisocyanate, furfurlidene dii-
socyanate, butane-1,4-diisocyanate, isophorone diisocyanate,
pentane-1,5-diisocyanate, etc.
THE POLYFUNCTIONAL COMPOUND
The polyfunctional compounds which are employed to
react with any of the above-listed polyisocyanates or mi~-
tures thereof may be selected from a large group of suit-
able chemical compounds of which the following are illus-
trative but not limitative:
- 8 -
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:-
7~2Z
Diols such as e-thylene glycol, propylene glycol,
butylene glycol, trime-thylene glycol, tetramethylene
glycol, pentamethylene glycol, hexamethylene glycol, neo-
pentyl glycol, etc.: tri.ols such as glycerol, 1,1,1-
tri~ethylol propane, l,l,l-tr.i.methylol ethane, 1,2,3-
butanetriol, 1,~,4-butanetriol, 1,2,3-pentanetriol, :L,2,3-
hexanetriol, 1,2,~-hexanetriol, 1,2,5-hexanetriol, 1,2,~-
hexanetriol, 2,3,4-hexanetriol, 1,3,6-hexanetriol, etc.:
tetrols such as erythritol, pentaerythritol, etc: ether~
type polyols which are adduct products o~ the above polyols
with alkylene oxides having from 2 to 5 carbon atoms, such
as ethylene oxide, propylene oxide, trimethylene oxide,
1,2-butylene oxide, isobutylene oxide, 1,4-tetramethylene
oxide, pentamethylene oxide, and mixtures thereof, and
e:specially diethylene glycol, trie~hylene glycol, tetra-
ethylene glycol, pentaethylene glycol, and higher mole-
cular weight poly.alkylene glycols having the general for-
mula HO~CnH2n)XOH, etc: ester-type polyols which are con-
densation products of the above polyols with polycarboxy-
lic acids such as oxalic, ~alonic, succinic, glutaric,
. pinelic, suberic, azelaic, sebacic, fumaric, phthalic,
isophthalic, terephthalic, mellitic, etc.: polyamines such
as ethylene diamine, propylene diamine, trimethylene
diamine, tetramethylene diamine, pentamethylene diamine,
hexamethylene diamine, diethylene diamine, triethylene
diamine, tetraethylene diamine, tetraethylene pentamine,
isophorone diamine, piperazine, etc.: poly mercaptans
such as ethylene dimercaptans, 1,3-propanedithiol, 1,4-
butanedithiol, 2,2-dimercaptodiethyl ether, glycol dimer-
capto acetate, glycerol dimercapto propionate, trimethylol-
g _
~ mab/
Z
propane tri(3-mercapto propionate) etc.: hydroxyamines
such as monoethanolamine, diethanolamine, 3-aminopropanol-
l, 4-aminobutanol-l, etc.: hydroxymercaptans such as l-
thioglycerol, 2--thioglycerol, 2-mercapkoethanol, 2,3-
dimercapto propanol-l, etc.
THE HYDROXYALK~L ACR~LATES
- Examples of preferred and typical hy~roxyalkyl
acrylates include: hydroxymethyl acrylate, hydroxyethyl
acrylate, hydroxypropyl acrylate, and mixtures thereof. If
desired, the hydroxyalkyl acrylates may be replaced h~
hydroxyalkyl methacrylates or by hydroxyalkyl-containing
vinyl compounds to yield essentially polyurethane structures
having terminal methacrylate or vinyl functionality. ~xam-
ples of preferred and typical hydroxymethacrylates are:
hydroxyethyl methacrylate, hydroxymethyl methacrylate,
r hydroxypropyl methacrylate, and mi~tures thereof. Examples
of preferred and typical hydroxyalkyl-containing v1nyl com-
pounds include: B-hydroxyethyl vinyl ether, B hydroxyethyl
sulfide, etc.
The acrylated polyurethane resins may also be made
by other conventional methods disclosed in the pr1or art,
such as those disclosed in United States Patent ~,100,318
which issued on ~uly 11, 1978.
The thickness of the substantially uniformly applied
vinyl resin wear layer is the range of from about 0.001 inch
to about 0.030 inch, and preferably from about 0.005 inch
to about 0.025 inch.
The vinyl resin wear layer containing the added
acrylates or the acrylated polyurethanes, or mixtures
thereof is then passed through a heated oven maintained at
-- 10 --
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,;
an elevated temperature of about 250F. to about 460F. and
preferably from about 270F. to about 450F. for a period of
time of from about 1 1/2 minu-tes to abou-t 10 minutes and pre~
ferably rom ~bout 2 minu-tes to about 8 minutes whereupon the
vinyl resin in the wear layer gels and fuses and the vinyl re~in
in the base synthetic polymeric plastisol layer fuses, ac-
companied by the blowing and foaminy thereo~.
THE TOP SURFACE COATING
The polyurethane or the UV curable acrylated poly-
urethane resin which is used in the formulation of the top sur-
face coating that is applied to the vinyl resin wear layer does
not relate to the essence of the present invention. The poly-
urethane resin may be any conventional polyurethane resin and
the UV curable polyurethane resin may be the same as that pre-
viously included in the vinyl resin wear layer.or it may be a
different UV curable acrylated polyurethane. .However, regard-
less of which resin is used and regardless of the precise method
of its manufacture-or the precise components which enter its
formulation, there must be from about 0~5 percent to about 20
percent by weight of free available isocyanate thèrein, and
preferably from about 2 percent to about 10 percent by weight,
based on the total weight of the top surface layer.formulation.
Additionally, there is included in the top surface
layer formulation from about 0.5 percent by weight to about 20
percent by weight, and preferably- ~rom about 2 percent by weight
to about 10 percent by weight of a free radical polymerization
initiator r or catalyst, such as an organic peroxide, such per-
centages being based on the total weight of the top surface
layer formulation.
THE FREE RADICAL POLYMERIZATION INITIATOR
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2Z
Specific free radical polymeriæation initiators, or catalys-ts,
notc~b.ly organic peroxides, useful for the appliccation of -the principles
of the presen-t inventlon include the follcwing, as illus-trative but not
limitative:
di-t-butyl peroxide, 2,5-dime-thyl~Z,5-bis(t~butylperoxy)
hexane, 2,5-dinethyl-2,5-bis(t-butylperoxy)hexyne-3, di-t~amyl peroxide,
t-butyl-2-hydroxye-thyl peroxide, a,a'-bis(t-butylperox~)diisopropyl
benzene, benzoyl peroxide, diisobutyryl peroxide, 2,4-dichlorobenzcyl
peroxide, diisononanoyl peroxide, decanoyl peroxide, lauroyl peroxide,
aoetyl peroxide, succinic acid peroxide, bis-p-chlorobenzoyl peroxide,
2,5-dihydroperoxy-2,5-dimethylhexane, cumene hydroperoxide, -t-butyl
hydroperoxide,p-methc~ne hydroperoxide, dilsopropylbenzene hydroperoxide,
1,1,3,3-tetranethyl butyl hydroperoxide, dicu~yl peroxide, di(n-propyl)
peroxy dicarbonate, diisopropyl peroxydicarbonate, di(sec-butyl)peroxy-
dicarbonate, di(2-ethylhexyl) peroxydicarbonate, dicyclohexyl peroxydi-
carbonate, dicetyl peroxydic æbonate, bis(4-t-butylcyclohexyl)peroxydi-
carbonate, t-butylperoxy isopropyl monocarbonate, 2,2-azobis(isobutyroni-
trile), l,l-bis(t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl peroxy-
acetate, t-butyl peroxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-
butyI perox~t pivalate, t-butyl peroxyneodecanoate, t-butyl peroxymaleic
acid, di-t-butyl diperoxyph-thalate, 2,5-dimethyl-2,5-bis(benzoylperoxy)
hexane, 2,3-dimethyl-bis(octanoylperoxy)hexane, t-butyl peroctoate, t-
butyl perbenzoate, acetylcyclohexyl sufonyl peroxide, acetyl sec-heptyl
sulfonyl peroxide, 2-t-butylazo-2-cyano-4-methoxy-4-methyl pentane, 2-
t-butylazo-2-cyano-4-methyl pentane, 2-t-butylazo-2-cyanopropane, methyl
ethyl ketone peroxide, 2,4-pentanedione peroxide, cyclohexanone peroxide,
etc.
It is to be noted tha-t, if the free radical polymerization
initiator, or catalyst, or organic peroxide, is a powdered material,
SU~I as lauroyl peroxide, for example~ it should be dissolved in a small
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llZ7~Z;~
amoun-t of a suitable solvent, such as vinyl acetate, for exa~le,
prior -to actual use. If the free radical polymerization ini-tia-tor, or
catalyst, or organic per.oxide, is a liqlid, it may be used direct.ly
.in that forrn.
The thickness of the applied top coa-ting layer is norrnally
in the range of from about 1 mil to about 15 mils, depen~:iny upon the
future re~uirements or the product being made.
Curing conditions for acryla-ted polyurethane re.sins differ
from those normally employed for more conventional polyurethane .resins,
in that the acrylated polyurethane resin is cured by being passed through
an actinic radiation source, such as, for example, an ultraviolet lam~
ping..unit oYen. Radiation curing by electron beam, gamma and x-ray
treatment, and other suitable sources may be employed. ~l-traviolet
radiation is the preferred and typical source. In the presence of photo-
initiators, such radiation induces a photc-chemical reaction which
produ oes free radicals which are capable of inducing ~ polyrnerization.
Sour oe s of ultraviolet radiati~on may be mercury vapor arc lamps, plasma
arcs, pulsed xenon lamps and carbon arcs. Mercury vapor lamps are pre-
ferred and typical for most cases. Special wavelengths of light which
are most effective will vary, aepending primarily upon the particular
acrylated polyurethane coating used and the particular photo-sensitizer
employed. In some instances, combinations of conventional thermal and
radiation curing conditions may be used.
During the actinic radiation curing conditionsr polymerization
of the acrylated polyurethanernaterialstakes place~ along wi-th polyfneri~
zation of other resinous materials which are present, and with sufficient
chemical inter-reaction between the acrylates or acrylated polyurethanes
in the vinyl resin wear layer and the polyurethanes and acrylated poly-
urethanes in the top surface layer as initiated by ~he free radical poly-
merization initiator or the organic peroxide in the top coating layer.
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As a result, there is created a strong and permanent primary chemical
bond between the vinyl resin wear layer and the polyurethane or acrylated
polyurethane resin layer which is additioI~al to any existiny secondary
bonds, such as hydrogen bonds or van der Waals forces. Such a strong and
permanent bond is capc~ble oE resisting delamina-tion forces very well.
The inven-tion will be further described in greater de-tail by
the followiny specific working examples. Althou(Jh these examples may
describe in very particuLar detail some of the more specific features of
the present invention, they are given primarily for purposes of illus-
tration and the invention in its broader aspects is not to be considered
as limited thereto.
.- ' EX~LE 1 ,
m e base layer or substrate comprises a relatively flat, 0.040
inch thick fibrous sheet of felted or matted asbestos fibers with an acrylic
smoothing or leveling coating thereon. The asbestos fiber sheet is coated
with a substantially uniform coating to a thickness ~wet) of about 0.015
inch with the following potentially foamable polyvinyl chloride plastisol
composition: -
Parts
- Polyvinyl chloride, l~w mol, wt., general purpose dis-
persion resin, inh.vis. 0.99 (ASTM D-1243-661 30.2
Polyvinyl chloride, med. mol wt., dispersion grade
resin, inherent viscosity 1.0 8 2
Polyvinyl chloride, med. mol. wt., blending resin,
inherent viscosity 0.9 17.1
~nhydrous alumin silicate filler 6.9
Alkyl benzyl phthalate plasticizers 24.7
Polydodecyl benzene 7.4
Azodicarbonamide 1.1
Accelerator~stabilizer 0.4
Titanium dioxide 2.5
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Dioctyl ph-thalate 1.5
Wetting agent 0.03
(Parts by weigh-t)
Gel:Ling and firrning of the potentially foamable polyvinyl
chloride plastisol is accamplished in an oven a-tmosphere which is main-tained
at an elevated temperature oE about 300E. for a period o~ tir~ of ~bout
3 n ~ utes. The te~,perature is not that elevated as to activate or de~orn-
pose the blcwing or foaming agent which is present.
The gelled, firmed potentially foamable polyvinyl ehloride
plastisol is the~ printed with a mul;ticolored decorative pattern or design
using (1) a conventional or standard printing ink camposition and (2) an
inhioitor-containing printing ink cGr~position, as follows:
Printing ink cc~,position (1):
Parts
- Solution grade copolymer of vinyl chloride (90 parts)
and vinyl acetate (10 parts) 15
,~ Methyl ethyl ketone 85
Pigment or colorant, as desired
Printing ink composition (2):
Parts
Solution grade copolymer of vinyl chloride (90 parts)
and vinyl acetate (10 parts) 12
Met~yl ethyl ketone 68
Trimellitic ar~ydride 20
Pigment or colorant! as desired
m e printed, gelled and firmed potentially foamable polyvinyl
chloride plastisol is then allcwed to air-dry and a polyvinyl chloride
plastisol wear layer is substantially uni~ormly applied thereto to a wet
thickness of about 0.015 inch depth and having the follewing formulation
by weight:
Parts
Polyvinyl chloride,-dispersion grade, high rnol. wt.89.36
Polyvinyl chloride, blending r~sin, inherent viscosity
- 15-
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~7~Z
0.86 (ASTM ~-12~3-66) 10.64
Butyl benzyl phthala-te plasticizer 7.5
2,2,4--trimethyL-1,3-pentanediol diisobutyrate 7.5
Polyethylene y:Lycol dimethacrylate 30.0
Epoxy plas-ticizer 5.0
Ba-Zn stabilizer 3.0
Toner 0.21
W absorber 0.32
Gelling and firming of the polyvinyl chloride plastisol wear
layer takes place at an elevated temperature of about 300F. for a period
of time of about 3 minutes, followed by fusing, blowing or foaming at a
more elevated temperature of about 430DF. for a period of about 1 minute
and 40 seconds.
The base synthetic polymeric l~yer and the wear layer having
cooled, they are subsequently pre-warmed to an elevated temperature of
about 260F. before being substantially uniformly coated with a W curable
acrylated urethane top surface coating having the follcwing composition
by weight:
Parts
Lauroyl peroxide 5
20 AcLylated urethane resin ' 60
Polyether polyol 650 10
Vinyl acetate 30
Isobutyl ether of benzoin photoinitiator 3%
Dibutyl tin dilaurate 0.5%
The curing of the W curable acrylated urethane resin top coating
takes place by passage through an ultraviolet unit having a length of about
3 feet (2 lamp parallel unit, 12 inches long, 200 watts each lamp, medium
pressure, mercury lampj and a nitrogen atmosphere at a rate of about 10
feet per minute.
The adhesion or bond between the vinyl resin wear layer and the
~ - 16 ~
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, ~ .
acryla-ted polyurethc~ne resin top corating layer is tes-ted and is found
to be strong and permanent and capable of resisting dela~ination very
well. The results are generally comparable to the results ob-tained in
repeated tests.
EX~MPLE II
m e procedures decribed in Example I æ e ~ollowed substantial~y
as set forth -therein with the excep-tion tha-t the formulation of the vinyl
resin wear layer is changed to the follcwing:
Parts
Polyvinyl chloride, dispersion grade, high mol. w-t. 89.36
Polyvinyl chloride, blending resin, inh. vis. 0.86 10.63
Butyl benzyl phthalate plasticizer 7.S
2,2,4-trimethyl-1,3-pentanediol diisobutyrate 15.0
Polyethylene glycol dimethacrylate 22.5
Epoxy plasticizer 5.0
Ba-Zn stabilizer 3.0
Toner ; 0.21
W absorber - - 0.32
m e adhesion or bond between the vinyl resin layer and -the acryl-
ated polyurethane resin top coating layer is tested and is found to be
strong and permanent and to resist delaminàtion ~ery well. The results
are generally comparable to the results of Example I.
EX~MPLE III
The procedures described in Example Iare follcwed substantiall~
as set ~orth therein with thè exception that the formulation of the vinyl
resin wear layer is changed to the follcwing composition by weight:
Parts
Polyvinyl chloride, dispersion grade, high mol. wt. 89.36
Polyvinyl chloride, blending resin, inh. vis. 0.86 10.63
Epoxy plc~sticizer 5.0
Ba-Zn stabilizer 3.0
Trimethylol propane trimethacrylate 45.0
' ' , I
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mab/
,
~1~27~Z2
Butyl ben~yl phthalate plasticizer 6.0
Toner 0.21
W absorber 0.32
Ihe adhesion or bond between the vinyl resin wear l~yer and the
acrylated polyurethane resin top coating layer is tes-ted and is found to
be excellent and capab:le of resisting deLamination very well. 'l~e resul-t~
are generally comparable to those of Examp:Le I.
_ _ _
The procedures described in Example I are followed substantially
as set forth therein with the exception that the lauroyl peroxide in the
W curable acrylated polyurethane resin top coating layer is replaced by
10 parts of t-butylperoxy isopropyl monocarbonate as the free radical
polymerization initiator.
The results are generally comparable to the results obtained
in Example I. The adhesion of the bond between the vinyl resin layer and
the acrylated polyurethane top surface coating is tested and is found to
be excellent and to resist delamination very well.
EXAMPLE V
The procedures of Example I are follcwed substantially as set
forth therein with the exception that the lauroyl peroxide is replaced
by dicu~lyl peroxide as the free radical polymerization initiator.
The results of this Example are found to be generally comparable
to the results obtained in Example I. Ihe bond or adhesion between the
vinyl resin layer and the acrylated polyurethane layer is tested and is
found to be excellent and well capable of resisting dek~mination.
F~ PIE VI
The procedures described in Example I are follcwed substan-
tially as set forth therein with the exception that the polyethylene
glycol dimethacrylate in the wear layer formulà-tion is replaced by an
equal amount of methoxy polyethylene glycol 300 mono-acrylate.
- 18 -
.
:
.
~27~
l~e results of this example are yenerally c~lparable to -the
results ob-tained in Example X. m e bond or adhesion between the vinyl
resin wear layer and the acrylated polyurethane resin layer is tested and
found to be excellent.
EXPMPLE VII
The procedures described ln Example I are ~ollcwed substanti~ll*
as set forth therein with the exception -~hat the polyet~lene ylycol
dimethacrylate in the vinyl resin wear layer is replaced by an acrylic
urethane prep æed by reactiny 4,4'-methylene-biscyclohexyl diisocyanate
and Teraco ~ 650 polytetrame-thylene e-ther glycolr and hydroxye-thyl
methacrylate.
I'he results of this Example æe generally comparable to the re-
sults obtained in Example I. The bond or adhesion between the vinyl
resin wear layer and the acrylated polyurethane resin layer is tested
and is found to be excellent and to resist delamination very well.
. EXAMPLE VIII
The procedures described in Example I æe followed substan-
tially as set forth therein with the exception that the polyethylene
; glycol dimethacrylate is replaced by an acrylated polyurethane resin
derived from reacting 4,4'-methylene-bis-cyclohexyl diisocyanate,
Pluraco ~ 450 polyoxyaIkylene polyol based on pentaerythritol, and
hydroxy ethyl methacrylate.
The results of this Example are yenerally co~parable to the
results of Example I. Ihe bond between t~e vinyl resin wear layer and
the acrylated polyurethane resin layer is tested and found to be excel-
lent and well capable of resisting delamination.
EXAMPLE IX
~he procedures described in Example I are followed substan-
tially as set forth therein with the exception that the polyethylene
glycol dimethacrylate is replaced by an acrylated polyurethane resin
19
mab/
.
7~
derived by reacting isophorone diisocyana~e, Teracol 550 polytetra-
methylene ether g1ycol, and hyclroxyethyl methacrylate.
rlhe results of this Example are cJenerally cc~mparable to the
res~lts obtained in Exclrple I. r~he bond or adhesion between the vinyl
resin wear layer and -the acrylated polyur~-thane res:in layer i~ ~ested
and is found to be excellent and well capable of resis-tiny delamination.
E~MPLE X
...
The procedures described in Exa~ple VII are follcwed substan-
tially as set forth therein with the excep-tion that the hydroxye-thyl
methacrylate used in the formation of the acrylated polyurethane for
the ~inyl resin wear layer is replaced by hyclroxyethyl acrylate.
The results of this Example are generally comparable to the
results obtained in Example VII. The bond or adhesion between the
vinyl resin wear layer and the acrylated polyurethane resin top coatiny
layer is tested and is found to be excellent and well capable of resis-
~iny dela~ination.
. .
T~e procedures described in Example ~II are follcwed substan-
tially as set forth therein with the exception that the hydroxyethyl
methacrylate used in the form~llation of the acrylated polyu~ethane fQr
- the ~inyl resin wear layer ;s replaced by hydroxypropyl acrylate.
e results of this Example æ e generally comparable to the
results obtained in Exclmple VII. The bond or adhesion between the vinyl
- resin wear layer and the acrylated polyurethane top coating layer is
tested and is found to be excellent and well capable of resisting
delamination.
... ... ..
EX~MPLE XII
The procedures set forth in Example I are follcwed substan~
tially as described therein with the added definition that the acrylated
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m~b/
' ~
z
urethane resin used in the top swrface coatincJ is th~ reaction prodw-t
of: (XIIa) 4,4'-methylene-bis-cyclohexyl diisocyanate, polyte-tra-
methylene ether glycol, and hyc1ro~yethyl acryla-te: (XIIb) 4,4'-
methylene-bis-cyclohexyl diisocyanate, polyoxyaIkylene polyol basecl on
pen-taerythri-tol, and hydroxyethyl me-thacrylate: (XIIc) isophorone di-
isocyana-te, polytetramethylene ether glycol, and hyclroxymethacrylate:
(XIId) isophorone diisocyanate, polyoxyalkylel1e polyol base~ on pent~~
erythritol, and hyclroxyethyl methacrylate: ~XIIe) 4,~'-meth~lene-bis-
cyclohexyl diisocyanate, polytetrameth~lene ether glycol, and h~dro~y-
methyl acrylate: (XIIf) 4,4'-methylene-bis-cyclohexyl diisocyanate,
polytetramethylene ether glycol, and hydroxypropyl methacrylate.
The results of these Examples are all generally co~parable to
the results obtained in EXample I. The bond or adhesion between the
Yinyl resin wear layer and the acrylated polyurethane resin top surface
coating layer is strong and permanent and is capable of resisting de-
lamination very well.
- EXAMPLE'XIII
The procedures of Example I are followed substantially as
set forth therein with the exception that a different top surface
coating layer is used which is formulated as follcws: a conventional'
polyurethane resin is prepared from an aliphatic diisocyanate (hexa-
methylene dii~socyanate) as the NCO source; the reacting polyhydrox~
groups are provided for a ~QXture of polyols, the polyols (both polyester
polyol types and polyether polyol types, with the polyester forming
the ~ajor proportion and the polyethers forming the nur.or proportion),
and the catalyst being a ~xture of tetrakis-2 hydroxypropyl ethylene
diamine, a tertiary amine, and dibutyl tin dilaurate. Five percent
by weight of lauroyl peroxide is included as the orgam c peroxide.
The conventional polyurethane resin top surface coating layer
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~b/ .
~,12'~f~Z
is applied to the vinyl resin wear layer and is subseq~lently heated
in an oven at an elevated temperature of about 385F~ for a period
of time of about 2 minutes and 45 seconcls. Fusion *akes place, along
with the blowing and Eoaming of the polyvinyl chloride base synthetic
polymeric layer con-taining the blowing or foaming agent.
rrhe results of this Example are generally ccmparable ~o the
results obtained in Example I. rrhe bond or adhesion between the
vinyl resin wear layer and the polyurethane resin top surface coating
layer is tested and is f,ound to be s-trong and permanent and capable
of resisting delamination very well.
Although several specific working Examples,of the inventiye
concept have been described in particularity, the invention in its
broader aspects should not be construed as limited thereto but should
be considered as including various other equivalen-t features as set
forth and encompassed by the appended claims. Any suitable changes,
modifications and variations may be made without departing f,,rom the
scope and the spirit of such appended claims.
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.
