Decorative covering material

Decorative sheet-type covering material and method for making same. The material has a substrate comprising a porous mat saturated and completely coated on both sides with foamed, flexible urethane. The substrate is made by coating one side of a porous mat with reactive urethane mixture which is then allowed to foam.

BACKGROUND OF THE INVENTION 
Decorative, flexible, sheet-type covering materials such as wall or floor 
coverings are conventionally manufactured with non-woven organic or glass 
fiber mats or woven cloth as a substrate. Where glass fiber mats are used, 
it is desirable to insure that both faces of the glass mat are covered 
with a protective coating to protect those handling the covering material 
from the skin irritation associated with handling glass fiber material. 
Availability of a suitable surface for printing is also desirable. 
Satisfactory substrates using glass mats are especially desirable as a 
replacement for the more commonly used asbestos felt substrates in view of 
the currently recognized hazards to health involved in the use of 
asbestos. 
While glass mats coated with protective material are known, the use of such 
mats coated on both sides or faces with protective material has in the 
past involved the use of release paper or lamination of coatings. In other 
applications, glass mats has been coated on one side with cured polyvinyl 
chloride (PVC) plastisol or organosol as illustrated for instance in U.S. 
Pat. No. 3,490,985 to Marzocchi et al. 
SUMMARY OF THE INVENTION 
It is an object of the invention to provide improved, decorative, flexible 
sheet-type covering material which has a substrate comprising a porous mat 
saturated and completely coated on both faces with foamed, heat cured 
flexible urethane. A further object of the invention comprising coating 
one side only of the porous mat with heat curable, foamable, flexible 
urethane mixture, causing said mixture to completely penetrate said mat, 
foaming said mixture so as to saturate said mat and completely coat said 
mat on both sides with the thus foamed flexible urethane polymer and then 
curing the thus foamed urethane polymer to provide sheet-type covering 
material of the invention. 
DETAILED DESCRIPTION OF THE INVENTION 
As mentioned above, the decorative, flexible, sheet-type covering material 
of the invention has a substrate comprising a porous mat saturated and 
completely coated on both faces with heat cured, foamed, flexible urethane 
polymer. While the invention is applicable to porous mats made from any 
flexible material, the preferred material is glass fibers in woven or 
non-woven form with non-woven glass fiber mats being especially preferred. 
Mats for use in the invention should have openings of a suitable size so 
that the urethane reaction mixture can penetrate the mat as described 
below to insure saturation of the mat and thorough coating of the mat on 
both sides with foamed urethane. Complete coverage of both sides of the 
mat is essential to protect those handling the finished covering material 
from exposure to the glass fibers making up the mat. When using the 
preferred urethane polymers described below, non-woven glass fiber mats 
suitable for use in the invention generally have openings averaging 
between about 1 and about 20 mils in the smallest linear dimension with at 
least about 50% of such openings having smallest linear dimensions between 
about 2 and about 10 mils. Preferred mats include those having a thickness 
between about 10 and about 40 mils and a density between about 1 and about 
4 pounds per 100 square foot. Such mats may be manufactured by 
conventional techniques used for manufacturing non-woven glass mats with 
the glass fibers used preferably having an average diameter between about 
5 and about 20 microns, more preferably between 7 and 15 microns, and 
fiber lengths between about 0.2 and about 1.5 inches. Binders 
conventionally used for coating glass fibers may be used and where used 
are normally present in amounts between about 1 and about 50 wt% of the 
mat. Suitable binders for coating glass fibers of the mats used in the 
invention include, for instance, urea-formaldehyde, latexes, thermosetting 
resins such as polyester resins, epoxy resins and the like and may 
include, among other conventional binders, those mentioned in U.S. Pat. 
3,554,851 to Modigliani, the disclosure of which is incorporated herein by 
reference. The binder may, of course, be applied to the glass fibers in a 
conventional manner. 
Where heating to cause penetration of the mat is used as a separate 
manufacturing step, the urethane foam coated mat is preferably heated to a 
temperature less than about 200.degree. F. Curing temperatures between 
about 200.degree. F. and 400.degree. F. are preferred to allow cure time 
between about 0.5 and about 3 minutes. 
Decorative, flexible, sheet-type covering material contemplated by the 
invention includes conventional wall and floor coverings and especially 
material such as sheet vinyl, linoleum and the like. Such sheet vinyl 
flooring frequently has one or more foamed or unfoamed vinyl layers of the 
PVC type generally used in vinyl flooring over the substrate. 
The vinyl layer may comprise any of the PVC resin materials normally used 
in connection with the manufacture of sheet vinyl flooring and may 
specifically include but is not limited to those described in U.S. Pat. 
No. 3,458,337, the disclosure of which is incorporated herein by 
reference. The vinyl layer in such flooring materials is typically on the 
order of between about 5 and about 25 mils thick and may be opaque, 
translucent or transparent as desired. Other layers of sealer, pigmented 
layers, plastisols, wear layers, etc. known in the art may, of course, be 
used. Where transparent or translucent vinyl layers are used, it is 
frequently desirable to apply a printed design to the coated substrate 
formed in accordance with the invention. Since the foamed coating on the 
substrate may not always be sufficiently smooth for direct printing of 
some designs, a conventional sealing or priming coat of latex or of 
plastisol or organosol as described for instance in U.S. Pat. No. 
3,519,460 may be used. Conventional latex containing an acrylic polymer 
such as the prime coat described in the above-mentioned U.S. Pat. No. 
3,458,337 is, for instance, suitable for this purpose. 
Heat curable, flexible, foamable urethane mixtures suitable for use in the 
invention include a wide variety of urethane materials. By the term "heat 
curable, foamable flexible urethane mixture" is meant a mixture which, 
when foamed and cured in the form of an unreinforced 1/4 inch urethane 
foam sheet, can be bent 180.degree. F. around a one inch mandrel without 
permanent set. In general suitable urethanes include the reaction product 
of an organic compound having at least two active hydrogen atoms, such as, 
a hydroxy-terminated polyester, polyesteramine, amide or polyether, and an 
organic polyisocyanate. 
In general, any organic compound containing at least two active hydrogen 
atoms may be employed herein for reaction with the polyisocyanate to 
produce a flexible polyurethane foam. Examples of suitable types of 
organic compounds containing at least two active hydrogen groups are 
castor oil, hydroxy-containing polyesters, polyalkylene polyether polyols, 
hydroxy-terminated polyurethane polymers, polyhydric polythioethers, 
alkylene oxide adducts of acids of phosphorus, aliphatic polyols, as well 
as mixtures thereof. 
Any suitable hydroxyl-containing polyester may be used such as are 
obtained, for example, for polycarboxylic acids and polyhydric alcohols. 
Any suitable polycarboxylic acid may be used, such as oxalic acid, malonic 
acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic 
acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, glutaconic 
acid, -butyl- -ethyl-glutaric acid, - -diethylsuccinic acid, isophthalic 
acid, terephthalic acid, hemimellitic acid, and 
1,4-cyclohexanedicarboxylic acid. Any suitable polyhydric alcohol 
including both aliphatic and aromatic may be used, such as ethylene 
glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 
1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentane diol, 1,4-pentane 
diol, 1,3-pentane diol, 1,6-hexane diol, 1,7-heptane diol, glycerol, 
1,1,1-trimethylolpropane, 1,1,1-trimethylolethane, hexane-1,2,6-triol. 
Also included within the term "polyhydric alcohol" are compounds derived 
from phenol, such as 2,2-(4,4-hydroxyphenyl) propane, commonly known as 
Bisphenol A. 
Any suitable polyalkylene polyether polyol may be used, such as 
polymerization product of an alkylene oxide or of a mixture of alkylene 
oxides with a polyhydric alcohol. Any suitable alcohol may be used, such 
as those disclosed above for use in the preparation of the 
hydroxyl-containing polyesters. Any suitable alkylene oxide may be used, 
such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, 
and heteric or block copolymers of these oxides. The polyalkylene 
polyether polyols may be prepared from other starting materials, such as 
tetrahydrofuran and alkylene oxide-tetrahydrofuran copolymers; 
epihalohydrins, such as epicholorohydrin; as well as aralkylene oxides, 
such as styrene oxide. The polyalkylene polyether polyols may have either 
primary or secondary hydroxyl groups and, preferably, are polyethers 
prepared from alkylene oxides having from 2 to 6 carbon atoms, such as 
polyethylene ether glycols, polypropylene ether glycols and polybutylene 
ether glycols. The polyalkylene polyether polyols may be prepared by any 
known process, such as, for example, the process disclosed by Wurtz in 
1859 in Encyclopedia of Chemical Technology, vol. 7, pp. 257-262, 
published by Interscience Publishers, Inc. (1951) or in U.S. Pat. No. 
1,922,459. 
Typical polyether polyols include polyoxyethylene glycols, 
poly-1,2-oxybutylene and polyoxyethylene glycols polytetramethylene 
glycol, block copolymers, e.g., combinations of polyoxypropylene and 
polyoxyethylene glycols, poly-1,2-oxybutylene and polyoxyethylene glycols 
and poly-1,4-oxybutylene and polyoxyethylene glycols, and random copolymer 
glycols prepared from blends or sequential addition of two or more 
alkylene oxides. Also, adducts of the above with trimethylolpropane, 
glycerine and hexanetriol may be employed. The polyether polyols generally 
have an average equivalent weight from about 150 to 5000 and preferably 
have an average equivalent weight from about 200 to 2000. Polyoxypropylene 
glycols having molecular weights from about 400 to 2500 corresponding to 
equivalent weights from about 200 to 1250 and mixtures thereof are 
particularly useful as polyol reactants. Also, polyol blends such as a 
mixture of high molecular weight polyether polyols with lower molecular 
weight polyether polyols or monomeric polyols can be used in preparing the 
polyurethane. 
Any suitable polyhydric polythioether may be used, such as, for example, 
the condensation product of thiodiglycol or the reaction product of a 
dihydric alcohol, such as is disclosed above for the preparation of the 
hydroxyl-containing polyesters with any other suitable thioether glycol. 
The hydroxyl-containing polyester may also be a polyester amide such as is 
obtained by including some amine or amino alcohol in the reactants for the 
preparation of the polyesters. Thus, polyester amides may be obtained by 
condensing an amino alcohol, such as ethanol-amine, with the 
polycarboxylic acids set forth above or they may be made using the same 
components that make up the hydroxyl-containing polyester with only a 
portion of the components being a diamine, such as ethylene diamine. 
Alkylene oxide adducts of acids of phosphorus which may be used include 
those neutral adducts prepared from the alkylene oxides disclosed above 
for use in the preparation of polyalkylene polyether polyols. 
The organic polyisocyanates which are advantageously employed in the 
present invention can be represented by the formula: 
EQU R(NCO).sub.z 
wherein R is a polyvalent organic radical selected from the group of 
aliphatic, aromatic, arylalkyl and alkylaryl organic radicals as well as 
mixtures thereof; and z is an integer corresponding to the valence number 
of R and is at least 2. Representative of the organic polyisocyanates 
contemplated herein includes, for example, the aromatic diisocyanates, 
such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, mixture of 
2,4-and 2,6-toluene diisocyanate, crude toluene diisocyanate, methylene 
diphenyl diisocyanate, crude methylene diphenyl diisocyanate and the like. 
Other organic polyisocyanates include polymethylene polyphenylisocyanate, 
hydrogenated methylene diphenylisocyanate, m-phenylene diisocyanate, 
naphthylene-1,5-diisocyanate, 1-methoxyphenyl-2,4 -diisocyanate, 
diphenylmethane-4,4'-diisocyanate, 4,4'-biphenylene diisocyanate, 
3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-diphenylmethane- 
4,4'-diisocyanate. 
These polyisocyanates are prepared by conventional methods known in the art 
such as the phosgenation of the corresponding organic amine. 
Still another class of organic polyisocyanates contemplated by the present 
invention are the so-called "quasi-prepolymers." These quasi-prepolymers 
are prepared by reacting an excess of organic polyisocyanate or mixtures 
thereof with a minor amount of an active hydrogen containing compound as 
determined by the well-known Zerewitinoff test, as described by Kohler in 
J. Am. Chem. Soc., 49,3181 (1927). These compounds and their method of 
preparation are well known in the art. The use of any one specific active 
hydrogen compound is not critical hereto, rather, any such compound that 
can be used to prepare a quasi-prepolymer can be employed herein. 
Generally speaking, the quasi-prepolymers are prepared by reacting an 
organic polyisocyanate with less than a stoichiometric amount, based on 
the weight of the polyisocyanate of the active hydrogen-containing 
compound. Suitable active hydrogen-containing groups are those 
hereinbefore described. 
In the practice of the present invention, it is preferred to use as the 
isocyanate either crude toluene diisocyanate, an 80:20 weight mixture of 
2,4- and 2,6-toluene diisocyanate, polymethylene polyphenyl 
polyisocyanate, crude methylene di(phenylisocyanate) or mixtures thereof, 
or the quasi-prepolymer described above. 
In accordance with the present invention, a polyisocyanate is employed at 
an isocyanate index of from about 105 to 115. As used herein, the term 
isocyanate index means the actual amount of isocyanate used divided by the 
theoretically required stoichiometric amount of isocyanate multiplied by 
one hundred. See Bender, Handbook of Foamed Plastics, Lake Publishing 
Corp., Libertyville, Ill. (1965). Conventional catalysts, such as tertiary 
amines and the like, may be incorporated into the foam formulation in 
order to provide the products envisioned hereby. This same fact is true 
with regard to conventional diamine cross-linking agents. 
Suitable catalysts include tertiary amines, such as diethylene triamine 
ketimine, tetramethylene, diamine, triethylene diamine, tetramethylbutane 
diamine, tetramethyl guanidine, trimethyl piperazine and metalloorganic 
salt catalysts which are polyvalent metal salts of an organic acid having 
up to about eighteen carbon atoms and being void of active hydrogen atoms. 
The organo portion of the salt may be either linear or cyclic and 
saturated or unsaturated. Generally, the polyvalent metal has a valence 
from about two to four. Typical metalloorganic salts include stannous 
acetate, stannous butyrate, stannous 2-ethylhexoate, stannous laurate, 
stannous oleate, stannous stearate, lead cyclopentane carboxylate, cadmium 
cyclohexane carboxylate, lead naphthenate, lead octoate, cobalt 
naphthenate, zinc naphthenate, bis(phenyl mercury) dodecyl succinate, 
phenyl mercuric benzoate, cadmium naphthenate, dibutyltin dilaurate, and 
dibutyltin dilaurate, and dibutyltin-di-2-ethylhexoate. Generally, these 
catalysts, when used, will be employed in an amount ranging from about 
0.01 part to 7.5 parts by weight, based on the weight of polyether polyol, 
and preferably, from about 0.05 part to 4.0 parts by weight thereof per 
100 parts by weight of polyether polyol. 
Suitable optional cross-linking agents include, for example, hindered, 
aromatic diamines like 4,4'-methylene-bis(2-chloroaniline) and 
3,3'-dichlorobenzidine; tetiary amines containing hydroxyl groups and 
capable of cross-linking such as triethanolamine, triisopropanolamine, 
N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine as well as other 
condensation products of alkylene oxides and ethylenediamine or 
diethylenetriamine and low molecular weight polyols such as glycerol, 
trimethylolpropane and butanediol. 
In addition to the previously defined ingredients useful in the preparation 
of the foam, other ingredients, such as surfactants, fillers, pigments and 
the like can also be included. Surfactants which can be used are the 
conventional surfactants used in urethane preparation such as the 
polysiloxanes or the alkylene oxide adducts of organic compounds 
containing reactive hydrogen atoms. 
Generally, the surfactant is employed in an amount ranging from about 0.1 
part to 5 parts by weight thereof per hundred parts of polyol. 
Conventional fillers for use herein include, for example, aluminum 
silicate, calcium silicate, magnesium silicate, calcium carbonate, barium 
sulfate, calcium sulfate, carbon black and silica. The filler is nominally 
present in an amount ranging from about 5 parts to 50 parts by weight 
thereof per hundred parts by weight of polyol, and preferably, from about 
15 parts to 45 parts by weight thereof per one hundred parts by weight of 
polyol. 
The pigment which can be used herein can be selected from any conventional 
pigment heretofore disclosed in the art, titanium dioxide, zinc oxide, 
iron oxides, antimony oxide, chrome green, chrome yellow, iron blue, 
siennas, molybdate oranges, organic pigments such as para reds, benzidine 
yellow, toluidine red, toners, and phthalocyanines. 
Also, conventional blowing agents, such as water, halohydrocarbons, 
hydrocarbons, and the like can be employed herein in their conventional 
mode. 
Urethane foam mixtures used in making foams suitable for the invention 
should have cream times (time from formation of the mixture to beginning 
of foaming) sufficient to allow penetration of at least about one-half the 
thickness of the mat before foaming begins. Where mixtures are formed at 
waiting temperatures and immediately coated onto the mat, cream times of 
at least about three seconds preferred. Creaming will of course occur when 
the urethane is heated to curing temperature if creaming has not 
previously occurred. 
While a wide variety of flexible urethanes may be suitable for use in the 
product and process of the invention, selection of a particular urethane 
formulation or mixture thereof suitable for a given application preferably 
takes into account such factors as the nature of the porous mat to be 
saturated and coated, the viscosity of the reaction mixture, etc. 
Generally the most important factors are the nature of the mat, especially 
the size of the openings in the mat, reaction time (cream and gel time) of 
the urethane, and the viscosity of the urethane mixture before reaction 
begins. For ease of application to the mat and to insure complete 
saturation and coating of both sides of the mat by the foamed urethane, it 
is preferred that the urethane be of a suitable viscosity so that it can 
be coated onto one surface only of the porous mat and allowed to penetrate 
the mat either at the coating temperature or by increase in temperature 
after the coating step. If urethane of too great a viscosity is used, 
complete penetration, saturation and coating of both sides of the mat will 
not take place and the finished substrate may well of the type desired in 
the above-mentioned U.S. Pat. No. 3,490,985 rather than the type which is 
the subject of the present invention. If urethane mixture of too low a 
viscosity is used, the material will tend to pass through the porous mat 
too readily prior to foaming thereof and proper saturation and coating may 
not be obtained. 
While suitable viscosities for urethane used in the present invention may 
vary widely depending upon the type of mat and coating the foaming 
conditions used, preferred viscosities when using preferred glass fiber 
mats of the type described above include urethane reaction mixtures having 
viscosities between about 300 and about 10,000 centipoises (cp) at coating 
temperatures as measured on a Brookfield RVF viscometer with a number 3 
spindle at 20 RPM. While coating is frequently carried out at room 
temperature, this is by no means essential and coating temperatures 
between about 50.degree. and about 150.degree. F. are suitable with many 
of the commonly used urethanes. In a preferred embodiment of the 
invention, coating is carried out at between about 50.degree. and about 
120.degree. F. using a urethane which penetrates the mat to a depth of 
between about one-half and about three fourths the thickness of the mat at 
coating temperature. The coating may then be heated to cause it to 
completely penetrate the mat. Heating to cause penetration of the mat may 
be a separate manufacturing step or may be part of the heating process 
used to form and cure the urethane. Where heating to cause penetration of 
the mat is used as a separate manufacturing step, the urethane foam coated 
mat is preferably heated to a temperature less than about 200.degree. F. 
Curing temperatures between about 200.degree. and about 400.degree. F. are 
preferred to allow cure times between about 0.5 and about 3 minutes. 
Application of urethane reaction mixture to porous mats in accordance with 
the invention may be by any suitable means such as knife coating or roll 
coating. Using the preferred glass fiber mats and urethanes described 
above, urethane coatings between about 10 and about 20 mils thick are 
generally satisfactory to provide complete saturation and coverage of both 
faces of the mat when the urethane is foamed.

The following examples illustrate preferred embodiments of the invention 
but are not intended to limit the scope of the invention. 
EXAMPLE I 
To demonstrate the utility of the invention, a metered coating 
approximately 12 mils thick of flexible, foamable urethane mixtures may be 
drawn onto a non-woven fiberglass mat using a conventional knife coater. 
The mat may be made up of glass fibers having an average diameter of about 
9 microns and an average length of about 0.75 inch. The fibers may be 
coated with urea-formaldehyde binder with the binder making up about 15 
weight percent of the mat. The mat may have a total density of 1.4 lbs per 
100 square feet with openings in the mat having smallest linear dimensions 
averaging about 5 mils. The mat may be 15 mils thick. The urethane may be 
coated onto the mat from a continuous mixing and dispersing machine at a 
temperature of 75.degree. F. The urethane mixture may have the following 
composition: 
______________________________________ 
Ingredient Parts by Weight 
______________________________________ 
STREAM I 
Urethane prepolymer, based on 
poly (tetramethylene glycol) and 
toluene diisocyanate, having 6.35% 
NCO 100 
Methylene chloride blowing agent 
8 
Silicone copolymer surfactant 
2 
STREAM 2 
Butanediol crosslinking agent 
6.5 
Triethylene diamine catalyst 
0.05 
______________________________________ 
After coating of the mat as described above, the coated mat may then be 
heated to a temperature of 180.degree. F. whereby the urethane mixture, 
which has an original viscosity at coating temperature of about 800 cps 
and has previously penetrated about one-half the thickness of the mat, is 
allowed to completely penetrate the mat. The urethane may then be foamed 
and cured at a temperature of 300.degree. F. with a cure time of about 2 
minutes. Upon foaming of the urethane, it will be found that the finished 
substrate is completely saturated and coated on both sides with the foamed 
flexible urethane. 
EXAMPLE II 
Utility of the invention may be further demonstrated by coating 
approximately a 12 mil thick layer of foamable urethane onto one face only 
of a non-woven fiberglass mat approximately 18 mils thick and weighing 
approximately 2.3 lbs per 100 square feet using a conventional three roll 
reverse roll coater. The urethane used may be the same as that described 
in Example I. The glass mat may be similar to that used in Example I 
except that the binder is a latex binder making up about 40 weight percent 
of the mat. Except as mentioned immediately above, Example II may be 
conducted in the same manner as Example I. As in Example I, the mixture 
will penetrate about one-half the thickness of the mat until subsequent 
heating and curing when the urethane will completely penetrate the mat and 
the foamed urethane will expand to completely saturate the mat and cover 
both faces thereof. 
While the invention has been described with respect to preferred 
enbodiments thereof, it will be understood by those skilled in the art 
that various changes and modifications may be made without departing from 
the spirit or scope of the invention.