Multilayer polymeric shaped article

A shaped multilayer polymeric article, and a method for manufacturing said article, comprising a top layer comprised of thermoset polyester resin, a supporting layer underneath said top layer comprised of high density polyurethane foam, said supporting layer having a density and thickness at least effective to provide support to said top layer; an intermediate layer underneath at least a portion of said supporting layer comprised of low density polyurethane foam; and a bottom layer underneath at least said intermediate layer comprised of high density polyurethane foam.

FIELD OF THE INVENTION 
This invention relates to composite resinous shaped articles such as a 
bathtubs, bathtub and shower enclosures, basins, shower enclosures, and 
the like. 
BACKGROUND OF THE INVENTION 
Composite shaped articles such as bathtubs, bathtub and shower enclosures, 
shower stalls, basins, and the like comprised of synthetic resinous 
materials are known and have become increasingly popular due, inter alia, 
to their light weight, ease of installation, and easy maintenance. One 
such type of resinous shaped article is comprised of a relatively thin gel 
top coat comprised of thermoset polyester, a supporting layer underneath 
said top coat comprised of a chopped glass fiber filled or reinforced 
thermoset polyester, an intermediate layer underneath said supporting 
layer comprised of polyurethane foam containing no reinforcing fibers, and 
a bottom layer underneath said intermediate layer comprised of chopped 
glass fiber reinforced thermoset polyester. 
While such resinous composite shaped articles are very useful and 
satisfactory, they suffer from one drawback. This drawback is present in 
the manufacturing process used to produce said article. This composite 
article is made by first depositing the gel top coat layer on the outer 
surface of a mold, then depositing the supporting layer onto the gel coat 
layer, followed by depositing the intermediate layer on the supporting 
layer, and finally depositing the bottom layer on the intermediate layer. 
Since the gel top coat layer is quite thin and thus susceptible to 
puncture, deformation, and other damage, the supporting layer must be free 
of voids, air-pockets, and the like. However, the fiber glass filled 
thermosettable polyester supporting layer, as deposited by spraying, 
generally is not sufficiently free of such voids, airpockets, and the 
like. These imperfections must be removed from the polyester resin before 
the thermosettable polyester resin is cured or thermoset. This may be 
accomplished by passing a roller over the glass filled thermosettable 
polyester deposit to remove any voids, airholes, and the like present 
therein. However, this is a rather time consuming and labor intensive 
procedure, particularly if the composite article is of a complex shape or 
form. 
Furthermore, it would be advantageous if such a composite article were 
provided which exhibited a similar strength and rigidity while being 
lighter in weight. 
The present invention provides a composite article wherein the rolling step 
in the preparation of the supporting layer is eliminated, and provides a 
composite article having substantially similar strength an rigidity but 
being lighter in weight. 
SUMMARY OF THE INVENTION 
The present invention relates to resinous shaped articles such as bathtubs, 
bathtub and shower enclosures, shower stalls and surrounds, basins, and 
the like. The shaped article is comprised of a plurality of layers 
comprised of resinous materials, preferably thermoset resinous materials, 
including a relatively thin top layer comprised of thermoset polyester; at 
least one supporting layer beneath said top layer comprised of 
polyurethane foam having a relatively high density; an intermediate layer 
beneath at least a portion of said supporting layer in surface-to-surface 
contact with said supporting layer comprised of a polyurethane foam; and 
at least one bottom layer comprised of a polyurethane foam beneath said 
intermediate layer and in surface-to-surface contact with said 
intermediate layer and, where said intermediate layer is absent, beneath 
and in surface-to-surface contact with said supporting layer. The 
polyurethane foam of the intermediate layer has a lower density than the 
polyurethane foam of the supporting layer. The polyurethane foam of the 
bottom layer preferably has a higher density than the polyurethane foam of 
the intermediate layer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
FIG. 1 illustrates one embodiment of the shaped article, e.g., bathtub, on 
the mold after all the various resinous layers have been applied and cured 
and just prior to its removal from mold 11. The mold 11 has an exterior 
surface 12 which is configured to a pre-determined, desired shape. A thin 
coating comprised of thermosettable polyester resin is applied onto 
surface 12 of mold 11. After this thermosettable polyester resin is cured 
or thermoset to form top layer 20 comprised of a thermoset polyester 
resin, a coating comprised of thermosettable polyurethane foam having a 
density, in its cured state, of at least about 10 lbs/cu. ft. is applied 
onto layer 20. After this coating comprised of thermosettable polyurethane 
foam is cured or thermoset to form supporting layer 30 comprised of 
thermoset polyurethane foam, a second intermediate coating of 
thermosettable polyurethane foam is applied onto layer 30. This 
intermediate coating is allowed to foam and cure or thermoset to form 
intermediate layer 40 comprised of thermoset polyurethane foam. The 
thermoset polyurethane foam of layer 40 preferably has a lower density 
than the polyurethane foam of layer 30. After this intermediate 
polyurethane foam layer 40 is formed, a bottom coating of thermosettable 
polyurethane foam is applied onto layer 40 and cured or thermoset to form 
bottom layer 50. The thermoset polyurethane foam comprising layer 50 
preferably has a higher density than the polyurethane foam of layer 40. 
After the bottom layer 50 is formed, the shaped article is removed from the 
mold and may be subjected to further processing such as trimming and the 
like. The shaped article 10 after removal from the mold 11 is illustrated 
in FIG. 2. 
The mold 11 may be of any type well know in the art. Mold 11 may also 
contain various well known mold release agents such as waxes and the like 
on surface 12 in order to facilitate removal of the article 10 from the 
mold. 
Layers 20, 30, 40 and 50 do not contain fiber reinforcing materials such as 
for example glass fibers. 
The polyurethane foam of supporting layer 30 has a relatively high density 
in order to provide support and backing for the relatively thin gel coat 
top layer 20. If the density of the polyurethane foam of layer 30 is too 
low, not enough support will be provided by layer 30 to layer 20, and 
consequently layer 20 may be relatively easily punctured or deformed. 
Gel coat top layer 20 is quite thin and is comprised of thermoset polyester 
resin. Thermoset polyester resins are well known to those skilled in the 
art. The thermoset polyester resins may generally be formed by 
condensation reaction of anhydrides such as maleic anhydride or carboxylic 
acids such as maleic acid with alcohols; generally anhydrides or 
dicarboxylic acids with polyols such as ethylene glycol and the like, and 
including optionally an aromatic unsaturated polycarboxylic acid or 
anhydride such as phthalic acid or anhydride, isophthalic acid or 
anhydride, terephthalic acid or anhydride, orthophthalic acid or anhydride 
and the like. The bond resulting from the condensation reaction is an 
ester bond. Generally the mixture is dissolved in an unsaturated monomer 
such as styrene, the unsaturated polyesters usually being cross-linked 
through their double bonds in the presence of a suitable unsaturated 
monomer such as styrene. In the presence of catalysts, and generally of 
heat, the resins will cure to form a hard thermoset. 
Polyester resins are formed from a variety of materials including maleic 
acid or anhydride, fumaric acid, phthalic acid or anhydride, isophthalic 
acid or anhydride, and the like with alcohols such as ethylene glycol, 
propylene glycol, diethylene glycol and dipropylene glycol. The most 
common cross-linking agents are styrene and diallyl phthalate. 
Peroxide catalysts such as benzoyl peroxide, methyl ethyl ketone peroxide, 
tertiary butyl perbenzoate and cumene hydroperoxide are usually added to 
the polyester resin to effect curing. A number of other peroxide catalysts 
such a cyclohexanone peroxide, 2,4-dichlorobenzoyl peroxide, 
bis-(para-bromobenzoyl) peroxide, and acetyl peroxide, are also used. 
Polymerization inhibitors may be added to polyester resins to prevent 
polymerization of the polyester resin at room temperature in the absence 
of catalysts. Some typically used inhibitors include hydroquinone, 
paratertiary-butyl-catechol, phenolic resins, aromatic amines, pyrogallol, 
chloranil, picric acid and quinones. 
General literature references relevant to polyester resins which may be 
used in preparing resin compositions in accordance with the invention are 
the Condensed Chemical Dictionary (10th Ed.), G. D. Hawley (Reviser), Van 
Nostrand Reinhold (NY), 1981, p 830; Encyclopaedia of Polymer Science and 
Technology, H. F. Mark, N. G. Gaylord, and N. M. Bikales (Eds.), John 
Wiley and Sons, NY, 1969, Vol. 11, p 62-168, U.S. Pat. No. 3,396,067; and 
U.S. Pat. No. 2,255,313, the disclosures thereof being incorporated herein 
by reference. 
The thermosettable polyester resin composition may also optionally contain 
a solvent so that it may readily be sprayed on the mold 11. Any of the 
nonreactive solvents normally in making polyester resin compositions 
suitable for spraying may be used. Representative examples of these 
include benzene, toluene, the paraffinic naphthas, the naphthenic 
naphthas, the aromatic naphthas, ethyl formate, propyl formate, butyl 
formate, amyl formate, ethyl acetate, propyl acetate, methyl acetate, 
butyl acetate, amyl acetate, acetone methyl ethyl ketone, diethyl ketone, 
methyl isoamyl ketone, cellosolve acetate, cellosolve propylate, 
cellosolve acetate butyrate, dioxane, lower nitroparaffins, etc. Mixtures 
of solvents may be used. 
Generally, sufficient solvent is added to form a solution containing from 
about 40 to about 65 percent solids. However, a higher or lower 
concentration of solids can be used. 
This thermosettable polyester composition may also optionally include 
pigments, flame retardants, surfactants, inert fillers such as talc, mica, 
etc., mold release agents, and other well known processing fillers which 
give a composition that can be sprayed as a heavy even coat without 
sagging, pinholing, eyeholing or other processing defects. 
The thermosettable polyester resin composition does not contain any fibrous 
reinforcing material such as glass fibers. Thus, the gel coat top layer 20 
is likewise free of reinforcing fibers. 
The coating of thermosettable polyester composition is deposited, 
preferably by spraying, onto the surface 12 of mold 11. The thickness of 
the thermosettable composition coating deposited onto the surface 12 of 
mold 11 is generally a thickness which upon thermosetting of said 
polyester provides a thermoset polyester layer having a thickness of from 
about 10 to about 30 mils. Generally, this coating thickness is from about 
12 to about 34 mils. The thermosettable polyester is then cured or 
thermoset. This is generally accomplished by heating at about 80.degree. 
to about 110.degree. F. for a period of from about 15 to about 30 minutes. 
It is to be understood that curing time may be decreased by increasing the 
curing temperature. 
The gel coat top layer 20 preferably has a smooth and shiny outer surface 
21 simulating the appearance of porcelain. This is accomplished by the 
surface 12 of the mold upon which the thermosettable polyester resin 
composition is sprayed being smooth and polished. 
The gel coat top layer 20 generally has a thickness of from about 10 to 
about 30 mils, preferably from about 14 to about 20 mils. 
Supporting layer 30 is comprised of high density thermoset polyurethane 
foam. The polyurethane foams are well known in the art and are described, 
inter alia, in "Encyclopedia of Chemical Technology", Kirt-Othmer, Second 
Edition, Volume 21, pages 84-94, Interscience publishers, a division of 
John Wiley and Sons, Inc., New York, N.Y., incorporated herein by 
reference. 
Polyurethanes may generally be prepared by reacting an organic 
polyisocyanate with an active hydrogen-containing compound such as a 
polyol or a polyamine. 
By the term "polyurethane" is meant a polymer whose structure contains 
predominately urethane 
##STR1## 
linkages between repeating units. Such linkages are formed by the addition 
reaction between an organic isocyanate group R--[--NCO] and an organic 
hydroxyl group [HO--]--R. In order to form a polymer, the organic 
isocyanate and hydroxyl group-containing compounds must be at least 
difunctional. However, as modernly understood, the term "polyurethane" is 
not limited to those polymers containing only urethane linkages, but 
includes polymers containing allophanate, biuret, carbodiimide, 
oxazolinyl, isocyanurate, uretidinedione, and urea linkages in addition to 
urethane. The reactions of isocyanates which lead to these types of 
linkages are summarized in the Polyurethane Handbook, Gunter Vertel, Ed., 
Hanser Publishers, Minich, 001985, in Chapter 2, pages 7-41; and in 
Polyurethanes: Chemistry and Technology, J. H. Saunders and K. C. Frisch, 
Interscience Publishers, New York, 1963, Chapter III, pages 63-118. In 
addition to polyols (polyhydroxyl-containing monomers), the most common 
isocyanate-reactive monomers are amines and alkanolamines. In these cases, 
reaction of the amino group leads to urea linkages interspersed within the 
polyurethane structure. 
The urethane forming reaction is generally catalyzed. Catalysts useful are 
well know to those skilled in the art, and many examples may be found for 
example, in the Polyurethane Handbook, Chapter 3, .sctn.3.4.1 on pages 
90-95; and in Polyurethanes: Chemistry and Technology in Chapter IV, pages 
129-217. Most commonly utilized catalysts are tertiary amines and 
organotin compounds, particularly dibutyltin diacetate and dibutyltin 
dilaurate. Combinations of catalysts are often useful also. 
In the preparation of polyurethanes, the isocyanate is reacted with the 
active hydrogen-containing compound(s) in an isocyanate to active hydrogen 
ratio of from 0.5 to 1 to 10 to 1. The "index" of the composition is 
defined as the --NCO/active hydrogen ratio multiplied by 100. While the 
extremely large range described previously may be utilized, most 
polyurethane processes have indices of from 90 to about 120 or 130, and 
more preferably from 95 to about 110. In the case of polyurethanes which 
also contain significant quantities of isocyanurate groups, indices of 
greater than 200 and preferably greater than 300 may be used in 
conjunction with a trimerization catalyst in addition to the usual 
polyurethane catalysts. In calculating the quantity of active hydrogens 
present, in general all active hydrogen containing compounds other than 
non-dissolving solids are taken into account. Thus the total is inclusive 
of polyols, chain extenders, functional plasticizers, etc. 
Hydroxyl group-containing compounds (polyols) useful in the preparation of 
polyurethanes are described in the Polyurethane Handbook in chapter 3, 
.sctn.3.1 pages 42-61; and in Polyurethanes; Chemistry and Technology in 
Chapter II, .sctn..sctn.III and IV, pages 32-47. Many hydroxyl-group 
containing compounds may be used, including simple aliphatic glycols, 
dihydroxy aromatics, bisphenols, and hydroxyl-terminated polyethers, 
polyesters, and polyacetals, among others. Extensive lists of suitable 
polyols may be found in the above references and in many patents, for 
example in columns 2 and 3 of U.S. Pat. No. 3,652,639; columns 2-6 of U.S. 
Pat. No. 4,421,872; and columns 4-6 of U.S. Pat. No. 4,310,632; those 
three patents being hereby incorporated by reference. 
Preferably used are hydroxyl-terminated polyoxyalkylene and polyester 
polyols. The former are generally prepared by well known methods, for 
example by the base catalyzed addition of an alkylene oxide, preferably 
ethylene oxide (oxirane), propylene oxide (methyloxirane) or butylene 
oxide (ethyloxirane) to an initiator molecule containing on the average 
two or more active hydrogens. Examples of preferred initiator molecules 
are dihydric initiators such as ethylene glycol, propylene glycol, 
butylene glycol, neopentyl glycol, 1,6-hexanediol, hydroquinone, 
recorcinol, the disphenols, aniline and other aromatic monoamines, 
aliphatic monoamines, and monoesters of glycerine; trihydric initiators 
such as glycerine, trimethylolpropane, trimethylolethane, 
N-alkylphenylenediamines, mono-, di-, and trialkanolamines; tetrahydric 
initiators such as ethylene diamine, propylenediamine, 2,4'-, 2,2'-, and 
4,4'- methylenedianiline, toluenediamine, and pentaerythritol; pentahydric 
initiators such as diethylenetriamine; and hexahydric and octahydric 
initiators such as sorbitol and sucrose. 
Addition of alkylene oxide to the initiator molecules may take place 
simultaneously or sequentially when more than one alkylene oxide is used 
resulting in block, heteric and block-heteric polyoxyalkylene polyethers. 
The number of hydroxyl groups will generally equal the number of active 
hydrogens in the initiator molecule. Processes for preparing such 
polyethers are described both in the Polyurethane Handbook and 
Polyurethanes; Chemistry and Technology as well as in many patents, for 
example U.S. Pat. Nos. 1,922,451; 2,674,619; 1,922,459; 3,190,927; and 
3,346,557. 
Polyester polyols also represent preferred poly-urethane-forming reactants. 
Such polyesters are well known in the art and are prepared simply by 
polymerizing polycarboxylic acids or their derivatives, for example their 
acid chlorides or anydrides, with a polyol. Numerous polycarboxylic acids 
are suitable, for example malonic acid, citric acid, succinic acid, 
glutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 
maleic acid, fumaric acid, terephthalic acid, and phthalic acid. Numerous 
polyols are suitable, for example the various aliphatic glycols, 
trimethylolpropane and trimethyloethane, a-methylglucoside, and sorbitol. 
Also suitable are low molecular weight polyoxyalkylene glycols such as 
polyoxyethylene glycol, polyoxypropylene glycol, and block and heteric 
polyoxyethylene-polyoxypropyene glycols. These lists of dicarboxylic acids 
and polyols are illustrative only, and not limiting. An excess of polyol 
should be used to ensure hydroxyl termination, although carboxy groups are 
also reactive with isocyanates. Methods of preparation of such polyester 
polyols are given in the Polyurethane Handbook and in Polyurethanes; 
Chemistry and Technology. 
Also suitable as the polyol are polymer modified polyols, in particular the 
so-called graft polyols. Graft polyols are well known to the art, and are 
prepared by the in situ polymerization of one or more vinyl monomers, 
preferably acrylonitrile and styrene, in the presence of a polyether or 
polyester polyol, particularly polyols containing a minor amount of 
natural or induced unsaturation. Methods of preparing such graft polyols 
may be found in columns 1-5 and in the Examples of U.S. Pat. No. 
3,652,639; in columns 1-6 and the Examples of U.S. Pat. No. 3,823,201; 
particularly in columns 2-8 and the Examples of U.S. Pat. No. 4,690,956; 
and in U.S Pat. No. 4,524,157; all of which patents are herein 
incorporated by reference. 
Non-graft polymer modified polyols are also preferred, for example those 
prepared by the reaction of a polyisocyanate with an alkanolamine in the 
presence of a polyol as taught by U.S. Pat. Nos. 4,293,470; 4,296,213; and 
4,374,209; dispersions of polyisocyanurates containing pendant urea groups 
as taught by U.S. Pat. No. 4,386,167; and polyisocyanurate dispersions 
also containing biuret linkages as taught by U.S. Pat. No. 4,359,541. 
Other polymer modified polyols may be prepared by the in situ size 
reduction of polymers until the particle size is less than 20)m, 
preferably less than 10)m. 
Also useful in preparing polyurethanes are monomers containing other 
functional groups which are reactive with isocyanates. Examples of these 
are preferably the amines, for example the substituted and unsubstituted 
toluenediamines and methylenedianilines; the alkanolamines; the 
amino-terminated polyoxylalkylene polyethers; and sulfhydryl terminated 
polymers, to name but a few. The alkanolamines and amines, particularly 
diamines, are particularly useful, as the aminogroup reacts faster than 
the hydroxyl group and thus these molecules can act as isocyanate chain 
extenders in situ without the need to prepare prepolymers. Examples of 
hindered, alkyl substituted aromatic diamines which are particularly 
useful are disclosed in U.S. Pat. No. 4,218,543. 
Many isocyanates are useful in the preparation of urethanes. Examples of 
such isocyanates may be found in columns 8 and 9 of U.S. Pat. No. 
4,690,956, herein incorporated by reference. The isocyanates preferred are 
the commercial isocyanates toluenediisocyanate (TDI) 
methylenediphenylene-diisocyanate (MDI), and crude or polymeric MDI. Other 
isocyanates which may be useful include isophoronediisocyanate and 
tetramethylxylylidenediisocyanate. Other isocyanates may be found in the 
Polyurethane Handbook, Chapter 3, .sctn.3.2 pages 62-73 and Polyurethanes: 
Chemistry and Technology Chapter II, .sctn.II, pages 17-31. 
Modified isocyanates are also useful. Such isocyanates are generally 
prepared through the reaction of a commercial isocyanate, for example TDI 
or MDI, with a low molecular weight diol or amine, or alkanolamine, or by 
the reaction of the isocyanates with themselves. In the former case, 
isocyanates containing urethane, biuret, or urea linkages are prepared, 
while in the latter case isocyanates containing allophanate, carbodiimide, 
or isocyanurate linkages are formed. 
Chain extenders may also be useful in the preparation of polyurethanes. 
Chain extenders are generally considered to be low molecular weight 
polyfunctional compounds or oligomers reactive with the isocyanate group. 
Aliphatic glycol chain extenders commonly used include ethylene glycol, 
propylene glycol, 1,4-butanediol, and 1,6-hexanediol. Amine chain 
extenders include aliphatic monoamines but especially diamines such as 
ethylenediamine and in particular the aromatic diamines such as the 
toluenediamines and the alkylsubstituted (hindered) toluenediamines. 
Other additives and auxiliaries are commonly used in polyurethanes. These 
additives include plasticizers, flow control agents, fillers, 
antioxidants, flame retardants, pigments, dyes, mold release agents, and 
the like. Many such additives and auxiliary materials are discussed in the 
Polyurethane Handbook in Chapter 3, .sctn.3.4, pages 90-109; and in 
Polyurethanes: Chemistry and Technology, Part II, Technology. 
Polyurethane foams contain an amount of blowing agent which is inversely 
proportional to the desired foam density. Blowing agents may be physical 
(inert) or reactive (chemical) blowing agents. Physical blowing agents are 
well known to those in the art and include a variety of saturated and 
unsaturated hydrocarbons having relatively low molecular weights and 
boiling points. Examples are butane, isobutane, pentane, isopentane, 
hexane, and heptane. Generally the boiling point is chosen such that the 
heat of the polyurethane-forming reaction will promote volatilization. 
The most commonly used physical blowing agents, however, are currently the 
halocarbons, particularly the chlorofluorocarbons. Examples are methyl 
chloride, methylene chloride, trichlorofluoromethane, 
dichlorodifluoromethane, chlorotrifluoromethane, chlorodifluoromethane, 
the chlorinated and fluorinated ethanes, and the like. Brominated 
hydrocarbons may also be useful. Blowing agents are listed in the 
Polyurethane Handbook on page 101. 
Chemical blowing agents are generally low molecular weight species which 
react with isocyanates to generate carbon dioxide. Water is one practical 
chemical blowing agent, producing carbon dioxide in a one-to-one mole 
ratio based on water added to the foam formulation. Unfortunately, 
completely water-blown foams have not proven successful in many 
applications, and thus it is common to use water in conjunction with a 
physical blowing agent. 
Blowing agents which are solids or liquids which decompose to produce 
gaseous by-products at elevated temperatures can in theory be useful, but 
have not achieved commercial success. Air, nitrogen, argon, and carbon 
dioxide under pressure can also be used in theory, but have not proven 
commercially viable. Research in such areas continues, particularly in 
view of the trend away from chlorofluorocarbons. 
Polyurethane foams generally require a surfactant to promote uniform cell 
sizes and prevent foam collapse. Such surfactants are well known to those 
skilled in the art, and are generally polysiloxanes or polyoxyalkylene 
polysiolxanes. Such surfactants are described, for example, in the 
Polyurethane Handbook on pages 98-101. Commercial surfactants for these 
purposes are available from a number of sources, for example from Wacker 
Chemie, the Union Carbide corporation, and the Dow-Corning Corporation. 
Processes for the preparation of polyurethane foams and the equipment used 
therefore are well known to those in the art, and are described, for 
example, in the Polyurethane Handbook in Chapter 4, pages 117-160 and in 
Polyurethane; Chemistry and Technology, Part II, Technology, in Chapter 
VII, .sctn..sctn.III and IV on pages 7-116 and Chapter VIII, 
.sctn..sctn.III and IV on pages 201-238. 
Polyurethane useful in this invention may be prepared by reacting a 
reactive hydrogen-containing material such as a polyol or a reactive 
hydrogen-containing polymeric material with a polyisocyanate according to 
the following general procedure which is known as the prepolymer method: 
The reactive hydrogen-containing material such as a polymeric material is 
reacted with the organic polyisocyanate in proportions such that the ratio 
of isocyanate groups to the reactive hydrogen-containing groups of the 
reactive hydrogen-containing material such as a polymeric material is from 
about 1.1/1 to about 12/1 and preferably about 1.2/1 to about 2.5/1. These 
materials are generally reacted at temperatures from about 20.degree. C. 
to about 150.degree. C. The reactive hydrogens of the reactive 
hydrogen-containing material such as a polymeric material are supplied by 
hydroxyl groups and amine groups. When the reactive hydrogen-containing 
material is a polymeric material this prepolymer is then usually dissolved 
or dispersed in the solvent to form a solution or dispersion which is then 
mixed with a catalyst, chain extending agent, and/or a cross-linking agent 
to form a polyurethane reaction mixture. 
Other methods known to those skilled in the art of preparing polyurethane 
reaction mixtures with or without solvents being present may also be used. 
As mentioned supra agents which promote chain extension and cross-linking 
of the polymer are also useful and are sometimes known as curing agents 
which facilitate reacting the polyurethane reaction mixture. Aromatic 
diamines, hydrocarbon diols, such as ethylene glycol and propylene glycol, 
hydroxyl-amines such as triisopropanolamine, are used in this invention as 
such agents. When these agents are used they are usually added to the 
prepolymer in a ratio of from about 0.5/1 to about 1.5/1 and, preferably, 
about 0.8/1 to about 1.0/1 amine and or hydroxyl groups of the chain 
extending and cross-linking agent for each isocyanate group in excess of 
the reactive hydrogen groups of the reactive hydrogen-containing polymeric 
material. Bifunctional materials such as glycols and diamines are 
generally preferred as chain extending and cross-linking agents. In 
general the bifunctional materials yield products having superior spraying 
properties. Representative classes of compounds suitable for use as such 
agents are glycols, diamines having primary or secondary amino groups, 
dicarboxylic acids, hydroxy amines, hydroxy-carboxylic acids, and 
amino-carboxylic acids. Representative examples of suitable compounds 
belonging to these classes are glycols such as ethylene glycol, 
1,3-propane-diol, 1,4-butane-diol and glycerol; aliphatic diamines such as 
ethylene diamine, trimethylene diamine, and tetramethylene diamine; 
aromatic diamines such as m-phenylene diamine, o- and m-dichlorobenzidine, 
2,5-dichlorophenylene diamine, 3,3'-dichloro-4,4'-diamino-diphenyl 
methane, dianisidine, 4,4'-diamino-diphenyl methane, the naphthylene 
diamines, toluene-2,4-diamine, p-aminobenzyl aniline, and o- and 
p-aminodiphenyl-amine; hydroxy amines such as triethanol amine, 
2-amino-ethyl alcohol, 2-amino-1-naphthol and m-aminophenyl; hydroxy 
carboxylic acids such as glycolic acid and alpha-hydroxy propionic acid; 
and amino carboxylic acids such as amino acetic acid and amino benzoic 
acid. The preferred crosslinking agents are butane diol and the 
chloroamines such as orthodichlorobenizine and methylene 
bis-orthochloroaniline. Generally the chain extending or cross-linking 
agents having acid groups tend to from a cellular polyurethane. 
In one embodiment a solvent may be used to prepare the polyurethane 
reaction mixture. Any of the nonreactive solvents normally used in 
preparing compositions suitable for spraying are useful for the 
polyurethane reaction mixtures which may be used in this invention. 
Representative examples of these are benzene, toluene, the paraffinic 
naphthas, the naphthenic naphthas, the aromatic naphthas, ethyl formate, 
propyl formate, butyl formate, amyl formate, ethyl acetate, propyl 
acetate, methyl acetate, butyl acetate, amyl acetate, acetone methyl ethyl 
ketone, diethyl ketone, methyl isoamyl ketone, cellosolve acetate, 
cellosolve propylate, cellosolve acetate bytyrate, dioxane, lower 
nitroparaffins, etc. Mixtures of solvents may be used. 
Generally, sufficient solvent is added to form a solution containing from 
about 40 to about 65 percent solids. However a higher or lower 
concentration of solids can be used. 
In a preferred embodiment of the instant invention the isocyanate component 
is mixed with the polyol component in the spray gun before spraying. In 
this embodiment the isocyanate component is stored in one container or 
drum. The second container or drum contains the polyol component, the 
catalyst, the blowing agent, and other optionally present materials such 
as surfactant, flame retardants, chain extenders, and the like. The 
contents of the two containers are mixed just before application to form a 
reaction mixture, and this reaction mixture is then applied or used to 
form the polyurethane. 
It is critical that the high density thermoset polyurethane foam comprising 
layer 30 has a density and thickness at least effective to provide support 
to said top layer 20. Thus, the high density thermoset polyurethane foam 
has a density of at least about 10 lbs/ft.sup.3, preferably at least about 
15 lbs/ft.sup.3, and more preferably at least about 20 lbs/ft.sup.3. The 
upper range of density is not critical and is governed by factors such as 
the design of the spraying equipment and economics. Generally, the density 
should not exceed about 70 lbs/ft.sup.3, preferably it should not exceed 
about 50 lbs/ft.sup.3, and more preferably it should not exceed about 35 
lbs/cu. ft. The minimum thickness of layer 30 is at least about 30 mils 
thick, preferably at least about 60 mils thick. Layer 30 is from about 30 
mils to about 400 mils thick, preferably from about 60 mils to about 250 
mils thick. If the density is less than about 10 lbs/cu. ft. and layer 30 
is thinner than about 30 mils, layer 30 will not provide sufficient 
support to layer 20. 
The thermosettable, foamable polyurethane composition which when thermoset 
and foamed comprises supporting layer 30 is deposited onto layer 20 as a 
coating having a thickness effective to provide a thermoset, foamed 
polyurethane layer having a thickness of at least about 30 mils. Since, 
upon foaming, the thermosettable, foamable polyurethane expands to about 
twice its thickness, this coating thickness is at least about 15 mils. 
This coating of thermosettable, foamable, polyurethane composition is 
preferably deposited onto layer 20 by spraying. 
The thermosettable, foamable polyurethane coating is then allowed to foam 
and cure or thermoset. This generally requires from about 20 to about 40 
minutes. Since this reaction is exothermic, the application of heat is not 
required to form the thermoset, high density polyurethane foam comprising 
supporting layer 30. 
Intermediate layer 40 is comprised of a thermoset polyurethane foam. The 
thermoset polyurethane foam of layer 40 preferably has a lower density 
than the thermoset polyurethane foam of layer 30 and is a low density 
polyurethane foam. Generally the density of the thermoset polyurethane 
foam comprising layer 40 may range from about 1.25 lbs/ft.sup.3 to about 
15 lbs/ft.sup.3, preferably from about 1.5 lbs/ft.sup.3 to about 10 
lbs/ft.sup.3, more preferably from about 1.5 lbs/ft.sup.3 to about 3 
lbs/ft.sup.3. 
Layer 40 is formed by depositing a coating comprised of thermosettable, 
foamable polyurethane composition onto layer 30. This coating composition 
is then allowed to thermoset and foam to provide a thermoset polyurethane 
foam comprising layer 40. The preferred method of depositing this coating 
composition onto layer 30 is by spraying. 
The thickness of the thermosettable, foamable polyurethane coating 
deposited on layer 30 is an amount which is effective to provide a 
thermoset polyurethane foam layer 40 having a thickness of from about 250 
mils to about 1,500 mils. Since this is a low density system, i.e., a 
highly foamable system, the coating of thermosettable, foamable 
polyurethane composition required to produce the required thickness of the 
thermoset polyurethane foam layer 40 is relatively thin, e.g., from about 
20 to about 100 mils. 
The polyurethane foam coating is sprayed onto layer 30 after the 
polyurethane foam comprising layer 30 has foamed and cured or thermoset. 
The thermosettable, foamable polyurethane composition is then allowed to 
foam and cure or thermoset thus forming layer 40. The curing generally 
takes from about 20 to about 40 minutes. 
Layer 40 is generally thicker than layer 30. Layer 40 generally has a 
thickness of from about 250 mils to about 1,500 mils, preferably from 
about 500 mils to about 800 mils. 
After the thermosettable, foamable polyurethane has foamed and cured or 
thermoset to form the thermoset polyurethane foam layer 40 a coating 
comprised of thermosettable, foamable polyurethane composition is 
deposited onto layer 40. 
This thermosettable foamable polyurethane composition coating is generally 
similar to or the same as the thermosettable foamable polyurethane 
composition used to produce supporting layer 30, and is generally applied 
in the same or similar manner as the composition used to form layer 30. 
This thermosettable, foamable polyurethane composition is allowed to foam 
and cure or thermoset thereby forming bottom layer 50. 
The thermoset polyurethane foam comprising bottom layer 50 generally has a 
density of from about 10 lbs/ft.sup.3 to about 70 lbs/ft.sup.3, preferably 
from about 15 to about 50 lbs/ft.sup.3, and more preferably from about 20 
to about 35 lbs/ft.sup.3. 
Layer 50 is generally from about 30 mils to about 400 mils thick, 
preferably from about 40 mils to about 200 mils thick. 
After layer 50 is formed the shaped article is removed from the mold 11 and 
may be subjected to further processing such as trimming and the like. 
The instant invention also includes a method of manufacturing a composite 
shaped article. In one embodiment, as illustrated in FIGS. 1 and 2, the 
method comprises applying a thermosettable polyester resin composition 
coating onto surface 12 of mold 11; heating this composition coating at an 
elevated temperature and for a period of time effective to substantially 
or completely thermoset said thermosettable polyester resin thereby 
forming top layer 20; applying a coating comprised of foamable, 
thermosettable polyurethane composition free of any reinforcing fibrous 
material such as glass fibers onto layer 20; allowing the foamable, 
thermosettable polyurethane composition coating to cure thereby forming 
supporting layer 30; applying a coating comprised of thermosettable 
foamable polyurethane composition free of any reinforcing fibrous material 
such as glass fibers onto said supporting layer 30; allowing this 
thermosettable, foamable polyurethane composition to foam and cure or 
thermoset thereby forming intermediate layer 40; applying a coating 
comprised of thermosettable, foamable polyurethane composition free of any 
reinforcing fibrous material such as glass fibers onto said intermediate 
layer 40; allowing the thermosettable, foamable polyurethane composition 
to foam and cure or thermoset to thereby form bottom layer 50; and 
removing the composite article from the mold. 
In the embodiment illustrated in FIG. 3 the intermediate thermoset 
polyurethane foam layer 40 is disposed on only a portion of supporting 
layer 30. It is disposed mainly at those areas which are subjected to the 
greatest stress and load forces, e.g., at the sides and bottom of the tub. 
Where layer 40 is absent bottom layer 50 is disposed directly on and in 
surface-to-surface contact with supporting layer 30. 
This structure is prepared substantially in accordance with the procedure 
described for the embodiment illustrated in FIGS. 1 and 2 with the 
exception that the thermosettable, foamable polyurethane composition 
forming layer 40 is applied, preferably sprayed, on only a portion of the 
supporting layer 30. This intermediate coating composition is allowed to 
foam and cure to a thermoset and foamed state to form intermediate layer 
40. Bottom layer 50 is then disposed on intermediate layer 40 in those 
areas where intermediate layer 40 is present, and directly onto supporting 
layer 30 in those areas where intermediate layer 40 is not present. 
In the embodiments illustrated in FIGS. 4-6 the shaped structure, in this 
case a bathtub, is provided with a support structure comprised of members 
60 and 61 on the bottom wall 14 at area A. Member 60 is a flat, 
horizontally extending member comprised of fiberboard, plywood, and the 
like. Member 61 is generally a 2" by 4" piece of wood attached, by 
fasteners such as nails, to member 60. As illustrated in FIG. 6 the bottom 
of the tub does not rest directly on floor 100 but is supported by the 
support structure. 
In making the shaped articles of the embodiments illustrated in FIGS. 4-6 
the thermoset polyester top layer 20 is first formed on the surface 12 of 
mold 11 as described above. A coating comprised of thermosettable, 
foamable polyurethane composition is then deposited on layer 20 and cured 
or thermoset to form layer 30 having a thickness and density as described 
supra. This composition is deposited and cured to form layer 30 as 
described above except at the bottom wall 14 of the tub at area A where 
the support member is disposed. 
Over area A the thickness of this coating composition which is deposited on 
layer 20 is less than that required to provide, upon curing or 
thermosetting and foaming, layer 30 having a thickness of at least about 
30 mils. Generally, the thickness of this coating at A is sufficient to 
form a thermoset polyurethane foam layer, herein referred to as layer 30', 
having a thickness of at least about one half of the total thickness of 
the cured layer 30, i.e., at least about 15 mils, generally from at least 
about 15 mils to about 200 mils depending upon the thickness of the cured 
layer 30. The coating composition is then allowed to cure or thermoset to 
form layer 30' comprised of a thermoset polyurethane foam which has a 
thickness of at least about 15 mils, preferably at least about 30 mils. 
Layer 30' generally has a thickness from at least about 15 mils to about 
200 mils. Once layer 30' is formed a second coating of this foamable, 
thermosettable polyurethane composition is deposited on layer 30'. The 
thickness of this second coating is sufficient to form a second layer, 
hereinafter referred to as layer 30", comprised of a thermoset 
poloyurethane foam which, when combined with the thickness of layer 30', 
will produce layer 30 having the thickness described supra. Generally, 
layer 30" will have a thickness of from at least about 15 mils to about 
200 mils. Before this second coating composition is cured to form layer 
30" the supporting member 60 is pressed against this uncured composition. 
Since this uncured composition is quite tacky, it acts as an adhesive to 
adhere member 60 to cured layer 30'. Once the supporting member 60 is in 
place and adheres to layer 30' on the bottom wall 14 at area A of the tub, 
more of this thermosettable, foamable polyurethane composition is 
deposited onto the surface of support member 60 and around the edges of 
the support member 60. Generally sufficient composition is deposited on 
and around member 60 to form a cured layer 30a having a thickness of from 
about 30 to about 400 mils. The coating composition deposited on layer 30' 
and on and around member 60 are then allowed to cure or thermoset to form 
layers 30" and 30a, respectively. Supporting member 60 is thus laminated 
or bonded to the shaped article 10, more specifically to layer 30'. 
As can be seen from the foregoing layers 30', 30" and 30a are all comprised 
of the same or substantially the same thermoset polyurethane foam. 
Furthermore, layers 30' and 30" form layer 30 at area A which has a 
thickness of at least about 30 mils. Layer 30 outside area A is formed in 
a one step process. Layer 30 in area A is formed by a two step process 
which includes first forming layer 30' and then forming layer 30" on layer 
30'. Layer 30 outside area A is identical in composition to layer 30 in 
area A. Both layers 30 in area A and outside area A have a minimum 
thickness of at least about 30 mils. 
In the embodiment illustrated in FIGS. 4 and 5 the intermediate layer 40 
and bottom layer 50 are then deposited onto supporting layer 30 as 
described above. As seen in FIGS. 4 and 5 layers 40 and 50 do not extend 
over layer 30a. 
The embodiment illustrated in FIG. 6 is similar to the embodiment 
illustrated in FIG. 3 in that intermediate layer 40 is deposited only over 
a portion of supporting layer 30, with the portions of layer 30 which do 
not have layer 40 deposited therein being in contact with bottom layer 50. 
The tub structure illustrated in FIGS. 2, 3, 5, 6 and 7 is comprised of 
side walls 13 and a bottom wall 14. In the embodiment illustrated in FIG. 
2 the intermediate layer 40 is present in both the side walls 13 and the 
bottom wall 14. In the embodiment illustrated in FIG. 3 the intermediate 
layer 40 is present in only part of the side walls 13 and in the bottom 
wall 14. In those areas of the side walls where intermediate layer 40 is 
absent bottom layer 50 is disposed directly on supporting layer 30. 
In the embodiment illustrated in FIGS. 5, 6 and 7 the supporting structure 
60 and 61 does not extend along the entire length of the bottom wall 14 of 
the tub. The supporting structure, as illustrated in FIG. 7, is generally 
located in approximately the center section of the bottom wall. In these 
areas of the bottom wall 14 where the supporting structure is not present 
bottom layer 50 is disposed directly on the bottom surface or side of 
supporting layer 30, e.g., intermediate layer 40 is not present in the 
bottom wall 14. 
In the embodiment illustrated in FIG. 5 the intermediate layer 40 is 
disposed on supporting layer 30 in the side walls 13, while in the bottom 
wall 14 intermediate layer 40 is absent and the bottom layer 50 is 
disposed directly on the bottom surface or side of supporting layer 30 in 
those portions of the bottom wall not covered by the supporting structure 
60 and 61. 
In the embodiment illustrated in FIG. 6 the intermediate layer is present 
in only a portion of the side walls 13. In those portions of the side 
walls 13 where intermediate layer 40 is absent the bottom layer 50 is 
disposed directly on supporting layer 30. The intermediate layer 40 is 
absent from the bottom wall 14 and in bottom wall 14 bottom layer 50 is 
disposed directly on supporting layer 50 in those portions of bottom wall 
14 not covered by the supporting structure 60 and 61. 
In both the embodiments illustrated in FIG. 5 and 6, as best illustrated in 
FIG. 7, bottom layer 50 is not present on supporting structure 60 and 61. 
Instead, member 60 of the supporting structure has layer 30a disposed 
thereover. The following examples are presented to further illustrate the 
present invention. They are presented by way of illustration rather than 
limitation. 
EXAMPLE 1 
This example illustrates the preparation of a bathtub illustrated in FIG. 
2. There is provided a bathtub shaped mold 11 having substantially the 
shape illustrated in FIG. 1. A first coating comprising thermosettable 
unsaturated polyester composition is sprayed onto the exterior surface 12 
of the mold. The thermosettable polyester composition comprises the 
following components in percent by weight: 
21.17% of a dicyclopentadiene polyester resin (derived from diethylene 
glycol and maleic acid) in styrene monomer; 
38.39% of a neopentyl glycol orthopthalic polyester resin in styrene 
monomer; 
13.62% styrene monomer; 
8.86% talc filler; 
0.04% lecithin 
3.54% zeothix 
10.63% titanium dioxide 
2.84% Zeolex 80 (alumina silicate) 
0.36% silicone 
0.13% vegetable oil 
0.18% of a 12% cobalt catalyst 
0.17% dimethylacetoamine 
This composition is mixed with a stream of 2 weight percent of methyl ethyl 
ketone peroxide catalyst as it exits the nozzle of the spray gun, and this 
resultant composition containing 2 weight percent methyl ethyl ketone 
peroxide is sprayed onto the mold. The first coating thickness is about 20 
mils. This coating is cured and the thermosettable polyester resin 
thermoset at about 40 degree Centigrade for a period of about 20 minutes 
to form top layer 20. Top layer 20 is about 15 mils thick. 
After top layer 20 is formed a second coating comprised of high density, 
thermosettable, foamable polyurethane composition is sprayed onto layer 
20. The polyurethane composition components are stored in two separate 
tanks and are mixed in about a 50/50 weight % basis in a spray gun, and 
the resultant reaction mixture is then ejected from the nozzle of the 
spray gun. One tank contains polymethylenepolyphenylene polyisocyanate 
commercially available from BASF Corporation under the designation 
LUPRANATE.TM. M20S. The other tank contains less than about 85 weight % 
polyol (comprised of a mixture of a monoethanolamine-initiated 
polyoxypropylene-polyoxyethylene copolymer having a nominal equivalent 
weight of 112; a toluene diamine/ethylenediamine-initiated 
polyoxyethylene-polyoxypropylene copolymer having a nominal equivalent 
weight of 187; and a polyethylene terephthalate-based aromatic polyester 
polyol having a nominal equivalent weight of 160); about 5 weight 
glycerine; about 1% water blowing agent, about 2 weight % silicone 
surfactant; about 2 weight % dimethylcyclohexylamine; and less than about 
10 weight % trichloropropyl phosphate flame retardant. The resultant 
reaction mixture coating composition is deposited on the surface of layer 
20. The thickness of this coating is about 50 mils. The polyurethane 
composition is then allowed to cure or thermoset at about 35.degree. 
Centigrade for about 20 minutes to form supporting layer 30. Supporting 
layer 30 has a thickness of about 125 mils. The thermoset, high density 
polyurethane foam comprising supporting layer 30 has a density of about 25 
pounds per cubic foot. 
After supporting layer 30 is formed a third coating is sprayed onto 
supporting layer 30. This third coating is comprised of low density 
thermosettable, foamable polyurethane composition. The polyurethane 
composition components are stored in two separate tanks and are mixed on 
about a 50/50 weight % basis in a spray gun, and the resultant reaction 
mixture is then ejected from the nozzle of the spray gun and sprayed onto 
supporting layer 30. One tank contains polymethylenepolyphenylene 
polyisocyanate commercially available from BASF Corporation under the 
designation LUPRANATE.TM. M20S. The other tank contains about 60 weight 
percent polyol (comprised of a mixture of a monoethanolamine-initiated 
polyoxypropylene-polyoxyethylene copolymer having a nominal equivalent 
weight of 112; a toluene diamine/ethylenediamine-initiated 
polyoxyethylene-polyoxypropylene copolymer having a nominal equivalent 
weight of 187; and a polyethylene terephthalate-based aromatic polyester 
polyol having a nominal equivalent weight of 160); about 10 weight percent 
silicone; about 4 weight percent dimethylcycolhexane; and about 25 weight 
% trichlorofluoromethane blowing agent. This reaction mixture coating 
composition is deposited on the surface of supporting layer 30. The 
thickness of this coating is about 100 mils. The polyurethane composition 
is then allowed to cure or thermoset at about 25.degree. Centigrade for 
about 2 minutes to form intermediate layer 40. The low density thermoset 
polyurethane foam comprising intermediate layer 40 has a density of about 
2 pounds per cubic foot. Intermediate layer 40 is about 750 mils thick. 
After intermediate layer 40 is formed a fourth coating is sprayed onto 
intermediate layer 40. This fourth coating is comprised of high density, 
thermosettable, foamable polyurethane composition. This fourth coating is 
the same as the second coating described above. The thickness of this 
fourth coating is about 30 mils. The polyurethane composition is allowed 
to cure at about 35 degree Centigrade for about 20 minutes to form bottom 
layer 50. Bottom layer 50 is the same as supporting layer 30, e.g., the 
thermoset high density polyurethane foam has a density of about 25 pounds 
per cubic foot. Bottom layer 50 is about 75 mils thick. 
Once layer 50 is formed the article is removed from the mold and subjected 
to finishing operations such as trimming, etc. 
EXAMPLE 2 
This example illustrates the preparation of a bathtub illustrated in FIG. 
3. The procedure of Example 1 is substantially repeated with the exception 
that the third coating of Example 1 is sprayed only on a portion of 
supporting layer 30 on side walls 13. The top portions of side walls 13, 
as illustrated in FIG. 3, are left free of the third coating. The third 
coating is allowed to cure as set forth in Example 1 to form intermediate 
layer 40. 
The fourth coating of Example 1 is then sprayed onto intermediate layer 10 
where present and onto supporting layer 30 where intermediate layer 40 is 
absent. The fourth coating is then allowed to cure as set forth in Example 
1 to form bottom layer 50. 
The article is then removed from the mold. The article produced by this 
example is illustrated in FIG. 3. 
EXAMPLE 3 
This Example illustrates the preparation of a bathtub illustrated in FIG. 
5. 
There is provided a bathtub shaped mold 11. The first coating of Example 1 
is sprayed onto the exterior surface 12 of the mold 11. The first coating 
has a thickness of about 20 mils. This coating is cured at about 
40.degree. Centigrade for a period of about 20 minutes to form top layer 
20. Top layer 20 is about 15 mils thick and is comprised of thermoset 
polyester resin. 
After top layer 20 is formed, a second coating of Example 1 comprised of 
the high density, thermosettable, foamable polyurethane composition is 
sprayed onto layer 20. However, this second coating is sprayed onto layer 
20 in two different thicknesses. The thickness of the second coating on 
area A on bottom wall 14 is less than the thickness of the coating on the 
side walls 13 and on the bottom wall 14 outside area A. The thickness of 
the second coating on area A is about 25 mils. The thickness of the second 
coating on the side walls 13 and on the bottom wall 14 outside area A is 
about 50 mils. The high density, thermosettable, foamable polyurethane 
composition comprising the second coating is allowed to cure at about 
35.degree. Centigrade for a period of about 20 minutes to form the 
supporting layer 30 comprised of thermoset, high density polyurethane foam 
as described in Example 1. In area A the supporting layer 30 has a 
thickness of about 63 mils, while on the side walls 13 and on bottom wall 
14 outside area A the supporting layer 30 has a thickness of about 125 
mils. 
After this supporting layer 30 is formed more of this second coating 
composition (hereinafter referred to as the third coating) is sprayed onto 
area A to form a coating having a thickness of about 25 mils (this third 
coating thickness is sufficient to provide a cured layer having a 
thickness of about 63 mils). Thus, the supporting layer 30 on area A will 
have a thickness substantially equal or equal to the thickness of the 
supporting layer on the side walls 13 and on the bottom wall 14 outside 
area A, i.e., about 125 mils). Before this third coating composition on 
area A is cured, e.g., while it is still tacky, the support structure 
comprised of fiberboard with a 2" by 4" board attached thereto is pressed 
against the third coating in area A. 
More of this second coating composition (hereinafter referred to as the 
fourth coating) is then sprayed onto the surface and around the edges of 
the support structure. The thickness of this fourth coating is about 50 
mils. The third and fourth coatings are then allowed to cure thereby 
laminating the support structure to the article. The cured third coating 
forms part of the supporting layer 30, while the cured fourth coating 
forms laminating layer 30a. Laminating layer 30a has a thickness of about 
125 mils. The composition of the laminating layer 30a is the same as the 
composition of the supporting layer 30. 
A fifth coating comprised of thermosettable, low density, foamable 
polyurethane composition (which is the same as the third coating 
composition in Example 1) is sprayed onto the supporting layer 30 on only 
the side walls 13. The fifth coating thickness is about 100 mils. The 
fifth coating is allowed to cure at about 35.degree. Centigrade for about 
2 minutes to form intermediate layer 40. Intermediate layer 40 has the 
same composition as intermediate layer 40 in Example 1. The thickness of 
intermediate layer 40 is about 750 mils. 
After intermediate layer 40 is formed a sixth coating comprised of 
thermosettable, high density, foamable polyurethane composition (which is 
the same as the fourth coating composition of Example 1) is sprayed onto 
the intermediate layer 40 on the side walls 13. This sixth coating has a 
thickness of about 30 mils. This sixth coating is allowed to cure at about 
35.degree. Centigrade for a period of about 20 minutes to form bottom 
layer 50. Bottom layer 50 has a thickness of about 75 mils and is of the 
same composition as bottom layer 50 of Example 1. 
The second, third, fourth and sixth coatings are generally comprised of the 
same thermosettable, high density, foamable polyurethane composition, 
i.e., the second coating composition of Example 1. 
The outside is then removed from the mold and subjected to additional 
processing such as trimming, cutting and the like. 
EXAMPLE 4 
This Example illustrates the preparation of a bathtub illustrated in FIG. 
6. 
The procedure of Example 3 is substantially repeated except that the fifth 
coating is sprayed only on a portion of supporting layer 30 on side walls 
13. The top portions of side walls 13, as illustrated in FIG. 6, are left 
free of the fifth coating. The fifth coating is allowed to cure as in 
Example 3 to form intermediate layer 40. 
The sixth coating of Example 3 is then sprayed onto intermediate layer 40 
where present and onto supporting layer 30 on the side walls 13 where 
intermediate layer 40 is absent. The sixth coating is allowed to cure as 
in Example 3 to form bottom layer 50. As seen in FIG. 6, bottom layer 50 
is present on intermediate layer 40 where intermediate layer 40 is present 
and on supporting layer 30 on those portions of side walls 13 where 
intermediate layer 40 is absent.