U.S. patent number RE28,682 [Application Number 05/585,154] was granted by the patent office on 1976-01-13 for decorative laminate.
This patent grant is currently assigned to Rohm & Haas Company. Invention is credited to Charles E. Hoey.
United States Patent |
RE28,682 |
Hoey |
January 13, 1976 |
**Please see images for:
( Certificate of Correction ) ** |
Decorative laminate
Abstract
A procedure is provided for producing a laminate having a
textile backing, a crushed, thermoset plastic foam bonded thereto,
and a transparent polymeric film, preferably also a thermoset,
which may be printed or colored overall overlying the foam. The
structure is self-bonded, i.e., no adhesive is used to bond the
laminate to one another. The preferred procedure is to apply a thin
layer of foamed latex of a thermosettable polymer on a textile
followed by drying the foam, the thickness of the foam being
between about 10 mils and 150 mils. The transparent film,
preferably thermosetting, is suitably formed by casting a latex
upon a release surface such as silicone release paper and drying
the same without causing thermosetting (if a thermosettable polymer
is utilized). The dry film, still on the release paper, is then
suitably coated or printed with a decorative design. The decorated
side of the film is then placed against the dried foam layer and
bonded thereto by pressure. The thermosetting may be done
simultaneously with bonding or subsequently thereto.
Inventors: |
Hoey; Charles E. (Marlton,
NJ) |
Assignee: |
Rohm & Haas Company
(Philadelphia, PA)
|
Family
ID: |
26945023 |
Appl.
No.: |
05/585,154 |
Filed: |
June 9, 1975 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
Reissue of: |
255879 |
May 10, 1972 |
03804700 |
Apr 16, 1974 |
|
|
Current U.S.
Class: |
428/196; 428/159;
428/202; 428/314.2; 428/201; 428/211.1 |
Current CPC
Class: |
B44C
5/04 (20130101); B44F 11/02 (20130101); Y10T
428/249975 (20150401); Y10T 428/24851 (20150115); Y10T
428/24934 (20150115); Y10T 428/24504 (20150115); Y10T
428/2486 (20150115); Y10T 428/2481 (20150115) |
Current International
Class: |
B44F
11/02 (20060101); B44C 5/00 (20060101); B44C
5/04 (20060101); B44F 11/00 (20060101); B32B
003/26 () |
Field of
Search: |
;428/159,196,201,202,211,315,321,322 ;156/77,78,79 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Plastics/Paper, Warren Co. Div. Scott Paper, Nov. 1968, 6 pages.
.
Release Paper Information, Warren Co. Div. Scott Paper, Nov. 1970,
2 pages. .
Plastics/Paper, Warren Co. Div. Scott Paper, 1971, 14 pages. .
Rohm and Haas Reporter, Vol. XXVII, No. 2, Mar. -Apr. 1969, pages
12-15..
|
Primary Examiner: Van Balen; William J.
Attorney, Agent or Firm: Strobaugh; Terence P.
Claims
I claim:
1. A laminate consisting of
a. a transparent plastic surface film of a thermoset emulsion
polymer .Iadd.transferred from a release surface and
.Iaddend.adhered to
b. a crushed, crosslinked thermoset resilient foam of a thermoset
emulsion polymer adhered to
c. a textile fabric substrate, with
d. a decorative layer between (a) and (b) the crushed foam layer
(b) being self-bonded to the substrate (c) and the surface
film.
2. The article of claim 1 in which the surface film has printed
thereon a decorative layer (d) between (a) and (b), the article has
a fabric like hand, and the crushed foam is less than about 90 mils
in thickness.
3. The article of claim 1 in which reaction products of one or more
of a crosslinking group of the structure ##EQU8## provides the
crosslinking.
4. The article of claim 3 in which the foam (b) and the film (a)
contain a polymerized unsaturated acid and the crosslinking is
provided by a water soluble condensate of formaldehyde with urea,
N,N'-ethyleneurea, dihydroxyethyl ureas or a triazine.
Description
This invention relates to a decorative laminate such as a simulated
oil painting and a process for its manufacture. The laminate
consists of a substrate such as a textile fabric, a crushed,
thermoset foam self-adhered thereto and a top layer of of a clear
film, which may be printed or otherwise colored by coating,
pigmenting, or dyeing. The printed or coated side of the film can
be adhered to the foam to encapsulate the color in order to protect
it from abrasion, cleaning, etc. Preferably the film is also
thermoset. The laminae are self-adhered or self-bonded; i.e., no
extraneous adhesive is needed.
In the past, similar laminates have been made without a foam
interlayer, and unless the clear film is exceptionally thick, the
product is not subject to embossing in such a way as to keep the
backing in substantially planar form. Where an interlayer has been
used between the decorative material and the substrate, it has
either been a resilient material of a relativelly massive thickness
or in some cases a thermoplastic material. Where forms have been
used for this function, the foam is either of such light weight and
low density that a fabric-like hand could not be obtained, or is a
dense foam provided by controlling the amount of blowing or foaming
agent or controlling the extent of expansion, the product thus
being relatively stiff and inflexible and again does not have the
hand of a soft fabric. Commonly in laminating fabrics to foams or
foams to other layers such as a transparent film, the practice is
to use a separate adhesive layer for such bonding or to use
thermoplastic materials which can be softened and bonded by heat
and pressure. The present invention makes it unnecessary to use
such adhesive, thus substantially reducing the number of operations
necessary to achieve the product of the invention.
In a preferred embodiment of the present invention, the clear film
is prepared from a latex as is the foam interlayer. Also, it is
preferred that the clear film be thermosetting and that it be cured
only after being in contact with the dry thermosettable foam and
that the curing take place, of course, subsequent to or
simultaneous with crushing or embossing the foam. Curing of the
composite may also be delayed until fabrication, where the
composite can be heat sealed to produce seams without sewing.
In a specific preferred embodiment, a clear cross-linkable or
thermosettable acrylic film is desposited in the form of a latex
onto release paper coated with a silicone release coating, the film
is dried without thermosetting, and a decorative material is
printed on the dried clear film while still on the release paper. A
similar crosslinkable acrylic polymer in latex form is foamed,
preferably by means of whipped in air and in the presence of a foam
stabilizer, the foam is then applied to a fabric, woven or
non-woven, and gelled and dried without causing crosslinking. The
printed side of the clear film and the foamed surface of the
fabric-foam laminate are then juxtaposed, the foam is reduced in
thickness by pressure, with or without embossing a design in the
laminate, and the clear film and foam layer are heated to a
temperature sufficiently high to crosslink and thermoset the
polymers. Other clear films may be used and other thermosettable
foams may be used, but in every case the foam is thermoset only
after being reduced in thickness. The foam, when a latex, is
initially foamed to a wet foam density of about 0.5 to 0.05 grams
per cubic centimeter and is applied in a thickness of from about 10
to 150 mils. The density, of course, will vary with the presence or
absence of pigments and fillers and their identity. The foam is
then dried without causing thermosetting, crosslinking, or
vulcanization to a sensibly dry condition, for example, to an
air-dry or sensibly dry state, for example, by heating at a
temperature below that which causes said thermosetting,
crosslinking, or vulcanization, an example being from 1 to 10
minutues at an oven temperature of 200.degree.-350.degree.F.,
followed preferably after having placed the decorated side of the
clear film and the surface of the foam together, by crushing the
foam to a thickness between 5 percent and 25 percent of its
original dry thickness to give a density of about 0.2 to 3
g./cc..sup.3, followed by curing of the crushed foam. In general,
the thickness of the dried foam prior to crushing may be
substantially less than that of the wet foam, there at times being
some shrinkage. This shrinkage is in the range of 0 to 30 percent
of the thickness of the wet foam being lost during drying. Suitable
moisture contents range from 5 percent to 15 or 20 percent in order
to qualify as air dry or sensibly dry materials. The criteria as to
moisture content is that the foam must be stable enough to be
self-bonded to the top film. Of course, in a system wherein a
chemical blowing agent is used to form the foam or in which a
solvent system is utilized to form the foam, when the foam is dried
it is essentially anhydrous. In some cases cross-linking may be
accomplished by catalysis rather than primarily by the application
of heat. Of course, the foam may be crushed before it is
self-bonded to the surface film, but in this case a crushing roll
having a release coating such as a silicone or Teflon is desirable.
Normally no adhesive is needed between the foam and the textile or
between the decorated surface of the clear film and the surface of
the foam, since a thermosettable foam is used, and the final curing
of the foam causes a firm bond between the layers.
Crushed foam is essential, since if the initial foam is formed to
the final density by control of the amount of foaming agent or by
means such as using a chemical blowing agent and restraining the
expansion in order to get the final density, the walls or struts
connecting the air spaces are relatively thick. A crushed foam, on
the other hand, initially having expanded to a number of times its
final thickness, has connective walls or struts of a thin flexible
nature. The result is that the crushed foam is much more flexible
than a foam initially expanded to the density noted above. These
foams are inherently opaque. The opacity can be compared with the
opacity of whipped egg whites; the liquid egg white is
substantially transparent and the gas cells incorporated therein
confer opacity upon the whipped froth.
When pigmented compositions are contemplated, examples of the
pigments that may be employed include clays especially of the
kaolin type, calcium carbonate, blanc fixe, talc, titanium dioxide,
colored lakes and toners, ochre, carbon black, graphite, aluminum
powder or flakes, chrome yellow, molybdate orange, toluidine red,
copper phthalocyanines, such as the "Monastral" blue and green
lakes. If dyed compositions are used, examples of dyes for acrylic
film and foam include basic and dispersed dyes. Other composites
could be made dyeable, if not inherently so, through the use of
additives such as methyl cellulose, hydroxyl ethyl cellulose, and
the like. Other dyes which could be used include acid dyes, vat
dyes, direct dyes, and fiber reactive dyes.
The clear film is preferably cast from a single acrylic latex
(thickened if necessary) or other suitable latex such as
carboxylated SBR containing antioxidants or UV stabilizers,
polyvinyl chloride, ethylene polyvinyl chloride, polyvinylidene
chloride, polyvinyl acetate, polyvinyl alcohol as well as
copolymers of these latices. The film has delayed cure properties
built into it where strigent durability requirements (resistance to
multiple washing and drycleaning) exist.
The film may be cast from two or more latices to achieve specific
effects. For example, the "first-down" basecoat latex can be
selected for its toughness and its freedom from residual tackiness.
The "second-down" topcoat can be a softer material providing more
plastic flow under heat and pressure to achieve embossing,
lamination and heat sealing where necessary.
The finish on release paper (or other suitable release medium) can
be picked up by the transfer film when it is pulled off of the
release medium to provide a surface finish for other specific
effects. For example, silicone surfaced release paper can be
engineered so that some of the silicone goes with the film when it
is pulled off the release paper to provide the water
repellency.
Solvent systems can be used instead of latices alone, or in
combination with aqueous systems where multilayer films are made as
previously described. For example, a solvent saran first-down coat
can be topped with an aqueous coating so that the composite film,
when pulled off release paper and inverted, would expose a
tack-free saran outer surface.
The films can be made breathable by mechanically foaming the latex
before casting, mechanically puncturing the film, using chemical
blowing agents or dissolving or digesting out temporary fillers
placed in the latex before it is cast. An example of the latter
method would be the use of starch granules in the mix before
casting, subsequently digesting the starch granules with an enzyme
leaving pores in the film.
For specialty effects, the film can be colored by pigmenting the
liquid medium before casting, adding dyes to the liquid medium
before casting, post-dyeing the composite or vacuum metalizing the
film after casting. Another includes printing or coating the
release medium with pigments or ink which would be transferred to
the film after it is dried and pulled away from the release
medium.
A delayed cure acrylic film is preferred which provides freedom
from plasticizer as a means of minimizing pollution as well as
avoiding the possibility that plasticizer migration will cause the
foam and film to separate eventually. In addition, there is a
distinct likelihood that the presence of plasticizers in either the
film or the foam will cause printing inks to bleed distorting
decorative effects.
While the preferred clear (essentially transparent) film is that
obtained from a crosslinkable acrylic latex as suggested herein,
other crosslinkable latices are useful as are preformed films.
Examples of other latices are crude rubber in which 3 percent of
the polymer is in the form of combined maleic anhydride,
butadiene-styrene polymers and butadiene-acrylonitrile polymers
containing 3 percent to 5 percent carboxylated groups, carboxylated
polyisoprene, and other natural and artificial polymers modified to
have cross-linkable or thermosettable functionality. In each case,
external crosslinkers such epoxy exposy resins are used. As is
implied by the above, the same general types of crosslinkable
polymers are useful for both the clear film and the foam.
Thermoplastic films which may be used include polyvinyl chloride,
ethylene-vinyl chloride copolymer, polyvinylidene chloride,
polyvinyl acetate, polyvinyl alcohol and copolymers thereof, saran,
polyurethane, Mylar, Tedlar (polyvinyl fluoride), ethylene-vinyl
acetate, and the like. Similar preformed films can be made from
ethylene-Vinyl acetate, ethylene-methyl acrylate, ethylene-ethyl
acrylate copolymers, ionomers, vinyl chloride-propylene, vinyl
chloride-ethylene, vinly chloride-acrylate, polyethylene, nylons,
and chlorotrifluoroethylene, polyester, polycarbonate, and the
like. While many of the clear theromplastic films are useful, they
are not nearly so desirable as the thermosetting clear films
deposited from latices, or less desirably from an organic solvent
solution.
An embossed textured surface will not always be necessary and the
composite can be made by simply adhering the film/foam/textile
having a flat surface. Where a three dimensional effect is desired,
this can be achieved by using embossed rolls or plates, nipping the
composite through rolls or plates at the same time as embossed
paper is passed through the nip or casting the film on release
paper which has previously been embossed to such a depth that a
flat surface of film is achieved for printing if necessary.
Subsequently, the film on embossed release paper and the foam on
the supporting substrate are run through a plain nip and the
embossed pattern is imparted through the composite by the embossed
release paper on which the film was originally cast. After the
marriage, the embossed release paper can be pulled away from the
composite and reused. After crushing the foam and embossing, if
used, the laminate is cured (thermoset, cross-linked) by heating at
a suitable temperature, for example, 1 to 5 minutes at
275.degree.-375.degree. F.
An important advantage in utilizing a dried but uncured foam of a
crosslinkable polymer and a dried but uncured clear film, printed
or not, is that the two elements can be passed through the nip of a
pair of rollers, the distance between which is small enough to
"marry" the two but insufficient to crush the dried foam, all
without using an adhesive to bond the foam to the fabric or other
substrate and to bond the foam to the clear printed or unprinted
film. Of course, bonding of the dry foam and the clear film can be
done at a pressure sufficient to crush the foam with or without
embossing the same. Even after crushing, the foam has sufficient
resilience to be embossed with a patterned roller. If desired, the
embossing roller may be heated to the curing temperature of the
thermosetting film and foam, although normally a period of time is
required which necessitates passing the laminate through an
oven.
For a description of suitable conventional foaming procedures and
foam stabilizers and foaming agents, reference is made to Madge, E.
W., "Latex Foam Ruber," John Wiley and Sons, New York (1962) and
Rogers, T. H., "Plastic Foams," Paper, Reg. Tech. Conf., Palisades
Sect., Soc. Plastics Engrs., New York, November, 1964. Most common
are the alkali metal, ammonia, and amine soaps of saturated or
unsaturated acids having, for example, from about 12 to about 22
carbon atoms. Examples of suitable soaps include tallow soaps and
coconut oil soaps, preferably the volatile amine or ammonia soaps,
so that the volatile portion is vaporized from the foam. Other
useful foaming-foam-stabilizing agents include lauryl
sulfate-lauryl alcohol, lauryl sulfate-lauric acid, sodium lauryl
sulfate, and other commonly used foamed stabilizers or foaming
agents.
It is to be understood that the foam may be laminated to other
substrates. Examples of such substrates include woven and non-woven
fabrics, plastic films, rigid plastics, leather substitutes,
leather, paper, wood including plywood, metals such as of steel,
iron, aluminum, copper, brass, zinc which may be bare or primed
such as with an epoxy or with an epoxy/aminoplast priming layer,
and so forth.
Suitable woven and non-woven textile substrates include fiberglass,
nylon taffetas and tricots, texturized polyester fabrics, cotton
duck, Spandex knits, woolens and worsteds, flocked fabrics, rayon
fabrics and blends of natural and synthetic fibers. The textile may
be simply a functional supporting substrate or a textile having a
pre-finished "face" to serve as the outer surface of the composite
or as a lining. An example is a synthetic pile fur fabric, the back
of which is used to function as the supporting substrate for the
foam/film to end up with a composite having two functional and
aesthetically appealing surfaces. Such a composite could be used to
make a reversible coat which would have a leather-like texture on
one side and a fur texture on the other. Non-wovens are made by air
lay, dry lay, wet lay and spun-bonded processes. Various forms of
paper and paperboard may also be used. Tissue is included as paper
in this description.
The latex, when formulated with the foam stabilizer and optionally,
suitable pigments, is readily convertible into the foamed state.
The polymer composition is such that excessive thickening of the
formulation is not encountered under the acid or alkaline
conditions employed to assure the most efficient operation of the
foam stabilizing agent. In addition the copolymer is such that the
crushed foam retains its softness and its flexibility at low
temperatures at least to a temperature as low as 10.degree. F., and
after curing is non-tacky. In addition, the foam is resistant to
washing in normal detergents used for cleaning of textiles in
general and drapery fabrics in particular and is resistant to
drycleaning. By providing a foam that is durable to drycleaning and
to washing the foam is quite useful for textiles which are
frequently subjected to drycleaning and washing operations.
An important property of the polymer for both the foam and the
clear film is the glass transition temperature (Tg) thereof, and
consequently the selection of monomers and proportions thereof
depends upon their influence on the Tg. The Tg of the polymer for
the foam is suitably between -60.degree. and 35.degree. C. For the
clear film, it is normally between -30.degree. and 100.degree. C.
"Tg" is a conventional criterion of polymer hardness and is
described by Flory, "Principles of Polymer Chemistry," pp. 56 and
57, (1953), Cornell University Press. While actual measurement of
the Tg is preferred, it may be calculated as described by Fox,
Bull. Am. Physics Soc. 1, 3, p. 123 (1956). Examples of the Tg of
homopolymers and the inherent Tg thereof which permits such
calculations are as follows:
Homopolymer of Tg ______________________________________ n-octyl
acrylate -80.degree.C. n-decyl methacrylate -60.degree.C.
2-ethylhexyl acrylate -70.degree.C. octyl methacrylate
-20.degree.C. n-tetradecyl methacrylate 9.degree.C. methyl acrylate
9.degree.C. n-tetradecyl acrylate 20.degree.C. methyl methacrylate
105.degree.C. acrylic acid 106.degree.C.
______________________________________
These or other monomers are blended to give the desired Tg of the
copolymer. As is known, for a given number of carbon atoms in the
alcohol moiety, the extent and type of branching markedly
influences the Tg, the straight chain products giving the lower Tg.
Most of the esters of acrylic acid or methacrylic acid having a low
Tg are well known in the art.
One of the monomers utilized in a substantial proportion to prepare
the preferred clear films and foam is a "soft" monomer which may be
represented by the following formula: ##EQU1## wherein R is H or
alkyl having one to four carbon atoms and R' is the straight chain
or branched chain radical of a primary or secondary alkanol,
alkoxyalkanol or alkylthiaalkanol, and having up to about 14 carbon
atoms, examples being ethyl, propyl, n-butyl, 2-ethylhexyl, heptyl,
hexyl, octyl, propyl, 2-methylbutyl, 1-methylbutyl, butoxybutyl,
2-methylpentyl, methoxymethyl, ethoxyethyl, cyclohexyl, n-hexyl,
isobutyl, ethylthiaethyl, methylthiaethyl, ethylthiapropyl,
n-octyl, 6-methylnonyl, decyl, dodecyl, and the like, said radicals
R.sup.1, when alkyl, having from two to about 14 carbon atoms,
preferably from three to 12 carbon atoms, when R is H or methyl.
When R is alkyl and R.sup.1 is alkyl, R.sup.1 should have from
about six to about 14 carbon atoms and when R is H and R.sup.1 is
alkyl, R.sup.1 should have from about two to about 12 carbon atoms,
in order to qualify as a soft monomer.
Other ethylenically unsaturated copolymerizable monomers having a
Tg of above 0.degree. C. are useful in combinations with the above
mentioned soft monomers provided they do not adversely affect the
desired properties of the polymer (e.g., unduly raise the overall
Tg) and do not seriously interfere with the crosslinking. These may
be represented by the formula: ##EQU2## wherein R is as above.
R.sup.2 is preferably alkyl and is methyl or alkyl having from
about 13 to about 20 carbon atoms when R is H, and is alkyl of from
one to about five carbon atoms or alkyl of from about 15 to about
20 carbon atoms when R is methyl. It can be seen from about that
for alkyl acrylates and alkyl methacrylates the Tg at first
decreases with an increased chain length of the alkyl group and
then the Tg again increases; i.e., both hard and soft monomers are
known to occur in each group of monomers. Examples of these hard
monomers and other hard monomers include: methyl acrylate,
acrylamide, vinyl acetate, tetradecyl acrylate, pentadecyl
acrylate, methyl methacrylate, ethyl methacrylate, t-butyl
acrylate, butyl methacrylate, styrene, pentadecyl methacrylate,
vinyl toluene, methacrylamide, and N-methylolacrylamide.
The preferred emuslion copolymers, for both the foam and the clear
layer, having a molecular weight of between about 70,000 and
2,000,000, and preferably between about 250,000 and 1,000,000 and
are made by the emulsion copolymerization of the several monomers
in the proper proportions. Conventional emulsion polymerization
techniques are described in U.S. Pat. Nos. 2,754,280 and 2,795,564.
Thus, the monomers may be emulsified with an anionic, a cationic,
or a nonionic dispersing agent, about 0.05 percent to 10 percent
thereof ordinarily being used on the weight of the total monomers.
The acid monomer and many of the other functional or polar monomers
may be soluble in water so that the dispersing agent serves to
emulsify the other monomer or monomers. A polymerization initiator
of the free-radical type, such as ammonium or potassium persulfate,
may be used alone or in conjunction with an accelerator, such as
potassium metabisulfite, or sodium thiosulfate. Organic peroxides,
such as benzoyl peroxide and t-butyl hydroperoxide are also useful
initiators. The initiator and accelerator, commonly referred to as
catalyst, may be used in proportions of 0.1 percent to 10 percent
each based on the weight of monomers to be compolymerized. The
amount, as indicated above, may be adjusted to control the
intrinsic viscosity of the polymer. The temperature may be from
room temperature to 60.degree. C. or more as is conventional.
Suitable dispersing agents useful in emulsion polymerization
include anionic types such as the sodium salts of the higher fatty
acid sulfates, such as that of lauryl alcohol, the higher fatty
acid salts, such as the oleates or stearates or morpholine,
2-pyrrolidone, triethanolamine or mixed ethanolamines, or any of
the nonionic types, such as ethylene oxidemodified alkyl phenols,
of which tert-octyl phenol modified by 20 to 40 ethylene oxide
units is representative, ethylene oxide-modified higher fatty
alcohols such as lauryl alcohol, containing 20 to 50 ethylene oxide
units, similarly modified long-chain mercaptans, fatty acids,
amines, or the like. Mixtures of nonionic and anionic dispersing
agents are also useful.
Although emulsion polymers are preferred, polymers prepared in
organic solutions, e.g., in xylene, methyl "Cellosolve" and the
like, by well-known conventional means such as free-radical
initiation with benzoyl peroxide or the like are also useful.
Solution polymers useful in the invention preferably have a
molecular weight of between about 10,000 and 1,000,000.
There are essentially two types of latent cross-linking which can
be used. These are (1) crosslinking subsequent to polymerization by
including monomers in the polymer recipe which have functional
groups capable or crosslinking by various mechanisms including
self-crosslinking, or mutual crosslinking by different functional
groups, both in the polymer chain, and (2) latent crosslinking by
means of an external separately added chemical compound.
Combinations can be used.
The foam is subjected to latent crosslinking, after drying and
crushing. Where addition polymers are involved, monomers which are
suitable for this function include certain acrylics having
crosslinkable functionality exemplified below.
Examples of the crosslinking reactions which are possible using
heat, aging, and/or catalysis are: ##EQU3## In the above, R is H or
CH.sub.3. Addition polymerizable unsaturated monomers containing
such groups are well known in the art, examples being isocyanates
such as isocyanatoethyl methacrylate, epoxy compounds such as
glycidyl methacrylate, aminoalkyl compounds such as
methylaminoethyl methacrylate, and t-butylaminoethyl methacrylate,
amides such as methacrylamide, guanamines such ad
4-pentenoquanamine, hydroxyalkyl esters such as hydroxypropyl
methacrylate and hydroxyethyl methacrylate, nitriles such as
methacrylonitrile, N-alkoxyalkyl amides such as methoxymethyl
methacrylamide, hydroxyalkyl amides such as N-methylol
methacrylamide, the analogs of the above methacrylic acid
derivatives with other unsaturated acids such as acrylic acid and
itaconic acid, such acids themselves, dicarboxylic acids such as
maleic acid and half esters and half amides thereof, vinyl ethers
of glycols such as ethylene glycol, and so forth.
As may be seen, the crosslinkable addition polymerizable
unsaturated monomers have reactive polar groups selected from those
including --OH, --SH, ##EQU4## Such groups may be included as are
mutually or self-crosslinkable, or separate crosslinking compounds
such as a triazine-formaldehyde resin may be added, as is well
known.
Of course, water sensitive materials such as isocyanates should not
be used in aqueous systems unless they are blocked by groups such
as phenol groups which protect the isocyanate groups until
subsequent heating or the use of other reaction mechanisms such as
the use of a calcium, zinc, or tin compound catalyst conventional
in the art.
There is thus included within the copolymer up to 20 percent by
weight of such functional, polar, or reactive monomer, preferably
an unsaturated carboxylic acid, half esters and half amides of
.alpha.-unsaturated dicarboxylic acids, and salts thereof with
ammonia, an alkali-metal, such as sodium, potassium or lithium, or
with a volatile water-soluble amine such as dimethylamine or
triethylamine, in order to provide the cross-linking functionality.
Examples of copolymerizable ethylenically unsaturated
monocarboxylic or polycarboxylic acids are sorbic, cinnamic, vinyl
furoic, .alpha.-chlorosorbic, p-vinylbenzoic, acrylic, methacrylic,
maleic, fumaric, aconitic, atropic, crotonic, and itaconic acid, or
mixtures thereof, with itaconic acid and the .alpha.,
.beta.-unsaturated monocarboxylic acids, particularly methacrylic
acid and acrylic acid, being preferred. Other copolymerizable acid
monomers include the alkyl half esters or partial esters of
unsaturated polycarboxylic acids such as of itaconic acid, maleic
acid, and fumaric acid, or the partial amides thereof. Preferred
half esters are the lower alkyl (C.sub.1 to C.sub.6) esters such as
methyl acid itaconate, butyl acid itaconate, methyl acid fumarate,
butyl acid fumarate, methyl acid maleate, and butyl acid maleate.
Such partial esters and partial amides are considered to be
".alpha.,.beta.-unsaturated monocarboxylic acids," and the term as
used herein includes such esters and amides.
In addition to or in place of the acids, amides such as acrylamide
and methacrylamide, 2-sulfoethyl methacrylate, the materials
disclosed in U.S. Pat. No. 3,446,777 to W. D. Emmons, U.S. Pat. No.
3,150,118 to D. H. Clemens, and U.S. Pat. No. 3,266,930 to W. D.
Emmons and E. Hankins Owens, and various other functional, polar,
or monomers having groups which remain reactive after the polymer
is formed, for example, falling within the definitions of formulas
II, III, IV, and V, are also useful, as follows: ##SPC1##
where R.sup.0 is selected from the group consisting of H and alkyl
groups having one to four carbon atoms, and
n is an integer having a value of 1 to 4,
Ch.sub.2 = c(r)aynr.sup.1 r.sup.2 (iii)
where R is selected from the group consisting of H and
CH.sub.3,
A is selected from the group consisting of O, S, ##EQU5## Y is an
alkylene group having two to four carbon atoms, R.sup.1 is selected
from the group consisting of H and an alkyl group having one to
four carbon atoms, and
R.sup.2 is selected from the group consisting of H and an alkyl
group having one to four carbon atoms, ##EQU6## where R is the same
as above, and Z is an alkylene group having two to three carbon
atoms.
Examples of compounds of formula II include: 2-vinylpyridine;
4-vinylpyridine; 2-methyl-5-vinylpyridine;
5-methyl-2-vinylpyridine; 4-methyl-2-vinylpyridine;
2-ethyl-5-vinylpyridine; 2,3,4-trimethyl-5-vinylpyridine;
3,4,5,6-tetramethyl-2-vinylpyridine; 3-ethyl-5-vinylpyridine;
2,6-diethyl-4-vinylpyridine.
Examples of compounds of formula III include: dimethylaminoethyl
acrylate and methacrylate; diethylaminoethyl acrylate and
methacrylate dimethylaminopropyl acrylate and methacrylate;
diethylaminopropyl acrylate and methacrylate; dipropylaminoethyl
acrylate and methacrylate; di-n-butylaminoethyl acrylate and
methacrylate; di-sec-butylaminoethyl acrylate and methacrylate;
di-t-butylaminoethyl acrylate and methacrylate; dimethylaminoethyl
vinyl ether and sulfide; diethylaminoethyl vinyl ether and sulfide;
aminoethyl vinyl ether and sulfide; monomethylaminoethyl vinyl
ether and sulfide; N,N-dimethylaminoethyl acrylamide and
methacrylamide; N,N-diethylaminoethyl acrylamide and
methacrylamide.
Examples of compounds of formula IV include:
N-[.beta.-(.alpha.-methacryloxyacetamido)ethyl]-N,N'-ethyleneurea;
N-[.beta.-(.alpha.-acryloxyacetamido)ethyl]-N,N'-ethyleneurea;
N-[.beta.-(.alpha.-acryloxyacetamido)ethyl]-N,N'-trimethyleneurea;
N-[.beta.-(.alpha.-methacryloxyacetamido)ethyl]-N,N'-trimethyleneurea.
##EQU7## where R and Z are as defined above, of which an example is
N-[.beta.-(methacrylamido)ethyl]-N,N'-ethyleneurea.
Generally, such functional monomers are present in amounts of from
0.05 to 20 percent, preferably from 0.3 to 10 percent by weight,
and more preferably 0.5 to 4.5 percent, based on the total monomers
that form the coating or foamable resin.
The separate added crosslinker, when used, is useful with or
without the use of mutual crosslinking groups and self-crosslinking
groups. Among the external crosslinking methods or compounds is the
use of organic peroxides such as benzoyl peroxide; the use of epoxy
resins such as that obtained from bis-phenol A and epichlorohydrin;
esterification, by means of dicarboxylic acids reacting with
hydroxyl groups in the polymers, or by reacting diols or polyols
such as neopentyl glycol, trimethylol propane, trimethylol ethane,
or ethylene glycol with carboxyl groups in the polymer; use of
aminoplasts such as melamine formaldehyde, urea formaldehyde, or
butylated melamine formaldehyde; diamines and polyamines such as
hexamethylene diamine, ethylene diamine, and the Versamids;
polyisocyanates such as toluylene diisocyanate; compounds with
mixed functionality such as ethanolamine, and other well-known
external crosslinkers. The invention is not in the use of
crosslinking per se but in the utilization of crosslinking and/or
the bodying agent to obtain the desired physical characteristics of
the foam or clear resin of the invention.
EXAMPLE 1
An emulsion compolymer dispersion prepared from 2,575 parts
deionized water, 87 parts sodium lauryl sulfate, 90 parts acrylic
acid, 315 parts acrylamide, 900 parts acrylonitrile, and 7,695
parts n-butyl acrylate is compounded in the following
formulation:
Product Solids ______________________________________ Dispersion
200 100 Titanium Dioxide (Titanox RA-45) 25 25 Clay (Acme WW) 30 30
Melamine-Formaldehyde Resin (Aerotex MW) 4.6 3.7 Ammonium Stearate
14 4.6 Water 70 -- Ammonia (28%) 4 -- 347.6 163.3 Solids - 47.0%
______________________________________
All parts and percentages are by weight unless otherwise
stated.
Foams are made by whipping air into the formulation using a
Kitchen-Aid Mixer (Model C) to a wet density of about 0.16 g.
cm..sup.3. The foam is then cast at 60 mils onto contton twill
cloth, 19 mils thick and dried for 1.75 minutes at 280.degree. F.
to give a dry foam 45 mils thick.
On a silicone coated release paper 5 mils thick, a latex (50
percent solids) of 65 parts ethyl acrylate, 25 parts butyl
acrylate, 5 parts acrylonitrile, 3.5 parts acrylamide and 1.5 parts
itaconic acid is cast in a thickness to give a dry film 2 mils
thick and dried at 95.degree. C. for 3 minutes. The exposed side of
the clear film is printed with a decorative design, and the printed
side and dried foam are then placed together and passed through a
pair of rollers, at room temperature, with a nip of 20 mils. The
release paper is then peeled off. The laminate is then passed
between a smooth and an embossed roller, both heated to
250.degree.-300.degree. F., the embossed roll being adjacent the
clear film. This embosses the film and foam, crushes the 45 mil
thick dry foam to about 8 mils thick, and firmly bonds the film,
foam, and fabric. To achieve more complete crosslinking of the foam
and film, the composite is heated in an oven for 2 minutes at
300.degree. F.
The crushed foam has a cold-flex temperature of -15.degree. F.
EXAMPLE 2
Example 1 is repeated except that 135 parts of itaconic acid, 315
parts of acrylamide, 5,850 parts of ethyl acrylate, 405 parts of
acrylonitrile and 2,305 parts of n-butyl acrylate are used as the
monomers for the foam.
EXAMPLE 3
Example 1 is repeated except that for the foam 675 parts of
acrylonitrile and 2,035 parts of n-butyl acrylate are used and
polymer drapery fabric is used. The resultant crushed foam has a
cold-flex temperature of 15.degree. F.
EXAMPLE 4
Example 1 is repeated except that 180 parts of acrylic acid, 315
parts of acrylamide, 900 parts of acrylonitrile and 7,605 parts of
n-butyl acrylate are used as the monomers, for the foam.
EXAMPLE 5
Example 1 is repeated except that 45 parts of acrylic acid, 315
parts of acrylamide, 1,800 parts of acrylonitrile and 6,840 parts
of n-butyl acrylate are used as the monomers, for the foam.
EXAMPLE 6
Example 1 is repeated but the monomers for the foam consist of 270
parts methacrylic acid, 180 parts acrylamide, 375 parts
acrylonitrile, 2,250 parts butyl acrylate, and 5,925 parts ethyl
acrylate.
EXAMPLE 7
The procedure described in Example 6 is repeated except the
methacrylic acid is replaced with 45 parts of itaconic acid and the
amount of butyl acrylate is changed to 2,475 parts.
EXAMPLE 8
The procedure described in Example 1 is followed with an emulsion
polymer of 170 parts itaconic acid, 200 parts methacrylic acid, 135
parts acrylamide, 450 parts acrylonitrile, 2,700 parts butyl
acrylate, and 3,485 parts ethyl acrylate, to prepare the foam.
EXAMPLE 9
The procedure described in Example 1 is carried out with an
emulsion polymer of 135 parts methacrylic acid, 180 parts
acrylamide, 630 parts acrylonitrile, 5,400 parts butyl acrylate,
and 3,655 parts isopropyl acrylate.
EXAMPLE 10
Example 1 is repeated with an emulsion polymer of 135 parts
itaconic acid, 270 parts acrylamide, 630 parts acrylonitrile, 5,400
parts butyl acrylate, 1,285 parts ethyl acrylate, and 1,285 parts
methyl acrylate, as the foam. Similar results are obtained when
isobutyl acrylate or 2-ethylhexyl acrylate are used in place of
butyl acrylate or ethyl acrylate.
* * * * *