U.S. patent number 3,673,611 [Application Number 05/037,464] was granted by the patent office on 1972-07-04 for molded hats having improved shape retention and recoverability.
This patent grant is currently assigned to Deering Milliken Research Corporation. Invention is credited to James P. Cain, John H. Cross.
United States Patent |
3,673,611 |
Cain , et al. |
July 4, 1972 |
MOLDED HATS HAVING IMPROVED SHAPE RETENTION AND RECOVERABILITY
Abstract
A molded hat having improved shape retention and recoverability
properties wherein the fabric of the crown and brim comprises a
single unit eliminating the need for sewing the brim to the crown,
said fabric containing a stabilizing polymeric composition. These
molded hats are prepared by placing the stabilized fabric in a hat
mold and thereafter applying heat and pressure to effect the
desired shape. The improved shape retention and recoverability
properties result from the presence of the polymeric composition in
the fabric.
Inventors: |
Cain; James P. (Spartanburg,
SC), Cross; John H. (Anderson, SC) |
Assignee: |
Deering Milliken Research
Corporation (Spartanburg, SC)
|
Family
ID: |
21894493 |
Appl.
No.: |
05/037,464 |
Filed: |
May 18, 1970 |
Current U.S.
Class: |
2/175.1; 8/127.6;
8/128.1; 223/12; 264/258; 264/324; 2/200.1 |
Current CPC
Class: |
A42C
1/02 (20130101); A41C 5/005 (20130101) |
Current International
Class: |
A41C
5/00 (20060101); A42C 1/02 (20060101); A42C
1/00 (20060101); A42b 001/00 (); A42c 001/00 ();
D06m 003/00 () |
Field of
Search: |
;161/82,88,89,98,170
;264/257,258,324 ;2/175,192,194 ;8/128,127.6 ;223/12 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Burnett; Robert F.
Assistant Examiner: Linker, Jr.; Raymond O.
Parent Case Text
This application is a continuation of Application Ser. No. 624,511,
filed Mar. 20, 1967, now abandoned.
Claims
What is claimed is:
1. A hat having improved shape retention and recoverability
properties including as a principal component thereof a molded
woven, knitted or braided fabric forming a crown portion and a
surrounding brim portion, said fabric including at least about 20
percent keratin fibers which have been stabilized prior to molding
by reaction with a polymeric composition selected from the class
consisting of reactive copolymers and terpolymers based on vinyl
type monomers, reactive polyurethanes, and reactive polyolefins;
said polymeric composition comprising between about 2 and 20
percent by weight of said fabric.
2. The molded hat of claim 1 wherein the fabric of the crown and
brim is a laminated fabric.
3. The molded hat of claim 1 wherein the stabilizing polymeric
composition is a reactive polyethylene composition.
Description
BACKGROUND OF THE INVENTION
This invention relates to shaped articles of wearing apparel, and
more particularly, to the manufacture of molded hats wherein the
crown and brim comprises a single unit.
The manufacture of wearing apparel and other textile articles by
the molding or shaping of textile fabrics has been an attractive
goal for many years. Most articles of the nature, for example,
hats, brassiere cups, shoe uppers, gloves, raincoats, etc., have
been prepared from a relatively large number of pieces of material
which are cut to the desired shape and stitched together. For
example, the crown of a hat can comprise from four to eight
separate pieces cut in a particular shape and secured together. The
brim of a hat is made of one or more additional strips of fabric
cut to the shape and secured to the lower edge of the crown. These
types of hats do not present the smart pleasing appearance of hats
which are made of one piece. One reason, among others, for this
lack of smart appearance is that these hats have a number of
unsightly seams running up the crown. Furthermore, hats prepared in
this manner do not usually possess the desired degree of shape
retention and resilience, and must, therefore, be reblocked and
reshaped periodically to restore the hats to their original shape.
Needless to say, such operations are costly and time consuming.
Attempts to improve the shape retention of such hats and other
shaped articles by utilizing linings of rubber, paper and other
materials which can impart a desired degree of stiffness to the
article have been somewhat successful. Attempts have also been made
to treat or spray the fabrics, generally after the article has been
formed, with a liquid such as shellac or enamel to improve the
shape retention properties of the articles. However, articles
treated in this manner are necessarily very stiff and do not have
the desirable amount of resiliency.
The use of thermoplastic fabrics for the manufacture of wearing
apparel and other articles has been somewhat successful although
such a method is not too desirable where the finished article must
be flexible and possess a smooth hand. The preparation of such
articles from thermoplastic fabrics is generally accomplished by
the application of heat to the thermoplastic material while
permitting deformation or stretching into the desired shape. After
formation is complete, the fabric is then set by an effective
reduction of temperature. During the procedure, however, a greater
degree of strain is exerted in certain fabric areas by the
application of stress or tension sufficient to obtain the required
displacement. For instance, in the manufacture of hats, there is a
maximum amount of displacement found in the area of the crown of
the hat as compared to the minimum fabric displacement required for
the brim. The non-uniform application of stretching tension results
in a finished product characterized by undesirable differences in
fabric porosity and general appearance. Additionally, structural
weaknesses within the shaped article are produced, and the desired
flexibility is substantially diminished. Furthermore, molded
articles of wearing apparel prepared exclusively from thermoplastic
fabrics are generally stiff and inflexible as a result of the
temperatures required during the shaping process.
Molded hats from flat-needle felted fabrics having an intermediate
thermoplastic shrinkable member therein have been prepared by
needling batting materials on each side of the intermediate
thermoplastic layer and then shrinking and molding the felted
fabric to form the molded hats. The procedure described in U.S.
Pat. No. 3,156,926 involves preheating the needle-felted fabric,
and while the thermoplastic layer is still warm and in a plastic
state, molding the fabric in an unheated mold of the desired shape
to cause the fabric to be stretched and molded to the desired
shape.
Molded articles of wearing apparel also have been prepared from
textile fabrics comprised of natural fibers in the form of discrete
fiber assemblies, for example, woven or knitted woolen fabrics, by
preparing a composition of the textile fabric and a layer of a
fixed structure of a synthetic thermoplastic composition are
described in co-pending Application Ser. No. 624,510, now
abandoned.
The preparation of molded hats from composite fabrics comprising a
layer of synthetic thermoplastic compositions and at least one
layer of a textile fabric containing keratin fibers wherein the
textile fabric is treated with a reducing agent and an
aldehyde-generating compound prior to molding is described in
co-pending Application Ser. No. 627,251 now U.S. Pat. No. 3,542,616
issued Nov. 24, 1970. Although the molded articles of wearing
apparel described in the co-pending applications exhibit an unusual
degree of shape retention and resiliency, there remains a need for
a method of preparing molded hats with the desired degree of
stability and resistance to stress release and puckering without
the use of fixed structures of thermoplastic resins which account
for the substantial portion of the cost of the materials used to
prepare molded hats. Heretofore, the use of such thermoplastic
layers has been believed to be necessary to provide hats with the
desired properties.
SUMMARY OF THE INVENTION
These desirable properties are obtained without the use of a layer
of fixed structure of a synthetic thermoplastic composition by
providing a molded hat wherein the fabric of the crown and brim
comprises a single unit, said fabric containing a stabilizing
polymeric composition and being resistant to shrinking and
distortion.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a view of a molded hat body immediately after coming out
of the mold.
FIG. 2 is a front view of a machine for molding hats, partially
sectioned, with the composite fabric in place.
FIG. 3 is an enlarged transverse sectional view of the outer crown
and brim mold and the annular brim die showing the composite fabric
held in position between the outer crown and brim mold and the
annular brim die.
FIG. 4 is a view similar to FIG. 3 with the inner crown die lowered
into the cavity of the outer crown mold and the composite fabric
between the inner crown die and the outer crown mold and between
the inner brim die and the outer brim mold.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The molded hats of this invention generally are prepared by
treating a textile fabric with a stabilizing polymeric composition,
preparing a laminate (generally two-ply) from said treated fabric,
and thereafter converting the laminate to the desired hat shape in
a molding apparatus similar to the apparatus described in FIGS.
2-4. Hat shells also have been prepared from a single ply of
treated fabric and from laminates composed of one layer of treated
fabric and a layer of non-treated fabric. As can be seen, at least
one layer of fabric must be treated with the stabilizing polymeric
compositions of this invention prior to molding.
The fabrics which are useful in the preparation of the hats of this
invention are textile fabrics containing at least some natural
fibers such as cellulosic and protein fibers. Such fibers include
cotton, flax, raime, wool, alpaca, vicuna, mohair, cashmere,
guanaco, camel hair, llama, fur, leather, suede and silk. While the
stabilizing polymeric compositions are particularly effective on
fabrics composed essentially of natural fibers, especially those
composed entirely of wool fibers, the compositions are also
effective on fabrics wherein synthetic fibers are blended (up to
about 60 to 80%) with the natural fibers. Preferred synthetic
fibers include polyamides, such as polyhexamethylene adipamide;
polyesters such as polyethylene terephthalate; and acrylic fibers
such as acrylonitrile, homopolymers or copolymers of acrylonitrile,
such as acrylonitrile/methyl acrylate (85:15); and cellulosic
derivatives such as cellulose acetate and viscose rayon. The
textile fabrics which may be used in the preparation of the hats of
this invention include those obtained from discrete fiber
assemblies such as yarns by weaving, knitting, or braiding, as well
as felts or layers of fibers in batt form.
It has now been discovered that if the fabric is treated with a
stabilizing polymeric composition and then molded into a hat having
the desired shape, the resulting product exhibits improved shape
retention and recoverability properties. For example, it is
possible to manually deform the hat by pressing down on the crown
and by twisting the hat, and upon releasing the pressure or
twisting force, the molded hat immediately returns to its original
shape. Typical examples of such stabilizing treatments include
additive type treatments wherein polymeric compounds are added to
the textile fabric. Although it is preferred to use polymeric
compounds which react with the natural fibers in the textile
fabric, the stabilization of the fabric also may be accomplished by
simply coating the fibers with a non-reactive polymeric coating
composition so as to provide the desired degree of stability and
body to the fabric. Systems which have been found to be especially
suitable for stabilizing the fabrics are interfacial polymerization
systems such as those involving the formation of
poly-(hexamethylene sebacate) through interfacial polymerization
techniques, treatments with reactive copolymers and terpolymers
based on the vinyl type monomers, treatments with
polyepoxide-polyamine compositions, treatments with reactive and
non-reactive polyurethanes, treatments with reactive and
non-reactive polyolefins, and treatments with emulsions of certain
acrylic esters such as, for example, polymethylene methacrylate,
polyethyl methacrylate, polypropyl methacrylate and polybutyl
methacrylate.
Treatment of the fabrics with isocyanate reaction products produces
fabrics which are especially useful in the preparation of the
molded hats. Among the isocyanate reaction products which may be
employed are isocyanate reaction products selected from the
following general categories: urethanes prepared from a
polyfunctional isocyanate and polymeric polyhydroxy compound; and
the reaction products of a polyfunctional isocyanate and polymeric
polyfunctional compounds such as polyesters, polyamides,
polyepoxides, formaldehyde resins and polyepichlorohydrins. The
isocyanate reaction products may be applied to the fabric as a
solution in pre-polymer form or in separate two-step applications
forming the urethane on the fabric in situ.
Regardless of the system utilized, however, it is preferred that
the ratio of isocyanate to active hydrogen compounds in the system
be at least about 0.4 and most preferably greater than 1.0. By
"pre-polymer" as employed herein is meant the reaction products of
polyfunctional isocyanate and the second polymeric compound carried
to an extent below which a gel is formed which is insoluble in one
of the organic solvents, and particularly the chlorinated
hydrocarbons.
Among the suitable isocyanates that may be used in accordance with
this invention are included aryl diisocyanates such as 2,4-tolylene
diisocyanate, 4,4'-diphenyl methane diisocyanate, 1,5-naphthylene
diisocyanate, 1-isopropyl benzene-3,5-diisocyanate and
benzene-1,2,4-triisocyanate; aliphatic diisocyanates such as
hexamethylene diisocyanate; as well as mixtures thereof including
the equivalent isothiocyanates .
Any of the above isocyanate-terminated compounds, either in
pre-polymer or monomer form (as in the "one-shot" technique) may be
blocked if desired, with phenol or any of the well-known blocking
agents for isocyanates. The blocking group is activated by heat and
removed to provide available isocyanate groups for reaction with
the functional groups of the natural fibers.
By "polymeric polyhydroxy compound" is meant a linear long-chain
polymer having a terminal hydroxy group including branched,
polyfunctional, polymeric hydroxy compounds as set forth below.
Among the suitable polymeric polyhydroxy compounds, there are
included polyether polyols such as the polyalkylene ether glycols,
polyalkylene-aryleneether-thioether glycols and polyalkyleneether
triols. Mixtures of these polyols may be used when desired.
The polyalkylene ether glycols may be represented by the formula
HO(RO).sub.n H, wherein R is an alkylene radical which need not
necessarily be the same in each instance, and n is an integer.
Examples of such glycols include polyethyleneether glycol and
polypropyleneether glycol. The polyalkyleneether triols are
prepared by reacting one or more alkylene oxides with one or more
low molecular aliphatic triols. The alkylene oxides most commonly
used have molecular weights between about 44 and 250, and these
include, for example, ethylene oxide, propylene oxide,butylene
oxide and 1,2-epoxy octane.
By "polymeric polyfunctional compound" is meant a long-chain
polymer containing at least two groups having at least one active
hydrogen atom as determined by the Zerewitinoff method. Examples of
such compounds include polyesters, polyamides, polyepoxides,
formaldehyde resins and polyepihalohydrins.
The polyesters generally are prepared by condensing an excess of a
polymeric or monomeric polyhydroxy compound with a polyacid, or by
esterifying a hydroxy substituted acid with a polyhydroxy compound.
Among the suitable acids are the alkane dibasic acids, alkene
dibasic acids and aryl dibasic acids. The polyols which are reacted
with these acids to form polyesters have been discussed
previously.
The polyepoxides which are reacted with polyisocyanates are organic
compounds containing at least two epoxy groups per molecule and may
be saturated or unsaturated, aliphatic, cyclo-aliphatic, aromatic
or heterocyclic and may be substituted with non-interfering groups
such as hydroxy groups, ether radicals etc. Polyepoxides containing
ether groups may be prepared as well known in the art by reacting a
polyol with a halogen-containing epoxide employing at least two
moles of the epoxide per mole of polyol. Thus, for example,
epichlorohydrin may be reacted without a polyhydric alcohol in an
alkaline medium. In the other techniques the halogen-containing
epoxide is reacted with a polyhydric alcohol in the presence of an
acidic catalyst such as boron trifluoride, and the product is then
reacted with an alkaline compound to effect a dehydrohalogenation.
Examples of such halogen-containing epoxides include
epichlorohydrin, epibromohydrin and 3-chloro-1,2-poxybutane.
Polyepoxides which do not contain ether groups may be employed.
However, the polyepoxides containing ether groups are preferred.
More particularly, the polyepoxide polyethers of the class of
glycidyl polyethers of polyhydric alcohols or polyhydric phenols
are preferred. These compounds may be considered as being derived
from a polyhydric alcohol or polyhydric phenol by etherification
with at least two glycidyl groups having the structure
Typical examples of such compounds include glycidyl polyethers of
glycerol, glycol, or any of the other polyols listed previously as
useful for reaction with halogen hydrogen containing epoxides.
Mixtures of different polyepoxides are also contemplated as useful
in the reaction with isocyanates.
The polyamides used in the reactions of the isocyanates are those
derived from polyamines and polybasic acids by any of the methods
known in the art. The polyamines include ethylene diamine,
diethylene triamine and tetraethylene pentamine. Typical
polycarboxylic acids include glutaric acid, adipic acid,
terephthalic acid and malonic acid. The polyamides may have
molecular weights varying from about 1,000 to 10,000 and melting
points from about 20.degree. to 200.degree. C.
As mentioned previously, the fabrics of this invention may be
stabilized by treatment with polymeric polyepoxides per se or with
a cured polyepoxide obtained by treating the fabric with a solution
containing polyepoxide, preferably a polyether polyepoxide, and an
amine catalyst and thereafter subjecting the treated fabric to an
elevated temperature to cure the polyepoxide in the fibers of the
fabric. Any of the polyepoxides and amine catalysts listed
previously, as well as those known in the art, such as those
disclosed in U.S. Pat. No. 2,829,071 may be used to stabilize the
fabrics in accordance with the process of this invention.
Polyolefins which are useful for treating the fabrics used to
prepare the molded hats of this invention include high molecular
weight polyethylenes, polypropylenes, polybutenes and mixtures
thereof as well as reactive derivatives thereof such as the chloro
sulfonated polyethylenes, vinyl acetate, vinyl chloride, vinyl
alcohol etc.
The incorporation of acid polymers into the fabric also provides
molded hats with the desired properties. Acid polymers contemplated
as being useful within the present invention are prepared from any
of the polymerizable acids, i.e., those containing unsaturated
groups. These polymers may be homopolymers of the acids or
interpolymers of the acid and other monomers. Such acids include,
for example, acrylic acid, maleic acid, methacrylic acid,
polymerizable sulfonic acids and polymerizable phosphoric acids.
Suitable monomers which may be copolymerized with the above acids
include esters of the above acids such as ethylacrylate and methyl
methacrylate; alkyl fumarates and maleates; vinyl halides such as
vinyl chloride; and other vinyl monomers such as styrene,
acrylonitrile and butadiene. Generally, the acid polymers and
copolymers must contain at least 10 percent by weight of the acid
monomer.
The acid polymers, as a general rule, are emulsion polymers
containing varying amounts of solids, normally in the range of
about 25 to 50 weight percent. The polymer emulsion should be
present in the pad bath or other application mediums in the range
of about 2.5 to 40 weight percent.
Mixtures of the above-described monomers and polymers also may be
applied to the fabrics of this invention to provide the desired
properties. For example, terpolymers of ethylene, sodium
methacrylate and methacrylic acid manufactured by E. I. du Pont de
Nemours & Co. under the tradename "Surlyn," and terpolymers of
vinyl acetate, methacrylolyl chloride and ethylene available under
the tradename "Zeset" from E. I. du Pont de Nemours & Co. are
particularly useful. Mixtures of the above terpolymers with
polymeric polyepoxides in the presence of an amine catalyst also
provide the desired results.
The various polymeric compositions may be applied to the fabrics by
conventional techniques such as by knife-coating, rolling,
printing, dipping and spraying, although the polymeric coatings are
generally applied with ordinary pad rolls. The compositions may be
deposited as solutions, dispersions or emulsions as long as the
solvent or liquid carrier is not reactive with polymeric
compositions. Thus, aqueous or organic solvents may be utilized.
Suitable organic solvents include halogenated hydrocarbons such as
trichloroethylene, methylene chloride, perchloroethylene and
chloroform; aromatic solvents such as toluene and benzene; and
other solvents such as n-butyl acetate, dioxane, methyl isobutyl
ketone and N,N-dimethyl formamide.
The polymeric stabilizing compositions or solutions thereof
generally are applied to the fabric to provide from about 2 to
about 50 percent or more, based on the weight of the fabric, of dry
polymer. In some instances, it is possible to deposit greater
amounts of polymer without affecting the desirable properties of
the fabric. As a general rule, however, the use of large amounts of
polymeric composition provides fabrics which are moldable but are
characterized by undesirable stiffness. Thus, the fabric, depending
upon its style and composition, preferably contains from about 2 to
20 percent based on the weight of the fiber, of the polymeric
stabilizing composition. The precise amounts can be readily
determined by one skilled in the art taking into consideration the
fabric, the polymeric composition and the desired properties.
The fabrics of this invention may be rendered water repellent by
application of any of the well known water-repellency treatments
such as wax emulsions, silicones, organo-chromium compounds and the
fluoro-chemicals. The fluorochemicals are a particularly useful
class of water-repellents since these also offer some measure of
oil-repellency to treated fabrics. The fluorochemicals used for
water-repellency include compounds based on chromium complexes of
perfluorocarboxylic acids, chromium complexes of
perfluoralkylmonocarboxylic acids and fluorinated acrylic and
methacrylic esters.
While fluorochemicals can be used alone to confer water-and
oil-repellency to the fabrics, the results obtained can be
considerably improved by the addition of other conventional
water-repellents to the finishing bath. For example, Minnesota
Mining and Manufacturing Company's "Scotchgard" process is based on
a mixture containing about 0.6 percent of fluorochemical solids, 1
to 2 percent of a conventional durable water-repellent and from
about 1 to about 1.5 percent of an aminoplast, e.g., melamine
formaldehyde. The water-repellent mixtures are applied to the
fabric by any of the well known methods such as padding, dipping,
rolling, etc., squeezed, dried and baked at temperatures up to
200.degree. C.
In most applications, it is preferred that more than one layer of
the treated fabric be combined to form the molded hat. The use of
laminates of two or more layers of fabric results in hats having
superior shape retention and resilience although the use of
excessive layers of fabric results in hats which are too heavy and
bulky. The adhesive which is used to bond the various layers of
textile fabric are preferably curable polymeric compositions which
are non-tacky after curing. Elastomers which are soluble or
dispersible in a liquid carrier are particularly useful as
adhesives, and these include, for example, those elastomers
prepared from acrylates, natural rubber, styrene-butadiene,
butadiene-acrylonitrile, butyl rubber, ethylene propylene rubber,
chloro sulfonated polyethylene, fluorocarbon rubber, and urethane
elastomers prepared from either polyesters or polyethers. Optimum
resilience is achieved when the adhesive is natural rubber or a
synthetic rubber such as the chloroprene rubbers. Where it is
desired to produce a molded hat which is particularly resistant to
chlorinated solvents and aging, cross-linked neoprene rubbers are
used. The textile fabric layers may be bonded together by applying
the adhesive to the fabric and thereafter pressing the layers
together. The adhesive can be applied to the substrates as a
continuous or discontinuous layer by conventional techniques such
as knife-coating and pad rolls.
The amount of adhesive applied to the fabric is not critical
although enough adhesive should be applied to provide a
satisfactory bond between the layers of the laminate. Generally,
from about 2.5 to about 25 percent by weight of adhesive, based on
the weight of the fabric, is used.
Molded hats having particularly desirable properties are prepared
from two-ply laminates wherein two layers of fabric are bonded
together with an adhesive composition. Such two-ply laminates allow
the preparation of a one-piece molded hat which can be molded in
one operation eliminating the need for sewing the brim of the hat
to the crown. This embodiment also eliminates the need for
subsequent application of a lining material. Furthermore, the two
layers of fabric need not be identical. This is, where only one
layer may be exposed or visible, the second layer, generally an
inner layer, may be combined of less expensive fibers which have
particularly aesthetic properties such as a pleasing hand. Examples
of such inner layers include inexpensive cotton fabrics or smooth
fabrics such as silk.
On the other hand, where both layers of the textile fabric will be
visible, it is often desirable that both layers be comprised of the
same textile fabric. For example, in molded hats, both sides of the
brim (top and bottom) should be comprised on the same textile
fabric. In applications where the molded hat is characterized by
greater strength, it may be desirable to use a plurality of layers
of textile fabric. The exact nature of the laminates prepared in
accordance with this invention will be determined by the
anticipated end use and the generally accepted properties of such
end uses.
The fabric treatments which have been discussed above may be
applied to the fabric either before or after the laminate has been
prepared, although it is preferred to apply the solution prior to
the formation of the laminate. Although any or all of the
compositions applied to the fabric may be applied separately, prior
to or after the formation of the laminate, the preparation and
application of one solution, dispersion, etc., containing all of
the desired additives to the textile fabric prior to formation and
cutting of the laminate is preferred. The following mixtures
illustrate the solutions, dispersions etc., which are useful in
this invention.
MIXTURE A % by Weight
__________________________________________________________________________
"Epon 812" (An aliphatic polyepoxide having an epoxide equivalent
of about 179-194; available from Shell Chemical Company) 20.0
Diethylene triamine 3.0 Trichloroethylene 77.0
MIXTURE B "Epon 812" (An aliphatic polyepoxide having an epoxide
equivalent of about 179-194; available from Shell Chemical Company)
20.0 Diethylene triamine 2.0 Trichloroethylene 78.0
MIXTURE C Sodium bisulfite 3.0 N-methylol acetamide 7.0 Textile
resin "FC-208" (A water repellent polymeric mixture available from
Minnesota Mining and Manufacturing Company) 1.5 Water 88.5
MIXTURE D "Epon 1001" (An aromatic polyepoxide available from Shell
Chemical Company and having an epoxide equivalent of about 450 to
525) 2.0 Diethylene triamine 0.5 Dioctyl phthalate 0.2
Trichloroethylene 97.3
MIXTURE E "Epon 1001" 1.5 Diethylene triamine 0.4 Dioctyl phthalate
0.2 Trichloroethylene 97.9
MIXTURE F "Eponite-100" (An aliphatic polyepoxide having an epoxide
equivalent of about 75 available from Shell Chemical Company) 5.0
Diethylene triamine 1.5 Wetting agent: condensation product of
nonyl phenol : ethylene oxide (1 : 9.5 molar ratio) 0.2 Water
93.3
MIXTURE G "Surlyn D-1002" (A high molecular weight interpolymer of
ethylene, sodium methacrylate and methacrylic acid available from
E. I. du Pont de Nemours & Co.) 5.0 Water 95.0
MIXTURE H Diepoxide prepared from the reaction of one mole of
diethylene glycol and two moles of epichlorohydrin followed by
reaction with two moles of sodium hydroxide 15.0 Diethylene
triamine 3.0 Acetic acid (glacial) 5.0 Wetting agent described in
Mixture F 0.2 Water 76.8
MIXTURE I Sodium metabisulfite 1.5 N-methylol acetamide 4.9
"Textile Resin FC-208" 1.5 Wetting agent described in Mixture F 0.1
Water 92.0
MIXTURE J "Hypalon 20" (A chlorosulfonated poly- ethylene available
from E. I. du Pont de Nemours & Co.) 5.0 "Adiprene L-100
Elastomer" (A liquid 1,4- oxybutylene glycol/toluene diisocyanate
polymer of about 2000 molecular weight available from E. I. du Pont
de Nemours & Co.) 1.0 Trichloroethylene 94.0
MIXTURE K Sodium bisulfite 4.3 N-methylol methyl carbamate 17.9
Ethylene glycol 14.3 Diammonium phosphate 1.0 Deceresol OT-75 0.3
Water 62.2
MIXTURE L "Epon 1001" 2.0 "Eponite 100" 1.0 Diethylene triamine 0.6
Dioctyl phthalate 0.2 Trichloroethylene 96.2
MIXTURE M Bisulfite addition product of 1,6- hexamethylene
diisocyanate prepared by reacting 84 grams of the diisocyanate with
310 parts of a 33% aqueous solution of sodium bisulfite 2.5 Wetting
agent of Mixture F 0.5 Urea 3.0 Water 94.0
__________________________________________________________________________
In carrying out the shaping operation, any suitable device or
expedient may be employed. For instance, the flat composite fabric
may be placed between the male and female members of a mold-like
device of desired shape, either or both of which may be heated
internally or externally by ordinary steam, super heated steam,
steam under pressure, electrical resistance, flames and the like.
Such devices may be provided with means, such as perforations or
jets to supply steam to the textile fabric in order to facilitate
the shaping of the composite.
While the shaping operation may be carried out in any suitable
device, a preferred apparatus for preparing hats is shown in FIGS.
2 to 4 wherein a frame 60 is provided with a base 61 on which is
mounted an outer crown and brim mold 20 having an outer upper
annular flat surface 21, an intermediate curved upper annular brim
surface 22 and a crown cavity 23. Extending above the base is a
pair of posts 34 having their upper ends joined together by a cross
bar 36. Slidably mounted on these posts is an annular inner brim
die 30 with extension rods 31, said brim die 30 having a curved
inner lower annular surface 32 and the open center 33. The inner
brim die 30 is mounted above the outer crown and brim mold 20 and
aligned so that when lowered down to and against the fabric 11, the
curved inner lower annular surface 32 of inner brim die 30 will be
aligned with the intermediate curved upper annular surface 22 of
the outer crown and brim mold 20 as shown in FIG. 3.
An inner crown die 40 is attached to support bar 42 which is
slidably mounted to the posts 34 above the annular inner brim die
30 and adapted to be moved downwardly through the open center 33 of
the brim die 30 contacting the fabric 11 moving a portion of said
fabric 11 downwardly and against the sides of the cavity 23 of the
outer crown and brim mold 20 as shown in FIG. 4.
While manual or mechanical means for moving the annular inner brim
die 30 and inner crown die 40 downwardly into the positions shown
in FIGS. 3 and 4 may be employed, they are illustrated in FIG. 2 as
an air pressure actuated means (partially shown). Two cylinders 50
are mounted to the ends of the posts 34 above the cross bar 36,
said cylinders having piston rods 52 connected to the annular brim
die 30 through U-brackets 53 and extension rods 31. These cylinders
50 and piston rods 52 are actuated by air pressure controlled by a
manually operated valve 54, the amount of pressure being controlled
by adjustable pressure valve 56. In the embodiment illustrated in
FIG. 2, the downward motion of the inner crown die 40 and its
support 42 which is slidably mounted to posts 34 is controlled by
cylinder 44 which is mounted above the cross bar 36 and connected
to support 42 by way of piston rod 46. Said cylinder 44 and piston
rod 46 are actuated by air pressure (not shown), and the amount of
pressure exerted by inner crown die 40 and support 42 when in the
lowered position illustrated in FIG. 4 is controlled by an
adjustable pressure valve (not shown). The timer 48 controls the
length of time the inner crown die 40 and support 42 remains in the
lowered position illustrated in FIG. 4, and automatically releases
the air pressure thereby raising support 42 and inner crown die 40
at the end of the selected time.
Since heat as well as pressure is necessary to effect the desired
degree of permanency to the shaped bodies, and particularly the
hats prepared in the apparatus described above, heating means (not
shown) are provided for heating support 42, the inner crown die 40
and the outer crown and brim mold 20. Although annular inner brim
die 30 may be heated directly, the temperature of the die is raised
sufficiently as a result of its contact with support 42. Generally,
the die 30 is maintained in contact with heated support 42 when the
apparatus is not being used.
In the normal operation of the apparatus illustrated in FIGS. 2 to
4, a piece of the fabric 11 approximately 20 inches square is
placed above the outer crown and brim mold 20. The outer crown and
brim mold 20 and inner crown die 40 and support 42 can be heated to
a temperature of from 100.degree. C. to about 200.degree. C., the
exact temperature being determined after considering the nature and
properties of the components of fabric 11. The annular upper brim
die 30 is lowered into the position shown in FIG. 3 by opening
valve 54 which activates cylinders 50 and piston rods 52. The
downward pressure exerted by brim die 30 on the composite fabric
which is now in place between the brim die 30 and crown and brim
mold 20 is generally within the range of from about 1 to 100 p.s.i.
The ideal pressure will vary depending on the fabric construction
since the pressure exerted serves to control the rate and manner in
which the fabric 11 is forced into the cavity 23 of outer crown
brim mold 20. The use of an annular brim die with the smooth lower
outer flat surface 33 which is aligned directly above the outer
upper annular flat surface 21 of outer crown and brim mold 20 is
preferred over other methods for applying restraining pressures to
the outer edges of fabric 11 since this method results in a more
uniform restraining pressure on the fabric. Other methods of
restraining the fabric such as by manual restraint or other known
mechanical means such as blade-type retainers or mechanically
operated fingers may be utilized but are not as efficient. Uneven
restraining pressure can result in stretching and thinning out of
the fabric, and the formation of wrinkles which are permanently
molded into the hat.
After the brim die 30 is in position as shown in FIG. 3 and the
desired pressure is applied, the heated inner crown die 40 and
support 42 are lowered into the position shown in FIG. 4 by setting
the timer 48 which also controls the length of time the inner crown
die 40 will remain within the cavity 23. The speed at which support
42 is lowered is controlled so that the heated inner crown die will
engage and progressively force the fabric 11 into and against the
sides of heated cavity 23 to form a crown 17 of the hat body 15 as
shown in FIG. 4. As the inner crown die completes its downward
motion, the support 42 increases the downward pressure exerted by
the inner brim die 30 and the pressure exerted on fabric 11 between
elements 32 and 22 forming the brim 16 of the hat. The downward
pressure exerted on the fabric by the inner crown die 40 and
support 42 is generally between 20 to 100 p.s.i., and preferably
between 60 to 70 p.s.i. Generally, the apparatus is maintained in
the position illustrated in FIG. 4 for a period of from about 15
seconds to 5 minutes and preferably from about 30 seconds to 3
minutes to complete the molding of the hat body 15. The preferred
times will depend upon the pressure exerted, the temperature of the
mold and die and the nature of the fabric. If the fabric 11 is
heated for too long a period of time, the fabric may be seriously
affected resulting in the formation of hats which are discolored
and/or stiff.
After the fabric has been subjected to the desired temperature and
pressure for the selected period of time, the inner crown die 40
and support 42 and annular inner brim die 30 are raised. The molded
hat body 15 is removed and has an appearance as illustrated in FIG.
1. That portion of the fabric which is maintained between flat
surfaces 33 and 21 appears as the annular strip designated as
element 19 in FIG. 1 while the fabric maintained between curved
elements 22 and 32 during the molding operation appears as the brim
16 of the hat body. After the hat body is cooled, the crown 17 of
the hat may be subjected to any desired forming operation such as
can be obtained in the standard heated hat blocks. The edge of the
brim 18 may then be trimmed with any suitable cutting tool, and the
hat can be finished by any of the usual procedures known in the
art.
The following examples illustrate the manner in which the hats of
this invention may be prepared. Unless otherwise specified, all
parts and percentages are by weight.
EXAMPLE 1
Several pieces (22 inches by 20 inches) of an all wool woven fabric
which is 46.7 mils in thickness and weighs 7.46 ounces per square
yard are treated with Mixtures A or B to a 100 percent wet pickup,
dried for 5 minutes at 70.degree. C. and cured for 5 minutes at
130.degree. C. Any excess of unreacted diethylene triamine is
removed by gentle scouring, and the fabrics are dried in a
forced-air oven at 105.degree. C.
Mixture C is applied to some of the above-treated fabrics as well
as to untreated fabrics to a 100 percent wet pickup and then dried
for 30 minutes at 65.degree. C.
Various combinations of the treated fabrics are laminated with
acrylic adhesive "E-358" available from Rohm & Haas and
thickened with a polyester "T-12" available from National Latex and
Rubber Company in the weight ratio 1,000:80. The following table
illustrates the various two-ply laminated fabrics prepared in this
manner.
Laminate Inside Layer Outside Layer No. Treatment Treatment
__________________________________________________________________________
1 Mixtures B and C Mixtures B and C 2 Mixtures A and C Mixtures A
and C 3 Mixtures A and C Mixture C 4 Mixture C Mixture C 5 Mixture
A Mixture A 6 Mixtures A and C Mixture C
__________________________________________________________________________
hat shells are prepared from the above described two-ply laminates
utilizing the molding apparatus described in FIGS. 2-4. In this
experiment, the temperature of the inner crown die 40 and the outer
crown and brim mold 20 is maintained at about 165.degree. C. The
apparatus is operated as described previously and the inner crown
die 40 is maintained in its lowered position as shown in FIG. 4 for
a period of 2 minutes exerting a downward pressure on the fabric of
about 10 lbs. per square inch. The inner crown die 40 and the inner
brim die 30 are raised and the molded hat body is removed from
cavity 23 and allowed to cool. The hat shells are then "blocked" in
a conventional hat block mold for 3 minutes at 150.degree. C. The
hats obtained in this manner are free of wrinkles and exhibit shape
retention and recoverability properties. For example, it is
possible to deform the hat body by pressing down on the crown or by
twisting the hat body itself, and upon releasing the pressure or
twisting forces, the molded hat returns to its original desired
shape.
EXAMPLE 2
Samples of the all wool fabric described in Example 1 (20 inches by
22 inches) are treated with Mixtures D-H to a 100 percent wet
pickup, dried at 75.degree. C. for 5 minutes and cured by heating
at a temperature of 130.degree. C. for 5 to 12 minutes. The polymer
treated squares are laminated together in pairs using natural
rubber as the adhesive and then treated with Mixture I to a 100
percent wet pickup, dried at 60.degree. C. and molded into
single-unit hats as described in Example 1. The various two-ply
laminates treated with Mixture I and converted into hats in the
manner described in Example 1 are summarized below.
Laminate Inside Layer Outside Layer No. Treatment Treatment
__________________________________________________________________________
7 Mixture D Mixture D 8 Mixture A Mixture G 9 Mixture D None 10
Mixture E Mixture E 11 Mixture F Mixture G 12 Mixture H Mixture H
__________________________________________________________________________
the hats obtained from these laminates exhibited improved shape
retention and recoverability properties.
EXAMPLE 3
A molded hat is prepared from a laminate obtained from two 20 inch
squares of the all wool fabric described in Example 1 by padding
two layers of the fabric to a 100 percent wet pickup with Mixture
J, pressing the two layers together and allowing the laminate to
dry. A molded hat prepared from this laminate in accordance with
the procedure described in Example 1 exhibits good shape retention,
resilience and flexibility.
EXAMPLE 4
A polymeric coating composition is prepared as follows: Into a
jacketed stainless steel reactor is poured 225 pounds of
polypropylene glycol adduct of glycerin having a molecular weight
of about 5,000. The reactor is then closed and the pressure therein
reduced to about 10 mm. mercury after which the reactor is flushed
with dry nitrogen. After the pressure regulation and flushing
operation is repeated for 3 cycles, 23 pounds of dry toluene is
poured into the reactor. A blanket of nitrogen gas is maintained in
the vessel throughout the reaction. The pressure is again reduced
to 10 mm. mercury and the reactor is heated to 140.degree. C. to
distill off the toluene, after which it is cooled to room
temperature using cold water in the jacket around the reactor. The
pressure is returned to normal, and after stirring for 15 minutes
to thoroughly mix the components, about twice the stoichiometric
quantity for reaction with the glycol of tolylene-2,4-diisocyanate
is added rapidly and stirred until the heat of reaction ceases and
the temperature has risen slowly up to 40.degree.- 45.degree. C.
The temperature of the reaction mixture is then raised at the rate
of about 2.degree. C. per minute to a temperature of 146.degree. C.
where it is held for 18 minutes; thereafter, the mixture is cooled
at a rate of about 2.degree. C. per minute to a temperature of
100.degree. F. Sufficient trichloroethylene is added to provide a
solution containing 70 percent of the resulting pre-polymer. The
pre-polymer solution is then transferred from the reactor to a
pre-dried drum under a dry nitrogen atmosphere to avoid water
contamination. At the time of the transfer, the pre-polymer
solution has a color of from colorless to a very pale straw
color.
Samples of an all wool fabric as described in Example 1 are padded
to a 100 percent wet pickup with a trichloroethylene solution
containing 25 percent of the pre-polymer composition prepared above
and 3 percent Quadrol (N,N', N'-tetrakis-2-hydroxypropyl
ethylenediamine marketed by Wyandotte Chemical Corporation), dried
for 5 minutes at 70.degree. C. and cured for 7 minutes at
125.degree. C.
A laminate was prepared by spraying two layers of the treated
fabric with a methylene chloride solution containing 20 percent
Urethane Adhesive 200 and 3 percent zinc naphthenate, and
thereafter pressing the layers together allowing the solvent to
evaporate. A hat shell prepared in accordance with the procedures
described in Example 1 is free of wrinkles and exhibits shape
retention and recoverability properties.
EXAMPLE 5
Samples of the all wool fabric described in Example 1 are padded to
a 100 percent wet pickup with a trichloroethylene solution
containing 5 percent of "Zeset" TP, a terpolymer of ethylene, vinyl
acetate and methacryloyl chloride having a molecular weight of
about 50,000 and available from E. I. du Pont de Nemours & Co.
The treated fabric is dried at 38.degree. C., and a two-ply
laminate is prepared using the adhesive described in Example 4. A
hat shell prepared from this two-ply laminate in accordance with
the procedure described in Example 1 exhibits excellent shape
retention and recoverability properties.
EXAMPLE 6
Samples of the all wool fabric described in Example 1 are padded
with "Zeset" TP to provide a 3 percent dry pickup on the fabric.
These treated samples are then padded to a 70 percent wet pickup
with Mixture K and dried at 75.degree. C. Two-ply laminates are
prepared using a Neoprene adhesive, and the laminates are converted
to hat shells according to the procedure described in Example
1.
EXAMPLE 7
The procedure of Example 6 is repeated except that the wool fabric
is replaced with a wool: rayon blend containing 50 percent
rayon.
EXAMPLE 8
Samples of acrilan/wool fabric (55:45) are padded to 100 percent
wet pickup with Mixture G or L, dried at 75.degree. C. and cured at
130.degree. C. Those fabrics treated with Mixture L are delicately
washed for 4 minutes to remove excess amine and then dried. Two-ply
laminates were prepared by bonding one layer of fabric treated with
Mixture G and one layer of fabric treated with Mixture L with a
natural rubber adhesive. Hat shells are prepared so that the
outside layer is a fabric treated with Mixture G according to the
procedure described in Example 1 except that the downward pressure
exerted by the annular brim die is 40 pounds per square inch and
the downward pressure exerted by the inner crown die is 80 pounds
per square inch. The hat shells were molded on a conventional
blocking mold at 150.degree. C. for 3 minutes and exhibited the
usual desirable properties.
EXAMPLE 9
A hat shell having the desirable properties is prepared by treating
the all wool fabric described in Example 1 with an aqueous
dispersion containing 5 percent of a copolymer of ethylacrylate:
acrylic acid (70:30) to a 100 percent wet pickup and drying the
fabric prior to formation of a two-ply laminate utilizing Urethane
200 containing zinc naphthenate catalyst as the adhesive.
EXAMPLE 10
The procedure of Example 2 is repeated except that the all wool
fabric is a felted fabric prepared by washing the woolen fabric 5
times with detergent at 60.degree. C. The felt like hat obtained in
this manner exhibits the desired properties of shape retention and
resilience.
EXAMPLE 11
The procedure of Example 1 is repeated except that the laminate is
prepared from one layer of the treated woolen fabric and one layer
of a hat lining material such as rayon or silk.
EXAMPLE 12
The procedure of Example 1 is repeated except that the hat shell is
prepared from a single layer of the treated wool fabric.
EXAMPLE 13
Samples of the all woolen fabric described in Example 1 are padded
to a 100 percent wet pickup with Mixture M and air-dried. A two-ply
laminate is prepared from two layers of the treated fabric bonded
together with a natural rubber adhesive. The laminate is converted
to a hat shell in accordance with the procedure described in
Example 1, and the hat shell obtained in this manner exhibits the
desirable properties of shape retention and resilience.
EXAMPLE 14
The all wool fabric described in Example 1 is impregnated with a
sulfuric acid solution (1N) containing ferrous ammonium sulfate to
provide the fabric with 0.2 percent of the weight of the fabric of
ferrous ammonium sulfate. This fabric is then introduced into an
aqueous solution containing 5 percent methacrylic acid and 0.02
parts per liter of hydrogen peroxide (30 percent). A 25 percent wet
pickup (by weight) was obtained. After drying the treated fabric,
two layers were bonded together with Urethane 200 TCE adhesive and
a hat shell was prepared in accordance with the procedure of
Example 1.
EXAMPLE 15
A piece of an all wool fabric as described in Example 1 is padded
to a 100 percent wet pickup with an aqueous solution containing 12
percent acrylamide and 0.1 percent of a non-ionic wetting agent
obtained by condensating nonyl phenol with ethylene oxide in a
molar ratio of 1:9.5. The wool is then dried for 10 minutes at
95.degree. C. and allowed to stand at room temperature for 4
hours.
The dried fabric is then subjected to irradiation in an insulated
core transformer manufactured by High Voltage Engineering
Corporation of Burlington, Mass. The fabric is passed through the
irradiation equipment at a rate of 40 yards per minute at a setting
on the transformer of 500 kilovolts and 15 milliamps to produce a
dosage of 2 megarads. A two-ply laminate is prepared from this
treated fabric using a natural rubber adhesive and converted into a
hat shell in the apparatus described in Example 1 at a temperature
of 163.degree. C., under a pressure of 10 pounds per square inch
for 2 minutes and 20 seconds.
EXAMPLE 16
The procedure of Example 15 is repeated except that the two-ply
laminate is prepared prior to the irradiation.
As can be seen from the above description and Examples this
invention provides a method for preparing hats having unusual shape
retention qualities. The hats are further characterized by improved
shape definition and resistance to stress release and puckering.
For example, the hats obtained from this invention which are
deformed, either by crushing or twisting, wet with water or
dry-cleaned by conventional methods will return to and maintain
their molded shape without the necessity of subsequent refinishing.
Furthermore, since the hats are prepared under conditions which do
not adversely affect the nature and characteristics of the textile
fabric utilized, normal and unusual effects can be produced by the
selection of particular patterns of fabrics.
* * * * *