U.S. patent number 3,660,138 [Application Number 04/796,930] was granted by the patent office on 1972-05-02 for metallized article.
This patent grant is currently assigned to King Seeley Thermos Co.. Invention is credited to John H. Gorrell.
United States Patent |
3,660,138 |
Gorrell |
May 2, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
METALLIZED ARTICLE
Abstract
Fibrous article with heat-and-light reflecting quality provided
by a metal coating. The metal coating is overcoated with a mixed
resin system. The article thus produced has enhanced stability of
the fibrous substrate due to the heat and light protection provided
by the coatings and also has enhanced strength due to the coatings
consistent with substantially retaining hand and softness of the
fibrous article. The metal coating is uniquely abrasion and mar
resistant, water repellent and launderable and dry cleanable
consistent with high moisture vapor transmission of the article
(breathability).
Inventors: |
Gorrell; John H. (Billerica,
MA) |
Assignee: |
King Seeley Thermos Co. (Ann
Arbor, MI)
|
Family
ID: |
25169420 |
Appl.
No.: |
04/796,930 |
Filed: |
February 5, 1969 |
Current U.S.
Class: |
442/230; 428/336;
428/425.8; 428/447; 428/425.5; 428/463 |
Current CPC
Class: |
D06Q
1/04 (20130101); Y10T 428/31605 (20150401); Y10T
428/31598 (20150401); Y10T 428/31663 (20150401); Y10T
428/31699 (20150401); Y10T 428/265 (20150115); Y10T
442/3398 (20150401) |
Current International
Class: |
D06Q
1/04 (20060101); D06Q 1/00 (20060101); B44d
001/12 (); B44d 001/02 () |
Field of
Search: |
;117/132A,132BE,76,35R,35V,135.1,138.8N,161KP,161ZA,71,154 ;161/64
;28/75 ;204/192 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Whitby; Edward G.
Claims
What is claimed is:
1. A fibrous article comprising a fiber substrate having at least
two sides and coated with a metallic layer on at least one side,
the metallic layer being overcoated with a layer of mixed resins
adhering to the metal, the metal coating having a thickness between
10.sup.-.sup.7 and 10.sup.-.sup.4 inches and being essentially in a
single layer along the coated side of the fiber and the resin
coating including a resin which forms a film and a component which
is hydrophobic and cross-linked with the film forming resin, the
mixed resin layer being sufficiently thin and transparent to
radiation in the region of visible to near infra red wavelengths to
preserve a reflectance of the article to said radiation which is at
least 90 percent of the reflectance with no resin overcoating, the
article having a moisture vapor transmission with the mixed resin
higher than that without the resin and wherein the hydrophobic
component comprises a silicone water repellent and a silicone
coupling agent.
2. The article of claim 1 wherein the mixed resins as a coating
mixture comprises 1-10 percent by weight of included solids in
liquid dispersed form, the solids comprising 50-90 percent by
weight of an adherent film forming resin and 2-50 percent by weight
of a resin modifying component comprising at least one polysiloxane
substituted with substituents selected from the group consisting of
hydrogen, alkyl, aryl, aralkyl, cycloaliphatic or alkenyl radicals.
Description
This invention relates to fibrous articles -- e.g. fabric (woven or
bonded), paper and fiber (filament or yarn) to be formed into
fabric or paper and particularly to fibrous articles coated with
metal to provide heat and light reflectance for decorative and
functional (insulation) purposes.
The principal known fabric or fiber metallizing methods are (1)
application of metal flakes in a plastic matrix, e.g. U.S. Pat.
Nos. 2,630,620; 2,767,104 and 3,220,871 embodied in Milium
(registered trademark of Deering - Milliken Company) and (2) vacuum
metallizing of a fabric or fiber, e.g. British Pat. Nos. 663,251;
721,879; 800,093; 816,906; and U.S. Pat. Nos. 2,912,345; 2,921,864;
2,907,678 and German Pat. No. 1,182,631 embodied in Metalon and
Insalune (registered trademarks) fabrics (see Man Made Textiles
Magazine (Jan. 1965) 43 and Textile World (May 1965) 113).
Both of these processes have significant limitations in regard to
abrasion and mar resistance and launderability of the metal
coating.
It is the object of the invention to provide improved metallized
fibrous articles characterized by improved abrasion and mar
resistance, corrosion resistance, launderability, dry cleanability
and water repellence consistent with high moisture vapor
transmission (breathability) of the articles.
It is a further object of the invention to provide enhanced
strength and stability of the articles consistent with the
foregoing object.
It is a further object of the invention to provide substantially
unimpaired hand and softness of the treated fibrous article
consistent with the foregoing objects.
It is a further object of the invention to provide very high heat
and light reflectance consistent with the foregoing objects.
It is a further object of the invention to provide an economical
method of manufacturing such an article with a single step post
coating following metallizing.
In general the improved fibrous article is made by metallizing a
fibrous article in a vacuum chamber, removing the article from the
vacuum chamber and dipping it into a mixed resin solution to form
an overcoat resin layer over the metal layer.
The metallizing may be practiced on a filament or yarn later formed
into a fabric or directly on a woven or bonded fabric or paper. The
fiber involved may be natural or synthetic or a mixture as in
cotton-polyester woven fabrics. Metal may be applied directly to
the fiber or the fiber may be pre-coated prior to the application
of metal to reduce outgassing from the fiber in the metallizing
vacuum chamber and to enhance adhesion of metal to fiber
substrate.
Preferably the metal is applied to a thickness of about
10.sup.-.sup.6 inches but may be as thin as 10.sup.-.sup.7 or as
thick as 10.sup.-.sup.4 inches. The metal forms a continuous layer
along at least one side of the fibrous article but without bridging
gaps or openings in the article, to leave the breathability of the
article unhindered. The continuity of the film provides a better
reflectance than a flake coating or a similar metallized film which
simulates a flake coating due to crocking or crazing or removal of
intermittent portions thereof due to abrasion or laundering or the
like.
The overcoat is a mixed resin system of high adhesion to the metal
and low cohesion within itself. The overcoat is applied with a
carrier of organic solvent or water which is driven off by heating
to effect cure of the mixed resin system. The resultant product is
found to have a higher moisture vapor transmission with the
overcoat than without it (where fibers are metallized, the moisture
vapor transmission can only be evaluated after subsequently forming
into a fabric). The overcoat is selected to provide a high
transparency to infrared radiation in the range of visible to near
infrared wavelength (including 8-9 microns) so that reflectance of
the article to such radiation with the overcoat is at least 90
percent of reflectance without it.
In a first and preferred embodiment of the invention, the overcoat
is made of a mixed polyurethane-silicone resin system with organic
solvent carrier. In other embodiments, mixed polyacrylic-silicone
resin systems with water carrier are used. The urethane-silicone
coating is designed primarily for outdoor application with the
constituents selected for ultraviolet stability, fungus and mold
resistance, resistance to weather and humidity extremes as well as
water repellency and the other objects stated above. The water
based acrylic-silicone coatings are the most readily adaptable to
the padder-tenter applicator arrangements common in the textile
industry and more adaptable to aerosol spraying for consumer use
(and less flammable than the organic system), but afford water
repellency to a lesser degree.
The mixed resin system perform overlapping functions. The first
resin in the coating -- a film forming polymer, e.g. acrylic
(including methacrylic etc.) or the urethane -- provides an
adherent protective layer for the metal. Among acrylics, melamine
cross linked acrylic acid polymers are preferred (e.g. Union
Carbide LKSB 0200). The film is very thin to afford high
reflectance of radiation by the article as a whole. The second
resin is a mixture of silicones including typically, the
conventional water repellent polydimethyl siloxane marketed as Dow
Corning's DC-200 or General Electric's SF-96 solutions or Dow
Corning DC-36 emulsion. Also included are a mar resistant silicone
(e.g. Dow Corning DC-11) and a coupling agent (e.g. Dow Corning
DC-600). The film forming polymer alone would bridge over and block
moisture vapor in the absence of the silicones. The silicones alone
would not adhere well to metal.
The practice of the invention will be best understood from the
following nonlimiting examples:
EXAMPLE 1 (05158-3B)
a. 74 parts (by volume) of solvent (70 toluene; 14 Cellosolve)
mixed with 8 parts of polyurethane solution (25 percent solids in
xylene solvent) and mixed rapidly with pneumatic agitation.
b. a 10 percent solution of polyvinyl butyral in alcohol was mixed
with solvent (3 parts PVB, 1 solvent). The solvent was 1 percent
glyoxal in Cellosolve. The glyoxal per se was 40 percent solids in
water.
c. Modified silicones were similarly mixed (1 part SF-96, 1 part
DC-600, 1.5 part DC-11) Before mixing the SF-96 was reduced to 1
percent intoluol, the DC-600 to 1 percent in Cellosolve, the DC-11
to 0.5 percent in Cellosolve.
d. The three components (a) (b) (c) were mixed. Then 0.1 parts of
Dow Corning F-1-1522 (glycol modified polydimethylsiloxane) was
added to 100 parts of the mixture and this was mixed.
e. Swatches of Dacron (trademark) polyester fabric and ripstop
nylon fabric were placed in a vacuum metallizing chamber and
aluminum was evaporated in the chamber under vacuum and condensed
on the fabric substrates to a decorative grade thickness (about
10.sup.-.sup.6 inches). The fabrics were removed from the chamber
and dipped in the mixture with some fabrics set aside for control.
After dipping the fabrics were squeezed through rollers and then
exposed to a radiant heater to raise their temperature over
250.degree. F for 5-30 minutes or over 300.degree. F for 1-3
minutes.
The fabrics were laundered in a washing machine (warm water
settings -- 100.degree.-120.degree. F) with household detergent
(alkaline). Those nylon fabrics which had only metal coating lost
their metal on one washing. Polyester fabrics with metal only lost
metal in some cases, retained it in others. Both nylon and
polyester fabrics with metal and resin overcoat retained their
metal coating with repeated washings.
Radiation reflectance of the fabrics was measured with a
spectrophotometer in the wavelength range from visible light to 2.5
microns (near infrared). Averages of measured values were
##SPC1##
EXAMPLE 2 (4048-4 SERIES)
A variation of the Example 1 coating was prepared as follows:
urethane (TG-100*) 12 parts toluene 73 parts modified SF-96** 5
parts modified DC-600*** 5 parts modified DC-11**** 5 parts
Ripstop nylon was vacuum metallized to decorative grade thickness
and overcoated with the above resin mixture by immersion, pressing
between rollers and suspending in an oven to heat to about
250.degree. F for 5 minutes and in some cases for 30 minutes.
The fabrics were home laundered as in Example 1. Uncoated (no
resin) fabrics lost their metal completely in one washing. Fabrics
having the overcoat retained substantially all their metal. Best
retention of metal and metal luster was in a fabric which had a 30
minute cure.
Swatches of the fabrics were submitted to Lowell Technological
Institute Research Foundation for laundering and dry cleaning per
tests:
Laundering:
AATCC Method 96-1960T, Test II
Dry Cleaning:
AATCC Method 108-1963T using both perchloroethylene and stoddard
solvent.
The sample swatches after testing showed the same results as the
home laundering. The nonresin coated swatches had lost all metal.
But the overcoated samples retained it (entirely for laundering and
stoddard solvent, but with some blushing for perchloroethylene
solvent).
EXAMPLE 3
Nylon and polyester fabrics metallized and overcoated as in Example
1 were made into bags and filled with water with 1 to 2 inches head
and suspended in air. These bags held the water several weeks
without dripping. The bags were also exposed to spilled coffee and
no stain resulting. Similar bags made of metallized fabric without
overcoating would not hold water. Measurements were made of
moisture vapor transmission and it was found that the metallized
and overcoated fabrics had higher transmission than the fabrics, as
uncoated, or coated with metal alone.
EXAMPLE 4 (12028)
A cotton fabric was vacuum aluminized and topcoated with a resin
system of Example 1. The metal was lost in washing due to poor
adhesion of the metal per se to the cotton.
A further attempt was made to overcome this by pre-washing a cotton
fabric and pre-coating it with a base coat prepared as follows:
a. Mix 34 parts (by volume) of water with 1 part of a solution of 4
percent hydroxymethyl cellulose in water
b. Mix (a) with 20 parts acrylic emulsion HA-8 or Rohm & Haas
K-87 (conventionally used in fabric finishing)
c. Mix (b) with 1 part diluted acetic acid (10 percent in H.sub.2
O)
d. Mix (c) with 1 part sodium silicate - 3H.sub.2 O
e. Filter (d) through sheer Dacron and let stand. Cure at
350.degree. F for 3 minutes.
The pre-coated cotton was aluminized to decorative grade thickness
and topcoated as in Example 1. It exhibited excellent resistance to
laundering at 104.degree. F water and cold water detergent with no
apparent metal loss.
EXAMPLE 5
In variations of the Example 4 experiment it was observed that
standing for a week enhanced the adhesion of metal coating and
topcoat. It was also observed that the base coat as applied to
cotton and other natural and synthetic fabrics gave the metal coat
a substantial resistance to laundering even without topcoat.
However the above topcoat improved the resistance to laundering and
is also necessary for abrasion resistance and corrosion resistance
in outdoor use.
EXAMPLE 6
A top coat was prepared as follows:
a. Mix 10 parts acrylic (0200) solution (55 percent solids) with 73
parts water
b. Mix (a) with 10 parts DC-600 silicone (reduced to 20 percent in
Cellosolve)
c. Mix 5 parts DC-11 silicone (1 percent in Cellosolve) with
(b)
d. Mix 2 parts DC-36 silicone with (c).
A metallized ripstop nylon was immersed in it, squeezed and dried
at 300.degree. F for 3 minutes. Upon laundering it held most of its
metal, but with some dulling, while a similar metallized fabric
without topcoat lost its metal in laundering. The fabric hand was
similar with and without top coat.
EXAMPLE 7
50 parts of the Example 6 topcoat buffered with a small addition of
NH.sub.4 Cl to 8 ph, were mixed with 50 parts distilled water and
90 parts of the mixture was mixed with 2 parts DC-37 silicone.
Metallized triacetate fabric was topcoated with this mixture and
dried at 300.degree. F for 15 minutes. The resultant fabric
laundered with only slight metal loss, exhibited a bright luster
and good hand was breathable.
EXAMPLE 8
The Example 7 coating, without the additional DC-37 silicone, was
applied to metallized Tyvek (DuPont registered trademark) bonded
polyethylene fabric with similar results (good resistance to
laundering compared to essentially no resistance for metallized
Tyvek without topcoat) and was breathable (through pinholes punched
through prior to metallizing). Curing of the top coat was limited
to 150.degree. F, to avoid damaging the Tyvek.
EXAMPLE 9
The following modified acrylic-water base formulation was found to
give the best protection to Tyvek and Reemay fabrics consistent
with good hand:
85 parts distilled water
3 parts Rhoplex K-87 self-cross-linking acrylic
1 part DC-36 silicone
2.5 parts Acetic acid (4 percent in water)
5 parts NH.sub.4 Cl (10 percent in water)
2 parts xylene
0.5 parts DC-100 (1 percent in Cellosolve)
0.5 parts DC-11 (1 percent in Cellosolve)
0.5 parts Dow Corning F-1-522 glycol modified
dimethylpolysiloxane.
Three compositions of the invention are now stated with total
solvent and/or water stated separately and on a weight of liquid
component basis (expressed as approximate percent of total weight
of the composition). The second column gives the percent of solids
in each component (dissolved or emulsified). Exact proportions are
not critical.
COMPOSITION A
Component Quantity (1%) % Solids
__________________________________________________________________________
Amine cross linked acrylic 11% 55 DC-36 hydrophobic silicone 2 35
SF-96 hydrophobic silicone (50 Centistokes) 2 100 DC-600 coupling
silicone .2 63 DC-11 mar resist silicone .04 10 Cellosolve 23 0
Distilled Water 62 0
__________________________________________________________________________
COMPOSITION B
Component Quantity (%) % Solids
__________________________________________________________________________
Self cross link acrylic emulsion 3.2% 46 DC-36 1 35 DC-600 .000045
63 DC-11 .000045 10 Dow Corning F-1-1522 .4 100 Cellosolve .85 0
Xylene 875 0 Ammonium Chloride .025 100 Glacial Acetic Acid 1.15 0
Distilled Water 92.5 0
__________________________________________________________________________
COMPOSITION C
Component Quantity (%) % Solids
__________________________________________________________________________
Polyurethane 9.7% 25 DC-600 .01 63 DC-11 .01 10 F-1-1522 .1 100
SF-96 .01 100 Polyvinyl butyral .3 100 glyoxol 1.8 40 Cellosolve 18
0 isopropyl alcohol 2.3 0 toluol 68 0
__________________________________________________________________________
The scope of the invention includes various other metals -- copper,
zinc, tin, gold, silver, bright platinum, bronze, Wood's metal and
equivalent metals of which can be applied to fibrous article
substrates as thin films to afford bright reflectance. The coating
may also be deliberately absorbent such as a platinum black
coating. The coating may also be in sub-layers for providing
iridescent effects, but such sub-layers would add up to a single
thin deposited layer, in contrast to the three dimensional
structure of Milium coatings which have overlapping and nonparallel
metal flakes in a plastic matrix. The metal layers of the present
invention are essentially continuous in local zones, but are, of
course, discontinuous to the extent the fabric is discontinuous in
the openness of its weave for moisture vapor transmission and may
be made further discontinuous by application of the metal in a
screen pattern or the like for decorative effects.
The method of application of the metal(s) may be vacuum
evaporation, sputtering, pyrolytic or chemical vapor deposition, or
electroless or any method which provides a sufficiently thin metal
coat which is continuous to the extent indicated and also not
bridge over an open fabric weave.
The film forming resin has as a basic criterion that it must be
capable of reacting and cross-linking with the hydrophobic
component (silicone) when cured. The film forming polymer resin
used in the topcoat may be acrylic, acetal, ester, phenolic, ethers
and epoxies, vinyls and urethane base polymers including copolymers
thereof. The key criteria is a film forming capability without
excessive use of plasticizers and avoidance of stiffening the
fabric substrate. Cohesiveness of the resin is limited by the
combination with the hydrophobic silicone of the topcoat and
enhanced adhesion is obtained to the metal in metal coated fabric
areas and to the fabric in fabric areas uncoated with metal.
Coupling of several of the water repellent topcoats of the present
invention to fiber surface is not a surprising result. Coupling to
substantially continuous metal surface to the degree indicated
herein and consistent with the objects of the invention is
unique.
The finished fibrous article (whether treated as a fabric or
treated as a fiber and then formed to a fabric or paper) may be
used for clothing, draperies, clothing linings, tentage, outdoor
boat and car covers, umbrellas, sleeping bags and the like. In
connection with use near engines, the article has enhanced
resistance to gasoline or oil attack.
The combination of metal and topcoat protects the substrate (e.g.
nylon fiber) from actinic decay due to ultraviolet and infrared
radiation. The principal protection in this regard is provided by
the metal while the topcoat protects the metal from attack by dust,
bacteria, chemicals and water exposure of outdoor use as well as in
laundering and dry cleaning.
The metal coat also affords static resistance to the article.
The finished article also has enhanced strength which is
particularly noticeable for sheer fabrics and paper. The strength
of Kleenex tissues was doubled when metallized and topcoated as set
forth herein.
The metal is normally applied to one side of a fabric or fiber but
may be applied to both sides. The topcoat is applied to both
sides.
The essential features of the topcoat system are (a) a film forming
polymer resin adherent to the metal which may be in polymer form as
mixed or after curing, and (b) a hydrophobic (including mar
resistant) silicone of known composition R.sub.n SiO(4-n)/2 where R
is selected from the group consisting of hydrogen, alkyl, aryl,
aralkyl, cycloaliphatic, or alkenyl radicals and n is from 1.0 to
2.9. Water in amounts which may be small are necessary to enhance
silicone polymerization in accordance with known practice for use
of these compositions and (c) carrier.
The "solids" coating of the initial mixture composition (including
liquid form components of 100 percent "solids" composition) is from
1 to 10 percent of the total topcoat composition, the balance being
carrier water and/or solvents essentially all removed during
curing.
The component (a) is 50-98 percent of the solids content and the
component (b) is 2-50 percent of the solids content. The component
(b) includes a major portion of a hydrophobic silicone (including
mar resistant) or mixture of such compositions and a minor portion
(1 to 50 percent) of a coupling agent effective to couple to the
hydrophobic silicone and the component (a). It is optional whether
the coupling agent or agents are also capable of coupling
effectively to the metal and/or fabric. The coupling agent is not
necessarily hydrophobic, per se. The Dow Corning handbook entitled
"Silane Coupling Agents" (published 1967) gives a particularly good
analysis of coupling agents for various film forming polymers.
While the handbook analysis is not in terms of coupling the polymer
to another silicone component, it has been determined by my
experiments that the selections stated in the book are adequate for
this purpose to the extent necessary in protecting metallized
fabrics.
The silicones now widely used or useful as conventional water
repellent fabric finishes all serve to varying degrees the purpose
of reducing the web forming tendency of the components (a).
Preferred choices have been indicated above.
* * * * *