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Publication numberUS3646749 A
Publication typeGrant
Publication dateMar 7, 1972
Filing dateDec 24, 1969
Priority dateDec 24, 1969
Publication numberUS 3646749 A, US 3646749A, US-A-3646749, US3646749 A, US3646749A
InventorsClough Philip J, Keough Allen H
Original AssigneeKing Seeley Thermos Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Machine-washable metallized fibrous article and method of making same
US 3646749 A
Abstract
Fibrous article with heat-and-light reflecting quality provided by a metal coating on synthetic fiber substrates. The metal coating is undercoated and overcoated with resin systems. The article thus produced has functional heat and light-reflecting quality and decorative quality due to the metal coating of the fiber substrates due to the consistent with substantially retaining hand and softness of the fibrous article. The article is machine washable (i.e., retains its metal coat), abrasion and mar resistant, water repellent and dry cleanable consistent with high-moisture vapor transmission of the article (breathability).
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Description  (OCR text may contain errors)

14 1 Mar. 7, 1972 United States Patent Clough et a1.

[54] MACHINE-WASHABLE METALLIZED 2,921,864 1/1960 Heberlein et FIBROUS ARTICLE AND METHOD ()1? 3,113,888 12/1963 Gold et a1. MAKING SAME 3,326,713 6/1967 SmIth et a1.

17/62 Traumann...................1l7/I38.8 N X 3,476,581 11/1969 Weitzeletal. 3,297,471 1/1967 [72] Inventors: Philip J. Clough, Cape Elizabeth, Maine;

Allen H. Keough, Sudbury, Mass.

Primary ExaminerAlfred L. Leavitt [73] Assignee: King-Seeley Thermos Co., Ann Arbor, Assistant Examiner--C.l(.Wei1Tenbach Anorney-Hamess, Dickey & Pierce [22] Filed: Dec. 24, 1969 ABSTRACT [21] Appl. No.: 888,002

Fibrous article with heat-and-light reflecting quality provided a metal coating on synthetic fiber substrates, The metal coating is undercoated and overcoated with resin systems. The

cle thus produced has functional heat and light-reflecting quality and decorative quality due to the metal coating of the fiber substrates due to the consistent with substantially retaining hand and softness of the fibrous article. The article is machine washable (i.e., retains its metal coat), abrasion and mar resistant, water repellent and dry cleanable consistent y m b a TRMMNTM 6 1 6 %U W 6 4 IWlMlAG B 5 l s -5 n ums1n 8 33 m E S 3 21C... H m 5 37 95 5 37 n m w 1 H A1 m8 M7 "8 132 "3 W1 "1 MW mM m m WWIR m "h 5 2 m n m7 m mmw 1 n 7 1 l C cm 5 m n U IF .1 ll. 2 00 5 55 .l [l

with high-moisture vapor transmission of the article (breathability).

References Cited 10 Claims, 2 Drawing Figures UNITED STATES PATENTS PAIENIEUIIIIR 7 I872 WATER .REPELLANT METALLIZED ARTICLE FIBER PRODUCTION (YARN, MONOFILAMENT,

FIBRILLATION, ETC.)

WEAVING BONDING, ETC.

FABRIC, FELT CLEANING, SIZING IFABRIC, FELT, (FIBROUS ARTICLE) P RE- COAT {PRECOATED FIBROUS ARTICLE METALLIZE +METALLIZED FIBROUS ARTICLE (HAND WASHABLE, DRY CLEANABLE) TOP- COAT lMAcuINE WASHABLE,

Fig 2.

,- -fi FIBER SUBSTRATE MAClllINE-WASHABLE METALLIZED FIBROUS ARTICLE AND METHOD OF MAKHNG SAME This invention relates to fibrous articles e.g., fabric (including woven, nonwoven or bonded or felt and including also a beam" of fibers, a fibrillated or slit film) or a single fiber (including filament or yarn) to be formed into fabric and particularly to fibrous articles coated with metal to provide heat and light reflectance for decorative and functional (insulation and reflection) purposes. Related applications are Ser. No. 794,399 filed Jan. 24, 1969 now abandoned and Ser. No. 796,930 filed Feb. 5, 1969, both of common assignment with the present application.

The principal known fabric or fiber metallizing methods are (1) application of metal flakes in a plastic matrix, e.g., US. Pat. Nos. 2,630,620; 2,767,104 and 3,220,871 embodied Milium (registeredtrademark 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 US. Pat. Nos. 2,912,345; 2,921,864; 2,907,678 and German Pat. No. 1,182,631 embodied in Metalon and lnsalume (registered trademarks) fabrics (see Man Made Textiles Magazine-Jan. 1965 and Textile World Magazine-May 1965).

Both of these processes have significant limitations in regard to abrasion and mar resistance and launderability of the metal coating and/or moisture vapor transmission (breath ability). It is the primary object of this invention to provide commercially sufficient machine washability to a metallized polyamide (nylon) fibrous article as measured by visually observed retention of substantially all metal throughout the class II machine washability test of the American Association of Textile Chemists & Colorists (AATCC) consistent with retaining full breathability of the article. It is a further object of the invention to similarly improve other metallized synthetic fibers.

It is a further 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 highmoisture vapor transmission of the articles.

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.

In general the improved fibrous article is made by precoating a fibrous article with a resin, metallizing the fibrous article in a vacuum chamber, removing the article from the vacuum chamber and top-coating it with a hydrophobic resin.

The process may be practiced on individual fibers such as monofilament fiber or yarn or slit or fabrillated film, which fibers are later formed into a fabric or felt, or practiced directly on a woven or bonded fabric or felt. The latter is preferred in cases where abrasion of weaving or bonding would remove metal coating despite resin protection e.g., in working with glass fiber substrates. The fiber involved should be synthetic but maybe part of a mixture of natural and synthetic fibers as in cotton-polyester woven fabrics. It is preferably wholly synthetic, preferably nylon, to realize the machine washability object to the highest degree.

Preferably the metal is applied to a thickness of about inches but may be as thin as 10 or as thick as 10"inches. The metal fonns a single-thin film continuous layer along the individual fibers on at least one side of the fibrous article but without bridging gaps or openings between fibers in the article, to leave the breathability (moisture vapor transmission) 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 metal is vapor deposited, preferably vacuum deposited; it may be applied also through sputtering, pyrolytic or chemical vapor deposition or electroless vapor plating. Broad areas of the substrate may omit metal (through masking during deposition or removal of metal) for functional or decorative purposes.

The invention will be best understood from the following specific description taken in conjunction with the accompanying drawings wherein HO. 1 shows a portion of a woven fabric with one of the fibers in cross section and FIG. 2 shows a typical textile process flow chart including as a portion thereof the use of the present invention.

In FIG. 1, the fibers shown in the article W (a woven fabric) are warp W and fill F with a high spot of the weave indicated at H. In the cross section, it is seen that the fiber comprises in this instance a monofilament synthetic, e.g., nylon (polyamide). A first under-or base-coat layer 12 of resin surrounds the fiber substrate. A midlayer 14 of metal is deposited over the base-coated fiber and a topcoat of hydrophobic resin 16 imparts water repellency.

The metal layer is applied by vacuum evaporation of metal and condensation of it on the fibrous article W. The metal vapors move in the direction M, through crossover points of the fabric as indicated at C are masked and receive no metal. However such points do receive top and base-coats if applied by immersion.

The fibrous article substrate is preferably, and with distinct advantage in the combination selected from nylon and polyester (e.g., Dacron brand) fiber. The fiber may be in the form of multifilament yarn or in monofilament form, but the latter is particularly advantageous in connection with the invention. A woven fabric substrate provides the best utilization of the inventions breathability retaining and high-reflectance characteristics.

The base coat layer 12 has a weight of 3-15 percent of the weight of the fibrous article (nylon fabric) and conforms to individual fiber surfaces, essentially without bridging adjacent fibers. The base coat is the polymerization product of a hydrophillic polar unsaturated resin deposited in an emulsion bath and cured after deposition to form a surface coating on the fiber of improved level (smoothness) compared to the uncoated surface. The midlayer 14 of vapor deposited metal has sufficient thickness, as indicated above, to afford reflectances to light and heat radiation. Curing of the base coat should be complete so that it does not outgas during metallizing and interfere with metal adhesion. The top coat layer 16 is a cured hydrophobic resin with a weight of 0.5 to 5 percent of the fibrous article weight (including base coat and metal).

It is preferred and distinctly advantageous to have the top coat extend beyond the metallized area of the fibrous article to prevent edge attack by water in washing or usage of the article. Preferably the top coat surrounds the fibers. The base coat should also extend beyond the metallized area, under the top coat and preferably completely surrounding the fibers to provide a bondable surface for the top coat.

P16. 2 diagrammatically illustrates the method of producing the machine washable metallized fibrous article of the invention. The diagram in part includes steps beyond the intended scope of the invention and old in the art, which are listed for purposes of establishing context of the invention.

Step A is conventional production or selection of fiber.

Step B is convention consolidation of fibers through weaving, bonding or the like.

Step C is the conventional cleaning and sizing e.g., scour and heat set" of the fibrous article whether it be a fiber or fabric. Conventional textile processing procedures are involved and the resultant fibrous article is then said to be ready for finish" e.g., through water proof coats, hand and finish modifying coats, strengthening coats, etc. If a fiber is to be eventually incorporated into a fabric it is preferable to complete the fabric production prior to the coating steps listed below to avoid damage to the coatings through abrasion, heat and chemical attack inherent in weaving procedures.

The present process invention includes as a first step (d) the precoating of the fibrous article. Preferably, this is done by immersion in an emulsion containing an acrylic resin in prepolymer form, squeezing (or otherwise removing excess emulsion pickup) and heating in an air oven to dry and polymerize the resin coat. It is preferred to support side edges of a long web on a tenter frame during this curing step. However the step may include other means of application and drying and choices of coating offering equivalent functioning in the total coating system described herein. To the extent practical, it is preferred to consolidate portions of (or eliminate redundant portions of) the steps of cleaning and sizing (c) and of precoating (d). For instance, the conventional cleaning step which generally involves immersion in a solvent cleaner, rinsing and drying could be modified to insert the precoating immersion step after rinsing, and before drying (heat-set sizing) to eliminate one redundant drying step.

The metallizing step involves placing the precoated fibrous article in a vacuum chamber, evacuating the chamber, outgassing the precoated fibrous article if necessary and then exposing the fibrous article to a source of evaporating metal in the chamber which metal condenses on the fibrous article. In commercial practice a roll of fabric yard goods constitutes the fibrous article and it is metallized in apparatus of the kind shown in US. Pat. No. 2,971,862 of Baer et al. The roll of goods is unrolled, passed over the metal source at speeds of several hundred feet per minute and rerolled. Prior to metallizing the goods should be unrolled and rerolled in vacuum to assure freedom from outgassing. it is sufficient if the outgassing does not raise chamber pressure above torr. For small scale runs, a bell jar coater can be used with no relative movement of substrate (the precoated fibrous article) and metal source. The metallization increases opacity by about 75 percent. It is checked for adequate adhesion by the conventional Scotch tape test. At this point, the metallized article is hand washable and dry cleanable.

The metallized fibrous article is then topcoated preferably by immersion in a solution containing a silicon resin in prepolymer form, squeezing and heating in an air oven to dry and polymerize the resin, as in the precoat process. This renders the article machine washable and water repellent.

Subsequent steps can include cutting, stitching and other processing of the fibrous article.

The preferred embodiments of the invention are now further illustrated through the following nonlimiting examples.

EXAMPLE I A scoured and heat set nylon woven fabric cloth of 90 X 108 taffeta weave was precoated by immersion in a bath containing the following constituents (with percentages indicated on a weight basis):

Rohm 8L Haas PIA-8 acrylic emulsion (50% solids in water) 30 oxalic acid catalyst 0.15% Philadelphia Quartz N" sodium silicate 0.25% water balance The bath was maintained at a temperature of 75F. The cloth was squeezed between nip rolls after immersion and passed through a drying chamber, containing air heated at 315F., in 90 seconds. The precoating produced, after drying, a solids pickup of 6 percent of weight of the original cloth.

After precoating, the cloth was passed through a vacuum coater and vacuum aluminized to produce a metal coating of about 10- inches on one side. The coating corresponds to what would be a 2 ohm per square coating on a film substrate.

Then the cloth was immersed in another bath having the following ingredients (by weight):

Silicon (Dow Corning FC-227) 30 1: Catalyst (Dow Corning 27) 0.6% Adhesive (Dow Corning X(-42067) 0.9% Toluene balance The bath was at 75 F. Drying was accomplished as in the precoat step to produce a solid weight pickup of 1% (based on the precoated and metallized cloth).

The cloth was successfully machine washed in accordance with AA'lCC-ll Test. No loss of metal was observed. The fabric was as breathable as before treatment.

EXAMPLE [1 Processing as'in Example 1 with a topcoat mix of Silicone 20 1: Catalyst 0.4% Adhesive 0.6% Toluene balance (including metallizing and base coating as in l) was apparently similarly successful on white nylon cloth, but showed spots of blue in metallized blue cloth after washing, leading to the observation that the total coating system cracks or abrades at high spots (which is functionally acceptable but esthetically less desired).

EXAMPLE 111 The results of Examples 1 and 11 were repeated in processes in which the base coat composition was varied to UCar 891 acrylic-latex copolymer emulsion (50% in water) 20 I: diammoniurn phosphate powder 0.5% water balance Unsuccessful results re machine washability (i.e., failure to hold metal through AATCC-ll Test) were obtained when the systems described in the above cited patent applications Ser. Nos. 794,399 and 796,930 were used. Unsuccessful results were obtained from:

a. direct metallizing with no base coat or top coat b. precoat plus metallizing without top coat c. top coated metallized cloths without precoat d. acrylic base (as in Example 1), metallize, acrylic top coat e. silicon base, metallize, silicone top coat it is desirable to assure uniformity of base and top coats, e.g., by the use of rubber surfaced nip rolls in the drying process and avoidance of abrasion in handling the cloth. in the above examples, handling conditions were less than ideal, including use of a chrome surfaced nip roll.

Addition of fireproofing agents to the base coat is also desirable. Chlorinated resin substitutes for the base coat resin accomplish this. Dispersion of fireproofing salts in the base coat as in Example 111, above, is another way to accomplish the same result.

it is thus apparent that there is a synergistic effect in the combinations of the type illustrated in the above examples. Alternative ingredients for the base coat in lieu of or with acrylic and acrylic-latex polymers and copolymers are epoxy resins, polyvinyl chloride, cross linkable olefins, vinyl acrylic, vinylester copolymers. Alternative ingredients for the top coat in lieu of or with silicone are epoxy resins. Urethane resin top coat may be utilized but is less advantageous because it reduces transmission of infrared heat radiation to a substantially greater extent than silicone resin.

Water repellent resin coating systems are described in US. Pat. Nos. 3,081,193; 3,398,017; 3,326,713; 2,588,366; 3,434,875 and 3,076,926. See also the references cited above at the beginning of this specification.

The scope of the invention includes various other metals copper, zinc, tin, gold, silver, bright platinum, bronze, Wood s metal and equivalent metals. The metal coating may also be in sublayers providing iridescent reflective effects, but such sublayers would add up to a single-thin deposited layer in contrast the three dimensional structure of Milium coatings which have overlapping and nonparallel metal flakes in a plastic matrix.

Still further equivalents within the scope of the invention will be apparent to those skilled in the art once given the benefit of the foregoing disclosure. Accordingly it is intended that the foregoing disclosures shall be read as illustrative and not in a limiting sense.

What is claimed is:

1. A metallized fibrous article comprising individual synthetic fiber substrates which are coated with a multilayer coating comprising:

a. a base-coat layer of cured resin with a total weight of 3 to percent of the article weight and conforming to individual fiber surfaces, essentially without bridging adjacent fibers, said cured resin selected from the group consisting of acrylic and acrylic-latex polymers and copolymers, epoxy resins, polyvinyl chloride, cross linkable olefins, vinyl acrylic and vinyl ester copolymers;

b. a midlayer of vapor deposited metal in sufficient thickness to afford reflectance to light and heat radiation;

c. a topcoat layer of cured hydrophobic resin with a total weight of 0.5 to 5 percent of the fiber weight and conforming to individual fiber surfaces, essentially without bridging adjacent fibers.

2. The article of claim 1 as a woven fabric.

3. The article of claim 1 with the fibrous article substrate composition selected from the class consisting of nylon and polyester.

4. The article of claim 1 with individual fiber substrates comprising monofilament's.

5. The article of claim 1 with the individual fiber substrates comprising multifilament yarn.

6. The article of claim 1 with the individual fiber substrates comprising a monofilament.

7. The article of claim 1 with the base-coat layer completely surrounding the fiber substrates in cross section.

8. The article of claim 1 with the hydrophobic topcoat layer completely surrounding the fiber substrates in cross section.

9. The article of claim 1 wherein the base-coat layer is acrylic resin and the topcoat layer is silicone resin.

10. The article of claim 1 wherein portions of the base-coat layer and the topcoat layer extend beyond the midlayer such that the base-coat and topcoat layers are directly bonded to each other.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2921864 *Jul 25, 1955Jan 19, 1960Heberlein Patent CorpProcess for metalizing textiles and products therefrom
US3081193 *Jan 12, 1961Mar 12, 1963Ucb SaProcess for the treatment of polyamide fabrics
US3113888 *Mar 3, 1961Dec 10, 1963Nat Starch Chem CorpDirect method for metalization of cast-coated paper
US3297471 *Apr 8, 1965Jan 10, 1967Du PontAcrylic or methacrylic acid grafting copolymerized on nylon and forming salt of said graft
US3326713 *Jan 29, 1964Jun 20, 1967Burlington Industries IncBreathable and waterproof coated fabric and process of making same
US3476581 *Oct 18, 1965Nov 4, 1969Deering Milliken Res CorpTreatment of textiles with cross-linkable acrylic polymers and the resulting products
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3914472 *Oct 24, 1974Oct 21, 1975Toray IndustriesProcess for metallizing the surface of a polyamide resin molded article
US4312913 *May 12, 1980Jan 26, 1982Textile Products IncorporatedHeat conductive fabric
US4614684 *Sep 16, 1982Sep 30, 1986Bayer AktiengesellschaftReinforced composite comprising resin impregnated metallized polyaramide fabric and method of making same
US5090053 *Jan 3, 1991Feb 25, 1992Dalton EnterprisesComposite shock absorbing garment
US5469895 *May 3, 1994Nov 28, 1995Page Automated Telecommunications Systems, Inc.Smart skin array woven fiber optic ribbon and arrays and packaging thereof
US5855733 *Oct 13, 1995Jan 5, 1999Marathon Belting LimitedPress pad
US7675619May 30, 2008Mar 9, 2010The United States Of America As Represented By The Administrator Of The National Aeronautics And Space AdministrationMicro-LiDAR velocity, temperature, density, concentration sensor
US7785509Dec 21, 2005Aug 31, 2010Pascale Industries, Inc.Expansible yarns and threads, and products made using them
US7805907Oct 25, 2007Oct 5, 2010E.I. Du Pont De Nemours And CompanyBreathable low-emissivity metalized sheets
US7851062May 21, 2008Dec 14, 2010The United States Of America As Represented By The Administrator Of The National Aeronautics And Space AdministrationEach layer includes an arrangement of fibers ( glass fiber, carbon fiber, aramid fiber) and coated with a metal (pt, pd, ni etc.) and a a polymer matrix ( epoxy resins) permeating each such arrangement; improved impact resistance, damage tolerance, and permeation resistance
US8017190 *Oct 18, 2010Sep 13, 2011United States Of America As Represented By The Administrator Of The National Aeronautics And Space AdministrationMetal/fiber laminate and fabrication using a porous metal/fiber preform
US8431209Oct 25, 2007Apr 30, 2013E I Du Pont De Nemours And CompanyBreathable low-emissivity metalized sheets
US8497010Oct 25, 2007Jul 30, 2013E I Du Pont De Nemours And CompanyBreathable low-emissivity metalized sheets
WO2006121935A2 *May 8, 2006Nov 16, 2006Noble Biomaterials IncProcess for creating spun yarn
WO2008150716A1 *May 22, 2008Dec 11, 2008Us Adm Nat AeronauticsMetal/fiber laminate and fabrication using a porous metal/fiber preform
Classifications
U.S. Classification442/188, 28/169, 428/394, 427/407.1, 28/166, 428/413, 139/425.00R, 428/381, 428/378
International ClassificationD06Q1/04, D06Q1/00
Cooperative ClassificationD06Q1/04
European ClassificationD06Q1/04
Legal Events
DateCodeEventDescription
Jun 3, 1986AS02Assignment of assignor's interest
Owner name: KING-SEELEY THERMOS CO., A CORP OF DE.
Owner name: METALLIZED PRODUCTS, INC., 37 EAST STREET, WINCHES
Effective date: 19860523
Jun 3, 1986AS06Security interest
Owner name: METALLIZED PRODUCTS, INC., A CORP OF MA.
Effective date: 19860523
Owner name: UNITED STATES TRUST COMPANY, 40 COURT STREET, BOST
Jun 3, 1986ASAssignment
Owner name: METALLIZED PRODUCTS, INC., 37 EAST STREET, WINCHES
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:KING-SEELEY THERMOS CO., A CORP OF DE.;REEL/FRAME:004554/0538
Owner name: UNITED STATES TRUST COMPANY, 40 COURT STREET, BOST
Free format text: SECURITY INTEREST;ASSIGNOR:METALLIZED PRODUCTS, INC., A CORP OF MA.;REEL/FRAME:004554/0526
Effective date: 19860523