US3809663A - Textile sizing,water and oil repellent composition - Google Patents

Textile sizing,water and oil repellent composition Download PDF

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Publication number
US3809663A
US3809663A US00631167A US63116767A US3809663A US 3809663 A US3809663 A US 3809663A US 00631167 A US00631167 A US 00631167A US 63116767 A US63116767 A US 63116767A US 3809663 A US3809663 A US 3809663A
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United States
Prior art keywords
water
starch
oil
compositions
composition
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Expired - Lifetime
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US00631167A
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English (en)
Inventor
V Elkind
J Yurko
R Hunter
H Narder
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Colgate Palmolive Co
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Colgate Palmolive Co
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Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US00631167A priority Critical patent/US3809663A/en
Priority to DE19681769112 priority patent/DE1769112A1/de
Priority to DK156168AA priority patent/DK124414B/da
Priority to AT03399/68A priority patent/AT291929B/de
Priority to CH1193268D priority patent/CH1193268A4/xx
Priority to CH1193268A priority patent/CH535317A/de
Priority to CH535268A priority patent/CH476149A/de
Priority to NO01421/68A priority patent/NO129914B/no
Priority to ES352792A priority patent/ES352792A1/es
Priority to FR1561678D priority patent/FR1561678A/fr
Priority to IE442/68A priority patent/IE31874B1/xx
Priority to BE713777D priority patent/BE713777A/xx
Priority to GB08134/68A priority patent/GB1217590A/en
Priority to NL6805432A priority patent/NL6805432A/xx
Application granted granted Critical
Publication of US3809663A publication Critical patent/US3809663A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine

Definitions

  • a textile sizing or starching composition which also imparts water and oil-repellency and dry soil resistance containing a water-soluble starch and a fluoro polymer latex used, preferably, as an aerosol.
  • the present invention relates to a new and outstanding textile treating composition and particularly to compositions of the type normally used preparatory to ironing and textiles, such compositions serving primarily to size and/or stiffen the textile and in many instances to add gloss to the textile surface, and more particularly to sizing compositions, commonly referred to as laundry starch compositions, which in the present invention not only effect a sizing, stiffening and glossy surface but also impart to the treated textile outstanding waterand oilrepellency as well as excellent resistance to soiling.
  • starch as a size and stiffening agent for textile materials is probably as old as textiles themselves. It is only within the last several decades that the housewife has been offered such a product in an already prepared liquid form for application to the textile before ironing.
  • Such starching compositions are now available in a variety of forms and among the most popular is an aerosol type formulation. While starch, or starch derivatives, or modified starches form the major basis for the starching compositions presently available, there have been developed numerous non-starch, synthetic resinbased starching materials for the same general purposes.
  • starch refers to any suitable sizing material or stiffening composition which may be applied from a water dispersion (solution or suspension) as a preparatory treatment to an ironing step and while generally the natural starch materials are preferred, and this includes the numerous starch derivatives such as oxidized starches, acylated starches, starch ethers, hydrolyzed starches, enzyme-treated starches and the like, the compositions of the present invention encompass not only these natural and modified starches as a component thereof but the various synthetic products which are comparable and equivalent thereto.
  • the present invention provides a sizing or stiffening composition, i.e., a starch composition, which not only produces the desired degree of size and stiffness, which not only affords control by the consumer or housewife of these characteristics by virtue of the nondurability between washings of this finish, but also provides water and oil repellency which is durable in nature, which continues to build-up during the subsequent washings and treatments before ironing, and each build-up of permanence nevertheless does not interfere with the nondurability of the stiffening agent and does not produce a build-up of this component, notwithstanding the fact that all of these characteristics and effects are produced at one time from a single composition.
  • a starch composition which not only produces the desired degree of size and stiffness, which not only affords control by the consumer or housewife of these characteristics by virtue of the nondurability between washings of this finish, but also provides water and oil repellency which is durable in nature, which continues to build-up during the subsequent washings and treatments before ironing, and each build-up of permanence nevertheless does not interfere with the non
  • Another further object of this invention is to provide in aerosol form, compositions for treating textile materials preparatory to ironing same including therein a sizing starch and a fluorocarbon polymer.
  • Still another object of this invention lies in the provision of processes for treating textile materials to produce a sized and stiffened product and which is further characterized by water and oil repellency as well as resistance to staining by both water and oil-borne stains and still further by resistance by soiling.
  • compositions of the present invention comprise as the essential ingredients thereof, a water soluble or water dispersible sizing material, which is preferably a polyszccharide as exemplified by the various natural starches and the various starch derivatives which have been described above in combination with a thermo-plastic filmforming fluorocarbon polymer as hereinafter described.
  • a water soluble or water dispersible sizing material which is preferably a polyszccharide as exemplified by the various natural starches and the various starch derivatives which have been described above in combination with a thermo-plastic filmforming fluorocarbon polymer as hereinafter described.
  • additives which do not adversely effect the attainment of nondurable stiffening along with durable and permanent water and oil repellency.
  • additional materials include anti-stick agents such as the siloxane resins, polyethylene and the like; extenders for the fluorocarbon polymer such as urea-formaldehyde resins, acrylate and methacrylate polymers and copolymers and the like; additional water repellent materials such as long chain fatty quaternary ammonium compounds; anti oxidants; anti foamers; stabilizers; bacteriacides; surface active agents; coloring materials; perfumes; textile fiberreactive chemicals, e.g., formaldehyde, glyoxal; crease resistant and crease proofing agents, and the like.
  • compositions of this invention is a self-propelling liquid composition wherein the major carrier liquid is water and the propellant is a suitable low boiling hydrocarbon or halogenated hydrocarbon as exemplified by methylchloride, methylenechloride, isobutane and the various chlorinated fiuorinated methanes, ethanes, and the like such as dichloro difluoro methane and the like.
  • the propellant is a suitable low boiling hydrocarbon or halogenated hydrocarbon as exemplified by methylchloride, methylenechloride, isobutane and the various chlorinated fiuorinated methanes, ethanes, and the like such as dichloro difluoro methane and the like.
  • the nondurable size or stiffening component is preferably selected from the general class of starches and starch derivatives and among these the most preferred material is an acetylated amylopectin which is a thin boiling cook-up type starch and is illustrative of the preferred class of products of high fluidity i.e., 30 to 100 (intrinsic viscosity of from 1.0 to 0.3).
  • Other starch products which may be employed include the following: gelatinized corn starch, gelatinized wheat starch, gelatinized rice starch, gelatinized tapioca ethoxylated starch, gelatinized carboxymethyl starch, nitrogenated starch, oxidized corn starch, alkylated starch, dextrins and the like.
  • the amount of starch material which may be employed in the compositions of this invention may be varied widely, but in general from about 1% to about thereof based on the total weight of the aerosol formulation may be used. More important than the specific amount of sizing material is the ratio of the latter to the fluorocarbon polymer employed. in general, the ratio of these two components may vary from about 1:2 to 100:1 (size to fiuoro polymer) and within this range it is preferred to employ a ratio of from about 2:1 to 20: 1.
  • the fluoropolymer component of the compositions of this invention comprise a thermoplastic polymeric material in the form of a latex which is characterized by the ability to dry to a continuous cohesive film.
  • Fluoro polymers are well known but those which are preferred in the present invention comprise the general class of the perfluoro acrylates and alpha-substituted acrylates such as methacrylates.
  • the fiuoro polymers which may be used in the present invention, mention may be made of the following;
  • X is hydrogen, chlorine or fluorine.
  • X is hydrogen, lower alkyl (C to C or halogen and at least 70% but not less than 6 of the Xs are fluorine; interpolymers (i.e., copolymers and terpolymers of the aforementioned monomers, with polymerizable vinyl compounds, said interpolymer containing at least 25 mole percent of fluoro monomer (I).
  • Suitable comonomers include:
  • alkyl vinyl ketones ( alkyl C to C alkyl acrylates (alkyl C to C alkyl methacrylates (alkyl C to C vinylidene halides acrylic acid acrylonitrile acrylamide N- methylol acrylamide; N-methoxy methyl acrylamide styrene; alkyl styrenes 1,3-butadiene alkyl esters alkyl halides monoand di-acrylate esters of alkanediols monoand di-vinyl esters of alkanedioic acids,
  • a low molecular weight fluoropolymer latex which dries by itself to a brittle film.
  • Such products are prepared from similar monomers as described above but include a chain transfer agent, e.g., alkanethiol such as dodecyl mercaptan, to terminate the polymer.
  • resin emulsions may be added to the compositions of this invention to give special benefits.
  • Typical formulations of starch and fluoropolymers include the following:
  • concentrations are selected to give a solid pick-up based on the material treated of between 0.1% to 10% by weight. Since in order to obtain uniform treatment of a textile, it is desirable to have from about 1 to 200% and preferably from about 25 to 100% wet pick-up the concentrations of active components in the treating composition for the preferred pickup will vary from about 40% down to 0.1%. Clearly, such concentrations are not critical and are subject to the wide variation and great latitude indicated above.
  • the aqueous compositions are formulated with a suitable propellant.
  • propellants include trichloromonofluoromethane, dichlorotetrafluoroethane, dichloromonofluoromethane, monochlorotrifluoromethane, isobutane,
  • propellants are water-immiscible or only slightly soluble in water with vapor pressures at 70 F. of from about 0.2 to about 500 ps./g.
  • vapor pressures at 70 F. of from about 0.2 to about 500 ps./g.
  • the preferred propellants are the low density compounds and mixtures of low density which form a separate and upper liquid phase in the aerosol package providing thereby a three-phase system. While it is not intended to foreclose the use of higher density propellants (i.e., higher than the aqueous latex phase) in which case the propellant will be on the bottom in the aerosol package, this is not preferred because of the inadequacies of the mechanics of the package required for dispensing such compositions and further because other means for making such systems workable (i.e. shortened dip tube) create undesirable economic factors (eg cannot discharge a high percent of the active ingredients). In order to achieve the benefits of this invention, however, any technique aerosol or otherwise may be employed notwithstanding the fact that the optimum results may be obtained with certain specific formulations and techniques and these might, in general, be preferred especially by the housewife.
  • propellant as well as the specific one or ones used will vary depending upon the pressure limitations on the package and the spray pattern desired. Generally from 5 to 25 by weight of propellant circumscribes the practical range thereof, and as pointed out above, among these the low density, medium vapor pressure hydrocarbons such as isobutane are preferred.
  • compositions of this invention may be used in the compositions of this invention, some with particularly noteworthy results.
  • incorporation of a polyethylene emulsion in amounts ranging from 10% to 300% by weight based on the weight of fluoropolymer gives rise to unique ironing characteristics to textiles sprayed with such modified embodiments.
  • Siloxane emulsions for similar purposes are also contemplated.
  • Example 1 is repeated except that the fiuoropolymer used is a terpolymer containing 2.5% n-butyl acrylate and 0.5% N-methylol acrylamide. The results are somewhat superior to those of Example 1.
  • composition 3F lies in its unusual and unexpected improved laundering characteristics, as hereinafter demonstrated.
  • EXAMPLE 4 Swatches of 80 x 80 cotton are sprayed with the composition of Example 1 to give a 50% wet pick-up and ironed at 400 F. 33 sec./ft. to dryness. Excellent water and oil repellency results. The swatches are then artificially soiled as described below and then laundered. Untreated swatches are also soiled in a similar manner and laundered. The untreated samples launder better (i.e. as measured on a Photovolt Reflectance Meter) than the treated swatches.
  • Example 1 gives excellent water and oil rcpellency and as will be evident in further examples also gives excellent repellency to both water and oil borne stains, such treated materials, although more resistant to soiling nevertheless once they are soiled, do not launder as well as an untreated textile.
  • the soiling procedure is as follows:
  • the standardized soil is prepared by the method described in Salisbury et al. Soil Resistant Treatment of Fabric, American Dyestuff Reporter, Mar. 26, 1956, page 199.
  • the test using the standardized soils is as follows:
  • the end-over-end tumbling is carried out in a 6" diameter by 12' long cylindrical stainless steel jar rotating at 43 r.p.m.
  • Six (6) No. 8 Neoprene rubber stoppers (average weight 41.5+0.5 gram) are distributed evenly with the soil among the specimens. After tumbling, the specimens are removed and each shaken 15 times by hand to remove free soil by holding one corner 8 times and the diagonally opposite corner 7 times.
  • Each swatch is cut in half after repellency reflectance readings to produce two 5" x 3 /2" pieces (22 pairs total). Twenty-two swatches, one from each pair, are washed in an automatic Washer using 50 grams of Fab in the cotton cycle with 5 pounds additional dummy load and then dried 5 minutes in an automatic dryer at the high setting and lightly hand ironed.
  • the degree of soil before and after washing is determined with the Photovolt Reflectance Meter
  • the meter is standardized by placing the probe head on a block of MgCO (freshly ground against an identical block); then readings are taken on a porcelain plate used as a secondary standard. Readings using the Model 610Y probe with tri-blue filter and the Model 610D probe with tri-green filter have proved comparable with synthetic soil. Eight readings are taken with small probe and 6 readings with the large probe (610D) and the average value is reported.
  • Example 4 is repeated and instead of artificially soiling the swatches with the synthetic dry soil they are stained as follows:
  • the water-repellency is determined according to the AATCC Standard Test Method 221952.
  • test specimen fastened securely and wrinkle-free in a metal hoop having a diameter of 6 inches, is placed and centered 6 inches under a standard spray nozzle at an angle of 45 to the horizontal.
  • Two hundred and fifty milliliters of water at 80i2 F. is poured into a funnel attached above the spray nozzle.
  • the spray lasts 25 to seconds at the end of which time the hoop is taken 25 by one edge and the opposite edge tapped smartly once against a solid object with the wet side facing the solid; this procedure is repeated with the hoop reversed 180.
  • the swatches treated in Example 4 are further characterized by a stiffness rating (Stiffness Handle-O-Meter 30 using a swatch 4" x 4") of 44.
  • An untreated, laundered swatch gives a value of 21 (befor laundering it is 34).
  • EXAMPLE 7 The treated swatches of Example 6 are laundered and a second treatment is given. The water repellency is found to be 100 both before and after another laundering and the oil repellency is 6 before and 5 after this other laundering.
  • a concomittant increase in stain repellency is also noted as follows:
  • Example 8 The procedure in Example 7 is repeated through sprays, each followed by an ironing and a laundering with a final oil repellency value of 7, a stiffness rating before the last laundering of 53.5 (note, again, no buildup of stiffness), stain, dry soil repellency, and stain and soil removal equivalent to that shown in Example 6.
  • Example 9 A composition employing the components of Example 6 is prepared as follows: (percent on an active basis) Percent Acetylated amylopectin 3.75 Terpolymer of Example 2 0.30 Interpolymer XVI 0.10 Polyethylene (Example 6) 0.28 Formaldehyde 0.35 Isobutane 6. 17 Water 89.00
  • This composition is outstanding for dispensing as an aerosol with an excellent spray pattern and no valve clogging. Upon application to fabrics the results are similar to what is described in the previous examples.
  • Oil repellency 5. Water repellency: 80.
  • Oil repellency 4. Water repellency: 80.
  • EXAMPLE 12 In the following table various aqueous compositions are set forth which give excellent oil and water repellency, outstanding dry soil resistance and a highly desirable stifiness to cotton textiles treated therewith. The balance of the composition is water. As in the previous example the polymers are in latex form.
  • Example 1 mer II. (D) 6% amylopectin 0.5% interpoly- 0.3% polyethylene, 1.0%
  • Example 1 mer XIII. urea-formaldehyde crease-proofing agent.
  • Example 9 is repeated except that the propellant and amount thereof is varied as follows: (with a corresponding change in percent water)
  • EXAMPLE 14- Example 1 is repeated using the following water-soluble carbohydrates in the indicated amounts. Where more or less than 2.7% is used, there is a corresponding change in the water present:
  • Example 9 Homopoly-1H,1H-perfluorodecyl methacrylate
  • Example 9 is repeated using in place of the terpolymer of Example 2 and interpolymer XVI, the following in the indicated amounts:
  • A Modified cornstarch-fluidity 60 2.2
  • B Modified cornstarch-fluidity 60 7.5
  • C Modified cornstarch-fluidity 75 5.0
  • E Thin boiling wheat starch-fluidity 87 5.0
  • F Oxyethylated starch-fluidity 65 3.75
  • G Gelatinized starch-fluidity 8O 2.5
  • compositions of this invention produce excellent sizing along with unique water and oil-repellency on textiles.
  • the compositions may be applied to the textile in any convenient manner although they are most superior when used in an aerosol form.
  • the package structure will, obviously, vary from those packages or container used with propellants which are less dense and form an upper, discrete liquid phase. Regardless of these variations, however, excellent properties are forthcoming in all instances.
  • compositions of this invention may be added to the compositions of this invention, as pointed out above, and as will be obvious to one skilled in the art, the parameters are extremely varied, particularly in view of the fact that none of the additives need be soluble either in water or the selected propellant.
  • a compound may be added as a solution in a suitable solvent and such solution added to the aqueous compositions producing in most instances a dispersion of the said compound in the compositions.
  • Many other variations will be apparent and it is clear that these may be resorted to without departing from the spirit and scope of this invention and that the specific embodiments 5 Out herein are in no way limitative thereof.
  • a containerized selfpropelling aqueous textile treating composition which imparts simultaneously stilfening and oil and water repellency which comprises (A) a water-soluble starch,
  • a terpolymer in the form of a latex comprising (1) a polymerizable thermoplastic perfluoroalkylethylmethacrylate of the formula wherein X is selected from the group consisting of hydrogen, C, to C alkyl, chlorine and fluorine; X is selected from the group consisting of hydrogen, chlorine and fluorine, n has a value of 3 to 30; and at least 70%, but at least 6, of the X's are fluorine; (2) butylacrylate, and (3) N-methylol acrylamide; and, (C) propellant selected from the group consisting of hydrocarbons, halogenated hydrocarbons, and mixtures thereof;
  • ratio of starch to terpolymer is 2:1 to 20:1, and wherein said water-soluble starch is from 1 to 10% and said propellant is from 5 to 25% by weight of total composition.
  • a composition as defined in claim 1 wherein also present in the form of a latex is a copolymer of perfluoroalkylethylmethacrylate and butyl acrylate prepared in the presence of a chain transfer agent, and wherein the ratio of terpolymer to copolymer is 3:1.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US00631167A 1967-04-17 1967-04-17 Textile sizing,water and oil repellent composition Expired - Lifetime US3809663A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US00631167A US3809663A (en) 1967-04-17 1967-04-17 Textile sizing,water and oil repellent composition
DE19681769112 DE1769112A1 (de) 1967-04-17 1968-04-05 Textilbehandlungsmittel
AT03399/68A AT291929B (de) 1967-04-17 1968-04-08 Textilbehandlungsmittel
DK156168AA DK124414B (da) 1967-04-17 1968-04-08 Middel til stivning af tekstilmateriale og til gøre det vand- og olieafvisende.
CH535268A CH476149A (de) 1967-04-17 1968-04-09 Textilbehandlungsmittel
CH1193268A CH535317A (de) 1967-04-17 1968-04-09 Verfahren zum Stärken und zur gleichzeitigen wasser- und fettabweisenden Ausrüstung von Textilmaterialien
CH1193268D CH1193268A4 (cs) 1967-04-17 1968-04-09
ES352792A ES352792A1 (es) 1967-04-17 1968-04-16 Un procedimiento para tratar materiales textiles y produciren ellos un acabado de apresto y repelente al agua y a la grasa.
NO01421/68A NO129914B (cs) 1967-04-17 1968-04-16
IE442/68A IE31874B1 (en) 1967-04-17 1968-04-17 Textile sizing,water & oil repellent compositions
FR1561678D FR1561678A (cs) 1967-04-17 1968-04-17
BE713777D BE713777A (cs) 1967-04-17 1968-04-17
GB08134/68A GB1217590A (en) 1967-04-17 1968-04-17 Textile sizing, water & oil repellent compositions
NL6805432A NL6805432A (cs) 1967-04-17 1968-04-17

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US00631167A US3809663A (en) 1967-04-17 1967-04-17 Textile sizing,water and oil repellent composition

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US3809663A true US3809663A (en) 1974-05-07

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US00631167A Expired - Lifetime US3809663A (en) 1967-04-17 1967-04-17 Textile sizing,water and oil repellent composition

Country Status (12)

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US (1) US3809663A (cs)
AT (1) AT291929B (cs)
BE (1) BE713777A (cs)
CH (3) CH1193268A4 (cs)
DE (1) DE1769112A1 (cs)
DK (1) DK124414B (cs)
ES (1) ES352792A1 (cs)
FR (1) FR1561678A (cs)
GB (1) GB1217590A (cs)
IE (1) IE31874B1 (cs)
NL (1) NL6805432A (cs)
NO (1) NO129914B (cs)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070059537A1 (en) * 2003-11-21 2007-03-15 Peter Hupfield Polymeric products useful as oil repellents
US8771470B2 (en) * 2012-01-17 2014-07-08 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT299121B (de) * 1968-06-19 1972-06-12 Colgate Palmolive Co Mittel zum Appretieren und Fett- und Wasserabweisendmachen von Textilien
EP0079143A3 (en) * 1981-10-20 1984-11-21 Adnovum Ag Pseudoplastic gel transfer
US6159548A (en) * 1998-09-24 2000-12-12 Moody; Richard J. After-treatment method for oil-and water-repellency of fibrous substrates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070059537A1 (en) * 2003-11-21 2007-03-15 Peter Hupfield Polymeric products useful as oil repellents
US7645518B2 (en) * 2003-11-21 2010-01-12 Dow Corning Corporation Polymeric products useful as oil repellents
US7855264B2 (en) 2003-11-21 2010-12-21 Dow Corning Corporation Polymeric products useful as oil repellents
US8771470B2 (en) * 2012-01-17 2014-07-08 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
US9133584B2 (en) 2012-01-17 2015-09-15 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
US9499943B2 (en) 2012-01-17 2016-11-22 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom

Also Published As

Publication number Publication date
DE1769112A1 (de) 1971-06-03
AT291929B (de) 1971-07-15
CH535317A (de) 1973-03-31
FR1561678A (cs) 1969-03-28
BE713777A (cs) 1968-09-16
DK124414B (da) 1972-10-16
CH1193268A4 (cs) 1972-10-13
NO129914B (cs) 1974-06-10
GB1217590A (en) 1970-12-31
CH535268A4 (cs) 1969-09-15
CH476149A (de) 1969-09-15
IE31874B1 (en) 1973-01-24
ES352792A1 (es) 1969-09-01
IE31874L (en) 1968-10-17
NL6805432A (cs) 1968-10-18

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