EP1805233A2 - Liant de fibres de verre hydrofuge comportant un polymere fluore - Google Patents

Liant de fibres de verre hydrofuge comportant un polymere fluore

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Publication number
EP1805233A2
EP1805233A2 EP05809963A EP05809963A EP1805233A2 EP 1805233 A2 EP1805233 A2 EP 1805233A2 EP 05809963 A EP05809963 A EP 05809963A EP 05809963 A EP05809963 A EP 05809963A EP 1805233 A2 EP1805233 A2 EP 1805233A2
Authority
EP
European Patent Office
Prior art keywords
binder
fiberglass
product
polymer
polyol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05809963A
Other languages
German (de)
English (en)
Other versions
EP1805233A4 (fr
Inventor
Philip Francis Miele
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Johns Manville
Original Assignee
Johns Manville
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johns Manville filed Critical Johns Manville
Publication of EP1805233A2 publication Critical patent/EP1805233A2/fr
Publication of EP1805233A4 publication Critical patent/EP1805233A4/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/24—Coatings containing organic materials
    • C03C25/26—Macromolecular compounds or prepolymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C09J167/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl - and the hydroxy groups directly linked to aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J127/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers
    • C09J127/02—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J127/12—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Adhesives based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/587—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives characterised by the bonding agents used
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/58—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives
    • D04H1/64—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity

Definitions

  • the subject invention pertains to polycarboxy polymer binding resins having improved water repellancy properties. More particularly, the subject invention pertains to thermosetting, acrylic acid-based binder resins which cure by crosslinking with a poly- functional, hydroxyl group-reactive curing agent, which binders containing such resins exhibit minimal water absorption. Such binders are useful as replacements for formaldehyde-based binders in non-woven fiberglass goods.
  • Fiberglass binders have a variety of uses ranging from stiffening applications where the binder is applied to woven or non-woven fiberglass sheet goods and cured, producing a stiffer product; thermo-forming applications wherein the binder resin is applied to a sheet or lofty fibrous product, following which it is dried and optionally B- staged to form an intermediate but yet curable product; and to fully cured systems such as building insulation.
  • Fibrous glass insulation products generally comprise matted glass fibers bonded together by a cured thermoset polymeric material. Molten streams of glass are drawn into fibers of random lengths and blown into a forming chamber where they are randomly deposited as a mat onto a traveling conveyor. The fibers, while in transit in the forming chamber and while still hot from the drawing operation, are sprayed with an aqueous binder.
  • a phenol-formaldehyde binder has been used throughout the fibrous glass insulation industry.
  • the residual heat from the glass fibers and the flow of air through the fibrous mat during the forming operation are generally sufficient to volatilize the majority to all of the water from the binder, thereby leaving the remaining components of the binder on the fibers as a viscous or semi-viscous high solids liquid.
  • the coated fibrous mat is transferred to a curing oven where heated air, for example, is blown through the mat to cure the binder and rigidly bond the glass fibers together.
  • Fiberglass binders used in the present sense should not be confused with matrix resins which are an entirely different and non-analogous field of art.
  • binder resins While sometimes termed "binders", matrix resins act to fill the entire interstitial space between fibers, resulting in a dense, fiber reinforced product where the matrix must translate the fiber strength properties to the composite, whereas "binder resins" as used herein are not space-filling, but rather coat only the fibers, and particularly the junctions of fibers. Fiberglass binders also cannot be equated with paper or wood product "binders” where the adhesive properties are tailored to the chemical nature of the cellulosic substrates. Many such resins are not suitable for use as fiberglass binders. One skilled in the art of fiberglass binders would not look to cellulosic binders to solve any of the known problems associated with fiberglass binders.
  • Binders useful in fiberglass insulation products generally require a low viscosity in the uncured state, yet characteristics so as to form a rigid thermoset polymeric mat for the glass fibers when cured.
  • a low binder viscosity in the uncured state is required to allow the mat to be sized correctly.
  • viscous binders tend to be tacky or sticky and hence they lead to accumulation of fiber on the forming chamber walls. This accumulated fiber may later fall onto the mat causing dense areas and product problems.
  • a binder which forms a rigid matrix when cured is required so that a finished fiberglass thermal insulation product, when compressed for packaging and shipping, will recover to its as-made vertical dimension when installed in a building.
  • thermosetting fiberglass binder resins From among the many thermosetting polymers, numerous candidates for suitable thermosetting fiberglass binder resins exist. However, binder-coated fiberglass products are often of the commodity type, and thus cost becomes a driving factor, generally ruling out such resins as thermosetting polyurethanes, epoxies, and others. Due to their excellent cost/performance ratio, the resins of choice in the past have been phenol/formaldehyde resins. Phenol/formaldehyde resins can be economically produced, and can be extended with urea prior to use as a binder in many applications. Such urea-extended phenol/formaldehyde binders have been the mainstay of the fiberglass insulation industry for years, for example.
  • VOCs volatile organic compound emissions
  • One such candidate binder system employs polymers of acrylic acid as a first component, and a polyol such as glycerine or a modestly oxyalkylated glycerine as a curing or "crosslinking" component.
  • a polyol such as glycerine or a modestly oxyalkylated glycerine
  • crosslinking component
  • the preparation and properties of such poly(acrylic acid)-based binders, including information relative to the VOC emissions, and a comparison of binder properties versus urea formaldehyde binders is presented in "Formaldehyde-Free Crosslinking Binders For Non-Wovens", Charles T. Arkins et al., TAPPI JOURNAL, Vol. 78, No. 11 , pages 161-168, November 1995.
  • the binders disclosed by the Arkins article appear to be B-stageable as well as being able to provide physical properties similar to those of urea/formaldehyde
  • U.S. Patent No. 5,340,868 discloses fiberglass insulation products cured with a combination of a polycarboxy polymer, a -hydroxyalkylamide, and an at least one trifunctional monomeric carboxylic acid such as citric acid.
  • the specific polycarboxy polymers disclosed are poly(acrylic acid) polymers. See also, U.S. Patent No. 5,143,582
  • U.S. Patent No. 5,318,990 discloses a fibrous glass binder which comprises a polycarboxy polymer, a monomeric trihydric alcohol and a catalyst comprising an alkali metal salt of a phosphorous-containing organic acid.
  • thermosetting acrylic resins have been found to be more hydrophilic than the traditional phenolic binders, however. This hydrophilicity can result in fiberglass insulation that is more prone to absorb liquid water, thereby possibly compromising the integrity of the product. Also, the thermosetting acrylic resins now being used as binding agents for fiberglass have been found to not react as effectively with silane coupling agents of the type traditionally used by the industry.
  • silicone as a hydrophobing agent results in problems when abatement devices are used that are based on incineration. Also, the presence of silicone in the manufacturing process can interfere with the adhesion of certain facing substrates to the finished fiberglass material. Overcoming these problems will help to better utilize polycarboxy polymers in fiberglass binders.
  • Yet another object of the present invention is to provide such a binder which allows one to prepare fiberglass insulation products which are more water repellent and less prone to absorb liquid water.
  • Still another object of the present invention is to provide a fiberglass insulation product which exhibits good recovery and rigidity, is formaldehyde-free, and is more water-proof.
  • the binder composition of the present invention comprises a polycarboxy polymer, a polyol, and a fluorinated polymer. It is also preferred that the binder comprise a catalyst, such as an alkaline metal salt of a phosphorus-containing organic acid.
  • a catalyst such as an alkaline metal salt of a phosphorus-containing organic acid.
  • An important aspect of the binder of the present invention is that the binder composition, in addition to the polycarboxy polymer and the polyol, contains a fluorinated polymer. The presence of the fluorinated polymer in the binder is believed to render the binder, and hence the fiberglass mat to which the binder is applied, essentially waterproof. As a result, fiberglass insulation made with the binder of the present invention avoids the possible problem of coming apart when subjected to water, as the binder of the present invention has been found to repel the water and maintain the integrity of the bond with the fiberglass.
  • the glass fiber mats can be used as thermal or sound insulation, as well as filtration media in filtering air or liquids.
  • the binder of interest with regard to the present invention is a formaldehyde free binder useful for glass fibers.
  • a binder composition compound of a polycarboxy polymer and a polyol are described, for example, in U.S. Patent No.6,331 ,350, which is hereby expressly incorporated by reference in its entirety.
  • the polycarboxy polymer used in the preferred binder of the present invention comprises an organic polymer or oligomer containing more than one pendant carboxy group.
  • the polycarboxy polymer may be a homopolymer or copolymer prepared from unsaturated carboxylic acids including but not necessarily limited to, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2- methylmaleic acid, itaconic acid, 2-methylitaconic acid, .,-methyleneglutaric acid, and the like.
  • unsaturated carboxylic acids including but not necessarily limited to, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2- methylmaleic acid, itaconic acid, 2-methylitaconic acid, .,-methyleneglutaric acid, and the like.
  • unsaturated carboxylic acids including but not necessarily limited to, acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, cinnamic acid, 2- methylmaleic acid, itaconic acid
  • the polycarboxy polymer of the present invention may additionally comprise a copolymer of one or more of the aforementioned unsaturated carboxylic acids or anhydrides and one or more vinyl compounds including, but not necessarily limited to, styrene, -methylstyrene, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, n- butyl acrylate, isobutyl acrylate, methyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, glycidyl methacrylate, vinyl methyl ether, vinyl acetate, and the like.
  • Methods for preparing these copolymers are well-known in the art.
  • Preferred polycarboxy polymers comprise homopolymers and copolymers of polyacrylic acid. It is particularly preferred that the molecular weight of the polycarboxy polymer, and in particular polyacrylic acid polymer, is less than 10000, more preferably less than 5000, and most preferably about 3000 or less. The low molecular weight polycarboxy polymer results in a final product which exhibits excellent recovery and rigidity.
  • the formaldehyde-free curable aqueous binder composition of the present invention also contains a polyol containing at least two hydroxy! groups.
  • the polyol must be sufficiently nonvolatile such that it will substantially remain available for reaction with the polyacid in the composition during heating and curing operations.
  • the polyol may be a compound with a molecular weight less than about 1000 bearing at least two hydroxyl groups such as, for example, ethylene glycol, glycerol, pentaerythritol, trimethylol propane, sorbitol, sucrose, glucose, resorcinol, catechol, pyrogallol, glycollated ureas, 1 ,4-cyclohexane diol, diethanolamine, triethanolamine, and certain reactive polyols such as, for example, -hydroxyalkylamides such as, for example, bis[N,N-di.(-hydroxyethyl)]adipamide, as may be prepared according to the teachings of U.S. Patent No.
  • 4,076,917 hereby incorporated herein by reference in its entirety, or it may be an addition polymer containing at least two hydroxyl groups such as, for example, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, and homopolymers or copolymers of hydroxyethyl (meth) acrylate, hydroxypropyl(meth) acrylate, and the like.
  • the most preferred polyol for the purposes of the present invention is triethanolamine (TEA).
  • the ratio of the number of equivalents of carboxy, anhydride, or salts thereof of the polyacid to the number of equivalents of hydroxyl in the polyol is from about 1/0.01 to about 1/3.
  • a low ratio, approaching 1/0.7 has been found to be of particular advantage especially when combined with a low molecular weight polycarboxy polymer as described above, and also preferably with a lower pH binder.
  • the pH of the binder of the present invention also be low, i.e., no greater than 4.5, and preferably less than 3.5, for it has been found that the combination of low molecular weight polycarboxy polymer with a lowered pH provides a binder exhibiting minimal processing difficulties and a final product with excellent recovery and rigidity. Maintaining the pH in the range of from 3.5 to 4.5 allows one to avoid serious problems with corrosion of the equipment while still realizing the benefits of the low pH. However, a lower pH can also be used, e.g., less than 3.5, and is actually preferred due to beneficial results, with appropriate handling precautions.
  • the binder of the present invention also contains a fluorinated polymer, as an additive.
  • the presence of the fluorinated polymer has been found to render the polycarboxy/polyol binder of the present invention less prone to absorb water, while still allowing excellent products and good processing of those products, e.g., thermal and sound insulation products and filtration media in filtering air or liquids.
  • its presence may better maintain the integrity of the bond between the binder and glass fiber, and hence the integrity of the entire mat product, when exposed to liquid water.
  • the binder bond, and hence the overall product, is more water-proof.
  • the preferred fluorinated polymer is a copolymer prepared from a fluorine containing acrylate monomer with styrene or some other commonly used acrylate comonomer.
  • fluorinated polymers are available, for example, under the trademark ParaChem RD-F25TM.
  • any suitable fluorine-containing polymer in which fluorine has been substituted for hydrogen in an organic polymer can be employed. This would include the vinyl fluoride polymers and the tetrafluoroethylene polymers.
  • the homopolymers of tetrafluoroethylene, as well as its copolymers with hexafluoropropylene, perfluorovinylether and ethylene can also be used to impart hydrophobicity to the polycarboxy/polyol binder of the present invention.
  • the fluorinated polymers employed are generally added to the polycarboxy/polyol binder as a dispersion or emulsion, and can be added directly to the binder composition which is then employed in the formation of the fiberglass products. Alternatively, the fluorinated polymer can be sprayed onto the fiberglass product itself once it has been formed and cured. A combination of these two events can also be employed. It is preferred, however, that the fluorinated polymer be added directly to the binder composition used in the formation of the fiberglass product.
  • the amount of fluorinated polymer employed is generally such that the final fiberglass product contains from .005 to .5 wt. % of the fluorine-containing polymer. More preferably, the amount of fluorine-containing polymer in the final product can generally range from about .01 to about .3 wt. %, even more preferably from about .04 to .1 wt. %, and most preferably in the range of about .05 to .09 wt. %. It has been found that the use of the fluorine-containing polymer can be at levels much lower than silicone materials to achieve similar water repellency, while also overcoming the problems often inherent in using silicone hydrophobing agents. Use of the more preferred ranges, e.g., from .05 to .09 wt. % of the fluorine-containing polymer, offers excellent water repellency while using only a small amount of the additive, thus making the use economical as well.
  • the formaldehyde-free curable aqueous binder composition of the present invention also contain a catalyst.
  • the catalyst is a phosphorous-containing accelerator which may be a compound with a molecular weight less than about 1000 such as, for example, an alkali metal polyphosphate, an alkali metal dihydrogen phosphate, a polyphosphoric acid, and an alkyl phosphinic acid or it may be an oligomer or polymer bearing phosphorous-containing groups such as, for example, addition polymers of acrylic and/or maleic acids formed in the presence of sodium hypophosphite, addition polymers prepared from ethylenically unsaturated monomers in the presence of phosphorous salt chain transfer agents or terminators, and addition polymers containing acid-functional monomer residues such as, for example, copolymerized phosphoethyl methacrylate, and like phosphonic acid esters, and copolymerized vinyl sulfonic acid monomers, and their salts.
  • the phosphorous- containing accelerator may be used at a level of from about 1 % to about 40%, by weight based on the combined weight of the polyacid and the polyol. Preferred is a level of phosphorous-containing accelerator of from about 2.5% to about 10%, by weight based on the combined weight of the polyacid and the polyol.
  • the formaldehyde-free curable aqueous binder composition may contain, in addition, conventional treatment components such as, for example, emulsifiers, pigments, filler, anti-migration aids, curing agents, coalescents, wetting agents, biocides, plasticizers, organosilanes, anti-foaming agents, colorants, waxes, and anti-oxidants.
  • conventional treatment components such as, for example, emulsifiers, pigments, filler, anti-migration aids, curing agents, coalescents, wetting agents, biocides, plasticizers, organosilanes, anti-foaming agents, colorants, waxes, and anti-oxidants.
  • the formaldehyde-free curable aqueous binder composition may be prepared by admixing the polyacid of the present invention, the polyol, and the phosphorous- containing accelerator using conventional mixing techniques.
  • a carboxyl- or anhydride-containing addition polymer and a polyol may be present in the same addition polymer, which addition polymer would contain both carboxyl, anhydride, or salts thereof functionality and hydroxy! functionality.
  • the salts of the carboxy-group are salts of functional alkanolamines with at least two hydroxyl groups such as, for example, diethanolamine, triethanolamine, dipropanolamine, and di- isopropanolamine.
  • the polyol and the phosphorous- containing accelerator may be present in the same addition polymer, which addition polymer may be mixed with the modified polyacid of the present invention.
  • the carboxyl- or anhydride-containing addition polymer, the polyol, and the phosphorous-containing accelerator may be present in the same addition polymer.
  • the carboxyl groups of the polyacid may be neutralized to an extent of less than about 35% with a fixed base before, during, or after the mixing to provide the aqueous composition. Neutralization may be partially effected during the formation of the polyacid.
  • the composition of the polyacid, the poiyol and the fluorinated polymer has been prepared, in a preferred embodiment, other additives, can then be mixed in with the composition to form the final composition to be sprayed on the fiberglass.
  • the fibers As molten streams of glass are drawn into fibers of random lengths and blown into a forming chamber where they are randomly deposited as a mat onto a traveling conveyor, the fibers, while in transit in the forming chamber, are sprayed with the aqueous binder composition of the present invention, which includes the modified polyacid. More particularly, in the preparation of fiberglass insulation products, the products can be prepared using conventional techniques.
  • a porous mat of fibrous glass can be produced by fiberizing molten glass and immediately forming a fibrous glass mat on a moving conveyor.
  • the expanded mat is then conveyed to and through a curing oven wherein heated air is passed through the mat to cure the resin.
  • the mat is slightly compressed to give the finished product a predetermined thickness and surface finish.
  • the curing oven is operated at a temperature from about 150DC to about 325DC.
  • the temperature ranges from about 180D to about 225DC.
  • the mat resides within the oven for a period of time from about /4 minute to about 3 minutes.
  • the time ranges from about 3 A minute to about VA minutes.
  • the fibrous glass having a cured, rigid binder matrix emerges from the oven in the form of a bat which may be compressed for packaging and shipping and which will thereafter substantially recover its vertical dimension when unconstrained.
  • the formaldehyde-free curable aqueous composition may also be applied to an already formed nonwoven by conventional techniques such as, for example, air or airless spraying, padding, saturating, roll coating, curtain coating, beater deposition, coagulation, or the like.
  • the waterborne formaldehyde-free composition of the present invention after it is applied to a nonwoven, is heated to effect drying and curing.
  • the duration and temperature of heating will affect the rate of drying, processability and handleability, and property development of the treated substrate.
  • Heat treatment at about 120DC, to about 400DC, for a period of time between about 3 seconds to about 15 minutes may be carried out; treatment at about 150DC, to about 250DC, is preferred.
  • the drying and curing functions may be effected in two or more distinct steps, if desired.
  • the composition may be first heated at a temperature and for a time sufficient to substantially dry but not to substantially cure the composition and then heated for a second time at a higher temperature and/or for a longer period of time to effect curing.
  • B-staging may be used to provide binder-treated nonwoven, for example, in roll form, which may at a later stage be cured, with or without forming or molding into a particular configuration, concurrent with the curing process.
  • the heat-resistant nonwovens may be used for applications such as, for example, insulation batts or rolls, as reinforcing mat for roofing or flooring applications, as roving, as microglass-based substrate for printed circuit boards or battery separators, as filter stock, as tape stock, as tape board for office petitions, in duct liners or duct board, and as reinforcement scrim in cementitious and non-cementitious coatings for masonry. Most preferably, the products are useful as thermal or sound insulation.
  • the nonwovens can also be used as filtration media for air and liquids.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Nonwoven Fabrics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)

Abstract

La présente invention a trait à un liant de fibres de verre comportant un polymère d'acide polycarboxylique, un polyol et un polymère fluoré. De préférence, le liant comporte également un catalyseur qui est un sel de métal alcalin d'un acide organique phosphoré. Le liant obtenu présente des difficultés minimales de traitement et un produit en fibres de verre présentant une absorption d'eau minimale.
EP05809963A 2004-10-07 2005-10-04 Liant de fibres de verre hydrofuge comportant un polymere fluore Withdrawn EP1805233A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/960,617 US20060078719A1 (en) 2004-10-07 2004-10-07 Water repellant fiberglass binder comprising a fluorinated polymer
PCT/US2005/035694 WO2006041848A2 (fr) 2004-10-07 2005-10-04 Liant de fibres de verre hydrofuge comportant un polymere fluore

Publications (2)

Publication Number Publication Date
EP1805233A2 true EP1805233A2 (fr) 2007-07-11
EP1805233A4 EP1805233A4 (fr) 2008-01-16

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP05809963A Withdrawn EP1805233A4 (fr) 2004-10-07 2005-10-04 Liant de fibres de verre hydrofuge comportant un polymere fluore

Country Status (7)

Country Link
US (1) US20060078719A1 (fr)
EP (1) EP1805233A4 (fr)
JP (1) JP2008515761A (fr)
KR (1) KR20070088596A (fr)
CN (1) CN101039968A (fr)
CA (1) CA2582889A1 (fr)
WO (1) WO2006041848A2 (fr)

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DE102008062765A1 (de) 2008-12-18 2010-07-01 Vb Autobatterie Gmbh & Co. Kgaa Textiles flächiges Material für eine Batterieelektrode
KR101827528B1 (ko) 2009-02-26 2018-02-09 존슨 컨트롤스 테크놀러지 컴퍼니 배터리 전극 및 배터리 전극을 제조하는 방법
JP5421730B2 (ja) * 2009-10-28 2014-02-19 日本無機株式会社 ガラス繊維フィルタの製造方法
US8114197B2 (en) * 2009-12-22 2012-02-14 Hollingsworth & Vose Company Filter media and articles including dendrimers and/or other components
CN101880965A (zh) * 2010-06-30 2010-11-10 李世安 玻纤增强改性胶的生产工艺
JP6418847B2 (ja) * 2014-08-25 2018-11-07 株式会社日本触媒 ノニオン性多価アルコール含有結合剤
CN105887487B (zh) * 2016-05-17 2018-06-08 江西国桥实业有限公司 拒水拒油改性丙烯酸酯类胶粘剂的制备方法
WO2018017262A1 (fr) 2016-07-20 2018-01-25 Super Insulation, LLC Matériaux d'isolation thermique hydrophobes en fibre de verre
JP7096457B2 (ja) * 2016-09-06 2022-07-06 オウェンス コーニング インテレクチュアル キャピタル リミテッド ライアビリティ カンパニー パイプライナ及び引抜成形用途のための耐腐食性不織布
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Also Published As

Publication number Publication date
WO2006041848A2 (fr) 2006-04-20
WO2006041848A3 (fr) 2006-12-07
KR20070088596A (ko) 2007-08-29
CA2582889A1 (fr) 2006-04-20
CN101039968A (zh) 2007-09-19
US20060078719A1 (en) 2006-04-13
EP1805233A4 (fr) 2008-01-16
JP2008515761A (ja) 2008-05-15

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