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WO2001034689A1 - Systeme de revetement du sol a faible odeur - Google Patents

Systeme de revetement du sol a faible odeur Download PDF

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Publication number
WO2001034689A1
WO2001034689A1 PCT/US2000/030339 US0030339W WO0134689A1 WO 2001034689 A1 WO2001034689 A1 WO 2001034689A1 US 0030339 W US0030339 W US 0030339W WO 0134689 A1 WO0134689 A1 WO 0134689A1
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WO
WIPO (PCT)
Prior art keywords
latex
dispersed polymeric
aqueous dispersed
aqueous
styrene
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.)
Ceased
Application number
PCT/US2000/030339
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English (en)
Inventor
Rick L. Tabor
Si-Ho Lee
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Dow Chemical Co
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Dow Chemical Co
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Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to AU14600/01A priority Critical patent/AU1460001A/en
Publication of WO2001034689A1 publication Critical patent/WO2001034689A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds

Definitions

  • This invention relates to floor coverings. More particularly, it relates to aqueous dispersed polymeric compositions containing a zeolite as an odor control agent and a method for preparing a low odor floor covering system therefrom.
  • tufted ca ⁇ ets minimally consist of tufted fibers through a primary backing and a precoat. Tufted ca ⁇ ets may also have additional layers such as a laminate layer, a secondary layer, and a foam layer. Moreover, the tufted ca ⁇ et may have more than one secondary layer.
  • Precoat, laminate, and foam layers may be prepared from a butadiene-acrylonitrile latex, an ethylene-vinyl acetate latex, a styrene-butadiene-butyl acrylate latex, a polychloroprene latex, a polyethylene copolymer latex, an ethylene-styrene latex, a styrene- butadiene-vinylidene chloride latex, a styrene-alkyl acrylate latex, a vinyl latex, or an acrylic latex.
  • they are usually prepared from a polyurethane material or a styrene-butadiene latex.
  • A-side formulation an isocyanate formulation
  • B-side formulation a polyol formulation
  • A+B chemistry Preparing a polyurethane layer by A+B chemistry can result in unpredictable loss of production and inefficiency due to problems that can occur in carrying out the reaction at the manufacturing site, such as premature gellation.
  • the polyurethane layer may be applied as an aqueous polyurethane (PU) dispersion.
  • Aqueous PU dispersions can be prepared by polymerizing the polyurethane reactants in an organic solvent followed by dispersion of the resulting solution in water, and optionally followed by removal of organic solvent. See, for example, U.S. Patent Nos. 3,437,624; 4,092,286; 4,237,264; 4,742,095; 4,857,565; 4,879,322; 5,037,864; and 5,221,710.
  • an aqueous polyurethane dispersion may be prepared by first forming a prepolymer, next dispersing the prepolymer in water, and finally conducting a chain extension in the water as disclosed in WO 98/41552, published September 24, 1998.
  • the aqueous polyurethane dispersion will preferably have water as a continuous phase.
  • U.S. Patent No. 4,296,159 to Jenkines et al. discloses preparing a tufted or woven article having a unitary backing prepared by applying a polyurethane forming composition to the underside of the tufted or woven article.
  • the polyurethane layer may be applied as a blown formulation.
  • the blown formulation is generally prepared by mixing the A-side components with the B-side components in the presence of a gas, which is either mechanically introduced or chemically produced, to form bubbles that yield a cell-like structure in the cured polyurethane.
  • Mechanical whipping of gas into a polyurethane formulation is also termed "frothing.” While the odor emission problem is occasionally noticeable with ca ⁇ ets prepared with aqueous polyurethane dispersions, odor emission problems may also arise with ca ⁇ ets prepared with other latexes. Accordingly, it is desirable to control these odor emissions in all such ca ⁇ ets.
  • an aqueous dispersed polymeric composition for preparing a low odor floor covering system comprises an aqueous dispersed polymeric material and a zeolite.
  • the aqueous dispersed polymeric material is an aqueous polyurethane dispersion composition.
  • a method for preparing a low odor floor covering system using the aqueous dispersed polymeric composition is provided.
  • the aqueous dispersed polymeric composition for preparing a low odor floor covering system comprises an aqueous dispersed polymeric material and a zeolite as an odor control agent.
  • the aqueous dispersed polymeric material is selected from the group consisting of an aqueous polyurethane dispersion composition, a styrene-butadiene latex, a butadiene-acrylonitrile latex, an ethylene-vinyl acetate latex, a styrene-butadiene-butyl acrylate latex, a polychloroprene latex, a polyethylene copolymer latex, an ethylene-styrene latex, a styrene-butadiene-vinylidene chloride latex, a styrene- alkyl acrylate latex, a vinyl latex, an acrylic latex, and mixtures thereof.
  • polyurethane can refer to a polyurethane compound, a polyurea compound, or mixtures thereof.
  • a polyurethane compound can be obtained by the reaction of a polyol with a polyisocyanate.
  • a polyurea compound can be obtained by the reaction of an amine with a polyisocyanate.
  • a polyurethane compound or polyurea compound can contain both urea and urethane functionality, depending on what compounds are included in the A and/or B-side formulations. For the pu ⁇ oses of the present application, no further distinction will be made herein between the polyurethane compounds and polyurea compounds.
  • the term "polyurethane” will be used generically to describe a polyurethane compound, a polyurea compound, and mixtures thereof.
  • An aqueous polyurethane dispersion composition useful in the practice of the present invention includes water, and a polymeric compound selected from the group consisting of a polyurethane compound, a mixture of polyurethane-forming compounds, and mixtures thereof.
  • the aqueous polyurethane dispersion will have water as a continuous phase.
  • Polyurethane-forming compounds as used in the present invention are compounds that are capable of forming polyurethane polymers.
  • Polyurethane-forming compounds include, for example, polyurethane prepolymers.
  • Prepolymers useful in the practice of the present invention are prepared by the reaction of active hydrogen compounds with any amount of isocyanate in excess material relative to active hydrogen material. The isocyanate functionality can be present in an amount of from 0.2 weight percent to 40 weight percent.
  • a suitable prepolymer can have a molecular weight in the range of from
  • Prepolymers useful in the practice of the present invention should be substantially liquid under the conditions of dispersion.
  • Active hydrogen compounds can be described as compounds having functional groups that contain at least one hydrogen atom bonded directly to an electronegative atom such as nitrogen, oxygen or sulfur. Suitable active hydrogen compounds can be polyols of molecular weight of less than about 6000. A styrene-butadiene latex useful for practicing the present invention is disclosed in
  • U.S. Patent No. 5,741,393 discloses a method for preparing a butadiene-acrylonitrile latex that is useful for practicing the present invention.
  • U.S. Patent Nos. 3,644,262 and 4,164,489 disclose methods for preparing ethylene-vinyl-acetate latexes that are useful for practicing the present invention.
  • U.S. Patent No. 5,591,806 discloses a method for preparing an ethylene acrylic acid aqueous dispersion that is useful for practicing the present invention.
  • U.S. Patent Nos. 3,890,261 and 5,661,205 disclose methods for preparing polychloroprene latexes useful for practicing the present invention.
  • U.S. Patent No. 5,380,785 discloses a method for preparing a butyl acrylate-acrylonitrile-styrene latex that is useful for practicing the present invention.
  • U.S. Patent Nos. 4,689,256 and 5,300,551 disclose methods for preparing vinyl chloride polymer latexes that are useful in practicing the present invention.
  • U.S. Patent No. 5,591,806 discloses a method for preparing a ethylene acrylic acid copolymer latex that is useful in practicing the present invention.
  • U.S. Patent No. 4,714,728 discloses a method for preparing an aqueous dispersion of acidic ethylene inte ⁇ olymers that are useful in practicing the present invention.
  • U.S. Patent No. 4,228,058 discloses a method for preparing a mixture of vinylidene chloride latex and a styrene-butadiene latex useful in practicing the present invention.
  • Other methods of preparing useful aqueous dispersed polymeric compositions would be readily apparent to a person of ordinary skill in the art in view of this disclosure. Those methods and aqueous dispersed polymeric compositions are within the scope of the invention with regard to preparing useful aqueous dispersed polymeric compositions.
  • An odor control agent of the present invention is a zeolite.
  • a zeolite is a hydrated aluminosilicate of the general formula: xAl 2 O 3 »ySiO 2 »zH 2 0, wherein x, y, and z are natural numbers.
  • the zeolite clinoptilolite has the formula (K 2 , Ca 2 , Na 2 )O»Al 2 O 3 , 10SiO 2 , 8H 2 O.
  • Natural and synthetic zeolites are useful as odor control agents.
  • the natural zeolites include analcite, chabazite, clinoptilolite, heulandite, natrolite, stilbite, and thomosonite.
  • Synthetic zeolites include permutite.
  • the preferred zeolite is clinoptilolite, which is commercially available from National Zeolite Industries, 5210 Manhassett Drive, Arlington, TX 76018.
  • the zeolite is preferably added in a concentration from 0.1 to 30 pph (parts per hundred) based on the polymer concentration. More preferably, it is added in a concentration from 2.5 to 15 pph.
  • the aqueous polyurethane dispersion as described herein can include chain extenders, catalysts, fillers, filler wetting agents, surfactants, blowing agents, frothing agents, dispersants, foam stabilizers, thickeners, fire retardants, defoamers, pigments, antistatic agents, reinforcing fibers, antioxidants, preservatives, acid scavengers, and other materials useful in polyurethane formulations.
  • a chain extender is used herein to build the molecular weight of the polyurethane prepolymer by reaction of the chain extender with the isocyanate functionality in the polyurethane prepolymer, that is, chain extend the polyurethane prepolymer.
  • a suitable chain extender is typically a low equivalent weight active hydrogen containing compound, having about 2 or more active hydrogen groups per molecule.
  • the active hydrogen groups can be hydroxyl, mercaptyl, or amino groups.
  • An amine chain extender can be blocked, encapsulated, or otherwise rendered less reactive. Other materials, particularly water, can function to extend chain length and so are chain extenders for pu ⁇ oses of the present invention.
  • Polyamines are preferred chain extenders. It is particularly preferred that the chain extender be selected from the group consisting of amine terminated polyethers such as, for example, TEXREVI TR401TM from Huntsman Chemical
  • the chain extender is often used as a solution of chain extender in water.
  • chain extender can be advantageously used.
  • the chain extender is employed at a level sufficient to react with from zero (0) to 100 percent of the isocyanate functionality present in the prepolymer, based on one equivalent of isocyanate reacting with one equivalent of chain extender. It can be desirable, under certain conditions, to allow water to act as a chain extender and react with some or all of the isocyanate functionality present.
  • a catalyst can be used to promote the reaction between a chain extender and an isocyanate. Suitable catalysts include tertiary amines, organometallic compounds, similar compounds, and mixtures thereof.
  • suitable catalysts include di-n-butyl tin bis(mercaptoacetic acid isooctyl ester), dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin sulfide, stannous octoate, lead octoate, ferric acetylacetonate, bismuth carboxylates, triethylenediamine, N-methyl mo ⁇ holine, similar compounds, and mixtures thereof.
  • An amount of catalyst is advantageously employed such that a relatively rapid cure to a tack- free state can be obtained.
  • an organometallic catalyst such a cure can be obtained by using from 0.01 to 0.5 parts per 100 parts of the polyurethane-forming composition, by weight.
  • a tertiary amine catalyst is employed, the catalyst preferably provides a suitable cure using from 0.01 to 3 parts of tertiary amine catalyst per 100 parts of the polyurethane-forming composition, by weight. Both an amine type catalyst and an organometallic catalyst can be employed in combination.
  • the aqueous polyurethane dispersion of the present invention can include conventional fillers such as milled glass, calcium carbonate, aluminum trihydrate, talc, bentonite, antimony trioxide, kaolin, fly ash, or other known fillers.
  • a suitable filler loading in a polyurethane dispersion can be from 100 to 1000 parts of filler per 100 parts of the polyurethane compound.
  • the filler material can be loaded in an amount of at least about 200 pph, more preferably at least about 300 pph, most preferably at least about 400 pph.
  • the aqueous polyurethane dispersion of the present invention can include a filler wetting agent.
  • a filler wetting agent generally renders the filler material compatible with a polyurethane-forming composition.
  • Useful wetting agents include phosphate salts such as sodium hexametaphosphate.
  • a filler wetting agent can be included in a polyurethane- forming composition of the present invention at a concentration of at least about 0.1 parts per 100 parts of filler, by weight.
  • Useful surfactants to make an aqueous polyurethane dispersion include cationic and anionic surfactants.
  • anionic surfactants include sulfonates, carboxylates, and phosphates.
  • cationic surfactants include quaternary amines.
  • Surfactants can be either external or internal. External surfactants are surfactants are not chemically reacted into the polymer during dispersion preparation. Internal surfactants are chemically reacted into the polymer during dispersion preparation.
  • a surfactant can be included in an amount ranging from 0.01 to 20 parts per 100 parts by weight of polyurethane component.
  • blowing agents examples include gases such as air, carbon dioxide, nitrogen, argon, and helium; liquids such as water, low molecular weight hydrocarbons, and volatile halogenated alkanes; and azo-blowing agents such as azobis(formamide).
  • Volatile halogenated alkanes include the various chlorofluoromethanes and chlorofluoroethanes.
  • a frothing agent can differ from a blowing agent in that frothing agents are typically introduced by mechanical whipping into the polyurethane formulation.
  • An aqueous polyurethane dispersion of the present invention can be stored for later application to the back of a ca ⁇ et. Storage for this pu ⁇ ose requires that the dispersion be storage-stable.
  • the polyurethane dispersion can be applied in a continuous manner to the back of a ca ⁇ et primary backing. That is, the dispersion can be applied to the back of a ca ⁇ et as the dispersion is obtained.
  • Polyurethane dispersions applied to a ca ⁇ et in a continuous manner are not required to be storage-stable, and can have higher solids content and/or larger mean particle size than typical storage-stable polyurethane dispersion formulations.
  • a suitable storage-stable polyurethane dispersion as defined herein is any polyurethane dispersion having a mean particle size of less than about 5 micrometers; a more preferable mean particle size is less than about 1 micrometer.
  • a polyurethane dispersion that is not storage-stable can have a mean particle size of greater than 5 micrometers.
  • a suitable dispersion can be prepared by mixing a polyurethane prepolymer with water and dispersing the prepolymer in the water using a commercial blender.
  • a suitable dispersion can be prepared by feeding a prepolymer into a static mixing device along with water, and dispersing the water and prepolymer in the static mixer.
  • a frothed polyurethane backing it is often preferable to premix all of the components except the polyisocyanate (and the blowing agent when a gas is used) to form a "B" component.
  • the polyisocyanate and the B component are admixed and then the blowing agent gas is blended in using, for example, an OAKES FROTHER* (*OAKES FROTHER is a trade designation of the E.T. Oakes Co ⁇ oration).
  • OAKES FROTHER* is a trade designation of the E.T. Oakes Co ⁇ oration.
  • the composition is preferably applied to a textile or other substrate prior to any significant level of curing using equipment such as a doctor knife, air knife, or extruder to apply and gauge the layer.
  • the composition may be applied by (1) forming it into a layer on a moving belt or other suitable apparatus, (2) dehydrating or partially curing, and (3) finally, marrying it to the ca ⁇ et primary backing. It may be married to the ca ⁇ et primary backing with equipment such as a double belt laminator (also known as double band) or a moving belt with an applied foam cushion.
  • the polyurethane is then allowed to cure by applying heat by means of an infrared oven, open flame forced draft convection impingement oven, heated plates or the like.
  • an aqueous polyurethane dispersion is applied as a layer of preferably uniform thickness onto one surface of a ca ⁇ et primary backing.
  • Aqueous polyurethane dispersions of the present invention can be applied as a precoat, a laminate layer, or a foam layer.
  • Polyurethane precoats, laminate layers, and foam layers can be prepared by methods known in the art. Precoats, laminate layers and foam layers prepared from latexes are described in P. L. Fitzgerald, "Integral Latex Foam Ca ⁇ et Cushioning", J. Coat. Fab. 1977, Vol. 7 (pp.107 - 120), and in R. P.
  • the polyurethane-forming composition can be applied to one surface of a ca ⁇ et primary backing before it cures to a tack-free state.
  • a polyurethane dispersion containing no unreacted isocyanate functionality can be applied, thereby removing the need to cure the polymer.
  • the polyurethane-forming composition is applied to the surface attached to a primary backing.
  • the amount of polyurethane-forming composition used can vary widely, from 5 to 500 ounces per square yard (0.17 to 16.95 kg/sq. meter), depending on the characteristics of the textile.
  • Example Nos. 1 and 2 were prepared using a standard polyurethane ca ⁇ et backing formulation. However, Example No. 2 also contained 10 pph of the zeolite clinoptilolite. Each of the samples was divided into five test specimens. The finished ca ⁇ ets were analyzed according to industry conditions. The results are reported in Table 1. The data indicates that the zeolite of the present invention facilitates odor control. Moreover, the data indicates that the zeolite did not adversely affect ca ⁇ et performance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition polymère dispersée aqueuse destinée à préparer un système de revêtement du sol à faible odeur. La composition polymère dispersée aqueuse renferme une matière polymère dispersée aqueuse et une zéolite. L'invention concerne également un procédé de préparation d'un système de revêtement du sol à faible odeur utilisant la composition polymère dispersée aqueuse.
PCT/US2000/030339 1999-11-10 2000-11-03 Systeme de revetement du sol a faible odeur Ceased WO2001034689A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU14600/01A AU1460001A (en) 1999-11-10 2000-11-03 Low odor floor covering system

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US43739699A 1999-11-10 1999-11-10
US09/437,396 1999-11-10

Publications (1)

Publication Number Publication Date
WO2001034689A1 true WO2001034689A1 (fr) 2001-05-17

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PCT/US2000/030339 Ceased WO2001034689A1 (fr) 1999-11-10 2000-11-03 Systeme de revetement du sol a faible odeur

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005041106A3 (fr) * 2003-10-08 2005-10-27 Milliken & Co Tissu comportant une couche d'absorption d'odeurs
CN1730542B (zh) * 2005-07-29 2010-05-05 上海普利特复合材料有限公司 低气味丙烯腈-丁二烯-苯乙烯三元共聚树脂材料及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4040369A1 (de) * 1989-12-18 1991-06-20 Enimont Augusta Ind Stabile waessrige suspensionen anorganischer, in wasser unloeslicher materialien auf der basis von siliciumdioxid
US5423999A (en) * 1992-07-01 1995-06-13 Coatex S.A. Stable aqueous suspensions of zeolites, methods of producing same, and use of the suspensions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4040369A1 (de) * 1989-12-18 1991-06-20 Enimont Augusta Ind Stabile waessrige suspensionen anorganischer, in wasser unloeslicher materialien auf der basis von siliciumdioxid
US5423999A (en) * 1992-07-01 1995-06-13 Coatex S.A. Stable aqueous suspensions of zeolites, methods of producing same, and use of the suspensions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199328, Derwent World Patents Index; Class A17, AN 1993-219932, XP002162164 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005041106A3 (fr) * 2003-10-08 2005-10-27 Milliken & Co Tissu comportant une couche d'absorption d'odeurs
CN1730542B (zh) * 2005-07-29 2010-05-05 上海普利特复合材料有限公司 低气味丙烯腈-丁二烯-苯乙烯三元共聚树脂材料及其制备方法

Also Published As

Publication number Publication date
AU1460001A (en) 2001-06-06

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