WO2008127934A1 - Polyurethane carpet backing systems based on natural oil polyols and polymer polyols - Google Patents

Polyurethane carpet backing systems based on natural oil polyols and polymer polyols Download PDF

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WO2008127934A1
WO2008127934A1 PCT/US2008/059719 US2008059719W WO2008127934A1 WO 2008127934 A1 WO2008127934 A1 WO 2008127934A1 US 2008059719 W US2008059719 W US 2008059719W WO 2008127934 A1 WO2008127934 A1 WO 2008127934A1
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polyol
polyurethane
weight
carpet
textile
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PCT/US2008/059719
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French (fr)
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Randall C. Jenkines
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Dow Global Technologies, Inc.
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Priority to US60/923,280 priority
Application filed by Dow Global Technologies, Inc. filed Critical Dow Global Technologies, Inc.
Publication of WO2008127934A1 publication Critical patent/WO2008127934A1/en

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/36Hydroxylated esters of higher fatty acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4072Mixtures of compounds of group C08G18/63 with other macromolecular compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • C08G18/4837Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/4841Polyethers containing oxyethylene units and other oxyalkylene units containing oxyethylene end groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/63Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/632Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6637Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N7/00Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material, e.g. fibrous top layer with resin backing, plastic naps or dots on fabrics
    • D06N7/0063Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf
    • D06N7/0071Floor covering on textile basis comprising a fibrous top layer being coated at the back with at least one polymer layer, e.g. carpets, rugs, synthetic turf characterised by their backing, e.g. pre-coat, back coating, secondary backing, cushion backing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00Foams
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00Macromolecular materials of the coating layers
    • D06N2203/04Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/045Vinyl (co)polymers
    • D06N2203/047Arromatic vinyl (co)polymers, e.g. styrene
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2203/00Macromolecular materials of the coating layers
    • D06N2203/06Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06N2203/068Polyurethanes
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00Condition, form or state of the materials
    • D06N2205/02Dispersion
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06NWALL, FLOOR OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2205/00Condition, form or state of the materials
    • D06N2205/04Foam
    • D06N2205/045Froth

Abstract

Polyurethane carpet backings are made from a polyurethane- forming composition that contains a mixture of at least one natural oil polyol and at least one polymer polyol. The resulting polyurethane carpet backings have good physical properties, in particular tensile and elongation.

Description

POLYURETHANE CARPET BACKING SYSTEMS BASED ON NATURAL OIL

POLYOLS AND POLYMER POLYOLS

The application claims benefit of United States Provisional Application No. 60/923,280, filed 13 April 2007. The invention relates to methods for manufacturing polyurethane carpet backing products.

Many carpet products have an attached polyurethane backing. These have been commercially available for many years. Methods for making those carpets are described, for example, in U. S. Patent Nos. 3,849,156, 4,296,159, 4,336,089, 4,405,393, 4,483,894, 4,611,044, 4,696,849, 4,853,054, 4,853,280, 5,104,693, 5,646,195, 6,140,381, 6,372,810 and 6,790,872. The polyurethane carpet backings come in several different types, all of which perform specific functions. The various types of polyurethane carpet backings include precoats, unitary coatings, laminate (tie) coatings, foam coatings and hardback cap coatings. The polyurethane backings are produced in the reaction of a polyisocyanate compound with a mixture of polyols. The polyol mixture in most cases includes at least one high (>250) equivalent weight polyol. The high equivalent weight polyol of choice has been a polyether that is made by polymerizing propylene oxide or a mixture of propylene oxide with a small quantity of ethylene oxide. In rare instances, polyesters have been used as the high equivalent weight polyol.

The polyether and polyester polyols are derived from fossil feedstocks. Because of concerns about the long-term availability of these feedstocks, and because of price volatility in fossil feedstocks due to geopolitical matters, there has developed an interest in developing new polyol materials that are based on annually renewable resources. Various types of polyols have been developed, which are prepared using natural (vegetable- or animal-origin) oils as a raw material. These include, for example, hydroxymethyl group -containing polyester polyols of the type described in WO 04/096882 and WO 04/096883, fatty acid esters that contain pendant hydroxyl- functional ester groups as described in WO 2007/019051, amide-containing polyols as described in WO 2007/019063, and "blown" vegetable oil-based polyols as described in US Published Patent Applications US Patent No. 6,962,636 and US Patent No. 7,063,877. Vegetable oils such as castor oil that naturally contain multiple hydroxyl groups have also been proposed. In WO 2006/047432, US Patent No. 6,962,636 and US Patent No. 7,063,877, various types of these vegetable oil-based polyols have been proposed for use in making polyurethane carpet backings. The substitution of the vegetable oil-based polyol for a portion of the conventional polyether polyols produces polyurethane carpet backings which tend to have significantly poorer elongation and tensile strength. This leads to a variety of performance problems. These can include, depending on the particular product type, poor foam durability, increased tendency for the carpet to delaminate, and poor adhesion of facing fibers to the underlying backing materials.

It would therefore be desirable to provide a polyurethane carpet backing, prepared using a significant proportion of natural oil-based polyols, which exhibits tensile and elongation properties more comparable to those exhibited by conventional polyurethane carpet backings.

This invention is a textile having an attached polyurethane backing, wherein the polyurethane backing comprises a reaction product of at least one polyisocyanate and a polyol mixture, the polyol mixture containing (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one dispersion of polymer particles in a polyol (hereinafter referred to as a "polymer polyol"), the proportions of (1) and (2) being such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol.

This invention is also a textile having an attached polyurethane cushion, wherein the polyurethane cushion comprises a cellular reaction product of at least one polyisocyanate and a polyol mixture, the polyol mixture containing (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one polymer polyol, the proportions of (1) and (2) being such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol.

This invention is a method comprising (I) applying a frothed polyurethane- forming composition to the underside of a textile and (II) curing the polyurethane- forming composition to form a cellular polyurethane coating that is adhered to the textile, wherein the polyurethane-forming composition contains at least one polyisocyanate and a polyol mixture, the polyol mixture containing (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one polymer polyol, the proportions of (1) and (2) being such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol.

This invention is also a carpet comprising (I) a primary backing, (II) a yarn tufted or woven through the primary backing thereby creating a yarn bundle on the underside of the resulting carpet, and (III) a polyurethane applied to the underside of the carpet thereby adhering the yarn bundle to the primary backing, wherein the polyurethane is a reaction product of at least one polyisocyanate and a polyol mixture, the polyol mixture containing (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one polymer polyol, the proportions of (1) and (2) being such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol.

This invention is also a method comprising (I) applying a polyurethane -forming composition to the underside of a carpet having a primary backing and a yarn tufted or woven through the primary backing to form a yarn bundle on the underside of the carpet and (II) curing the polyurethane-forming composition to form a polyurethane coating that adheres the yarn bundle to the primary backing, wherein the polyurethane-forming composition contains at least one polyisocyanate and a polyol mixture, the polyol mixture containing (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one polymer polyol, the proportions of (1) and (2) being such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol.

This invention is also a carpet comprising a primary backing and a secondary backing adhered directly or indirectly to the primary backing with a polyurethane laminate layer, wherein the polyurethane laminate layer is the reaction product of a polyisocyanate component and a polyol mixture, the polyol mixture containing (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one polymer polyol, the proportions of (1) and (2) being such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol. This invention is also a method for adhering a secondary backing to a carpet, comprising applying a polyurethane-forming composition to the secondary backing or to the carpet, joining the carpet to the secondary backing such that the polyurethane- forming composition is intermediate to the secondary backing and the carpet, and curing the polyurethane-forming composition, wherein the polyurethane-forming composition includes at least one polyisocyanate and a polyol mixture, the polyol mixture containing (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one polymer polyol, the proportions of (1) and (2) being such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol.

It has surprisingly been found that the tensile and elongation properties of the polyurethane tend to be improved significantly when a dispersion of polymer particles is present in the polyurethane-forming composition that is used to make the attached backing. The polyurethane backing is made from a polyurethane-forming composition that includes at least one polyisocyanate and a polyol mixture. The polyol mixture contains (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one polymer polyol. The proportions of these (and other polyol components, if any) are such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol.

A natural-oil based polyol, or NOP, is a material containing hydroxyl groups, wherein the hydroxyl groups are bonded directly or indirectly to one or more fatty acid residues. The fatty acid residues correspond to one or more constituent fatty acids of at least one vegetable oil or animal fat. The NOP should have an equivalent weight per hydroxyl group of at least 250, preferably at least 300, more preferably at least 400 and even more preferably at least 600. The NOP equivalent weight can be up to 15,000. It is preferably up to 6000, more preferably up to 2000 and especially up to about 1200. The NOP should have an average hydroxyl functionality of from 1.8 to 4, preferably from 2 to 3.3, and more preferably from 2 to 3, hydroxyl groups per molecule.

The NOP can be of several types. The NOP may be a naturally-occurring vegetable oil or animal fat that contains at least two hydroxyl groups per molecule. The most prevalent NOP of this type is castor oil. The NOP may be a hydroxymethyl- containing polyester polyol of the type described in detail below and in WO 04/096882 and WO 04/096883. The NOP may be a Hydroxy Ester-Substituted Fatty Acid Ester (HESFAE), of the type described below and in more detail in WO 2007/019051. The NOP may be an amide-containing polyol as described in WO 2007/019063. The NOP may be a "blown" vegetable oil of the type described in US Patent Nos. 6,962,636 and 7,063,877. Hydroxymethyl-containing polyester polyols are conveniently prepared by reacting a hydroxymethyl-group containing fatty acid having from 12 to 26 carbon atoms, or an ester of such a hydroxymethylated fatty acid, with a polyol, hydroxylamine or polyamine initiator compound having an average of at least 2.0 hydroxyl, primary amine and/or secondary amine groups/molecule. Proportions of starting materials and reaction conditions are selected such that the resulting hydroxymethyl-containing polyester polyol contains an average of at least 1.3 repeating units derived from the hydroxmethyl-group containing fatty acid or ester thereof for each hydroxyl, primary amine and secondary amine group in the initiator compound, and the hydroxymethyl- containing polyester polyol has an equivalent weight of at least 250, preferably at least 400, up to about 15,000.

These hydroxymethyl-containing polyester polyols typically are a mixture of compounds having the following average structure:

[H-X](z.p)-R-[X-Z]p (I)

wherein R is the residue of an initiator compound having z hydroxyl and/or primary or secondary amine groups, where z is at least two; each X is independently — O — , — NH — or — NR' — in which R' is an inertly substituted alkyl, aryl, cycloalkyl, or aralkyl group, p is a number from 1 to z representing the average number of [X — Z] groups per hydroxymethyl-containing polyester polyol molecule, Z is a linear or branched chain containing one or more A groups, provided that the average number of A groups per molecule is > 1.3 times z, and each A is independently selected from the group consisting of Al, A2, A3, A4 and A5, provided that at least some A groups are Al, A2 or A3. Al is:

O — C I— (CH2)m— CH-CH2-OB (II)

Figure imgf000006_0001
wherein B is H or a covalent bond to a carbonyl carbon atom of another A group; m is number greater than 3, n is greater than or equal to zero and m + n is from 8 to 22, especially from 11 to 19. A2 is: O CH2OB

— C Il— (CH2)v— C IH- (CH2)r— CH- CH2-OB (III)

Figure imgf000007_0001

wherein B is as before, v is a number greater than 3, r and s are each numbers greater than or equal to zero with v + r + s being from 6 to 20, especially 10 to 18. A3 is:

O CH2OB

— C Il— (CH2)v— C IH- (CH2)r— (IV)

Figure imgf000007_0002
wherein B, v, each r and s are as defined before, t is a number greater than or equal to zero, and the sum of v, r, s and t is from 5 to 18, especially from 10 to 18. A4 is

O

Figure imgf000007_0003
where w is from 10 to 24, and A5 is

O

— C Il— R' (VI) where R' is a linear or branched alkyl group that is substituted with at least one cyclic ether group and optionally one or more hydroxyl groups or other ether groups. The cyclic ether group may be saturated or unsaturated and may contain other inert substitution. The hydroxyl groups may be on the alkyl chain or on the cyclic ether group, or both. The alkyl group may include a second terminal -C(O)- or -C(O)O- group through which it may bond to another initiator molecule. A5 groups in general are lactols, lactones, saturated or unsaturated cyclic ethers or dimers that are formed as impurities during the manufacture of the hydroxylmethyl- group containing fatty acid or ester. A5 groups may contain from 12 to 50 carbon atoms.

A is preferably Al, a mixture of Al and A2, a mixture of Al and A4, a mixture of Al, A2 and A4, a mixture of Al, A2 and A3, or a mixture of Al, A2, A3 and A4, in each case optionally containing a quantity of A5. Mixtures of Al and A2 preferably contain Al and A2 groups in a mole ratio of 10:90 to 95:5, particularly from 60:40 to 90:10. Mixtures of Al and A4 preferably contain Al and A4 groups in a mole ratio of 99.9:0.1 to 70:30, especially in a ratio of from 99.9:0.1 to 85:15. Mixtures of Al, A2 and A4 preferably contain from about 10 to 95 mole percent Al groups, 5 to 90 percent A2 groups and up to about 30 percent A4 groups. More preferred mixtures of Al, A2 and A4 contain about 25-70 mole-% Al groups, 15-40% A2 groups and up to 30% A4 groups. Mixtures of Al, A2 and A3 preferably contain from about 30-80 mole-% Al, from 10-60% A2 and from 0.1 to 10% A3 groups. Mixtures of Al, A2, A3 and A4 groups preferably contain from 20 to 50 mole percent Al, 1 to about 65 percent A2, from 0.1 to about 10 percent A3 and up to 30 percent A4 groups. Especially preferred polyester polyols of the invention contain a mixture of about 20-50% Al groups, 20-50% A2 groups, 0.5 to 4% A3 groups and 15-30% A4 groups. In all cases, A5 groups advantageously constitute from 0-7%, especially from 0-5%, of all A groups.

Preferred mixtures of A groups conveniently contain an average of about 0.8 to about 1.5 -CH2OH and/or -CH2OB groups/A group, such as from about 0.9 to about 1.3 -CH2OH and/or -CH2OB groups/A group or from about 0.95 to about 1.2 -CH2OH and/or -CH2OB groups/A group. Such proportions of A groups (1) allow the initiator functionality to mainly determine the functionality the polyester polyol and (2) tend to form less densely branched polyester polyols.

"Inertly substituted" groups are groups that do not react with an isocyanate group and which do not otherwise engage in side reactions during the preparation of the hydroxymethyl-group containing polyester polyol. Examples of such inert substituents include aryl, cycloalkyl, silyl, halogen (especially fluorine, chlorine or bromine), nitro, ether, ester, and the like.

The hydroxymethyl-containing polyester polyol generally contains some unreacted initiator compound, and may contain unreacted hydroxymethylated fatty acids (or esters). The hydroxymethyl-containing polyester polyol may be alkoxylated, if desired, to introduce polyether chains onto one or more of the hydroxymethyl groups.

Another suitable NOP is a Hydroxy Ester-Substituted Fatty Acid Ester, or HESFAE. The HESFAEs contain at least two different ester groups. One ester group corresponds to the reaction product of the carboxylic acid group of a fatty acid with a compound having two or more hydroxyl groups. The second ester group is pendant from the fatty acid chain, being bonded to the fatty acid chain through the -O- atom of the ester group. The pendant ester group is conveniently formed by epoxidizing the fatty acid (at the site of carbon-carbon unsaturation in the fatty acid chain), followed by reaction with a hydroxy acid or hydroxy acid precursor. The pendant ester group includes at least one free hydroxyl group.

Amide-containing NOPs are described in WO 2007/019063 and contain at least one amide (>N-C(O)-) group. The amide-containing NOP has at least one hydroxyl- containing organic group bonded to the nitrogen atom of the amide group. The compound further has a branched or straight chain C7-23 hydrocarbon group bonded directly to the carbonyl carbon of the amide group. The C7-23 hydrocarbon group is substituted with at least one hydroxymethyl group, N-hydroxyalkyl aminoalkyl group or hydroxyl-containing ester group. These amide compounds are conveniently prepared in several steps using vegetable oils or animal fats, or unsaturated fatty acids obtained from vegetable oils or animal fats, as a starting material. The amide-containing NOP will typically be a mixture of materials having on average from one to eight or more hydroxyl groups per molecule.

The polyol mixture contains, in addition to the NOP, at least one polymer polyol. A "polymer polyol" is, for purposes of this invention, a dispersion of polymer particles in a continuous liquid polyol phase. The dispersed polymer particles typically have longest dimensions of no more than 10 microns and as small as 10 nanometers. The dispersed polymer particles may be, for example, polymers of one or more ethylenically unsaturated monomers, such as, for example, vinyl chloride, methyl methacrylate, α- methylstyrene, p-methylstyrene, methacrylonitrile, vinylidene chloride, styrene, acrylonitrile, hydroxyethyl acrylate, butadiene, isoprene, chloroprene and methacrylonitrile, or a mixture of any two or more thereof. Preferred ethylenically unsaturated monomers are styrene and acrylonitrile. More preferred are mixtures of styrene with another monomer, with styrene constituting 50% or more by weight of the mixture. Especially preferred are mixtures of styrene and acrylonitrile, in weight ratios of 80:20 to 20:80, more preferably 70:30 to 30:70, and especially from 65:35 to 35:65 are preferred. Polymer polyols of this type are conveniently prepared by the in-situ polymerization of the monomer or monomers in the continuous phase polyol ('base polyol'), usually in the presence of a macromer or preformed stabilizer which promote the formation of a stable dispersion. Methods of making polymer polyols of this type are well known and described, for example, in US Patent Nos. 3,304,273, 3,383,351, 3,523,093, 3,652,639, 3,823,201, 3,931,092; 3,953,393; 4,104,236, 4,111,865, 4,119,586, 4,125,505, 4,172,825, 4,463,107; 4,524,157, 4,690,956, 5,324,774 and 5,814,699. Alternatively, the dispersed polymer particles may be polyurea particles, or polyurethane-urea particles. Dispersions of these types are sometimes known as PHD polyols or PIPA polyols. PHD polyols are typically made in the in situ reaction of a polyisocyanate with a diamine and/or hydrazine in a base polyol. PIPA polyols are made in the in situ polymerization of a polyisocyanate with a glycol or an aminoalcohol in a base polyol.

The polymer polyol (of any of the foregoing types) includes at least one base polyol which makes up the continuous phase of the dispersion. The base polyol(s) suitably have equivalent weights and hydroxyl functionalities as described before with respect to the NOP. The base polyol may be of any type (including a NOP), but is preferably one or more polyethers, especially a homopolymer of propylene oxide or a copolymer (random and/or block) of propylene oxide with up to 20% by weight ethylene oxide.

In addition to the NOP and polymer polyol, the polyol mixture may contain one or more additional high equivalent weight polyols (which are not NOPs), one or more chain extenders and one or more crosslinkers. Suitable high equivalent weight polyols include polyether polyols and polyester polyols, with polyether polyols generally being more preferred. Particularly suitable polyether polyols are polymers of propylene oxide, which may contain up to 20% by weight terminal poly(ethylene oxide) blocks, random copolymers of propylene oxide and up to about 15% by weight ethylene oxide, poly(tetramethylene oxide) polymers and poly(butylene oxide) polymers.

For purposes of this invention, a chain extender is a material having two isocyanate-reactive groups/molecule and an equivalent weight per isocyanate-reactive group of from about 30 to 150. A crosslinker, for purposes of this invention, is a compound having three or more isocyanate reactive groups and an equivalent weight per isocyanate-reactive group of 150 or less. The isocyanate-reactive groups may be hydroxyl, primary amine or secondary amine groups. Chain extenders and crosslinkers having hydroxyl groups are preferred because hydroxyl groups react more slowly and thus provide more time to apply and gauge the polyurethane-forming layer. Examples of suitable chain extenders include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-dimethylolcyclohexane, diethyltoluene diamine, 1,4-butane diol, 1,6-hexane diol, 1,3-propane diol, amine- terminated polyethers such as Jeffamine D-400 from Huntsman Chemical Company, amino ethyl piperazine, 2-methyl piperazine, l,5-diamino-3-methyl-pentane, isophorone diamine, ethylene diamine, hexane diamine, hydrazine, piperazine, mixtures thereof and the like. Amine chain extenders can be blocked, encapsulated, or otherwise rendered less reactive in order to reduce the reactivity of the formulation and provide more working time to apply and gauge the foam layer. Chain extenders advantageously constitute up to about 30%, especially up to about 20% of the total weight of the polyol mixture.

The proportions of components in the polyol mixture are selected such that the mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol. The polyol mixture may contain at least 8% or at least 10% by weight of dispersed polymer particles. It may contain as much as 40%, as much as 25% or as much as 15% by weight of dispersed polymer particles. The polymer mixture may contain at least 10% or at least 20% by weight of the NOP, and may contain as much as 80%, as much as 50%, as much as 40%, or as much as 30% by weight of the NOP. The polyol mixture preferably contains no more than 20%, preferably no more than 10% by weight of chain extenders and/or crosslinkers.

The content of dispersed polymer particles in the polyol mixture depends on the amount of polymer polyol that is used, as well as the solids content of the polymer polyol. The polymer polyol may contain from 10% to 60% or more dispersed polymer particles (by weight). For reasons of economics, it is often preferable to produce the polymer polyol at relatively high solids content (such as 40 to 60% by weight dispersed polymer particles) and to dilute it with additional polyol to adjust the solids level to the desired level in the polyol mixture. It is possible to use a polymer polyol having a solids content as low as about 10%. A preferred polyol mixture for use in the invention includes at least one NOP, a polymer polyol, an additional high equivalent weight polyol, and at least one hydroxyl- terminated chain extender. In the preferred polyol mixture, the NOP is most preferably castor oil, a "blown" vegetable oil or a hydroxymethyl-containing polyester polyol. In the preferred polyol mixture, the polymer polyol is preferably a dispersion of styrene or styrene-acrylonitrile polymer particles in a homopolymer of propylene oxide or a copolymer of propylene oxide and up to 20% by weight ethylene oxide. In the preferred polyol mixture, the chain extender is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butane diol or a mixture of any two or more of these. The preferred polyol mixture most preferably contains from 8 to 15% by weight dispersed polymer particles.

The polyurethane-forming composition also includes at least one organic polyisocyanate, which may be an aromatic, cycloaliphatic, or aliphatic isocyanate. Examples of suitable polyisocyanates include m-phenylene diisocyanate, toluene-2,4- diisocyanate, toluene-2,6-diisocyanate, hexamethylene-l,6-diisocyanate, tetramethylene- 1,4-diisocyanate, cyclohexane-l,4-diisocyanate, hexahydrotoluene diisocyanate, naphthylene-l,5-diisocyanate, methoxyphenyl-2,4-diisocyanate, diphenylmethane-4,4'- diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenyl diisocyanate, 3,3'-dimethyl-4-4'-biphenyl diisocyanate, 3,3'-dimethyldiphenyl methane-4,4'- diisocyanate, 4,4',4"-triphenyl methane triisocyanate, a polymethylene polyphenylisocyanate (PMDI), toluene-2,4,6-triisocyanate and 4,4'- dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate. Preferably the polyisocyanate is diphenylmethane-4,4'-diisocyanate, diphenylmethane-2,4'-diisocyanate, PMDI, toluene- 2-4-diisocyanate, toluene-2-6-diisocyanate or mixtures thereof. Diphenylmethane-4,4'- diisocyanate, diphenylmethane-2,4'-diisocyanate and mixtures thereof are generically referred to as MDI, and all can be used. Toluene-2,4-diisocyanate, toluene-2,6- diisocyanate and mixtures thereof are generically referred to as TDI, and all can be used. Polyisocyanate compounds or mixtures thereof having from about 1.8 to about 2.5 isocyanate groups/molecule, on average, are preferred, especially those having an average of about 1.9 to about 2.3 isocyanate-groups/molecule. Prepolymers made by reacting a stoichiometric excess of any of the foregoing polyisocyanates with an isocyanate-reactive compound such as those described below can be used as well. Suitable prepolymers include soft segment prepolymers as described in U. S. Patent No. 5,104,693 and hard segment prepolymers as described in U. S. Patent No. 6,372,810.

When the polyurethane backing is substantially non-cellular, as in a precoat, unitary or laminate layer, it is preferably formulated with careful control of the functionality of the components, as described in U. S. Patent Nos. 4,296,159 and 4,737,455. By selecting components having an actual average functionality of very close to 2.0, a more dimensionally stable product can be obtained. Control over functionality need not be so stringent when a polyurethane foam cushion is prepared.

The polyurethane-forming composition preferably contains one or more catalysts, which promote the reaction of the polyisocyanate with the isocyanate-reactive materials. Suitable catalysts include tertiary amines, organometallic compounds, or mixtures thereof. Specific examples of these include di-n-butyl tin bis(mercaptoacetic acid isooctyl ester), dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, stannous octoate, lead octoate, ferric acetylacetonate, bismuth carboxylates, triethylenediamine, N-methyl morpholine, like compounds and mixtures thereof. An amine-blocked tin (IV) catalyst, such as those described in U. S. Patent No. 5,491,174, can be used. An amount of catalyst is advantageously employed such that a relatively rapid cure to a tack-free state can be obtained, while providing enough open time that the polyurethane composition can be dispensed and spread over the carpet back before curing. If an organometallic catalyst is employed, such a cure can be obtained using from about 0.01 to about 0.5 parts per 100 parts of the polyurethane-forming composition, by weight. If a tertiary amine catalyst is employed, the catalyst preferably provides a suitable cure using from about 0.01 to about 3 parts of tertiary amine catalyst per 100 parts of the polyurethane-forming composition, by weight. An amine type catalyst and an organometallic catalyst can be employed in combination. The catalyst may be a mixture of nickel acetylacetonate, cadmium acetylacetonate or copper acetylacetonate (or two or more thereof), with a sulfur- containing organotin catalyst, in which each tin atom in the catalyst is bonded to one or more sulfur atoms. Dialkyltin mercaptides and dialkyltin mercaptoacetates, in which the alkyl groups contain from 1 to 12 carbon atoms, preferably from 1 to 8 carbon atoms, are examples of the sulfur-containing organotin catalyst. Di-n-butyltin sulfide is a preferred example of the sulfur-containing organotin catalyst.

The polyurethane-forming composition preferably contains a filler, which reduces overall cost and may improve flame resistance, firmness and other physical properties. The filler may be present in an amount from about 5 to about 1000 parts by weight per 100 parts by weight isocyanate-reactive materials. Suitable fillers include talc, mica, montmorillonite, marble, barium sulfate (barytes), milled glass, granite, milled glass, calcium carbonate, aluminum trihydrate, carbon, aramid, silica, silica- alumina, zirconia, talc, bentonite, antimony trioxide, kaolin, coal-based fly ash and boron nitride. The filler is present in the form of finely divided particles. Particle size may range widely from as little as 10 nm to as much as 250 microns. Preferred filler levels are from 130 to 600, especially from 250 to 400, parts by weight of filler per 100 parts by weight of the polyol mixture.

Some fillers may tend to affect the pH of the polyurethane-forming composition, which may in turn adversely affect catalyst performance. It is generally preferred to adjust the pH of the formulated polyol/filler blend to within the range of 7.5 to 11.5. Phosphoric acid can be added to lower pH, as can other mineral and organic acids.

The presence of high levels of fillers can cause the polyurethane-forming composition to become very viscous. For that reason, the composition preferably contains at least one filler wetting agent, which can help to reduce viscosity. Suitable filler wetting agents include ethoxylated phosphate esters, which are generally available in an organic carrier. Examples of such wetting agents include those sold under the trade names Maphos™ 56 (available from BASF) and Code 5027 (Fibro Chem, Inc.). About 0.5 to 1.5 parts by weight of such a filler wetting agent, per 100 parts by weight isocyanate-reactive materials, is usually effective.

If a polyurethane cushion is to be formed, the polyurethane-forming composition will also include at least one surfactant, which serves to stabilize the foam bubbles until the composition has cured. Organosilicone surfactants, such as those described in U. S. Patent No. 4,483,894, are preferred. Typically about 0.5 to about 3 parts of surfactant are used per 100 parts by weight polyol or polyol mixture.

Similarly, the polyurethane-forming composition may include water or a physical blowing agent, in order to provide some supplemental blowing and added expansion, in cases where a cellular polyurethane backing is to be applied. If a blowing agent is used at all, water is preferred and if used is suitably present in an amount of at least 0.10 part by weight per 100 parts by weight of the polyol. Suitable amounts are from 0.10 to about 3.0 parts of water per 100 parts by weight polyol, especially from 0.25 to 2.5 parts by weight of water per 100 parts by weight polyol. It is usually preferred not to include a blowing agent in the polyurethane-forming composition.

Other additives may be used, including fire retardants, pigments, antistatic agents, reinforcing fibers, antioxidants, preservatives, water scavengers, thixotropes, and the like.

General methods for applying a polyurethane composition to a substrate are well- known and described, for example, in U. S. Patent Nos. 3,849,156, 4,296,159, 4,336,089, 4,405,393, 4,483,894, 4,611,044, 4,696,849, 4,853,054, 4,853,280, 5,104,693, 5,646,195, 6,140,381, 6,372,810 and 6,790,872. The general methods described there are applicable to this invention. The main processing steps are the blending of all the components, (including surfactants (if used) and the catalysts), optional frothing, dispensing, and gauging. It is usually convenient to form a partially formulated polyol component beforehand. The component includes the polyol mixture, filler and typically the surfactant (when used). The formulated polyol component is blended with the polyisocyanate immediately prior to dispensing (or frothing, in cases where the composition is frothed). The catalyst can be added into the formulated polyol, added simultaneously with the polyisocyanate, or added during or after a frothing step. It is generally desired to delay adding the catalyst as long as possible in order to maximize the time that is available to complete the remaining process steps. When the catalyst is added after a frothing step, the froth and catalyst are advantageously passed through a static mixing device (such as a Chemineer-Kenics mixer, TAH mixer or other motionless mixing device), in order to more uniformly blend the components. A static or motionless mixer tends not to significantly degrade the froth or the distribution of the frothing gas within the froth.

It is preferred to froth the polyurethane-forming composition prior to dispensing and gauging it, even when a substantially non-cellular backing is applied. Frothing increases the volume of the composition and thus makes it easier to dispense and gauge accurately. In these cases, the composition preferably contains very little or no surfactant that can stabilize the gas bubbles that are formed in the frothing step. The lack of stabilizing surfactant allows the bubbles to collapse and the frothing gas to escape during or after the gauging step, so a non-cellular polyurethane is produced.

If a cellular attached cushion is to be formed, the polyurethane-forming composition must be blown or frothed. Frothing is by far the preferred method, as blown systems tend to be too reactive. It is possible to use a combination of blowing and frothing techniques. The composition is frothed by whipping, air, nitrogen, argon or other gas into it before it is dispensed and applied, using any convenient apparatus such as an Oakes mixer, a Lessco mixer or a Hansa Frothing Unit. Methods of preparing such a mechanically frothed mixture are described in U. S. Patent Nos. 4,853,054, 5,104,693, 5,908,701, 6,040,381, 6,096,401 and 6,555,199, all incorporated herein by reference. The polyurethane-forming composition is generally frothed to a froth density of about 300 to 600, especially from 400 to 500, grams/liter prior to application.

The resulting polyurethane-forming composition, whether frothed or not, is dispensed to form a puddle on one side of the substrate. The puddle is formed into a layer of the desired thickness or coating weight, and the assembly is then heated to complete the cure. A variety of equipment types are suitable for dispensing the polyurethane-forming composition and forming it into a layer. A preferred method of dispensing the composition is through a traversing dispensing nozzle, hose or head, which travels back and forth across the substrate to dispense the composition more or less evenly across the surface of the substrate. The composition is suitably dispensed upstream of a doctor blade, which gauges the composition to a desired thickness and helps to force the composition onto the surface of the substrate. Another suitable apparatus for forming the polyurethane-forming composition into a layer and gauging it is an air knife. The composition is suitably applied at a coating weight of from about 10 to about

70 ounces/square yard (0.33-2.31 kg/m2), and in particular from about 15 to about 30 ounces per square yard (0.49-0.99 kg/m2). The thickness of the applied layer, when applied as a froth, is generally from about 0.05 to about 0.5 inches (0.13-1.3 cm), preferably from about 0.1 to about 0.25 inch (0.26-0.65 cm). If the cells of a froth are not stabilized, the applied layer will usually collapse as or after it passes under the doctor blade or air knife to form a thinner layer. When the composition contains an effective amount of a surfactant, the thickness of the layer after gauging will be close to or the same as the thickness of the layer as applied and gauged.

It is generally preferred to control the temperature of the polyurethane-forming composition to 50°C or less during the mixing, frothing, dispensing and gauging steps. A preferred temperature during these processing steps is up to 45°C and a more preferred temperature is up to 38°C. The processing temperature may be any lower temperature at which the composition is a fluid, but temperatures below 18°C are not preferred due to the increased viscosity of the composition. A preferred temperature is at least 24°C.

The polyurethane-forming composition is cured after the gauging step. Curing is preferably effected by subjecting the applied layer of polyurethane-forming composition to an elevated temperature. The curing temperature is selected to provide a rapid cure without degrading any components of the composition or the substrate. A temperature range of from 80 to 180°C, especially from 120 to 150°C, is suitable. The composition preferably becomes cured in less than 3 minutes, and more preferably less than 2.5 minutes and especially less than 2.0 minutes.

After the polyurethane is cured sufficiently, the product may be cooled to below 40°C, especially below 35°C, before being flexed or bent (such as by rolling or cascading it into an accumulator device). This cooling before flexing or bending is especially preferred in cases where the product is intended to be die-cut or designed to function as independent modules, as in the case of carpet tiles.

A wide variety of materials can function as the substrate, including, for example, polymeric films or sheets, carpet (including pile yarn carpet), textile fabrics, paper sheets, rigid materials such as wood, veneers, metal foils or sheets, or composites, among many others.

A substrate of particular interest is a tufted or woven carpet material. The carpet includes a primary backing that defines multiple openings through which a facing fiber is tufted or woven to produce a carpet face. The primary backing is generally in the form of a woven or nonwoven scrim, and can be made of any convenient material, such as, for example, jute, polypropylene, nylon, a polyester, a polyacrylate, cotton, wool, or other material. The facing fiber also can be of any convenient material, such as wool, cotton, nylon, a polyester, an acrylic fiber, polypropylene, polyethylene, a blend of any two or more of these, or the like. The facing fiber is typically in the form of fiber bundles that are tufted or woven through the primary backing to produce a carpet face and an opposing underside. In one embodiment, a non-cellular polyurethane is applied in accordance with the invention to form a non-cellular backing, such as a precoat, laminate, unitary, tie-coat or hard back cap coating. Alternatively or additionally, a cellular polyurethane cushion can be attached to the carpet in accordance with the invention.

The polyurethane backing thus formed often exhibits a greater tensile strength (at the same elongation), or greater elongation to break (at same tensile strength), than polyurethane backings that are prepared from an otherwise similar polyol mixture that does not contain the dispersed polymer particles. Often, tensile strength and elongation are simultaneously increased. This effect is considered to be quite unexpected, as the use of polymer polyols in other polyurethane systems tends to be related to load-bearing and/or cell opening, rather than improvements in tensile and/or elongation. In coated textile applications, improvements in tensile and elongation properties often translates to improvements in properties such as tuft bind, edge ravel and edge curl.

When the polyurethane backing of the invention is used as a precoat which binds woven or tufted face fibers to a primary backing, the precoated textile advantageously exhibits a tuftbind, measured according to ASTM D1335, of at least 10 Ib (44.5N), more preferably at least 13 Ib (58N) and even more preferably at least 15 Ib (67N). Normalized to coating weight, the tuftbind is advantageously at least 0.40 lb/ounce/square yard (5.38 nr2), preferably at least 0.48 (6.46 nr2) and more preferably at least about 0.52 lb/ounce/square yard (7 m 2), when coating weights are in the 25-35 ounce/square yard (0.85-1.19 kg/m2) range. Wet tuftbind values are advantageously at least 5.5 Ib (24N), more preferably at least 8.8 Ib (39N) and even more preferably at least 11 Ib (49N). Normalized to coating weight (for coating weights in the 25-35 ounces/square yard (0.85-1.19 kg/m2) range), wet tuftbinds of at least 0.26 lb/ounce/square yard (3.5 nr2), such as at least 0.35 (4.71 nr2) or at least 0.40 lb/ounce/square yard (5.38 m 2) are desirable. Wet tuftbind is measured according to ASTM D1335 after soaking the carpet sample in room temperature tap water for 20 minutes.

A precoated textile made in accordance with the invention desirably has an edge curl of no greater than 2.54 cm, preferably no greater than 1.8 cm, more preferably no greater than 1.3 cm and even more preferably no greater than 0.8 cm, in each of the machine and cross machine direction. Edge curl is measured by first submerging three 2" X 6" (5 cm X 15 cm) carpet samples in room temperature water for 30 seconds. Excess water is shaken off the samples and they are placed face up on a flat surface. A panel is applied over the sample, leaving a 2" X 2" (5 cm X 5 cm) portion exposed. After 30 minutes, the distance from the flat surface to the underside of the outer exposed edge of the carpet sample is measured. The average of the three measurements is reported as the edge curl.

A precoated carpet in accordance with the invention also advantageously exhibits excellent pilling and fuzzing resistance and high edge ravel (such as greater than 78N, especially greater than 98N or greater than 108N on the test described below). Edge ravel is measured on samples conditioned at ~21°C and ~50% humidity for 24 hours. Tuft rows are pulled from the sample until two complete rows are pulled out. About l-1/. to 2 inches (4-5 cm) of a third row is pulled out, leaving the resulting partially pulled row otherwise attached to the carpet. The sample is placed in the lower jaw of an Instron 4465 tensile tester equipped with 100 Ib (45 kg) tension cell, and the free end of the partially pulled tuft row is placed in the upper jaw. The jaws are then pulled apart at the rate of 10 inches (25.4 cm)/minute. The force is measured on three duplicate sample and the average reported as edge ravel.

A precoated carpet preferably exhibits a "hand punch" (a measure of flexibility described below) of 133N or less. Hand punch is measured by a test that simulates the action of pushing the carpet into a corner during installation. A 9" X 12" (21.6 cm X 30.5 cm) sample of the carpet is conditioned at 50% relative humidity and 250C for two hours. The carpet is placed face up over a hollow cylinder with a 5.5" (14 cm) internal diameter. An Instron 4465 tensile tester is equipped with a 1 kN compression/extension load cell and a compression foot having a 2.25" (5.7 cm) outside diameter. The compression foot is then forced 0.65 inch (1.65 cm) into the carpet at a rate of 12 inches/minute (30 cm/minute). The force at 0.5 inch (1.27 cm) deflection is reported. The test is repeated three more times, with the carpet being reversed each time. "Hand" is the average of the four measurements. A precoated carpet also advantageously exhibits good flame retardancy, antimicrobial/antifungal activity, low 24-hour total volatile organic components (TVOC), good liquid barrier functionality as measured by the British spill passage test (United Kingdom Health Care Specifications Method E), and excellent castor chair resistance to backing delamination and zippering (measured according to ASTM D6962, using the Feingerate Baumberg Roller Chair Testing Device).

The carpet backings of the invention have particular applicability in the residential and commercial carpet industry as well as in carpeting for recreational use, such as boats, cars, patios, synthetic tuft, etc.

The following examples illustrate the present invention but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated. Unless stated otherwise, all molecular weights expressed herein are weight average molecular weight.

Example 1 and Comparative Sample A Two commercial 14 inch (36 cm) Oakes frothers equipped to process multi- component streams are used to prepare a mechanically froth/chemically blown foam formulation for application to a substrate on a 12 foot (3.66 m) tentered production coater. The resulting product is a low density cushion underlay for residential padding.

A compounded polyol mixture is prepared by mixing: 221.0 kg of Polyol A (a 2000 molecular weight, nominally difunctional polymer of propylene oxide with a 12% EO cap, available commericially as VORANOL 9287A polyol from The Dow Chemical Company); 97.4 kg #1 imported castor oil; 58.5 kg of a dispersion containing 43%of styrene-acrylonitrile copolymer particles dispersed in Polyol A;

12.9 kg ethylene glycol;

3.9 kg of an ethoxylated phosphate ester (commercially available as Code 5027 viscosity depressant from Fibro Chem);

740.4 kg calcium carbonate particles.

The polyol mixture (exclusive of filler and viscosity reducer) contains 25% of a NOP (castor oil) and 6.4% of dispersed polymer particles.

The foregoing components are blended in a Cowles mixer until the temperature of the compound reaches 490C due to waste heat from the mixing process. It is then cooled to about 18.90C.

The following streams are separately metered into the first Oakes mixer:

1. The foregoing compound, at a rate of 28.58 kg/min;

2. A polymeric MDI polyisocyanate (PAPI 7940 isocyanate, from Dow Chemical), at a rate of 6.08 kg/min;

3. A blend of 25 wt % Niax™ L5614 surfactant in Polyol A, at a rate of 0.29 kg/min; and

4. A blend of 25 wt % water in Polyol A, at a rate of 0.83 kg/min.

The mixed ingredients exiting the first Oakes mixer are mixed further and then introduced into the second Oakes frother. The mixture is frothed with air to a 400 g/L cup weight with compressed air in the second Oakes mixer. The uncatalyzed froth enters the second Oakes mixer and is mixed with a blend of 0.05% of dibutyltin sulfide in Polyol A, which is fed at the rate of 0.15 kg/min. The resulting froth is delivered via a traversing hose to the back of an 11X18 pic FLW woven primary fabric to form a puddle, and formed into a layer on the fabric using a blade over roller gapped at 2.5 mm. The primary fabric is conveyed under the blade at the rate of 9.8 meters/minute using a 12 foot (3.66m) tenter. A 0.025 mm polyurethane film traveling over the blade is laid onto the surface of the froth. The composition is cured in a multi-zoned gas fire/forced air oven at 14O0C for 3.5 minutes and then cooled to ambient temperature. After cool down, the product is sent to roll-up. The density of the attached cushion and its thickness are as reported in Table 1 below. Compression set, indentation load deflection, compression load detention, ball rebound and fatigue are all determined on the foam using ASTM methods. Results are as reported in Table 1. Comparative Sample A is made in the same manner, except the compounded polyol is prepared without the polymer polyol, using the following ingredients:

1. 280.2 kg VORANOL 9137CA polyol,

2. 97.4 kg #1 imported castor oil,

3. 12.1 kg ethylene glycol;

4. 3.9 kg of Code 5027 viscosity depressant (available from Fibro Chem) and

5. 740.4 kg calcium carbonate.

The polyol mixture used to make Comparative Sample A contains 25% of a NOP and no dispersed polyol particles. Foam cushion properties are measured for Comparative Sample A, and are as reported in Table 1.

Table 1

Figure imgf000021_0001

*Not an example of the invention.

Fatigue testing and ball rebound shows a significant improvement in Example 1.

Example 2 and Comparative Sample B

A precoat compound is made by mixing together in a plastic cup 8.0 g of Polyol B (a 2000 molecular weight, nominally difunctional poly(propylene oxide) commercially available as Voranol® 9120A polyol from Dow Chemical), 30 g of the polymer polyol described in Example 1, 50.0 g of bifunctional castor oil (commercially available as BFCO, from Jayant Agro-Organic Ltd.), 12.0 g of dipropylene glycol, 1.0 g of Code 5027 viscosity depressant and 200 g of a particulate coal fly ash. The compound is mixed in an Cowles mixer until its temperature is raised to 490C and is then allowed to cool to 250C. The polyol mixture (exclusive of filler and viscosity reducer) used in this example contains 50% of a NOP (castor oil) and 12.9% of dispersed polymer particles.

The compounded polyol is mixed with 58.8 g. of a hard segment MDI prepolymer which is available commercially from Dow Chemical as Isonate 7594A isocyanate, and catalyzed with a blend of 0.05% dibutyl tin sulfide catalyst in Polyol A). The catalyzed precoat formulation is deposited onto a tufted carpet (style Capitol, available from Shaw Industries, Inc.) using a coating knife. The carpet and applied precoat are conveyed into a lab oven and cured at 13O0C for 12 minutes. The cured carpet precoat backing is tested for physical properties, with results as indicated in Table 2.

Comparative Example B is made in the same manner, but without any polymer polyol. The compounded polyol in this case is made with 39 g of Polyol B, 50.0 g of bifunctional castor oil (commercially available as BFCO, from Jayant Agro-Organic Ltd.), 11.0 g of dipropylene glycol, 1.0 g of Code 5027 viscosity depressant and 200 g of a particulate coal fly ash. The polyol mixture (exclusive of filler and viscosity reducer) in this case contains 50% of a NOP (castor oil) and no dispersed polymer particles.

Comparative Example B is tested in the same manner as is Example 2, with results as indicated in Table 2.

Table 2

Figure imgf000022_0001

*Not an example of the invention.

The presence of the dispersed polymer particles in Example 2 leads to better tuftbind, edge ravel and edge curl properties. Example 3 and Comparative Sample C

A compounded polyol is prepared by mixing the following components using a 10 cm Cowles blade:

1. 2672 g Polyol A; 2. 1781 g of a hydroxymethyl-containing polyester polyol having a hydroxyl number of 89 and a hydroxyl functionality of 3.0;

3. 2138 g of the polymer polyol described in Example 1;

4. 534 g diethylene glycol;

5. 35.6 g of Code 5027 6. 3919 g of coal-based fly ash; and

7. 3919 g calcium carbonate particles.

The polyol mixture contains 25% of the NOP and 12.9% dispersed polymer particles.

The components are compounded by mixing until they achieve a temperature of 490C, and are then cooled to about 18.30C. The following streams are separately metered into a 2-inch (5-cm) Oakes mixer which is equipped to handle multiple component streams:

1. The foregoing compound, at a rate of 210.5 g/min;

2. A polymeric MDI polyisocyanate (PAPI 7940 isocyanate, from Dow Chemical), at a rate of 35.1 g/min; 3. A blend of 25 wt % Niax™ L5614 surfactant in Polyol A, at a rate of 4.0 g/min; and

4. A blend of 25 wt % water in Polyol A, at a rate of 1.6 g/min.

The streams are mixed and frothed with 0.33 L/min compressed air to a froth density of 400 g/L. The frothed foam is delivered via a hose to the backside of the tufted carpet (style Capitol, from Shaw Industries, Inc.) which has been previously coated with a polyurethane precoat layer. The froth is gauged over the precoated carpet using a blade over bedplate gapped at 3.2 mm. A 0.08 kg/m2 nonwoven polyester scrim is laid onto the surface of the froth and the resulting composite is cured in a 1210C forced air oven for 6 minutes. The product is then cooled to a temperature of 250C. Physical properties are evaluated from samples of the resulting foam cushion, according to ASTM methods. Results are as indicated in Table 3.

Comparative Sample C is made in the same way, except the compounded polyol is made by blending:

1. 4810 g Polyol A; 2. 1781 g of the hydroxymethyl-containing polyester polyol having a hydroxyl number of 89 and a hydroxyl functionality of 3.0;

3. 534 g diethylene glycol;

4. 35.6 g of Code 5027;

5. 3919 g of coal-based fly ash; and

6. 3919 g calcium carbonate particles.

Comparative Sample C and Example 4 are tested for physical properties after being subjected to 25000 castor chair cycles. The foam made with the polymer polyol showed improved toughness.

Table 3

Figure imgf000024_0001

Here, the presence of the dispersed polymer particles leads to improvements in tensile strength, elongation, toughness and modulus.

From the foregoing, it will be observed that numerous variations and modifications may be effected without departing from the true spirit and scope of the novel concepts of the invention.

Claims

WHAT IS CLAIMED IS:
1. A textile having an attached polyurethane backing, wherein the polyurethane backing comprises a reaction product of at least one polyisocyanate and a polyol mixture, the polyol mixture containing (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one dispersion of polymer particles in a polyol (hereinafter referred to as a "polymer polyol"), the proportions of (1) and (2) being such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol.
2. The textile of claim 1, wherein the polyol mixture contains at least 8% by weight of dispersed polymer particles and at least 20% by weight of the NOP.
3. The textile of claim 2, wherein the polyol mixture includes up to 20% by weight of at least one chain extender or crosslinker.
4. The textile of claim 2, wherein the NOP is castor oil or a hydroxylmethyl-containing polyester polyol, the polymer polyol is a dispersion of styrene or styrenen acrylonitrile polymer particles in as homopolymer of propylene oxide or a copolymer of propylene oxide and up to 20% by weight ethylene oxide, and further wherein the polyol mixture includes ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol or a mixture of any two or more of these, and the polymer mixture contains from 8 to 15% by weight dispersed polymer particles.
5. The textile of any of claims 1-4, wherein the attached polyurethane backing is cellular.
6. The textile of any of claims 1-4, wherein the textile is a carpet comprising (I) a primary backing and (II) a yarn tufted or woven through the primary backing thereby creating a yarn bundle on the underside of the resulting carpet, and wherein the attached polyurethane backing is applied to the underside of the carpet thereby adhering the yarn bundle to the primary backing.
7. The textile of any of claims 1-4 wherein the textile is a carpet comprising a primary backing and a secondary backing adhered directly or indirectly to the primary backing by the attached polyurethane backing.
8. A method for preparing the textile of claim 1, comprising (I) applying a polyurethane-forming composition to the underside of a textile and (II) curing the polyurethane-forming composition to form a polyurethane coating that is adhered to the textile, wherein the polyurethane-forming composition contains at least one polyisocyanate and a polyol mixture, the polyol mixture containing (1) at least one natural oil-based polyol (NOP) having a hydroxyl equivalent weight of at least 250 and (2) at least one polymer polyol, the proportions of (1) and (2) being such that the polyol mixture contains at least 5% by weight of dispersed polymer particles and at least 10% by weight of the natural oil-based polyol.
9. The method of claim 8, wherein the polyurethane-forming composition is frothed and cures to form a cellular polyurethane coating.
10. The method of claim 8 wherein the textile is a carpet comprising (I) a primary backing and (II) a yarn tufted or woven through the primary backing thereby creating a yarn bundle on the underside of the resulting carpet,wherein the polyurethane-forming composition is applied to the underside of the carpet and cured, thereby adhering the yarn bundle to the primary backing.
11. The method of claim 8 wherein the textile is a carpet and wherein the polyurethane-forming composition is applied to a secondary backing or to the carpet, the carpet is joined to the secondary backing such that the polyurethane-forming composition is intermediate to the secondary backing and the carpet, and the polyurethane-forming composition is cured.
PCT/US2008/059719 2007-04-13 2008-04-09 Polyurethane carpet backing systems based on natural oil polyols and polymer polyols WO2008127934A1 (en)

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US9481759B2 (en) 2009-08-14 2016-11-01 Boral Ip Holdings Llc Polyurethanes derived from highly reactive reactants and coal ash
US9932457B2 (en) 2013-04-12 2018-04-03 Boral Ip Holdings (Australia) Pty Limited Composites formed from an absorptive filler and a polyurethane
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GB2454990A (en) * 2007-11-21 2009-05-27 3Gates Patent Ltd Polyurethane or polyisocyanurate foam compositions
WO2011019997A1 (en) * 2009-08-14 2011-02-17 Boral Material Technologies Inc. Filled polyurethane composites and methods of making same
WO2011020004A1 (en) * 2009-08-14 2011-02-17 Boral Material Technologies Inc. Filled polyurethane composites and methods of making same
US8846776B2 (en) 2009-08-14 2014-09-30 Boral Ip Holdings Llc Filled polyurethane composites and methods of making same
US9481759B2 (en) 2009-08-14 2016-11-01 Boral Ip Holdings Llc Polyurethanes derived from highly reactive reactants and coal ash
US9932457B2 (en) 2013-04-12 2018-04-03 Boral Ip Holdings (Australia) Pty Limited Composites formed from an absorptive filler and a polyurethane
US10324978B2 (en) 2013-04-12 2019-06-18 Boral Ip Holdings (Australia) Pty Limited Composites formed from an absorptive filler and a polyurethane
US10138341B2 (en) 2014-07-28 2018-11-27 Boral Ip Holdings (Australia) Pty Limited Use of evaporative coolants to manufacture filled polyurethane composites

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