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WO2007053466A1 - Apprêt anti-tache en poly(hydroxystyrène) - Google Patents

Apprêt anti-tache en poly(hydroxystyrène) Download PDF

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Publication number
WO2007053466A1
WO2007053466A1 PCT/US2006/042077 US2006042077W WO2007053466A1 WO 2007053466 A1 WO2007053466 A1 WO 2007053466A1 US 2006042077 W US2006042077 W US 2006042077W WO 2007053466 A1 WO2007053466 A1 WO 2007053466A1
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Prior art keywords
mole
alkyl
independently
carpet
formula
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PCT/US2006/042077
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Inventor
Steven Willis Shuey
Stephen Ernest Jacobson
Melea Rena Langley
Peter Michael Murphy
Mukesh Chimanlal Shah
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to EP06836596A priority Critical patent/EP1945679A1/fr
Publication of WO2007053466A1 publication Critical patent/WO2007053466A1/fr
Anticipated expiration legal-status Critical
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
    • C08F8/36—Sulfonation; Sulfation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D06M15/233—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated aromatic, e.g. styrene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/31—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated nitriles

Definitions

  • Allen describes stain resist compositions formed from (a) from about 8% to about 40% of a styrene, substituted styrene or phenolic monomer free of carboxylic acid groups and strong acid groups, (b) from about 9% to about 20% of an ethylenically unsaturated strong acid monomer having a pKa below 2, and (c) from about 10% to about 62% of an ethylenically unsaturated weak acid monomer having a pKa of 3 - 11 , with the weight percentages described in a ternary diagram.
  • Allen discloses (a) a preferred system in which the polymers are mixed with sulfonated phenolic condensates, and (b) that the aromatic neutral monomer must be free of acidic groups. Allen does not describe the use of phenols that have weakly acidic groups, nor the use of a preformed co-polymer that is sulfonated.
  • stain blockers having improved performance.
  • improved stain resistance to coffee and mustard stains is desirable while maintaining UV fastness and durability of the properties.
  • the present invention provides such a stain blocker composition, method for its use, and substrates treated therewith.
  • the present invention comprises a composition comprising a polymer having the following repeating units, said units occurring in any sequence
  • RI is H, methyl or ethyl
  • R 2 and R 3 are each independently H, Ci to about Ci o alkyl, -COOR 4 , CONR 5 R 6 , or -CN;
  • R 4 is M, Ci to about C20 alkyl, or Cg to CIQ aryl;
  • R 5 and R 6 are each independently H, Ci to Ci Q alkyl, Cg to CIQ aryl, or R 5 and R 6 together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring;
  • R ⁇ is a C4 to Cg alkyl group
  • M is H, an alkali metal or alkali earth metal
  • h is about 10 to 100 mole %
  • i is O to about 80 mole %
  • j is 0 to about 60 mole %
  • k and n are each independently 0 to about 40 mole %
  • m is 0.01 to about 0.5; provided that h + i +j + k + n equals 100, and provided that i + j + k + n is greater than zero, except when h is 100%.
  • the present invention further comprises a method of providing resistance to stains in substrates comprising contacting the substrate with a polymer of Formula IA having the following repeating units, said units in any sequence
  • RI is H, methyl or ethyl
  • R 2 and R 3 are each independently H, Ci to about CIQ alkyl, -COOR 4 , CONR 5 R 6 , or -CN;
  • R 4 is M, C i to about C20 alkyl, or Cg to C 10 aryl;
  • R 5 and R 6 are each independently H, C ⁇ to C ⁇ Q alkyl, Cg to C ⁇ o aryl, or R 5 and R 6 together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring;
  • R ⁇ is a C4 to Cg alkyl group
  • M is H, an alkali metal or alkaline earth metal
  • h is about 10 to 100 mole %
  • i is 0 to about 80 mole %
  • j is 0 to about 60 mole %
  • k and n are each independently 0 to about 40 mole %
  • p is 0 to about 0.5; provided that h + i +j + k + n equals 100, and provided that i + j + k + n is greater than zero, except when h is 100%.
  • the present invention further comprises a substrate treated with a polymer of Formula IA as described above.
  • the present invention further comprises a composition comprising a polymer of Formula 2 having the following repeating units, said units occurring in any sequence
  • R1 is H, methyl or ethyl
  • R 2 and R 3 are each independently H, Ci to about Cio alkyl, -COOR 4 , CONR 5 R 6 , or -CN;
  • R 4 is H 3 Ci to about C20 alkyl, or Cg to Ci 0 aryl;
  • R 5 and R 6 are each independently H, Ci to Ci Q alkyl, Cg to Ci Q aryl, or R 5 and R ⁇ together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring;
  • R7 is a C4 to Cg alkyl group;
  • R 8 is H, Ci to about C20 alkyl, or C ⁇ to Ci 0 aryl;
  • R 9 Is H 5 R 1 ⁇ Or C(O)R 11 ;
  • R 10 is Ci to about C4 alkyl
  • R 11 is Ci to about C4 alkyl, or Cg to CIQ aryl; h is about 10 to 1 OO mole %; i is O to about 80 mole %; j is 0 to about 60 mole %; k and n are each independently 0 to about 40 mole %; and m is 0.01 to about 0.5; provided that h + i +j + k + n equals 100, and provided that i + j + k + n is greater than zero, except when h is 100%.
  • (alkyl)acrylic indicates acrylic or alkylacrylic
  • (alkyl)acrylate indicates acrylate or alkylacrylate
  • the first embodiment of the present invention comprises polymers of Formula 1 having the following repeating units occurring in any sequence.
  • R1 is H, methyl or ethyl and preferably H or methyl
  • R 2 and R 3 are each independently H, Ci to about CI Q alkyl, -COOR 4 , CONR 5 R 6 , or -CN;
  • R 4 is M, Ci to about C20 alkyl, or Cg to Cj Q aryl
  • R 5 and R 6 are each independently H, Cj to C ⁇ 0 alkyl, Cg to C ⁇ Q aryl, or R 5 and R 6 together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring
  • R7 is a C4 to Cg alkyl group
  • M is H, an alkali metal or an alkaline earth metal, and preferably Na or K; h is about 10 to 100 mole % and preferably about 40 to about 70 mole %; i is 0 to about 80 mole % and preferably about 30 to about 60 mole %; j is 0 to about 60 mole % and preferably about 30 to about 60 mole %; k and n are each independently 0 to about 40 mole % and preferably about O to about 10 mole %; m, also denoted herein as the degree of sulfonation, is from about 0.01 to about 0.5, and preferably from about 0.01 to about 0.4 sulfonic acid groups per hydroxystyrene monomer residue; and h + i + j + k + n equals 100, and i + j + k + n is greater than zero, except when h is 100%.
  • the sulfonated homopolymer of hydroxystyrene is represented by Formula 1 in which i, j, k, and n are zero.
  • the sulfonation of the hydroxystyrene is random throughout the polymer.
  • the polymers of the present invention are useful to provide stain resistance to substrates. In particular, improved resistance to staining by coffee and mustard is provided to substrates treated with the polymers of the present invention.
  • Polymers of the structure of Formula 1 are formed by polymerization of (a) hydroxystyrene, t-butoxystyrene, acetoxystyrene, alkoxystyrene, or other protected hydroxystyrenes, and (b) one or more monomers of i) monomers of the structure of Formula 3 (see below), ii) maleic anhydride, iii) styrene, and iv) a terminally unsaturated alkene.
  • the monomer of Formula 3 is an (alkyl)acrylic acid or an (alkyl)acrylate ester having the following formula:
  • R2R3C C(R 1 )-COOR 8 Formula 3 wherein RI is H, methyl or ethyl, and preferably H or methyl;
  • R 2 and R 3 are each independently H, Ci to about CJQ alkyl, -COOR 4 , CONR 5 R 6 , or -CN, and preferably R 2 is H and R 3 is -COOR 4 ;
  • R 5 and R 6 are each independently H, C ⁇ to C ⁇ Q alkyl, Cg to C ⁇ Q aryl, or R 5 and R 6 together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring, and preferably R 5 and R 6 are independently H or methyl, and
  • R ⁇ is H, C ⁇ to about C20 alkyl, or Cg to Cj Q aryl, and preferably H or methyl.
  • Examples of Formula 3 are (alkyl)acrylic acids, such as (meth)acrylic acids, and their esters, such as methyl and t-butyl (meth)acrylates.
  • the free acids are preferred for emulsion polymerization, and the esters for solution polymerization.
  • the esters are used, the alkyl group R ⁇ is removed during subsequent hydrolysis steps.
  • the preparation of the polymers of Formula 1 is by use of polymerization procedures known to those skilled in the art. Polymerizations and the removal of protective groups are discussed in Sheehan et al. in US Patent 2002156199, Watanabe et al. in US Patent 5,412,050, and Lin et al., in "Sequence Distribution and Polydispersity Index affect the Hydrogen-Bonding Strength of Poly(vinylphenol-co-methyl methacrylate) Copolymers", Macromolecules, 2005 . , 3_8, 6435-6444, each herein incorporated by reference. Emulsion and solution polymerization procedures are well know to those skilled in the art, for instance Rupp et al.
  • any hydroxystyrene, t-butoxystyrene, acetoxystyrene, alkoxystyrene, or other protected hydroxystyrene isomer or mixture thereof may be used, the para isomers are preferred.
  • Several factors are involved with the choice of t-butoxystyrene, acetoxystyrene, or hydroxystyrene as the monomer introducing the hydroxystyrene moiety into the polymer. Hydroxystyrene is relatively unstable and can be the source of undesirable impurities. Polymers made with hydroxystyrene may be discolored or require the use of special solvents.
  • the polymerization yields an intermediate polymer having the structure of Formula 2 below.
  • RI is H, methyl or ethyl
  • R 2 and R 3 are each independently H, Cj to about CIQ alkyl, -COOR 4 , CONR 5 R 6 , or -CN;
  • R 4 is H, Ci to about C20 alkyl, or Cg to Cj Q aryl;
  • R 5 and R 6 are each independently H, C ⁇ to Cj Q alkyl, Cg to C ⁇ Q aryl, or R 5 and R 6 together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring;
  • R ⁇ is a C4 to Cg alkyl group
  • R 8 is H, C ⁇ to about C20 alkyl, or Cg to Cj Q aryl;
  • W is H, R , 1 i 0 ⁇ , or C(O)R 1 1 1
  • R , 1 1 0 U is Ci to about C4 alkyl;
  • R 11 is Cj to about C4 alkyl, or Cg to C ⁇ o aryl;
  • h is about 10 to 100 mole %;
  • i is 0 to about 80 mole %;
  • j is 0 to about 60 mole %;
  • k and n are each independently 0 to about 40 mole %; and
  • m is 0.01 to about 0.5; provided that h + i +j + k + n equals 100, and provided that i +j + k + n is greater than zero, except when h is 100%.
  • These intermediate polymers of Formula 2 comprise a further embodiment of the present invention, and are useful in making the polymers of Formula 1. Hydrolysis of the polymer of Formula 2 yields the polymer of Formula 1.
  • any alkoxy groups, for instance acetoxy groups, if present, are removed by hydrolysis or preferably by base-mediated transesterification as described by Sheehan et al, in US Patent 6,759,483.
  • the ester group C(O)OR 4 is removed by suitable hydrolysis based on the type of ester group, for example the t-butyl group is removed by acid hydrolysis effected by well known reagents such as HCl or trifluoroacetic acid.
  • the cyclic anhydride ring is opened by base hydrolysis.
  • the hydroxystyrene monomer residues are optionally sulfonated.
  • the alkoxy groups are to be removed after polymerization whether or not the polymer is subsequently sulfonated. All protecting groups impede sulfonation.
  • alkoxy groups include, but are not limited to, t-butoxy, acetoxy, and methoxymethyl (-CH2OCH3).
  • the t-butoxy and methoxymethyl groups are easily removed by acid hydrolysis, while the acetoxy group is readily removed by base hydrolysis or transesterification. Although the acetoxy group is less easy to remove, requiring base hydrolysis, the monomer is less expensive and more readily available.
  • the maleic anhydride ring (Formula 1 wherein j is greater than zero) is opened by a base hydrolysis before use as the stain resist.
  • the anhydride ring is opened after the alkoxy (for instance acetoxy) group has been removed. Hydrolysis of the polymer of Formula 2 yields the polymer of Formula 1.
  • sulfonation of the hydoxystyrene moieties in the polymers of Formula 1 is also accomplished by means known to those skilled in the art.
  • sulfonation can be achieved by treatment of the polymer with sulfuric acid of various concentrations, by the use of fuming sulfuric acid, and most readily by the use of sulfur trioxide or its complexes, including the dimethylformamide complex or the dioxane complex.
  • Sulfonation occurs on the hydroxystyrene residue, predominantly ortlio to the hydroxy group for p- hydroxystyrene or ortho or para to the hydroxy group for other hydroxystyrene isomers.
  • styrene monomer is present in the polymer, sulfonation occurs preferentially on the hydroxystyrene monomer moiety.
  • degree of sulfonation represented by m in Formula 1 is used to describe the average number of sulfonic acid groups per hydroxystyrene residue.
  • a degree of sulfonation of zero is the unsulfonated polymer, a degree of sulfonation greater than zero to less than 1.0 denotes an average of less than one sulfonic acid group per hydroxystyrene residue.
  • the degree of sulfonation for Formula 1 is from about 0.01 to about 0.5 and preferably about 0.01 to about 0.4.
  • Sulfonation adds a strongly acidic group to the polymer which is expected to exist in an anionic state under conditions relevant to application of stain blockers to substrates. This renders unoccupied dye sites in the treated substrate less available to potential staining. Sulfonation also increases the water solubility of the polymers and hydrolyzed polymers, an important factor in their application as stainblockers.
  • the sulfonated polymer of Formula 1 is isolated. For example, by removing the dimethylformamide solvent and then precipitating in a non-solvent such as diethyl ether or hexane.
  • the solid polymer thus obtained can be re- dissolved in a solvent such as methanol and optionally reprecipitated to remove impurities.
  • the polymer is then redissolved or dispersed in water at a concentration of from about 15% to about 30% by weight solids to provide a formulation for treatment of substrates.
  • the aqueous solutions are adjusted to a neutral pH range of about 6 to about 7.
  • Unsulfonated polymers are also useful in the present invention to provide stain resistance to substrates. These are included in Formula IA below.
  • R 1 , R 2 , R 3 , R 4 , R 7 , M, h, i, j, k, and n are defined as in Formula 1 and p is O to about 0.5.
  • Formula IA is the same structure as Formula 1 except that p is O to about 0.5, and preferably O to about 0.4.
  • Unsulfonated polymers of Formula IA are prepared and isolated as described above for the sulfonated polymers except that the sulfonation step is omitted when p is zero.
  • p represents the degree of sulfonation as described above for m of Formula 1.
  • the present invention comprises the use of aqueous solutions or dispersions of (a) polymers of Formula 1, (b) polymers of Formula IA, or (c) mixtures thereof as stain resist agents for substrates.
  • the invention comprises a method of treating substrates to provide stain resistance comprising contacting the substrate with at least one polymer of the structure of Formula 1 or Formula IA as described above, or mixtures thereof.
  • the dispersions or solutions of the polymers of Formula 1, Formula IA, or mixtures thereoif, are applied conventionally to the substrate, dried, and cured.
  • Application methods include spray, foam flex-nip, pad, kiss-roll, beck, skein, and winch, brush, roll, spray, and immersion, each method optionally with heat and with humidity in the range of dry to saturated steam (100% relative humidity).
  • spray, foam, flex-nip, nip (dip and squeeze), liquid injection, overflow flood, and other application methods well known to those skilled in the art are suitable for use for simultaneous, tandem or sequential application of the stain resist polymers of the present invention and other surface effect agents.
  • a low wet pickup bath system can be interchanged with a low wet pickup spray or foam system
  • a high wet pickup bath system can be interchanged with other high wet pickup systems, e.g., flex-nip system, foam, pad, or flood.
  • the method employed determines the appropriate wet pickup and whether the application is made from one side of the substrate (spray and foam applications) or both sides (flex-nip and pad).
  • the application is by exhaution at a wet pickup of 500% at a concentration of polymer of from about 0.5% to about 3% active ingredient on weight of fiber (owf), preferably from about 1 to about 2% active ingredient owf.
  • the percent active ingredient owf is equal to the wet pickup multiplied by (percent solids of polymer times amount of polymer in g divided by weight of application bath).
  • treatment aids that are known to those skilled in the art may be added to the solutions or dispersions of polymers of the structure of Formula 1, Formula IA, or mixtures thereof, including additional components such as treating agents or finishes to achieve additional surface effects, or additives commonly used with such agents or finishes.
  • additional components comprise compounds or compositions that provide surface effects such as no iron, easy to iron, shrinkage control, wrinkle free, permanent press, moisture control, softness, strength, anti-slip, anti-static, anti-snag, anti-pill, stain repellency, stain release, soil repellency, soil release, water repellency, oil repellency, odor control, antimicrobial, sun protection, and similar effects.
  • One or more such treating agents or finishes can be combined with the aqueous solution or dispersion of Formula 1 or IA and applied to the fibrous substrate.
  • Other additives commonly used with such treating agents or finishes may also be present such as surfactants, blocked isocyanates, pH adjusters, cross linkers, wetting agents, hydrocarbon extenders, wax extenders, and other additives known by those skilled in the art.
  • Suitable surfactants include anionic, cationic, and nonionic.
  • the present invention comprises substrates treated with at least one composition of Formula 1, or at least one composition of Formula IA, or mixtures thereof.
  • Substrates suitable for use in the present invention comprise fibrous substrates and include fibers, yarns, fabrics, textiles, nonwovens, carpets, leather, or paper.
  • the fibrous substrates are made with natural fibers such as wool, cotton, jute, sisal, sea grass, paper, coir and cellulose, or mixtures thereof; or are made with synthetic fibers such as polyamides, polyesters, polyoleflns, polyaramids, acrylics and blends thereof; or blends of at least one natural fiber and at least one synthetic fiber.
  • fabrics is meant natural or synthetic fabrics, or blends thereof, composed of fibers such as cotton, rayon, silk, wool, polyester, polypropylene, polyolefins, nylon, and aramids such as “NOMEX” and "KEVLAR.”
  • fabric blends is meant fabric made of two or more types of fibers. Typically these blends are a combination of at least one natural fiber and at least one synthetic fiber, but also can be a blend of two or more natural fibers or of two or more synthetic fibers.
  • the substrates are treated with the polymer of Formula 1 or Formula IA or mixtures thereof as described above. Preferably, the substrates are treated in accordance with the method of the present invention described above.
  • Substrates so treated were superior to current commercial products in blocking coffee and mustard stains, while many retained stain resistance to red dyes such as KOOL-AID, wash fastness and lightfastness.
  • the superior stain resistance of the polymers and treated substrates of the present invention provide several advantages. For example, the superior resistance to coffee and mustard stains is advantageous in use of the treated substrates in fabrics and textiles used in garments, home furnishings, carpets, and other consumer products. The durability of the stain resistance when subjected to washing or UV light results in superior performance over time.
  • Sulfur trioxide N,N-dimethylformamide complex (SO 3 .DMF), is available from Aldrich Chemical, Milwaukee WI.
  • Poly(p-hydroxystyrene), polyf ⁇ -hydroxystyrene-co-t-butylacrylate) (61:39), poly ⁇ -hydroxystyrene-co-t-butylacrylate) (61:39), and poly(p- hydroxystyrene) branched are all available from Du Pont Electronic Polymers, LLP, Corpus Christi TX.
  • Comparative Example A is a commercially available stain blocker composition which is an aqueous dispersion of an olefin/maleic acid polymer with phenol-formaldehyde resin and surfactant, obtained from E. I. du Pont de Nemours and Company, Inc., Wilmington DE
  • the carpet material is a residential cut pile two ply 1150, 3.5 turns per square inch (1.4 turns/cm), 5/32 gauge, pile height 0.5 inch (2.5 cm), 30 oz. per square yard (1.2 kg/m ⁇ ), dyed light blue and available from Invista, Wilmington,
  • Test Method 1 Application of Stain Resist onto Residential Carpet with Exhaust in a Microwave Oven Dyed and unbacked residential carpet (with various colors, styles, and fiber types) were cut into approximately 4 inch x 4 inch squares (approximately 10cm x 10cm) and each square weighed as dry carpet samples. The weight was typically about 13 g. Each carpet sample was saturated with water and then most of the water in the carpet was removed by mechanical means (such as by spin- drying or vacuum extraction) until the weight of water remaining in the carpeting was about 40% of the dry carpet weight.
  • the stain blocker application solutions were diluted to 2% active ingredient on weight of fiber (owf) (2% of the total water bath by weight).
  • Surfactant, DOWFAX 2A4 (1 to 2 g) was added to the solution, and the solution was adjusted to pH 2 with sodium bisulfate.
  • the solution was applied to the carpet at 500% wet pick up.
  • the weight of carpet sample (grams) x 500% grams of stain blocker solution applied.
  • the stain blocker application solution was applied evenly to the wetted carpet samples in an amount equal to 500% of the dry carpet sample (500% wet pickup), and manually worked into the substrate until the substrate was fully saturated.
  • a single layer of one or more of the treated carpet samples was placed on the bottom of a microwave-safe plastic tray (any microwaveable plastic tray of adequate size may be used) with the pile side up. A few holes were punctured in the lid to prevent steam buildup, and the lid was placed on the plastic tray.
  • the carpet was heated in the plastic tray at full power level until the temperature reached between 195+/-2 0 F (91+/-1°C) and the temperature held atthat temperature for 2 minutes.
  • the microwave oven temperature probe was used to control the temperature.
  • the samples were then rinsed thoroughly with water. Most of the water in the carpet sample was removed by spin-drying with an extractor until the weight of water remaining in the carpeting was about 20 to 40% of the dry carpet weight.
  • the carpet sample was then completely dried in an oven at between 160°F and 180°F (7O 0 C and 8O 0 C); typically for about 25 to 35 minutes.
  • the quantities of the stainblocker suitable for application to the carpet substrate are the amounts as calculated to achieve the 500% wet pick up. In the present invention, these amounts can range from about 0.5% to about 3% AI owf based on the weight of the substrate carpet sample, preferably from about 1 to about 2% AI owf. Test Method 2 - Coffee Stain Test
  • the coffee was poured into a suitable volumetric dispenser, capable of dispensing 50 mL portions and the dispenser placed in the hot water bath at 62 0 C.
  • the coffee was allowed to come to a temperature 140°F +/- 5°F (60° +/- 2.8°C) and remain at that temperature for 30 +/- 5 minutes prior to staining.
  • a ring, in the shape of an open-ended cylinder was used, having a diameter of the smaller opening of 2.75 inch (7 cm). Such a ring is described for a different purpose in AATCC Test Method 175.
  • the ring was placed at the center of the carpet sample, with the smaller diameter opening against the pile.
  • the coffee dispenser was set to measure 50 mL, and purged once prior to staining.
  • the colorimetric delta E values from the coffee stain resist test on a sample and control was used to calculate the "Percent Coffee Blocked".
  • the percent blocking of the stain is calculated as: lOOQDelta E ⁇ ed - Delta EtreatedV Delta Entreated- Higher values denote better stain blocking.
  • a 2 inch (5.1 cm) brass ring is placed in the center of a 4 to 6 inch (10.2 to 15.2 cm) square sample of carpet placed on a non-absorbent surface.
  • For the mustard stain test fifteen grams of French's yellow mustard available from Reckitt Benckiser, Inc., Wayne, NJ, were used to create a stain by placing the mustard in the middle of the brass ring on the carpet, and then spreading and pressing the stain into the carpet surface. After setting for 24 h, the excess mustard was (a) scraped off, (b) thoroughly rinsed with water, (c) extracted using vacuum, and (d) air-dried for 24 hours on a non-absorbent surface. The mustard stains obtained by this procedure were rated using a visual stain rating scale
  • AATCC Red 40 Stain Scale from AATCC Test Method 175.
  • a visual rating of 10 (complete stain removal) to 1 (maximum or unchanged stain) was used that approximated the AATCC Red 40 Stain Scale (Test Method #175) with the mustard stains having the same discoloration as the numbered colored film.
  • the mustard stain was yellow while the discoloration of the AATCC Red 40 Stain Scale was red. Higher values indicate greater mustard stain resistance.
  • Cherry KOOL-AID stain testing was conducted on carpet samples 15 cm by 15 cm. Acid dye stain resistance was evaluated using a procedure based on the American Association of Textile Chemists and Colorists (AATCC) Method 175, "Stain Resistance: Pile Floor Coverings.” A staining solution was prepared by mixing 36.5 grams of sugar sweetened cherry KOOL-AID and 500 mL water.
  • KOOL-AID is a trademark of Kraft General Foods, Inc.
  • the carpet sample to be tested was placed on a flat non-absorbent surface and a hollow plastic cylinder having a 2-inch (5-cm) diameter was placed tightly over the carpet sample.
  • Twenty mis. of KOOL-AID staining solution was poured into the cylinder and the solution was allowed to absorb completely into the carpet sample. The stain was worked into the carpet.
  • the cylinder was then removed and the stained carpet sample was allowed to sit undisturbed for 24 h. Then the carpets were rinsed thoroughly under cold tap water for at least 10 minutes until the rinse water was clear.
  • the carpet samples were extracted using vacuum and air-dried for 24 hours on a non-absorbent surface.
  • the KOOL-AID stains obtained by this procedure were rated using a visual stain rating scale (AATCC Red 40 Stain Scale) from AATCC Test Method 175.
  • a visual rating of 10 (complete stain removal) to 1 (maximum or unchanged stain) was obtained by using the AATCC Red 40 Stain Scale (Test Method #175) with the KOOL-AID stains having the same discoloration as the numbered colored film. Higher values represent superior stain resistance.
  • UV fastness was conducted according to the American Association of Textile Chemists and Colorists (AATCC) Test Method 16.
  • AATCC American Association of Textile Chemists and Colorists Test Method 16.
  • the Nylon carpet samples were rated in accordance with the Grey Scale for color change after exposure to 40 AATCC AFU (adjusted fade units).
  • a visual rating ranged from 5 (complete color fastness compared to an unexposed sample) to 1 (complete loss of color).
  • a higher rating indicated superior UV light stability.
  • the carpet sample was submerged for 5 minutes at room temperature in a detergent solution consisting of "DUPONOL WAQE"(300 g WAQE/18.92 L).
  • "DUPONOL WAQE” is a 30-40% aqueous solution of sodium alkane sulfonates, available from Witco Corporation, Greenwich CT. The solution was adjusted with 10% sodium phosphate to apH of 9.8 tol ⁇ .2.
  • the carpet sample was then removed, rinsed thoroughly under tap water, de-watered by squeezing, extracted by spinning dry, and allowed to dry at ambient temperature. The dry carpet sample was then tested and rated on a scale of 1 to 10 according to Test Method 4. A higher value indicates superior wash durability of the stain resist.
  • Example 1 Into a 500-mL round-bottom flask was added poly(p-hydroxystyrene) (20 g, M. W. 11,200, Triquest LP) and dimethyl formamide (DMF, 160 mL). To the resulting solution was added sulfur trioxide N 5 N- dimethylformamide complex (SO 3 -DMF, 12.7g g, 83.33 mmol). The reaction mixture was heated at 150°C for 18 h in which time the solution went from yellow to amber. After cooling to room temperature the solvent was removed on a rotary evaporator. The resulting oil was re-evaporated several times from 50 mL methanol. The resulting oil was triturated with diethyl ether until a solid formed.
  • poly(p-hydroxystyrene) (20 g, M. W. 11,200, Triquest LP) and dimethyl formamide (DMF, 160 mL).
  • SO 3 -DMF sulfur trioxide N 5 N- dimethylformamide complex
  • Example 2 Into a 500-mL round-bottom flask was added poly(p-hydroxystyrene-t- butylacrylate) polymer (20 g, 61:39; Dupont Electronic Polymers LLP, Lot No# 10020-51 -FDP, see Materials) and DMF (12OmL). To the resulting solution was added SO 3 .DMF (7.6g) and the resulting solution heated at 150°C with stirring for 18 h. The reaction mixture was cooled to room temperature and the solvent removed in vacuo to give a brown oil. The oil was added to diethyl ether (200 mL) and stirred for 30 min.; decanting the diethyl ether and repeating the procedure several times caused the polymer to solidify.
  • poly(p-hydroxystyrene-t- butylacrylate) polymer (20 g, 61:39; Dupont Electronic Polymers LLP, Lot No# 10020-51 -FDP, see Materials
  • DMF (12OmL
  • Example 3 Into a 500-mL round-bottom flask was added poly(p-hydroxystyrene-t- butylacrylate) polymer (20 g, 61:39; Dupont Electronic Polymers LLP, Lot No. 10020-51-FDP, see Materials) and DMF (12OmL). To the resulting solution was added SO 3 .DMF (3.8 g) and the resulting solution heated under nitrogen to 150°C with stirring for 18 h. The reaction mixture was cooled to room temperature and the solvent removed in vacuo to give a brown oil. The oil was added to diethyl ether (150 mL) and stirred for 30 min. Decanting the diethyl ether and repeating the procedure several times caused the polymer to solidify.
  • poly(p-hydroxystyrene-t- butylacrylate) polymer (20 g, 61:39; Dupont Electronic Polymers LLP, Lot No. 10020-51-FDP, see Materials) and DMF (12OmL).
  • Example 6 To a solution of poly(p-hydroxystyrene-tert-butylacrylate ester) (61:39 ratio, 25.0 g, 110.74mmol; M. W 12,800; Lot No: 10020-51-FDP; from Dupont Electronic Polymers LLP, see Materials) in 1,4-dioxane (100 mL) was slowly added 2N hydrochloric acid (113.16 mL). The reaction mixture was heated at reflux for 19 h. After cooling reaction mixture to room temperature, the solvent was removed under vacuum to obtain a solid. To the solid was slurried with 250 mL water and transferred to a glass frit.
  • Example 8 Example 6 was repeated except tetrahydrofuran was employed instead of
  • a sample for stain blocker testing was prepared by dissolving the above polymer (23 g) in deionized water (100 mL) and 10% NaOH (23 mL) to give a solution with 18.8% solids. This solution was applied to carpet using Test method 1. The carpet was evaluated for stain resistance using test Methods 2, 3, 4, 5, and 6. Test results are shown in Tables 2,3 and 4.
  • Example 10 Into a 250-mL round bottomed flask was added poly(-hydroxystyrene-t- butylacrylate)(31g, , 60:40 monomer ratio by weight, from Dupont Electronic Technologies LLP, see Materials) and DMF(80g). The solution was heated to 100°C and purged subsurface with nitrogen for 0.5 hours. Then a DMF- SO 3 (11.5g) slurry in DMF(20g) was added over a 20 minute period. The solution was heated for 10 hours at 100 0 C. The solution was then cooled and the DMF removed in vacuo.
  • a sample for testing was prepared by adding the above solid (31 g) to deionized water (250 mL) and of 10% NaOH (12 mL) to give a solution with 11.1 wt% solids. This solution was applied to carpet using Test Method 1. The carpet was evaluated for stain resistance using Test Methods 2, 3, 4, and 6. Test results are shown in Tables 2 and 4.
  • Example 13 was repeated to yield 32% sulfonated poly(p-hydroxystyrene) 29.2 g. Elemental analysis: S 4.91%.
  • a sample for stain blocker testing was prepared by dissolving the above polymer (10 g) in deionized water (50 mL) and 10% NaOH (8 mL). This solution was applied to carpet using Test Method 1. The carpet was evaluated for stain resistance using Test Methods 2, 4 and 6. Test results are shown in Table 2.
  • Example 15 Example 15
  • a sample for stain blocker testing was prepared by dissolving the above polymer (64 g) in deionized water (350 mL) and 10% NaOH (60 mL) and heating to 70°C to give a solution with 13.5% solids. This solution was applied to carpet using Test Method 1. The carpet was evaluated for stain resistance using Test Method 2, 3, and 4. Test results are shown in Tables 2, 3 and 4. Comparative Example A
  • Comparative Example A was diluted and applied to carpet using Test Method 1 and tested using Test Methods 2, 3, 4, 5, and 6. Test results are shown in Tables 2, 3 and 4. Comparable Example B
  • poly(p-hydroxystyrene-t- butylacrylate) co-polymer (20 g, 61:39%, Dupont Electronic Polymers LLP, Lot No. 10020-51-FDP, see Materials) and DMF (12OmL).
  • SO 3 -DMF 15.19g
  • the reaction mixture was cooled to room temperature and the solvent removed in vacuo to give a brown oil.
  • the oil was added to diethyl ether (200 mL) and stirred for 30 min.; decanting the diethyl ether and repeating the procedure several times caused the polymer to solidify.
  • poly(p-hydroxystyrene) (20.0 g, branched, Dupont Electronic Polymers LLP; Lot no: PB5-8007B; M. W. 4934, see Materials) and DMF (11 OmL).
  • poly(p-hydroxystyrene) (20.0 g, branched, Dupont Electronic Polymers LLP; Lot no: PB5-8007B; M. W. 4934, see Materials)
  • DMF 11 OmL
  • Comparative Example D Into a 250 mL round-bottomed flask was added poly(p- hydroxystyrene(20g, from DuPont Electronic Polymers LLC) and dioxane(120g). The solution was heated to 40°C and stirred until the polymer was dissolved in solution. The DMF.SO 3 (24.5g) was added over a 30-minute period. The temperature was increased to 85 0 C and it was stirred for 24 hours. A dark brown oil precipitated. The solution was decanted off and the oil was washed with acetone(3-100mL portions). The polymer was dried in an oven at 60 0 C in vacuo to give an 86% sulfonated product. Elemental Analysis: S, 14.95%.
  • a sample for stain blocker testing was prepared by dissolving the above polymer (20.0 g) in deionized water (100 mL) and 10% NaOH (42 mL) to give a solution of 19.8% solids. This solution was applied to carpet using Test Method 1. The carpet was evaluated for stain resistance using Test Methods 2, 4 and 6. Test results are shown in Tables 2 and 4.
  • Example 13 was repeated except twice the amount of DMF-SO3 adduct (15.0 g) was employed, yielding 63% sulfonated poly(p-hydroxystyrene).
  • a sample for stain blocker testing was prepared by dissolving the above polymer (43 g) in deionized water (150 mL) and 10% NaOH (20 mL) to yield a 12.1 weight % solution. This solution was applied to carpet using Test Method 1. The carpet was evaluated for stain resistance using Test Methods 2, 4, and 6. Test results are shown in Table 2.
  • PpHS Poly(para-hydroxystyrene),
  • AA acrylic acid
  • STYR styrene
  • Example 2 The data in Table 3 showed the sulfonated and unsulfonated p- hydroxystyrene polymers of the present invention also demonstrated superior UV light stability by Test Method 5 when compared to commercial polycarboxylate (Comparative Example A). The results further demonstrated that the compositions of the present invention (see Example 2) have a better combination of properties.
  • Example 2 was equal or to or better than Comparative Example A in resistance to red dye (KOOL-AID), durability, and light fastness, and much better in coffee stain blocking.

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  • Engineering & Computer Science (AREA)
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  • General Chemical & Material Sciences (AREA)
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Abstract

Composition destinée à être utilisée comme agent anti-tache et procédé de traitement de substrats avec celle-ci, ladite composition comprenant un polymère de formule (I) ayant les motifs suivants en séquence aléatoire : (I) dans laquelle R1 est H, un méthyle ou un éthyle ; R2 et R3 sont chacun indépendamment H, un alkyle en C1 à environ C10, -COOR4, -CONR5R6 ou -CN ; R4 est M, un alkyle en C1 à environ C20 ou un aryle en C6 à C10 ; R5 et R6 sont chacun indépendamment H, un alkyle en C1 à C10 , un aryle en C6 à C10 ou bien R5 et R6 forment avec l'atome d'azote un cycle morpholine, pyrrolidine ou pipéridine ; R7 est un groupe alkyle en C4 à C8 ; M est H, un métal alcalin ou un métal alcalinoterreux ; h vaut environ 10 à 100 mol% ; i vaut 0 à environ 80 mol% ; j vaut 0 à environ 60 mol% ; k et n valent chacun indépendamment 0 à environ 40 mol% ; et m vaut 0,01 à environ 0,5 ; à condition que la somme h + i + j + k + n soit égale à 100 et à condition que la somme i + j + k + n soit supérieure à 0, sauf lorsque h vaut 100 %.
PCT/US2006/042077 2005-10-28 2006-10-27 Apprêt anti-tache en poly(hydroxystyrène) Ceased WO2007053466A1 (fr)

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US7914890B2 (en) * 2007-12-19 2011-03-29 E.I. Dupont De Nemours And Company Cyclic olefin-maleic acid copolymers for stain resists
CA2679022A1 (fr) * 2008-10-31 2010-04-30 Rohm And Haas Company Articles a traitement superficiel et avec resistance a l'adherence, et methodes
CN102718902B (zh) * 2012-03-09 2014-01-29 北京师范大学 一种基于聚对羟基苯乙烯的单组分化学增幅光致抗蚀剂材料、其合成方法及其用途

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2072508A (en) * 1980-02-27 1981-10-07 Maruzen Oil Co Ltd An antifungal and antibacterial agent
JPH01177397A (ja) * 1988-01-04 1989-07-13 Kao Corp めっき浴添加剤およびこれを用いためっき浴
EP0400642A2 (fr) * 1989-05-31 1990-12-05 Kao Corporation Composition en pâte électroconductrice
US4978399A (en) * 1988-01-04 1990-12-18 Kao Corporation Metal surface treatment with an aqueous solution
EP0456390A2 (fr) * 1990-05-01 1991-11-13 Ciba Specialty Chemicals Water Treatments Limited Copolymères avec propriétés antitaches
EP1025832A1 (fr) * 1999-02-05 2000-08-09 L'oreal Composition cosmétique comprenant un poly (hydroxystyrène) dans un milieu aqueux

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3544555A (en) * 1963-10-09 1970-12-01 Allied Chem Sulfation of alcohols with a solution of a complex of so3 with dimethylformamide
US4883839A (en) * 1987-12-21 1989-11-28 E. I. Du Pont De Nemours And Company Stain-resistant agents for textiles
JPH01195720A (ja) * 1988-01-04 1989-08-07 Nec Corp 半導体集積回路
US5061763A (en) * 1989-04-20 1991-10-29 Peach State Labs, Inc. Stain resistant treatment for polyamide fibers
US4940757A (en) * 1989-04-20 1990-07-10 Peach State Labs, Inc. Stain resistant polymeric composition
US5310828A (en) * 1989-04-20 1994-05-10 Peach State Labs, Inc. Superior stain resistant compositions
US5428117A (en) * 1993-10-18 1995-06-27 Interface, Inc. Treatment for imparting stain resistance to polyamide substrates and resulting stain resistant materials
US5952409A (en) * 1996-01-31 1999-09-14 3M Innovative Properties Company Compositions and methods for imparting stain resistance and stain resistant articles
FR2745014B1 (fr) * 1996-02-20 1998-04-03 Rhone Poulenc Chimie Procede de traitement antisalissure des articles a base de coton tisse
US6280648B1 (en) * 1998-10-20 2001-08-28 Sybron Chemicals, Inc. Stain resistant composition for polyamide containing substrates
US6680286B1 (en) * 2000-11-14 2004-01-20 Sanyo Chemical Industries, Ltd. Detergent composition comprising a quaternary ammonium salt of a carboxyl containing polymer
US6524492B2 (en) * 2000-12-28 2003-02-25 Peach State Labs, Inc. Composition and method for increasing water and oil repellency of textiles and carpet
US6736857B2 (en) * 2001-05-25 2004-05-18 3M Innovative Properties Company Method for imparting soil and stain resistance to carpet

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2072508A (en) * 1980-02-27 1981-10-07 Maruzen Oil Co Ltd An antifungal and antibacterial agent
JPH01177397A (ja) * 1988-01-04 1989-07-13 Kao Corp めっき浴添加剤およびこれを用いためっき浴
US4978399A (en) * 1988-01-04 1990-12-18 Kao Corporation Metal surface treatment with an aqueous solution
EP0400642A2 (fr) * 1989-05-31 1990-12-05 Kao Corporation Composition en pâte électroconductrice
EP0456390A2 (fr) * 1990-05-01 1991-11-13 Ciba Specialty Chemicals Water Treatments Limited Copolymères avec propriétés antitaches
US5574106A (en) * 1990-05-01 1996-11-12 Allied Colloids Limited Acrylic polymers and their use in stain resistant polyamide textile products
EP1025832A1 (fr) * 1999-02-05 2000-08-09 L'oreal Composition cosmétique comprenant un poly (hydroxystyrène) dans un milieu aqueux

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