WO1992007131A1 - Polymeres aromatiques sulfones resistant aux taches - Google Patents

Polymeres aromatiques sulfones resistant aux taches

Info

Publication number
WO1992007131A1
WO1992007131A1 PCT/US1991/007351 US9107351W WO9207131A1 WO 1992007131 A1 WO1992007131 A1 WO 1992007131A1 US 9107351 W US9107351 W US 9107351W WO 9207131 A1 WO9207131 A1 WO 9207131A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfonated
ethylenically unsaturated
polymer
unsaturated aromatic
styrene
Prior art date
Application number
PCT/US1991/007351
Other languages
English (en)
Inventor
Theodor Arthur Liss
Nandakumar Seshagiri Rao
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Publication of WO1992007131A1 publication Critical patent/WO1992007131A1/fr

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—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
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • D06P1/5214—Polymers of unsaturated compounds containing no COOH groups or functional derivatives thereof
    • D06P1/5221—Polymers of unsaturated hydrocarbons, e.g. polystyrene polyalkylene
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes

Definitions

  • the present invention relates to polyamide textile substrates treated with stain-resistant compositions comprising sulfonated aromatic polymers, and processes for their preparation.
  • Polyamide substrates such as nylon carpeting, upholstery fabric and the like, are subject to staining by a variety of agents, e.g., foods and beverages.
  • An especially troublesome staining agent is FD&C Red Dye No.40, commonly found in soft drink preparations.
  • Different types of treatments have been proposed to deal with staining problems., For example, Liss et al., in U.S. Patent Application Serial No. 07/124,866, filed 23 November 1987, disclose stain-resistant synthetic polyamide textile substrates having deposited on them sulfonated phenol/formaldehyde polymeric condensation products.
  • condensation products disclosed in the Liss et al. application have been modified by acylation or etherification of some of the phenolic hydroxyls.
  • Liss et al. dissolve the modified condensation products in a hydroxy-containing solvent, such as ethylene glycol, prior to their being applied to the textile substrate.
  • the present invention provides polyamide textile substrates treated with sulfonated aromatic polymers so as to impart stain-resistance to the substrates, and methods for preparing the same.
  • the treated polyamide textile substrates possess stain- resistance but do not suffer from yellowing to the extent that some previously known materials have.
  • the sulfonated polymers suitable for the purposes of this invention contain between about 0.1 and 10 polymer units derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from a sulfonated ethylenically unsaturated aromatic monomer.
  • Polymers containing about 0.9 polymer unit derived from one or more ethylenically unsaturated aromatic monomers per polymer unit derived from a sulfonated ethylenically unsaturated aromatic monomer are most effective in imparting stain-resistance to textile substrates.
  • aromatic monomers can be used for the purposes of this invention, e.g., styrene, alpha- ethylstyrene, 4-methylstyrene, 4-methoxy- styrene, vinylbenzene-4-carboxylic acid, and the like, and mixtures of the same, with styrene being preferred.
  • styrene alpha- ethylstyrene
  • 4-methylstyrene 4-methoxy- styrene
  • vinylbenzene-4-carboxylic acid and the like
  • styrene is preferred.
  • sulfonated monomers which can be used for the purpose of this invention.
  • the sulfonated monomers usually are water-souble; for example, the alkali metal and ammonium salts.
  • Particular examples include sodium p-styrene sulfonate, sodium vinyl p-toluene sulfonate, ammonium p-styrene sulfonate.
  • the foregoing ethylenically unsaturated aro atics can be sulfonated at the para and/or ortho positions and be used for the purposes of this invention.
  • An acrylic monomer can be added to either of the above-described two classes of monomers to give a terpolymer having useful dying properties, e.g. methacrylic acid, acrylic acid, itaconic acid, their lower alkyl esters and the like.
  • the sulfonated polymers of this invention should have number average molecular weights in the range between about 500 and 7000, preferably between about 500 and 5000, most preferably 900 to 3000. They are readily soluble, even at high concentrations, in water at 25-90*C and a pH of 2 or above; increasing dilution is needed at pHs below 2. They are also soluble in lower alcohols, such as methanol, ethylene glycol, propylene glycol, mixtures of ethylene and hexylene glycols, and are somewhat soluble in acetic acid.
  • the polymers suitable for the purposes of this invention can be conveniently prepared by a variety of free radical-initiated polymerization reactions using methods known to the art for limiting the molecular weight of the products.
  • One example is the benzoyl peroxide-initiated polymerization of styrene and sodium styrene sulfonate.
  • Molecular weight control can be accomplished by the use of large quantities of benzoyl peroxide, in the order of 10%, based on weight of monomers.
  • chain transfer agents such as dodecyl mercaptan may be used with lesser amounts of benzoyl peroxide.
  • Another preparative method is the solution polymerization of the monomers using Vazo*67 2,2'-azobis(2-methylbutyro- nitrile) as an initiator and mercaptosuccinic acid as a chain transfer agent.
  • Vazo*67 2,2'-azobis(2-methylbutyro- nitrile) as an initiator
  • mercaptosuccinic acid as a chain transfer agent.
  • a convenient range of monomers plus initiator concentrations in the solvent is about 20 to 35%.
  • the sulfonated aromatic polymers of this invention not only cover the surface of the treated substrate, but particularly in the case of a fibrous substrate, the polymer at least in part permeates the fiber.
  • the polymers can be used as such in treating polyamide textile substrates. They can be applied to dyed or undyed polyamide textile substrates.
  • sulfonated polymers can be applied to textile substrates in a variety of ways, e.g. during conventional beck and continuous dyeing procedures.
  • the quantities of the polymers of this invention which are applied to the textile substrate are amounts effective in imparting stain-resistance to the substrate.
  • the amounts can be varied widely; in general, one can use between 0.5 and 5% by weight of them based on the weight of the textile substrate, usually 2% by weight or less.
  • the polymers can be applied, as is common in the art, at pHs. ranging between 4 and 5. However, more effective exhaust deposition can be obtained at a pH as low as 2.
  • pH of 2 is used, the preferred level of application to the textile substrate is about 1.2% by weight of polymer, based on the weight of the textile substrate. More effective stainblocking is obtained if the sulfonated polymers are applied to the textile substrate at higher temperatures.
  • stain-resistance can be obtained at room temperature, or even at the temperature of cold tap water (10-15'C), if higher levels of stainblockers are employed.
  • the sulfonated polymers of this invention can also be applied in-place to polyamide carpeting which has already been installed in a dwelling place, office or other locale. They can be applied as a simple aqueous preparation or in the form of aqueous shampoo preparation, with or without one or more polyfluoro-organic oil-, water-, and/or soil-repellent materials. They may be applied at the levels described above, at temperatures described, and at a pH between about 1 and 12, preferably between about 2 and 9.
  • Example 1 The following Examples are illustrative of the invention. Unless otherwise indicated, all parts and percentages are by weight and temperatures in the Examples and Tests are in degrees Celsius. In the examples that follow, stain-resistance and yellowing were measured by the techniques described below. Number average molecular weights are usually determined by vapor-phase osmometry. However, that method cannot be applied to compositions of this invention because of the presence of glycols and other interfering lower molecular weight substances. In Example 1, number average molecular weights were approximated by gel permeation chromatography. On the other hand, gel permeation chromatography determinations are difficult to run; consequently, no molecular weight determinations were made for the compositions of Examples 2-7.
  • stain-resists to carpeting is carried out in a Launder-O-Meter automated dyeing machine.
  • One carpet piece is contained in each of several (up to twenty) stainless steel, screw-cap canisters.
  • the canisters are held in a rack that rotates in a water bath whose temperature is automatically controlled for rate of heating, time at temperature and cooling.
  • For a typical application bath one uses a 20 to 1 liquor to goods ratio with 2.5 weight % of the stain-resistant composition.
  • the stain-r ⁇ i ⁇ tant compositions can be applied at pH 2 or pH 5. At pH 2, an excess of sulfamic acid is used.
  • an excess of ammonium sulfate is used, as well as 3g/L of magnesium sulfate and lg/L of an alkyl aryl sulfonate (Alkanol*ND) or a suitable leveling agent.
  • a solution of the stain-resist composition is added to the Launder-o-Meter canister.
  • the carpet sample to be treated is then placed in the canister, tufted side out, the size of the carpet sample,, relative to the size of the canister, being such that no portion of the sample touches another portion of the sample.
  • the canisters are placed in the Launder-O-Meter and the water bath temperature is held at 110"F for 5 minutes.
  • the temperature of the water bath is then raised to the desired temperature for application of the stain-resist composition.
  • the temperature of the water bath is raised to 170*F +/- 5*F, and for application at pH 5, the temperature of the water bath is raised to 200'F +/- 5*F.
  • the bath water reaches the desired temperature, it is held there for 20 in. and then cooled to 100'F.
  • the treated carpet sample is removed from the canister and rinsed by squeezing in deionized water at room temperature. Three successive rinses in fresh deionized water are given, each rinse being at 40 volumes of water per volume of sample.
  • the rinsed carpet sample is centrifuged to remove excess liquid and dried at 200'F. in a forced draft oven for 30 minutes. The dry carpet sample can then be tested by use of the tests described below.
  • the stain test is used to measure the extent to which carpeting is stained by a commercial beverage composition which contains. FD&C Red Dye No. 40 (an acid dye) .
  • the staining liquid if sold commercially as a liquid, is used as is.
  • the commercial product is in the form of a solid.
  • the beverage preparation in dry, solid form, is dissolved in deionized water so as to provide 0.1 g of FD&C Red Dye No. 40 per liter of water.
  • Sufficient wetting agent Du Pont Merpol ⁇ SE liquid nonionic ethylene oxide condensate
  • test sample is DuPont type 1150 Nylon 6,6 (white); Superba heatset, mock dyed level loop carpet, 3/8 inch pile height, 30 ounces per yard, 1/10 inch gauge, 10 stitches per inch, woven polypropylene primary backing.
  • the test sample is wetted completely with water, and excess water is removed by centrifuging.
  • the damp sample is placed tufted face down in a pan and covered with ten times its face weight of stain fluid. Entrained air is expelled from the sample by squeezing or pressing. The sample is turned over and again the air is expelled. The sample is then returned to a face down position, and the pan is covered for storage for test period of 30 minutes.
  • the stored stain sample is rinsed in running cool water until no more stain is visually detectable in the rinse water.
  • the rinsed sample is extracted in a centrifuge and dried at 200 degrees F. Staining is evaluated with the Minolta Chroma Meter tristimulus color analyzer in the L*A*B Difference Mode with the target sample set for the unstained carpet.
  • the "a" value is a measure of redness, with a value of 43 equal to that obtained on an untreated carpet.
  • the stain-resistance of the resulting carpet sample is visually determined by the amount of color left in the stained area of the carpet sample according to the following scale:
  • UV YELLOWING TEST The light-fastness of carpet samples treated with a stainblocker is determined by exposing the treated samples to UV light for 20 Hours.
  • a sample piece of carpet that has been treated with a stain-blocker is placed in a box containing its hinged top a standard fluorescent fixture fitted with two forty watt lamps. Centered under the pair of lamps in the bottom of the box is a sliding tray having a 3 inch x 40 inch recess for holding carpet, specimens. The depth of the recess is such that the distance from the carpet face to the plane defined by the lamp surfaces is 1 inch.
  • the current to the lamp is controlled by a timer so that a twenty-hour exposure can be obtained automatically.
  • the reflectance of CIE White Light Source C from the carpet is compared with the reflectance from an unexposed sample and the CIELAB delta "to” noted.
  • Delta “to” is a measure of the yellow component of white light.
  • a Minolta Chroma Meter model CR-110 reflectance meter is used to make the measurements and to calculate delta "to” automatically from stored data on the unexposed sample. The value of "to” is reported as the measure of yellowing with increasing positive values of "to” corresponding to increased degrees of yellowing.
  • the Minolta Chroma Meter is used in the Hunter L*a*b color-deviation measuring mode [Richard Hunter, "Photoelectric Colorimetry with Three Filters," J. Opt. Soc.
  • the instrument measures the color differences between a "target" color, whose tristimulus color values have been entered into the microprocessor as a reference, and the sample color presented to the measuring head of the instrument.
  • a target color whose tristimulus color values have been entered into the microprocessor as a reference
  • the "target" color entered is that of the carpet before yellowing or staining.
  • the color reflectance of the yellowed or stained carpet is then measured with the instrument and reported as: *E, the total color difference, *L, the lightness value,
  • Ethylene glycol, 800 g was added to a 2 liter flask, heated to 70 ⁇ C with a nitrogen sparge and held at that temperature for 1 hour. It was cooled to 25 ⁇ C and sodium styrene sulfonate, 150 g (0.73 ol) , was added with agitation in about 5 minutes. Agitation was continued until a solution was obtained, about 45 minutes. A solution of styrene, 50 g (0.48 mol), in hexylene glycol, 200 g, was added over 15 minutes, and the reaction mixture was allowed to warm to 65-70". Benzoyl peroxide, 40.0 g (0.165 mol) , was added in 3 portions, each portion 1/2 hour apart.
  • the temperature was allowed to rise to about 85" during these additions.
  • the mass was maintained at 80" for 8 hours.
  • Example 1 was repeated with 91.8 g (0.44 mol), of sodium styrene sulfonate and 108.6 (1.04 mol), of styrene. The reaction proceeded in fashion similar to that of Example 1.
  • Ethylene glycol 98.0 g
  • a solution of styrene 98.0 g
  • Ethylene glycol, 73 g was heated to 70* with a nitrogen sparge and held at that temperature for 1 hour with agitation. It was cooled to 25* and sodium styrene sulfonate, 40.6 g (0.2 mol), and dodecyl mercaptan, 3.6 g (0.016 mol), were added. A solution of styrene, 31.5 (0.3 mol), in hexylene glycol, 73 g, was added over 5 minutes and the reaction mixture was allowed to warm to 65-70'.
  • Nylon film treated with a solution of this product showed no staining with FD&C Red Dye No. 40.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Substrats textiles en polyamide résistant aux tâches traités à l'aide de compositions comprenant des polymères aromatiques sulfonés contenant entre environ 0,1 et 10 unités polymères dérivées de 1 ou de plusieurs monomères aromatiques à insaturation d'éthylène par unité polymère dérivée d'un monomère aromatique sulfoné à insaturation d'éthylène, et leurs procédés de préparation. Les substrats textiles en polyamide traités possèdent une résistance aux tâches et ils sont moins sujets au jaunissement que certaines matières connues de l'art antérieur.
PCT/US1991/007351 1990-10-18 1991-10-15 Polymeres aromatiques sulfones resistant aux taches WO1992007131A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59928490A 1990-10-18 1990-10-18
US599,284 1990-10-18

Publications (1)

Publication Number Publication Date
WO1992007131A1 true WO1992007131A1 (fr) 1992-04-30

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Application Number Title Priority Date Filing Date
PCT/US1991/007351 WO1992007131A1 (fr) 1990-10-18 1991-10-15 Polymeres aromatiques sulfones resistant aux taches

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AU (1) AU9034191A (fr)
WO (1) WO1992007131A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6485786B2 (en) * 2000-04-26 2002-11-26 Rohm And Haas Company Aqueous stain-blocking coating composition
US6736857B2 (en) 2001-05-25 2004-05-18 3M Innovative Properties Company Method for imparting soil and stain resistance to carpet
US7320956B2 (en) 2004-04-01 2008-01-22 3M Innovative Properties Company Aqueous cleaning/treatment composition for fibrous substrates
JP2016204646A (ja) * 2015-04-15 2016-12-08 東ソー有機化学株式会社 水溶性共重合体及びその製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2700001A (en) * 1951-02-28 1955-01-18 Monsanto Chemicals Process of providing textile material with an antistatic finish
FR1443521A (fr) * 1964-07-01 1966-06-24 Hoechst Ag Agents et procédé d'apprêtage de matières fibreuses
EP0329899A2 (fr) * 1987-12-21 1989-08-30 E.I. Du Pont De Nemours And Company Polymères aromatique/anhydride maléique résistant aux salissures
EP0333500A2 (fr) * 1988-03-17 1989-09-20 Ciba Specialty Chemicals Water Treatments Limited Produits textiles en polyamide résistants aux taches
EP0456390A2 (fr) * 1990-05-01 1991-11-13 Ciba Specialty Chemicals Water Treatments Limited Copolymères avec propriétés antitaches

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2700001A (en) * 1951-02-28 1955-01-18 Monsanto Chemicals Process of providing textile material with an antistatic finish
FR1443521A (fr) * 1964-07-01 1966-06-24 Hoechst Ag Agents et procédé d'apprêtage de matières fibreuses
EP0329899A2 (fr) * 1987-12-21 1989-08-30 E.I. Du Pont De Nemours And Company Polymères aromatique/anhydride maléique résistant aux salissures
EP0333500A2 (fr) * 1988-03-17 1989-09-20 Ciba Specialty Chemicals Water Treatments Limited Produits textiles en polyamide résistants aux taches
EP0456390A2 (fr) * 1990-05-01 1991-11-13 Ciba Specialty Chemicals Water Treatments Limited Copolymères avec propriétés antitaches

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6485786B2 (en) * 2000-04-26 2002-11-26 Rohm And Haas Company Aqueous stain-blocking coating composition
US6736857B2 (en) 2001-05-25 2004-05-18 3M Innovative Properties Company Method for imparting soil and stain resistance to carpet
US7320956B2 (en) 2004-04-01 2008-01-22 3M Innovative Properties Company Aqueous cleaning/treatment composition for fibrous substrates
JP2016204646A (ja) * 2015-04-15 2016-12-08 東ソー有機化学株式会社 水溶性共重合体及びその製造方法

Also Published As

Publication number Publication date
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