WO2003027157A1 - Latex ameliore pour envers de tapis - Google Patents

Latex ameliore pour envers de tapis Download PDF

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Publication number
WO2003027157A1
WO2003027157A1 PCT/US2002/029740 US0229740W WO03027157A1 WO 2003027157 A1 WO2003027157 A1 WO 2003027157A1 US 0229740 W US0229740 W US 0229740W WO 03027157 A1 WO03027157 A1 WO 03027157A1
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WO
WIPO (PCT)
Prior art keywords
percent
latex
caφet
weight
carboxylic acid
Prior art date
Application number
PCT/US2002/029740
Other languages
English (en)
Inventor
Roger W. Bergman
Christine M. Lussier
David A. Spears
Original Assignee
Dow Global Technologies Inc.
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 Dow Global Technologies Inc. filed Critical Dow Global Technologies Inc.
Publication of WO2003027157A1 publication Critical patent/WO2003027157A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C08L13/02—Latex
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/08—Isoprene

Definitions

  • the present invention relates to latex compositions that are especially useful as binders for carpet backing.
  • carboxylated styrene butadiene latexes in ca ⁇ et backing compounds is well-known.
  • U.S. Patents 3,177,173 and 5,284,908 both disclose the preparation of latexes from broad ranges of aliphatic conjugated diene monomers and comonomers.
  • researchers are constantly striving to improve the balance of properties of the final product.
  • One challenge the researchers face is the tendency for properties to trade-off against each other. It is typical that increasing a given property will result in a decrease in at least one other property.
  • the present invention provides such a latex composition that comprises, in polymerized form, the following monomers:
  • the ca ⁇ et of the invention is a ca ⁇ et prepared from fibers, a backsizing compound, and optionally a backing, and wherein the compound comprises a latex as described in the preceding sentence.
  • the latex compositions of the present invention provide blister resistance, ca ⁇ et flexibility, ca ⁇ et durability, and a desirable ease of compounding with inorganic fillers.
  • the compositions of the invention also provide su ⁇ risingly improved dry and wet tuft bind and dry and wet delamination strength. Furthermore, they provide an unexpectedly good combination of flexibility and moisture barrier properties.
  • the latex polymer of the invention is a copolymer containing polymerized isoprene, as described above, that can provide an excellent combination of strength, flexibility, water resistance, blister resistance, and durability in ca ⁇ et backsizing applications.
  • the copolymer preferably contains from 23 to 68 weight percent of polymerized isoprene, based on the weight of monomers employed, and more preferably contains from 38 to 52 percent isoprene.
  • the latex of the invention is prepared from monomers such that the resulting copolymer (te ⁇ olymer etc.) with isoprene preferably has a glass transition temperature between — 30°C and 40°C and a gel content of the polymer in toluene between 5 and 75 percent.
  • one of the monomers is a monoethylenically unsaturated monomer that is not a carboxylic acid.
  • Examples of monoethylenically unsaturated non- carboxylic acid comonomers useful in polymerization of the latex polymer include: vinyl aromatic monomers, such as styrene, and substituted styrenes such as alpha methyl styrene, p-methyl styrene, vinyl toluene, ethylstyrene, tert-butyl styrene, monochlorostyrene, dichlorostyrene, vinyl benzyl chloride, fluorostyrene, and alkoxystyrenes such as paramethoxy styrene; acrylates and methacrylates, including methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, and other C 1 -C 12 alkyl or hydroxyalkyl acrylates and methacrylates;
  • Non-carboxylic acid monomers that can be employed in the manufacture of the latex composition include monoethylenically unsaturated substituted aliphatic hydrocarbons such as vinyl chloride and vinylidene chloride; and aliphatic vinyl esters such as vinyl formate, vinyl propionate and vinyl butyrate. Mixtures of non-carboxylic acid monomers can be employed. Styrene is the preferred non-carboxylic acid comonomer.
  • the non-carboxylic acid monomer is employed in an amount ranging from 30 to 75 weight percent, based on the total weight of monomers charged.
  • the total weight of non-carboxylic acid monomer present in the polymer is preferably from 40 percent to 65 percent; and more preferably is from 46 percent to 60 percent, based on the total weight of monomers charged.
  • Suitable carboxylic acid containing monomers include mono- or dicarboxylic acid monomers and derivatives thereof.
  • suitable carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and maleic acid, as well as the half esters of unsaturated dicarboxylic acids, including mixtures thereof.
  • Half esters of itaconic acid having d to Cj 2 alkyl groups, such as monomethyl itaconate, can also be used.
  • Copolymers of the unsaturated mono- or dicarboxylic acid monomers and of the half ester of the unsaturated dicarboxylic acid can also be used.
  • the preferred acid monomer is a mixture of acrylic acid and itaconic acid.
  • the preferred total weight of acid functional monomer present in the polymer is preferably from 0.5 percent to 5 percent; and more preferably is from 1 percent to 3 percent, based on the total weight of monomers charged.
  • the polymer can include crosslinking agents and other additives to improve various physical and mechanical properties of the polymer, the selection of which will be readily apparent to one skilled in the art.
  • Exemplary crosslinking agents include vinylic compounds (for example, divinyl benzene); allyllic compounds (for example, allyl methacrylate, diallyl maleate); and multifunctional acrylates (for example, di, tri and tetra (meth)acrylates).
  • the polymer molecular weight can be controlled by the addition of a suitable chain transfer agent as is known in the art.
  • the optionally employed chain transfer agent can be employed in an amount ranging from 0 to 1 weight parts per 100 parts monomer. Preferably, from 0.2 to 0.6 weight parts of chain transfer agent are employed per 100 weight parts of monomer.
  • Suitable chain transfer agents include, for example, alkyl mercaptans such as octyl mercaptan and decyl mercaptan, esters of mercaptoacetic acid, such as ethyl ester of mercaptoacetic acid and 2-ethylhexyl ester of mercaptoacetic acid, and esters of mercaptopropionic acid, such as isooctyl ester of mercaptopropionic acid, and compounds containing multiple mercapto functional groups, such as trimethylolpropane trimercaptopropionate.
  • the preferred chain transfer agent is t-dodecylmercaptan.
  • the chain transfer agent advantageously may further improve the water and blister resistance of the final ca ⁇ et without significant loss of strength.
  • at least one initiator or catalyst is used at a concentration sufficient to initiate or catalyze the polymerization reaction, as is well known in the art.
  • concentration sufficient to initiate or catalyze the polymerization reaction, as is well known in the art.
  • concentration will depend upon the specific monomer mixture undergoing reaction and the specific initiator employed, as is well known to those skilled in the art, and is frequently from 0.01 to 3 weight percent based on the weight of monomers charged; advantageously is from 0.05 to 2 weight percent, preferably is from 0.2 percent to 2 percent, and more preferably, ranges from 0.5 percent to 1.5 percent.
  • initiators include, for example: materials such as persulfates, such as ammonium persulfate, potassium persulfate, and sodium persulfate; organic peroxides, such as hydrogen peroxide, cumene hydroperoxide, dicumylperoxide, diisopropylbenzene hydroperoxide, and tert butyl hydroperoxide; peresters, and peracetic acid; and azo compounds such as azobis(isobutyronitrile); as well as any of the other known initiators.
  • Preferred initiators are persulfate initiators such as, for example, ammonium persulfate and sodium persulfate.
  • redox catalyst systems such as sodium persulfate-sodium formaldehyde sulfoxylate, cumene hydroperoxide-sodium metabisulfite, hydrogen peroxide-ascorbic acid, and the other known redox systems.
  • reductants include sodium bisulfite, erythorbic acid, and sodium thiosulfate. When these reductants are used it may be possible to reduce the polymerization temperature to 50°C or lower.
  • the polymerizable feed compositions can also contain any of the other known additives conventionally used in emulsion polymerization processes in the usual known quantities, such as crosslinkers, surfactants, dispersion aids, emulsifiers, photosensitizers, colorants, bactericides, fungicides, etc.
  • Emulsion polymerization techniques are well known.
  • the latex composition of the invention can be prepared by any suitable emulsion polymerization process, including batch, semi-continuous, and continuous processes. The components employed in the process are added according to techniques well-known in the art.
  • the polymerization temperature is from 70 to 110°C, and the monomer feed time from 1 to 12 hours.
  • a stripping step may be carried out to remove unreacted monomers and other components which may be present.
  • Any suitable and known technique may be used to carry out the stripping step including the use of steam (that is, steam stripping) alone or in combination with a redox system (that is, chemical stripping).
  • the latex preferably has a pH of from 5 to 9.
  • the weight average particle diameter of the polymer particles in the latex preferably is from 100 to 200 nanometers as measured by light scattering techniques.
  • the latex has a bimodal particle size distribution, with the average small particle size being from 35 to 75 nm in diameter and the average large particle size being from 100 to 300 nm.
  • the large particles make up from 65 to 95 volume percent of the total polymer particles.
  • the solids content of the latex can vary considerably and can be adjusted to desired levels using techniques well known in the art, but preferably is at least 54 weight percent solids, and more preferably is at least 56 weight percent solids.
  • High solids can be obtained by emulsion polymerizing the monomer charge to a specified conversion, then introducing a unimodal seed latex and continuing the polymerization.
  • the high solids advantageously can reduce drying time and improve blister resistance.
  • the latex of the invention is particularly useful in commercial ca ⁇ et backsizing applications.
  • Ca ⁇ et backsizing formulations are well known to those skilled in the art. Some typical ca ⁇ et backsizing formulations are described herein.
  • the backsizing needs to provide high tuft bind, high secondary backing adhesion, and retention of strength on exposure to moisture while being flexible for ease of ca ⁇ et installation and ca ⁇ et pattern matching.
  • the backsizing must be able to be applied at high coating weights without blistering during hot forced air drying.
  • the polymer described here provides these properties. Additionally, it is sometimes useful for ca ⁇ et backing to have moisture barrier properties.
  • the polymer described here provides improvement in moisture barrier properties compared to commonly used styrene-butadiene latex. Further improvements in moisture barrier properties may be obtained by the addition of hydrophobic materials such as waxes and salts of hydrophobic acids to the backsizing compound.
  • conventional surfactants can also be employed in the preparation of the ca ⁇ et backing compound formulation in an amount such that the resulting ca ⁇ et backing composition has a surfactant content preferably of less than 3.0 weight percent.
  • Any of the anionic or nonionic surfactants may be employed for the pu ⁇ oses of the invention.
  • Polymerizable surfactants that can be inco ⁇ orated into the polymer also can be used.
  • Nonionic surfactants can include suitable alkyl esters, alkyl phenyl ethers, and alkyl ethers of polyethylene glycol.
  • nonionic surfactants are selected from the family of alkylphenoxypoly (ethyleneoxy) ethanols where the alkyl group typically varies from C 7 -C ⁇ 8 and the ethylene oxide units vary from 4-100 moles.
  • Various preferred surfactants in this class include the ethoxylated octyl and nonyl phenols, and in particular ethoxylated nonyl phenols with a hydrophobic/lipophilic balance (HLB) of 15-19.
  • Anionic surfactants are preferred for the pu ⁇ oses of the invention and can be selected, for example, from the broad class of sulfonates, sulfates, ethersulfates, sulfosuccinates, and diphenyloxide disulfonates, and are readily apparent to anyone skilled in the art.
  • the anionic surfactants can include a salt of an alcohol sulfate (such as sodium lauryl sulfate); a salt of an alkylbenzenesulfonic acid (such as sodium dodecylbenzenesulfonate); and a sulfonic acid salt of an aliphatic carboxylic acid ester (such as sodium dioctylsulfosuccinate).
  • an alcohol sulfate such as sodium lauryl sulfate
  • an alkylbenzenesulfonic acid such as sodium dodecylbenzenesulfonate
  • a sulfonic acid salt of an aliphatic carboxylic acid ester such as sodium dioctylsulfosuccinate.
  • DOWFAX 2A1 is available from The Dow Chemical Company.
  • additives that can be added to the latex and/or the backing compound include other natural and synthetic binders, fixing agents, wetting agents, plasticizers (such as diisodecyl phthalate), softeners, foam-inhibiting agents, froth aids, other crosslinking agents (such as melamine formaldehyde resin), pH adjusting agents (such as ammonium hydroxide) flame retardants, catalysts (such as diammonium phosphate or ammonium sulfate), dispersing agents, chelating agents, etc., the selection of which will be readily apparent to one skilled in the art.
  • the pile ca ⁇ et comprises a primary backing and pile yarns extending from the front of the primary backing to form pile tufts.
  • the pile yarns have portions extending through the primary backing to the rear of the primary backing.
  • a back coating is applied to the rear of the primary backing to secure the pile yarns to the primary backing.
  • One or more back coatings of the same or different compositions referred to as "backsizing compounds" in the ca ⁇ et industry, may be applied to the pile yarn.
  • a secondary backing may be applied onto the rear of the back coated pile yarn. In this case the back coating secures this secondary backing to the pile yarn.
  • a coating may be applied to the secondary backing before it is brought into contact with the back coated pile yarn.
  • the coating may be the same or a different coating compound than the back coating compound.
  • This back coated pile yarn is then dried at elevated temperature.
  • the backing coating may be applied by any of a number of application techniques known in the industry, including roll or direct coating.
  • the ca ⁇ et has a dry bind and a wet tuft bind each greater than 15 pounds, a dry and wet delamination strength each greater than 6 pounds per inch, and a dry coating weight of about 36 ounces or less of backsizing compound per square yard
  • Latex was prepared by emulsion polymerizing a monomer composition comprising 51.75 weight parts styrene, based on 100 parts monomer, 46 weight parts diene, 1.5 weight parts acrylic acid, and 0.75 weight part itaconic acid in the presence of 1 weight part of DOWFAX 2A1 brand surfactant (available from The Dow Chemical Company), 0.4 parts of t-dodecyl mercaptan chain transfer agent, 0.25 part of seed latex (approximately 25 nanometers in diameter) and 1.5 parts of sodium persulfate.
  • the polymerization temperature was 95°C.
  • the monomers were fed over a period of 255 minutes.
  • Rewet Retention (percent) (Rewet Tuftbind / Tuftbind) * 100
  • Infra-Red Blister Test Ca ⁇ et samples applied with froth and non-froth compounds are subjected to radiant heat from a Radiant Heat Inc. infrared oven. A 9 inch X 9 inch coated ca ⁇ et sample is attached to a radiant panel board and placed 7.5 inches down from the source (third rack). The oven is set to operate at maximum intensity that produces a surface temperature of 400°F. The sample is left in the oven for 20 seconds if frothed and 30 seconds if non- frothed. The sample is then evaluated and rated on the following scale:
  • Ca ⁇ et samples applied with froth and non-froth compounds are dried in a Despatch forced air convection oven set at a temperature of 400°F until they reach a temperature of 265°F. The sample is then evaluated on the same scale mentioned above.
  • a ca ⁇ et sample with a known area is cut from a ca ⁇ et.
  • the greige weight (yam & primary backing) and secondary backing weight are subtracted from the sample total weight.
  • the pu ⁇ ose of the punch hand test is to quantify the flexing force required to punch the ca ⁇ et into a simulated comer as is done during ca ⁇ et installation. The higher the force required to flex, the stiffer is the ca ⁇ et and more difficult a task for the installer.
  • a tensile tester (such as an Instron 4501) is operated in the compression mode with a lkN load cell.
  • a compression foot (2.25 inch outside diameter) solid cylinder is attached to the load cell.
  • a hollow cylinder (5.5 inch inside diameter is attached to the base.
  • a 9 inch by 9 inch piece of ca ⁇ et pre-equilibrated at the test conditions for at least 2 hours) is placed between the compression foot and the hollow base.
  • the test conditions are 50 percent ( ⁇ 5 percent) relative humidity and 72°F ( ⁇ 2°C) temperature.
  • the gauge length (gap) between the foot and the top of the ca ⁇ et is set so that it just touches (0.05 to 0.10 pounds of deflection).
  • the instron crosshead is started down at 12 inches per minute until a deflection of 0.65 inches is reached then returned to its starting position.
  • the deflection of the ca ⁇ et is repeated while alternating the ca ⁇ et between face up and face down (a cycle).
  • a total of four (4) measurements that is, two cycles-up, down, up, down) are made.
  • the hand is expressed as the average of the force at 0.5 inches of deflection.
  • the British Spill test is run to determine moisture penetration of a methylene blue dye (diluted) through a ca ⁇ et product.
  • a 12"X12" square of ca ⁇ et is placed flat with the ca ⁇ et yam face up.
  • a funnel having a 10mm diameter spout is mounted 1 meter above the ca ⁇ et. While closing off the funnel outlet, for example with one finger, pour 100 ml of dilute blue dye solution in the funnel. After the funnel is filled, quickly open the funnel outlet, for example quickly remove the finger. After 24 hrs. check for dye transference through the ca ⁇ et. No blue dye transferred through the ca ⁇ et means the British Spill test is passed.
  • the caster wheel assembly was run over the ca ⁇ et for 25,000 revolutions.
  • a pass is defined as maintaining ca ⁇ et physical properties without cracking of the ca ⁇ et backing.
  • the properties of interest were determined for two control styrene-butadiene latexes (Latexes 1 and 2) and a styrene-isoprene latex of the invention (3).
  • the latexes were prepared via the Latex Preparation Method, with exceptions as shown in the following table.
  • a 200 load formulation (as shown above) was prepared using each of these latexes. Pile yam was back coated as described above to a dry coat weight of 34 ounces per square yard
  • the isoprene-containing latexes of the invention provide significantly better dry tuft bind, rewet tuft bind, dry delamination strength, rewet delamination strength, flexibility, durability, and resistance to blister compared to comparable butadiene-containing latexes.
  • the latexes of the invention can be employed to prepare ca ⁇ et capable of maintaining a water barrier even after the ca ⁇ et is subjected to flexure, such as flexure caused by walking on the ca ⁇ et or as measured by the durability test described above.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un latex utile dans la préparation d'un tapis, qui possède un meilleur équilibre entre résistance, flexibilité, résistance à l'eau, barrière contre l'humidité, et résistance au cloquage.
PCT/US2002/029740 2001-09-24 2002-09-20 Latex ameliore pour envers de tapis WO2003027157A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US32474601P 2001-09-24 2001-09-24
US60/324,746 2001-09-24

Publications (1)

Publication Number Publication Date
WO2003027157A1 true WO2003027157A1 (fr) 2003-04-03

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008054613A1 (fr) * 2006-10-30 2008-05-08 Dow Global Technologies Inc. Procédé pour préparer une pelouse artificielle
EP1967545A1 (fr) * 2007-03-09 2008-09-10 Rohm and Haas France SAS Latex en polymère cationique
EP2289991A1 (fr) * 2009-08-26 2011-03-02 University Of Waterloo Particules nanométriques polymères de latex à base de diène
US20110097535A1 (en) * 2008-05-06 2011-04-28 Bergman Roger W Frothable aqueous composition
US20120152459A1 (en) * 2010-12-16 2012-06-21 Basf Se Styrene-Acrylic-Based Binders and Methods of Preparing and Using Same
WO2020097507A1 (fr) * 2018-11-09 2020-05-14 Basf Se Liant de tapis à haute résistance au délaminage

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2131428A5 (fr) * 1971-03-27 1972-11-10 Huels Chemische Werke Ag
US5703157A (en) * 1992-01-10 1997-12-30 Sumitomo Dow Limited Process of preparing copolymer latex and use thereof
US6034005A (en) * 1996-04-18 2000-03-07 Omnova Solutions Inc. Nonwoven fabric of non-cellulose fibers and a method of manufacture

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2131428A5 (fr) * 1971-03-27 1972-11-10 Huels Chemische Werke Ag
US5703157A (en) * 1992-01-10 1997-12-30 Sumitomo Dow Limited Process of preparing copolymer latex and use thereof
US6034005A (en) * 1996-04-18 2000-03-07 Omnova Solutions Inc. Nonwoven fabric of non-cellulose fibers and a method of manufacture

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008054613A1 (fr) * 2006-10-30 2008-05-08 Dow Global Technologies Inc. Procédé pour préparer une pelouse artificielle
US8192504B2 (en) 2007-03-09 2012-06-05 Rohm And Haas Company Cationic polymer latex
EP1967546A1 (fr) * 2007-03-09 2008-09-10 Rohm and Haas Company Latex en polymère cationique
KR100958681B1 (ko) 2007-03-09 2010-05-20 롬 앤드 하아스 컴패니 양이온성 중합체 라텍스
EP1967545A1 (fr) * 2007-03-09 2008-09-10 Rohm and Haas France SAS Latex en polymère cationique
US20110097535A1 (en) * 2008-05-06 2011-04-28 Bergman Roger W Frothable aqueous composition
US8709574B2 (en) * 2008-05-06 2014-04-29 Dow Global Technologies, Llc Frothable aqueous composition for use in a carpet backing composition
EP2289991A1 (fr) * 2009-08-26 2011-03-02 University Of Waterloo Particules nanométriques polymères de latex à base de diène
EP2470577A1 (fr) * 2009-08-26 2012-07-04 University Of Waterloo Particules nanométriques de latex polymère à base de diènes
EP2470577A4 (fr) * 2009-08-26 2013-04-17 Univ Waterloo Particules nanométriques de latex polymère à base de diènes
US20120152459A1 (en) * 2010-12-16 2012-06-21 Basf Se Styrene-Acrylic-Based Binders and Methods of Preparing and Using Same
US9309351B2 (en) * 2010-12-16 2016-04-12 Basf Se Styrene-acrylic-based binders and methods of preparing and using same
WO2020097507A1 (fr) * 2018-11-09 2020-05-14 Basf Se Liant de tapis à haute résistance au délaminage

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