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WO2025090189A1 - Émulsion de copolymère de silicone-(méth)acrylate et sa préparation et utilisation de l'émulsion pour oléofuger des textiles - Google Patents

Émulsion de copolymère de silicone-(méth)acrylate et sa préparation et utilisation de l'émulsion pour oléofuger des textiles Download PDF

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Publication number
WO2025090189A1
WO2025090189A1 PCT/US2024/045245 US2024045245W WO2025090189A1 WO 2025090189 A1 WO2025090189 A1 WO 2025090189A1 US 2024045245 W US2024045245 W US 2024045245W WO 2025090189 A1 WO2025090189 A1 WO 2025090189A1
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WO
WIPO (PCT)
Prior art keywords
group
meth
silicone
independently selected
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/045245
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English (en)
Inventor
Anirudha BANERJEE
Devin FERGUSON
Matthew JELETIC
Douglas HASSO
Brian Macdonald
Jodi Mecca
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Dow Silicones Corp
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Dow Silicones Corp
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Publication date
Application filed by Dow Silicones Corp filed Critical Dow Silicones Corp
Priority to CN202480023867.0A priority Critical patent/CN120981626A/zh
Priority to PCT/US2024/052892 priority patent/WO2025090820A1/fr
Priority to PCT/US2024/052894 priority patent/WO2025090822A1/fr
Priority to PCT/US2024/052893 priority patent/WO2025090821A1/fr
Publication of WO2025090189A1 publication Critical patent/WO2025090189A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • D06M15/263—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
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • 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
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • 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
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • an emulsion formulation suitable for treating a textile and methods for preparation and use thereof are provided. More specifically, the emulsion formulation includes a silicone - (meth)acrylate copolymer. The emulsion formulation is useful for treating textiles to impart durable oil repellency thereto.
  • Fluorinated materials have dominated the water and oil repellent textile coating market for many years.
  • regulatory and customer pressures are contributing to an industry need for non-fluorocarbon-based textile treatments.
  • a silicone - (meth)acrylate copolymer comprises unit formula: each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D 2 is an independently selected divalent hydrocarbon group of 2 to 12 carbon atoms; and each R 2 is independently selected from the group consisting of H and methyl; each R 3 is a group of formula OSi(R 4 )3; where each R 4 is independently selected from the group consisting of R and DSi(R 5 )3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, a (poly) alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 is independently selected from the group consisting of R and DSi(R 6 )3; where each R 6 is independently selected from the group consisting of R and DSiRp with the proviso that R 4 , R 5 , and
  • An emulsion formulation suitable for treating a textile comprises the silicone - (meth)acrylate copolymer, a surfactant, water, and a blocked isocyanate. Methods for preparation and use of the silicone - (meth) acrylate copolymer and the emulsion formulation are also provided.
  • silicone - (meth) acrylate copolymer (copolymer) introduced above may be prepared by radical polymerization, via a method as described below, and that this method would form a terminal moiety for the copolymer.
  • the copolymer with the unit formula above further comprises a terminal moiety which may be derived from an initiator, a chain transfer agent, or both, as described, for example in Odian, George (2004). Principles of Polymerization (4th ed.). New York: Wiley-Interscience. ISBN 978-0-471-27400-1.
  • the copolymer may be prepared via a method comprising:
  • each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl; optionally (B) a silicone - (meth) acrylate co-macromonomer, wherein (B) the silicone - (meth)acrylate co-macromonomer has a formula selected from the group consisting of formula (B-l), formula (B-2), and a combination of both formula (B-l) and formula (B-2), wherein formula ( each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl; formula (B-2) is selected from the group consisting of H and methyl; D 2 is a divalent hydrocarbon group of 2 to 12
  • Step 1) of the method may comprise an emulsion polymerization reaction.
  • the additional starting materials further comprise (D) a surfactant and (E) water.
  • the emulsion polymerization described above may comprise forming an emulsion comprising starting material (A) the silicone - (meth)acrylate macromonomer, (B) the silicone - (meth) acrylate co-macromonomer (when present), (D) the surfactant, (E) water, and optionally one or more of (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound and thereafter adding (C) the initiator and copolymerizing.
  • Step 1) of the method described above may comprise forming an emulsion comprising starting materials (A) the silicone - (meth) acrylate macromonomer, (B) the silicone - (meth)acrylate co-macromonomer, (C) the initiator, (D) the surfactant, and (E) the water, and optionally an additional starting material selected from the group consisting of (H) the chain transfer agent, (I) the manganese ion source, (J) the phenolic compound, and a combination of two or more thereof. These starting materials may be mixed under shear to form the aqueous emulsion.
  • Mixing under shear may be performed by any convenient means for forming an aqueous emulsion, such as sonication and with subsequent microfluidization.
  • Equipment for mixing under shear such as sonicators, homogenizers, microfluidizers, and speedmixers are known in the art and are commercially available. Without wishing to be bound by theory, it is thought that mixing under shear may be used to obtain a submicron particle size in the emulsion.
  • starting materials comprising (A) the silicone - (meth) aery late macromonomer, (B) the silicone - (meth) acrylate co-macromonomer, (C) the initiator (and when present (H) the chain transfer agent) copolymerize to form (F) the silicone - (meth)acrylate copolymer in the aqueous emulsion with starting materials (D) the surfactant and (E) the water, and optionally (I) manganese ion source and (J) the phenolic compound.
  • step 1) the starting materials comprising (A) the silicone - (meth)acrylate macromonomer and (B) the silicone - (meth)acrylate co-macromonomer, and when present (H) the chain transfer agent may be combined under aerobic or anaerobic conditions, optionally with heating for extended times.
  • the starting materials comprising (A) the silicone - (meth) acrylate macromonomer and (B) the silicone - (meth)acrylate co-macromonomer, and when present one or more of (H) the chain transfer agent, (I) manganese ion source, and/or (J) the phenolic compound, may be emulsified with (D) the surfactant and (E) the water before adding (C) the initiator and copolymerizing in step 1).
  • step 1) combining the starting materials and copolymerizing in the method described above may be performed on a commercial scale under anaerobic or aerobic conditions optionally at elevated temperature, e.g., up to 100 °C, alternatively 40 °C to 80 °C, and alternatively 45 °C to 50 °C.
  • Copolymerizing may be performed in a batch process with a residence time of 15 minutes to 24 hours, alternatively 30 minutes to 12 hours, alternatively 40 minutes to 8 hours, and alternatively 40 minutes to 2 hours.
  • aerobic or anaerobic conditions means that oxygen is not required to be present in the gas in the headspace of the reactor where copolymerizing takes place, or dissolved in the liquid where copolymerizing takes place.
  • the balance of the gas in the headspace could be an inert gas such as nitrogen or argon.
  • the copolymer described above may be prepared by a method comprising dissolving one or more of the starting materials, such as (A) the silicone - (meth)acrylate macromonomer, (B) the silicone - (meth)acrylate co-macromonomer and optionally one or more of (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound, in an organic solvent (such as a monohydric alcohol) and copolymerizing starting materials (A) the silicone - (meth) acrylate macromonomer and (B) the silicone - (meth)acrylate co-macromonomer, and when present (H) the chain transfer agent in a method such as that disclosed in US Patent 10047199 to limura et al.
  • the starting materials such as (A) the silicone - (meth)acrylate macromonomer, (B) the silicone - (meth)acrylate co-macromonomer and optionally one or more of (H)
  • the resulting copolymer may be solvent borne. All or a portion of the solvent may be removed by any convenient means, such as by stripping or distillation with heat and optionally reduced pressure.
  • the resulting copolymer may be emulsified using (D) the surfactant and (E) the water.
  • the product prepared in step 1) is an aqueous emulsion comprising (F) the silicone - (meth)acrylate copolymer, (D) the surfactant, and (E) the water.
  • the aqueous emulsion may optionally further comprise (I) the manganese ion source and/or (J) the phenolic compound. This aqueous emulsion can be used to prepare the emulsion formulation useful for treating a textile.
  • the method for preparing the emulsion formulation suitable for treating the textile comprises practicing step 1) as described above, thereby preparing the aqueous emulsion, and 2) combining the aqueous emulsion prepared in step 1) and an additional starting material comprising (G) a blocked isocyanate.
  • Step 2) may optionally further comprise adding a further additional starting material, which may be selected from the group consisting of (K) a biocide, (L) additional water (which may be the same as starting material (E)), (M) a flame retardant, (N) a wrinkle reducing agent, (O) an antistatic agent, (P) a penetrating agent, (Q) an additive such as a softening agent, and a combination of two or more thereof.
  • Step 2) of this method may optionally further comprise adding additional (D) surfactant.
  • Step 2) of the process described above for making the emulsion formulation may be performed by any convenient means, such as mixing using a jacketed vessel equipped with an agitator. Step 1) and step 2), and any optional and/or additional steps as described above may be performed sequentially in the same vessel. Alternatively, step 1) and step 2) may be performed in different equipment. Step 2) may be performed at RT or elevated temperature, e.g., up to 100°C, alternatively 40°C to 80°C. Alternatively, heating may be performed in step 1), and step 2) may be performed at RT. Alternatively, step 2) may be performed at lower temperatures and elevated pressures, such as up to 5 atmospheres. The starting materials used in the method described above are further described below.
  • Starting material (A) used herein is a silicone - (meth) acrylate macromonomer.
  • the silicone - (meth)acrylate macromonomer has formula (A-l): each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl.
  • each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms.
  • the monovalent hydrocarbon group for R 1 may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms.
  • the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms.
  • each R 1 group may be methyl.
  • D 2 may have 2 to 10, alternatively 3 to 5, and alternatively 3 carbon atoms.
  • the divalent hydrocarbon group for D 2 may be exemplified by an alkylene group such as ethylene, propylene, or butylene.
  • the divalent hydrocarbon group for D 2 may be propylene.
  • D 2 may be linear, e.g., -(CH ) - or -(CH?)?-.
  • D 2 may be -(CH?)?-.
  • starting material (A) comprises formula (A-2): s described above.
  • Starting material (A) may comprise 3-(l ,1 ,1 ,5,5,5-hexamethyl-3-
  • (A) may be prepared by known methods, such as those disclosed in PCT Publication WO2020142388 and US Patent 6420504.
  • Starting material (B) is a silicone - (meth) acrylate co-macromonomer (co- macromonomer) that may optionally be copolymerized with (A) the silicone - (meth)acrylate macromonomer described above.
  • Starting material (B), the co-macromonomer may comprise formula (B-l), where formula ( each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl, each as described and exemplified above for formula (A-l).
  • formula (B-l) may comprise: are as described above.
  • formula (B-2) may comprise 3-(l, 1,1, 3,5,5, 5-heptamethyltrisiloxan-3- yl)propyl methacrylate of formula
  • each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms.
  • the divalent hydrocarbon group for D may be exemplified by an alkylene group such as ethylene, propylene, or butylene; an arylene group such as phenylene, or an alkylarylene each subscript u is independently 1 to 6, alternatively 1 to 2.
  • the divalent hydrocarbon group for D may be alkylene, and alternatively the divalent hydrocarbon group for D may be ethylene.
  • the (poly)alkylene oxide group for D may have 2 to 4 carbon atoms per unit, e.g., have formula D 5 (OD 6 ) V -OR, where D" 1 is an alkylene group of 2 to 4 carbon atoms, D 6 is an alkylene group of 2 to 4 carbon atoms, R is as described above, and subscript v’ is 0 to 12. Alternatively subscript v’ may be 0 or 1. Alternatively, subscript v’ may be 0. Examples of (poly) alkylene oxide groups include ethyleneoxide-propyleneoxide.
  • each D may be selected from an oxygen atom and a divalent hydrocarbon group.
  • each divalent hydrocarbon group for D may be an alkylene group such as ethylene.
  • each D may be oxygen.
  • some instances of D may be oxygen and other instances of D may be alkylene, e.g. , ethylene, in the same unit.
  • formula (B-2) may comprise formula (B-2-1): are as described above.
  • formula (B-2) may comprise formula (B-2-2): are as described above.
  • formula (B-2) may comprise formula (B-2-3):
  • formula (B-2) may comprise a co-macromonomer selected from the group consisting of:
  • Starting material (A) the silicone - (meth)acrylate macromonomer, and starting material (B) the silicone - (meth)acrylate co-macromonomer are used in the following amounts when making the copolymer: starting material (A) is used in an amount of > 25 weight % to 100 weight %, based on combined weights of starting materials (A) and (B); and starting material (B) is used in an amount of 0 to ⁇ 75 weight %, based on combined weights of starting materials (A) and (B).
  • starting material (A) may be used in an amount > 25 %, alternatively at least 40 %, alternatively at least 50%, alternatively at least 63%, and alternatively at least 75%, based on combined weights of starting materials (A) and (B); while at the same time the amount of starting material (A) may be up to 100%, alternatively up to 99%. Alternatively up to 95%, alternatively up to 75%, alternatively up to 63%, alternatively up to 50%, and alternatively up to 40%, on the same basis. Alternatively, the amount of starting material (A) may be 100%, and the amount of starting material (B) may be 0.
  • the starting materials used in step 1) may be free of crosslinkable (meth)acrylate monomers such organic (meth)acrylate monomers having crosslinkable groups as (2-acetoacetoxy)ethyl methacrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxyethylcaprolactone (meth)acrylate, hydroxypropyl (meth)acrylate, ureido (meth)acrylate, glycidyl (meth)acrylate (GMA), and poly(alkylene glycol) (meth)acrylate macromonomers such as poly(ethylene glycol) mono- (meth) acrylate (PEGMA) and poly(ethylene glycol) di(meth)acrylate.
  • crosslinkable (meth)acrylate monomers such organic (meth)acrylate monomers having crosslinkable groups as (2-acetoacetoxy)ethyl methacrylate, hydroxybutyl (meth)acrylate, hydroxye
  • the starting materials used in step 1) may be free of organosilyl monomers having crosslinkable groups, such as alkenyltrialkoxysilanes (e.g., 3-(trimethoxysilyl)propyl (meth)acrylate, vinyltriethoxysilane and vinyltrimethoxysilane).
  • the starting materials that copolymerize in step 1) may consist essentially of starting materials (A), (B), and (C), and when present (H).
  • the additional starting material comprises (C) an intiator.
  • the starting materials that copolymerize in step 1) may consist of starting materials (A) the macromonomer, (B) the co-macromonomer, and (C) the initiator, and when present (H) the chain transfer agent.
  • the starting materials used in step 1) may consist essentially of, or may consist of, (A) the macromonomer, (B) the co-macromonomer, (C) the initiator, (D) the surfactant, and (E) the water, and when present (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound, and these starting materials are described further below.
  • the peroxide compound may be a peroxide or a hydroperoxide, such as t-butylperoctoate, t- butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-amyl peroxide and combinations of two or more thereof.
  • di-peroxide initiators may be used alone or in combination with other initiators.
  • Such di-peroxide initiators include, but are not limited to, 1 ,4-bis-(t-butyl peroxycarbo)cyclohexane, 1 ,2-di(t-butyl peroxy)cyclohexane, and 2,5-di(t-butyl peroxy)-3-hexyne.
  • Suitable peroxide compounds are known in the art and are commercially available from various sources, such as Sigma- Aldrich, Inc.
  • the initiator may comprise isoascorbic acid.
  • the initiator is added depends on various factors including whether the initiator is water soluble and the type of initiator (e.g., whether a thermal initiator or a redox pair is used). Typically, when a thermal initiator is used, all the initiator is added at once at the beginning of step 1). Alternatively, when a redox pair is used, it may be metered in over time.
  • Starting material (D) is a surfactant.
  • the surfactant may be selected from the group consisting of (D-l) a cationic surfactant, (D-2) a nonionic surfactant, and (D-3) a combination of both the cationic surfactant and the nonionic surfactant.
  • Cationic surfactants useful herein include compounds containing quaternary ammonium hydrophilic moieties in the molecule which are positively charged, such as quaternary ammonium salts, which may be represented by formula (D-l-1): R 12 R 13 R 14 R 1S N + X’ _ where R 12 to R 15 are alkyl groups containing 1-30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soy; and X’ is a halogen, e.g., chlorine or bromine.
  • the quaternary ammonium compounds may be alkyl trimethylammonium and dialkyldimethylammonium halides, or acetates, having at least 8 carbon atoms in each alkyl substituent.
  • Dialkyl dimethyl ammonium salts can be used and are represented by formula (D-l-2): R 16 R 17 N + (CH3)2X’’ where R 16 and R 17 are alkyl groups containing 12-30 carbon atoms or alkyl groups derived from tallow, coconut oil, or soy; and X’ is halogen.
  • Representative quaternary ammonium halide salts are dodecyltrimethyl ammonium chloride/lauryltrimethyl ammonium chloride (LTAC), cetyltrimethyl ammonium chloride (CTAC), hexadecyltrimethyl ammonium chloride, didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, and didocosyldimethyl ammonium chloride.
  • These quaternary ammonium salts are commercially available under trademarks such as ADOGENTM, ARQUADTM, TOM AHTM, and VARIQUATTM.
  • Suitable cationic surfactants which can be used include fatty acid amines and amides and their salts and derivatives, such as aliphatic fatty amines and their derivatives.
  • cationic surfactants that are commercially available include compositions sold under the names ARQUADTM T27 W, ARQUADTM 16-29, by Akzo Nobel Chemicals Inc., Chicago, Illinois; and Ammonyx Cetac-30 by the Stepan Company, Northfield, Illinois, USA.
  • the amount of (D-l) the cationic surfactant may be 0.1% to 5%, based on weight of starting material (F) the silicone - (meth)acrylate copolymer in the aqueous emulsion.
  • the amount of cationic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%; while at the same time the amount of cationic surfactant may be up to 5%, alternatively up to 4%, alternatively up to 3%, alternatively up to 2%, alternatively up to 1%, on the same basis.
  • the amount of cationic surfactant may be 0.2% to 4%, alternatively 0.3% to 3%, alternatively 0.4% to 2.5%, and alternatively 0.5% to 2%; on the same basis.
  • Starting material (D-2) is a nonionic surfactant.
  • nonionic surfactants which can be used include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkylglucosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.
  • Nonionic surfactants which are commercially available include compositions such as (i) 2,6,8-trimethyl-4-nonyl polyoxyethylene ether sold under the names TERGITOLTM TMN-6 and TERGITOLTM TMN-10; (ii) the Cl 1-15 secondary alkyl polyoxyethylene ethers sold under the names TERGITOLTM 15-S-7, TERGITOLTM 15-S- 9, TERGITOLTM 15-S-15, TERGITOLTM 15-S-30, and TERGITOLTM 15-S-40, by the Dow Chemical Company, of Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the name TRITONTM X405 by the Dow Chemical Company; (iii) nonylphenyl polyoxyethylene (10) ether sold under the name MAKONTM 10 by the Stepan Company; (iv) ethoxylated alcohols sold under the name Trycol 5953 by Henkel Corp./Emery Group,
  • alkyl-oxo alcohol polyglycol ethers such as GENAPOLTM UD 050, and GENAPOLTM UDI 10
  • alkyl polyethylene glycol ether based on ClO-Guerbet alcohol and ethylene oxide such as LUTENSOLTM XP 79.
  • Suitable nonionic surfactants also include poly(oxyethylene)-poly(oxypropylene)- poly(oxy ethylene) tri-block copolymers.
  • Poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymers are also commonly known as Poloxamers. They are nonionic triblock copolymers composed of a central hydrophobic chain of polyoxypropylene (poly(propylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (poly(ethylene oxide)).
  • Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are commercially available from BASF of Florham Park, New Jersey, USA, and are sold under the tradename PLURONICTM, such as PLURONICTM L61, L62, L64, L81, P84.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol (such as polyethylene glycol having 23 ethylene-oxide units), polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, and polyoxyalkylene glycol modified polysiloxane surfactants.
  • nonionic surfactants which can be used include compositions such as 2,6,8-trimethyl-4-nonyloxy polyethylene oxyethanols (6EO) and (10EO) sold under the trademarks TERGITOLTM TMN-6 and TERGITOLTM TMN-10; alkyleneoxy polyethylene oxyethanol (Cn-i5 secondary alcohol ethoxylates 7EO, 9EO, and 15EO) sold under the trademarks TERGITOLTM 15-S-7, TERGITOLTM 15-S-9, TERGITOLTM 15-S-15; other C11-15 secondary alcohol ethoxylates sold under the trademarks TERGITOLTM 15-S-12, 15-S-20, 15-S-3O, 15-S-40; octylphenoxy polyethoxy ethanol (40EO) sold under the trademark TRITONTM X-405 ; and alcohol ethoxylates with tradename ECOSURFTM EH, such as ECOSURFTM EH-40.
  • 6EO 2,6,8-tri
  • surfactants are sold by the Dow Chemical Company.
  • Other useful commercial nonionic surfactants are nonylphenoxy polyethoxy ethanol (10EO) sold under the trademark MAKONTM 10 by Stepan Company; polyoxyethylene 23 lauryl ether (Laureth-23) sold commerciallyby Sigma Aldrich, Inc. of St. Louis, Missouri, USA; and RENEXTM 30, a polyoxyethylene ether alcohol available from Fisher Scientific.
  • the nonionic surfactant may also be a silicone polyether (SPE).
  • SPE silicone polyether
  • the silicone polyether as an emulsifier may have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure.
  • Suitable SPE’s include DOWSILTM OFX-5329 Fluid from Dow Silicones Corporation of Midland, Michigan, USA.
  • the nonionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides.
  • Such silicone-based surfactants may be used to form such aqueous emulsions and are known in the art, and have been described, for example, in US Patent 4122029 to Gee et al., US Patent 5387417 to Rentsch, and US Patent 5811487 to Schulz et al.
  • Starting material (D-2) the nonionic surfactant may be delivered in a dilution, and the amount used may be sufficient to provide 0.1% to 10% of the surfactant, based on weight of starting material (F) the silicone - (meth)acrylate copolymer in the aqueous emulsion.
  • the amount of nonionic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%, alternatively at least 1%, alternatively at least 2%, alternatively at least 3%, alternatively at least 4%; while at the same time the amount of nonionic surfactant may be up to 10%, alternatively up to 9%, alternatively up to 8%, alternatively up to 7%, alternatively up to 5%, alternatively up to 4%, alternatively up to 3%, alternatively up to 2%, alternatively up to 1%, on the same basis.
  • the amount of nonionic surfactant may be 1% to 10%, alternatively 2% to 10%, alternatively 3 to 10%, alternatively 5% to 9%, alternatively 6% to 8%, and alternatively 7%%; on the same basis.
  • starting materials (D-l) the cationic surfactant and (D-2) the nonionic surfactant may be present in combined amounts ⁇ 10%, based on weight of starting material (F) the silicone - (meth)acrylate copolymer in the aqueous emulsion.
  • Starting material (E) is water.
  • the water is not generally limited, for example, the water may be processed or unprocessed. Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, and combinations of two or more thereof, such that the water may be deionized, distilled, and/or filtered. Alternatively, the water may be unprocessed (e.g., may be tap water, i.e.. provided by a municipal water system or well water, used without further purification). The amount of water is sufficient to form an aqueous emulsion for emulsion polymerization in step 1) of the process described above. Additional water may be added after step 1).
  • the aqueous emulsion prepared as described above may be diluted with additional water to achieve a desired amount of starting materials before treating a textile with the emulsion formulation.
  • the water may be added in an amount of 20% to 97%, alternatively 30% to 90%, alternatively 40% to 80%, alternatively 50% to 97%, alternatively 50% to 90%, and alternatively 60% to 80%; based on combined weights of all starting materials in step 1).
  • the water may be added in an amount of at least 20%, alternatively at least 30%, alternatively at least 40%, alternatively at least 50%, and alternatively at least 60%; while at the same time the amount of water may be up to 97%, alternatively up to 96%, alternatively up to 95%, and alternatively up to 80%, on the same basis.
  • the silicone - (meth) acrylate copolymer, (F) may be prepared prepared by emulsion polymerization of starting materials comprising (A) the macromonomer and (C) the initiator (and optionally (B) the co-macromonomer) described above.
  • the silicone - (meth)acrylate copolymer is a reaction product of starting materials consisting essentially of starting materials (A) the macromonomer and (C) the initiator (and when present, (B) the co- macromonomer and/or (H) the chain transfer agent).
  • the silicone - (meth)acrylate copolymer is a reaction product of starting materials consisting of starting materials (A) and (C), (and, when present, (B) and/or (H)).
  • starting materials (D) and/or (E), or any other starting material added during the method may participate in the copolymerization reaction of starting materials comprising (A) and (C), and any optional starting materials (i.e., (B) and/or (H)), when present.
  • the silicone - (meth) acrylate copolymer comprises unit formula (F-l): each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D 2 is independently a divalent hydrocarbon group of 2 to 12 carbon atoms; and each R 2 is independently selected from the group consisting of H and methyl; each R 3 is a group of formula OSi(R 4 h; where each R 4 is independently selected from the group consisting of R and DSi(R 5 )3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, a (poly) alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 is independently selected from the group consisting of R and DSi(R 6 h; where each R 6 is independently selected from the group consisting of R and DSiR ; with the proviso that R 4 ,
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R, D, and D 2 are as described and exemplified above for formulas (A-l), (B-l) and (B-2).
  • each R 1 may be methyl
  • each R 2 may be methyl
  • each D 2 may be propylene
  • each R 3 may be the group of formula OSi(R 4 )3; where each R 4 is independently selected from the group consisting of R and OSi(R 5 )3, where each R is methyl; each R 5 is independently selected from the group consisting of R and OSi(R 6 )3; where each R 6 is independently selected from the group consisting of R and OSiR3; with the proviso that R 4 , R 5 , and R 6 are selected such that the silicone - (meth)acrylate co-macromonomer 10 to 16 silicon atoms per molecule.
  • subscript bl may have a value such that 0 ⁇ bl ⁇ 0.75, alternatively 0 ⁇ bl ⁇ 0.5, alternatively 0
  • the silicone - (meth) acrylate copolymer prepared as described above may have a weight average molecular weight measured by GPC of > 181,000 g/mol.
  • silicone - (meth)acrylate copolymer may have a weight average molecular weight measured by GPC of at least 200,000 g/mol; alternatively at least 210,000 g/mol; alternatively at least 212,000 g/mol; alternatively at least 225,000 g/mol; alternatively at least 230,000 g/mol; and alternatively at least 234,000 g/mol; while at the same time, weight average molecular weight may be up to 2,000,000 g/mol; alternatively up to 1,000,000 g/mol; alternatively up to 950,000 g/mol; alternatively up to 925,000 g/mol; alternatively up to 912,000 g/mol, alternatively up to 900,000 g/mol, alternatively up to 850,000 g/mol; alternatively up to 800,000 g/mol; and alternatively up to 750,000 g/mol; and alternatively up to 721,000 g/mol.
  • GPC weight average molecular weight measured by GPC of at least 200,000 g/mol; alternatively at least 210,000 g/
  • the silicone - (meth) acrylate copolymer may have a weight average molecular weight of 212,000 g/mol to 912,000 g/mol, measured by GPC.
  • the samples for GPC analysis may be prepared in THF eluent at concentration 10 mg/mL copolymer. The solution may be shaken on a flat-bed shaker at ambient temperature for 2 hours. The solution may then be filtered through a 0.45 m PTFE syringe filter prior to injection. A Waters e2695 LC pump and autosampler, equipped with two 5 uM Agilent PLG gel Mixed C columns in series and Shodex RI501 differential refractive index detector was used to analyze the samples.
  • Starting material (G) is a blocked isocyanate that is added to the emulsion formulation suitable for treating textiles.
  • the term “blocked isocyanate” encompasses mono-, di- and polyisocyanates in which an isocyanate group has been reacted with a blocking agent, which upon heating, release the isocyanate and the blocking agent.
  • Suitable blocking agents are known in the art such as amines, amides, compounds having an active hydrogen atom, alcohols, or oximes.
  • Blocked isocyanates are commercially available, such as ARKOPHOBTM DAN and ARKOPHOBTM SR from Archroma of Pratteln, Switzerland; RUCOTM-GUARD WEB and RUCOTM-LINK XCR from Rudolf GmbH of Geretsreid, explanation, Germany, and PHOBOLTM EXTENDER UXN and PHOBOLTM EXTENDER XAN from Archroma.
  • the blocked isocyanate may be an oxime blocked isocyanate, such as PHOBOLTM EXTENDER XAN.
  • the blocked isocyanate may comprise a nitrogen containing heterocycle (N-heterocycle) - blocked isocyanate.
  • the N-heterocycle-blocked isocyanate comprises an isocyanate compound and an N-heterocycle- blocking agent.
  • the isocyanate compound may be monomeric or polymeric.
  • the isocyanate compound may comprise, or maybe, a unit selected from the group consisting of IPDI, H12MDI, TMXDI, TMI, XDI, H 6 XDI, MDI, and HDI.
  • the polyisocyanate may be an aliphatic isocyanate where the NCO group is not directly attached to an aromatic ring.
  • the polyisocyanate may be HDI or MDI.
  • the N-heterocycle blocking agent may be2,6-dimethylpyrazine or a dimethylpyrazole, e.g., 3,5- dimethylpyrazole.
  • the blocked isocyanate may be free of species that may interfere with the performance of the isocyanate in the emulsion formulation, such as silicones and amines (that are not within the blocking group).
  • the blocked isocyanate may be delivered in an emulsion or dispersion that is free of anionic surfactant. Suitable aqueous additives are commercially available and may be delivered in aqueous dispersions, and examples thereof are shown below in Table 0.
  • the exact amount of (G) the blocked isocyanate compound depends on various factors including the type and amount of (F) silicone - (meth)acrylate copolymer formed in step 1) and the textile to be treated, however, the weight of (G) the blocked isocyanate may be sufficient to provide 0.25% to 3.75% on fabric weight, alternatively 0.25% to 1%, and alternatively 0.25% to 0.5%, on the same basis.
  • An additional starting material that may be added in step 1) of the method described above comprises (H) a chain transfer agent.
  • Suitable chain transfer agents include mercaptans such as alkyl mercaptans, e.g., n-octyl mercaptan, n-dodecyl mercaptan, dodecyl mercaptan (dodecane thiol), and/or 2,2-dimethyldecyl mercaptan.
  • the chain transfer agent may be water soluble, such as mercaptoacetic acid and/or 2-mercaptoethanol.
  • Starting material (H) is optional and may be added in an amount of 0 to 1%, based on combined weights of starting material (A), and when present starting material (B).
  • the chain transfer agent may be used in an amount of 0.5% to 0.6% on the same basis.
  • Starting material (I) is an optional manganese ion source, which may be a manganese (TI) compound.
  • Suitable manganese compounds include manganese (IT) acetate, manganese (TI) nitrite, manganese (II) propionate, manganese (II) oxide, manganese (II) hydroxide, manganese (II) chloride, manganese (II) phosphate, manganese (II) perchlorate, hydrates thereof (e.g., manganese (II) acetate tetrahydrate) and combinations thereof.
  • the manganese ion source may comprise manganese (II) acetate or manganese (II) acetate tetrahydrate, or a combination thereof.
  • Suitable manganese ion sources are commercially available from Millipore Sigma of St. Louis, Missouri, USA, Fisher Scientific of Waltham, Massachusetts, USA, and City Chemical LLC of Connecticut, USA.
  • the amount of manganese ion source depends on various factors including the selections and amounts of other starting materials used, however the amount may be 0.1 ppm to 5,000 ppm based on combined weights of starting material (A), and when present starting material (B).
  • the amount of the manganese ion source may be > 0 ppm, alternatively at least 0.5 ppm, alternatively at least 1 ppm, alternatively at least 1.5; while at the same time, the amount of manganese ion source may be up to 10 ppm, alternatively up to 5 ppm, alternatively up to 4 ppm, and alternatively up to 3 ppm, and alternatively up to 2 ppm, based on combined weights of all starting materials in the emulsion formulation for treating the textile.
  • Starting material (J) is an optional phenolic compound.
  • Suitable phenolic compounds include hydroquinone (HQ), 2-methylhydroquinone, 2-t-butylhydroquinone, dihydroxybenzene (catechol), 4-di-t-butyl dihydroxybenzene (4-di-t-butyl catechol), resorcinol, dihydroxyxylene, methoxyphenols such as guaiacol, p-methoxyphenol (also called methyl ether of hydroquinone or MeHQ), tert-butyl hydroquinone (tBuHQ), pyrogallol, methylpyrogallol, cresol, phenol, xylenols, butylated hydroxyl toluene, N-nitroso phenylhydroxylamine, butylated hydroxy anisole, and combinations thereof.
  • hydroquinone HQ
  • 2-methylhydroquinone 2-t-butylhydroquinone
  • the phenolic compound may be selected from the group consisting of HQ, MeHQ, tBuHQ, and a combination of two or more thereof. Suitable phenolic compounds are commercially available, e.g. , from Millipore Sigma of St. Louis, Missouri, USA. The amount of phenolic compound source depends on various factors including the selections and amounts of other starting materials used, however the amount may be 5 ppm to 5,000 ppm based on combined weights of starting material (A) and when present starting material (B).
  • the amount of the phenolic compound may be at least 5 ppm, alternatively at least 50 ppm, alternatively at least 100 ppm, alternatively at least 150 ppm; while at the same time, the amount of phenolic compound may be up to 500 ppm, alternatively up to 400 ppm, alternatively up to 350 ppm, and alternatively up to 320 ppm, based on combined weights of all starting materials in the emulsion formulation for treating the textile.
  • the inhibitor may comprise, or may be, nitrobenzene; 2,2-diphenyl-l -picrylhydrazyl (DPPH); phenothiazine; N,N-diethylhydroxylamine; (2,2,6,6-tetramethylpiperidin- l-yl)oxidanyl (TEMPO); 4-hydroxy-(2,2,6,6-tetramethylpiperidin-l-yl)oxidanyl (4-hydroxy TEMPO); or a combination of two or more thereof.
  • DPPH 2,2-diphenyl-l -picrylhydrazyl
  • TEMPO 2,2,6,6-tetramethylpiperidin- l-yl)oxidanyl
  • Starting material (K) is an optional biocide.
  • the amount of biocide will vary depending on factors including the type of biocide selected and the benefit desired. However, when used, the amount of biocide may be > 0% to 5% based on the combined weights of all starting materials in the emulsion formulation.
  • Starting material (K) is exemplified by (K-l) a fungicide, (K-2) an herbicide, (K-3) a pesticide, (K-4) an antimicrobial agent, or a combination thereof.
  • Suitable biocides are disclosed, for example, in U.S. Patent 9,480,977.
  • the emulsion formulation suitable for treating the textile may optionally further comprise starting material (P), a penetrating agent.
  • Suitable penetrating agents are exemplified by glycol ethers, which are commercially available from The Dow Chemical Company and include DOWANOLTM DPM, TPM, PPh, EPh, Methyl CARBITOLTM, and Butyl CARBITOLTM.
  • the emulsion formulation suitable for treating the textile may optionally further comprise an amount sufficient to impart softness to a textile without significantly decreasing water and/or oil repellency of (Q) a softening additive selected from (Q-l) an alkylpoly siloxane of formula each R 19 is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and subscript aa has an average value of 20 to 300, or (Q-2) a combination comprising 60 to 70 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-l) the alkylpolysiloxane, 29 to 39 weight %, based on combined weights of all starting materials in (Q- 2), the combination, of (Q-2- 1 ) a silicone resin having a hardness > 20 measured by Type A durometer according to JIS K 6249:2003, and 0 to 2 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-2
  • the (Q-l) alkylpoly siloxane has formula each
  • R 19 is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and subscript aa has an average value of 20 to 300.
  • the monovalent saturated hydrocarbon group for R 19 may be an alkyl group, alternatively an alkyl group of 1 to 6 carbon atoms.
  • the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms.
  • each R 19 may be methyl.
  • Suitable alkylpoly siloxanes e.g., bis- trimethylsiloxy-terminated polydimethylsiloxanes, are known in the art and are commercially available, e.g., as XIAMETERTM 200 Fluids from The Dow Chemical Company of Midland, Michigan, USA.
  • the softening additive may comprise a (Q-2) combination comprising: 60 to 70 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-l ) the alkylpolysiloxane described above, 29 to 39 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-1) a silicone resin having a hardness > 20 measured by Type A durometer according to JIS K 6249:2003, and 1 to 2 weight %, based on combined weights of all starting materials in (Q-2), the combination, of (Q-2-2) an amino-functional polyorganosiloxane having a functional group equivalent of 100 to 20,000 g/mol, wherein the equivalent means molecular weight of the amino-functional polyorganosiloxane per 1 mole of nitrogen atoms, and having a kinematic viscosity at 25 °C of 10 to 100,000 mnr/s measured by the method
  • the softening additive may be delivered in a second aqueous emulsion, which comprises (Q) the softening additive, (D’) a surfactant (which may be as described above for starting material (D) the surfactant) and (E’) water (which may be as described above for starting material (E)).
  • the second aqueous emulsion may be prepared by known methods, such as those described in U.S. Patent Application Publication 2020/0332148, by varying the types and amounts of starting materials as described herein.
  • starting materials to add to the aqueous emulsion prepared as described above in step 1) and the emulsion formulation formed in step 2) described above there may be overlap between types of starting materials because certain starting materials described herein may have more than one function.
  • the starting materials used in aqueous emulsion and/or the emulsion formulation may be distinct from one another.
  • the emulsion formulation suitable for treating the textile comprises: (F) the silicone - (meth)acrylate copolymer, (D) the surfactant, (E) the water, and (G) the blocked isocyanate, as described above.
  • the emulsion formulation may optionally further comprise an additional starting material selected from the group consisting of (I) the manganese ion source, (J) the phenolic compound, (K) the biocide, (L) additional water (as described above for starting material (E)), (M) the flame retardant, (N) the wrinkle reducing agent, (O) the antistatic agent, (P) the penetrating agent, (Q) the softening additive, and a combination of two or more of starting materials (K), (L), (M), (N), (O), (P), and (Q).
  • additional starting materials and their amounts are as described above.
  • the emulsion formulation described herein may be formulated with starting materials that are fluorocarbon-free.
  • the emulsion formulation may be free of any starting material that contains a fluorine atom covalently bonded to a carbon atom.
  • the emulsion formulation prepared as described above may be used for treating a textile.
  • a method for treating a textile comprises: I) coating the textile with the emulsion formulation described above, and II) heating the textile.
  • Step I) may be performed by any convenient method, such as padding, dipping, or spraying the textile with the emulsion formulation.
  • the method should be sufficient to deliver a sufficient amount of (F) the silicone - (meth)acrylate copolymer and (G) the blocked isocyanate sufficient to impart durable oil resistance properties to the textile, according to the methods described below.
  • Step II) may be performed by any convenient method, such as placing the textile in an oven. Heating the textile may be performed to remove all or a portion of the water and/or cure the emulsion formulation. The exact temperature depends on various factors including the temperature sensitivity of the type of textile selected and the desired drying time. However, heating may be performed at a temperature > 100 °C to remove water.
  • the temperature may be > 100 °C to 200 °C for a time sufficient to remove all or a portion of the water, de-block the blocked isocyanate, and/or cure (F) the silicone - (meth)acrylate copolymer.
  • the textile to be treated is not specifically restricted. Suitable textiles include naturally derived textiles such as fabrics of cotton, silk, linen, and/or wool; textiles derived from synthetic sources such as rayon, acetate, polyesters, polyamides (such as Nylons), polyacrylonitriles, and polyolefins such as polyethylenes and/or polypropylenes, and combinations of two or more thereof (e.g. , blends such as polyester/cotton blend).
  • the form of the textile is also not specifically restricted.
  • the emulsion formulation described herein is suitable for use on textiles in any form, e.g., woven fabrics, knitted fabrics, or nonwoven textiles.
  • silicone - (meth)acrylate copolymer emulsions were prepared as follows. All macromonomers, water and surfactant were added to a widemouth jar (-400 mL) in selections and amounts shown below in Table 2. A sonicator was used to make an emulsion (Fisherbrand Model 705 sonic dismembrator, amplitude 50, Power -62 W, for 2 min). The aqueous emulsion was then transferred to a reactor and heated to 65 °C. After the aqueous emulsion came to temperature, Initiator 1 was added (0.26 g), and the reactor contents were stirred for 6 h. The reactor contents were then cooled down to room temperature and the resulting copolymer emulsions were each poured into a bottle.
  • a sonicator was used to make an emulsion (Fisherbrand Model 705 sonic dismembrator, amplitude 50, Power -62 W, for 2 min). The aqueous
  • emulsion formulations were prepared, fabrics were treated, and oil repellency was evaluated as follows: All the fabrics were washed/dried before coating. The amount of water pickup for each fabric was measured and then emulsion formulations were made based on that pick up weight by adding a blocked isocyanate Additive. Table 3 provides the exact emulsion formulations recipes. Each emulsion formulation was then poured into Mathis HVF padder (roll speed of 2m/min at 60 psi) for coating. The fabric was passed through the coater until not more dry spots were observed (generally twice) then placed through a forced air Mathis LTF oven at 160 °C for 3 min. The fabric was weighed both before coating and after coating to get the actual weight coated.
  • Example 7 Each sample was - 2 wt% on fabric.
  • the sheets were laundered using a 90 °F wash followed by a cold rinse cycle ( ⁇ 70°F) in a Whirlpool model WTW4855HW1 washing machine (settings: normal cycle, hot wash temperature, deep water wash, auto sensing rinse).
  • Tide Free and Gentle Liquid Laundry Detergent was used as the detergent using 39g for 6 pound loads of fabric. For smaller loads, the detergent amount was modified proportionally.
  • the hot water for washing the samples went through a building wide water softening system.
  • the cold water was also softened and went through a PDIMX-60 water softener system from Franklin Electric using the standard settings (default 20 setting for hardness).
  • a Whirlpool model WED4850HW0 dryer was used to dry the samples (auto dry cycle on high- 140°F).
  • AATCC American Association of Textile Chemists and Colorists
  • Example 1 and Comparative Example 2 contained the same starting materials (i.e., emulsion of copolymer of 3MT-ALMA), except the blocked isocyanate was present in Example 1 and absent from Comp 2.
  • Example 1 had dramatically improved oil repellency under all conditions tested.
  • Example 4 showed dramatically improved oil repellency over Comparative Example 5 after 1 minute and 5 minutes.
  • Comparative Example 6 demonstrates that using stearyl acrylate in the copolymer unexpectedly does not provide pass performance.
  • Example 7 demonstrated unexpected wash durability without the any added crosslink points in the copolymer backbone.
  • Examples 1, 2, 5 and 6 demonstrated that multiple fabric types can be rendered oil repellent using the emulsion formulation described herein.
  • Example 1 and Comparative Example 2 demonstrated that oil repellency improved when the isocyanate additive was used.
  • silicone - (meth)acrylate copolymer emulsions were prepared as follows. All all starting materials (except initiator) were added to a widemouth jar (-400 mL) in selections and amounts shown below in Table 4. A sonicator was used to make an emulsion (Fisherbrand Model 705 sonic dismembrator, amplitude 50, Power -62 W, for 2 min). The aqueous emulsion was then transferred to a reactor and heated to 65 °C.
  • the resulting material was sonicated at an amplitude of 50 for two minutes using a sonicator (Fisher Brand Sonic Dismembrator) to create an emulsion.
  • the resulting emulsion was then transferred to a 500 mL 4 neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20) and thermocouple probe. This emulsion was stirred at 250 RPM using a Teflon blade and heated to 65 °C. After reaching temperature 0.25 g of 2,2’ Azobis(2-methylpropionamidine dichloride was added and the reaction was run for 6 hours. The resulting material was then allowed to cool to 30 to 40 °C with slow stirring before pouring off.
  • the aqueous copolymer emulsions prepared as described above are summarized below in Table 4. Amounts of each starting material in Table 4 are in grams.
  • emulsions were prepared as follows. Starting materials were weighed into a 400 mL wide mouth jar selections and amounts shown below in Table 4. The stearyl and behenyl acrylate monomers were melted first and added as a liquid. In addition, the emulsions were inhibited with Hydroquinone (50 ppm based on monomer), Mn(II) acetate HzO (1.5 ppm based on monomer) and methyletherhydroquinone (150 ppm based on monomer). The resulting material was sonicated at an amplitude of 50 for two minutes using a sonicator (Fisher Brand Sonic Dismembrator) to create an emulsion.
  • Hydroquinone 50 ppm based on monomer
  • Mn(II) acetate HzO 1.5 ppm based on monomer
  • methyletherhydroquinone 150 ppm based on monomer
  • the coarse emulsion is then, passed through a microfluidizer (Microfluidics Microfluidizer HOY) and set to 1,000 psi, twice.
  • the aqueous emulsion was then transferred to a reactor and heated to 65 °C. After the aqueous emulsion came to temperature, 2,2’-Azobis(2-methylpropionamidine) dihydrochloride (AIBN) was added (0.26 g), and the reactor contents were stirred for 6 h. The reactor contents were then cooled down to room temperature and the resulting aqueous copolymer emulsions were each poured into a bottle.
  • the aqueous copolymer emulsions prepared as described above are summarized below in Table 4. Amounts of each starting material in Table 4 are in grams. Table 4 - Starting Materials used for Syntheses according to Methods A-C- in Synthesis Examples 1 to 3
  • weight average molecular weights of some silicone - (meth)acrylate copolymers in Table 4 was measured by GPC as follows: Samples were prepared for GPC by dissolving 174.41 mg of the 29% emulsion copolymer sample described above in Table 4in 10 mL of THF (5 mg/mL) in a 20 mL vial. The samples were placed on a shaker for 2h. The sample was then filtered through a 0.45 pm PTFE filter before injecting in the GPC instrument. A Waters e2695 LC pump and autosampler, equipped with two 5uM Agilent PLG gel Mixed C columns in series and Shodex RI-501 differential refractive index detector was used to analyze the samples.
  • Table 5 - GPC data set [0077]
  • the aqueous copolymer emulsions described in Table 4 were used to prepare emulsion formulations, fabrics were treated, and oil repellency was evaluated using the same method described above in Reference Example 2.
  • the emulsion formulations and oil repellency results are shown below in Table 6.
  • PDMS resin 1 (as described in Example 1 of US Patent Publication 20230038369 was prepared as follows: 0.88 g (10 mmol) of 3MT-ALMA, 0.31 g (1 mmol) of vinyl trimethoxysilane and 0.033g (0.1 mmol) of azobisisobutyronitrile were added to a round bottom flask with 47.95 g of dry xylenes at room temperature. The round bottom flask was equipped with a condenser, nitrogen inlet, overhead stirrer and thermocouple probe. The system was purged with nitrogen for 5 min and then the solution was heated up to 65°C and then held for 24 h.
  • PDMS resin 2 was prepared as follows: An 80 DP amino terminated PDMS (30 g, 10 mmol), bisphenol A (2.28 g, 10 mmol) and paraformaldehyde (1.2 g, 40 mmol) were dissolved in 150 mL of chloroform in a 500 mL round bottom flask. The mixture was heated under reflux for 6 h to give a light yellow solution. After removing the solvent under vacuum, the residue was dissolved in 75 mL of methylene chloride. The material was washed with a saturated solution of NaHCOs (75 rnL x 5). The water was then distilled off leaving a light yellow liquid product. PDMS resin 2 gelled by the next day, so this resin could not be coated on a textile.
  • the fabric was then soaked in a 5% suspension of Ludox HS silica (5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water) until saturated ( ⁇ 4 sec) and then dried overnight at 80 °C.
  • Ludox HS silica 5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water
  • the pretreated 1x1 cm PES or nylon fabric samples were dip coated 3 times into PDMS resin 1. The samples were cured for 1 h at 200 °C.
  • a Ixlcm PES or Nylon fabric was washed with 200 proof ethanol and then dried in an oven 80 °C for 10 min. Then a silica sol was prepared by hydrolysis of tetraethoxysilane (2.08 g, 10 mmol) in 60 mL of ethanol/15 mL of DI water in the presence of ammonium hydroxide (2.75 mL). The fabric was dipped into the sol for 5 min and dried at room temperature ( ⁇ 30 min). This process was repeated 2 more times.
  • the fabric was then soaked in a 5% suspension of Ludox HS silica (5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water) until saturated ( ⁇ 4 sec) and then dried overnight at 80 °C.
  • Ludox HS silica 5 g of a 40% solution of Ludox HS-40 colloidal silica and 35 g of DI water
  • Comp 18 and Comp 19 correspond to example 2 disclosed in US Patent Publication US20230038369. These received a failing oil repellency grade after 5 min in the modified AATCC method 118.
  • the present invention e.g., as shown in examples 1 and 5 in Table 3, above
  • Comp 20 and Comp 21 removed the sol gel and nanoparticle treatment and tested the 3MT-ALMA/vinyl trimethoxysilane copolymer, and these examples also failed the modified AATCC method 118 after 5 min.
  • Comparative Example 24 the PES fabric was treated with 2 separate emulsions in 2 separate steps.
  • the fabric was treated with an emulsion of copolymer 1 from Table 2, above, in which 5.75 g of the Copolymer Emulsion 1 from Table 2 was combined with 69.25 g DI water using the same coating and curing methods described above in Reference Example 2.
  • Comparative example 24 shows a pretreatment method of the blocked isocyanate (XAN) additive similarly described in example 2 in US Patent Publication US20230038369 (Comp 18 and Comp 19 above). This comparative example 24 did not pass the modified AATCC method 118 after 10 sec and had worse oil repellency than Comp 18 and Comp 19 at 10 sec.
  • XAN blocked isocyanate
  • Comparative Example 25 In this Comparative Example 25, 3.83 g of Copolymer Emulsion 1 described above in Table 2 and 1.59 g of DOWSILTM IE-8749, a 70% solids silicone durable water repellent that is commercially available from The Dow Chemical Company, were added into a 125 g Nalgene plastic bottle. The bottle was then inverted twice to mix the contents. Fabric was coated and oil repellency was measured as described above in Reference Example 2. The fabric had a C rating after 10 s and a D rating after 30 s. Comparative 25 showed that a silicone material (the active in IE-8749) blended with a copolymer of 3MT-ALMA failed the oil repellency test herein after 30 s.
  • the additive may be free of species that may interfere with the performance of the isocyanate in the emulsion formulation, such as silicones and amines (that are not within the blocking group). And, without wishing to be bound by theory, it is thought that the blocked isocyanate may be delivered in an emulsion or dispersion that is free of anionic surfactant.
  • oil repellency means an A or B face ranking after a large oil drop contacts the textile for 5 minutes, as measured by the modified AATCC 118 test described above.
  • durable means that the textile can be washed at least 5 times after treatment with the emulsion formulation as described herein, and the fabric will still have oil repellency as described above (as shown above in Example 7).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne une formulation d'émulsion de traitement textile comprenant un copolymère de silicone-(méth)acrylate, un tensioactif, de l'eau et un isocyanate séquencé et un procédé pour sa préparation. L'émulsion de traitement textile peut être utilisée dans un procédé comprenant le revêtement de la formulation d'émulsion sur un textile et le chauffage du textile pour sécher la formulation d'émulsion. Ce procédé rend le textile oléofuge.
PCT/US2024/045245 2023-10-27 2024-09-05 Émulsion de copolymère de silicone-(méth)acrylate et sa préparation et utilisation de l'émulsion pour oléofuger des textiles Pending WO2025090189A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN202480023867.0A CN120981626A (zh) 2023-10-27 2024-09-05 硅酮-(甲基)丙烯酸酯共聚物乳液及其制备以及乳液赋予纺织品拒油性的用途
PCT/US2024/052892 WO2025090820A1 (fr) 2023-10-27 2024-10-25 Traitement du cuir à l'aide d'une émulsion de copolymère de silicone-(méth)acrylate conférant une résistance aux taches et un caractère oléofuge
PCT/US2024/052894 WO2025090822A1 (fr) 2023-10-27 2024-10-25 Papier de traitement avec une composition comprenant un copolymère de silicone-(méth)acrylate
PCT/US2024/052893 WO2025090821A1 (fr) 2023-10-27 2024-10-25 Traitement du cuir comprenant un copolymère de silicone-(méth)acrylate et un liant organique pour conférer des propriétés d'hydrofugation et d'oléofugation

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US202363593716P 2023-10-27 2023-10-27
US63/593,716 2023-10-27
US202463674322P 2024-07-23 2024-07-23
US63/674,322 2024-07-23

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