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CN-122029320-A - Textile treatments for imparting oil repellency include the use of non-crystalline silicone- (meth) acrylate copolymers, crystalline polymers, and blocked isocyanates

CN122029320ACN 122029320 ACN122029320 ACN 122029320ACN-122029320-A

Abstract

A textile treatment emulsion may be prepared by mixing an aqueous emulsion comprising a non-crystalline silicone- (meth) acrylate copolymer, an aqueous composition comprising a crystalline component, and an aqueous composition comprising a blocked isocyanate. The textile treatment emulsion may be applied to a fabric and heated to increase the oil repellency of the fabric.

Inventors

  • D. Malottky
  • A. Banerjee
  • E. Bruske
  • D. FERGUSON
  • M. Yeletick
  • D. Hasso
  • B. MCDONALD
  • J. Mecca

Assignees

  • 陶氏环球技术有限责任公司
  • 美国陶氏有机硅公司

Dates

Publication Date
20260512
Application Date
20240905
Priority Date
20231027

Claims (19)

  1. 1. A process for preparing a textile treatment emulsion, wherein the process comprises: i) Mixing a starting material comprising I) An aqueous copolymer emulsion comprising a non-crystalline silicone- (meth) acrylate copolymer, a nonionic surfactant, and water, Wherein the amorphous silicone- (meth) acrylate copolymer comprises the following unit formula: wherein 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; Each R 2 is independently selected from the group consisting of H and methyl; Each R 3 is a group of the formula OSi (R 4 ) 3 ; wherein Each R 4 is independently selected from the group consisting of R and DSi (R 5 ) 3 , wherein Each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; Each D is independently selected from the group consisting of an oxygen atom, a (poly) oxyalkylene group of 1 to 12 units and a divalent hydrocarbon group of 2 to 4 carbon atoms, and Each R 5 is independently selected from the group consisting of R and DSi (R 6 ) 3 ; wherein Each R 6 is independently selected from the group consisting of R and DSiR 3 ; Provided that R 4 、R 5 and R 6 are selected such that the amorphous silicone- (meth) acrylate co-macromer unit having subscript b2 has at least 5 silicon atoms; Subscripts a, b1, and b2 represent the weight fraction of units in the copolymer, and subscripts a, b1, and b2 have values such that 0.25< A≤1, and 0≤(b1+b2)<0.75; Ii) an aqueous composition comprising a crystalline component, a nonionic surfactant and water, Wherein the crystalline component has a crystallization temperature of 25 ℃ or more, and Wherein starting material i) and starting material ii) are used in amounts sufficient to provide a weight ratio of the amorphous silicone- (meth) acrylate copolymer to the crystalline component of from 1:3 to 3:1, and Iii) An aqueous additive comprising a blocked isocyanate and water; wherein iii) the aqueous additive is added in an amount sufficient to provide a weight ratio of the amorphous silicone- (meth) acrylate copolymer and the crystalline component to blocked isocyanate of 16:1 to 1:1 combination.
  2. 2. The method of claim 1, wherein the weight ratio of the silicone- (meth) acrylate copolymer to the crystalline component is from 1:3 to 1:1.
  3. 3. The method of claim 1 or claim 2, wherein the crystalline component is selected from the group consisting of alkyl carbamates, polyolefins, poly (meth) acrylates, and poly (meth) acrylates having pendant polyorganosiloxane moieties. A process according to any one of claims 1 to 3, wherein the crystalline component has a crystallization temperature of 25 ℃ to 130 ℃.
  4. 4. A process according to any one of claims 1 to 3, wherein the starting material ii) is selected from the group consisting of Zelan ™ R3 from komu, NEOSEED ™ NR-7080 from diw chemical, NEOSEED ™ NR-7090 from diw chemical, PHOBOTEX RSY from hounsmeh, DOWSIL ™ IE-9100 emulsion from DOW, DOW ™ DMDA-8965 NT7 high density polyethylene resin from DOW, aqueous emulsion of polyvinyl alcohol and water.
  5. 5. The method of any of claims 1-4, wherein the combined weight ratio of the amorphous silicone- (meth) acrylate copolymer and the crystalline component to blocked isocyanate is 8:1.
  6. 6. The method of any one of claims 1 to 5, wherein the blocked isocyanate comprises an oxime blocked isocyanate or an N-heterocyclic blocked isocyanate.
  7. 7. The process according to any one of claims 1 to 6, wherein starting material i) is prepared by a process comprising: 1) Copolymerizing a starting material comprising (A) A silicone- (meth) acrylate macromer of the formula: Wherein 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-macromer, wherein (B) the silicone- (meth) acrylate co-macromer has a formula selected from the group consisting of formula (B-1), formula (B-2), and a combination of both formulas (B-1) and (B-2), wherein Formula (B-1) is Wherein 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 Wherein R 2 is selected from the group consisting of H and methyl, D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms and each R 3 is a group of formula OSi (R 4 ) 3 ), wherein each R 4 is independently selected from the group consisting of R and DSi (R 5 ) 3 , wherein 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) oxyalkylene 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 ), wherein each R 6 is independently selected from the group consisting of R and DSiR 3 , provided that R 4 、R 5 and R 6 are selected such that the silicone- (meth) acrylate co-macromer of formula (B-2) has at least 5 silicon atoms per molecule; Wherein the starting materials (A) are present in an amount of > 25% to 100% by weight, based on the combined weight of starting materials (A) and (B), and Wherein the starting materials (B) are present in an amount of from 0% by weight to < 75% by weight, based on the combined weight of starting materials (A) and (B), and Wherein starting materials (a) and (B) are copolymerized in the presence of additional starting materials, wherein the additional starting materials comprise: (C) An initiator; optionally a chain transfer agent; an optional manganese ion source, and Optionally a phenolic compound, and Wherein one of the conditions (i) or (ii) is satisfied, Wherein condition (i) is that step 1) further comprises adding a solvent before or during step 1), removing the solvent after forming the amorphous silicone- (meth) acrylate copolymer, and forming i) the aqueous copolymer emulsion comprising the amorphous silicone- (meth) acrylate copolymer, the nonionic surfactant, and the water, and Wherein condition (ii) is that step 1) comprises an emulsion polymerization, said additional starting material further comprises said nonionic surfactant and said water, and Wherein the product of step 1) comprises i) the aqueous copolymer emulsion comprising the non-crystalline silicone- (meth) acrylate copolymer, the nonionic surfactant, and the water.
  8. 8. The method of any one of claims 1 to 7, further comprising: II) adding an additional starting material selected from the group consisting of biocides, additional water, flame retardants, wrinkle reducing agents, antistatic agents, penetrants, softeners, condensation reaction catalysts, and combinations of two or more thereof.
  9. 9. A textile treatment emulsion, the textile treatment emulsion comprising: a non-crystalline silicone- (meth) acrylate copolymer comprising the following unit formula: wherein 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; Each R 2 is independently selected from the group consisting of H and methyl; Each R 3 is a group of the formula OSi (R 4 ) 3 ; wherein Each R 4 is independently selected from the group consisting of R and DSi (R 5 ) 3 , wherein Each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; Each D is independently selected from the group consisting of an oxygen atom, a (poly) oxyalkylene group of 1 to 12 units and a divalent hydrocarbon group of 2 to 4 carbon atoms, and Each R 5 is independently selected from the group consisting of R and DSi (R 6 ) 3 ; wherein Each R 6 is independently selected from the group consisting of R and DSiR 3 ; Provided that R 4 、R 5 and R 6 are selected such that the amorphous silicone- (meth) acrylate co-macromer unit having subscript b2 has at least 5 silicon atoms; Subscripts a, b1, and b2 represent the weight fraction of units in the copolymer, and subscripts a, b1, and b2 have values such that 0.25< A≤1, and Less than or equal to 0 (b1+b2) <0.75, and A crystalline component having a crystallization temperature of greater than or equal to 25 ℃; Wherein the amorphous silicone- (meth) acrylate copolymer and the crystalline component are present in an amount such that the weight ratio of the amorphous silicone- (meth) acrylate copolymer to the crystalline component is from 3:1 to 1:3; Blocked isocyanates Wherein the blocked isocyanate is present in an amount such that the combined weight ratio of the non-crystalline silicone- (meth) acrylate copolymer and the crystalline component to blocked isocyanate is from 16:1 to 1:1; nonionic surfactant, and And (3) water.
  10. 10. The textile treatment emulsion of claim 9, wherein the crystalline component is selected from the group consisting of alkyl polyurethanes, polyolefins, poly (meth) acrylates, and poly (meth) acrylates having pendant polyorganosiloxane moieties. The textile treatment emulsion of claim 9 or claim 10, wherein the crystalline component has a crystallization temperature of 25 ℃ to 130 ℃.
  11. 11. The textile treatment emulsion of claim 9 or claim 10, wherein the weight ratio of the non-crystalline silicone- (meth) acrylate copolymer and crystalline component to blocked isocyanate combined is 8:1.
  12. 12. The textile treatment emulsion of any one of claims 9 to 11, wherein the blocked isocyanate comprises an oxime blocked isocyanate or an N-heterocyclic blocked isocyanate.
  13. 13. A method for imparting oil repellency to a textile, wherein the method comprises: step 1) applying the textile treatment emulsion prepared by the method according to any one of claims 1 to 8 or the textile treatment emulsion according to any one of claims 9 to 12 to a textile, and Step 2) drying the textile, thereby removing all or part of the water.
  14. 14. The method of claim 13, wherein the method consists of step 1) and step 2).
  15. 15. An oil repellent textile prepared by the method of claim 13 or claim 14.
  16. 16. The method of any one of claims 1 to 8, wherein the amorphous silicone- (meth) acrylate copolymer has a weight average molecular weight of >181,000g/mol as measured by gel permeation chromatography.
  17. 17. The method of claim 16, wherein the weight average molecular weight is from 212,000g/mol to 2,000,000g/mol.
  18. 18. The textile treatment emulsion according to any one of claims 9 to 12, wherein the silicone- (meth) acrylate copolymer has a weight average molecular weight of >181,000g/mol as measured by gel permeation chromatography.
  19. 19. The textile treatment emulsion of claim 18, wherein the weight average molecular weight is from 212,000g/mol to 2,000,000g/mol.

Description

Textile treatments for imparting oil repellency include the use of non-crystalline silicone- (meth) acrylate copolymers, crystalline polymers, and blocked isocyanates Cross Reference to Related Applications The present application claims priority from 35 USC ≡119 (e) to U.S. provisional patent application No. 63/593716 filed on 10 th month 27 of 2023, U.S. provisional patent application No. 63/674322 filed on 7 th month 23 of 2024, U.S. provisional patent application No. 63/674323 filed on 7 th month 23 of 2024, U.S. provisional patent application No. 63/674325 filed on 7 th month 23 of 2024, U.S. provisional patent application No. 63/674328 filed on 7 th month 23 of 2024, and U.S. provisional patent application No. 63/674329 filed on 7 th month 23 of 2024. U.S. provisional patent application nos. 63/593716, 63/674322, 63/674323, 63/674325, 63/674328, and 63/674329 are hereby incorporated by reference. Technical Field The textile treatment emulsion comprises a non-crystalline silicone- (meth) acrylate copolymer, a crystalline component, and a cross-linking agent. The textile treatment emulsion may be used to impart oil repellency to textiles. Background Perfluoro and polyfluoroalkyl materials (PFAS) have been the dominant textile coating market for many years, however, due to environmental regulations customers and regulatory authorities wish to eliminate PFAS. There is a continuing need in the textile industry to find alternatives to PFAS that impart oil repellency to textiles and are compatible with current capital infrastructure because plasma treatments and engineered surface structures are not typically accomplished at the factory with existing equipment. WO2023019044 discloses a silicone- (meth) acrylate copolymer emulsion that can impart water repellency to textiles. However, this publication does not address oil repellency. US11746268 discloses a surface treatment agent which is an aqueous dispersion containing a fluorine-free polymer having repeating units derived from a fluorine-free (meth) acrylate monomer, a wax, an aqueous medium and an emulsifier. Disclosure of Invention A method for preparing a textile treatment emulsion includes I) mixing a starting material comprising I) an aqueous copolymer emulsion comprising a non-crystalline silicone- (meth) acrylate copolymer, a nonionic surfactant, and water, ii) an aqueous composition comprising a crystalline component, a nonionic surfactant, and water, and iii) an aqueous additive comprising a blocked isocyanate and water. Textile treatment emulsions are useful in methods for imparting oil repellency to textiles. Detailed Description The starting materials i) described above, aqueous copolymer emulsions comprising a non-crystalline silicone- (meth) acrylate copolymer, a nonionic surfactant and water can be prepared as described in U.S. provisional patent application No. 63/593716, which is hereby incorporated by reference. In the starting material i), the amorphous silicone- (meth) acrylate copolymer comprises the unit formula: Wherein 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 of the formula OSi (a group of R 4)3; wherein each R 4 is independently selected from the group consisting of R and DSi (R 5)3, wherein 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 oxygen atoms, 1 to 12 units of a (poly) alkylene oxide group 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; wherein each R 6 is independently selected from the group consisting of R and DSiR 3; provided that R 4、R5 and R 6 are selected such that the silicone- (meth) acrylate co-macromer unit having subscript b2 has at least 5 silicon atoms, subscript a, b1 and b2 represent the weight fraction of units in the copolymer, and the subscripts a, b1 and b2 have values such that 0.25< a≤1, and 0≤b1+b2 <0.75. as described below, the amount (a+b1+b2) =1 based on the combined weight of the macromers used to prepare the copolymer. The amorphous silicone- (meth) acrylate copolymer can have a weight average molecular weight of >181,000g/mol as measured by GPC. Alternatively, the amorphous silicone- (meth) acrylate copolymer may have a weight average molecular weight of at least 200,000g/mol, alternatively at least 210,000g/mol, alternatively at least 212,000g/mol, alternatively at least 225,000g/mol, alternatively at least 230,000g/mol, and alternatively at least 234,000g/mol, as measured by GPC, while the weight average molecular weight may be at most 2,000,000g/mol, alternatively at most 1,000,000g/mol, alternatively at most 950,000g/mol, alternatively at most 925,000g/mol,