Organic silicon-(methyl) acrylate copolymer composition containing organic silicon additive and preparation method and application of organic silicon-(methyl) acrylate copolymer composition

Abstract

The emulsion formulation comprises a silicone-(meth) acrylate copolymer, a source of manganese ions, a phenolic compound, and a silicone additive. The emulsion formulation can be applied to a textile and dried to impart long-lasting water resistance and softness to the textile.

Description

Cross-reference to related applications

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 588056, filed October 5, 2023, pursuant to 35 USC §119(e). U.S. Provisional Patent Application Serial No. 63 / 588056 is incorporated herein by reference. Technical Field

[0002] A composition and a method for preparing the composition are provided, the composition comprising an organosilicon-(meth)acrylate copolymer (polymer), a manganese ion source, and a phenolic compound. An aqueous emulsion of the composition can be combined with an aqueous emulsion of an organosilicon additive to form an emulsion formulation suitable for treating textiles to impart durable water resistance and softness. Background Technology

[0003] In waterproof textile treatment applications, fluorocarbon materials dominate the market due to their ability to provide excellent and durable water resistance. However, regulatory and customer pressures are driving the industry to require textile treatments based on non-fluorocarbon compounds. Previously disclosed non-fluorocarbon textile treatment agents have the drawback of poor durability, where the water resistance of textiles treated with them decreases significantly after multiple washes. Summary of the Invention

[0004] Emulsion formulations suitable for treating textiles contain: (I) a silicone-(meth)acrylate copolymer, (II) an additive, (III) a water-dispersible crosslinking agent, (IV) a surfactant, (V) water, a manganese ion source, and a phenolic compound. Textiles can be treated by coating them with the emulsion formulation and then heating them. Detailed Implementation

[0005] A method for forming an emulsion formulation suitable for treating textiles includes combining the following substances: a first aqueous emulsion comprising (I) an organosilicon-(meth)acrylate copolymer, a manganese ion source, and a phenolic compound; and a second aqueous emulsion comprising (II) an additive, (III) a water-dispersible crosslinking agent, and optionally one or more additional starting materials as described below. Alternatively, a method for preparing the above emulsion formulation may include:

[0006] 1) Starting material (I) is prepared by emulsion polymerization of a starting material comprising the following substances: the organosilicon-(meth)acrylate copolymer:

[0007] 80% to 98.75% by weight of crystallizable monomers of formula (A) below: , where R 1 and R 2 As mentioned above;

[0008] 0.25% to 15% by weight of organosilicon-(meth)acrylate macromonomers of formula (B): , where R 2 D 2 and R 3 As mentioned above;

[0009] 1% to 5% by weight of (C) crosslinkable (meth)acrylate monomers of the following formula: , where R 7 D 3 D 4 subscripts v and R 8 As mentioned above;

[0010] The amounts of the starting materials (A), (B), and (C) shown above are based on a total of 100% by weight of the combined amounts of starting materials (A), (B), and (C). The starting materials used in step 1) of the method for preparing this composition also include:

[0011] (D) Surfactants;

[0012] (E) Water;

[0013] (F) Initiator;

[0014] (H) chain transfer agent;

[0015] (K) manganese ion source; and

[0016] (L) Phenolic compounds;

[0017] This forms the first aqueous emulsion comprising the organosilicon-(meth)acrylate copolymer described in (I);

[0018] 2) Provide a second aqueous emulsion comprising the additive described in (II), a surfactant (D'), and water (E'); and

[0019] 3) A mixture comprising the first aqueous emulsion prepared in step 1), the second aqueous emulsion from step 2), the water-dispersible crosslinking agent of (III), and optionally one or more additional starting materials selected from the group consisting of: additional surfactants, waxes, biocides, additional water, flame retardants, wrinkle reducers, antistatic agents, and penetrants.

[0020] (I) Organosilicon-(meth)acrylate copolymer

[0021] Organosilicon-(meth)acrylate copolymers (copolymers) contain the following unit formulas:

[0022]

[0023] Each R1 It is an alkyl group with 16 to 24 carbon atoms, chosen independently; each R 2 Independently selected from the group consisting of H and methyl groups; each D 2 It is a divalent hydrocarbon group with 2 to 12 carbon atoms; each R 3 It is the formula OSi(R) 4 )3 groups; wherein each R 4 Independently select R and DSi(R) 5 A group consisting of 3 Rs, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from a group consisting of an oxygen atom, 1 to 12 units of (poly)alkyleneoxy groups, and 2 to 4 divalent hydrocarbon groups; each R 5 Independently select R and DSi(R) 6 A group consisting of 3 groups; where each R 6 Independently select a group consisting of R and DSiR3; the prerequisite is that R 4 R 5 and R 6 Selected such that the organosilicon-(meth)acrylate macromonomer unit with subscript x has at least 6 silicon atoms; each R 7 Independently select the group composed of free oxygen atoms and NH; D 3 It is a divalent hydrocarbon group with 1 to 12 carbon atoms; D 4 It is an alkylene group or a divalent alkylarylene group with 2 to 4 carbon atoms; the subscript v indicates a unit with the subscript y in the formula (OD). 4 The number of units in R, and the subscript v has a value from 0 to 12; each R 8 For cross-linking groups; each R 9 It is a monovalent hydrocarbon group with 1 to 14 carbon atoms; each R 10 The copolymer is independently selected from the group consisting of halogen (e.g., chloride), acetate groups, or monovalent hydrocarbon groups of 1 to 14 carbon atoms; the subscripts w, x, y, z1, and z2 represent the relative weights of the units in the copolymer, with subscript x having a value of 0.25 to 15; subscript w having a value of 80 to 98.75; subscript y having a value of 1 to 5; subscript z1 having a value of 0 to 18.75; and subscript z2 having a value of 0 to 18.75, and the amount (w+x+y+z1+z2)=100. The copolymer also includes end portions.

[0024] In the above unit equation, R 1 It has 16 to 24 carbon atoms. Alternatively, R 1 It may have 16 to 22 carbon atoms, alternatively 18 to 24 carbon atoms, and alternatively 18 to 22 carbon atoms. R 1It may be selected from the group consisting of octadecyl, eicosyl, and docosyl. Alternatively, R 1 It can be octadecyl.

[0025] In the above unit equation, each R 3 It is the formula OSi(R) 4 )3 groups; wherein each R 4 Independently select R and DSi(R) 5 A group consisting of 3 Rs, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from a group consisting of an oxygen atom, 1 to 12 units of (poly)alkyleneoxy groups, and 2 to 4 divalent hydrocarbon groups; each R 5 Independently select R and DSi(R) 6 A group consisting of 3 groups; where each R 6 Independently select a group consisting of R and DSiR3; the prerequisite is that R 4 R 5 and R 6 Selected to ensure that the organosilicon-(meth)acrylate macromonomer unit with the subscript x has at least 6 silicon atoms. Alternatively, R is selected. 4 R 5 and R 6 Each unit has at least 6 silicon atoms, alternatively 6 to 20 silicon atoms, alternatively 7 to 19 silicon atoms, alternatively 8 to 18 silicon atoms, alternatively 9 to 17 silicon atoms, and alternatively 10 to 16 silicon atoms.

[0026] In the organosilicon-(meth)acrylate macromonomer unit, each R is a monovalent hydrocarbon group with 1 to 12 carbon atoms. The monovalent hydrocarbon group of R can be an alkyl group, such as an alkyl group with 1 to 6 carbon atoms. Alternatively, the alkyl group can have 1 to 3 carbon atoms, or alternatively 1 to 2 carbon atoms. Alternatively, each R group can be a methyl group.

[0027] Each D is independently selected from a group consisting of an oxygen atom, 1 to 12 units of (poly)alkylene oxide groups, and 2 to 4 carbon divalent hydrocarbon groups. Each D 2 It is a divalent hydrocarbon group with 2 to 12 carbon atoms. Alternatively, D 2 It may have 2 to 10, alternatively 3 to 5, and alternatively 3 carbon atoms. Each D 3 It is a divalent hydrocarbon group with 1 to 12 carbon atoms. Alternatively, each D 3 It can be an alkylene group; alternatively, desethylene. D 4 It is an alkylene group or a divalent alkylarylene group with 2 to 4 carbon atoms.

[0028] D 4Examples of divalent hydrocarbon groups may include alkylene groups, such as ethylene, propylene, or butylene; arylene groups such as phenylene; or alkylarylene groups such as: or Each subscript u is independently 1 to 6, or alternatively 1 to 2. Alternatively, the divalent hydrocarbon group may be alkylene, and alternatively, the divalent hydrocarbon group may be ethylene. D 2 and D 3 The divalent hydrocarbon group of D can be as described above, and alternatively can be methylene. The divalent hydrocarbon group of D can be alkylene, such as ethylene, propylene, or butylene. Alternatively, each D can be ethylene.

[0029] Each unit of the (poly)alkylene group of D can have 2 to 4 carbon atoms, for example, having the formula D 5 (OD 6 ) v’ -OR, where D 5 It is an alkylene group with 2 to 4 carbon atoms, D 6 It is an alkylene group with 2 to 4 carbon atoms, R as described above, and the subscript v' is 0 to 12. Alternatively, the subscript v' can be 0 or 1. Alternatively, the subscript v' can be 0. Examples of (poly)alkylene groups include ethylene oxide and propylene oxide.

[0030] Alternatively, each D may be selected from an oxygen atom and a divalent hydrocarbon group. Alternatively, each divalent hydrocarbon group of D may be an alkylene group, such as ethylene. Alternatively, each D may be oxygen. Alternatively, in the same unit, some instances of D may be oxygen, and other instances of D may be alkylene.

[0031] In the above unit equation, each R 7 Independently select the group composed of free oxygen atoms and NH. Alternatively, each R 7 It could be oxygen.

[0032] In the above unit equation, each R 8 It is a cross-linking group. Each R 8 It can be independently selected from the group consisting of hydroxyl, amino, epoxy, urea, and acetoxy groups. Alternatively, each R 8 The group consisting of hydroxyl and urea groups can be selected independently, and each R can be selected separately. 8 It can be a hydroxyl group.

[0033] In the above unit equation, each R 9 It is a monovalent hydrocarbon group that does not contain aliphatic unsaturation and can be straight-chain, branched, or cyclic (i.e., monocyclic or polycyclic), or a combination thereof. R 9It can be an alkyl group or an aryl group, which can be monocyclic or polycyclic, and optionally has straight-chain or branched groups. R 9 Examples of suitable alkyl groups may include methyl, tert-amyl, butyl (including tert-butyl), cyclohexyl, isodecyl, isobornyl, and 2-ethylhexyl. Examples of suitable aryl groups include phenyl, naphthyl, anthraceneyl, and benzyl.

[0034] In the above unit equation, R 10 It can be a halide, acetate, or monovalent hydrocarbon group, as mentioned above for R. 9 The halide may be a bromide (Br), chloride (Cl), fluoride (F) or iodide (I); alternatively Br, Cl or F; alternatively Br or Cl; and alternatively Cl.

[0035] In the above unit formula, the subscripts w, x, y, and z are the relative weights of each unit, and the quantity (w + x + y + z) can total 100. The subscript w has a value from 80 to 98.75. Alternatively, the subscript w can be at least 80, alternatively at least 81, alternatively at least 82, alternatively at least 83, alternatively at least 84, and alternatively at least 85. Meanwhile, the subscript w can be at most 98.75, alternatively at most 98, alternatively at most 97, alternatively at most 96, alternatively at most 97, alternatively at most 96, alternatively at most 95, alternatively at most 94, alternatively at most 93, alternatively at most 92, alternatively at most 91, and alternatively at most 90. Alternative locations, the subscript w can be 80 to 98, alternative locations 81 to 97, alternative locations 82 to 96, alternative locations 82 to 95, and alternative locations 85 to 90.

[0036] The subscript x has a value from 0.25 to 15. Alternatively, the subscript w is at least 0.25, at least 0.5, at least 0.75, at least 1, at least 2, at least 3, at least 4, or at least 5. Meanwhile, the subscript x can be at most 15, at most 14, at most 13, at most 12, at most 11, and at most 10. Alternatively, the subscript x can be 1 to 14, at most 2 to 13, at most 3 to 12, at most 4 to 11, at most 5 to 10, at most 5 to 15; and at most 10.

[0037] The subscript y has values ​​from 1 to 5. Alternatively, the subscript y can be at least 1, at least 1.25, at least 1.5, at least 2, and at least 1.75. Meanwhile, the subscript y can be at most 5, at most 4, at most 3, at most 2.75, at most 2.5, and at most 2.25. Alternatively, the subscript y can be 1 to 3, at most 1 to 2, at most 1.5 to 2.5, at most 1.75 to 2.25, and at most 2.

[0038] The subscript z1 can be 0. Alternatively, the subscript z1 can be at least 0.5, at least 1, or at least 2; meanwhile, the subscript x can be at most 18.75, at most 15, at most 10, at most 8, or at most 5. Alternatively, the subscript z1 can be 0 to 18.75, >0 to 18.75, 0.5 to 7, 1 to 6, or 2 to 5.

[0039] The subscript z2 can be 0. Alternatively, the subscript z2 can be at least 0.5, at least 1, or at least 2; meanwhile, the subscript z2 can be at most 8, at most 7, at most 6, at most 5, or at most 4. Alternatively, the subscript z2 can be 0 to 8, >0 to 8, 0.5 to 7, 1 to 6, or 2 to 5.

[0040] There is no particular limitation on the total number of units per molecule of copolymer. The units shown above can be in any order; for example, the copolymer can be a random copolymer or a block copolymer.

[0041] Those skilled in the art will recognize that copolymers can be prepared by free radical polymerization via the method described below, and that this method will form end portions of the copolymer. The copolymer also contains end portions that can be derived from self-initiators, chain transfer agents, or both, as exemplified by Odian, George (2004). [Principles of Polymerization (…] Principles of Polymerization As described in (4th edition). New York: Wiley-Interscience. ISBN 978-0-471-27400-1.

[0042] The copolymer can be prepared by a method including the following processes:

[0043] 1) Copolymerize the starting materials, said starting materials comprising

[0044] 80% to 98.75% by weight of (A) Crystallizable monomers, wherein R 1It is an alkyl group with 16 to 24 carbon atoms as described above, and R 2 Select from the group consisting of H and methyl groups, as described above;

[0045] 0.25% to 15% by weight of (B) Organosilicon-(meth)acrylate macromonomers, wherein each R 3 It is the formula OSi(R) 4 )3 groups; each R 4 Independently select R and DSi(R) 5 The group consists of 3 groups, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; each D is independently selected from a group consisting of an oxygen atom, 1 to 12 units of (poly)alkyleneoxy groups, and 2 to 4 divalent hydrocarbon groups; each R 5 Independently select R and DSi(R) 6 A group consisting of 3 groups; where each R 6 Independently select a group consisting of R and DSiR3; the prerequisite is as described above, R 4 R 5 and R 6 It was chosen to ensure that each molecule of the macromolecular monomer has at least 6 silicon atoms;

[0046] 1% to 5% by weight of (C) crosslinkable (meth)acrylate monomers of the following formula: R 7 Independently selected from oxygen and NH, D 3 It is a divalent hydrocarbon group with 1 to 12 carbon atoms, D 4 It is a divalent group with 2 to 4 carbon atoms, with subscripts v from 0 to 12, and R 8 These are cross-linking groups, each as described above;

[0047] (D) Surfactants;

[0048] (E) Water;

[0049] (F) Initiator;

[0050] (H) chain transfer agent;

[0051] (K) manganese ion source; and

[0052] (L) Phenolic compounds;

[0053] This results in an aqueous emulsion containing (I) an organosilicon-(meth)acrylate copolymer, (D) a surfactant, (E) water, (K) a manganese ion source, and (L) a phenolic compound.

[0054] In step 1), the above emulsion polymerization method may include forming an emulsion comprising starting materials (A), (B), (C), (D), (E), (K), and (L) (and optionally (H) and / or (J)), and then adding initiator (F) and copolymerizing. It is not intended to be theoretically rigorous, but it is thought that during the processing to combine and emulsify (A), (B), (C), (D), (E), (H), and (J), the starting materials (K) and (L) may inhibit the formation of acrylic acid radicals, which may affect copolymer formation during copolymerization in step 1).

[0055] A method for preparing an emulsion formulation suitable for the preparation of textiles may include performing step 1) above to form a first aqueous emulsion comprising an organosilicon-(meth)acrylate copolymer, a surfactant, water, a manganese ion source, and a phenolic compound; and 2) combining the first aqueous emulsion prepared in step 1) with a second aqueous emulsion comprising (II) an additive (as described above and in detail below), (III) a water-dispersible crosslinking agent (as described above and in detail below) and optionally one or more additional starting materials.

[0056] Alternatively, one or more additional starting materials may be added in step 1) to prepare the copolymer. For example, in step 1), an additional non-crystallizable monomer (J) may be added, which is different from each of (A), (B) and (C).

[0057] Step 1) of the above method may include forming an emulsion comprising starting materials (A), (B), (C), (D), (E), (F), (H), (K), and (L) (and optionally (J)). If the starting material (A) is solid at RT, the starting material may be heated to a temperature and time sufficient to melt the starting material (A), for example, 30°C to 50°C for 5 to 15 minutes. The resulting starting materials may be mixed under shear to form an aqueous emulsion. Shear mixing may be performed by any convenient means for forming an aqueous emulsion, such as ultrasonic treatment and subsequent microfluidization. Equipment for shear mixing (such as ultrasonicators, homogenizers, microfluidizers, and high-speed mixers) is known in the art and is commercially available. It is not intended to be theoretically construed that shear mixing can be used to obtain submicron particle sizes in emulsions. In step 1), the starting materials comprising (A), (B), (C) and (F) (and, when present, (H) and (J)) are copolymerized with the starting materials (D), (E), (K) and (L) in an aqueous emulsion to form (I) organosilicon-(meth)acrylate copolymer.

[0058] Step 2) of the above-described method for preparing emulsion formulations can be carried out in any convenient manner, such as mixing in a jacketed container equipped with a stirrer. Steps 1) and 2) can be carried out sequentially in the same container. Alternatively, steps 1) and 2) can be carried out in different devices. Steps 1) and / or 2) can be carried out at RT or at elevated temperatures (e.g., up to 100°C, alternatively 40°C to 80°C). Alternatively, heating can be carried out in step 1), and step 2) can be carried out at RT. Alternatively, one or both of steps 1) and 2) can be carried out at lower temperatures and elevated pressures (e.g., up to 5 atmospheres).

[0059] Prior to step 1), the starting materials comprising (A), (B), (C), (H), (K), (L), and (J) if present, can be combined under aerobic or anaerobic conditions, optionally heated for an extended time. For example, prior to the addition of the initiator and copolymerization in step 1), the starting materials comprising (A), (B), (C), (H), (K), (L), and (J) if present, can be emulsified with (D) and (E). In step 1), the starting materials are combined in the above method, and copolymerization can be carried out on a commercial scale under anaerobic or aerobic conditions, optionally at elevated temperatures (e.g., up to 100°C, alternatively 40°C to 80°C, and alternatively 45°C to 50°C). Copolymerization can be carried out in a batch manner, wherein the residence time is 15 minutes to 24 hours, alternatively 30 minutes to 12 hours, alternatively 40 minutes to 8 hours, and alternatively 40 minutes to 2 hours. For the purposes of this application, aerobic or anaerobic conditions mean that oxygen does not need to be present in the gas in the headspace of the reactor where copolymerization occurs, or dissolved in the liquid where copolymerization occurs. The remaining gas in the headspace can be an inert gas, such as nitrogen or argon.

[0060] Alternatively, compositions comprising the above-described copolymers, manganese ion sources, and phenolic compounds can be prepared by a method comprising dissolving one or more starting materials such as (A), (B), (C), (H), (K), (L), and (J) if present) in an organic solvent (such as a monohydric alcohol), and copolymerizing the starting materials (A), (B), (C), (F), (H), and (J) if present) by varying suitable starting materials and their amounts, such as in the method disclosed in U.S. Patent 10,047,199 to Iimura et al. The resulting compositions may be solvent-based. All or part of the solvent may be removed by any convenient means, such as by stripping or heated distillation and optionally by reduced pressure. The resulting compositions comprising the copolymers, manganese ion sources, and phenolic compounds may be emulsified using (D) a surfactant and (E) water. The starting materials for preparing the compositions and the emulsion formulations comprising the compositions are further described below.

[0061] The starting material (A) is a crystallizable monomer of formula (A-1): , where R 1 and R 2 As described above. Examples of crystallizable monomers used for starting material (A) include octadecyl (meth)acrylate, eicosyl (meth)acrylate, docosyl (meth)acrylate, and combinations thereof. Alternatively, when R 2 When hydrogen is present, the starting material (A) can be an acrylate selected from octadecyl acrylate, eicosyl acrylate, docosyl acrylate, and combinations thereof. Crystallizable monomers suitable for the starting material (A) are commercially available, for example, from Millipore Sigma, St. Louis, Missouri, USA, and BASF SE, Ludwigshafen, Germany. Crystallizable means that the starting monomer has a melting point of ≥25°C ± 5°C.

[0062] Based on the combined weight of starting materials (A), (B), and (C) and (if present) (J), starting material (A) is used in an amount of 80% to 98.75%. On the same basis, the amount of starting material (A) can be at least 80%, alternatively at least 81%, alternatively at least 82%, alternatively at least 83%, alternatively at least 84%, and alternatively at least 85%. Meanwhile, on the same basis, the amount of starting material (A) can be at most 98.75%, alternatively at most 98%, alternatively at most 97%, alternatively at most 96%, alternatively at most 97%, alternatively at most 96%, alternatively at most 95%, alternatively at most 94%, alternatively at most 93%, alternatively at most 92%, alternatively at most 91%, and alternatively at most 90%. Alternatively, on the same basis, the amount of starting material (A) may be 80% to 98%, alternatively 81% to 97%, alternatively 82% to 96%, alternatively 82% to 95%, alternatively 85% to 90%.

[0063] Starting material (B) is an organosilicon-(meth)acrylate macromonomer of formula (B-1): , where R 2 D 2 and R 3 As stated above.

[0064] Alternatively, the starting material (B) may include formula (B-2): , where R 2 R 4 and R 5 As stated above.

[0065] Alternatively, the starting material (B) may comprise a macromonomer selected from the group consisting of: 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propyl methacrylate of the formula: (Si10); 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxane-3-yl)propyl methacrylate: (Si16); and combinations thereof. The starting material (B) can be prepared by known methods, such as those disclosed in PCT Publication WO2020 / 142388 and U.S. Patent 6,420,504.

[0066] Based on the combined weight of starting materials (A), (B), and (C) and (if present) (J), starting material (B) is used in an amount from 0.25% to 15%. Alternatively, on the same basis, starting material (B) may be used in an amount of at least 0.25%, alternatively at least 0.5%, alternatively at least 0.75%, alternatively at least 1%, alternatively at least 2%, alternatively at least 3%, alternatively at least 4%, and alternatively at least 5%. Meanwhile, on the same basis, starting material (B) may be present in an amount of up to 15%, alternatively up to 14%, alternatively up to 13%, alternatively up to 12%, alternatively up to 11%, and alternatively up to 10%. Alternatively, based on the same criteria described above, the amount of starting material (B) may be 1% to 14%, alternatively 2% to 13%, alternatively 3% to 12%, alternatively 4% to 11%, alternatively 5% to 10%, alternatively 5% to 15%, and alternatively 10%.

[0067] Starting material (C) is a crosslinkable (meth)acrylate monomer.

[0068] The starting material (C) is a crosslinkable (meth)acrylate monomer of formula (C-1): , where R 2 R 7 D 3 R 8The subscript v is as described above. Examples of suitable crosslinkable (meth)acrylates for the starting material (C) include ethyl methacrylate (2-acetylacetoxy)methacrylate, hydroxybutyl methacrylate, hydroxyethyl methacrylate, hydroxyethylcaprolactone (meth)acrylate, hydroxypropyl methacrylate, urea methacrylate, glycidyl methacrylate (GMA), poly(ethylene glycol) (meth)acrylate (PEGMA), and combinations thereof. Urea methacrylate monomers may have the formula: , where R 11 It is an oxygen atom or NH moiety. Examples of urea monomers are known in the art and disclosed, for example, in U.S. Patent 9,212,292 to Pressley et al. Other crosslinkable (meth)acrylate monomers are known in the art and are commercially available, for example, from BASF SE. Other crosslinkable (meth)acrylates are commercially available as Sipomer WAM1 and 2.

[0069] Based on the combined weight of starting materials (A), (B), and (C) and (if present) (J), starting material (C) is used in an amount of 1% to 5%. On the same basis, the amount of starting material (C) may be at least 1%, alternatively at least 1.25%, alternatively at least 1.5%, alternatively at least 2%, and alternatively at least 1.75%. Meanwhile, on the same basis, the amount of starting material (C) may be at most 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2.75%, alternatively at most 2.5%, and alternatively at most 2.25%. Alternatively, on the same basis, the amount of starting material (C) may be 1% to 3%, alternatively 1% to 2%, alternatively 1.5% to 2.5%, alternatively 1.75% to 2.25%, and alternatively 2%.

[0070] Starting material (D) surfactant

[0071] The starting material (D) is a surfactant. The surfactant can be selected from the group consisting of (D-1) cationic surfactants, (D-2) nonionic surfactants, and (D-3) combinations of both cationic and nonionic surfactants. Cationic surfactants that can be used in this paper include compounds containing a positively charged quaternary ammonium hydrophilic moiety in their molecules, such as quaternary ammonium salts represented by formula (D-1-1): R 12 R 13 R 14 R 15 N + X' - , where R 12 To R 15X' is an alkyl group containing 1 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybean; and X' is a halogen, such as chlorine or bromine. Alternatively, the quaternary ammonium compound may be an alkyltrimethylammonium and dialkyldimethylammonium halide or acetate having at least 8 carbon atoms in each alkyl substituent. Dialkyldimethylammonium salts may be used, represented by formula (D-1-2): R 16 R 17 N + (CH3)2X' - , where R 16 and R 17 It is an alkyl group containing 12 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil, or soybean; and X' is a halogen. A monoalkyltrimethylammonium salt, represented by formula (D-1-3), can be used: R 18 N + (CH3)3X'' - , where R 18 It is an alkyl group containing 12 to 30 carbon atoms, or an alkyl group derived from tallow, coconut oil or soybean; and X'' is a halogen or an acetate.

[0072] Representative quaternary ammonium halide salts are dodecyltrimethylammonium chloride / lauryltrimethylammonium chloride (LTAC), hexadecyltrimethylammonium chloride (CTAC), hexadecyltrimethylammonium chloride, docosyldimethylammonium bromide, hexadecyldimethylammonium chloride, hexadecyldimethylammonium bromide, octadecyldimethylammonium chloride, disaccharide dimethylammonium chloride, and docosyldimethylammonium chloride. These quaternary ammonium salts can be branded as such as ADOGEN. ™ ARQUAD ™ TOMAH ™ and VARIQUAT ™ Acquired through commercial purchase.

[0073] Other suitable cationic surfactants that can be used include fatty acid amines and amides, as well as their salts and derivatives, such as aliphatic fatty amines and their derivatives. Commercially available cationic surfactants of this type include compositions produced by Akzo Nobel Chemicals Inc., Chicago, Illinois under the name ARQUAD. ™ T27 W, ARQUAD ™ 16-29 for sale; and sold by Stepan Company, Northfield, Illinois, USA, for Ammonyx Cetac-30.

[0074] Based on the weight of the starting material (I) organosilicon-(meth)acrylate copolymer in the aqueous emulsion, the amount of (D-1) cationic surfactant may be from 0.1% to 5%. Alternatively, on the same basis, 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 the amount of cationic surfactant may be at most 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2%, alternatively at most 1%. Alternatively, on the same basis, the amount of cationic surfactant may be from 0.2% to 4%, alternatively 0.3% to 3%, alternatively 0.4% to 2.5%, and alternatively 0.5% to 2%.

[0075] The starting material (D-2) is a nonionic surfactant. Some suitable nonionic surfactants that can be used include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, alkyl glucosides, polyoxyethylene fatty acid esters, sorbitol fatty acid esters, and polyoxyethylene sorbitol fatty acid esters. Commercially available nonionic surfactants include compositions such as: (i) those under the name TERGITOL ™ TMN-6 and TERGITOL ™ (ii) 2,6,8-trimethyl-4-nonyl polyoxyethylene ether sold by TMN-10; and (ii) TERGITOL manufactured by Dow Chemical Company, Midland, Michigan, USA. ™ 15-S-7, TERGITOL ™ 15-S-9, TERGITOL ™ 15-S-15, TERGITOL ™ 15-S-30 and TERGITOL ™ C11-15 secondary alkyl polyoxyethylene ether sold under the name TRITON by Dow Chemical Company, 15-S-40. ™ (iii) Octylphenyl polyoxyethylene (40) ether sold by X405; and (iii) MAKON by Stepan Company. ™ 10. Nonylphenyl polyoxyethylene (10) ether sold; (iv) Ethoxylated alcohol sold by Henkel Corp. / Emery Group, Cincinnati, Ohio, USA under the name Trycol 5953; (v) Croda Inc., Edison, New Jersey, USA under the name BRIJ ™L23 and BRIJ ™ L4 sells ethoxylated alcohols; (vi) alkyl-oxo alcohol polyethylene glycol ethers, such as GENAPOL. ™ UD 050 and GENAPOL ™ UD110; (vii) Alkyl polyethylene glycol ethers based on C10 Guerbert alcohol and ethylene oxides such as LUTENSOLS ™ XP 79.

[0076] Suitable nonionic surfactants also include poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers. Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers are also commonly referred to as poloxamers. Poloxamers are nonionic triblock copolymers composed of a central hydrophobic poly(propylene oxide) chain and two flanking hydrophilic poly(ethylene oxide) chains. Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers are commercially available from BASF, Florham Park, New Jersey, USA, under the trademark PLURONIC. ™ Such as PLURONIC ™ L61, L62, L64, L81, and P84 are for sale.

[0077] Other suitable nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleate, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol (such as polyethylene glycol having 23 ethylene oxide units), polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanol, and polyalkylene glycol-modified polysiloxane surfactants. Commercially available nonionic surfactants that can be used include compositions such as those marketed under the trademark TERGITOL. ™ TMN-6 and TERGITOL ™ TMN-10 is sold as 2,6,8-trimethyl-4-nonoxyethylene oxyethanol (6EO) and (10EO); under the trademark TERGITOL ™ 15-S-7, TERGITOL ™ 15-S-9, TERGITOL ™ 15-S-15 sold alkoxylated polyethylene oxyethanol (C 11-15 Secondary alcohol ethoxylates 7EO, 9EO and 15EO); under the trademark TERGITOL ™ Other C products sold under 15-S-12, 15-S-20, 15-S-30, and 15-S-40 11-15Secondary alcohol ethoxylates; under the trademark TRITON ™ X-405 sells octylphenoxy polyethoxyethanol (40EO); and products marketed under the name ECOSURF. ™ EH alcohol ethoxylates, such as ECOSURF ™ EH-40. All of these surfactants are sold by Dow Chemical Company.

[0078] Other useful commercial nonionic surfactants are produced by Stepan Corporation under the trademark MAKON. ™ 10. Nonylphenoxy polyethoxyethanol (10EO) for sale; by ICI Surfactants, Wilmington, Delaware, USA, under the trademark BRIJ. ™ 35L commercially available polyoxyethylene 23 lauryl ether (Laureth-23); and RENEX, also sold by ICI Surfactants. ™ 30, a polyoxyethylene ether alcohol.

[0079] Nonionic surfactants can also be silicone polyethers (SPEs). Silicone polyethers, as emulsifiers, can have a rake-like structure, in which polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymer structure, where A represents the polyether moiety and B represents the ABA-structured siloxane moiety. Suitable SPEs include DOWSIL from Dow Silicones Corporation, Midland, Michigan, USA. ™ OFX-5329 fluid. Alternatively, the nonionic surfactant may be selected from polyalkylene oxide-substituted silicones, silicone alkanolamides, silicone esters, and silicone glycosides. Such silicone-based surfactants can be used to form such aqueous emulsions and are known in the art and have been described, for example, in U.S. Patent 4,122,029 to Gee et al., U.S. Patent 5,387,417 to Rentsch, and U.S. Patent 5,811,487 to Schulz et al.

[0080] The starting material (D-2) nonionic surfactant can be delivered in the diluent, and the amount used is sufficient to provide 0.1% to 6% surfactant based on the weight of the starting material (I) silicone-(meth)acrylate copolymer in the aqueous emulsion. Alternatively, on the same basis, the amount of nonionic surfactant can 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 the amount of nonionic surfactant can be at most 5%, alternatively at most 4%, alternatively at most 3%, alternatively at most 2%, alternatively at most 1%. Alternatively, on the same basis, the amount of nonionic surfactant can be 0.2% to 4%, alternatively 0.3% to 3%, alternatively 0.4% to 2.5%, and alternatively 0.5% to 2%. Alternatively, based on the weight of the starting material (I) silicone-(meth)acrylate copolymer in the aqueous emulsion, the starting materials (D-1) cationic surfactant and (D-2) nonionic surfactant may be present in a combined amount of ≤10%.

[0081] Starting material (E) water

[0082] The starting material (E) is water. There are generally no restrictions on the type of water; for example, water can be treated or untreated. Examples of processes that can be used to purify water include distillation, filtration, deionization, and combinations of two or more of these, such that water can be deionized, distilled, and / or filtered. Alternatively, the water can be untreated (e.g., tap water, i.e., supplied by a municipal water supply 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 method described above. Additional water may be added after step 1). For example, the first aqueous emulsion and / or the second aqueous emulsion prepared as described above may be diluted with additional water to obtain the desired amount of starting material before treating textiles with the emulsion formulation. In step 1), water may be added in amounts of 20% to 97%, alternatively 30% to 90%, alternatively 40% to 80%, alternatively 50% to 97%, alternatively 50% to 90%, or alternatively 60% to 80%, based on the combined weight of all starting materials in step 1). Alternatively, on the same basis, water may be added in amounts of at least 20%, at least 30%, at least 40%, at least 50%, and at least 60%; while the amount of water may be at most 97%, at most 96%, at most 95%, and at most 80%.

[0083] Without being bound by theory, it is assumed that starting materials (A), (B), and (C), and (if present) (J), copolymerize to form (I) organosilicon-(meth)acrylate copolymer as described herein with starting material (I). Furthermore, it is assumed that starting material (D), surfactant, and (E), water, do not participate in the copolymerization reaction; however, copolymers including one or both of starting materials (D) and (E) are not excluded from the scope of this document.

[0084] Starting material (I) Organosilicon-(meth)acrylate copolymer

[0085] The silicone-(meth)acrylate copolymer is prepared by emulsion copolymerization comprising the starting materials (A), (B), (C), and (F) described above. Alternatively, the silicone-(meth)acrylate copolymer can be a reaction product of a starting material consisting essentially of starting materials (A), (B), (C), and (F) (and, when present, (H) chain transfer agent and / or (J) additional monomer). Alternatively, the silicone-(meth)acrylate copolymer can be a reaction product of a starting material consisting of starting materials (A), (B), (C), and (F) (and, when present, (H) chain and / or (J)). It is not desirable to be bound by theory, but rather to consider that starting materials (D) and (E) do not copolymerize with starting materials (A), (B), and (C), but only act as mediators for copolymerization. However, the possibility that one or more of the starting materials (D) and / or (E) or any other starting material added during the method may participate in the copolymerization reaction of the starting materials (A), (B), (C) and (F) should not be excluded in this paper.

[0086] In emulsion formulations suitable for treating textiles, the (I) silicone-(meth)acrylate copolymer may be present in an amount ranging from 57.2% to 88.5% based on the combined weight of all starting materials other than water in the emulsion formulation. Alternatively, the amount of (I) silicone-(meth)acrylate copolymer may vary depending on factors such as the type of fabric to be treated. For example, when the textile to be treated is polyester, the amount of (I) silicone-(meth)acrylate copolymer may be from 58.2% to 88.5% on the same basis. Alternatively, when the textile to be treated is polyamide such as nylon, the amount of (I) silicone-(meth)acrylate copolymer may be from 57.2% to 79.3% on the same basis.

[0087] Starting material (III) Water-dispersible crosslinking agent

[0088] Starting material (III) is a water-dispersible crosslinking agent (crosslinker) that can be added to an emulsion formulation for treating textiles, for example, to promote the curing of (I) a silicone-(meth)acrylate copolymer and (II) an additive. Starting material (III) may be combined with a first aqueous emulsion prepared in step 1). Alternatively, starting material (III) may be combined with a second aqueous emulsion in step 2) of a method for preparing an emulsion formulation suitable for treating textiles. Alternatively, the first and second aqueous emulsions may be combined to form a third aqueous emulsion, to which (III) water-dispersible crosslinker may be added. Suitable water-dispersible crosslinkers include capped isocyanates and glycols. The term "capped isocyanate" encompasses monoisocyanates, diisocyanates, and polyisocyanates in which the isocyanate groups have reacted with a capping agent, releasing the isocyanate and the capping agent upon heating. Suitable capping agents are known in the art, such as amines, amides, compounds having active hydrogen atoms, alcohols, or oximes. Terminal isocyanates are commercially available, such as ARKOPHOB from Archroma, Reinach, Switzerland. ™ DAN and ARKOPHOB ™ SR; RUCO-GUARD from Rudolf GmbH of Geretsreid, Bayern, Germany ™ WEB, and PHOBOL from Angco ™ UXN Incremental Agent and PHOBOL ™XAN extender. Diols include, for example, 1,2-propanediol; 1,3-propanediol; 1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol; 2-methyl-1,2-propanediol; 1,5-pentanediol; 2-methyl-2,3-butanediol; 1,6-hexanediol; 1,2-hexanediol; 2,5-hexanediol; 2-methyl-2,4-pentanediol; 2,3-dimethyl-2,3-butanediol; 2-ethylhexanediol; 1,2-octanediol; 1,2-decanediol; 2,2,4-trimethylpentanediol; 2-butyl-2-ethyl-1,3-propanediol; 2,2-diethyl-1,3-propanediol. Examples of suitable crosslinking agents are known in the art and disclosed, for example, in U.S. Patent Application 2017 / 0204558 to Knaup and U.S. Patent 9,777,105 to Hamajima et al. (starting from column 11, line 54), which are hereby incorporated by reference for the purpose of describing suitable crosslinking agents. The exact amount of crosslinking agent (III) depends on various factors, including the type and amount of the silicone-(meth)acrylate copolymer (I) formed in step 1) and the textile to be treated; however, based on the weight of the fabric, the weight of crosslinking agent (III) may be sufficient to provide 0.25% to 3.75%, alternatively 0.25% to 1%, and alternatively 0.25% to 0.5% on the same basis. Alternatively, the amount of crosslinking agent may be 9.1% to 30% based on the combined weight of all starting materials other than water in the emulsion formulation suitable for treating the textile. Alternatively, the amount of crosslinking agent (III) may vary depending on factors such as the type of fabric to be treated. For example, when the textile to be treated is polyester, the amount of (III) crosslinking agent may be 9.2% to 20.1%. Alternatively, when the textile to be treated is polyamide such as nylon, the amount of (III) crosslinking agent may be 9.1% to 30.7%.

[0089] Starting material (H) chain transfer agent

[0090] Additional starting materials that may be added in step 1) of the above method include (H) chain transfer agents. Suitable chain transfer agents include thiols, such as alkyl thiols, for example n-octyl thiol, n-dodecyl thiol, dodecyl thiol (dodecane thiol), and / or 2,2-dimethyldecyl thiol. Alternatively, the chain transfer agent may be water-soluble, such as mercaptoacetic acid and / or 2-mercaptoethanol. Suitable chain transfer agents are known in the art and have been disclosed, for example, in Peter Nesvadba's "Radical Polymerization in Industry," *Performance Chemical Research*, GASF Schweiz AG, Basel, Switzerland, and *Encyclopedia of Radicals in Chemistry, Biology and Materials*, Online. © 2012 John Wiley & Sons, Ltd.).

[0091] The starting material (H) chain transfer agent is optional and can be added in an amount of 0% to 1% based on the combined weight of the starting materials (A), (B), and (C) (and, when present, (J)). Alternatively, on the same basis, the (H) chain transfer agent can be used in an amount of 0.5% to 0.6%.

[0092] Starting material (F) initiator

[0093] In step 1) above, the starting material (F) initiator is also added. Suitable initiators include azo compounds and peroxide compounds. For example, the azo compound can be an aliphatic azo compound, such as 1-tert-pentylazo-1-cyanocyclohexane, azo-bis-isobutyronitrile and 1-tert-butylazo-cyanocyclohexane, 2,2'-azo-bis-(2-methyl)butyronitrile, 2,2'-azobis(2-methylpropionitrile), 2,2'-azobis(2-methylpropionamide) dihydrochloride, 2,2'-azobis(cyanopentanoic acid), or combinations of two or more thereof. Azo compounds are known in the art and are available from Chemours Company, Wilmington, Delaware, USA, for example, under the trademark VAZO. ™WSP is commercially available. The peroxide compound can be a peroxide or hydroperoxide, such as tert-butyl peroctanoate, tert-butyl perbenzoate, dicumyl peroxide, di-tert-butyl peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, di-tert-pentyl peroxide, and combinations of two or more of these. Alternatively, the dieperoxide initiator can be used alone or in combination with other initiators. Such dieperoxide initiators include, but are not limited to, 1,4-bis-(tert-butylperoxycarbonyl)cyclohexane, 1,2-bis(tert-butylperoxy)cyclohexane, and 2,5-bis(tert-butylperoxy)-3-hexyne. Suitable peroxide compounds are known in the art and are commercially available from various sources such as Sigma-Aldrich, Inc. Alternatively, the initiator may contain isoascorbic acid.

[0094] An initiator may be used alone as the starting material (F). Alternatively, the starting material (F) may be a redox pair comprising an initiator as both an oxidizing and a reducing component. Alternatively, redox pairs comprising isoascorbic acid and hydrophobic organic hydroperoxides such as tert-amyl hydroperoxide or tert-butyl hydroperoxide may be used as starting materials (F). Examples of suitable initiators and / or redox pairs for the starting material (F) are disclosed in U.S. Patent 6,576,051 to Bardman et al. (starting from column 11, line 16). How 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 initiators are added at once at the beginning of step 1). Alternatively, when a redox pair is used, it may be metered over time.

[0095] Alternatively, the initiator may also optionally comprise ferric(II) heptahydrate, potassium persulfate, or a combination thereof. Based on the weight of the organosilicon-(meth)acrylate copolymer, the initiator (F) may be sufficient to provide an amount of 0.01% to 3%, or alternatively 0.1% to 1.5%.

[0096] Starting materials (J) and additional monomers

[0097] Starting material (J) is an optional additional monomer that may be added in step 1). Starting material (J) is a non-crystallizable monomer that is different from the starting materials (A), (B), and (C) described above. Based on the weight of the organosilicon-(meth)acrylate copolymer (I), the additional monomer (if present) may be used in an amount >0 to 18.75% by weight. Suitable monomers include (meth)acrylate monomers such as methyl methacrylate, tert-amyl methacrylate, butyl methacrylate (such as tert-butyl methacrylate), cyclohexyl methacrylate, isodecyl methacrylate, isobornyl methacrylate, 2-naphthyl acrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, and combinations of two or more thereof. Alternatively, the additional monomer may be styrene or vinyl chloride. Suitable monomers for starting material (J) are known in the art and are commercially available, for example, from Polysciences, Inc. Alternatively, the additional monomer (J) may be selected from the group consisting of isobornyl methacrylate (IBMA), isobornyl acrylate (IBA), and combinations thereof. The additional monomer is optional and may be present in an amount from 0 to 18.75% based on the combined weight of the starting materials (A), (B), and (C) and (when present) (J). Alternatively, on the same basis, the additional monomer (J) may be present in an amount of at least 0.5%, alternatively at least 1%, alternatively at least 2%; while the additional monomer may be present in an amount of up to 18.75%, alternatively up to 15%, alternatively up to 10%, alternatively up to 8%, and alternatively up to 5%. Alternatively, on the same basis, the amount of the additional monomer (J) may be >0 to 18.75%, alternatively 0.5% to 7%, alternatively 1% to 6%, and alternatively 2% to 5%.

[0098] Starting material (K) manganese ion source

[0099] The starting material (K) is a manganese ion source, which may be a manganese(II) compound. Suitable manganese compounds include manganese(II) acetate, manganese(II) nitrite, manganese(II) propionate, manganese(II) oxide, manganese(II) hydroxide, manganese(II) chloride, manganese(II) phosphate, manganese(II) perchlorate, their hydrates (e.g., manganese(II) tetrahydrate), and combinations thereof. Alternatively, the manganese ion source may comprise manganese(II) acetate or manganese(II) tetrahydrate, or combinations thereof. Suitable manganese ion sources are commercially available from Millipore Sigma of St. Louis, Missouri, USA; Feissler Technologies, Waltham, Massachusetts, USA; and City Chemical LLC, Connecticut, USA. The amount of manganese ion source depends on various factors, including the selection and amount of other starting materials used; however, based on the combined weight of starting materials (A), (B), and (C), the amount can range from 0.1 ppm to 5,000 ppm. Alternatively, the amount of manganese ion source may be >0 ppm, alternatively at least 0.5 ppm, alternatively at least 1 ppm, alternatively at least 1.5 ppm; meanwhile, based on the combined weight of all starting materials in the emulsion formulation used to treat textiles, 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.

[0100] (L) Phenolic compounds

[0101] The starting material (L) is a phenolic compound. Suitable phenolic compounds include hydroquinone (HQ), dihydroxybenzene (catechol), resorcinol, dihydroxyxylene, methoxyphenol (such as guaiacol, p-methoxyphenol (also known as the methyl ether of hydroquinone or MeHQ)), tert-butylhydroquinone (tBuHQ), pyrogallol, methylpyrogallol, cresol, phenol, xylenol, and combinations thereof. Alternatively, the phenolic compound may be selected from the group consisting of HQ, MeHQ, tBuHQ, and combinations of two or more of them. Suitable phenolic compounds are commercially available, for example, from Millibo Sigma Corporation of St. Louis, Missouri, USA. The amount of phenolic compound source depends on various factors, including the selection and amount of other starting materials used; however, based on the combined weight of starting materials (A), (B), and (C), the amount can be from 5 ppm to 5,000 ppm. Alternatively, based on the combined weight of all starting materials in the emulsion formulation for treating textiles, the amount of phenolic compounds may be at least 5 ppm, alternatively at least 50 ppm, alternatively at least 100 ppm, or alternatively at least 150 ppm; while based on the combined weight of all starting materials in the emulsion formulation for treating textiles, the amount of phenolic compounds may be at most 500 ppm, alternatively at most 400 ppm, alternatively at most 350 ppm, or alternatively at most 320 ppm.

[0102] Following step 1) and / or step 2) of the method for preparing an emulsion formulation suitable for treating textiles, additional starting materials may optionally be added. The starting materials may be selected from the group consisting of (VI) additional surfactants (as described above for starting material (D), (VII) waxes, (VIII) biocides, (IX) additional water (as described above for starting material (E), (X) flame retardants, (XI) wrinkle reducers, (XII) antistatic agents, (XIII) penetrants, or combinations of two or more of the additional starting materials.

[0103] Starting material (VII) wax

[0104] The starting material (VII) is a wax, which may optionally be added to provide improved water resistance or softness to the textile to which the emulsion formulation will be applied. The amount of wax will vary depending on factors including the type of wax selected, the desired beneficial effect, and the fabric to be treated with the emulsion formulation. However, based on the weight of the silicone-(meth)acrylate copolymer (I), the amount of wax may be 0 to 75%, alternatively 0 to 50%, alternatively 25% to 50%. Alternatively, on the same basis, when used, the amount of wax may be >0%, alternatively at least 10%, and alternatively at least 25%, while the amount of wax may be at most 75%, alternatively at most 50%. Examples of suitable waxes include paraffin wax (e.g., n-alkanes, isoalkanes, and / or cycloalkanes), silicone waxes (such as silicone waxes having long-chain alkyl groups (e.g., alkylmethyl silicone waxes) and / or amino silicone waxes), and combinations of two or more of them. Suitable waxes are disclosed, for example, in U.S. Patent Application 2017 / 0204558 granted to Knaup and U.S. Patent 10,844,151 granted to Probst et al. Waxes can be delivered as water-based dispersions, such as Michelman Wax 743 and other waxes from Michelman, Cincinnati, Ohio, USA. Other waxes are also commercially available, for example, from Sasol Wax, Hamburg, Germany, and silicone waxes (such as DOWSIL). ™ AMS-C30 is available from Dow Silicones, Midland, Michigan, USA.

[0105] Starting material (VIII) biocides

[0106] The starting material (VIII) is an optional biocide. The amount of biocide will depend on factors including the type of biocide selected and the desired beneficial effect. However, based on the combined weight of all starting materials in the emulsion formulation, the amount of biocide may be >0% to 5% when used. Examples of starting materials (VIII) include (M-1) fungicides, (M-2) herbicides, (M-3) insecticides, (M-4) antimicrobials, or combinations thereof. Suitable biocides are disclosed, for example, in U.S. Patent 9,480,977.

[0107] Starting material (XIII) penetrant

[0108] The starting material (XIII) is a penetrant. Examples of suitable penetrants include glycol ethers, which are commercially available from Dow Chemical Company, and include DOWANOL. ™ DPM, TPM, PPh, EPh, Methyl CARBITOL ™and Butyl CARBITOL ™ .

[0109] (II) Additives

[0110] Emulsion formulations suitable for treating textiles also contain an amount of additive (II) sufficient to impart softness to the textiles without significantly reducing their water resistance, the additive being selected from alkyl polysiloxanes of formula (II-1): , where each R 19 It is an independently selected monovalent saturated hydrocarbon group having 1 to 18 carbon atoms, and the subscript a has an average value of 20 to 300, or a (II-2) combination comprising 60 to 70 wt% of (II-1) alkyl polysiloxane based on the combined weight of all starting materials in the (II-2) combination, 29 to 39 wt% of (II-2-1) organosilicon resin based on the combined weight of all starting materials in the (II-2) combination, and 0 to 2 wt% of (II-2-2) amino-functionalized polysiloxane based on the combined weight of all starting materials in the (II-2) combination, the organosilicon resin having a hardness of ≥20 as measured by a type A hardness tester according to JIS K 6249:2003, the organosilicon resin having a functional group equivalent of 100 g / mol to 20,000 g / mol, wherein the equivalent means the molecular weight of amino-functionalized polysiloxane per mole of nitrogen atom, and having a functional group equivalent as measured by a type A hardness tester according to JIS K 6249:2003. The measurement using method 2283:2000 at 25℃ is 10mm. 2 / s to 100,000mm 2 / s kinematic viscosity. Alternatively, on the same basis, (II-2-2)amino-functionalized polyorganosiloxanes may be present in amounts of 1% to 2%.

[0111] (II-1) Alkyl polysiloxanes have the following formula: , where each R 19 R is an independently chosen monovalent saturated hydrocarbon group with 1 to 18 carbon atoms, and the subscript a has an average value of 20 to 300. 19 The monovalent saturated hydrocarbon group can be an alkyl group, alternatively an alkyl group with 1 to 6 carbon atoms. Alternatively, the alkyl group may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms. Alternatively, each R... 19 It can be methyl. Suitable alkyl polysiloxanes, such as bis-trimethylsiloxy-terminated polydimethylsiloxanes, are known in the art and are commercially available, for example as XIAMETER from DSC. ™ 200 fluid.

[0112] Alternatively, (II) the additive may comprise a (II-2) combination comprising: 60% to 70% by weight of the combined weight of all starting materials in the (II-2) combination, of the (II-1) alkyl polysiloxane as described above; 29% to 39% by weight of the combined weight of all starting materials in the (II-2) combination, of a (II-2-1) silicone resin; and 1% to 2% by weight of the combined weight of all starting materials in the (II-2) combination, of a (II-2-2) amino-functionalized polysiloxane having a hardness of ≥20 as measured by a type A hardness tester according to JIS K 6249:2003, having a functional group equivalent of 100 g / mol to 20,000 g / mol, wherein the equivalent means the molecular weight of the amino-functionalized polysiloxane per mole of nitrogen atoms, and having a functional group equivalent of 10 mm at 25°C as measured by the method of JIS K 2283:2000. 2 / s to 100,000mm 2 kinematic viscosity / s.

[0113] The starting material (II) additive can be delivered in a second aqueous emulsion comprising the (II) additive, (D') a surfactant (which may be as described above for starting material (D)), and (E') water (which may be as described above for starting material (E)). The second aqueous emulsion can be prepared by known methods, such as those described in U.S. Patent Application Publication 2020 / 0332148, by varying the type and amount of the starting material as described herein.

[0114] In emulsion formulations suitable for treating textiles, additive (II) may be present in an amount of 0.4% to 29.3% based on the combined weight of all starting materials in the emulsion formulation excluding water. Alternatively, the amount of additive (II) may vary depending on the type of additive selected and / or the type of textile to be treated. For example, when the additive is (II-1) alkyl polysiloxane, the alkyl polysiloxane may be present in an amount of 0.7% to 28.5%. Alternatively, when the textile to be treated is polyester, the alkyl polysiloxane may be present in an amount of 0.7% to 28.5%. Alternatively, when the textile to be treated is polyamide such as nylon, the alkyl polysiloxane may be present in an amount of 1% to 28.5%. Alternatively, when the additive is the combination of (II-2) described above, the additive may be present in an amount of 0.4% to 29.3% based on the combined weight of all starting materials in the emulsion formulation excluding water. Alternatively, when the textile to be treated is polyester, the combination may be present in an amount of 0.4% to 29.3%. Alternatively, when the textile to be treated is polyamide such as nylon, the combination may be present in an amount of 0.8% to 28.5%.

[0115] When selecting starting materials to add to the first and second aqueous emulsions described above, and to emulsion formulations suitable for treating textiles, there may be overlap between the types of starting materials, as some of the starting materials described herein may have more than one function. The starting materials used in the first aqueous emulsion, the second aqueous emulsion, and / or the emulsion formulation may be different from each other.

[0116] Emulsion formulations suitable for treating textiles comprise: (I) a silicone-(meth)acrylate copolymer, (K) a manganese ion source, (L) a phenolic compound, (II) an additive, (III) a water-dispersible crosslinking agent, (IV) a surfactant (described above as starting material (D)), and (V) water (described above as starting material (E)). The emulsion formulation may also optionally comprise additional starting materials selected from the group consisting of (VII) waxes, (VIII) biocides, (IX) additional water, (X) flame retardants, (XI) wrinkle reducers, (XII) antistatic agents, (XIII) penetrants, and combinations of two or more of starting materials (VII), (VIII), (IX), (X), (XI), (XII), and (XIII), which may be added during or after the preparation of the emulsion formulation of a first aqueous emulsion comprising (I) a silicone-(meth)acrylate copolymer. These additional starting materials and their amounts are as described above. Furthermore, the emulsion formulations described herein may be formulated with starting materials free of fluorocarbons. For example, emulsion formulations may not contain any starting materials containing fluorine atoms covalently bonded to carbon atoms.

[0117] Additional starting materials may be optionally used in the above methods. For example, chelating agents may be used when preparing copolymers.

[0118] Methods for treating textiles

[0119] The emulsion formulation prepared as described above can be used to treat textiles. For example, methods for treating textiles include: I) coating the textiles with the emulsion formulation described above, and II) heating the textiles. Step I) can be carried out by any convenient method, such as padding, impregnating, or spraying the textiles with the emulsion formulation. However, based on the weight of the textiles, the method should be sufficient to deliver 0.25 wt% to 7.5 wt% of (I) silicone-(meth)acrylate copolymer, 0.01 wt% to 0.5 wt% of (II) additive, and 0.05 wt% to 0.5 wt% of (III) water-dispersible crosslinking agent, based on the weight of the fabric. When the (II) additive is a combination of (II-2), the amount of (I) silicone-(meth)acrylate copolymer and the amount of the (II-2) combination are sufficient to provide a (I):(II-2) weight ratio of 2:1 to <200:1.

[0120] Step II) can be performed by any convenient method, such as placing the textile in an oven. The textile may be heated to remove all or part 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 required drying time. However, heating may be performed at temperatures >100°C to remove water. Alternatively, the temperature may be >100°C to 200°C for a duration sufficient to remove all or part of the water, deseal the end-capped isocyanate crosslinking agent, and / or cure (I) the silicone-(meth)acrylate copolymer and (II) the additive.

[0121] There are no particular limitations on the textiles to be treated. 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, polyester, polyamides (such as nylon), polyacrylonitrile, and polyolefins (such as polyethylene and / or polypropylene), and combinations of two or more of these (e.g., blends such as polyester / cotton blends). There are also no particular limitations on the form of the textiles. The emulsion formulations described herein are suitable for any form of textile, such as woven fabrics, knitted fabrics, carpets, or nonwoven textiles.

[0122] Durable water resistance test :

[0123] The Bundesmann test was performed using the ISO 9865 method. Facial rating data were collected after 0, 1, 10, and 20 washes using an SDL Atlas M230 Bundesmann test apparatus. The instrument was calibrated so that the amount collected per cup after 150 seconds was between 190 mL and 210 mL. Facial ratings were assigned based on images from the ISO 9865 method, using half-increments as intermediate allocations. Facial ratings were repeatable and reported as averages. Acceptable values ​​were ≥4.5 to 5.

[0124] Problems to be solved

[0125] Organosilicon-(meth)acrylate hybrid copolymers can impart excellent and durable water resistance to various textiles; however, they may have the drawback of imparting rigidity, negative aesthetics, and poor hand feel. Known compositions for treating textiles, such as those disclosed in U.S. Patent Application Publication 2020 / 0332148, can impart sufficient aesthetics but may provide insufficient durable water resistance for some applications. Furthermore, there is a need to produce commercially viable non-fluorocarbon-based textile treatment agents that can stabilize monomer emulsions at higher temperatures for extended treatment times while maintaining excellent performance properties.

[0126] solution

[0127] Without being bound by theory, this invention provides an emulsion formulation that, when used to treat textiles, imparts softness and hand feel as well as good, durable water resistance, as measured by the Bundesmann test described herein. More specifically, the fabric can have a Bundesmann face rating of ≥4.5 after initial treatment and retain a face rating of ≥4.5 after 1 wash, 5 washes, 10 washes, and 20 washes. Without being bound by theory, it is believed that the use of a manganese ion source and phenolic compounds will result in better monomer emulsion stability and will impart improved post-polymerization water resistance to the fabric (compared to monomer emulsions that do not contain one or both of the manganese ion source and phenolic compounds).

[0128] Definition and use of terms

[0129] Unless otherwise specified, all quantities, ratios, and percentages herein are by weight. The summary of the invention and the abstract of the specification are incorporated herein by reference. Unless the context otherwise indicates, the articles “a,” “an,” and “the” refer to one (a kind) or more (a plurality of kinds). The transitional phrases “comprising,” “consistently comprising,” and “comprises” are used as described in Chapters §2111.03 I, II, and III of the Patent Examining Procedure Ninth Edition, revised January 2018, 08.2017. The use of “for example,” “for instance,” “such as,” and “including” to list exemplary examples does not imply limitation to the listed examples. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to” and covers other similar or equivalent examples. Abbreviations used herein have their definitions in Table Z.

[0130]

[0131] The invention has been described by way of example, and it should be understood that the terminology used is intended to be descriptive rather than restrictive. With respect to any Markush group relied upon herein for the description of a particular feature or aspect, different, specific, and / or unexpected results can be obtained from each member of the corresponding Markush group, independent of all other Markush members. Each member of the Markush group can be relied upon individually and / or in combination, and provides sufficient support for specific embodiments within the scope of the appended claims.

[0132] Furthermore, any scopes and subscopes relied upon in the description of this invention fall independently and collectively within the scope of the appended claims, and should be understood as describing and contemplating all scopes including all and / or some of the values, even if such values ​​are not explicitly stated herein. Those skilled in the art will readily recognize that the enumerated scopes and subscopes adequately describe and enable various embodiments of the invention, and that such scopes and subscopes may be further described as related halves, thirds, quarters, fifths, and any other subscopes included within that scope. By way of example only, scopes “16 to 24” may be further described as the lower third (i.e., 16 to 18), the middle third (i.e., 19 to 21), and the upper third (i.e., 22 to 24), and alternatively, scopes “16 to 24” include subscopes “18 to 22”, each individually and collectively within the scope of the appended claims, and may be relied upon individually and / or collectively to provide sufficient support for specific embodiments within the scope of the appended claims. Furthermore, with regard to language that limits or modifies a range, such as “at least,” “greater than,” “less than,” and “no more than,” it should be understood that such language includes subranges and / or upper or lower limits.

Claims

1. An emulsion formulation suitable for treating textiles, wherein the emulsion formulation comprises: (I) A silicone-(meth)acrylate copolymer, wherein the silicone-(meth)acrylate copolymer comprises the following unit formula Each R 1 It is an alkyl group with 16 to 24 carbon atoms, chosen independently; each R 2 Independently selected from the group consisting of H and methyl groups; each D 2 It is a divalent hydrocarbon group with 2 to 12 carbon atoms; each R 3 It is the formula OSi(R) 4 )3 groups; wherein each R 4 Independently select R and DSi(R) 5 A group consisting of 3 Rs, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from a group consisting of an oxygen atom, 1 to 12 units of (poly)alkyleneoxy groups, and 2 to 4 divalent hydrocarbon groups; each R 5 Independently select R and DSi(R) 6 A group consisting of 3 groups; where each R 6 Independently select a group consisting of R and DSiR3; the prerequisite is that R 4 R 5 and R 6 Selected such that the organosilicon-(meth)acrylate macromonomer unit with subscript x has at least 6 silicon atoms; each R 7 Independently select the group composed of free oxygen atoms and NH; D 3 It is a divalent hydrocarbon group with 1 to 12 carbon atoms; D 4 It is an alkylene group or a divalent alkylarylene group with 2 to 4 carbon atoms; the subscript v indicates the formula (OD). 4 The number of units in R, and the subscript v has a value from 0 to 12; each R 8 It is a cross-linking group; each R 9 It is a monovalent hydrocarbon group with 1 to 14 carbon atoms; each R 10 The copolymer is independently selected from the group consisting of halogen groups, acetate groups, or monovalent hydrocarbon groups of 1 to 14 carbon atoms; the subscripts w, x, y, z1, and z2 represent the relative weights of the units in the copolymer, with subscript x having a value of 0.25 to 15; subscript w having a value of 80 to 98.75; subscript y having a value of 1 to 5; subscript z1 having a value of 0 to 18.75; and subscript z2 having a value of 0 to 18.75, and the amount (w+x+y+z1+z2)=100; and the prerequisite is that the copolymer also includes end portions; (K) Manganese ion source; (L) Phenolic compounds; (II) Additives, said additives being selected from the group consisting of: (II-1) Alkyl polysiloxanes, wherein each R 19 It is an independently chosen monovalent saturated hydrocarbon group with 1 to 18 carbon atoms, and the subscript 'a' has an average value of 20 to 300, or (II-2) Combination, the combination comprising: Based on 60% to 70% by weight of the combined weight of all starting materials in the combination described in (II-2) of the alkyl polysiloxane described in (II-1), Based on 29% to 39% by weight of the combined weight of all starting materials in the combination described in (II-2), a silicone resin of (II-2-1) having a hardness of ≥20 as measured by a type A hardness tester according to JIS K 6249:2003, and Based on a combined weight of 0% to 2% (II-2-2) amino-functionalized polysiloxane of all starting materials in the combination described in (II-2), the amino-functionalized polysiloxane having a functional group equivalent of 100 g / mol to 20,000 g / mol, wherein the equivalent refers to the molecular weight of the amino-functionalized polysiloxane per mole of nitrogen atoms, and has a molecular weight of 10 mmHg at 25°C as measured by JIS K 2283:2000. 2 / s to 100,000mm 2 kinematic viscosity per second; (III) A water-dispersible crosslinking agent, in an amount sufficient to crosslink the starting material (I) and the starting material (II); (IV) Surfactants; and (V) Water.

2. The emulsion formulation according to claim 1, wherein R 1 It is an octadecyl group, with subscript w=95, D 2 It is –(CH2)3–, each R 3 It is –OSi(CH3)2(CH2)2Si(OSi(CH3)3), subscript x=3, R 7 It is O, subscript v=0, R 8 It is OH, with subscript y=2, subscript z1=0, and subscript z2=0.

3. The emulsion formulation according to claim 1 or claim 2, wherein the emulsion formulation further comprises one or more additional starting materials selected from the group consisting of: (VI) additional surfactants, (VII) waxes, (VIII) biocides, (IX) flame retardants, (X) wrinkle reducers, (XI) antistatic agents and (XII) penetrants.

4. The emulsion formulation according to claim 3, wherein (II) the additive is (II-2), and the emulsion formulation further comprises (XII) the penetrant.

5. The emulsion formulation according to any one of claims 1 to 4, wherein the water-dispersible crosslinking agent of (III) comprises a capped isocyanate.

6. The emulsion formulation according to any one of claims 1 to 5, wherein (I) the silicone-(meth)acrylate copolymer is present in an amount sufficient to provide 0.25% by weight to 7.5% by weight on the fabric; (II) the additive is present in an amount sufficient to provide 0.01% by weight to 0.5% by weight on the fabric; and (III) the water-dispersible crosslinking agent is present in an amount sufficient to provide 0.05% by weight to 0.5% by weight on the fabric, provided that when the additive is the combination described in (II-2), the amount of (I) the silicone-(meth)acrylate copolymer and the amount of the combination described in (II-2) are sufficient to provide a (I):(II-2) weight ratio of 2:1 to <200:

1.

7. The emulsion formulation according to any one of claims 1 to 6, wherein the manganese ion source comprises manganese(II) acetate, manganese(II) acetate tetrahydrate, or a combination thereof.

8. The emulsion formulation according to any one of claims 1 to 7, wherein the phenolic compound is selected from the group consisting of hydroquinone, monomethyl ether of hydroquinone, tert-butylhydroquinone, and combinations of two or more thereof.

9. A method for preparing an emulsion formulation according to any one of claims 1 to 8, the method comprising: 1) The organosilicon-(meth)acrylate copolymer of starting material (I) is prepared by emulsion polymerization of starting materials comprising the following substances: 80% to 98.75% by weight of crystallizable monomers of formula (A) below: , where R 1 and R 2 As mentioned above; 0.25% to 15% by weight of organosilicon-(meth)acrylate macromonomers of formula (B): , where R 2 D 2 and R 3 As mentioned above; 1% to 5% by weight of (C) crosslinkable (meth)acrylate monomers of the following formula: , where R 7 D 3 D 4 subscripts v and R 8 As mentioned above; The amounts of starting materials (A), (B), and (C) are based on a total of 100% by weight of the combined amounts of starting materials (A), (B), and (C); and the starting materials (A), (B), and (C) are copolymerized in the presence of additional starting materials, wherein the additional starting materials comprise: Chain transfer agent; Additional monomers optionally different from the starting materials (A), (B), and (C); and manganese ion source, and Phenolic compounds; (D) Surfactants; (E) Water; as well as (F) Initiator; This forms a first aqueous emulsion comprising the organosilicon-(meth)acrylate copolymer described in (I); 2) Provide a second aqueous emulsion comprising the additive described in (II), a surfactant (D'), and water (E'); as well as 3) A mixture comprising the first aqueous emulsion prepared in step 1), the second aqueous emulsion from step 2), the water-dispersible crosslinking agent of (III), and optionally one or more additional starting materials selected from the group consisting of: additional surfactants, waxes, biocides, additional water, flame retardants, wrinkle reducers, antistatic agents, and penetrants.

10. The method according to claim 9, wherein the starting material (A) is selected from the group consisting of octadecyl acrylate, octadecyl methacrylate, docosyl methacrylate and docosyl acrylate.

11. The method according to claim 9 or claim 10, wherein the starting material (B) has the formula... .

12. The method according to any one of claims 9 to 11, wherein the starting material (B) is selected from the group consisting of: 3-(5-((1,1,1,3,5,5,5-heptamethyltrisiloxane-3-yl)oxy)-1,1,1,3,7,9,9,9-octamethyl-3,7-bis((trimethylsilyl)oxy)pentasiloxane-5-yl)propyl methacrylate; 3-(1,5-bis(2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)-3-(((2-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)ethyl)dimethylsilyl)oxy)-1,1,5,5-tetramethyltrisiloxane-3-yl)propyl methacrylate; and combinations thereof.

13. The method according to any one of claims 9 to 12, wherein in the starting material (C), each R 8 The group consisting of hydroxyl, amino, epoxy, urea and acetoxy groups is selected independently.

14. The method according to any one of claims 9 to 14, wherein the starting material (D) and the starting material (D') are each independently selected from the group consisting of cationic surfactants, nonionic surfactants, and combinations thereof.

15. A method for treating textiles, the method comprising: I) Coating the textile with the emulsion formulation according to any one of claims 1 to 6 or the emulsion formulation prepared by the method according to any one of claims 9 to 14; and II) Heat the textile.

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