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WO2025090822A1 - Papier de traitement avec une composition comprenant un copolymère de silicone-(méth)acrylate - Google Patents

Papier de traitement avec une composition comprenant un copolymère de silicone-(méth)acrylate Download PDF

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Publication number
WO2025090822A1
WO2025090822A1 PCT/US2024/052894 US2024052894W WO2025090822A1 WO 2025090822 A1 WO2025090822 A1 WO 2025090822A1 US 2024052894 W US2024052894 W US 2024052894W WO 2025090822 A1 WO2025090822 A1 WO 2025090822A1
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Prior art keywords
group
alternatively
independently selected
subscript
meth
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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PCT/US2024/052894
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English (en)
Inventor
Cathy DONTAINE
Matthew JELETIC
Pierre Chevalier
Anirudha BANERJEE
Devin FERGUSON
Douglas HASSO
Brian Macdonald
Jodi Mecca
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Dow Silicones Corp
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Dow Silicones Corp
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Publication date
Priority claimed from PCT/US2024/045245 external-priority patent/WO2025090189A1/fr
Application filed by Dow Silicones Corp filed Critical Dow Silicones Corp
Publication of WO2025090822A1 publication Critical patent/WO2025090822A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/32—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/356—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms
    • D06M15/3568—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of other unsaturated compounds containing nitrogen, sulfur, silicon or phosphorus atoms containing silicon
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/59—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties

Definitions

  • a silicone - (meth)acrylate copolymer is useful for treating paper substrates. More particularly, a paper treatment composition comprising the silicone - (meth)acrylate copolymer can be used to render paper substrates both hydrophobic and oleophobic.
  • fluorocarbon materials have dominated the market due to their ability to provide excellent durable water repellency.
  • regulatory and customer pressures are contributing to an industry need for non-fluorocarbon- based textile treatments.
  • Previously disclosed fluorocarbon-free textile treatments suffer the drawback of providing poor durability, where water repellency of textiles treated therewith decreases significantly after multiple washings.
  • Silicone - (meth)acrylate copolymer compositions and emulsion formulations made with them have been proposed to address the need for non-fluorocarbon-based textile treatments.
  • such compositions are disclosed in PCT Publication WO2022197350 corresponding to US Patent Application Serial No. 18/258663; PCT Publication W02023010944 corresponding to US Patent Application Serial No. 18/558769; PCT Publication WO2023086692 corresponding to US Provisional Patent Application Serial No. 63/277671; US Provisional Patent Application Serial No. 63/588046; US Provisional Application Serial No. 63/588050; and US Provisional Application Serial No. 63/588056; each of which is hereby incorporated by reference.
  • none of these compositions and emulsions have been used to treat paper.
  • Oleophobic (e.g., greaseproof) properties are desirable for different articles such as paper or paperboard of different grammage in a wide range of applications including food applications like packaging or baking but also in composite filter for extractor or filter hoods as well as in any applications were anti-staining or anti-fingerprint protection is required.
  • Paper is typically a material in thin form obtained or derived from fibres of cellulose pulp from wood and other plant sources. Paper is usually available in thin sheets, bags or other containers. Paper can contain additives and/or can be treated to improve its properties such as resistance to various chemicals, resistance to harsh environments, or increased printability. Treated papers or special grades papers are useful in food related applications.
  • baking paper also called parchment paper or bakery release paper
  • the heat resistant, non-stick surface is obtained, for example, by treating the paper with sulphuric acid and with a silicone coating.
  • Sulphuric acid paper treatment provides mechanical strength, low permeability and greaseproofness.
  • the paper can be treated with a silicone composition to provide a silicone coating that enables water barrier and anti-adhesive performances for improved cold or warm food release.
  • Greaseproof papers permit packing food or wrapping fatty food (e.g., butter) in sheets, wrappers and other containers. They can be used as interleavers for sliced food like sliced cheese, bacon, deli meat, salmon, cookie dough or other food. Greaseproof papers withstand oil and fatty food from permeating the paper and soiling it. It may be desirable for the greaseproof paper to also have release properties such as non-tackiness to prevent food from sticking to the paper at ambient temperature (anti-adhesive properties) and/or after use at high temperature (microwaving or baking release properties). The greaseproof paper also desirably has water repellent properties useful for steam cooked food like dumplings, or for frozen food to prevent breakage upon de-freezing, piercing, or any damage to the paper packaging.
  • release properties such as non-tackiness to prevent food from sticking to the paper at ambient temperature (anti-adhesive properties) and/or after use at high temperature (microwaving or baking release properties).
  • the greaseproof paper also desir
  • Greaseproof papers can be made of special grades of papers, such as glassine, where cellulose fibres are treated to obtain a very low porosity, impeding grease and oil to penetrate in the paper.
  • the paper can be treated with wax (e.g., paraffinic wax), starch, alginate or cellulose gum to fill pores thereby hindering fatty products to penetrate the paper.
  • wax e.g., paraffinic wax
  • starch e.g., paraffinic wax
  • alginate or cellulose gum e.g., cellulose starch
  • alginate or cellulose gum e.g., cellulose gum
  • these treatments may be inefficient, and may detrimentally impact water barrier and food release properties.
  • Manufacturing such types of papers requires appropriate processes, such as calendaring or supercalendering, demanding further investments in the paper making process line that can add significantly to the cost price of the finished greaseproof paper.
  • greaseproof papers may be obtained by treating papers with compounds forming an oil- and grease repellent layer on the paper.
  • a known treatment is based on fluorinated compounds that are able to provide some non-stick properties by forming a film having low surface energy, which is resistant to chemical agents thereby providing oil, fat and water repellence to the treated paper.
  • environmental and health concerns were raised about fluorinated compounds which seem to accumulate in the environment and the trend is to restrict or ban their use by various regulations, especially in the food packaging area.
  • Another approach has been to treat papers with a mixture of polyvinyl alcohol and a chromate-fatty acid complex.
  • heavy metal such as chromium also raises environmental and health concerns in food packaging related uses.
  • Other treatments permit to confer some oleophobicity to the paper but they often require relatively high amounts of material to be effective and form a thick coating on the paper, which may be detrimental to the mechanical properties and durability upon creasing or folding of the paper and is not cost effective.
  • US Patent 10723891 discloses “an aqueous coating composition and a greaseproof article comprising a substrate bearing a coating formed by curing the composition.
  • the substrate is made of paper, acrylic material or polyethylene terephthalate or paper/plastics laminate material. . . . The . . . article is used for food packaging.
  • the aqueous coating composition is able to form a coating on a substrate upon curing by hydrosilylation.”
  • This aqueous coating composition may suffer from various drawbacks including being expensive due to the use of a platinum group metal hydrosilylation reaction catalyst and water dispersible ethylene vinyl alcohol (EVOH) additive.
  • EVOH water dispersible ethylene vinyl alcohol
  • the paper treatment should be preferably be free of fluorinated compounds.
  • the paper treatment should preferably be compatible with food contact requirements and meet the existing food contact materials regulations so as to be used in applications where the paper comes into contact with food.
  • the paper treatment should provide significant advantages in reasonable amount of material deposited by area and be effective as a film or coating in limited thickness so as to minimize cost of the treatment.
  • a method for treating a substrate comprising paper comprises I) coating the substrate with a paper treatment composition comprising a silicone - (meth)acrylate copolymer, a surfactant, water, a crosslinker, and a catalyst, and II) drying the substrate.
  • 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 formula OSi(R 4 h; where each R 4 is independently selected from the group consisting of R and DSi(R 5 )3, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, a (poly) alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms;
  • each R 5 is independently selected from the group consisting of R and DSi(R 6 h; where each R 6 is independently selected from the group consisting of R and DSiR ; with the proviso that
  • silicone - (meth) aery late copolymer (copolymer) introduced above may be prepared by radical polymerization, via a method as described below, and that this method would form a terminal moiety for the copolymer.
  • the copolymer with the unit formula above further comprises a terminal moiety which may be derived from an initiator, a chain transfer agent, or both, as described, for example in Odian, George (2004). Principles of Polymerization (4th ed.). New York: Wiley-Interscience. ISBN 978-0-471-27400-1.
  • the copolymer may be prepared via a method comprising: 1 ) copolymerizing starting materials comprising
  • 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
  • R 2 is selected from the group consisting of H and methyl; optionally (B) a silicone - (meth)acrylate co-macromonomer, wherein (B) the silicone -
  • (meth) acrylate co-macromonomer has a formula selected from the group consisting of formula
  • 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
  • R 2 is selected from the group consisting of H and methyl
  • formula (B-2) is selected from the group consisting of H and methyl
  • D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms
  • Step 1) of the method may comprise an emulsion polymerization reaction.
  • the additional starting materials further comprise (D) a surfactant and (E) water.
  • the emulsion polymerization described above may comprise forming an emulsion comprising starting material (A) the silicone - (meth)acrylate macromonomer, (B) the silicone - (meth) acrylate co-macromonomer (when present), (D) the surfactant, (E) water, and optionally one or more of (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound and thereafter adding (C) the initiator and copolymerizing.
  • Step 1) of the method described above may comprise forming an emulsion comprising starting materials (A) the silicone - (meth)acrylate macromonomer, (C) the initiator, (D) the surfactant, and (E) the water, and optionally an additional starting material selected from the group consisting of (B) the silicone - (meth)acrylate co-macromonomer, (H) the chain transfer agent, (I) the manganese ion source, (J) the phenolic compound, and a combination of two or more thereof.
  • These starting materials may be mixed under shear to form the aqueous emulsion.
  • Mixing under shear may be performed by any convenient means for forming an aqueous emulsion, such as sonication and with subsequent microfluidization.
  • Equipment for mixing under shear such as sonicators, homogenizers, microfluidizers, and speedmixers are known in the art and are commercially available. Without wishing to be bound by theory, it is thought that mixing under shear may be used to obtain a submicron particle size in the emulsion.
  • step 1) starting materials comprising (A) the silicone - (meth)acrylate macromonomer, (C) the initiator (and when present (B) the silicone - (meth)acrylate co-macromonomer and/or (H) the chain transfer agent) copolymerize to form (F) the silicone - (meth)acrylate copolymer in the aqueous emulsion with starting materials (D) the surfactant and (E) the water, and optionally (I) manganese ion source and (J) the phenolic compound.
  • the method described herein may optionally further comprise one or more additional steps.
  • the starting materials comprising (A) the silicone - (meth) aery late macromonomer and when present (B) the silicone - (meth) aery late co- macromonomer and/or (H) the chain transfer agent may be combined under aerobic or anaerobic conditions, optionally with heating for extended times.
  • the starting materials comprising (A) the silicone - (meth)acrylate macromonomer and when present (B) the silicone - (meth) acrylate co-macromonomer and one or more of (H) the chain transfer agent, (I) manganese ion source, and/or (J) the phenolic compound, may be emulsified with (D) the surfactant and (E) the water before adding (C) the initiator and copolymerizing in step 1).
  • step 1) combining the starting materials and copolymerizing in the method described above may be performed on a commercial scale under anaerobic or aerobic conditions optionally at elevated temperature, e.g., up to 100 °C, alternatively 40 °C to 80 °C, and alternatively 45 °C to 50 °C.
  • Copolymerizing may be performed in a batch process with a residence time of 15 minutes to 24 hours, alternatively 30 minutes to 12 hours, alternatively 40 minutes to 8 hours, and alternatively 40 minutes to 2 hours.
  • aerobic or anaerobic conditions means that oxygen is not required to be present in the gas in the headspace of the reactor where copolymerizing takes place, or dissolved in the liquid where copolymerizing takes place.
  • the balance of the gas in the headspace could be an inert gas such as nitrogen or argon.
  • the copolymer described above may be prepared by a method comprising dissolving one or more of the starting materials, such as (A) the silicone - (meth) acrylate macromonomer, and optionally one or more of (B) the silicone - (meth)acrylate co-macromonomer, (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound, in an organic solvent (such as a monohydric alcohol) and copolymerizing starting material (A) the silicone - (meth)acrylate macromonomer, and when present (B) the silicone - (meth)acrylate co-macromonomer, and/or (H) the chain transfer agent in a method such as that disclosed in US Patent 10047199 to limura, et al.
  • the starting materials such as (A) the silicone - (meth) acrylate macromonomer, and optionally one or more of (B) the silicone - (meth)acrylate co-macrom
  • the resulting copolymer may be solvent borne. All or a portion of the solvent may be removed by any convenient means, such as by stripping or distillation with heat and optionally reduced pressure.
  • the resulting copolymer may be emulsified using (D) the surfactant and (E) the water.
  • the product prepared in step 1) is an aqueous emulsion comprising (F) the silicone - (meth)acrylate copolymer, (D) the surfactant, and (E) the water.
  • the aqueous emulsion may optionally further comprise (I) the manganese ion source and/or (J) the phenolic compound. This aqueous emulsion can be used as the paper treatment composition.
  • this aqueous emulsion may be used to prepare the paper treatment composition, by a process comprising practicing step 1) as described above, thereby preparing the aqueous emulsion, and 2) combining the aqueous emulsion prepared in step 1) and an additional starting material.
  • the additional starting material may be selected from the group consisting of (K) a biocide, (L) additional water (which may be the same as starting material (E)), additional surfactant (which may be the same as starting material (D)), and a second silicone - (meth)acrylate copolymer (that differs from the silicone - (meth) acrylate copolymer described above) and a combination of two or more thereof.
  • Step 2) of this method may optionally further comprise adding additional (D) surfactant.
  • Step 2) of the process described above for making the paper treatment composition may be performed by any convenient means, such as mixing using a jacketed vessel equipped with an agitator. Step 1) and step 2), and any optional and/or additional steps as described above may be performed sequentially in the same vessel. Alternatively, step 1) and step 2) may be performed in different equipment. Step 2) may be performed at RT or elevated temperature, e.g., up to 100°C, alternatively 40°C to 80°C. Alternatively, heating may be performed in step 1), and step 2) may be performed at RT. Alternatively, step 2) may be performed at lower temperatures and elevated pressures, such as up to 5 atmospheres. The starting materials used in the method described above are further described below.
  • Starting material (A) used herein is a silicone - (meth) acrylate macromonomer.
  • the silicone - (meth)acrylate macromonomer has formula (A-l): each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl.
  • each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms.
  • the monovalent hydrocarbon group for R 1 may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms.
  • the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms.
  • each R 1 group may be methyl.
  • D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms.
  • D 2 may have 2 to 10, alternatively 3 to 5, and alternatively 3 carbon atoms.
  • the divalent hydrocarbon group for D 2 may be exemplified by an alkylene group such as ethylene, propylene, or butylene.
  • the divalent hydrocarbon group for D 2 may be propylene.
  • D 2 may be linear, e.g., -(CHzjz- or -(CFb -.
  • D 2 may be (CHi r-.
  • starting material (A) comprises formula (A-2): s described above.
  • Starting material (A) may comprise 3-(l,l,l,5,5,5-hexamethyl-3-
  • (A) may be prepared by known methods, such as those disclosed in PCT Publication
  • the amount of starting material (A) may be 23 % to 35 %, based on combined weights of starting materials (A), (B), (C), (D), and (E) used in emulsion polymerization.
  • Starting material (B) is a silicone - (meth) aery late co-macromonomer (co- macromonomer) that may optionally be copolymerized with (A) the silicone - (meth)acrylate macromonomer described above.
  • Starting material (B), the co-macromonomer may comprise formula (B-l), where formula ( each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms; D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl, each as described and exemplified above for formula (A-l).
  • the co-macromonomer may comprise a silicone - (meth)acrylate co-macromonomer of formula ( divalent hydrocarbon group of 2 to 12 carbon atoms; and R 2 is selected from the group consisting of H and methyl, each as described above for formula (A-l).
  • R 4 , R 5 , and R 6 are selected such that the unit has at least 5 silicon atoms, alternatively 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, per molecule.
  • each R is a monovalent hydrocarbon group of 1 to 12 carbon atoms.
  • the monovalent hydrocarbon group for R may be an alkyl group, such as an alkyl group of 1 to 6 carbon atoms.
  • the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms.
  • each R group may be methyl.
  • each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms.
  • the divalent hydrocarbon group for D may be exemplified by an alkylene group such as ethylene, propylene, or butylene; an arylene group such as phenylene, or an alkylarylene group such as: each subscript u is independently 1 to 6, alternatively 1 to 2.
  • the divalent hydrocarbon group for D may be alkylene, and alternatively the divalent hydrocarbon group for D may be ethylene.
  • the (poly)alkylene oxide group for D may have 2 to 4 carbon atoms per unit, e.g., have formula D 5 (OD 6 ) V ’-OR, where D 5 is an alkylene group of 2 to 4 carbon atoms, D 6 is an alkylene group of 2 to 4 carbon atoms, R is as described above, and subscript v’ is 0 to 12. Alternatively subscript v’ may be 0 or 1. Alternatively, subscript v’ may be 0. Examples of (poly) alkylene oxide groups include ethyleneoxide-propyleneoxide.
  • each D may be selected from an oxygen atom and a divalent hydrocarbon group.
  • each divalent hydrocarbon group for D may be an alkylene group such as ethylene.
  • each D may be oxygen.
  • some instances of D may be oxygen and other instances of D may be alkylene, e.g. , ethylene, in the same unit.
  • formula (B-2) may comprise formula (B-2-1): are as described above.
  • formula (B-2) may comprise formula (B-2-2):
  • formula (B-2) may comprise formula (B-2-3):
  • formula (B-2) may comprise a co-macromonomer selected from the group consisting of:
  • the co-macromonomer of formula (B-2) as described and exemplified above may be prepared by known methods, such as those disclosed in PCT Publication WO2020142388 and US Patent 6420504.
  • the amount of starting material (B) may be 0 to 26%, alternatively 0 to 17%, based on combined weights of starting materials (A), (B), (C), (D), and (E) used for emulsion polymerization.
  • Starting material (A) the silicone - (meth)acrylate macromonomer, and starting material (B) the silicone - (meth)acrylate co-macromonomer are used in the following amounts when making the copolymer: starting material (A) is used in an amount of > 25 weight % to 100 weight %, based on combined weights of starting materials (A) and (B); and starting material (B) is used in an amount of 0 to ⁇ 75 weight %, based on combined weights of starting materials (A) and (B).
  • starting material (A) may be used in an amount > 25 %, alternatively at least 40 %, alternatively at least 50%, alternatively at least 63%, and alternatively at least 75%, based on combined weights of starting materials (A) and (B); while at the same time the amount of starting material (A) may be up to 100%, alternatively up to 99%. Alternatively up to 95%, alternatively up to 75%, alternatively up to 63%, alternatively up to 50%, and alternatively up to 40%, on the same basis. Alternatively, the amount of starting material (A) may be 100%, and the amount of starting material (B) may be 0.
  • starting material (B) may be present, and the amount of starting material (B) may be > 0%, alternatively at least 1%, alternatively up to 5%, alternatively up to 10%, alternatively up to 15%, alternatively up to 20%, and alternatively at least 25%; while at the same time the amount of starting material (B) may be up to 60%, alternatively up to 50%, alternatively up to 37%, and alternatively up to 25%, on the same basis.
  • the starting materials used to make the copolymer (and the copolymer made as described herein) may optionally be free of crosslinkable groups.
  • the starting materials that copolymerize in step 1) of the method described herein may be free of crosslinkable (meth)acrylate monomers such as organic (meth)acrylate monomers having crosslinkable groups.
  • the starting materials used in step 1) may be free of crosslinkable (meth)acrylate monomers such organic (meth)acrylate monomers having crosslinkable groups as (2-acetoacetoxy)ethyl methacrylate, hydroxybutyl (meth)acrylate, hydroxyethyl (meth) acrylate, hydroxyethylcaprolactone (meth) acrylate, hydroxypropyl (meth)acrylate, ureido (meth)acrylate, glycidyl (meth)acrylate (GMA), and poly(alkylene glycol) (meth)acrylate macromonomers such as poly(ethylene glycol) mono-(meth)acrylate (PEGMA) and poly(ethylene glycol) di(meth)acrylate.
  • crosslinkable (meth)acrylate monomers such organic (meth)acrylate monomers having crosslinkable groups as (2-acetoacetoxy)ethyl methacrylate, hydroxybutyl (meth)acrylate, hydroxy
  • the starting materials used in step 1 may be free of organosilyl monomers having crosslinkable groups, such as alkenyltrialkoxysilanes (e.g., 3- (trimethoxysilyl)propyl (meth)acrylate, vinyltriethoxysilane and vinyltrimethoxysilane).
  • alkenyltrialkoxysilanes e.g., 3- (trimethoxysilyl)propyl (meth)acrylate, vinyltriethoxysilane and vinyltrimethoxysilane.
  • Starting material (A), and when present starting material (B), are copolymerized in the presence of an additional starting material.
  • the additional starting material comprises (C) the initiator.
  • the starting materials that copolymerize in step 1) may consist of starting materials (A) the macromonomer, and (C) the initiator, and when present, (B) the co- macromonomer and/or (H) the chain transfer agent.
  • the starting materials used in step 1) may consist essentially of, or may consist of, (A) the macromonomer, (C) the initiator, (D) the surfactant, and (E) the water, and when present one or more of (B) the co- macromonomer, (H) the chain transfer agent, (I) the manganese ion source, and (J) the phenolic compound, and these starting materials are described further below.
  • Suitable initiators include azo compounds and peroxide compounds.
  • the azo compound may be an aliphatic azo compound such as 1-t-amylazo-l- cyanocyclohexane, azo-bis- isobutyronitrile and 1-t-butylazo-cyanocyclohexane, 2,2’-azo- bis-(2-methyl)butyronitrile, 2,2’- azobis(2-methylpropionitrile), 2,2’-azobis(2-methylpropionamidine) dihydrochloride, 2,2’- azobis(cyanovaleric acid), or a combination of two or more thereof.
  • the peroxide compound may be a peroxide or a hydroperoxide, such as t-butylperoctoate, t- butyl perbenzoate, dicumyl peroxide, di-t-butyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-t-amyl peroxide and combinations of two or more thereof.
  • di-peroxide initiators may be used alone or in combination with other initiators.
  • Such di-peroxide initiators include, but are not limited to, 1 ,4-bis-(t-butyl peroxycarbo)cyclohexane, 1 ,2-di(t-butyl peroxy )cyclohexane, and 2,5-di(t-butyl peroxy)-3-hexyne.
  • Suitable peroxide compounds are known in the art and are commercially available from various sources, such as Sigma- Aldrich, Inc.
  • the initiator may comprise isoascorbic acid, which is also available from Sigma-Aldrich, Inc.
  • An initiator may be used alone as starting material (C).
  • starting material (C) may be a redox pair, which comprises an initiator as the oxidizing component and a reducing component.
  • a redox pair including isoascorbic acid and an organic hydroperoxide such as t-amyl hydroperoxide or t-butyl hydroperoxide may be used as starting material (C). Examples of suitable initiators and/or redox pairs for starting material (C) are disclosed in US Patent 6576051 to Bardman et al., beginning at col. 11, line 16.
  • the initiator is added depends on various factors including whether the initiator is water soluble and the type of initiator (e.g., whether a thermal initiator or a redox pair is used). Typically, when a thermal initiator is used, all the initiator is added at once at the beginning of step 1). Alternatively, when a redox pair is used, it may be metered in over time.
  • the initiator may optionally further comprise Iron(II) sulfate heptahydrate, Potassium persulfate, or a combination thereof.
  • the initiator (C) may be used in an amount sufficient to provide 0.01% to 3%, alternatively 0.1% to 1.5%, based on weight of the silicone - (meth)acrylate copolymer.
  • the initiator may be used in an amount of 0.15 % to 0.23 %, based on combined weights of starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization.
  • Starting material (D) is a surfactant.
  • the surfactant may be selected from the group consisting of (D-l) a cationic surfactant, (D-2) a nonionic surfactant, and (D-3) a combination of both the cationic surfactant and the nonionic surfactant.
  • Cationic surfactants useful herein include compounds containing quaternary ammonium hydrophilic moieties in the molecule which are positively charged, such as quaternary ammonium salts, which may be represented by formula (D-l- 1): R 12 R 13 R 14 R 1S N + X’‘ where R 12 to R 15 are alkyl groups containing 1-30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soy; and X’ is a halogen, e.g., chlorine or bromine.
  • quaternary ammonium salts which may be represented by formula (D-l- 1): R 12 R 13 R 14 R 1S N + X’‘ where R 12 to R 15 are alkyl groups containing 1-30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soy; and X’ is a halogen, e.g., chlorine or bromine.
  • the quaternary ammonium compounds may be alkyl trimethylammonium and dialkyldimethylammonium halides, or acetates, having at least 8 carbon atoms in each alkyl substituent.
  • Dialkyl dimethyl ammonium salts can be used and are represented by formula (D-l-2): R 16 R 17 N + (CH3)2X’ _ where R 16 and R 17 are alkyl groups containing 12-30 carbon atoms or alkyl groups derived from tallow, coconut oil, or soy; and X’ is halogen.
  • Monoalkyl trimethyl ammonium salts can be used and are represented by formula (D-l-3): R 18 N + (CH3)3X”' where R 18 is an alkyl group containing 12-30 carbon atoms or an alkyl group derived from tallow, coconut oil, or soy; and X” is halogen or acetate.
  • Representative quaternary ammonium halide salts are dodecyltrimethyl ammonium chloride/lauryltrimethyl ammonium chloride (LTAC), cetyltrimethyl ammonium chloride (CTAC), hexadecyltrimethyl ammonium chloride, didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, and didocosyldimethyl ammonium chloride.
  • These quaternary ammonium salts are commercially available under trademarks such as ADOGENTM, ARQUADTM, TOMAHTM, and VARIQUATTM.
  • Suitable cationic surfactants which can be used include fatty acid amines and amides and their salts and derivatives, such as aliphatic fatty amines and their derivatives.
  • cationic surfactants that are commercially available include compositions sold under the names ARQUADTM T27 W, ARQUADTM 16-29, by Akzo Nobel Chemicals Inc., Chicago, Illinois; and Ammonyx Cetac-30 by the Stepan Company, Northfield, Illinois, USA.
  • the amount of (D-l) the cationic surfactant may be 0.1% to 5%, based on weight of starting material (F) the silicone - (meth)acrylate copolymer in the aqueous emulsion.
  • the amount of cationic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%; while at the same time the amount of cationic surfactant may be up to 5%, alternatively up to 4%, alternatively up to 3%, alternatively up to 2%, alternatively up to 1%, on the same basis.
  • the amount of cationic surfactant may be 0.2% to 4%, alternatively 0.3% to 3%, alternatively 0.4% to 2.5%, and alternatively 0.5% to 2%; on the same basis.
  • Starting material (D-2) is a nonionic surfactant.
  • suitable nonionic surfactants which can be used include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, alkylglucosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters.
  • Nonionic surfactants which are commercially available include compositions such as (i) 2,6,8-trimethyl-4-nonyl polyoxyethylene ether sold under the names TERGITOLTM TMN-6 and TERGITOLTM TMN-10; (ii) the Cl 1-15 secondary alkyl polyoxyethylene ethers sold under the names TERGITOLTM 15-S-7, TERGITOLTM 15-S- 9, TERGITOLTM 15-S-15, TERGITOLTM 15-S-30, and TERGITOLTM 15-S-40, by the Dow Chemical Company, of Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the name TRITONTM X405 by the Dow Chemical Company; (iii) nonylphenyl polyoxyethylene (10) ether sold under the name MAKONTM 10 by the Stepan Company; (iv) ethoxylated alcohols sold under the name Trycol 5953 by Henkel Corp./Emery Group,
  • alkyl-oxo alcohol polyglycol ethers such as GENAPOLTM UD 050, and GENAPOLTM UDI 10
  • alkyl polyethylene glycol ether based on ClO-Guerbet alcohol and ethylene oxide such as LUTENSOLTM XP 79.
  • Suitable nonionic surfactants also include poly(oxyethylene)-poly(oxypropylene)- poly(oxy ethylene) tri-block copolymers.
  • Poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block copolymers are also commonly known as Poloxamers. They are nonionic triblock copolymers composed of a central hydrophobic chain of polyoxypropylene (polypropylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (poly(ethylene oxide)).
  • Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are commercially available from BASF of Florham Park, New Jersey, USA, and are sold under the tradename PLURONICTM, such as PLURONICTM L61 , L62, L64, L81 , P84.
  • the nonionic surfactant may also be a silicone polyether (SPE).
  • SPE silicone polyether
  • the silicone polyether as a surfactant may have a rake type structure wherein the polyoxyethylene or polyoxyethylenepolyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure.
  • the SPE may have a resinous structure, such as a polyorganosilicate resin having polyether groups bonded to silicon atoms therein. Suitable SPE’s include DOWSILTM OFX-5329 Fluid from Dow Silicones Corporation of Midland, Michigan, USA.
  • the nonionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides.
  • silicone-based surfactants may be used to form such aqueous emulsions and are known in the art, and have been described, for example, in US Patent 4122029 to Gee et al., US Patent 5387417 to Rentsch, and US Patent 5811487 to Schulz et al.
  • Other silicone polyether surfactants are known in the art and are also commercially available, e.g., DOWSILTM 502W and DOWSILTM 67 Additive are commercially available from Dow Silicones Corporation of Midland, Michigan, USA.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, polyoxyethylene lauryl ethers, polyoxyethylene sorbitan monooleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol (such as polyethylene glycol having 23 ethylene-oxide units), polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, and polyoxyalkylene glycol modified polysiloxane surfactants.
  • nonionic surfactants which can be used include compositions such as 2,6,8-trimethyl-4-nonyloxy polyethylene oxyethanols (6EO) and (10EO) sold under the trademarks TERGITOLTM TMN-6 and TERGITOLTM TMN-10; alkyleneoxy polyethylene oxyethanol (Cn-is secondary alcohol ethoxylates 7EO, 9EO, and 15EO) sold under the trademarks TERGITOLTM 15-S-7, TERGITOLTM 15-S-9, TERGITOLTM 15-S-15; other C11-15 secondary alcohol ethoxylates sold under the trademarks TERGITOLTM 15-S-12, 15-S-20, 15-S-3O, 15-S-40; octylphenoxy polyethoxy ethanol (40EO) sold under the trademark TRITONTM X-405; and alcohol ethoxylates with tradename ECOSURFTM EH, such as ECOSURFTM EH-40.
  • 6EO 2,6,8-trimethyl-4
  • surfactants are sold by The Dow Chemical Company.
  • Other useful commercial nonionic surfactants are nonylphenoxy polyethoxy ethanol (10EO) sold under the trademark MAKONTM 10 by Stepan Company; polyoxyethylene 23 lauryl ether (Laureth-23) sold commercially by Sigma Aldrich, Inc. of St. Louis, Missouri, USA; and RENEXTM 30, a polyoxyethylene ether alcohol available from Fisher Scientific.
  • Starting material (D-2) the nonionic surfactant may be delivered in a dilution, and the amount used may be sufficient to provide 0.1 % to 10 % of the surfactant, based on weight of starting material (F) the silicone - (meth)acrylate copolymer in the aqueous emulsion.
  • the amount of nonionic surfactant may be at least 0.1%, alternatively at least 0.2%, alternatively at least 0.3%, alternatively at least 0.4%, alternatively at least 0.5%, alternatively at least 1%, alternatively at least 2%, alternatively at least 3%, alternatively at least 4%; while at the same time the amount of nonionic surfactant may be up to 10%, alternatively up to 9%, alternatively up to 8%, alternatively up to 7%, alternatively up to 5%, alternatively up to 4%, alternatively up to 3%, alternatively up to 2%, alternatively up to 1%, on the same basis.
  • the amount of nonionic surfactant may be 1% to 10%, alternatively 2% to 10%, alternatively 3 to 10%, alternatively 5% to 9%, alternatively 6% to 8%, and alternatively 7%%; on the same basis.
  • starting materials (D-l) the cationic surfactant and (D-2) the nonionic surfactant may be present in combined amounts ⁇ 10%, based on weight of starting material (F) the silicone - (meth)acrylate copolymer in the aqueous emulsion.
  • (D) the surfactant may be used in an amount of 2% to 3.5 %, based on combined weights of starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization.
  • Starting material (E) is water.
  • the water is not generally limited, for example, the water may be processed or unprocessed. Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, and combinations of two or more thereof, such that the water may be deionized, distilled, and/or filtered. Alternatively, the water may be unprocessed (e.g., may be tap water, i.e., provided by a municipal water system or well water, used without further purification). The amount of water is sufficient to form an aqueous emulsion for emulsion polymerization in step 1) of the process described above. Additional water may be added after step 1).
  • the aqueous emulsion prepared as described above may be diluted with additional water to achieve a desired amount of starting materials before treating a paper substrate with the resulting paper treatment composition.
  • the water may be added in an amount of 20% to 97%, alternatively 30% to 90%, alternatively 40% to 80%, alternatively 50% to 97%, alternatively 50% to 90%, and alternatively 60% to 80%; based on combined weights of all starting materials in step 1).
  • the water may be added in an amount of at least 20 %, alternatively at least 30 %, alternatively at least 40 %, alternatively at least 50 %, and alternatively at least 60 %; while at the same time the amount of water may be up to 97 %, alternatively up to 96 %, alternatively up to 9 5%, and alternatively up to 80 %, on the same basis.
  • the amount of water may be 54 % to 82 %, based on combined weights of starting materials (A), (B), (C), (D), and (E) used in the emulsion polymerization to prepare (F), the silicone - (meth)acrylate copolymer.
  • the silicone - (meth) acrylate copolymer, (F) may be prepared by emulsion polymerization of starting materials comprising (A) the macromonomer and (C) the initiator (and optionally (B) the co-macromonomer) described above.
  • the silicone - (meth)acrylate copolymer may be a reaction product of starting materials consisting essentially of starting materials (A) the macromonomer and (C) the initiator (and when present, (B) the co- macromonomer and/or (H) the chain transfer agent).
  • the silicone - (meth)acrylate copolymer is a reaction product of starting materials consisting of starting materials (A) and (C), (and, when present, (B) and/or (H)).
  • starting materials (D) and/or (E), or any other starting material added during the method may participate in the copolymerization reaction of starting materials comprising (A) and (C), and any optional starting materials (z.e., (B) and/or (H)), when present.
  • each R 1 is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms
  • each D 2 is independently a divalent hydrocarbon group of 2 to 12 carbon atoms
  • each R 2 is independently selected from the group consisting of H and methyl
  • each R is a group of formula OSi(R 4 )3; where each R 4 is independently selected from the group consisting of R and DSi(R s h, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, a (poly) alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms;
  • each R 5 is independently selected from the group consisting of R and DSi(R 6 h; where each R 6 is independently selected from the group consisting of R and DSiRy with the proviso that
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R, D, and D 2 are as described and exemplified above for formulas (A-l), (B-l) and (B-2).
  • each R 1 may be methyl
  • each R 2 may be methyl
  • each D 2 may be propylene
  • each R 3 may be the group of formula OSi(R 4 h; where each R 4 is independently selected from the group consisting of R and OSi(R 5 )3, where each R is methyl; each R 5 is independently selected from the group consisting of R and OSi(R 6 )3; where each R 6 is independently selected from the group consisting of R and OSiR?; with the proviso that R 4 , R 5 , and R 6 are selected such that the silicone - (meth)acrylate co-macromonomer 10 to 16 silicon atoms per molecule.
  • subscript bl may have a value such that 0 ⁇ bl ⁇ 0.75, alternatively 0 ⁇ bl ⁇ 0.5, alternatively 0
  • the silicone - (meth) acrylate copolymer prepared as described above may have a weight average molecular weight measured by GPC of > 181,000 g/mol.
  • silicone - (meth)acrylate copolymer may have a weight average molecular weight measured by GPC of at least 200,000 g/mol; alternatively at least 210,000 g/mol; alternatively at least 212,000 g/mol; alternatively at least 225,000 g/mol; alternatively at least 230,000 g/mol; and alternatively at least 234,000 g/mol; while at the same time, weight average molecular weight may be up to 2,000,000 g/mol; alternatively up to 1,000,000 g/mol; alternatively up to 950,000 g/mol; alternatively up to 925,000 g/mol; alternatively up to 912,000 g/mol, alternatively up to 900,000 g/mol, alternatively up to 850,000 g/mol; alternatively up to 800,000 g/mol; and alternatively up to 750,000 g/mol; and alternatively up to 721,000 g/mol.
  • GPC weight average molecular weight measured by GPC of at least 200,000 g/mol; alternatively at least 210,000 g/
  • the silicone - (meth)acrylate copolymer may have a weight average molecular weight of 212,000 g/mol to 912,000 g/mol, measured by GPC.
  • the samples for GPC analysis may be prepared in THF eluent at concentration 10 mg/mL copolymer. The solution may be shaken on a flat-bed shaker at ambient temperature for 2 hours. The solution may then be filtered through a 0.45 m PTFE syringe filter prior to injection. A Waters e2695 LC pump and autosampler, equipped with two 5 uM Agilent PLG gel Mixed C columns in series and Shodex RI501 differential refractive index detector was used to analyze the samples.
  • An additional starting material that may be added in step 1) of the method for making the silicone - (meth) acrylate copolymer described above comprises (H) a chain transfer agent.
  • Suitable chain transfer agents include mercaptans such as alkyl mercaptans, e.g., n-octyl mercaptan, n-dodecyl mercaptan, dodecyl mercaptan (dodecane thiol), and/or 2,2-dimethyldecyl mercaptan.
  • the chain transfer agent may be water soluble, such as mercaptoacetic acid and/or 2-mercaptoethanol.
  • Suitable chain transfer agents are known in the art and have been disclosed, for example, in “Radical Polymerization in Industry” by Peter Nesvadba, Performance Chemical Research, GASF Sau AG, Basel, Switzerland, Encyclopedia of Radicals in Chemistry, Biology and Materials, Online ⁇ 2012 John Wiley & Sons, Ltd.
  • Starting material (H) is optional and may be added in an amount of 0 to 1%, based on combined weights of starting material (A), and when present starting material (B).
  • the chain transfer agent may be used in an amount of 0.5% to 0.6% on the same basis.
  • Starting material (I) is an optional manganese ion source, which may be a manganese (II) compound, a manganese (III) compound, or a combination thereof.
  • the manganese ion source may be a manganese (II) compound.
  • Suitable manganese (II) 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, hydrates thereof (e.g., manganese (II) acetate tetrahydrate) and combinations thereof.
  • the manganese ion source may comprise manganese (II) acetate or manganese (II) acetate tetrahydrate, or a combination thereof.
  • Suitable manganese ion sources are commercially available from Millipore Sigma of St. Louis, Missouri, USA, Fisher Scientific of Waltham, Massachusetts, USA, and City Chemical LLC of Connecticut, USA.
  • the amount of manganese ion source depends on various factors including the selections and amounts of other starting materials used, however the amount may be 0.1 ppm to 5,000 ppm based on combined weights of starting material (A), and when present starting material (B).
  • the amount of the manganese ion source may be > 0 ppm, alternatively at least 0.5 ppm, alternatively at least 1 ppm, alternatively at least 1.5; while at the same time, the amount of manganese ion source may be up to 10 ppm, alternatively up to 5 ppm, alternatively up to 4 ppm, and alternatively up to 3 ppm, and alternatively up to 2 ppm, based on combined weights of all starting materials in the emulsion formulation for treating the textile.
  • Starting material (J) is an optional phenolic compound.
  • Suitable phenolic compounds include hydroquinone (HQ), 2-methylhydroquinone, 2-t-butylhydroquinone, dihydroxybenzene (catechol), 4-di-t-butyl dihydroxybenzene (4-di-t-butyl catechol), resorcinol, dihydroxyxylene, methoxyphenols such as guaiacol, p-methoxyphenol (also called methyl ether of hydroquinone or MeHQ), tert-butyl hydroquinone (tBuHQ), pyrogallol, methylpyrogallol, cresol, phenol, xylenols, butylated hydroxyl toluene, N-nitroso phenylhydroxylamine, butylated hydroxy anisole, and combinations thereof.
  • hydroquinone HQ
  • 2-methylhydroquinone 2-t-butylhydroquinone
  • the phenolic compound may be selected from the group consisting of HQ, MeHQ, tBuHQ, and a combination of two or more thereof. Suitable phenolic compounds are commercially available, e.g. , from Millipore Sigma of St. Louis, Missouri, USA. The amount of phenolic compound source depends on various factors including the selections and amounts of other starting materials used, however the amount may be 5 ppm to 5,000 ppm based on combined weights of starting material (A) and when present starting material (B).
  • the amount of the phenolic compound may be at least 5 ppm, alternatively at least 50 ppm, alternatively at least 100 ppm, alternatively at least 150 ppm; while at the same time, the amount of phenolic compound may be up to 500 ppm, alternatively up to 400 ppm, alternatively up to 350 ppm, and alternatively up to 320 ppm, based on combined weights of all starting materials in the emulsion formulation for treating the textile.
  • the inhibitor may comprise, or may be, nitrobenzene; 2,2-diphenyl-l-picrylhydrazyl (DPPH); phenothiazine; N,N-diethylhydroxylamine; (2,2,6,6-tetramethylpiperidin-l-yl)oxidanyl (TEMPO); 4-hydroxy-(2,2,6,6-tetramethylpiperidin-l-yl)oxidanyl (4-hydroxy TEMPO); or a combination of two or more thereof.
  • DPPH 2,2-diphenyl-l-picrylhydrazyl
  • TEMPO 2,2,6,6-tetramethylpiperidin-l-yl)oxidanyl
  • Starting material (K) is an optional biocide.
  • the amount of biocide will vary depending on factors including the type of biocide selected and the benefit desired. However, when used, the amount of biocide may be > 0% to 5% based on the combined weights of all starting materials in the aqueous emulsion prepared as described above.
  • Starting material (K) is exemplified by (K-l) a fungicide, (K-2) an herbicide, (K-3) a pesticide, (K-4) an antimicrobial agent, or a combination thereof.
  • Suitable biocides are disclosed, for example, in US Patent 9480977.
  • the paper treatment composition described herein may optionally further comprise a second silicone - (meth)acrylate copolymer that differs from and in addition to the silicone - (meth) acrylate copolymer comprising unit formula (F-l) described above.
  • the second silicone - (meth)acrylate copolymer differs from and in addition to the silicone - (meth) acrylate copolymer comprising unit formula (F-l) described above.
  • (meth) aery late copolymer comprises unit formula (F-2): independently selected alkyl group of 16 to 24 carbon atoms; each R 2 is independently selected from the group consisting of H and methyl as described above for formula (F-l); each D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms as described above for formula (F-l); each R 3 is independently selected from the group consisting of R and a group of formula OSi( R 4 p; wherein each R 4 is independently selected from the group consisting of R and DSi(R s )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)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 is independently selected from the group consisting of R and DSi(R 6 )3; wherein each R 6 is independently selected from the group consisting of
  • R 101 has 16 to 24 carbon atoms.
  • R 101 may have at least 16, alternatively at least 17, alternatively at least 18 carbon atoms, while at the same time R 101 may have up to 24, alternatively up to 23, and alternatively up to 22 carbon atoms.
  • R 101 may have 17 to 23, carbon atoms, alternatively 16 to 22 carbon atoms, alternatively 17 to 24 carbon atoms, and alternatively 18 to 22 carbon atoms.
  • R 101 may be selected from the group consisting of stearyl, eicosyl, and behenyl. Alternatively, R 101 may be stearyl.
  • each R 3 is independently selected from the group consisting of R and a group of formula -OSi(R 4 )3; where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms as described above for unit formula (F-l).
  • each R 4 is independently selected from the group consisting of R (as defined above) and DSi(R 5 )3, wherein each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 is independently selected from the group consisting of R and DSi(R 6 )3; wherein each R 6 is independently selected from the group consisting of R and DSiRs; with the proviso that in the unit formula (F-2) R 3 , R 4 , R 5 , and R 6 are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 4, alternatively at least 6 silicon atoms, alternatively at least 7 silicon atoms, alternatively at least 8 silicon atoms, alternatively at least 9 silicon atoms, and alternatively at least 10 silicon atoms; while at the same time the silicone - (meth)acrylate macromonomer
  • R 3 , R 4 , R 5 , and R 6 may be selected such that the silicone - (meth)acrylate macromonomer unit has 4 to 16, alternatively 4 to 10, alternatively 6 to 16, and alternatively 6 to 10 silicon atoms, per unit.
  • Each D is independently selected from the group consisting of an oxygen atom, a (poly) alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms, each as described and exemplified above for unit formula (F-l).
  • each D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms as described above for formula (A-l).
  • each D 3 and each D is independently a divalent hydrocarbon group of 1 to 12 carbon atoms.
  • each D 3 and each D may be an alkylene group; alternatively, ethylene.
  • D 4 and D 1 are each independently an alkylene group of 2 to 4 carbon atoms or a divalent alkylarylene group.
  • the divalent hydrocarbon group for D 4 and D 1 may be exemplified by an alkylene group such as ethylene, propylene, or butylene; an arylene group such as phenylene, or an alkylarylene group such as: independently 1 to 6, alternatively 1 to 2.
  • the divalent hydrocarbon group may be alkylene, and alternatively the divalent hydrocarbon group may be ethylene.
  • the divalent hydrocarbon group for D, D 2 and D 3 in the unit formula (F-2) above may be as described above, and alternatively may be methylene.
  • D 2 may be methylene, ethylene or propylene; alternatively, propylene.
  • D 2 may be linear, e.g., -(CtErE- or -(CFb -.
  • each R 7 is independently selected from the group consisting of an oxygen atom and NH. Alternatively, each R 7 may be oxygen.
  • each R 8 is a crosslinkable group.
  • Each R 8 may be independently selected from the group consisting of hydroxy, amino, epoxy, ureido, and acetoxy.
  • each R 8 may be independently selected from the group consisting of hydroxy and ureido, and alternatively each R 8 may be hydroxy.
  • each R 1S is an oxygen atom or NH, alternatively oxygen.
  • Each R 16 is selected from the group consisting of -OH and alkoxy. Alternatively, the alkoxy group for R 16 may be -OCH3.
  • each R 9 is a monovalent hydrocarbon group, which is free of aliphatic unsaturation and which may be linear, branched, or cyclic (i.e., monocyclic or polycyclic), or combinations thereof.
  • R 9 may be an alkyl group or an aryl group, which may be monocyclic or polycyclic, and which may optionally have linear or branched groups.
  • suitable alkyl groups for R 9 may include methyl, t-amyl, butyl (including t-butyl), cyclohexyl, iso-decyl, isobomyl, and 2-ethylhexyl.
  • suitable aryl groups include phenyl, naphthyl, anthracyl, and benzyl.
  • R 10 may be a halide, an acetate, or a monovalent hydrocarbon group, as described above for R 9 .
  • the halide may be bromide (Br), chloride (Cl), fluoride (F) or iodide (I); alternatively Br, Cl or F; alternatively Br or Cl; and alternatively Cl.
  • subscripts w, x, y, y2, zl, and z2 are relative weights of each unit, and a quantity (w + x + y + y2 + zl + z2) may total 100.
  • Subscript w has a value of 80 to 98.75.
  • subscript w may be at least 80, alternatively at least 81, alternatively at least 82, alternatively at least 83, alternatively at least 84, alternatively at least 85, alternatively at least 86, alternatively at least 87, and alternatively at least 88; while at the same time, subscript w is up to 98.75, alternatively up to 98, alternatively up to 97, alternatively up to 96, alternatively up to 95, alternatively up to 94, alternatively up to 93, alternatively up to 92, alternatively up to 91, alternatively up to 90, alternatively up to 89, and alternatively up to 88.
  • subscript w may be 84 to 92, alternatively 85 to 91, alternatively 86 to 90, alternatively 87 to 89, and alternatively 88.
  • the unit with subscript x is the silicone - (meth) acrylate macromonomer unit.
  • Subscript x has a value of 1 to 15, alternatively 5 to 15.
  • subscript x may be at least 1, alternatively at least 5, alternatively at least 6, alternatively at least 7, alternatively at least 8, alternatively at least 9, alternatively at least 10; while at the same time, subscript x may be up to 15, alternatively up to 14, alternatively up to 13, alternatively up to 12, alternatively up to 11, and alternatively up to 10.
  • subscript x may be 1 to 14, alternatively 2 to 13, alternatively 3 to 12, alternatively 4 to 11, alternatively 5 to 10, alternatively 7 to 13; and alternatively 10.
  • subscript y has a value of 1 to 5.
  • subscript y may be at least 1, alternatively at least 1.25, alternatively at least 1.5, alternatively at least 1.75, and alternatively at least 2; while at the same time, subscript y may be up to 5, alternatively up to 4, alternatively up to 3, alternatively up to 2.75, alternatively up to 2.5, and alternatively up to 2.25.
  • subscript y may be 1 to 3, alternatively 1 to 2, alternatively 1.5 to 2.5, alternatively 1.75 to 2.25, and alternatively 2.
  • subscript y2 has a value of 0 to 5.
  • subscript y2 may be at least 1, alternatively at least 1.25, alternatively at least 1.5, alternatively at least 1.75, and alternatively at least 2; while at the same time, subscript y2 may be up to 5, alternatively up to 4, alternatively up to 3, alternatively up to 2.75, alternatively up to 2.5, and alternatively up to 2.25.
  • subscript y2 may be 0 to 3, alternatively 1 to 2, alternatively 1.5 to 2.5, alternatively 1.75 to 2.25, and alternatively 2.
  • subscript y2 may be 0 and the unit may be absent from the second silicone - (meth)acrylate copolymer.
  • subscript zl may be 0.
  • subscript zl may be at least 0.5, alternatively at least 1, and alternatively at least 2; while at the same time, subscript zl may be up to 18, alternatively up to 15, alternatively up to 10, alternatively up to 8, and alternatively up to 5.
  • subscript zl may be 0 to 18, alternatively > 0 to 18, alternatively 0.5 to 7, alternatively 1 to 6, and alternatively 2 to 5.
  • subscript z2 may be 0.
  • subscript z2 may be at least 0.5, alternatively at least 1, and alternatively at least 2; while at the same time, subscript z2 may be up to 8, alternatively up to 7, alternatively up to 6, alternatively up to 5, and alternatively up to 4.
  • subscript z2 may be 0 to 8, alternatively > 0 to 8, alternatively 0.5 to 7, alternatively 1 to 6, and alternatively 2 to 5.
  • the total number of units per molecule of the copolymer of unit formula (F-2) is not specifically restricted.
  • this second silicone - (meth) acrylate copolymer may have a number average molecular weight of > 100,000 g/mol, alternatively > 1,000,000 g/mol; by conventional methods based on the selection of each monomer and the chain transfer agent.
  • the units shown above may be in any order, e.g., the second silicone - (meth)acrylate copolymer may be a random copolymer or a block copolymer.
  • the second silicone - (meth)acrylate copolymer may be prepared by radical polymerization, via a process as described in the references cited below, and that this process would form the terminal moiety for the copolymer.
  • the second silicone - (meth)acrylate copolymer further comprises a terminal moiety which may be derived from an initiator, a chain transfer agent, or both, as described, for example in Odian, George (2004). Principles of Polymerization (4th ed.). New York: Wiley-Interscience. ISBN 978-0-471-27400-1.
  • the second silicone - (meth) acrylate copolymer may be prepared as described in PCT Publication WO2022197350 corresponding to US Patent Application Serial No. 18/258663; PCT Publication W02023010944 corresponding to US Patent Application Serial No. 18/558769; PCT Publication WO2023086692 corresponding to US Provisional Patent Application Serial No. 63/277671; US Provisional Patent Application Serial No. 63/588046; US Provisional Application Serial No. 63/588050; and US Provisional Application Serial No. 63/588056; each of which is hereby incorporated by reference.
  • the second silicone - (meth)acrylate copolymer may comprise unit formula (F-3): wherein each R 101 is the independently selected alkyl group of 16 to 24 carbon atoms as described above; each R 2 is independently selected from the group consisting of H and methyl; each D 2 is the divalent hydrocarbon group of 2 to 12 carbon atoms as described above; each R 3 is the group of formula OSi(R 4 )s; 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 the oxygen atom, the (poly)alkylene oxide group of 1 to 12 units, and the divalent hydrocarbon group of 2 to 4 carbon atoms; each R s 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,;
  • R 101 , R 2 , R, D 2 , D 3 , D 4 , R 7 , R 8 , R 9 , and R 10 are as described and exemplified above for unit formula (F-2).
  • each R 3 is the group of formula OSi(R 4 )s; where each R 4 , R 5 , and R 6 are as described above for unit formula (F-2), with the proviso that R 4 , R 5 , and R 6 are selected such that the silicone - (meth)acrylate macromonomer unit with subscript x has at least 6 silicon atoms.
  • R 4 , R 5 , and R 6 are selected such that the 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, per unit.
  • the monovalent hydrocarbon groups for R, and the (poly) alkylene oxide groups and divalent hydrocarbon groups for D are as described and exemplified above for unit formula (F-2).
  • subscripts w, x, y, zl, and z2 are relative weights of each unit, and a quantity (w + x + y + zl + z2) may total 100.
  • Subscript w has a value of 80 to 98.75.
  • subscript w may 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.
  • subscript w may be up to 98.75, alternatively up to 98, alternatively up to 97, alternatively up to 96, alternatively up to 97, alternatively up to 96, alternatively up to 95, alternatively up to 94, alternatively up to 93, alternatively up to 92, alternatively up to 91, and alternatively up to 90.
  • subscript w may be 80 to 98, alternatively 81 to 97, alternatively 82 to 96, alternatively 82 to 95, and alternatively 85 to 90.
  • subscript x has a value of 0.25 to 15.
  • subscript x is 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, alternatively at least 5.
  • subscript x may be up to 15, alternatively up to 14, alternatively up to 13, alternatively up to 12, alternatively up to 11, and alternatively up to 10.
  • subscript x 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.
  • subscript y has a value of 1 to 5.
  • subscript y 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.
  • subscript y may be up to 5, alternatively up to 4, alternatively up to 3, alternatively up to 2.75, alternatively up to 2.5, and altematively up to 2.25.
  • subscript y may be 1 to 3, alternatively 1 to 2, alternatively 1.5 to 2.5, alternatively 1.75 to 2.25, and alternatively 2.
  • subscript zl may be 0.
  • subscript zl may be at least 0.5, alternatively at least 1, and alternatively at least 2; while at the same time, subscript zl may be up to 18.75, alternatively up to 15, alternatively up to 10, alternatively up to 8, and alternatively up to 5.
  • subscript zl may be 0 to 18.75, alternatively > 0 to 18.75, alternatively 0.5 to 7, alternatively 1 to 6, and alternatively 2 to 5.
  • subscript z2 may be 0.
  • subscript z2 may be at least 0.5, alternatively at least 1, and alternatively at least 2; while at the same time, subscript z2 may be up to 8, alternatively up to 7, alternatively up to 6, alternatively up to 5, and alternatively up to 4.
  • subscript z2 may be 0 to 8, alternatively > 0 to 8, alternatively 0.5 to 7, alternatively 1 to 6, and alternatively 2 to 5.
  • the total number of units per molecule of the second silicone - (meth)acrylate copolymer of unit formula (F-3) is not specifically restricted.
  • the second silicone - (meth) acrylate copolymer may have a number average molecular weight of > 100,000 g/mol, alternatively > 100,000 g/mol to 4,000,000 g/mol; alternatively 200,000 g/mol to 3,000,000 g/mol measured by GPC.
  • the samples for GPC analysis may be prepared in THF eluent at concentration 10 mg/mL copolymer. The solution may be shaken on a flat-bed shaker at ambient temperature for 2 hours. The solution may then be filtered through a 0.45 m PTFE syringe filter prior to injection.
  • Agilent GPC software Cirrus version 3.3 may be used for data collection and for data reduction.
  • a total of 16 PS linear narrow molecular weight standards from Agilent having Mp values from 3750 to 0.58 kg/mol may be used for molecular weight calibration.
  • a 3 rd order polynomial was used for calibration curve fitting.
  • All molecular weight averages, distributions and references to molecular weight provided in this report are PS equivalent values.
  • the units of the copolymer shown above may be in any order, e.g., the copolymer may be a random copolymer or a block copolymer.
  • the second silicone - (meth)acrylate copolymer of formula (F-3) may be prepared by radical polymerization, via a process in the references cited below, and that this process would form the terminal moiety for the copolymer.
  • This copolymer may be prepared as described in PCT Publication WO2022197350 corresponding to US Patent Application Serial No. 18/258663, or US Provisional Patent Application Serial No. 63/588046.
  • the second silicone - (meth) aery late copolymer (e.g., of unit formula (F-2) or unit formula (F-3)) described above may be prepared via an emulsion polymerization process, wherein monomers, a surfactant, water, a chain transfer agent, and an initiator, and optionally a manganese ion source and a phenolic compound) may be combined to form an aqueous emulsion.
  • the surfactant, water, chain transfer agent, initiator, manganese ion source, and phenolic compound may be as described above.
  • an aqueous emulsion comprising the second silicone - (meth)acrylate copolymer, a surfactant, and water (and optionally a manganese ion source and a phenolic compound) may be prepared after formation of the second silicone - (meth)acrylate copolymer.
  • the resulting aqueous emulsion may comprise 20% to 97% of water and 0.1% to 10% of the surfactant, each based on weight of the second silicone - (meth)acrylate copolymer, with the balance to 100% being the second silicone - (meth) acrylate copolymer.
  • This (second) aqueous emulsion may optionally further comprise an additional starting material (e.g., a biocide) as described above.
  • the second aqueous emulsion comprises the second silicone - (meth)acrylate copolymer, the surfactant (which may be as described above for starting material (D), the water (which may be as described above for starting material (E).
  • the second aqueous emulsion of the second silicone - (meth)acrylate copolymer may be mixed with the aqueous emulsion of the silicone - (meth)acrylate copolymer comprising unit formula (F-l), prepared as described above to provide an intermediate emulsion comprising both the (F-l) silicone - (meth)acrylate copolymer and (F-2) the second silicone - (meth) acrylate copolymer.
  • Mixing may be performed by any convenient means in any convenient equipment.
  • a water dispersible crosslinker may optionally be used in the paper treatment composition.
  • Suitable crosslinkers include blocked isocyanates and diols.
  • the term “blocked isocyanates” encompasses mono-, di- and polyisocyanates in which an isocyanate group has been reacted with a blocking agent, which upon heating, release the isocyanate and the blocking agent.
  • Suitable blocking agents are known in the art such as amines, amides, compounds having an active hydrogen atom, alcohols, or oximes.
  • Blocked isocyanates are commercially available, such as ARKOPHOBTM DAN and ARKOPHOBTM SR from Archroma of Reinach, Switzerland; RUCO-GUARDTM WEB from Rudolf GmbH of Geretsreid, explanation, Germany, and PHOBOLTM XAN from Huntsman Corporation of the Woodlands, Texas, USA.
  • Diols include, for example, 1,2-propoanediol; 1,3-propanediol; 1,2-butanediol; 1,3 -butanediol; 1,4-butanediol; 2,3-butanediol; 2-methyl-l,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,
  • crosslinkers are known in the art and are disclosed, for example, in US Patent Application 2017/0204558 to Knaup; US Patent 9777105 to Hamajima et al., beginning at col. 11, line 54, which are hereby incorporated by reference for the purpose of describing suitable crosslinkers.
  • the crosslinker may be free of oxime blocking agents.
  • This crosslinker may comprise a nitrogen containing heterocycle (N-heterocycle) - blocked isocyanate.
  • the N- heterocycle-blocked isocyanate comprises an isocyanate compound and an N-heterocy deblocking agent.
  • the isocyanate compound may be monomeric or polymeric.
  • the isocyanate compound may comprise, or may be, a unit selected from the group consisting of IPDI, HnMDI, TMXDI, TMI, XDI, I LXDI, MDI, TDI, and HDI.
  • the polyisocyanate may be an aliphatic isocyanate where the NCO group is not directly attached to an aromatic ring.
  • the polyisocyanate may be HDI or MDI.
  • the N-heterocycle blocking agent may be caprolactam, 2,6-dimethylpyrazine or a dimethylpyrazole, e.g., 3,5-dimethylpyrazole.
  • This crosslinker may be free of oxime compounds. Suitable crosslinkers are commercially available and may be delivered in aqueous dispersions, and examples thereof are shown below in Table 1.
  • the exact amount of crosslinker depends on various factors including the type and amount of the silicone - (meth)acrylate copolymer, and the selection of paper to be treated.
  • the amount of crosslinker may be sufficient to provide > 1.83 % to ⁇ 6.9 %, based on combined weights of all starting materials (except water) in the paper treatment composition.
  • the amount of crosslinker may be at least 2%, alternatively at least 3%, alternatively at least 3.5%, alternatively at least 3.59%; while at the same time the amount may be up to 6%, alternatively up to 5%, alternatively up to 4%, and alternatively up to 3.59% on the same basis.
  • the paper treatment composition further comprises a catalyst.
  • the catalyst comprises a metal complex, which may be a metal carboxylate (e.g., a metal acetate or a metal acetylacetonate), wherein the metal is selected from the group consisting of manganese (Mn), zinc (Zn), and zirconium (Zr). Alternatively, the metal may be Zn or Zr, and alternatively Zn.
  • Suitable catalysts include manganese (II) acetate (CAS No. 638-38-0), manganese (II) acetate tetrahydrate (CAS No. 6156-78-1), manganese (II) acetylacetonate (CAS No.
  • manganese (III) acetylacetonate (CAS No. 14284-89-0), zinc acetate hydrate (CAS No. 16788- 43-5), zinc (II) acetate (CAS No. 557-34-6), zinc (II) acetate dihydrate (CAS No. 5970-45-6), zinc(II) acetylacetonate (CAS No. 14024-63-6), zinc (II) acetylacetonate hydrate (CAS No. 108503-47-5), zirconium acetate (CAS No. 7585-20-8), and zirconium (IV) acetylacetonate (CAS No. 17501-44-9), all of which are commercially available from Sigma Aldrich, Inc.
  • the amount of the catalyst depends on various factors including the types and amounts of the silicone - (meth)acrylate copolymer (and when present the second silicone - (meth)acrylate copolymer) and the crosslinker, however, the amount of the catalyst may be > 0 to 10%, alternatively 0.5% to 7.5%, alternatively > 0.5% to ⁇ 7.5%, based on combined weights of all starting materials in the paper treatment composition.
  • the paper treatment composition may comprise 0.31 weight % to 1.15 weight % of metal complex catalyst, based on combined weights of all starting materials in the paper treatment composition.
  • the paper treatment composition described above may be free of olefinic halohydrocarbons (e.g., vinyl chloride), and other materials that would be undesirable.
  • olefinic halohydrocarbons e.g., vinyl chloride
  • vinyl chloride is highly toxic, therefore, use of vinyl chloride would be undesirable in the present paper treatment composition because, if unreacted vinyl chloride remains on the paper substrate, this could make the treated paper substrate unsuitable for certain intended uses, such as food contact applications or applications in which a person’s skin comes in contact with the treated paper substrate.
  • the paper treatment composition may be prepared by any convenient means using any convenient equipment.
  • the silicone - (meth)acrylate copolymer may be provided in the aqueous emulsion described above.
  • the crosslinker may also be provided in an aqueous composition, and the method for making the paper treatment composition may comprise mixing the aqueous emulsion, the aqueous composition, and the catalyst in the amounts provided herein. Additional water may optionally be added.
  • aqueuous emulsion comprising the silicone - (meth)acrylate copolymer, the surfactant and water (prepared as described above), 0.48 weight part to 0.7 weight part of aqueous dispersion comprising the crosslinker, 0.8 weight part to 1.7 weight parts of the catalyst, with a balance to 100 weight parts of additional water.
  • the paper treatment composition prepared as described above may be used for treating a substrate comprising paper to impart water repellency and/or oil repellency.
  • a method for treating a substrate comprising paper comprises: I) coating the substrate with the paper treatment composition described above, and II) drying the substrate. Step I) may be performed by any convenient method, such as padding, dipping, or spraying the substrate with the paper treatment composition.
  • Step II) may be performed by any convenient method, such as heating the substrate.
  • Step II) may be performed by placing the substrate in an oven. Heating the substrate may be performed to remove all or a portion of the water and/or cure the paper treatment composition. The exact temperature depends on various factors including the temperature sensitivity of the type of paper substrate selected, the deblocking temperature of the crosslinker, when crosslinker is used, and the desired drying time. However, heating may be performed at a temperature > 100 °C to remove water.
  • the temperature may be > 90 °C to 200 °C, alternatively 100 °C to 200 °C, alternatively 110 °C to 160 °C, alternatively 110 °C to 150 °C , and alternatively 120 °C to 150 °C for a time sufficient to remove all or a portion of the water, deblock the blocked isocyanate crosslinker (when used), and/or cure the silicone - (meth)acrylate copolymer and/or the second silicone - (meth)acrylate copolymer, when present.
  • the heating time may depend on various factors including the temperature selected and coating thickness, however the time may be up to 5 min, alternatively 2 seconds to ⁇ 5 min, alternatively 2 seconds to 1 min, alternatively 2 seconds to 20 seconds.
  • the method may optionally further comprise one or more additional steps, such as repeating steps I) and II) to increase thickness of the coating on the substrate, and/or contacting the coated substrate with a material to be packaged, e.g., food.
  • the method described above may produce a paper substrate having a coating with a thickness of > 0 to ⁇ 1 pm, alternatively > 0 to 0.9 pm, alternatively > 0 to 0.75 pm, alternatively > 0 to 0.5 pm, alternatively > 0 to 0.25 pm, alternatively > 0 to 0.2 pm.
  • the film may have a thickness of 0.05 pm to ⁇ 1 pm, alternatively 0.05 pm to 0.9 pm, alternatively 0.05 pm to 0.8 pm.
  • the coating may have a thickness of 0.2 pm to ⁇ 1 pm, alternatively 0.2 pm to 0.9 pm, alternatively 0.2 pm to 0.8 pm, alternatively 0.2 pm to 0.7 pm, alternatively 0.2 pm to 0.6 pm; alternatively 0.2 pm to 0.5 pm; and alternatively 0.2 pm to 0.3 pm.
  • the substrate to which the paper treatment composition is applied comprises paper and may further comprise an additional material.
  • Substrates comprising paper are exemplified by Kraft paper, parchment paper (e.g., bakery paper), paperboard, cardboard, and corrugated cardboard.
  • the paper may be glazed or unglazed, calendared or un-calendared.
  • Other paper substrates include glassine paper, super calender paper, or clay coated Kraft paper.
  • the substrate may be a laminate of paper and plastic, such as polyethylene coated Kraft paper.
  • Paper substrates are known in the art and are commercially available, such as bakery paper (2094) and general packaging paper (313), both from Metsa.
  • paper has been used in the present description because the substrate used herein comprises paper as described above.
  • the paper treatment composition described herein is applied to paper, e.g., when the substrate comprises paper and an additional material.
  • the opposite (paper) side may be coated with the paper treatment composition of the present invention.
  • the paper substrate treated with the paper treatment composition, described above may be utilized in various applications, as described above, such as food contact applications.
  • Emulsion 1 was synthesized as follows: 3.75 g of EcoSurfTM EH40, 39.97 g 3MT-ALMA, 0.4 g of a 2.5% water solution of 4-methoxyphenol, 0.006 g of hydroquinone, 0.12 g of 0.7% water solution of Mn(II)acetate tetrahydrate, and 93.83 g of water were added to a widemouth jar. A sonicator was used to make an emulsion (Fisherbrand Model 705 sonic dismembrator, amplitude 50, Power ⁇ 62 W, for 2 min). The aqueous emulsion was then transferred to a reactor and heated to 65 °C.
  • paper treatment compositions were prepared by mixing all the starting materials in the amounts shown below in Table 3 using a bottle inversion (3x). Each sample of a paper coating composition was then applied with a bench top coating machine to the paper substrate. The coating was dried and cured with an oven at 150 °C for 5 minutes.
  • 3M Kit Value test (according to TAPPI Test Method T559) describes a procedure for testing the degree of oil repellency and / or the antiwicking characteristics of paper or paperboard treated with fluorochemical sizing agents. It is adopted as a test method to indicate the greaseproof level. The higher the number of Kit value, indicates higher greaseproofness of the substrate. Test method suggests to check the Kit solution that pre-formulated from reagents (Castro oil, toluene and heptane), drops Kit solution from a height 13 mm (0.5in) on the testing specimen. After 15 sec, excess test solution is wiped off. A manual visual examination on the test specimen checking for ‘darkening’ of paper on a grey surface, which is resulted from penetration of the solution into the test specimen.
  • the air permeability or air resistance of different paper substrates was measured with an L&W Air Permeability Tester by sensing the air flow through the sample and the pressure difference across the two sides.
  • the tester had a wide measuring range and was therefore able to measure grades of paper with high or low permeability.
  • Standard test methods such as SCAN-P 26:78 or TAPPI 536 om-12 for ‘Resistance of paper to passage of air (high-pressure Gurley method)’ were applied.
  • the air permeability was measured as the time, expressed in Gurley seconds or Gurley unit, for a given volume of air to pass through a test specimen such as a circular area of paper using a pressure differential of approximately 3 kPa.
  • Gurley seconds or Gurley unit for a given volume of air to pass through a test specimen such as a circular area of paper using a pressure differential of approximately 3 kPa.
  • the higher the air permeability time in Gurley the lower the air permeability of a paper specimen, the better the barrier was towards
  • Example 3 demonstrates that the silicone - (meth)acrylate copolymer prepared by emulsion polymerization of 3MT-ALMA, when mixed with a cross-linker and catalyst provided a beneficial combination of water resistance (Cobb ⁇ 8) oil resistance (Kit > 2.5) and air permeability (Guriy > 800).
  • Example 1 showed that when no crosslinker and no catalyst were used, insufficient water and oil repellency on paper were obtained under the conditions tested.
  • Example 2 showed that when too much crosslinker was used, air permeability (Gurley) was too low under the conditions tested.
  • Example 4 showed that when the amount of crosslinker was too low (1.83 wt%), water resistance was insufficient (Cobb > 8) under the conditions tested. .
  • Example 5 showed that using an aqueous emulsion of the second silicone - (meth)acrylate copolymer, without the (first) silicone - (meth)acrylate copolymer comprising unit formula (F-l) above, water repellency was insufficient (as shown by Cobb value > 8) under the conditions tested.
  • Example 7 showed that mixing the aqueous emulsion with the copolymer comprising unit formula (F- 1 ) above and the second aqueous emulsion comprising the second silicone - (meth) aery late copolymer comprising unit formula (F-2) above provided the beneficial combination of water repellency, oil repellency and air permeability described herein.
  • the paper treatment composition including the silicone - (meth)acrylate copolymer described herein can impart both water resistance and oil resistance to a paper substrate, while maintaining good air permeability.

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
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Abstract

Une composition de traitement de papier comprend un copolymère de silicone-(méth)acrylate, un tensioactif, de l'eau, un agent de réticulation et un catalyseur. La composition peut être appliquée sur du papier, séchée et durcie pour former un revêtement. Le revêtement confère une répulsion de l'eau et de l'huile au papier tout en maintenant la perméabilité à l'air. Le papier couché est utile pour des applications d'emballage alimentaire.
PCT/US2024/052894 2023-10-27 2024-10-25 Papier de traitement avec une composition comprenant un copolymère de silicone-(méth)acrylate Pending WO2025090822A1 (fr)

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Application Number Priority Date Filing Date Title
US202363593716P 2023-10-27 2023-10-27
US63/593,716 2023-10-27
US202463557810P 2024-02-26 2024-02-26
US63/557,810 2024-02-26
US202463637413P 2024-04-23 2024-04-23
US63/637,413 2024-04-23
US202463674322P 2024-07-23 2024-07-23
US63/674,322 2024-07-23
PCT/US2024/045245 WO2025090189A1 (fr) 2023-10-27 2024-09-05 Émulsion de copolymère de silicone-(méth)acrylate et sa préparation et utilisation de l'émulsion pour oléofuger des textiles
USPCT/US2024/045245 2024-09-05

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