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WO2025226624A1 - Traitement de papier avec un copolymère de silicone-(méth)acrylate - Google Patents

Traitement de papier avec un copolymère de silicone-(méth)acrylate

Info

Publication number
WO2025226624A1
WO2025226624A1 PCT/US2025/025676 US2025025676W WO2025226624A1 WO 2025226624 A1 WO2025226624 A1 WO 2025226624A1 US 2025025676 W US2025025676 W US 2025025676W WO 2025226624 A1 WO2025226624 A1 WO 2025226624A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
alternatively
subscript
paper
independently selected
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2025/025676
Other languages
English (en)
Inventor
Matthew JELETIC
Zhenbin NIU
Douglas HASSO
Pierre Chevalier
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Silicones Corp
Original Assignee
Dow Silicones Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Silicones Corp filed Critical Dow Silicones Corp
Publication of WO2025226624A1 publication Critical patent/WO2025226624A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1818—C13or longer chain (meth)acrylate, e.g. stearyl (meth)acrylate
    • 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
    • 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
    • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Definitions

  • a silicone - (meth) acrylate copolymer is useful for treating paper substrates. More particularly, an aqueous emulsion of 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 nonfluorocarbon-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, and water, and II) drying the substrate.
  • starting material (A) is the silicone - (meth)acrylate copolymer (copolymer).
  • the copolymer may comprise unit formula (Al):
  • each R 1 is an independently selected alkyl group of 16 to 24 carbon atoms
  • each R 2 is independently selected from the group consisting of H and methyl
  • each D 2 is a divalent hydrocarbon group of 2 to 12 carbon atoms
  • each R 3 is independently selected from the group consisting of R and a group of formula OSi(R 4 )a
  • each R 4 is independently selected from the group consisting of R and DSi(R 5 )s, wherein each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms
  • each D is independently selected from the group consisting of an oxygen atom, a (poly) 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
  • each R 6 is independently selected from the group consisting of R and DSiR ; with the proviso that R 4 , R 5 , and R 6 are selected such that the
  • R 1 has 16 to 24 carbon atoms.
  • R 1 may have at least 16, alternatively at least 17, alternatively at least 18 carbon atoms, while at the same time R 1 may have up to 24, alternatively up to 23, and alternatively up to 22 carbon atoms.
  • R 1 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 1 may be selected from the group consisting of stearyl, eicosyl, and behenyl. Alternatively, R 1 may be stearyl.
  • the unit with subscript x is a silicone - (meth) acrylate macromonomer unit.
  • each R 3 is independently selected from the group consisting of R and a group of formula -OSi(R 4 h; where each R is an independently selected 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. Alternatively, the alkyl groups may have 1 to 3 carbon atoms, alternatively 1 to 2 carbon atoms.
  • each R may be methyl.
  • each R 4 is independently selected from the group consisting of R (as defined above) and DSi(R 5 )s, 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 h; wherein each R 6 is independently selected from the group consisting of R and DSiRy with the proviso that R 3 , R 4 , R 5 , and R 6 are selected such that the silicone - (meth)acrylate macromonomer unit with subscript w 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 macromon
  • 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.
  • the divalent hydrocarbon group for D may be alkylene, such as ethylene, propylene, or butylene. Alternatively, each 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.
  • D may be oxygen and other instances of D may be alkylene in the same unit.
  • each 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.
  • 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 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 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., -(CTb - 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 -b- 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 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 (Al) is not specifically restricted.
  • the 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 copolymer may be a random copolymer or a block copolymer.
  • the 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 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 copolymer may be prepared as described in PCT Publication WO/2022/197350 corresponding to US Patent Application Serial No. 18/258663; PCT Publication WO/2023/010944 corresponding to US Patent Application Serial No.
  • the silicone - (meth) acrylate copolymer may comprise unit formula (A2): wherein each R 1 is the independently selected alkyl group of 16 to 24 carbon atoms; 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; each R 3 is the group of formula OSi(R 4 )3; wherein each R 4 is independently selected from the group consisting of R and DSi(R 5 h, 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 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
  • the copolymer further comprises a terminal moiety.
  • R 1 , 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 (Al).
  • each R 3 is the group of formula OSi(R 4 )3; where each R 4 is independently selected from the group consisting of R and DSi(R 5 )s, where each R is an independently selected monovalent hydrocarbon group of 1 to 12 carbon atoms, and each D is independently selected from the group consisting of an oxygen atom, a (poly)alkylene oxide group of 1 to 12 units, and a divalent hydrocarbon group of 2 to 4 carbon atoms; each R 5 is independently selected from the group consisting of R and DSi(R 6 )3; where each R 6 is independently selected from the group consisting of R and DSiRy with the proviso that R 4 , R s , 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 (Al).
  • 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 w 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 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 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 copolymer of unit formula (A2) is not specifically restricted.
  • the 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.
  • copolymer of formula (A2) 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 silicone - (meth) acrylate copolymer (e.g., of unit formula (Al) or unit formula (A2)) 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.
  • an aqueous emulsion comprising the 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 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 (A) the silicone - (meth) acrylate copolymer, with the balance to 100% being the silicone - (meth)acrylate copolymer.
  • the paper treatment composition used in the method described herein further comprises (B) a surfactant and (C) water, which may be introduced with the copolymer (e.g., in the aqueous emulsion prepared as described above) and/or which may be introduced with the crosslinker, when used (and as described further below) because the copolymer and the crosslinker may be delivered in aqueous emulsions or dispersions.
  • a surfactant e.g., in the aqueous emulsion prepared as described above
  • C water
  • Starting material (B) is the surfactant.
  • the surfactant may be selected from the group consisting of (B-l) a cationic surfactant, (B-2) a nonionic surfactant, and (B-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 1 R 14 R 15 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 (B-l-2): R 16 R 17 N + (CH 3 )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 (B-l-3): R 18 N+(CH 3 ) 3 X”- 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 (CT AC), hexadeclyltrimethyl 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 (B-l) the cationic surfactant may be 0.1% to 5%, based on weight of starting material (A) the silicone - (meth)acrylate copolymer in the paper treatment composition.
  • 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 (B-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 C 11-15 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 poly glycol 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.
  • 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 (C
  • surfactants are sold by the Dow Chemical Company.
  • Other useful commercial nonionic surfactants are polyoxyethylene 23 lauryl ether (Laureth-23) sold commercially under the trademark BRIJTM 35L by ICI Surfactants, of Wilmington, Delaware, USA; and RENEXTM 30, a polyoxyethylene ether alcohol also sold by ICI Surfactants.
  • the nonionic surfactant may also be a silicone polyether (SPE).
  • SPE silicone polyether
  • the silicone polyether as an emulsifier may have a rake type structure wherein the polyoxyethylene or polyoxyethylene-polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure.
  • Suitable SPE’s include DOWSILTM OFX-5329 Fluid from Dow Silicones Corporation of Midland, Michigan, USA.
  • the nonionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides.
  • Such silicone-based surfactants may be used to form such aqueous emulsions and are known in the art, and have been described, for example, in US Patent 4122029 to Gee et al., US Patent 5387417 to Rentsch, and US Patent 5811487 to Schulz et al.
  • 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 (A) the silicone - (meth)acrylate copolymer in the paper treatment composition.
  • 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%; while at the same time the amount of nonionic 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 nonionic 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 materials (B-l) the cationic surfactant and (B-2) the nonionic surfactant may be present in combined amounts ⁇ 10%, based on weight of starting material (A) the silicone - (meth)acrylate copolymer in the paper treatment composition.
  • the paper treatment composition may be in the form of an aqueous emulsion, wherein (A) the silicone - (meth)acrylate copolymer is in the discontinuous oil phase dispersed in a continuous aqueous phase comprising water.
  • the water in the paper treatment composition may be provided, in whole or in part, by the process used to make (A) the silicone - (meth)acrylate copolymer, e.g., the water used for hydrolysis of monomers, and/or water may be introduced with an additional starting material such as (B) the surfactant, and/or the crosslinker, when present and when the crosslinker is delivered in an aqueous dispersion or emulsion, as described below.
  • Additional water may optionally be added to dilute the paper treatment composition to a desired concentration of starting materials (A) and (B), and any optional additional starting materials, as described below.
  • the water is not generally limited, and may be utilized neat (i.e., absent any carrier vehicles and/or solvents), and/or pure (i.e., free from, or substantially free from, minerals and/or other impurities).
  • the water may be processed or unprocessed prior to use as described herein. Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, reverse osmosis, and combinations of two or more thereof, such that the water may be deionized, distilled, and/or filtered.
  • the water may be unprocessed (e.g. may be tap water, provided by a municipal water system or well water, used without further purification).
  • the water may be utilized in any amount, which will be selected by one of skill in the art, depending on various factors, e.g., the equipment and process conditions used to treat paper with the paper treatment composition, however, the amount of water may be 90% to ⁇ 100%, alternatively 91% to 99%, alternatively 94% to 98%, based on combined weights of all components in the paper treatment composition.
  • the paper treatment composition comprising starting materials (A), (B), and (C), described above may optionally further comprise an additional starting material.
  • the additional starting material may be selected from the group consisting of a manganese ion source; a phenolic compound; a water dispersible crosslinker comprising a blocked isocyanate; a wax; a flame retardant; an antistatic agent; a slimicide (e.g., an antimicrobial); a preservative; an antifoam; a wetting agent; a wet strength agent; a filler; a pigment; a surface refining and coating agent; a pH buffer; and a combination of two or more thereof.
  • Suitable additional starting materials are disclosed, for example, in US Patent Application Publication 20070099007 at paragraphs [0177] to [0184] and BfR36 XXXVI-Paper-and-Board-for-Food-Contact.pdf (bund.de).
  • exemplary preservatives include quarternary ammonium compounds (QATs), sodium benzoate and phenoxyethanol and methylisothiazolinone, which are commercially available as NeoIone PE Preservative, and other isothiazolones, and combinations thereof.
  • starting materials for the paper treatment composition described above there may be overlap between types of starting materials because certain materials described herein may have more than one function.
  • certain QATs may be useful as surfactants and as preservatives.
  • Certain particulates may be useful as fillers and as pigments, and even as flame retardants, e.g., carbon black.
  • the additional starting materials are distinct from one another.
  • the paper treatment composition described herein may be formulated with starting materials that are fluorocarbon-free.
  • the paper treatment composition may be free of any starting material that contains a fluorine atom covalently bonded to a carbon atom.
  • the manganese ion source which may be introduced into the paper treatment composition in the aqueous emulsion containing the copolymer when the manganese ion source is used during production of the copolymer and/or the aqueous emulsion used to deliver the copolymer.
  • the manganese ion source may be a manganese (II) compound or a manganese (III) compound.
  • the manganese ion source may be a manganese (II) compound Suitable manganese compounds for use herein 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) tetrahydrate), and combinations thereof.
  • the manganese ion source may comprise manganese (II) acetate or manganese (II) 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 materials (A) and (B) in the paper treatment composition.
  • 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 paper treatment composition.
  • the phenolic compound which may be introduced into the paper treatment composition via the aqueous emulsion containing the copolymer when the phenolic compound source is used during production of the copolymer and/or the aqueous emulsion used to deliver the copolymer.
  • Suitable phenolic compounds include hydroquinone (HQ), dihydroxybenzene (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, and combinations thereof.
  • 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 materials (A) and (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 paper treatment composition.
  • 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;
  • 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-heterocycle- blocking 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, H12MDI, TMXDI, TMI, XDI, HeXDI, 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. Table 1 - Commercially Available Crosslinkers
  • crosslinker depends on various factors including the type and amount of (A) the silicone - (meth)acrylate copolymer, and the selection of paper to be treated, however, the amount of crosslinker in the paper treatment composition may be sufficient to provide 0.1% to 0.75% of solids, on paper weight, alternatively 0.1% to 0.35%, on the same basis; wherein solids refers to the amount of blocked isocyanate that may be delivered in an aqueous dispersion with other components, e.g., water and a surfactant.
  • 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 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 (A) the silicone - (meth) acrylate copolymer.
  • 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 polyethlene 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 coted 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.
  • Si4 had formula:
  • Si 16 had formula:
  • silicone - (meth)acrylate copolymer emulsions were prepared by the following Method A: The total weight of the starting materials in the monomer emulsion was 125 g. All starting materials were weighed into a 400 mL wide mouth jar. The stearyl acrylate monomer was melted first and added as a liquid. In addition, the emulsions were inhibited with Hydroquinone (50 ppm based on monomer), Mn(II) acetate’Mf LO (1.5 ppm based on monomer) and methyletherhydroquinone (150 ppm based on monomer).
  • Hydroquinone 50 ppm based on monomer
  • Mn(II) acetate’Mf LO 1.5 ppm based on monomer
  • methyletherhydroquinone 150 ppm based on monomer
  • the resulting material was sonicated at an amplitude of 50 for two minutes using a sonicator (Fisher Brand Sonic Dismembrator) to create an emulsion.
  • the resulting emulsion was then transferred to a 500 mL 4 neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20) and thermocouple probe. This emulsion was stirred at 250 RPM using a Teflon blade and heated to 65 °C. After reaching temperature 0.24 g (0.66 wt% based on monomers) of 2,2’Azobis(2-methylpropionamidine dichloride was added and was run for 6 hours. The resulting aqueous emulsion was then allowed to cool to 30 to 40 °C with slow stirring before pouring off.
  • silicone - (meth)acrylate copolymer emulsions were prepared by the following Method B: The total weight of the starting materials in the monomer emulsion was 125 g. All starting materials were weighed into a 400 mL wide mouth jar. The stearyl and docosyl acrylate monomers were melted first and added as a liquid. In addition, the emulsions were inhibited with Hydroquinone (50 ppm based on monomer), Mn(II) acetate*4H2O (1.5 ppm based on monomer) and methyletherhydroquinone (150 ppm based on monomer).
  • Hydroquinone 50 ppm based on monomer
  • Mn(II) acetate*4H2O 1.5 ppm based on monomer
  • methyletherhydroquinone 150 ppm based on monomer
  • the resulting material was sonicated at an amplitude of 50 for two minutes using a sonicator (Fisher Brand Sonic Dismembrator) to create a coarse emulsion.
  • the coarse emulsion was then, optionally, passed through a microfluidizer (Microfluidics Microfluidizer HOY) and set to 5,000 psi, twice.
  • the resulting emulsion was then transferred to a 500 mL 4 neck flask equipped with a reflux condenser, nitrogen inlet, overhead stirrer (IKA RW20) and thermocouple probe. This emulsion was stirred at 250 RPM using a Teflon blade and heated to 45-60 °C. After reaching temperature, 2.5 g of solution C was added.
  • a redox initiator was then fed into the flask at 0.25 mL/min (where the redox initiator was solutions A and B, prepared as described below, and fed in separate feeds). The reaction was run for 45 min. The resulting material was then allowed to cool to 30 to 40 °C with slow stirring before pouring off.
  • Solution A preparation Added 0.0566 g of t-butylhydroperoxide (70% in water) and then enough water to make a 10 g solution.
  • Solution B preparation Added 0.0773 g of isoascorbic acid (70% in water) and then enough water to make a 10 g solution.
  • Solution C preparation Added 6 mg iron (II) sulfate heptahydrate and then enough water to make a 10 g solution.
  • Table 3 Wt% of starting materials in monomer emulsion before polymerization. Reactions were either thermally initiated or redox initiated (denotes method of making).
  • Table 4 Wt% of monomers in copolymers used in examples.
  • the samples prepared as described above were evaluated for oil repellency and water repellency using the test method AATCC 118.
  • the sample was deemed to pass if it had an A or B rating and failed with a C or D rating. Passing requires at least a rating of B after 30 seconds.
  • the stains were modified to only include olive oil and water.
  • the paper treatment composition including the silicone - (meth)acrylate copolymer described herein can impart both water resistance and oil resistance to a paper substrate.

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Abstract

Un procédé de traitement de papier comprend l'application d'une composition aqueuse de traitement de papier contenant un copolymère de silicone-(méth)acrylate sur le papier et le séchage du papier. La composition forme un revêtement sur le papier. Le papier couché présente des propriétés hydrophobes et oléophobes.
PCT/US2025/025676 2024-04-23 2025-04-22 Traitement de papier avec un copolymère de silicone-(méth)acrylate Pending WO2025226624A1 (fr)

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