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WO2025141369A1 - Films acryliques comprenant du (méth)acrylate de menthyle - Google Patents

Films acryliques comprenant du (méth)acrylate de menthyle Download PDF

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Publication number
WO2025141369A1
WO2025141369A1 PCT/IB2024/062449 IB2024062449W WO2025141369A1 WO 2025141369 A1 WO2025141369 A1 WO 2025141369A1 IB 2024062449 W IB2024062449 W IB 2024062449W WO 2025141369 A1 WO2025141369 A1 WO 2025141369A1
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Prior art keywords
acrylic film
meth
acrylate
acrylic
film
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Pending
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PCT/IB2024/062449
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English (en)
Inventor
Amanda K. LEONE
Kai U. CLAUSSEN
Kevin DE BRUYCKER
Jonathan E. JANOSKI
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3M Innovative Properties Co
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3M Innovative Properties Co
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Publication of WO2025141369A1 publication Critical patent/WO2025141369A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • 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
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/08—Homopolymers or copolymers of acrylic acid esters

Definitions

  • cured refers to joining polymer chains together by covalent chemical bonds, usually via crosslinking molecules or groups, to form a network polymer. Therefore, in this disclosure the terms “cured” and “crosslinked” may be used interchangeably.
  • a cured or crosslinked polymer is generally characterized by insolubility but may be swellable in the presence of an appropriate solvent.
  • the “Dahlquist Criterion for Tack” is widely recognized as a necessary condition of a pressure sensitive adhesives (PSA). It states that a PSA has a shear storage modulus (G') of less than 3xl0 6 dyne/cm 2 (0.3 MPa) at approximately room temperature (25° C) and a frequency of 1 hertz (Pocius, Adhesion and Adhesive Technology 3rd Ed., 2012, p. 288).
  • G' shear storage modulus
  • the acrylic film comprises polymerized units of at least one low Tg monomer having an alkyl group with 6 to 20 carbon atoms.
  • the low Tg monomer has an alkyl group with 7 or 8 carbon atoms.
  • Exemplary monomers include, but are not limited to, 2- ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, n-octyl (meth)acrylate, 2-octyl (meth)acrylate, isodecyl (meth)acrylate, and lauryl (meth)acrylate.
  • the monomer is an ester of (meth)acrylic acid with an alcohol derived from a renewable source, such as 2-octyl (meth)acrylate.
  • the acrylic fdm typically comprises at least 10, 15, 20 or 25 wt.-% of polymerized units of monofunctional alkyl (meth)acrylate low Tg monomer (i.e., having a homopolymer Tg of less than 0 °C.), based on the total weight of the polymerized units (i.e., excluding inorganic filler or other additives).
  • wt.-% of polymerized units refers to the wt-% based on the total weight of the (meth)acrylic polymer, polyvinyl acetal (e.g. butyral) polymer, and crosslinker when present.
  • the acrylic film typically comprises no greater than 60, 55, 50, 45, or 40 wt.-% of polymerized units of monofunctional alkyl (meth)acrylate monomer having a Tg of less than 0 °C., based on the total weight of the polymerized units.
  • the wt.-% of specified polymerized units is approximately the same as the wt.-% of such polymerized units present in the acrylic film composition.
  • the acrylic film comprises unpolymerized components, such as inorganic filler or other unpolymerizable additives the total acrylic film composition can comprise substantially less polymerized units.
  • the total amount of unpolymerizable additives may range up to 25 wt.-%.
  • the concentration of specified polymerized units can be as much as 5, 10, 15, 20, 25 wt.-% less, depending on the total concentration of such additives.
  • the concentration of low Tg monofunctional alkyl (meth) acrylate monomer may be 20% less, i.e. at least 8 wt.-%, 12 wt.-% etc.
  • the acrylic film generally comprises at least one (e.g. non-polar) high Tg monomer, i.e., a (meth)acrylate monomer that when reacted to form a homopolymer has a Tg greater than 0 °C.
  • the high Tg monomer more typically has a homopolymer Tg greater than 5 °C., 10 °C., 15 °C., 20 °C., 25 °C., 30 °C., 35 °C., or 40 °C.
  • the acrylic film comprises at least one high Tg monofunctional alkyl (meth)acrylate monomer including for example, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, isobomyl acrylate, isobomyl methacrylate, L- and/or D- menthyl (meth)acrylate, norbomyl (meth)acrylate, benzyl methacrylate, 3,3,5 trimethylcyclohexyl acrylate, cyclohexyl acrylate, and propyl methacrylate or combinations thereof.
  • monofunctional alkyl (meth)acrylate monomer including for example, t-butyl acrylate
  • the acrylic film comprises polymerized units of an acid functional monomer (a subset of high Tg monomers), where the acid functional group may be an acid per se, such as a carboxylic acid, or a portion may be salt thereof, such as an alkali metal carboxylate.
  • acid functional monomers include, but are not limited to, those selected from ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids, ethylenically unsaturated phosphonic acids, and mixtures thereof.
  • Such compounds include those selected from acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, oleic acid, 3 -carboxy ethyl (meth)acrylate, 2- sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2 -methylpropanesulfonic acid, vinylphosphonic acid, and mixtures thereof.
  • the acrylic film comprises 0.5 up to 20 or 25 wt.-% of polymerized units of acid functional monomers, such as acrylic acid. In some embodiments, the acrylic film comprises at least 1, 2, 3, 4, or 5 wt.-% of polymerized units of acid-functional monomers. In other embodiments, the acrylic film comprises less than 1.0, 0.5, 0.1 wt.-% or is free of polymerized units of acid-functional monomers.
  • the acrylic film comprises polymerized units of a non-acid-functional polar monomer.
  • the acrylic film comprises at least 0.5, 1, 2, 3, 4, or 5 wt.-% of polymerized units of nitrogen-containing monomers and typically no greater than 25 or 30 wt.-%. In other embodiments, the acrylic film comprises less than 1.0, 0.5, 0.1 wt.-% or is free of polymerized units of nitrogencontaining monomers.
  • the acrylic film comprises at least 0.5, 1, 2, 3, 4, or 5 wt.-% of polymerized units of alkoxy -functional (meth)acrylate monomers and typically no greater than 30 or 35 wt-%. In other embodiments, the acrylic film comprises less than 1.0, 0.5, 0.1 wt.-% or is free of polymerized units of alkoxy -functional (meth)acrylate monomers.
  • the acrylic film may optionally comprise polymerized units of vinyl monomers including vinyl esters (e.g., vinyl acetate and vinyl propionate), styrene, substituted styrene (e.g., alpha-methyl styrene), vinyl halide, and mixtures thereof.
  • vinyl monomers are exclusive of polar monomers.
  • the acrylic film comprises at least 0.5, 1, 2, 3, 4, or 5 wt.-% and typically no greater than 10 wt.-% of polymerized units of vinyl monomers. In other embodiments, the acrylic film comprises less than 1.0, 0.5, 0.1 wt.-% or is free of polymerized units of vinyl monomers.
  • the polymerized units of the (meth)acrylic polymer contain aliphatic groups and lack aromatic moieties.
  • the monomer(s) are polymerized to form a statistical (meth)acrylic copolymer.
  • the acrylic film comprises a polyvinyl acetal polymer as film former as described in greater detail in PCT/IJS2015/64215, filed Dec. 7, 2015.
  • the polyvinyl acetal polymer is typically a random copolymer.
  • block copolymer and tapered block copolymer may provide similar benefits as random copolymers.
  • the polyvinyl acetal polymer has a Tg of less than 60 °C.
  • higher concentrations of high Tg monomers may be employed in the acrylic film composition in comparison to those utilizing polyvinyl butyral polymer.
  • the Tg may be greater than 75 °C. or 80 °C.
  • the polyvinyl acetal polymer has a Tg of greater than 70 °C.
  • higher concentrations of low Tg monomers may be employed in acrylic film composition in comparison to those utilizing polyvinyl butyral polymer.
  • the acrylic film comprises 5 to 30 wt-% of polyvinyl acetal polymer such as polyvinyl butyral based on the total weight of the polymerized units of the (meth)acrylate polymer, polyvinyl acetal (e.g. butyral) polymer, and crosslinker when present.
  • the acrylic film comprises at least 10, 11, 12, 13, 14, or 15 wt-% of polyvinyl acetal (e.g. PVB) polymer.
  • the acrylic film comprises no greater than 25 or 20 wt.-% of polyvinyl acetal (e.g. PVB) polymer.
  • the acrylic fdm comprises a polyvinyl acetal (e.g.
  • the acrylic film comprises polymerized crosslinker units.
  • the crosslinker is a multifunctional crosslinker capable of crosslinking polymerized units of the (methjacrylic polymer such as in the case of crosslinkers comprising functional groups selected from (methjacrylate, vinyl, and alkenyl (e.g. C3-C20 olefin groups); as well as chlorinated triazine crosslinking compounds.
  • the crosslinking monomer comprises a (meth)acrylate group and an olefin group.
  • the olefin group comprises at least one hydrocarbon unsaturation.
  • Dihydrocyclopentadienyl acrylate is one example of this class of crosslinking monomer.
  • Other crosslinking monomers of this type comprising a C6-C20 olefin are described in WO2014/172185.
  • the crosslinking monomer comprises at least two terminal groups selected from allyl, methallyl, or combinations thereof.
  • the terminology (meth)allyl includes both allyl and methallyl groups. Crosslinking monomers of this types are described in PCT Publication WO 2015/157350.
  • the acrylic film may comprise a multifunctional crosslinker comprising vinyl groups, such as in the case of 1,3-divinyl tetramethyl disiloxane.
  • the crosslinker comprises hydroxyl-reactive groups, such as isocyanate groups, capable of crosslinking alkoxy group of the (meth)acrylic polymer (e.g. 2-hydroxyethyl acrylate (HEA)) or polyvinyl alcohol groups of the polyvinyl acetal (PVB).
  • hydroxyl-reactive groups such as isocyanate groups, capable of crosslinking alkoxy group of the (meth)acrylic polymer (e.g. 2-hydroxyethyl acrylate (HEA)) or polyvinyl alcohol groups of the polyvinyl acetal (PVB).
  • isocyanate groups capable of crosslinking alkoxy group of the (meth)acrylic polymer (e.g. 2-hydroxyethyl acrylate (HEA)) or polyvinyl alcohol groups of the polyvinyl acetal (PVB).
  • HOA 2-hydroxyethyl acrylate
  • PVB polyvinyl alcohol groups of the polyvinyl acetal
  • the crosslinker is typically present in an amount of at least 0.5, 1.0, 1.5, or 2 wt.-% ranging up to 5 or 10 wt.-% based on the total weight of the polymerized units of the (meth)acrylate polymer, polyvinyl acetal (e.g. butyral) polymer, and crosslinker.
  • the acrylic film comprises such amount of polymerized crosslinker units.
  • multifunctional (meth)acrylate crosslinkers are present in an amount less than 1 wt.-%.
  • the viscosity of the coatable composition is typically at least 1,000 or 2,000 cps ranging up to 100,000 cps at 25 °C. In some embodiments, the viscosity is no greater than 75,000; 50,000, or 25,000 cps.
  • the coatable composition is coated on a suitable substrate such as a release liner and polymerized by exposure to radiation.
  • the polymerization is preferably conducted in the absence of unpolymerizable organic solvents such as ethyl acetate, toluene and tetrahydrofuran, which are non-reactive with the functional groups of the solvent monomer and polyvinyl (e.g. PVB) acetal.
  • Solvents influence the rate of incorporation of different monomers in the polymer chain and generally lead to lower molecular weights as the polymers gel or precipitate from solution.
  • the acrylic film composition can be free of unpolymerizable organic solvent.
  • Suitable photoinitiators include those available under the trade designations OMNIRAD from IGM Resins (Waahvijk, The Netherlands) and include 1 -hydroxy cyclohexyl phenyl ketone (OMNIRAD 184), 2,2-dimethoxy-l,2-diphenylethan-l-one (OMNIRAD 651), bis(2,4,6- trimethylbenzoyl)phenylphosphineoxide (OMNIRAD 819), LUCIRIN TPO orLUCIRIN TPO-L, l-[4-(2- hy dro xy etho xy)phenyl] -2 -hydroxy -2 -methy 1-1 -propane- 1 -one (OMNIRAD 2959), 2-benzyl-2- dimethylamino-l-(4-morpholinophenyl)butanone (OMNIRAD 369), 2-methyl-l-[4-(methylthio)phenyl]-2- morpholinopropan
  • a difunctional alpha-hydroxy ketone means that the photoinitiator includes two alpha-hydroxy ketone groups.
  • a multifunctional alpha-hydroxy ketone means that the photoinitiator includes two or more alpha-hydroxy ketone groups.
  • Additional suitable photoinitiators include benzyl dimethyl ketal, 2-methyl-2 -hydroxypropiophenone, benzoin methyl ether, benzoin isopropyl ether, anisoin methyl ether, aromatic sulfonyl chlorides, photoactive oximes, and combinations thereof. Further suitable photoinitiators include mono-ethylenically unsaturated aromatic ketones.
  • the acrylic film of the present disclosure may include other components useful, for example, in sealant and adhesive compositions.
  • the composition can include at least one of toughening agents (e.g., acrylic core/shell polymers; styrene-butadiene/methacrylate core/shell polymers; acrylonitrilebutadiene mbber), plasticizers (e.g., aliphatic and aromatic hydrocarbons, alkyl esters, alkyl ethers, aryl esters, and aryl ethers), tackifiers, corrosion inhibitors, UV stabilizers, antioxidants, free radical inhibitors, flame retardants, thixotropic agents such as fumed silica, dyes, pigments (e.g., ferric oxide, brick dust, carbon black, and titanium oxide), reinforcing agents (e.g., silica, magnesium sulfate, calcium sulfate, and beryllium aluminum silicate), clays such as bentonite, other suitable filler (e.g
  • the composition of the present disclosure includes a filler.
  • fillers useful for some embodiments of the composition of the present disclosure include at least one of a micro-fibrillated polyethylene, a fumed silica, a talc, a wollastonite, an aluminosilicate clay (e.g., halloysite), phlogopite mica, calcium carbonate, kaolin clay, metal oxides (e.g., barium oxide, calcium oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide), nanoparticle fillers (e.g., nanosilica, nanozirconia).
  • L-MTA L-menthyl acrylate
  • the separated water was collected every 30 min to Ih throughout the complete reaction.
  • the mixture was heated to 120 °C and reacted for Ih, where tO is marked by the start of reflux from the Dean-Stark head.
  • the setpoint was increased to 140 °C, and the mixture was allowed to react for 5.5 h.
  • the mixture temperature was increased to 150 °C for another 2.5 h, after which the mixture was cooled to room temperature.
  • the conversion was determined via 1H-NMR and was found to be typically >98%.
  • the Dean-Stark head was replaced with a Claisen head and a distilling condenser. Vacuum was applied and the crude was heated to 80 °C for Ih. An ultimate vacuum of 5 mmHg was obtained. Next, the batch was heated from 115 °C to 135 °C to collect 545 g of the desired product (95-97°C at 5 mmHg), to which 10 mg of MEHQ (18 ppm) was added. A clear change in refractive index compared to lower boiling compounds can be observed when L-MTA is being distilled. The purity was determined to be >98 wt% via 1H-NMR.
  • DL-menthol 500 g, 3.20 mol, 1.00 eq.
  • acrylic acid 277 g, 3.84 mol, 1.20 eq.
  • phenothiazine 1.00 g, 2000 ppm
  • furfural 1.00 g, 2000 ppm
  • pTSA p-toluenesulfonic acid
  • cyclohexane 75.0 g, 15.0 wt%).
  • the flask was equipped with a 30 cm Vigreux column and a Dean-Stark head that was filled with cyclohexane containing 50 ppm of furfural.
  • the separated water was collected every 30min to Ih throughout the complete reaction.
  • the mixture was heated to 120 °C and reacted for Ih, where tO is marked by the start of reflux from the Dean-Stark head.
  • the setpoint was increased to 140 °C, and the mixture was allowed to react for 5.5 h.
  • the temperature was increased to 150 °C for another 2.5 h, after which the mixture was cooled to room temperature.
  • the conversion was determined via 1H-NMR and was found to be >98%.
  • the Dean-Stark head was replaced with a Claisen head and a distilling condenser. Vacuum was applied and the crude was heated to 80 °C for Ih. An ultimate vacuum of 5 mmHg was obtained. Next, the batch was heated from 115 °C to 135 °C to collect 5425 g of the desired product (95-97 °C at 5 mmHg), to which 10 mg of MEHQ (18 ppm) was added. A clear change in refractive index compared to lower boiling compounds can be observed when DL-MTA is being distilled. The purity was determined to be >98 wt% via 1H-NMR.
  • Acrylic Film Formulation Preparation Formulations were prepared by combining all components listed in Table 1 into a polypropylene mixing cup (from FlackTek, Inc., Landrum, SC). The cup was closed with a polypropylene lid and the mixture was high shear mixed at ambient temperature and pressure using a SPEEDMIXER (Hauschild SpeedMixer inc., Dallas Texas) for at least 30 s at 2000 revolutions per minute (rpm).
  • a polypropylene mixing cup from FlackTek, Inc., Landrum, SC.
  • the cup was closed with a polypropylene lid and the mixture was high shear mixed at ambient temperature and pressure using a SPEEDMIXER (Hauschild SpeedMixer inc., Dallas Texas) for at least 30 s at 2000 revolutions per minute (rpm).
  • AC475 Photocured Acrylic Film Preparation On a glass slide was placed a release liner (release side up) and a 15-mil rubber spacer with an approximately 20 mm x 6 mm rectangular cutout. The formulation was placed in the unfilled rectangle, filling the area. A second release liner was placed over the formulation slowly so as to not create any air bubbles (release side down). A second glass slide was placed over the release liner. Two clamps were placed over the glass slides in such a way that they secure the assembly but did not block the light from irradiating the material.
  • the setup was irradiated using the Omnicure AC475 (Poly Dispensing Systems, Orgeval, Ile-de-France, France) 365 nm light at 25% power from a height of two inches for 120 seconds.
  • Omnicure AC475 Poly Dispensing Systems, Orgeval, Ile-de-France, France
  • DMA Dynamic Mechanical Analysis
  • Test Method Temperature Ramp for formulations CE1-1, EXI, and CE1-2: The thickness of each acrylic film was measured. The films were mounted in the tensile grips of an DMA850 (TA Instruments, New Castle, DE, USA) with an initial grip separation of 12-16 mm. The measurement procedure was done to determine the precise grip separation with an initial/preload force of 0.1 N with a “Use Force Track” set to 150%. The samples were then tested at an oscillation of 0.2% strain and 1 Hz throughout a temperature ramp from at least -20 °C to 60 °C at a rate of 3 °C per minute. The temperatures at which the tan delta signal reached a maximum were recorded as the glass transition temperatures (Tg).
  • Tg glass transition temperatures
  • Test Method 3 Determination of T e via DMA
  • Preparation of 50% CN965 in IBOA or L-MTA A mixture of 50 wt.% CN965 and 50 wt.% of IBOA or L-MTA was prepared by weighing in both compounds and rolling at 35 RPM using a LABINCO LD209750 Rolling Bench jar roller (available from LABINCO, Breda, Netherlands).
  • composition formulations are provided in Table . All components were added to ajar with 4-HBA and AA being added last. B60H may be dissolved more quickly by first dispensing in hydrophobic monomers and then dissolving in more hydrophilic monomers. Rolling (35RPM, 2 days) was performed using a LABINCO LD209750 Rolling Bench jar roller (available from LABINCO, Breda, Netherlands).
  • Acrylic film formulations were coated using a notch bar setup. A closed face approach was used, coating in between two PET liners (75pm thickness each). The notch bars were set to provide acrylic films with a thickness of 90pm.

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Abstract

L'invention concerne des films comprenant une couche formée à partir d'une composition de film comprenant un monomère de (méth)acrylate de menthyle. L'invention concerne également un procédé de fabrication de tels films et des articles les comprenant.
PCT/IB2024/062449 2023-12-28 2024-12-10 Films acryliques comprenant du (méth)acrylate de menthyle Pending WO2025141369A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202363615529P 2023-12-28 2023-12-28
US63/615,529 2023-12-28
US202463638735P 2024-04-25 2024-04-25
US63/638,735 2024-04-25

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