WO2019199542A1 - Copolymères acryliques pour adhésifs sensibles à la pression humide - Google Patents

Copolymères acryliques pour adhésifs sensibles à la pression humide Download PDF

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Publication number
WO2019199542A1
WO2019199542A1 PCT/US2019/025588 US2019025588W WO2019199542A1 WO 2019199542 A1 WO2019199542 A1 WO 2019199542A1 US 2019025588 W US2019025588 W US 2019025588W WO 2019199542 A1 WO2019199542 A1 WO 2019199542A1
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WIPO (PCT)
Prior art keywords
pressure
alkyl
sensitive adhesive
ethyl
methyl
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Inventor
Matthias Gerst
Brylee B. TIU
Phillip Byron MESSERSMITH
Amir Peyman DELPARASTAN
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BASF SE
University of California Berkeley
University of California San Diego UCSD
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BASF SE
University of California Berkeley
University of California San Diego UCSD
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    • 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
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives 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; Adhesives based on derivatives of such polymers
    • C09J133/24—Homopolymers or copolymers of amides or imides

Definitions

  • the present technology relates to the synthesis of bio mimetic acrylic pressure sensitive adhesives with catechol motifs by copolymerizing butyl acrylate, acrylic acid and dopamine methacrylamide.
  • catechol-free adhesives the resulting materials have demonstrated significant performance improvements in dry and wet peel adhesion, tack strength, and even adhesive interactions with polystyrene and silica colloidal probes.
  • PSAs Pressure sensitive adhesives
  • These adhesives are typically composed of a thin, flexible backing strip coated with a permanently sticky adhesive, which is a soft viscoelastic material that can easily achieve molecular contact with a substrate but are cohesive enough to resist shear forces for long periods of time.
  • PSA typically, PSA’s successfully bond onto surfaces in dry conditions, but they typically perform poorly in wet environments, wherein water molecules interfere in the polymer- substrate interface and also alter the bulk rheological properties of the PSA due to trapped fluid pockets within the adhesive. 2
  • a pressure-sensitive adhesive comprising a polymerization product of a mixture comprising an alkylacrylate, acrylic acid, and a catecholalkylacrylamide, wherein the polymerization product exhibits a glass transition temperature of less than -20°C and a UV-vis (ultraviolet- visible spectroscopy) transmission of greater than 60% from 400 nm to 700 nm if deposited at a thickness of 20 to 60 g/m 2 on a clear and colorless 36 pm- thick PET backing material.
  • the polymerization product may be a polymer represented by Formula I or II:
  • R 1 is H or alkyl
  • R 2 is alkyl
  • each of R 3 , R 5 , R 6 , and R 7 is H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring;
  • R 8 is alkyl
  • R 9 is H or alkyl
  • R 10 and R 11 are H, a protecting group, or R 10 and R 11 may join together to form a ring with the oxygens to which they are attached;
  • each of x, y, and z is a designation of a repeat unit.
  • a process of preparing a pressure-sensitive adhesive comprising a polymer represented by Formula I or II, or a mixture of any two or more thereof:
  • R 1 is H or alkyl
  • R 2 is alkyl
  • each of R 3 , R 5 , R 6 , and R 7 is H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring;
  • R 8 is alkyl
  • R 9 is H or alkyl
  • R 10 and R 11 are H or they join together to form a ring with the oxygens to which they are attached;
  • each of x, y, and z is a designation of a repeat unit
  • the process comprising dissolving the polymer in a solvent to form a mixture; applying the mixture to a substrate;
  • a process for preparing a polymer comprising: combining monomers comprising an alkylacrylate, acrylic acid, and a catecholalkylacrylamide in the presence of a solvent, and a non-ultraviolet light activated, non-oxidative, free-radical initiator, and under conditions to effect polymerization of the monomers.
  • R 1 is H or alkyl
  • R 2 is alkyl
  • each of R 3 , R 5 , R 6 , and R 7 is H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring;
  • R 8 is alkyl
  • R 9 is H or alkyl
  • R 10 and R 11 are H, a protecting group, or R 10 and R 11 may join together to form a ring with the oxygens to which they are attached;
  • each of x, y, and z is a designation of a repeat unit
  • the polymer has a glass transition temperature of less than -20° C; and exhibits a UV-vis (ultraviolet- visible spectroscopy) transmission of greater than 60% from 400 nm to 700 nm.
  • FIG. 1 shows Differential Scanning Calorimetry (DSC) traces for the synthesized pressure sensitive adhesives with and without DOPA, according to the examples.
  • FIG. 2 is a graph of 180° peel adhesion measurements of the pressure- sensitive tapes on high density polyethylene (HDPE) and stainless steel 530 after 24 hours of storage in ambient conditions, according to the examples.
  • FIG. 3 is a graph of 180° peel adhesion measurements of the pressure- sensitive tapes on high density polyethylene (HDPE) and stainless steel 530 after 24 hours of immersion in deionized water, according to the examples.
  • FIG. 4 is a graph of loop tack strength of the pressure-sensitive tapes onto stainless steel 530, according to the examples.
  • FIG. 5 is a graph of loop tack strength of the pressure-sensitive tapes onto
  • HDPE highPE, according to the examples.
  • FIG. 8 is a graph of transmittance v. wavelength for various pressure sensitive adhesives and films, according to Example 4.
  • substituted refers to an alkyl, alkenyl, alkynyl, aryl, or ether group, as defined below (e.g., an alkyl group) in which one or more bonds to a hydrogen atom contained therein are replaced by a bond to non-hydrogen or non-carbon atoms.
  • Substituted groups also include groups in which one or more bonds to a carbon(s) or hydrogen(s) atom are replaced by one or more bonds, including double or triple bonds, to a heteroatom.
  • a substituted group will be substituted with one or more substituents, unless otherwise specified.
  • a substituted group is substituted with 1,
  • substituent groups include: halogens (i.e., F, Cl, Br, and I); hydroxyls; alkoxy, alkenoxy, alkynoxy, aryloxy, aralkyloxy, heterocyclyloxy, and heterocyclylalkoxy groups; carbonyls (oxo); carboxyls; esters; urethanes; oximes;
  • cyanates cyanates; thiocyanates; imines; nitro groups; nitriles (i.e., CN); and the like.
  • alkyl groups include straight chain and branched alkyl groups having from 1 to about 20 carbon atoms, and typically from 1 to 12 carbons or, in some embodiments, from 1 to 8 carbon atoms.
  • “alkyl groups” include cycloalkyl groups as defined below. Alkyl groups may be substituted or unsubstituted.
  • straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n- hexyl, n-heptyl, and n-octyl groups.
  • branched alkyl groups include, but are not limited to, isopropyl, sec-butyl, t-butyl, neopentyl, and isopentyl groups.
  • Representative substituted alkyl groups may be substituted one or more times with, for example, amino, thio, hydroxy, cyano, alkoxy, and/or halo groups such as F, Cl, Br, and I groups.
  • haloalkyl is an alkyl group having one or more halo groups. In some embodiments, haloalkyl refers to a per-haloalkyl group.
  • Cycloalkyl groups are cyclic alkyl groups such as, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl groups.
  • the cycloalkyl group has 3 to 8 ring members, whereas in other embodiments the number of ring carbon atoms range from 3 to 5, 6, or 7. Cycloalkyl groups may be substituted or unsubstituted.
  • Cycloalkyl groups further include polycyclic cycloalkyl groups such as, but not limited to, norbornyl, adamantyl, bornyl, camphenyl, isocamphenyl, and carenyl groups, and fused rings such as, but not limited to, decalinyl, and the like.
  • Cycloalkyl groups also include rings that are substituted with straight or branched chain alkyl groups as defined above.
  • Representative substituted cycloalkyl groups may be mono- substituted or substituted more than once, such as, but not limited to: 2,2-; 2,3-; 2,4-; 2,5-; or 2,6-disubstituted cyclohexyl groups or mono-, di-, or tri-substituted norbornyl or cycloheptyl groups, which may be substituted with, for example, alkyl, alkoxy, amino, thio, hydroxy, cyano, and/or halo groups.
  • aryl or“aromatic,” groups are cyclic aromatic
  • Aryl groups include monocyclic, bicyclic and polycyclic ring systems.
  • aryl groups include, but are not limited to, phenyl, azulenyl, heptalenyl, biphenylenyl, indacenyl, fluorenyl, phenanthrenyl, triphenylenyl, pyrenyl, naphthacenyl, chrysenyl, biphenyl, anthracenyl, indenyl, indanyl, pentalenyl, and naphthyl groups.
  • An aryl group with one or more alkyl groups may also be referred to as alkaryl groups.
  • aryl groups contain 6-14 carbons, and in others from 6 to 12 or even 6-10 carbon atoms in the ring portions of the groups.
  • the phrase“aryl groups” includes groups containing fused rings, such as fused aromatic-aliphatic ring systems (e.g., indanyl, tetrahydronaphthyl, and the like).
  • Aryl groups may be substituted or unsubstituted.
  • Heterocyclyl or heterocycle refers to both aromatic and nonaromatic ring compounds including monocyclic, bicyclic, and polycyclic ring compounds containing 3 or more ring members of which one or more is a heteroatom such as, but not limited to, N, O, and S.
  • heterocyclyl groups include, but are not limited to: unsaturated 3 to 8 membered rings containing 1 to 4 nitrogen atoms such as, but not limited to pyrrolyl, pyrrolinyl, imidazolyl, pyrazolyl, pyridinyl, dihydropyridinyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazolyl (e.g.
  • saturated 3 to 8 membered rings containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms such as, but not limited to, morpholinyl; unsaturated condensed heterocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, for example, benzoxazolyl, benzoxadiazolyl, benzoxazinyl (e.g.
  • unsaturated 3 to 8 membered rings containing 1 to 3 sulfur atoms and 1 to 3 nitrogen atoms such as, but not limited to, thiazolyl, isothiazolyl, thiadiazolyl (e.g.
  • saturated 3 to 8 membered rings containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms such as, but not limited to, thiazolodinyl; saturated and unsaturated 3 to 8 membered rings containing 1 to 2 sulfur atoms such as, but not limited to, thienyl, dihydrodithiinyl, dihydrodithionyl, tetrahydrothiophene, tetrahydrothiopyran; unsaturated condensed heterocyclic rings containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms such as, but not limited to, benzothiazolyl, benzothiadiazolyl, benzothiazinyl (e.g.
  • heterocyclyl group also include those described above in which one or more S atoms in the ring is double-bonded to one or two oxygen atoms (sulfoxides and sulfones).
  • heterocyclyl groups include tetrahydrothiophene oxide and tetrahydrothiophene l,l-dioxide. Typical heterocyclyl groups contain 5 or 6 ring members.
  • heterocyclyl groups include morpholinyl, piperazinyl, piperidinyl, pyrrolidinyl, imidazolyl, pyrazolyl, l,2,3-triazolyl, l,2,4-triazolyl, tetrazolyl, thiophenyl, thiomorpholinyl, thiomorpholinyl in which the S atom of the thiomorpholinyl is bonded to one or more O atoms, pyrrolyl, pyridinyl homopiperazinyl, oxazolidin-2-onyl, pyrrolidin-2-onyl, oxazolyl, quinuclidinyl, thiazolyl, isoxazolyl, furanyl, dibenzylfuranyl, and tetrahydrofuranyl.
  • Heterocyclyl or heterocycles may be substituted.
  • the term“carboxyl” or“carboxylate” as used herein refers to a -C(0)0H group or to its ionized form, -C(0)0-.
  • hydroxyl as used herein can refer to -OH or its ionized form, -0-.
  • amine refers to -NR 65 R 66 groups, wherein R 65 and R 66 are independently hydrogen, or a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, aryl, aralkyl, heterocyclylalkyl or heterocyclyl group as defined herein.
  • the amine is alkylamino, dialkylamino, arylamino, or alkylarylamimn
  • catecholalkylacrylamide is a an alkyacrylamide having a catechol group attached thereto.
  • Illustrative examples include the following structures, and any individual of which the term may be limited in various embodiments:
  • R a is typically H or alkyl
  • R b is H or alkyl
  • R c is alkyl
  • R d are groups that, if present, may be any of the substituent groups defined herein, and also including alkyl, aryl, or other fused ring structures.
  • a pressure-sensitive adhesive polymer includes a polymerization product of an alkylacrylate, acrylic acid, and an
  • catecholalkylacrylamide wherein the polymer exhibits a glass transition temperature of less than -20°C.
  • the polymerization products have a low color.
  • the polymerization product that is used as the adhesive has a UV-vis (ultraviolet- visible spectroscopy) transmission of greater than 60% from 400 nm to 700 nm.
  • the alkyacrylate may be a C1-C12 alkylacrylate.
  • the alkylacrylate may be ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, iso-pentyl acrylate, neo-pentyl acrylate, n-hexyl acrylate, 2-ethyl-hexylacrylate, iso- octylacrylate, or a mixture of any two or more thereof.
  • the polymer may be represented by Formula I or II:
  • R 1 may be H or alkyl
  • R 2 may be alkyl
  • each of R 3 , R 5 , R 6 , and R 7 may be H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring
  • R 8 may be alkyl
  • R 9 may be H or alkyl
  • R 10 and R 11 may be H, a protecting group, or R 10 and R 11 may join together to form a ring with the oxygens to which they are attached
  • each of x, y, and z designates of a repeat unit.
  • R 1 is H.
  • R 2 is a C1-C12 alkylene.
  • R 2 may be methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, or octylene.
  • R 8 may be C1-C12 alkyl and R 9 may be H or C1-C12 alkyl.
  • R 8 may be methyl, ethyl, propyl, butyl, or pentyl; and R 9 may be H, methyl, ethyl, propyl, butyl, or pentyl.
  • R 3 , R 5 , R 6 , R 7 , R 10 , and R 11 may be H.
  • R 1 is H;
  • R 2 is methylene, ethylene, or propylene;
  • R 3 , R 5 , R 6 , and R 7 are H;
  • R 10 and R 11 are H;
  • R 8 is ethyl, propyl, butyl, or pentyl; and
  • R 9 is H or methyl.
  • the polymerization product is of Formula III or IV:
  • R 1 is H
  • R 2 is methylene, ethylene, or propylene
  • R 3 , R 5 , R 6 , and R 7 are H
  • R 8 is ethyl, propyl, butyl, or pentyl
  • R 9 is H or methyl
  • R 12 and R 13 are individually H, methyl, or ethyl.
  • a weight ratio of the x, y, and z repeat units, based on wt%, are from 70-98:1-20:1-10. This may include the x, y, and z repeat units from 80-98:1- 15:1-5; about 90:5:5; or about 94:1 :5.
  • a pressure-sensitive adhesive in another aspect, includes a polymerization product of an alkylacrylate, acrylic acid, and an catecholalkylacrylamide, wherein the polymerization product exhibits a glass transition temperature of less than -20°C.
  • the polymerization products have a low color.
  • the polymerization product that is used as the adhesive has a UV-vis transmission of greater than 60% from 400 nm to 700 nm.
  • the alkyacrylate may be a C1-C12 alkylacrylate.
  • the alkylacrylate may be ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, iso-pentyl acrylate, neo-pentyl acrylate, n-hexyl acrylate, 2-ethyl-hexylacrylate, iso- octylacrylate, or a mixture of any two or more thereof.
  • the polymerization product is a polymer represented by Formula I or II:
  • R 1 may be H or alkyl
  • R 2 may be alkyl
  • each of R 3 , R 5 , R 6 , and R 7 may be H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring
  • R 8 may be alkyl
  • R 9 may be H or alkyl
  • R 10 and R 11 may be H, a protecting group, or R 10 and R 11 may join together to form a ring with the oxygens to which they are attached
  • each of x, y, and z designates of a repeat unit.
  • a protecting group may include an acetyl, acetonide (ring with the oxygens are attached), methyl ether, cyclic ethyl orthoformate, carboxybenzyl, t- butyldimethylsilyl, or methoxy methyl group.
  • R 1 is H.
  • R 2 is a C1-C12 alkylene.
  • R 2 may be methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, or octylene.
  • R 8 may be C1-C12 alkyl and R 9 may be H or C1-C12 alkyl.
  • R 8 may be methyl, ethyl, propyl, butyl, or pentyl; and R 9 may be H, methyl, ethyl, propyl, butyl, or pentyl.
  • R 3 , R 5 , R 6 , R 7 , R 10 , and R 11 may be H.
  • R 1 is H;
  • R 2 is methylene, ethylene, or propylene;
  • R 3 , R 5 , R 6 , and R 7 are H;
  • R 10 and R 11 are H;
  • R 8 is ethyl, propyl, butyl, or pentyl; and
  • R 9 is H or methyl.
  • the polymerization product is of Formula III or IV:
  • R 1 is H
  • R 2 is methylene, ethylene, or propylene
  • R 3 , R 5 , R 6 , and R 7 are H
  • R 8 is ethyl, propyl, butyl, or pentyl
  • R 9 is H or methyl
  • R 12 and R 13 are individually H, methyl, or ethyl.
  • a ratio of the x, y, and z repeat units are from 70-98:1-20:1-10. This may include the x, y, and z repeat units from 80- 98:1-15:1-5; about 90:5:5; or about 94:1 :5.
  • the mixture may also include monomers such as, but not limited to,
  • the polymerization product excludes monomers which contain groups that may cationic groups in the polymer backbone or pendant from the backbone.
  • the polymerization may exclude cationic ammonium or alkylammonium groups, or cationic phosphonium or alkylphosphonium groups.
  • the molecular weight of the polymerization product may be adjusted depending on the end use and they may be of a very wide range.
  • the acid- functional resin may have a number average molecular weight (M n ) of about 10,000 g/mol to about 500,000 g/mol. This may include M n of about 60,000 g/mol to about 250,000 g/mol.
  • the polymerization product may have a weight average molecular weight (M w ) of about 50,000 g/mol to about 1,000,000 g/mol.
  • the polymerization product may have a glass transition temperature (T g ) of less than -20 °C. This may include a T g of less than -30 °C, -35° C, -40° C, or -50° C. In some embodiments, the T g is from -20° C to -50° C, or from -35° C to -50° C.
  • the pressure sensitive adhesive may be a hot melt adhesive.
  • the hot melt adhesives may be characterized as having a viscosity of lower than 1000 pascals (Pa) at l30°C.
  • the pressure-sensitive adhesive may further include a backing material.
  • the backing material may be a release liner, a facestock, or other structure for pressure-sensitive adhesives.
  • Illustrative backing materials may include polyethylene terephthalate, polyethylene, polypropylene, paper, or a silicone.
  • pressure- sensitive adhesives may take the form of a hot melt adhesive, pressure-sensitive adhesive sheet, a self- wound tape, a single-coated tape, a double-coated tape, or an adhesive transfer tape.
  • a single-coated tape the polymer is coated onto a facestock and then overlaid with a release liner. In use the release liner is pulled off of the polymer the tape is applied to a substrate.
  • the polymer is coated to both sides of a carrier material which are then protected by a release liner such that the release liner is to be removed prior to application of the“double stick” adhesive.
  • a release liner such that the release liner is to be removed prior to application of the“double stick” adhesive.
  • the polymer is coated onto a release liner, and upon application of the open face of the adhesive the release liner is then removed such that another material may be adhered to the polymer.
  • the adhesive may include other materials to further improve performance of the adhesives.
  • Such other materials include, but are not limited to, rheology modifiers, tackifiers, or biocides. Such other materials may be added to the adhesives at a level of up to 30 wt% based upon the polymerization product.
  • the polymerization product is applied to one face of the backing material.
  • the polymerization product has a thickness from about 15 micrometers (pm) to about 500 pm.
  • the mixtures that are polymerized above may also include a monomer having a photocrosslinker bound thereto.
  • the mixture may be applied to the backing material at which point the mixture is irradiated with light of a wavelength sufficient to activate the photocrosslinker and cure/bond the mixture into the polymerization product.
  • Illustrative photoinitiators include those that may have an acrylate bound to a benzophenone, coumarin or anthracene group via an alkyl linker.
  • Other photocrosslinkers that may be used include those as described in U.S. 6,426,377.
  • a process for preparing a pressure-sensitive adhesive, where the adhesive includes a polymer as described above or as represented by Formula I or II, or a mixture of any two or more thereof:
  • R 1 may be H or alkyl
  • R 2 may be alkyl
  • each of R 3 , R 5 , R 6 , and R 7 may be H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring
  • R 8 may be alkyl
  • R 9 may be H or alkyl
  • R 10 and R 11 may be H, a protecting group, or R 10 and R 11 may join together to form a ring with the oxygens to which they are attached
  • each of x, y, and z designates of a repeat unit.
  • a protecting group may include an acetyl, acetonide (ring with the oxygens are attached), methyl ether, cyclic ethyl orthoformate, carboxybenzyl, t- butyldimethylsilyl, or methoxy methyl group.
  • the process may include dissolving the polymer in a solvent to form a mixture, applying the mixture to a substrate, and removing the solvent.
  • low (or no) solvent formulations may be used where the mixture includes a polymerizable photoinitiator and the mixture is applied to the substrate at which point the mixture is irradiated with light of a wavelength sufficient to activate the photoinitiator and cure/bond the mixture into the polymerization product.
  • the protecting group may include an acetyl, acetonide (ring with the oxygens are attached), methyl ether, cyclic ethyl orthoformate, carboxybenzyl, t- butyldimethylsilyl, or methoxy methyl group.
  • R 1 is H.
  • R 2 is a C1-C12 alkylene.
  • R 2 may be methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, or octylene.
  • R 8 may be C1-C12 alkyl and R 9 may be H or C1-C12 alkyl.
  • R 8 may be methyl, ethyl, propyl, butyl, or pentyl; and R 9 may be H, methyl, ethyl, propyl, butyl, or pentyl.
  • R 3 , R 5 , R 6 , R 7 , R 10 , and R 11 may be H.
  • R 1 is H;
  • R 2 is methylene, ethylene, or propylene;
  • R 3 , R 5 , R 6 , and R 7 are H;
  • R 10 and R 11 are H;
  • R 8 is ethyl, propyl, butyl, or pentyl; and
  • R 9 is H or methyl.
  • the polymerization product is of Formula III or IV:
  • R 1 is H
  • R 2 is methylene, ethylene, or propylene
  • R 3 , R 5 , R 6 , and R 7 are H
  • R 8 is ethyl, propyl, butyl, or pentyl
  • R 9 is H or methyl
  • R 12 and R 13 are individually H, methyl, or ethyl.
  • a ratio of the x, y, and z repeat units are from 70-98:1-20:1-10. This may include the x, y, and z repeat units from 80- 98:1-15:1-5; about 90:5:5; or about 94:1 :5.
  • the adhesive may include other materials to further improve performance of the adhesives.
  • Such other materials include, but are not limited to, rheology modifiers, or tackifiers.
  • Such other materials may be added to the adhesives at a level of up to 30 wt% based upon the polymerization product.
  • the substrate to which the polymer is applied may be a backing material.
  • the backing material may include polyethylene terephthalate, polyethylene, polypropylene, paper, or a silicone.
  • the backing material in some embodiments, is a release liner.
  • the process described above may further include transferring the
  • the polymer in the solvent or hot-melt state may be applied to a substrate that is a release liner.
  • a facestock is then applied to the polymer. The facestock and polymer are then removed from the release liner as a unitary object.
  • a process for preparing the above polymerization products for the pressure-sensitive adhesives includes combining monomers comprising an alkylacrylate, acrylic acid, and a catecholalkylacrylamide in the presence of a solvent, and a non-ultraviolet light activated, non-oxidative, free-radical initiator, and under conditions to effect polymerization of the monomers.
  • the catecholalkylacrylamide may be a compound represented by Formula IX, X, or a mixture of any two or more thereof:
  • R 1 may be H or alkyl
  • R 2 may be alkylene
  • each of R 3 , R 5 , R 6 , and R 7 may be H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring
  • R 9 may be H or alkyl
  • each of R 10 and R 11 are H or R 10 and R 11 join together to form a ring.
  • the non-ultraviolet light activated, non-oxidative, free-radical initiator includes azobisisobutyronitrile or a reversible addition fragmentation chain transfer agent (RAFT agent).
  • RAFT agent reversible addition fragmentation chain transfer agent
  • Illustrative RAFT agents include, but are not limited to, 2-cyano-2- propyl benzodithioate.
  • the reaction conditions include a temperature of about 40° C to about 80°C.
  • the process may be run solvent-free using the monomers as a reaction medium, or it may be ran a solvent.
  • Illustrative solvents may include an alcohol, an aromatic, or an amide.
  • the solvent may include ethanol, toluene, or dimethylformamide.
  • PSA Sensitive Adhesives
  • x, y, and z are merely there to indicate the repeat units of the oligomer or polymer. To the extent that a value for each of these is required, the percentages of the types of residues/repeat units described herein may be used.
  • bicarbonate (8 g) and sodium tetraborate decahydrate (20 g) were dissolved in 250 mL deionized water and degassed with nitrogen gas for 30 minutes.
  • Dopamine hydrochloride (10 g) was then added.
  • methacrylic anhydride (9.4 mL) was mixed with tetrahydrofuran (50 mL) and added dropwise to the aqueous dopamine mixture. The solution was allowed to stir for 17 hours under nitrogen. Afterward, the mixture was washed twice with 100 mL ethyl acetate, acidified to pH less than 2, and extracted with 100 mL ethyl acetate three times.
  • the ethyl acetate layers were combined, dried over MgS0 4 , and condensed to an approximate volume of 50 mL.
  • the product was then precipitated by adding 450 mL hexane and storing at 4°C overnight.
  • the precipitates were dissolved in minimum tetrahydrofuran, reprecipitated in hexane and dried under high vacuum to reveal a light grey solid.
  • the catechol-based copolymers were synthesized via free radical polymerization. Typically, after passing through a packed column of inhibitor removers, butyl acrylate and acrylic acid were combined with DOMA, AIBN (1 mol % of the three monomers) and anhydrous ethanol; no catechol monomers were added for control experiments. The total monomer content in the solution is 40 (w/v)%. The mixture was degassed via four freeze-pump-thaw cycles and backfilled with nitrogen. The polymerization was carried out at 60°C for 24 hour with continuous stirring. To isolate the product, the solvent was evaporated and the polymer was reprecipitated twice in tetrahydrofuran/0°C hexane. The resulting pale yellow viscous glue was dried under high vacuum for at least 24 hr. The monomer feed composition of the various polymer PSAs synthesized are listed in Table 1.
  • the samples used for the GPC measurements were polymerized using acetonide-protected DOMA since the unprotected catechol-bearing polymers are clogging in the GPC columns.
  • M W is 304 kDa and M n is 158.5 kDa while the control PSA BA95 % -AA5 % had an M w and M n of 103.9 kDa and 40.8 kDa respectively.
  • the number-average molecular weight M Dust and the weight-average molecular weight M w were determined using GPC and analyzed using polystyrene standards.
  • Tg glass transition temperature
  • DSC differential scanning calorimetry
  • Example 2 Preparation of PSA samples.
  • the PET films coated with catechol- functionalized polymers was heated at l00°C for 5 minutes and stored in ambient conditions for 24 hours prior to use in order to remove the solvent. In bulk, the catechol polymers have a pale yellow color, however once they are coated onto the PET substrates, the resulting pressure sensitive adhesives do not have noticeable color.
  • Example 3 The following testing presents the performance of the catechol
  • PSA PSA
  • adhesion towards stainless steel 530 and high density polyethylene (HDPE) were measured through the 180° peel test and loop tack tests.
  • HDPE high density polyethylene
  • the substrates were thoroughly cleaned by dispensing either methyl ethyl ketone (MEK) or ethyl acetate onto the test panels and wiped to dryness using a KimwipeTM. The cleaning step was repeated for three times followed by rinsing with acetone and dried in vacuum chamber for at least an hour before use.
  • the 180° peel adhesion test (FINAT Test Method no. 1) evaluates the permanence of adhesion by measuring the force required to pull a pressure- sensitive tape from test substrate at a 180° angle and at a speed of 300 mm/min.
  • the PSA tape was cut into 25 mm x 175 mm strips and, after removing the release layer, was adhered onto the test substrates.
  • a standard FINAT 2 kg-hand roller was rolled twice in each direction at 10 mm/min. The test samples were stored in ambient conditions for 24 hours before testing.
  • test samples were then immersed in water for 24 hour, dried with a KimwipeTM and then mounted in the Instron tensile testing system for the peel adhesion test.
  • the resulting peel adhesion data after water treatment is shown in FIG. 3.
  • the control polymer BAy '/; -AA 3 ⁇ 4 decreased its peel adhesion by 70-80% as compared to the dry peel adhesion results from Table 4.
  • B Ayo3 ⁇ 4 - A A 3 ⁇ 4 - DOM A 3 ⁇ 4 still achieved 9.75 ⁇ 2.66 N/25 mm and 11.72 ⁇ 0.98 N/25 mm of peel adhesion for HDPE and stainless steel respectively, which were an order of magnitude higher than the control sample.
  • Tack Adhesion The tack or quick stick is the most important and probably the hardest property to measure for pressure sensitive tapes. Tack adhesion is the ability of PSA’s to immediately wet and adhere onto surfaces under low external pressure. This property can be measured using the‘loop’ tack measurement (FINAT Test Method no. 9 or PSTC-16), wherein the PSA is made into a loop (with the adhesive as the outermost layer) and is allowed to be in contact with a specified area of a test substrate; the force required to separate the PSA tape from the substrate is recorded.
  • BA95 % -AA5 % had a tack adhesion of 6.45 ⁇ 0.95 N, which was further increased to 10.86 ⁇ 1.33 N, by incorporation of only 1% of the DOPA monomer.
  • colloidal Probe Force Spectroscopy In addition to bulk PSA adhesion testing, the performance of the synthesized PSA copolymers was also evaluated using colloidal probe force spectroscopy, which is a highly sensitive and powerful technique in measuring the interaction forces of a well-defined colloidal particle (/. ⁇ ? ., micrometer- sized spherical particle) and any planar substrate. Similar to any conventional atomic force microscopy experiment, this technique utilizes a cantilever with either a sharp tip or, for this instance, a colloidal probe, which is driven to approach a substrate at a desired speed and subsequently interact with the polymers adsorbed on the substrate.
  • the cantilever is then retracted from the substrate causing the interactions between the probe and the polymer to break.
  • the force and energy values corresponding to these rupture events are calculated using the spring constant of the probes and can be used to quantify the level of adhesion between the probe and the polymer or substrate.
  • the area under the resulting force-distance curves can be interpreted as the measure of adhesion energy between the surfaces, the energy required to detach the probe from the substrate.
  • AFM atomic force microscopy
  • Ethanol was selected since it is a good solvent for the copolymers, which causes the removal of excess polymer leaving only a single monolayer of polymer on the surface. This ensures that all interactions observed in the force-distance curves correspond to the interaction between the polymer coatings and the substrates.
  • the cantilever was then made to approach the surface with a piezo speed of 1000 nm/s and a dwelling time (time of contact between probe and surface) of 1 s over a piezo range of 1 pm. More than thousands of force-distance curves were recorded to achieve statistically representative results. Histograms and average values for the area under the force-distance curves for the copolymers using both probes are presented in FIGs. 6 and 7, and in Table 8.
  • Example 4 A number of pressure sensitive adhesive laminates were subjected to UV-visible transmittance spectroscopy and the results are shown in FIG. 8.
  • the copolymers BA95 % -AAs % and B Ago3 ⁇ 4 - A A 3 ⁇ 4 - DOM A 3 ⁇ 4 have been coated onto clear and colorless 36 micron-thick PET film (Product code: 2261 N, Mitsubishi Polyester Film, Greer, SC) to have a target dry thickness of 60 g/m 2 .
  • PET polyethylene terephthalate
  • a light yellow Kapton ® film (a polyimide-based pressure
  • a pressure-sensitive adhesive comprising a polymerization product of a mixture comprising an alkylacrylate, acrylic acid, and a catecholalkylacrylamide, wherein the polymerization product exhibits a glass transition temperature of less than -20°C and a UV-vis (ultraviolet- visible spectroscopy) transmission of greater than 60% from 400 nm to 700 nm if deposited at a thickness of 20 to 60 g/m 2 on a clear and colorless 36 pm-thick PET backing material.
  • Para. 2 The pressure-sensitive adhesive of Para. 1, wherein the alkyacrylate is a C1-C12 alkylacrylate.
  • Para. 3 The pressure-sensitive adhesive of Para. 1 or 2, wherein the alkylacrylate is ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, sec- butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, iso-pentyl acrylate, neo-pentyl acrylate, n-hexyl acrylate, 2-ethyl-hexylacrylate, or iso-octylacrylate.
  • the alkylacrylate is ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, sec- butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-pentyl acrylate, iso
  • Para. 4 The pressure-sensitive adhesive of any one of Paras. 1-3, wherein the polymerization product is a polymer represented by Formula I or II:
  • R 1 is H or alkyl
  • R 2 is alkyl
  • each of R 3 , R 5 , R 6 , and R 7 is H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring;
  • R 8 is alkyl;
  • R 9 is H or alkyl
  • R 10 and R 11 are H, a protecting group, or R 10 and R 11 may join together to form a ring with the oxygens to which they are attached;
  • each of x, y, and z is a designation of a repeat unit.
  • Para. 5 The pressure-sensitive adhesive of Para. 4, wherein the protecting group comprises an acetyl, acetonide (ring with the oxygens are attached), methyl ether, cyclic ethyl orthoformate, carboxybenzyl, z-butyldimethylsilyl, or methoxy methyl group.
  • the protecting group comprises an acetyl, acetonide (ring with the oxygens are attached), methyl ether, cyclic ethyl orthoformate, carboxybenzyl, z-butyldimethylsilyl, or methoxy methyl group.
  • Para. 6 The pressure-sensitive adhesive of Para. 4 or 5, wherein R 1 is H.
  • Para. 7 The pressure-sensitive adhesive of any one of Paras. 4-6, wherein R 2 is C1-C12 alkylene.
  • Para. 8 The pressure-sensitive adhesive of any one of Paras. 4-7, wherein R 2 is methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, or octylene.
  • Para. 9 The pressure-sensitive adhesive of any one of Paras. 4-8, wherein R 8 is C1-C12 alkyl and R 9 is H or C1-C12 alkyl.
  • Para. 10 The pressure-sensitive adhesive of any one of Paras. 4-9, wherein R 8 is methyl, ethyl, propyl, butyl, or pentyl; and R 9 is H, is methyl, ethyl, propyl, butyl, or pentyl.
  • Para. 11 The pressure-sensitive adhesive of any one of Paras. 4-10, wherein
  • R 3 , R 5 , R 6 , and R 7 are H and R 10 and R 11 are H.
  • Para. 12 The pressure-sensitive adhesive of any one of Paras. 4-11, wherein
  • R 1 is H;
  • R 2 is methylene, ethylene, or propylene;
  • R 3 , R 5 , R 6 , and R 7 are H;
  • R 10 and R 11 are H;
  • R 8 is ethyl, propyl, butyl, or pentyl; and
  • R 9 is H or methyl.
  • Para. 13 The pressure-sensitive adhesive of any one of Paras. 4-12, wherein the polymer is of Formula III or IV :
  • R 1 is H;
  • R 2 is methylene, ethylene, or propylene;
  • R 3 , R 5 , R 6 , and R 7 are H;
  • R 8 is ethyl, propyl, butyl, or pentyl;
  • R 9 is H or methyl;
  • R 12 and R 13 are individually H, methyl, or ethyl.
  • Para. 14 The pressure-sensitive adhesive of any one of Paras. 4-13, wherein a weight ratio of the x, y, and z repeat units are from 70-98:1-20:1-10.
  • Para. 15 The pressure-sensitive adhesive of Para. 14, wherein a weight ratio of the x, y, and z repeat units are from 80-98:1-15:1-5.
  • Para. 16 The pressure-sensitive adhesive of Para. 14, wherein a weight ratio of the x, y, and z repeat units are about 90:5:5.
  • Para. 17 The pressure-sensitive adhesive of Para. 14, wherein a weight ratio of the x, y, and z repeat units are about 94:1:5.
  • Para. 18 The pressure-sensitive adhesive of any one of Paras. 1-17 further comprising a rheology modifier, a tackifier (up to 30 wt% based upon polymer), or a biocide.
  • Para. 19 The pressure-sensitive adhesive of any one of Paras. 1-18 further comprising a backing material on which the polymerization product is disposed.
  • Para. 20 The pressure-sensitive adhesive of Para. 19, wherein the backing material comprises polyethylene terephthalate, polyethylene, polypropylene, paper, or silicone.
  • Para. 21 The pressure-sensitive adhesive of Para. 19 or 20, wherein the polymerization product on the backing material has a thickness from about 15 pm to about 500 pm.
  • Para. 22 The pressure-sensitive adhesive of any one of Paras. 1-21 which is a hot melt adhesive.
  • Para. 23 The pressure-sensitive adhesive of Para. 21, wherein the hot melt adhesive has a viscosity of less than 1000 Pa at l30°C.
  • Para. 24 The pressure-sensitive adhesive of any one of Paras. 1-23, wherein the mixture further comprises a monomer having a photo initiator bound thereto.
  • Para. 25 The pressure-sensitive adhesive of Para. 24, wherein the monomer having a photoinitiator bound thereto has an acrylate bound to a benzophenone group via an alkyl linker.
  • R 1 is H or alkyl
  • R 2 is alkyl
  • each of R 3 , R 5 , R 6 , and R 7 is H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring;
  • R 8 is alkyl
  • R 9 is H or alkyl
  • R 10 and R 11 are H or they join together to form a ring with the oxygens to which they are attached;
  • each of x, y, and z is a designation of a repeat unit
  • the process comprising dissolving the polymer in a solvent to form a mixture
  • Para. 27 The pressure-sensitive adhesive of Para. 26, wherein the protecting group comprises an acetyl, acetonide (ring with the oxygens are attached), methyl ether, cyclic ethyl orthoformate, carboxybenzyl, z-butyldimethylsilyl, or methoxy methyl group.
  • the protecting group comprises an acetyl, acetonide (ring with the oxygens are attached), methyl ether, cyclic ethyl orthoformate, carboxybenzyl, z-butyldimethylsilyl, or methoxy methyl group.
  • Para. 28 The process of Para. 26 or 27, wherein R 1 is H.
  • Para. 29 The process of any one of Paras. 26-28, wherein R 2 is C1-C12 alkylene.
  • Para. 30 The process of any one of Paras. 26-29, wherein R 2 is methylene, ethylene, propylene, butylene, or pentylene.
  • Para. 31 The process of any one of Paras. 26-30, wherein R 8 is C1-C12 alkyl and R 9 is H or C1-C12 alkyl.
  • Para. 32 The process of any one of Paras. 26-31, wherein R 8 is methyl, ethyl, propyl, butyl, or pentyl; and R 9 is H, is methyl, ethyl, propyl, butyl, or pentyl.
  • Para. 33 The process of any one of Paras. 26-32, wherein R 3 , R 5 , R 6 , and R 7 are H and R 10 and R 11 are H.
  • Para. 34 The process of any one of Paras. 26-33, wherein R 1 is H; R 2 is methylene, ethylene, or propylene; R 3 , R 5 , R 6 , and R 7 are H; R 10 and R 11 are H; R 8 is ethyl, propyl, butyl, or pentyl; and R 9 is H or methyl.
  • Para. 35 The process of any one of Paras. 26-34, wherein the polymer is of
  • R 1 is H;
  • R 2 is methylene, ethylene, or propylene;
  • R 3 , R 5 , R 6 , and R 7 are H;
  • R 8 is ethyl, propyl, butyl, or pentyl;
  • R 9 is H or methyl;
  • R 12 and R 13 are individually H, methyl, or ethyl.
  • Para. 36 The process of any one of Paras. 26-35, wherein a weight ratio of the x, y, and z repeat units are from 85-95:1-5:1-10.
  • Para. 37 The process of any one of Paras. 26-35, wherein a weight ratio of the x, y, and z repeat units are from 90-95:1-5:1-5.
  • Para. 38 The process of any one of Paras. 26-35, wherein a weight ratio of the x, y, and z repeat units are about 90:5:5.
  • Para. 39 The process of any one of Paras. 26-35, wherein a weight ratio of the x, y, and z repeat units are about 94:1 :5.
  • Para. 40 The process of any one of Paras. 26-39, wherein the substrate is a backing material.
  • Para. 41 The process of any one of Paras. 26-39, wherein the process comprises transfer coating the pressure sensitive adhesive to a backing material.
  • Para. 42 The process of any one of Paras. 26-41, wherein the mixture further comprises a rheology modifier, a tackifier (up to 30 wt% based upon polymer), or a biocide.
  • Para. 43 A process for preparing a polymer the process comprising: combining monomers comprising an alkylacrylate, acrylic acid, and a
  • catecholalkylacrylamide in the presence of a solvent, and a non-ultraviolet light activated, non-oxidative, free-radical initiator, and under conditions to effect polymerization of the monomers.
  • Para. 44 The process of Para. 43, wherein the catecholalkylacrylamide comprises a compound of Formula IX, X, or a mixture of any two or more thereof:
  • R 1 is H or alkyl
  • R 2 is alkylene
  • each of R 3 , R 5 , R 6 , and R 7 is H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring;
  • R 9 is H or alkyl
  • each of R 10 and R 11 are H or R 10 and R 11 join together to form a ring.
  • Para. 45 The process of Para. 43 or 44, wherein the non-ultraviolet light activated, non-oxidative, free-radical initiator comprises azobisisobutyronitri!e or a reversible addition fragmentation chain transfer agent (RAFT agent).
  • RAFT agent reversible addition fragmentation chain transfer agent
  • Para. 46 The process of Para. 45, wherein the RAFT agent comprises .2- cyano-2-propyl benzodithioate.
  • Para. 47 The process of any one of Paras. 44-46, wherein the conditions comprise a temperature of about 40° C to about 80°C.
  • Para. 48 The process of any one of Paras. 44-47, wherein the combining further comprising mixing the monomers in a solvent.
  • Para. 49 The process of Para. 48, wherein the solvent comprises an alcohol, aromatic, or amide.
  • Para. 50 The process of Para. 49, wherein the solvent comprises ethanol, toluene, or dimethylfbrmamide.
  • R 1 is H or alkyl
  • R 2 is alkyl
  • each of R 3 , R 5 , R 6 , and R 7 is H, OH, F, Cl, Br, I, NO2, alkyl, or where any two adjacent R 5 , R 6 , or R 7 join to form a ring;
  • R 8 is alkyl
  • R 9 is H or alkyl
  • R 10 and R 11 are H, a protecting group, or R 10 and R 11 may join together to form a ring with the oxygens to which they are attached;
  • each of x, y, and z is a designation of a repeat unit
  • the polymer has a glass transition temperature of less than -20° C; and a UV-vis transmission of greater than 60% from 400 nm to 700 nm if

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Abstract

Un polymère comprend des unités structurales d'un alkylacrylate, d'acide acrylique et d'un arylalkylacrylamide, et leurs procédés de fabrication, et des adhésifs sensibles à la pression qui comprennent ceux-ci. L'arylalkylacrylamide peut être un catéchol alkylacrylamide.
PCT/US2019/025588 2018-04-10 2019-04-03 Copolymères acryliques pour adhésifs sensibles à la pression humide Ceased WO2019199542A1 (fr)

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WO2026000997A1 (fr) * 2024-06-28 2026-01-02 比亚迪股份有限公司 Composition de liant d'électrode négative, liant d'électrode négative et son procédé de préparation, feuille d'électrode négative, élément de batterie et batterie

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US20220315808A1 (en) * 2019-07-30 2022-10-06 Nitto Denko Corporation Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet
US12359099B2 (en) * 2019-07-30 2025-07-15 Nitto Denko Corporation Pressure-sensitive adhesive composition, pressure-sensitive adhesive layer, and pressure-sensitive adhesive sheet
WO2026000997A1 (fr) * 2024-06-28 2026-01-02 比亚迪股份有限公司 Composition de liant d'électrode négative, liant d'électrode négative et son procédé de préparation, feuille d'électrode négative, élément de batterie et batterie

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