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WO2025179215A1 - Compositions de revêtement antiadhésif sans fluor pour adhésifs en silicone et procédés d'utilisation associés - Google Patents

Compositions de revêtement antiadhésif sans fluor pour adhésifs en silicone et procédés d'utilisation associés

Info

Publication number
WO2025179215A1
WO2025179215A1 PCT/US2025/016901 US2025016901W WO2025179215A1 WO 2025179215 A1 WO2025179215 A1 WO 2025179215A1 US 2025016901 W US2025016901 W US 2025016901W WO 2025179215 A1 WO2025179215 A1 WO 2025179215A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
free
composition
tape
crosslinking agent
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/US2025/016901
Other languages
English (en)
Inventor
Tsukasa Mizuhara
Matt GRAY
Marco Antonio DIAZ MENJIVAR
Garrett GODSHALL
Tyson C. DAVIS
Tyler Hayes
Scotty SQUIRE
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.)
Adhesives Research Inc
Original Assignee
Adhesives Research Inc
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 Adhesives Research Inc filed Critical Adhesives Research Inc
Publication of WO2025179215A1 publication Critical patent/WO2025179215A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • C09J7/401—Adhesives in the form of films or foils characterised by release liners characterised by the release coating composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of 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; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09D183/04—Polysiloxanes
    • 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
    • C09J2483/00—Presence of polysiloxane
    • 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
    • C09J2483/00—Presence of polysiloxane
    • C09J2483/005—Presence of polysiloxane in the release coating

Definitions

  • the present invention generally relates to silicone release coating compositions used on release liners in connection with silicone adhesives, in particular silicone pressure sensitive adhesives (PSAs).
  • PSAs silicone pressure sensitive adhesives
  • PSAs are used in a variety of consumer and industrial adhesive products, each designed to provide for adhesion of a PSA (and, if present, any backing material) onto a substrate, with permanent tack, using pressure, and without the need for a solvent or heat, as the PSA does not undergo a liquid to solid phase change.
  • adhesive products include, among others, tapes and labels, with tapes including single-sided, double-sided and transfer tapes.
  • Single-sided tapes may be used for sealing, packaging, and surface protection and include, by way of illustration, wound dressings, packing tapes, electrical tapes, and masking tapes. Double sided tapes may be used for mounting, bonding, splicing and laminating, while transfer tapes may be used in applications that require precise adhesion with minimal visual and physical impact, e.g., electronics assembly.
  • the release coating whether part of a release liner or on the backing material, contacts that portion of the PSA intended to be adhered onto a substrate to protect the PSA from damage or unwanted adhesion prior to use.
  • the release layer or coated backing layer
  • the PSA is applied onto the desired substrate.
  • the backing material in these tapes may be provided in any shape, but is desirably in the form of a strip having two (first and second) opposing surfaces.
  • This non-adhesive material desirably provides strength, flexibility and other desired functional properties (e.g., thermal insulation, electrical conductivity) to the PSA tape.
  • a polymer film such as polyethylene and polypropylene
  • polyethylene and polypropylene may be used as a backing material in general purpose tapes, such as those suitable for sealing packages or for bonding two surfaces together
  • polyvinyl chloride may be used as a backing material in electrical tapes due to its insulating properties.
  • Foam may be used as a backing material to provide cushioning and in applications that require gap filling, while paper is useful (e.g., masking tapes) in tapes wherein ease of tearing is desired.
  • the release liner used in tapes and labels comprises two layers: a substrate and a release coating.
  • the substrate comprises two flat opposing surfaces, is desirably flexible, and in the case of tapes may be provided in the form of a relatively long strip.
  • a variety of materials may be used for the substrate, including paper or a polymer film, with the latter being desired in applications requiring durability, moisture resistance, and precise release.
  • the release coating may be a relatively thin and uniform layer residing on at least one side of the substrate, and is intended to contact the PSA.
  • This coating provides a surface that allows the PSA to separate easily from the release liner, and the composition of the coating is selected based on the particular composition of the PSA to ensure desired performance.
  • PSAs are available in a variety of compositions, e.g., rubber, acrylic and silicone PSAs, and are commonly selected based on the intended application and cost. Factors often considered to be relevant to the proper selection of a particular PSA include: low and high-temperature resistance, flexibility, chemical resistance, and whether the PSA is to be applied onto a low-energy surface.
  • Rubber PSAs are relatively low-cost, but are not designed to withstand temperatures above about 80°C.
  • Acrylic adhesives prepared using acrylic polymers, offer relatively higher temperature resistance (e.g., up to about 120°C) and can adhere to certain low energy surfaces.
  • Silicone adhesives, prepared from silicone polymers are known to provide exceptional low and high-temperature (e.g., up to about 250°C) resistance, excellent flexibility, chemical resistance, and strong adhesion to low-energy surfaces, but are relatively costly.
  • silicone PSAs - Materials which exhibit a low-energy surface - a surface on which it can be difficult to form a strong adhesive bond and which may benefit from the use of surface treatments and/or specialized adhesives such as silicone PSAs - may generally be described as exhibiting a surface energy below about 40 mN/m.
  • materials include by way of illustration and not limitation: polyolefins (e.g., polyethylene (PE); polypropylene (PP)); polytetrafluoroethylene (PTFE); ethylene propylene diene monomer (EPDM); silicone rubber; and metals that are powder coated or chromed.
  • silicone PSAs Other materials that do not exhibit relatively low surface energy may nevertheless benefit from the use of silicone PSAs, depending on the final use and whether the material interacts with and degrades when in contact with the adhesive.
  • materials with a relatively higher surface energy (at least about 40 mN/m) that may benefit from the use of silicone PSAs include by way of illustration and not limitation: polyvinyl chloride (PVC), particularly PVCs that include additives such as plasticizers which make silicone PSAs a more reliable choice for bonding; polystyrene (PS); polyethylene terephthalate (PET or PETE); polycarbonate (PC); polyurethane (PU); acrylics (e.g., polymethylmethacrylate (PMMA), polyacrylates, and acrylonitrile butadiene styrene) (ABS); rubbers (e.g., natural and synthetic rubbers, such as polyisoprene, styrene-butadiene rubber (SBR), butadiene rubber (SBR
  • the relatively strong adhesion provided by silicone PSAs does affect the selection of a release liner, and in particular the release coating thereon.
  • the release liner is a critical component, as it protects the adhesive surface of the PSA, and facilitate its handling, storage, and application.
  • the release liner includes a release coating that covers the PSA adhesive surface and prevents undesired premature bonding, accumulation of contaminants thereon and degradation prior to use, acceptable temperature resistance and dimensional stability, while being able to be readily removed with an appropriate release force from the PSA when desired without leaving residue or compromising the PSA adhesive surface which can result in less than optimal bonding.
  • Silicone PSAs require specific types of release liners that can withstand their unique properties, including their ability to strongly adhere to a wide variety of surfaces.
  • Release liners with release coatings that comprise fluoropolymers are commonly used in connection with silicone PSAs, as they are compatible with silicone adhesives, provide a low and stable release force, and are resistant to silicone contamination.
  • the present invention comprises various aspects, including curable, and cured, fluorine-free, release coating compositions; release liners comprising, consisting essentially of, or consisting of a substrate having a surface and a curable, or cured, fluorine-free, release coating composition on the substrate surface; and composites (e.g., single-sided and double-sided tapes, labels and transfer tapes) comprising, consisting essentially of, or consisting of a PSA, preferably a silicone PSA, and a release liner comprising a substrate having a surface and a cured, fluorine- free, release coating composition on the substrate surface, wherein the PSA resides on the cured, fluorine-free, release coating composition; as well as related methods for the preparation and use of the curable, and cured, release coating compositions, release liners and composites.
  • release liners comprising, consisting essentially of, or consisting of a substrate having a surface and a curable, or cured, fluorine-free, release
  • Advantages of the inventive fluorine-free release coating compositions include, among others, providing a relatively low, consistent and stable removal force when a cured release coating composition in contact with an adhesive, particularly a silicone adhesive, is removed (separated) from the adhesive, even across silicone adhesives having differing relaxation forces or DMT (Derjaguin-Muller-Toporov) moduli (which may more commonly be referred to as “soft” or “hard” silicone adhesives), can be formulated to provide a differential release force useful in double sided and transfer tapes wherein different release forces are desirably present for each side of the coated release liner, and are able to withstand the coating and curing processes used with PSAs, and particularly silicone PSAs, including processes wherein the PSA is directly cast onto the release coating composition, and, importantly, exhibiting a relatively low level of extractables in the cured release coating composition after the release liner is separated from the adhesive.
  • DMT Dermat-Muller-Toporov
  • the present invention provides curable, fluorine-free, release coating compositions comprising, consisting essentially of, or consisting of, a fluorine-free polymer, a fluorine-free crosslinking agent and a crosslinking catalyst, as well as, optionally, a catalyst inhibitor and/or adhesion promoter.
  • Vinylmethylsiloxane - dimethylsiloxane copolymers useful in certain aspects of the invention may desirably include mole% of vinylmethylsiloxane ranging from about 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 to about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, or 13.
  • these copolymers may have a mole% of vinylmethylsiloxane desirably ranging from about 1 to about 8, and even more desirably from about 4 to about 8, while in still other aspects these copolymers may have a mole% of vinylmethylsiloxane ranging from about 48 to about 52.
  • Mixtures of vinylmethylsiloxane - dimethylsiloxane copolymers having different mole% of vinylmethylsiloxane also are contemplated by the invention.
  • the vinylmethylsiloxane - dimethylsiloxane copolymers also may include a vinyl Eq/kg ranging from about 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.10 or 0.11 to about 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6 or 6.5.
  • the vinylmethylsiloxane - dimethylsiloxane copolymers that are trimethylsiloxy terminated on at least one terminal end, and are desirably trimethyl silyl terminated on the other terminal end, may further have the following chemical structure, wherein m and n represent the number of their respective monomeric units: with these copolymers preferably having a molecular weight (MW) ranging from about 10,000 g/mol to 500,000 g/mol.
  • MW molecular weight
  • Illustrative of fluorine-free vinylmethylsiloxane - dimethylsiloxane copolymers that are hydride terminated on at least one terminal end, and have a hydromethylsilyl ether group on the other terminal end, and which may be included in the release coating compositions alone, or in combination with one or more other polymers, include a 0.8 - 1.2% vinylmethylsiloxane - dimethylsiloxane copolymer, a vinyl Eq/kg from about 0.3 to about 0.5, a MW of about 8,000 to about 10,000 g/mol; and a viscosity of about 150 to about 250 cSt.
  • the fluorine-free terpolymer comprising vinylmethylsiloxane may be a fluorine-free vinylmethylsiloxane - (ethyl, phenyl or octyl)m ethyl siloxane - dimethyl siloxane terpolymer that is trimethylsiloxy terminated on at least one terminal end, and desirably trimethylsilyl terminated on the other terminal end.
  • this terpolymer has the following structure, wherein R is a C1-C8 alkyl or phenyl, and more preferably phenyl or octyl, wherein m, n and p represent the number of their respective repeating monomers:
  • the terpolymer comprises about 3 - 5%> vinylmethylsiloxane and about 35% to about 40% phenyl (or octyl)methylsiloxane, desirably with a vinyl eq/Kg of about 0.2 to about 0.3.
  • the MW of this terpolymer may range from about 2,000 g/mol to about 15,000 g/mol, and desirably from about 2,500 g/mol to about 12,000 g/mol.
  • the terpolymer in the case of the terpolymer comprising phenylmethylsiloxane, the terpolymer may have a molecular weight (MW) ranging from about 2,500 g/mol to about 3,000 g/mol, and in the case of the terpolymer comprising octylmethylsiloxane, the terpolymer may have a molecular weight (MW) ranging from about 10,000 g/mol to about 12,000 g/mol.
  • MW molecular weight
  • release coating compositions of the present invention in addition to the polymers and other components described herein, further include one or more fluorine-free crosslinking agents.
  • the crosslinking agent may be a copolymer of an alkylhydrosiloxane and a dialkylsiloxane, more desirably a copolymer of methylhydrosiloxane and dimethylsiloxane, and even more desirably a trimethylsiloxy terminated copolymer, which more desirably is terminated by a trimethyl silyl group at the other terminal end.
  • the copolymer has the following structure, wherein m and n represent the number of their respective repeating monomers:
  • Additional aspects of the invention include a crosslinking agent that is a fluorine-free hydride functional siloxane having the structure:
  • a crosslinking agent that is a fluorine-free methylhydrosiloxane - octylmethylsiloxane copolymer, desirably being trimethylsiloxy terminated on at least one terminal end, more desirably trimethylsilyl terminated on the other terminal end, and even more desirably having the following structure, wherein m and n represent the number of their respective repeating monomeric units: desirably having a molecular weight (MW) ranging from about 1,000 g/mol to about 3,000 g/mol, and preferably from about 1,600 g/mol to about 2,400 g/mol.
  • MW molecular weight
  • Catalysts also are contemplated as a component in the inventive release coating compositions. This component was found to be useful in assisting the initiation of reactions involving the reactive components in the release coating compositions, such reactions believed to include hydrosilylation. Moreover, these catalysts are fluorine-free, compatible with the other components in the compositions, e.g., some are provided as siloxane complexes, and desirably provide catalytic activity for the inventive release coating compositions at room temperature.
  • organometallic complexes and other forms of such metals, may be utilized as the hydrosilylation reaction catalyst.
  • catalysts for the hydrosilylation reaction which comprise rhenium (Re), molybdenum (Mo), Group IV transition metals (i.e., titanium (Ti), zirconium (Zr), and/or hafnium (Hf)), lanthanides, actinides, and Group I and II metal complexes (e.g. those comprising calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations thereof, complexes thereof (e.g. organometallic complexes), and other forms of such metals, may be utilized as the hydrosilylation reaction catalyst.
  • the inhibitor may be present in the release coating composition in an amount suitable to provide the desired reaction rate and other advantages, and desirably may range from about 0.01 to about 3 wt.%, more desirably from about 0. 1 to about 0.5 wt.%, and even more desirably from about 0.1 to about 0.3 wt.%, wherein the weight percent is based on the weight of the non-volatile ingredients in the composition.
  • adhesion promoter which is also fluorine-free.
  • Suitable adhesion promoters are those that provide enhanced bond strength of the cured release coating composition to the substrate relative to a cured release coating composition without such promoter, are compatible with the other ingredients in the release coating composition, and are desirably solvent-free.
  • adhesion promoters are present in relatively low amounts, e.g., from about 0.1 wt.% to about 5 wt.%, and desirably from about 1 wt.% to about 2 wt.%, of the release coating composition.
  • the fluorine-free crosslinking agent may be a copolymer of an alkylhydrosiloxane and a dialkylsiloxane, more desirably a copolymer of methylhydrosiloxane and dimethylsiloxane, and is trimethylsiloxy terminated at one terminal end and trimethyl silyl terminated at the other terminal end, desirably having the following chemical structure, wherein m and n represent the number of monomeric units: and more desirably wherein the molecular weight (MW) of the crosslinking agent ranges from about 1,000 to about 10,000, even more desirably from about 1,000 about 6,500 or from about 1,000 to about 2,000.
  • MW molecular weight
  • the vinylmethylsiloxane - dimethylsiloxane copolymer may be present in the composition at from about 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 or 60 wt.% up to about 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84 or 85 wt.%, desirably from about 50 to about 85, more desirably from about 55 to about 80, and even more desirably from about 60 wt.% to about 75 wt.%, and/or the crosslinking agent may be present in the composition at from about 15 wt.% to about 45
  • the vinylmethylsiloxane - dimethylsiloxane copolymer has a mole% of vinylmethylsiloxane of from about 4 to about 5 and/or a vinyl Eq/kg from about 0.5 to about 0.7 and/or a MW of about 25K g/mol to about 30K g/mol, and further may be present in the composition at from about 70 wt.% to about 85 wt.% of the composition, and the crosslinking agent is a copolymer of an alkylhydrosiloxane and a dialkylsiloxane, or a more desired species thereof as described herein, and comprises about 10 wt.% to about 30 wt.% of the composition, wherein the weight percent is based on the weight of the non-volatile ingredients in the composition.
  • the fluorine-free crosslinking agent may have following structure, wherein n represents the number of repeating monomeric units and wherein the molecular weight (MW) of the crosslinking agents is from about 1,000 to about 3,000, and desirably from about 1,400 to about 2,400.
  • the fluorine-free crosslinking agent has the following structure: and may comprise about 1 wt.% to about 10 wt.% of the first composition, and wherein the vinylmethylsiloxane - dimethylsiloxane copolymer (including species thereof as described herein) comprises about 60 wt.% to about 80 wt.%, and desirably from 65 wt.% to about 75 wt.%, of the composition, wherein the weight percent is based on the weight of the non-volatile ingredients in the first composition.
  • this composition may further comprise a second crosslinking agent which is a copolymer of an alkylhydrosiloxane and a dialkylsiloxane, more desirably a copolymer of methyl hydrosil oxane and dimethylsiloxane, and is tri m ethyl si 1 oxy terminated at one terminal end and trimethyl silyl terminated at the other terminal end, wherein the second crosslinking agent most desirably has a chemical structure as follows, wherein m and n represent the number of monomeric units: and wherein the molecular weight (MW) of the crosslinking agent ranges from about 1,000 g/mol to about 10,000 g/mol, this additional crosslinking agent further and desirably comprising about 5 wt.% to about 35 wt.%, and desirably abut 10 wt.% to about 30 wt.%, of the first composition, wherein the weight percent is based on the weight
  • the fluorine-free vinylmethylsiloxane - dimethyl siloxane copolymer may be present in the composition in an amount ranging from about 10 wt.% to about 40 wt.%, the composition may comprise about 30 wt.% to about 85 wt.% of a crosslinking agent that is a copolymer of an alkylhydrosiloxane and a dialkylsiloxane, more desirably a copolymer of methylhydrosiloxane and dimethyl siloxane, and is trimethyl siloxy terminated at one terminal end and trimethyl silyl terminated at the other terminal end, wherein the crosslinking agent most desirably has a chemical structure as follows, wherein m and n represent the number of monomeric units: wherein the molecular weight (MW) of the crosslinking agent ranges from about 1,000 g/mol to about 10,000 g/mol, with the first composition further comprising MW
  • the crosslinking agent is a fluorine-free methylhydrosiloxane - phenylmethylsiloxane copolymer, desirably being dimethylsilyl (-Si(CH3)2H) terminated on one terminal end and dimethylsiloxane (-O-Si(CH3)2H terminated on the other terminal end, and more desirably having the following structure, wherein m and n represent the number of repeating monomeric units:
  • the fluorine-free release coating composition comprises, consists essentially of, or consists of a fluorine-free dimethylsiloxane - vinylmethylsiloxane - (ethyl, phenyl, diphenyl or octyl)methylsiloxy terpolymer, a fluorine-free crosslinking agent, a fluorine-free catalyst and, optionally, a fluorine-free catalyst inhibitor and/or adhesion promoter, wherein the terpolymer is trimethylsiloxy terminated on at least one terminal end, and desirably trimethylsilyl terminated on the other terminal end.
  • the terpolymer is a fluorine-free dimethylsiloxane - vinylmethylsiloxane - (diphenyl)methylsiloxane terpolymer, and desirably comprises about 6-7% diphenylsiloxane and/or about 0.2 to 0.3 mole% vinylmethylsiloxane.
  • the terpolymer is a fluorine-free vinylmethylsiloxane - (ethyl, phenyl or octyl)methylsiloxane - dimethylsiloxane terpolymer, a fluorine-free crosslinking agent and a fluorine-free crosslinking catalyst, wherein the terpolymer is trimethylsiloxy terminated on at least one terminal end, and desirably trimethylsilyl terminated on the other terminal end, and wherein the terpolymer desirably has the following chemical structure, wherein m, n and p represent the number of monomeric units: and wherein R is a Ci-Cs alkyl or phenyl, and more preferably phenyl or octyl, and more desirably the terpolymer has a MW ranging from about 2,000 g/mol to about 15,000 g/mol, and desirably from
  • release coating compositions of the present invention are useful in connection with a wide variety of silicone adhesives, particularly silicone PSAs, it was found that release coating compositions comprising fluorine-free vinylmethylsiloxane polymers, and in particular vinylmethylsiloxane - dimethylsiloxane copolymers, and more specifically in compositions comprising at least about 20, 30, 40, 50, 60, 70 or 80 wt.% of such copolymers, exhibited undesirable release properties when included in release liners for relatively soft silicone adhesives such as silicone PSAs, e.g.
  • fluorine-free vinyl terminated siloxanes in release coating compositions with no or relatively low amounts of vinylmethylsiloxane - dimethylsiloxane copolymers provided desirable release properties from silicone adhesives, including silicone PSAs, and in particular those adhesives that exhibit relatively low relaxation force, e.g., no more than about 200g, 180g, 160g, 140g, 120g, 100g, 80g, 60g, 40g, 20g or 10g down to about 5, 2, or 1 g or, expressed in terms of surface DMT modulus, a modulus of no greater than about 50, 45, 40, 35, 30, 25, 20, 15, 10 or 5 down to about 1, 0.5 or 0.1 MPa.
  • the fluorine-free release coating compositions comprise, consist essentially of, or consist of: a fluorine-free siloxane, desirably a vinylmethylsiloxane - di methyl siloxane copolymer which is vinyl terminated on at least one terminal end, and desirably on both terminal ends; a crosslinking agent comprising a methylhydrosiloxane — dimethylsiloxane copolymer that is trimethylsiloxane terminated on at least one terminal end, and desirably trilethylsilyl terminated on the other terminal end, and a methylhydrosiloxane — phenylmethylsiloxane copolymer that is dimethylsilyl terminated on one terminal end, and more desirably dimethyl siloxane terminated on the other terminal end; and a catalyst, as well as,
  • Illustrative of fluorine-free vinyl terminated siloxanes, which are vinyl terminated on at least one terminal end, and desirably vinyl terminated on each terminal end, that may be used in release coating compositions such as, e.g., the fourth composition, in connection with silicone adhesives having a relatively low relaxation force or surface DMT modulus include one or more of: (a) a dimethylsiloxane having the following structure, wherein n represents the number of repeating monomers: which include a vinyl terminated polydimethylsiloxane; (b) a vinylmethoxysiloxane homopolymer, desirably having a molecular weight (MW) ranging from about 800 g/mol to about 1,000 g/mol, wherein n represents the number of repeating monomers: and/or (c) a (diphenylsiloxane)-dimethylsiloxane copolymer, e.g., vinyl terminated (4-6% diphenylsi
  • this agent have a relatively low molecular weight (MW), e.g., from about 1,000 g/mol to about 3,000 g/mol, more desirably from about 1,500 g/mol about 2,500 g/mol, and even more desirably from about 1,800 g/mol to about 2,200 g/mol.
  • MW molecular weight
  • the second copolymer in the crosslinking agent of this composition tis a fluorine-free (45-50%)methylhydrosiloxane - phenylmethylsiloxane copolymer, desirably dimethylsilyl terminated on one terminal end, and more desirably dimethylsiloxane terminated on the other terminal end, and more desirably has the following structure, wherein m and n represent the number of repeating monomeric units: this agent having a MW of from about 100 g/mol to about 300 g/mol, and more desirably from about 150 g/mol to about 350 g/mol, and even more desirably about 300 g/mol.
  • the fluorine-free siloxanes desirably dimethylsiloxane polymers, which are vinyl terminated on at least one terminal end, and desirably on both terminal ends, may be present in the release coating compositions in an amount ranging from about 80 wt.% to about 98 wt.%, desirably from about 85 wt.% to about 95, wt.%, more desirably from about 90 wt.% to about 95 wt.%, with a crosslinking agent present in an amount ranging from about 1 to about 15 wt.%, and desirably from about 2 to about 10 wt.%, all weight percents based on the weight of the non-volatile ingredients in the release coating composition.
  • these compositions comprise or consist of: a diphenylsiloxane — dimethylsiloxane copolymer that is vinyl terminated on each terminal end; a crosslinking agent comprising a methylhydrosiloxane — dimethylsiloxane copolymer that is trimethylsiloxane terminated on one terminal end and trilethylsilyl terminated on the other terminal end and a methylhydrosiloxane — phenylmethylsiloxane copolymer that is dimethylsilyl terminated on one terminal end and dimethylsiloxane terminated on the other terminal end; and a catalyst, as well as, optionally, a catalyst inhibitor and/or an adhesion promoter.
  • the dimethyl siloxane copolymer in these compositions is a diphenyl siloxane — dimethylsiloxane copolymer
  • the fluorine-free release coating compositions comprise, consist essentially of, or consist of: about 80 to about 95 wt.%, desirably from about 85 wt.% to about 95, wt.%, and more desirably from about 90 wt.% to about 95 wt.%, of a diphenylsiloxane — dimethylsiloxane copolymer which is vinyl terminated on at least one terminal end, and desirably on both terminal ends; about 1 to about 10 wt.%, desirably about 1 wt.% to about 5 wt.%, and more desirably about 2 wt.% to about 5 wt.%, of a methylhydrosiloxane — dimethylsiloxane cop
  • compositions comprising one or a plurality of non-fluorine-containing crosslinking agents described herein, one or a plurality of non-fluorine-containing vinylmethylsiloxane homopolymers or copolymers with dimethylsiloxane having a mole% of vinylmethylsiloxane, a vinyl Eq/kg and/or amounts in the release composition, each within the numerical ranges described herein therefor, and a catalyst, wherein these compositions may further include one or more of a catalyst inhibitor and an adhesion promotor.
  • the release coating compositions may be provided as a solventless composition, a composition diluted by a suitable solvent (e.g., xylene, toluene, hexane, and/or isopropanol), which solvent is desirably volatilized during curing, or as an aqueous emulsion, desirably having from about 20 to about 100 wt.% solids, and may further desirably have a viscosity suitable for the method to be used for applying the release composition onto the substrate, e.g., about 25 centipoise to about 150 centipoise for microgravure coating.
  • the desired viscosity may be provided via the addition of a suitable solvent, with the solvent desirably being a volatile solvent which is volatilized during curing.
  • aspects of the invention comprise the fluorine-free, release coating compositions described herein that have been cured. Curing may be undertaken via exposing the release coating composition to a heated environment, e.g., an oven, for a few minutes. Typically, about 3 to about 5 minutes at 150°C is sufficient to cure the inventive release coating compositions, although minor alterations in time and temperature may be made to ensure complete curing of the composition.
  • the composites described herein optionally may include additional treatments or layers to enhance its performance, e.g., polymer coatings for added strength and moisture resistance, and/or anti-static coatings to prevent dust or particles from adhering to the composite (e.g., release liners), which is particularly important in electronics or clean room applications.
  • additional treatments or layers to enhance its performance e.g., polymer coatings for added strength and moisture resistance, and/or anti-static coatings to prevent dust or particles from adhering to the composite (e.g., release liners), which is particularly important in electronics or clean room applications.
  • the release coating compositions of the present invention may be prepared mixing the copolymers and/or polymers, crosslinking agent, and any optional ingredients, until they are thoroughly mixed, commonly for a few minutes at about 2,000 rpm to about 4,000 rpm, with 3,000 rpm being preferred. Thereafter, the catalyst is added (and, if desired, the catalyst inhibitor), and the resulting combination is mixed for a few minutes at about 2,000 rpm to about 4,000 rpm, with 3,000 rpm being preferred.
  • the release coating composition may be applied onto a desired substrate by any conventional technique known in the coating art, such as, roller coating, curtain coating, brushing, spraying, reverse roll coating, doctor knife, dipping, die coating, and offset gravure techniques, with microgravure being desirably used because it is capable of providing a uniform, smooth and relatively thin release coating on the substrate, which results in the cured composition having a substantially uniform thickness across the surface area of the substrate.
  • the release coating compositions of the present invention may be employed to provide cured release coating compositions (which also may be referred to as a release coating) on primed or unprimed substrates such as paper, vinyl, polyvinyl chloride films, polyester films, polyolefin films (e.g., polyethylene, such as polyethylene terephthalate), polyisobutylene, polymethylpentene, polypropylene (such as biaxially oriented polypropylene (BOPP)), non-woven fabrics, glass, steel, aluminum, etc.
  • primed or unprimed substrates such as paper, vinyl, polyvinyl chloride films, polyester films, polyolefin films (e.g., polyethylene, such as polyethylene terephthalate), polyisobutylene, polymethylpentene, polypropylene (such as biaxially oriented polypropylene (BOPP)), non-woven fabrics, glass, steel, aluminum, etc.
  • BOPP biaxially oriented polypropylene
  • the silicone adhesive compositions contemplated for use in connection with aspects of the invention include those that are curable, desirably with the use of platinum or peroxide cure systems.
  • Such adhesives possess relatively high adhesion (commonly comprising polydimethyl siloxane gums) and and may be dispersed in a hydrocarbon, e.g., xylene (about 50 - 60% solids), and desirably cure at relatively low temperatures (e.g., about 100°C in a few minutes).
  • these adhesives are useful as PSAs, and are commonly used in the preparation of tapes, transfer tapes, labels and other products.
  • the platinum catalyst is added to the silicone adhesive and mixed thoroughly, with the adhesive mixture being applied onto a cured release coating composition (the latter as part of a release liner) within several hours after the addition of the platinum.
  • the adhesive may then be cured in an over for a few minutes at a relatively high temperature, e.g., 80°C to 150°C.
  • This configuration may be used when the single-sided tape is wound about a central core (e.g., an adhesive tape roll) for ease of storage, unrolling and use, and is designed to prevent the adhesive from undesirably strong adhesion to the uncoated side of the material, thereby adversely affecting the desired use of the tape.
  • a central core e.g., an adhesive tape roll
  • a single-sided tape may comprise, consists essentially of, or consist of: (a) a release liner comprising, consisting essentially of, or comprising: (i) a substrate having at least one surface, and desirably two (e g., first and second) surfaces and (ii) a cured fluorine-free, release coating composition (any of the compositions described herein) on the (first) substrate surface; (b) a backing material having a least one surface; and (c) a silicone adhesive composition, desirably a PSA, on the surface of the backing material, wherein the cured release coating composition of the release liner contacts the silicone adhesive.
  • This configuration provides protection for the adhesive prior to use, and permits ease of release liner removal and exposure of the silicone adhesive when desired.
  • the invention provides a transfer tape.
  • the transfer tape comprises, consists essentially of, or consists of: (a) two release liners, each comprising, consisting essentially of, or comprising: (i) a substrate having at least one surface and (ii) a cured, fluorine- free, release coating composition (any of the compositions described herein) on the substrate surface; and (b) a silicone adhesive, desirably as PSA, having two (e.g., first and second) opposing surfaces, wherein each opposing surface of the adhesive contacts the cured release coating of a release liner.
  • the transfer tape may, or may not, include a carrier material for the adhesive.
  • a label constitutes another aspect of the invention.
  • the label may comprise, consist essentially of, or consist of: (a) a backing material, e.g., paper or polymer film, having two opposing surfaces, with pre-printing on one surface; (b) a silicone adhesive composition, desirably a PSA, on the second opposing surface of the backing material; and (c) a release liner comprising, consisting essentially of, or comprising: (i) a substrate having at least one surface and (ii) a cured, fluorine-free, release coating composition (any of the compositions described herein) on the substrate surface, wherein the silicone adhesive contacts the cured release coating of the release liner.
  • the release liner provides protection for the adhesive prior to use, and permits ease of release liner removal and exposure of the silicone adhesives when a user desires to adhere the label onto a surface.
  • Tables 1 and 2 provide a series of illustrative fluorine-free release coating compositions in accordance with the present invention.
  • the release coating compositions after curing, also exhibit a relatively low percentage of extractables.
  • release liner coating compositions may comprise an ingredient with one or more vinyl functionalities and a crosslinking agent.
  • a measurement of extractables may be used to assist in an evaluation of the extent to which the vinyl-containing ingredients and crosslinking agent have reacted, with a relatively high extent of such reaction being preferred.
  • Relatively high levels of extractables are typically, but not always, indicative of relatively low level of, and undesirable, crosslinking reactions in the liner coating composition.
  • Acceptable release force values for the separation of the release liner from the cured silicone adhesive can vary in accordance with the desired application. Generally, however, using the methodology described herein, the release force required to separate the release liner from a cured silicone adhesive should not exceed 200 gram/2 inch (g/2 in), more desirably should not exceed 150, 125, 100, 75 or 50 gram/2 inch. Generally, the force may desirably range from about 1 gram/2 inch to about 100, 95, 90, 85, 80, 75, 70, 65, 60, 55, 50, 45, 40, 35, 30, 25, 20, 15, 10 or 5 gram/2 inch.
  • the release force for the relatively “tight” release liner i.e., the liner that exhibits the highest release force
  • the release force for the ’’tight” liner may be about 50 g/2in
  • the release force for the relatively “easy” liner may be about 17 g/2in. It should be understood, however, that this 3: 1 ratio is approximate and may vary depending on the specific adhesive and coating composition used.
  • copolymers and any polymers, crosslinking agent, catalyst inhibitor, and any optional ingredients were added to a mixing vessel, and mixed at 3,000 rpm for 1 minute.
  • a catalyst composition was added thereto, with the mixture again being mixed at 3,000 rpm for 1 minute.
  • the release composition was coated onto a substrate (i.e., Melinex® D316 (2 mil PET, primed, available from DuPont Teijin Films) as follows.
  • the release composition was then cured by subjecting the coated substrate to heat, i.e., in an oven, for 5 mins at 150°C (oven temperature setting).
  • Peroxide-cure Silicone Adhesive B a silicone adhesive (34.4g), toluene (16.1g) and Benzoyl Peroxide (0.57g) were introduced into a mixing vessel, and then mixed at 3,000 rpm for 2 min Speed Mixer from Flack Tek (Landrum, South Carolina) to obtain Silicone Adhesive B.
  • a silicone adhesive (Silicone Adhesive A or B) was coated on the Release Liner (i.e., the substrate with the cured release coating composition thereon) using a knife-over-roll down coater (e.g., Chemlnstruments Laboratory Drawdown Coater) and, after coating, was baked in an oven set at 65°C for 3 minutes, and then at 150°C for 5 min, to cure the silicone adhesive. After baking, a 2 mil PET fdm was applied onto the cured adhesive to provide a composite comprising the Release Liner, adhesive and PET film. The thickness of the cured adhesive ranged from 3 to 4 mils, as measured by a Mitutoyo Absolute Digital Thickness Gage.
  • a knife-over-roll down coater e.g., Chemlnstruments Laboratory Drawdown Coater
  • a 2 inch x 10 inch section of each composite was mounted onto a TMI Lab Master® Release & Adhesion Tester (New Castle, Delaware) set at 300 inches/minute at 180 degrees, and subjected to testing. The test provided the force (in ounces, converted to grams) required to separate the Release Liner from the silicone adhesive.
  • a texture analyzer was used to determine the foregoing force parameters. After the adhesive is cured, a probe, which is part of the texture analyzer, was moved into contact with the adhesive and force applied, with the maximum force encountered as the probe penetrates the adhesive being recorded as the peak force. After reaching peak force, the probe is held at a specific depth, and the adhesive is allowed to relax, and the force is then recorded as the relaxation force.
  • Table 3 provides data for peak force (grams), relaxation force (grams) and % loss, for several silicone adhesives.
  • A a peroxi de-cured silicone adhesive
  • B a platinum-cured silicone adhesive
  • C a platinum-cured silicone adhesive
  • D a platinum-cured silicone adhesive
  • E a silicone gel adhesive Assessment of Extractables from the Cured Release Composition
  • the amount of extractables, as a % loss, from a cured release coating compositions was assessed as follows.
  • a release liner comprising the release liner substrate and cured release coating composition thereon, was weighed using an X-streme 8000 available from Oxford Instruments (Abingdon, UK) before and after soaking in methyl isobutyl ketone (i.e., 4- methylpentan-2-one, or MZBK) for 30 minutes.
  • A a vinylmethylsiloxane - dimethyl siloxane copolymer, trimethylsiloxy terminated
  • B a vinylmethylsiloxane - dimethylsiloxane copolymer, trimethylsiloxy terminated
  • C a vinyl terminated polyvinylmethylsiloxane homopolymer
  • J a methylhydrosiloxane - dimethylsiloxane copolymer, trimethylsiloxane terminated
  • K a methylhydrosiloxane - dimethylsiloxane copolymer, trimethyl siloxane terminated
  • L a methylhydrosiloxane - dimethylsiloxane copolymer, trimethylsiloxy terminated, hydride functional
  • liners coated with certain fluorine-free release coating compositions were able to provide release from a silicone adhesive (PSA) with relatively low, and desirable, levels of force.
  • PSA silicone adhesive
  • experiments wherein the liner release force is below 200 g/2 inch are most desirable for many applications, with lower liner release forces being more desirable, e.g., less than 150, less than 100, less than 50, and less than 30, and less than 20 g/2 inch.
  • Adhesive A was applied onto commercially-available substrates (Hostaphan® 2PRKN, a one-side silicone-coated PET film available from Mitsubishi Chemical; SILPHAN S50 M1R13007, a silicone-coated PET film available from Siliconature), cured, and subjected to the liner release force test as described herein.

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Abstract

L'invention concerne des compositions antiadhésives sans fluor durcissables et durcies d'adhésif en silicone ; des revêtements antiadhésifs comprenant, consistant essentiellement en, ou constitués d'un substrat ayant une surface et une composition antiadhésive sans fluor durcissable et durcie d'adhésif en silicone sur la surface du substrat ; ainsi que des composites comprenant, consistant essentiellement en, ou constitués d'un adhésif en silicone et d'un revêtement antiadhésif comprenant un substrat ayant une surface et une composition antiadhésive sans fluor durcie d'adhésif en silicone, sur la surface du substrat, l'adhésif se trouvant sur la composition antiadhésive sans fluor durcie d'adhésif de silicone ; ainsi que des procédés associés pour leur préparation et leur utilisation.
PCT/US2025/016901 2024-02-23 2025-02-21 Compositions de revêtement antiadhésif sans fluor pour adhésifs en silicone et procédés d'utilisation associés Pending WO2025179215A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100255205A1 (en) * 2006-08-14 2010-10-07 Stephen Cray Silicone Release Coating Compositions
US20190169478A1 (en) * 2015-12-09 2019-06-06 Henkel IP & Holding GmbH Debondable compositions
US20190316000A1 (en) * 2016-12-23 2019-10-17 Dow (Shanghai) Holding Co., Ltd. Polyorganosiloxane release coating and method for its preparation and use
US20220177743A1 (en) * 2019-06-03 2022-06-09 3M Innovative Properties Company Release coating compositions for pressure sensitive adhesive articles and methods
US20220195121A1 (en) * 2019-03-25 2022-06-23 Lord Corporation Moldable silicone elastomers having selective primerless adhesion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100255205A1 (en) * 2006-08-14 2010-10-07 Stephen Cray Silicone Release Coating Compositions
US20190169478A1 (en) * 2015-12-09 2019-06-06 Henkel IP & Holding GmbH Debondable compositions
US20190316000A1 (en) * 2016-12-23 2019-10-17 Dow (Shanghai) Holding Co., Ltd. Polyorganosiloxane release coating and method for its preparation and use
US20220195121A1 (en) * 2019-03-25 2022-06-23 Lord Corporation Moldable silicone elastomers having selective primerless adhesion
US20220177743A1 (en) * 2019-06-03 2022-06-09 3M Innovative Properties Company Release coating compositions for pressure sensitive adhesive articles and methods

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