WO2022236796A1 - Fluorosilicone release coating composition and release liner - Google Patents

Fluorosilicone release coating composition and release liner Download PDF

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Publication number
WO2022236796A1
WO2022236796A1 PCT/CN2021/093762 CN2021093762W WO2022236796A1 WO 2022236796 A1 WO2022236796 A1 WO 2022236796A1 CN 2021093762 W CN2021093762 W CN 2021093762W WO 2022236796 A1 WO2022236796 A1 WO 2022236796A1
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Prior art keywords
groups
component
mass
carbon atoms
content
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Ceased
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PCT/CN2021/093762
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French (fr)
Inventor
Ruihua LU
Chao Ma
Lingxuan Kong
Qing Cao
Fuming Huang
Yan Zhou
Zhihua Liu
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Dow Silicones Corp
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Dow Silicones Corp
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Priority to CN202180097097.0A priority Critical patent/CN117178026A/en
Priority to PCT/CN2021/093762 priority patent/WO2022236796A1/en
Priority to JP2023567182A priority patent/JP7741201B2/en
Priority to EP21941367.1A priority patent/EP4337727A4/en
Priority to KR1020237042310A priority patent/KR20240008331A/en
Priority to US18/287,001 priority patent/US20240034916A1/en
Publication of WO2022236796A1 publication Critical patent/WO2022236796A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
    • 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
    • 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
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • 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
    • C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/005—Presence of halogenated polymer in the release coating
    • 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 relates to a fluorosilicone release coating composition and a release liner using the same.
  • Si-PSAs Silicone pressure-sensitive adhesives
  • Si-PSAs are widely used in many applications such as electronics, industrial processing, packaging, protect films, and vehicles due to their good wetting, heat resistance, cold resistance, weather resistance, chemical resistance, electrical insulation, and the like.
  • Si-PSAs are typically used in the form of one or two sides tapes, or Si-PSA films.
  • fluorosilicone (F-Si) based release liners are generally used to form laminates with the tapes or the films.
  • F-Si based release liner can provide the Si-PSA with protection and easy debonding in use.
  • Patent Document 1 discloses a curable silicone composition
  • a curable silicone composition comprising: (A) an organopolysiloxane having alkenyl groups and perfluoroalkenyl-subsitituted organic groups; an organohydrogenpolysiloxane, and a catalyst for addition reaction, wherein the composition can form a cured coating which adheres firmly to various substrates and has good release properties, stability in the release properties, water-and oil-repellency, and solvent resistance.
  • Patent Document 2 discloses a silicone composition
  • a silicone composition comprising: (A) an organopolysiloxane having at least two alkenyl groups and at least one perfluoropolyether-substituted alkyl groups per molecule, and having a fluorine content of from 20 to 40 %by weight; (B) an organohydrogenpolysiloxane having at least three silicon atom-bonded hydrogen atoms per molecule; (C) a straight-chain perfluoropolyether anti-forming agent; and (D) a platinum group metal catalyst, wherein the composition provides a cured coating which needs only a low release force and hardly gives reduction in the residual ashesive ratio.
  • Patent Document 3 discloses a solventless releaser composition for use with silicone pressure-sensitive adhesives, comprising: (A) an organopolysiloxane having at least two alkenyl groups and at least one perfluoropolyether-substituted alkyl group per molecule, and having a fluorine content of 30 to 50%by weight of the molecule and a viscosity of 100 to 2,000 mPa ⁇ sat 25 °C; (B) an organohydrogenpolysiloxane having at least three silicon atom-bonded hydrogen atoms per molecule; (C) a reaction regulator; and (D) a platinum group metal catalyst, wherein the composition is coated and cured to a substrate to from a release liner for use with Si-PSAs.
  • an organopolysiloxane having at least two alkenyl groups and at least one perfluoropolyether-substituted alkyl group per molecule, and having a fluorine content of 30 to 50%by weight
  • Patent Document 4 discloses a silicone release coating composition for Si-PSAs, comprising: (A) an organopolysiloxane having at least two alkenyl groups per molecule, and having a fluoroalkyl group and a fluoropolyether group; (B) an organohydrogenpolysiloxane having at least three silicon atom-bonded hydrogen atoms per molecule; and (C) a platinum group metal-type catalyst, wherein the composition can form a cured coating in which the release force can be controlled within a range of medium to heavy release force against Si-PSAs.
  • Patent Document 5 discloses a silicone release coating composition
  • a silicone release coating composition comprising: (A) a linear or branched organopolysiloxane having at least two alkenyl group-containing organic groups and at least one aryl group-containing organic group per molecule, and not having a fluorine-containing organic group; (B) a linear or branched organopolysiloxane having at least one alkenyl group-containing organic group and at least one fluorin-containing organic group per molecule; (C) an organohydrogenpolysiloxane having at least three silicone atom-bonded hydrogen atoms per molecule and not having a fluorine-containing organic group; (D) a platinum group metal-based catalyst; and (E) an organohydrogenpolysiloxane having at least one silicon atom-bonded hydrogen atom per molecule and having a fluorin-containing organic group, wherein the composition can form a release film with an extremely low release force with respect to Si-PSAs and
  • the OCA film is required to exhibit a high adhesion and a low glass transition temperature, and further is required to pass the hundreds of thousands of folding tests. These high requirements for Si-PSA lead to the high requirement for F-Si release liners and come to F-Si release coating composition.
  • compositions mentiond above have a problem in forming a release liner that can be peeled with a low release force from Si-PSAs. That is, the current F-Si release coating could’t provide enough low release performance in light side with dry lamination and tight side with wet coating.
  • a release liner that can be peeled with sufficiently low release force from Si-PSA having a low glass transition temperature of 30°C or below used as OCA for dry lamination at the same time, there is a problem in forming a release liner that can provide the middle release force in Si-PSA having a low glass transition temperature of 30°C or below used as OCA with direct coating.
  • Patent Document 1 U.S. Patent No. 5,204,436 A
  • Patent Document 2 U.S. Patent Application Publication No. 2004/0186225 A1
  • Patent Document 3 U.S. Patent Application Publication No. 2011/0251339 A1
  • Patent Document 4 Japanese Patent Application Publication No. 2017-165893 A
  • Patent Document 5 International Publication No. WO 2020/137835 A1
  • An object of the present invention is to provide a fluorosilicone release coating composition capable of forming a release film having a stable and low release force with respect to a silicone pressure-sensitive adhesive having a low glass transition temperature, and to further provide a release film having a stable and low release force with respect to a silicone pressure-sensitive adhesive having a low glass transition temperature.
  • the fluorosilicone release coating composition of the present invention comprises:
  • a content of component (A) is in a range of from about 40 to about 90.5 mass%
  • a content of component (B) is in a range of from about 9 to about 56 mass%
  • a content of component (C) is in a range of from about 0.5 to about 4 mass%, each based on a total mass of components (A) to (C)
  • a content of component (D) is in a range of from about 1 to about 15 parts by mass with respect to 100 parts by mass of a total mass of components (A) to (C) .
  • component (A) has the fluoroalkyl groups in an amount such that a content of fluorine atoms associated with the fluoroalkyl groups in a molecule is at least 30 mass%.
  • component (A) is an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 1 3 SiO 1/2 and a D siloxane unit represented by the general formula: R 1 2 SiO 2/2 , wherein R 1 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least two R 1 are the alkenyl groups and at least one R 1 is the fluoroalkyl group.
  • R 1 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7
  • component (B) has the fluoroalkyl groups in an amount such that a content of fluorine atoms associated with the fluoroalkyl groups in a molecule is at least 15 mass%.
  • component (B) is an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 2 3 SiO 1/2 , a D siloxane unit represented by the general formula: R 2 2 SiO 2/2 and a Q siloxane unit represented by the formula: SiO 4/2 , wherein R 2 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least one R 2 is the fluoroalkyl group.
  • R 2 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aral
  • component (C) has the fluoroalkyl groups in an amount such that a content of fluorine atoms associated with the fluoroalkyl groups in a molecule is at least 20 mass%.
  • component (C) is an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 3 3 SiO 1/2 and a D siloxane unit represented by the general formula: R 3 2 SiO 2/2 , wherein R 3 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least one R 3 is the fluoroalkyl group.
  • R 3 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least one R 3 is the fluor
  • the fluorosilicone release coating composition further comprises: (F) a hydrosilylation reaction inhibitor, in an amount of from about 0.01 to about 5 parts by mass with respect to 100 parts by mass of a total mass of components (A) to (C) .
  • the fluorosilicone release coating composition further comprises: (G) an arbitrary amount of a solvent.
  • the fluorosilicone release coating composition is used for a silicone pressure sensitive adhesive.
  • the release liner of the present invention is obtained by coating a substrate with the fluorosilicone release coating composition described above.
  • the substrate is a plastic film.
  • the fluorosilicone release coating composition of the present invention can be cured to form a release coating exhibiting a stable and low release force with respect to a silicone pressure-sensitive adhesive having a low glass transition temperature.
  • the release liner of the present invention has a stable and low release force with respect to a silicone pressure-sensitive adhesive having a low glass transition temperature.
  • Component (A) is a linear organopolysiloxane having at least two alkenyl groups and at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom.
  • alkenyl groups include alkenyl groups having from 2 to 12 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and so forth, among these, vinyl groups are preferable.
  • fluoroalkyl groups include fluoroalkyl groups having from 1 to 12 carbon atoms, such as 3, 3, 3-trifluoropropyl groups, 3, 3, 4, 4, 4-pentafluorobutyl groups, 3, 3, 4, 4, 5, 5, 5-heptafluoropentyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups, 3,3, 4, 4, 5, 5, 6, 6, 7, 7, 7-undecafluoroheptyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 9-pentadecafluorononyl groups, and so forth, among these, 3, 3, 4, 4, 5, 5, 5-heptafluoropentyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 7-undecafluoroheptyl groups, and 3, 3, 4, 4, 5, 5, 6, 5, 6,
  • silicon atom-bonded groups other than the alkenyl groups and fluoroalkyl groups include alkyl groups having from 1 to 12 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, and so forth; aryl groups having from 6 to 12 carbon atoms, such as phenyl, tolyl, xylyl, and so forth; aralkyl groups having from 7 to 12 carbon atoms such as benzyl, phenethyl, and so forth; among these, methyl groups are preferable.
  • the content of fluorine atoms associated with the fluoroalkyl groups in a molecule is preferably at least 30 mass%, alternatively at least 35 mass%, or alternatively at least 40 mass%. This is because when the content of fluorine atoms in component (A) is greater than or equal to the lower limit described above, a release coating obtained by crosslinking the present composition exhibits a good release force with respect to a silicone pressure-sensitive adhesive.
  • the upper limit of the content of fluorine atoms in component (A) is not particularly limited, however, when the content is too high, component (A) itself tends to not dissolve in the solvent, which diminishes the handleability, and the content therefore is preferably at most 60 mass%, alternatively at most 50 mass%. Note that a small amount of hydroxyl groups or alkoxy groups having from 1 to 3 carbon atoms may be bonded to the silicon atoms in component (A) within a range that does not diminish the object of the present invention.
  • Component (A) is preferably an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 1 3 SiO 1/2 and a D siloxane unit represented by the general formula: R 1 2 SiO 2/2 .
  • R 1 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, examples of which are the same as those described above. Note that, in a molecule, at least two R1 are the alkenyl groups and at least one R 1 is the fluoroalkyl group.
  • the organopolysiloxane for component (A) may contain small amount of other siloxane units such as a M siloxane unit represented by the general formula: (X) R 1 2 SiO 1/2 within a range that does not diminish the object of the present invention.
  • X is a hydroxyl group or an alkoxy group having from 1 to 3 carbon atoms.
  • Component (B) is a branched organopolysiloxane having at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom.
  • fluoroalkyl groups include the same as those described above, and 3, 3, 3-trifluoropropyl groups are preferable.
  • silicon atom-bonded groups other than the fluoroalkyl groups include alkyl groups having from 1 to 12 carbon atoms, alkeyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, and aralkyl groups having from 7 to 12 carbon atoms, examples of which are the same as those described above, and methyl groups and vinyl groups are preferable.
  • the content of fluorine atoms associated with the fluoroalkyl groups in a molecule is preferably at least 15 mass%, alternatively at least 20 mass%, or alternatively at least 25 mass%. This is because when the content of fluorine atoms in component (B) is greater than or equal to the lower limit described above, a release coating obtained by crosslinking the present composition exhibits a good release force with respect to a silicone pressure-sensitive adhesive.
  • the upper limit of the content of fluorine atoms in component (B) is not particularly limited, however, when the content is too high, component (B) itself tends to not dissolve in the solvent, which diminishes the handleability, and the content therefore is preferably at most 60 mass%, alternatively at most 50 mass%. Note that a small amount of hydroxyl groups or alkoxy groups may be bonded to the silicon atoms in component (B) within a range that does not diminish the object of the present invention.
  • Component (B) is preferably an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 2 3 SiO 1/2 , a D siloxane unit represented by the general formula: R 2 2 SiO 2/2 and a Q siloxane unit represented by the formula: SiO 4/2 .
  • R 2 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, examples of which are the same as those described above. Note that, in a molecule, at least one R 2 is the fluoroalkyl group.
  • the organopolysiloxane for component (B) may contain small amount of other siloxane units such as a M siloxane unit represented by the general formula: (X) R 2 2 SiO 1/2 , a T siloxane unit represented by the general formula: R 2 SiO 3/2 within a range that does not diminish the object of the present invention.
  • X is a hydroxyl group or an alkoxy group having from 1 to 3 carbon atoms.
  • a viscosity of component (B) at 25°C is not limited, but in various embodiments is in a range of from about 100 mPa ⁇ sto about 100,000 mPa ⁇ s, alternatively in the range of from about 200 mPa ⁇ sto about 50,000 mPa ⁇ s, alternatively in the range of from about 300 mPa ⁇ sto about 50,000 mPa ⁇ s.
  • viscosity is the value measured using a type B viscometer according to ASTM D 1084 at 23 ⁇ 2 °C.
  • Component (C) is a linear organopolysiloxane having at least one fluoroalkyl group per molecule, and having neither an aliphatic unsaturated group nor a silicon atom-bonded hydrogen atom.
  • fluoroalkyl groups include the same as those described above, and 3, 3, 4, 4, 5, 5, 5-heptafluoropentyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 7-undecafluoroheptyl groups, and 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl groups are preferable.
  • Examples of silicon atom-bonded groups other than the fluoroalkyl groups include alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, and aralkyl groups having from 7 to 12 carbon atoms, examples of which are the same as those described above, and methyl groups are preferable.
  • the content of fluorine atoms associated with the fluoroalkyl groups in a molecule is preferably at least 20 mass%, alternatively at least 25 mass%, or alternatively at least 30 mass%.
  • the content of fluorine atoms in component (C) is greater than or equal to the lower limit described above, a release coating obtained by crosslinking the present composition exhibits a good release force with respect to a silicone pressure-sensitive adhesive.
  • the upper limit of the content of fluorine atoms in component (C) is not particularly limited, however, when the content is too high, component (C) itself tends to not dissolve in the solvent, which diminishes the handleability, and the content therefore is preferably at most 60 mass%, alternatively at most 50 mass%.
  • a small amount of hydroxyl groups or alkoxy groups having from 1 to 3 carbon atoms may be bonded to the silicon atoms in component (C) within a range that does not diminish the object of the present invention.
  • Component (C) is preferably an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 3 3 SiO 1/2 and a D siloxane unit represented by the general formula: R 3 2 SiO 2/2 .
  • R 3 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, examples of which are the same as those described above. Note that, in a molecule, at least one R 3 is the fluoroalkyl group.
  • the organopolysiloxane for component (C) may contain small amount of other siloxane units such as a M siloxane unit represented by the general formula: (X) R 3 2 SiO 1/2 within a range that does not diminish the object of the present invention.
  • X is a hydroxyl group or an alkoxy group having from 1 to 3 carbon atoms.
  • a viscosity of component (C) at 25°C is not limited, but in various embodiments is in a range of from about 1,000 mPa ⁇ sto about 100,000 mPa ⁇ s, alternatively in the range of from about 2,000 mPa ⁇ sto about 100,000 mPa ⁇ s, alternatively in the range of from about 3,000 mPa ⁇ sto about 100,000 mPa ⁇ s. This is because when the viscosity of component (C) is greater than or equal to the lower limit of the range described above, the characteristics of the resulting release coating are sufficiently, while when the viscosity is less than or equal to the upper limit of the range described above, the resulting composition has a suitable viscosity in processing and handling. Note that in the present specification, viscosity is the value measured using a type B viscometer according to ASTM D 1084 at 23 ⁇ 2 °C.
  • a content of component (A) is in a range of from about 40 to about 90.5 mass%, a content of component (B) is in a range of from about 9 to about 56 mass%, and a content of component (C) is in a range of from about 0.5 to about 4 mass%, pereferably the content of component (A) is in a range of from about 40 to about 85.5 mass%, the content of component (B) is in a range of from about 14 to about 56 mass%, and the content of component (C) is in a range of from about 0.5 to about 4 mass%, alternatively the content of component (A) is in a range of from about 40 to about 80.5 mass%, the content of component (B) is in a range of from about 19 to about 56 mass%, and the content of component (C) is in a range of from about 0.5 to about 4 mass%, each based on a total mass of components (A) to (C) .
  • Component (D) is an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule.
  • groups bonded to silicon atoms in component (D) include alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, and fluoroalkyl groups having from 1 to 12 carbon atoms, examples of which are the same as those described above, among these, methyl groups, 3, 3, 4, 4, 5, 5, 5-heptafluoropentyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 7- undecafluoroheptyl groups, and 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl groups are preferable.
  • the content of fluorine atoms associated with the fluoroalkyl groups in a molecule is not particularly limited but is preferably at least 20 mass%, at least 25 mass%, at least 30 mass%, or at least 35 mass%. This is because when the content of fluorine atoms in component (D) is greater than or equal to the lower limit described above, the compatibility with components (A) to (C) is enhanced, and a release coating obtained by crosslinking the present composition exhibits a good peeling force with respect to a silicone pressure-sensitive adhesive.
  • the upper limit of the content of fluorine atoms in component (D) is not particularly limited, however, when the content is too high, component (D) itself tends to not dissolve in the solvent, which diminishes the handleability, so the content is preferably at most 60 mass%or at most 50 mass%. Note that a small amount of hydroxyl groups or alkoxy groups having from 1 to 3 carbon atoms may be bonded to the silicon atoms in component (D) within a range that does not diminish the object of the present invention.
  • a molecular structure of component (D) is not limited. Examples thereof include a straight-chain structure, a branched-chain structure, a partially branched straight-chain structure, a resinous structure, and a cyclic structure, and a straight-chain structure or a partially branched straight-chain structure is preferable.
  • a content of component (D) is in a range of from about 1 to about 15 parts by mass, preferably in a range of from about 1 to about 13 parts by mass, alternatively in a range of from about 2 to about 15 parts by mass, alternatively in a range of from about 3 to about 15 parts by mass, alternatively in a range of from about 2 to about 13 parts by mass, alternatively in a range of from about 3 to about 13 parts by mass, with respect to 100 parts by mass of a total mass of components (A) to (C) .
  • Component (E) is a hydrosilylation reaction catalyst for promoting the curing of the present composition.
  • platinum-based catalysts examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferable.
  • platinum-based catalyst examples include platinum fine powder, platinum black, platinum supporting silica fine powder, platinum supporting activated carbon, chloroplatinic acid, alcohol solutions of chloroplatinic acid, olefin complexes of platinum, and alkenylsiloxane complexes of platinum.
  • a content of component (E) is an effective amount that promotes the curing of the present composition and is specifically an amount in which the platinum atoms in the catalyst are within a range of from about 0.1 to 1,000 ppm in mass units with respect to the present composition. This is because when the content of component (E) is greater than or equal to the lower limit of the range described above, the curing of the resulting composition progresses, while when the content is less than or equal to the upper limit of the range described above, the resulting cured product becomes less susceptible to discoloration.
  • the present composition may also comprise (F) a hydrosilylation reaction inhibitor in order to control the crosslinking reactions thereof.
  • component (F) include: alkyne alcohols such as 1-ethynylcyclohexan-1-ol, 2-methyl-3-butyn-2-ol, 3, 5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol; enyne compounds such as 3-methyl-3-penten-1-yne and 3, 5-dimethyl-3-hexen-1-yne; methyl alkenyl siloxane oligomers such as 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetravinylcyclotetrasiloxane and 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetrahexenylcyclotetrasiloxane; alkynoxysilanes such as dimethyl bis (3-methyl-1-butyn-3-oxy) silane and methylvinyl bis
  • a content of component (F) is not limited, and from the perspective of imparting sufficient pot-life to the present composition, the content is preferably in a range of from about 0.01 to about 5 parts by mass, alternatively in a range of from about 0.05 to about 5 parts by mass, or alternatively in a range of from about 0.05 to about 3 parts by mass, with respect to 100 parts by mass of a total mass of components (A) to (C) .
  • This is because when the content of component (F) is greater than or equal to the lower limit of the range described above, the pot-life of the present composition is sufficiently for use, while when the content is less than or equal to the upper limit of the range described above, the curability of the present composition is good for use.
  • the present composition may comprise (G) a solvent in order to reduce the viscosity thereof and to improve the application workability or wettability.
  • component (G) include: hydrocarbon-based solvents such as aromatic hydrocarbon-based solvents such as toluene and xylene, aliphatic hydrocarbon-based solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin, industrial gasoline (rubber solvents or the like) , petroleum benzene, and solvent naphtha; ketone-based solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, and cyclohex
  • a content of component (G) is arbitrary and may be adjusted appropriately as necessary, but the content is typically not greater than aout 2,000 parts by mass with respect to 100 parts by mass of a total mass of components (A) to (C) .
  • the present composition may comprise an antioxidant, a reactive diluent, a leveling agent, a filler, an antistatic agent, an antifoaming agent, a pigment, or the like within a range that does not impair the object of the present invention.
  • the release liner can be produced by applying the present composition to a substrate and curing the composition.
  • Examples of the substrate may include a paper, a plastic film, a glass, and a metal film.
  • Examples of paper include high-quality paper, coated paper, art paper, glassine paper, polyethylene laminate paper, and craft paper.
  • plastic films include polyethylene films, polypropylene films, polyester films, polyimide films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, polycarbonate films, polytetrafluoroethylene films, polystyrene films, ethylene-vinyl acetate copolymer films, ethylene-vinyl alcohol copolymer films, triacetyl cellulose films, polyether ether ketone films, and polyphenylene sulfide films.
  • the glass is not particularly limited in terms of thickness, type, or the like, and may be subjected to chemical reinforcement treatment or the like.
  • glass fibers may also be applied, and glass fibers may be used alone or in combination with another resin.
  • metals include aluminum foil, copper foil, gold foil, silver foil, and nickel foil. When used as a release film, a polyester film is preferable.
  • a method of applying the present composition to a substrate is not limited, and a known coating method may be used.
  • the coating method include a wire bar, a comma coater, a lip cpater, a roll coater, a die coater, a knife coater, a blade coater, a rod coater, a kiss coater, a gravure coater, screen coating, immersion coating, and cast coating.
  • An amount of the present composition applied to the substrate is also not limited and is preferably within a range of from about 0.1 to about 2 g/m 2 or within a range of from about 0.2 to about 1.8 g/m 2 in terms of solid content. Curing conditions are also not limited, however, the composition is preferably heated for about 10 to about 180 seconds or about 15 to about 150 seconds within a range of from about 80 to about 180 °C or within a range of from about 90 to about 160 °C.
  • a silicone pressure-sensitive adhesive may be applied to the release liner produced in this way.
  • a commercially available composition may be used as the silicone pressure-sensitive adhesive composition.
  • a method of applying the silicone pressure-sensitive adhesive composition may be a known coating method, examples of which include a comma coater, a lip coater, a roll coater, a die coater, a knife coater, a blade coater, a rod coater, a kiss coater, a gravure coater, screen coating, immersion coating, and cast coating.
  • An amount of the silicone pressure-sensitive adhesive that is applied may be an amount such that a thickness after curing is from about 0.1 to about 300 ⁇ m and is preferably an amount such that a thickness after curing is from about 0.5 to about 200 ⁇ m.
  • curing conditions of the silicone pressure-sensitive adhesive composition may be from about 10 seconds to about 10 minutes at about 80 to about 150 °C.
  • Viscosity at 23 ⁇ 2 °C was measured by using a type B viscometer (Brookfield HA or HB Type Rotational Viscometer with using Spindle #52 at 5 rpm) according to ASTM D 1084 “Standard Test Methods for Viscosity of Adhesive. ”
  • Fluorosilicone release coating composition shown in Table 1 were prepared using the components mentioned below. Firstly, components (A) , (B) , (C) and (F) were mixed homogeneously, and a suitable solvent, e.g., isopropyl ether, heptane, fluorinated solvent, or a mixture thereof as component (G) was loaded to adjust a non-volatile content. Next, components (D) and (E) were added to produce fluorosilicone release coating compositions. Note each non-volatile content of the fluorosilicone release coating compositions was adjusted to 9 mass%. The compositions were coated on PET substrates by a coater, and then cured under 140 °C for 30 seconds. The performances of the compositions were also shown in Table 2.
  • a suitable solvent e.g., isopropyl ether, heptane, fluorinated solvent, or a mixture thereof as component (G) was loaded to adjust a non-volatile content.
  • component (A) The following components were used as component (A) .
  • component (a-1) a mixture of an organopolysiloxane composed of Me 2 SiO 2/2 , M eR f1 SiO 2/2 , ViMeSiO 2/2 and ViMe 2 SiO 1/2 unites, and having a vinyl group conte nt of 0.16 mass%and a fluoro atom content of 42.1 mass%component (a-2) : an organopolysiloxane composed of Me 2 SiO 2/2 , MeR f1 SiO 2/2 , V iMeSiO 2/2 and Me 3 SiO 1/2 unites, and having a vinyl group content of 0.20 mass %and a fluoro atom content of 41.9 mass%
  • component (B) The following component was used as component (B) .
  • component (b-1) an organopolysiloxane composed of SiO 4/2 , Me 2 SiO 2/2 , MeR f2 SiO 2/2 , Me 3 SiO 1/2 , and ViMe 2 SiO 1/2 units, and having a viscosity of about 500 mPa ⁇ s, a vinyl group content of 0.44 mass%, a fluoro atom content of 26 mass%
  • component (C) The following component was used as component (C) .
  • component (c-1) an organopolysiloxane composed of Me 2 SiO 2/2 , MeR f1 SiO 2/2 . an d Me 3 SiO 1/2 , and having a viscosity of 66,000 mPa ⁇ sand a fluoro atom content o f 32.4 mass%
  • component (D) The following component was used as component (D) .
  • component (d-1) an oragnohydrogenpolysiloxane composed of MeHSiO 2/2 , MeR f1 SiO 2/2 . and Me 3 SiO 1/2 , and having a viscosity of 66,000 mPa ⁇ s, a fluoro atom content of 38 mass%and silicon atom-bonded hydrogen atom content of 0.50 mass%
  • component (E) The following component was used as component (E) .
  • component (e-1) 1.5 mass%of Pt-1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex in dimethyvinylsiloxy-terminated dimethylpolysiloxane having a viscosity of 450 mPa ⁇ s
  • component (F) The following components were used as component (F) .
  • silicone presure-sensitive adhesives were used to evaluate the fluorosilicone release coating compositions of Practical and Comparative Examples.
  • Si-PSA 1 a silicone pressure-sensitive adheseive having a glass transition temperature of -11 °C.
  • Si-PSA 2 a silicone pressure-sensitive adheseive having a glass transition temperature of -18 °C.
  • Si-PSA 3 a silicone pressure-sensitive adheseive having a glass transition temperature of 30 °C.
  • Dry laminate laminate cured Si-PSA1 or Si-PSA2 tapes on coated release coating, load weight of 20 g/cm 2 on laminated sample and left under room temperature (RT) or 70 °C for 20 hrs. or 3 days. After 20 hrs. or 3 days, remove the load and wait for 30 mins. Then test the release force with liner side by ChemInstruments AR-1500. Refer to FINAT Test Method No. 10 (FINAT Technical Handbook 7 th edition, 2005) .
  • the Si-PSA was directly coating on coated release liner and cured and laminate a blank PET on PSA surface and then cut with 1 inch width.
  • the fluorosilicone release coating composition of the present invention can form a release coating exhibiting a low release force with respect to Si-PSAs having a low glass transition temperature, so the composition is effective as F-Si release coating composition for producing a release liner for Si-PSAs for the OCA protection.

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Abstract

Provided is a fluorosilicone release coating composition comprising: (A) a linear organopolysiloxane having at least two alkenyl groups and at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom: (B) a branched organopolysiloxane having at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom; (C) a linear organopolysiloxane having at least one fluoroalkyl group per molecule, and having neither an aliphatic unsaturated group nor a silicon atom-bonded hydrogen atom; (D) an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms and at least one fluoroalkyl group per molecule; and (E) a hydrosilylation reaction catslyst. The composition can form a release coating exhibiting a stable and low release force with respect to a silicone pressure-sensitive adhesive having a low glass transition temperature．

Description

FLUOROSILICONE RELEASE COATING COMPOSITION AND RELEASE LINER Technical Field
The present invention relates to a fluorosilicone release coating composition and a release liner using the same.
Background Art
Silicone pressure-sensitive adhesives (Si-PSAs) are widely used in many applications such as electronics, industrial processing, packaging, protect films, and vehicles due to their good wetting, heat resistance, cold resistance, weather resistance, chemical resistance, electrical insulation, and the like. Si-PSAs are typically used in the form of one or two sides tapes, or Si-PSA films. In order to get easy release, fluorosilicone (F-Si) based release liners are generally used to form laminates with the tapes or the films. Thus F-Si based release liner can provide the Si-PSA with protection and easy debonding in use.
For example, Patent Document 1 discloses a curable silicone composition comprising: (A) an organopolysiloxane having alkenyl groups and perfluoroalkenyl-subsitituted organic groups; an organohydrogenpolysiloxane, and a catalyst for addition reaction, wherein the composition can form a cured coating which adheres firmly to various substrates and has good release properties, stability in the release properties, water-and oil-repellency, and solvent resistance.
Patent Document 2 discloses a silicone composition comprising: (A) an organopolysiloxane having at least two alkenyl groups and at least one perfluoropolyether-substituted alkyl groups per molecule, and having a fluorine content of from 20 to 40 %by weight; (B) an organohydrogenpolysiloxane having at least three silicon atom-bonded hydrogen atoms per molecule; (C) a straight-chain perfluoropolyether anti-forming agent; and (D) a platinum group metal catalyst, wherein  the composition provides a cured coating which needs only a low release force and hardly gives reduction in the residual ashesive ratio.
Patent Document 3 discloses a solventless releaser composition for use with silicone pressure-sensitive adhesives, comprising: (A) an organopolysiloxane having at least two alkenyl groups and at least one perfluoropolyether-substituted alkyl group per molecule, and having a fluorine content of 30 to 50%by weight of the molecule and a viscosity of 100 to 2,000 mPa·sat 25 ℃; (B) an organohydrogenpolysiloxane having at least three silicon atom-bonded hydrogen atoms per molecule; (C) a reaction regulator; and (D) a platinum group metal catalyst, wherein the composition is coated and cured to a substrate to from a release liner for use with Si-PSAs.
Patent Document 4 discloses a silicone release coating composition for Si-PSAs, comprising: (A) an organopolysiloxane having at least two alkenyl groups per molecule, and having a fluoroalkyl group and a fluoropolyether group; (B) an organohydrogenpolysiloxane having at least three silicon atom-bonded hydrogen atoms per molecule; and (C) a platinum group metal-type catalyst, wherein the composition can form a cured coating in which the release force can be controlled within a range of medium to heavy release force against Si-PSAs.
Patent Document 5 discloses a silicone release coating composition comprising: (A) a linear or branched organopolysiloxane having at least two alkenyl group-containing organic groups and at least one aryl group-containing organic group per molecule, and not having a fluorine-containing organic group; (B) a linear or branched organopolysiloxane having at least one alkenyl group-containing organic group and at least one fluorin-containing organic group per molecule; (C) an organohydrogenpolysiloxane having at least three silicone atom-bonded hydrogen atoms per molecule and not having a fluorine-containing organic group; (D) a platinum group metal-based catalyst; and (E) an organohydrogenpolysiloxane having at least one silicon atom-bonded hydrogen atom per molecule and having a fluorin-containing organic group,  wherein the composition can form a release film with an extremely low release force with respect to Si-PSAs and excellent post-release resisual adhesive force.
Recent years, consumer electronics become more and more popular like in smart phones, pads, and even foldable phones. These applications, in especial, foldable optical clear adheseive (OCA) applications require high performance Si-PSAs. The Si-PSA for the OCA is normally coated on the F-Si release liner to cure thus form a film, and the other side of the film will be laminated another layer of F-Si release liner thus form a sandwich structure. Each F-Si release liners for the two sides requires enough a low release force, e.g., less than 10 gf/inch in one side and middle release force, e.g., less than 40 gf/inch in another side. The OCA film is required to exhibit a high adhesion and a low glass transition temperature, and further is required to pass the hundreds of thousands of folding tests. These high requirements for Si-PSA lead to the high requirement for F-Si release liners and come to F-Si release coating composition.
However, the compositions mentiond above have a problem in forming a release liner that can be peeled with a low release force from Si-PSAs. That is, the current F-Si release coating couldn’t provide enough low release performance in light side with dry lamination and tight side with wet coating. In particular, there is a problem in forming a release liner that can be peeled with sufficiently low release force from Si-PSA having a low glass transition temperature of 30℃ or below used as OCA for dry lamination, at the same time, there is a problem in forming a release liner that can provide the middle release force in Si-PSA having a low glass transition temperature of 30℃ or below used as OCA with direct coating.
Prior Art Documents
Patent Documents
Patent Document 1: U.S. Patent No. 5,204,436 A
Patent Document 2: U.S. Patent Application Publication No. 2004/0186225 A1
Patent Document 3: U.S. Patent Application Publication No. 2011/0251339 A1
Patent Document 4: Japanese Patent Application Publication No. 2017-165893 A
Patent Document 5: International Publication No. WO 2020/137835 A1
Summary of the Invention
Technical Problems
An object of the present invention is to provide a fluorosilicone release coating composition capable of forming a release film having a stable and low release force with respect to a silicone pressure-sensitive adhesive having a low glass transition temperature, and to further provide a release film having a stable and low release force with respect to a silicone pressure-sensitive adhesive having a low glass transition temperature.
Solution to Problem
The fluorosilicone release coating composition of the present invention comprises:
(A) a linear organopolysiloxane having at least two alkenyl groups and at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom;
(B) a branched organopolysiloxane having at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom;
(C) a linear organopolysiloxane having at least one fluoroalkyl group per molecule, and having neither an aliphatic unsaturated group nor a silicon atom-bonded hydrogen atom;
(D) an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms and at least one fluoroalkyl group per molecule; and
(E) an effective amount of a hydrosilylation reaction catalyst,
wherein a content of component (A) is in a range of from about 40 to about 90.5 mass%, a content of component (B) is in a range of from about 9 to about 56 mass%, and a content of component (C) is in a range of from about 0.5 to about 4 mass%, each based on a total mass of components (A) to (C) ; and a content of component (D) is in a range of  from about 1 to about 15 parts by mass with respect to 100 parts by mass of a total mass of components (A) to (C) .
In various embodiments, component (A) has the fluoroalkyl groups in an amount such that a content of fluorine atoms associated with the fluoroalkyl groups in a molecule is at least 30 mass%.
In various embodiments, component (A) is an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 1 3SiO 1/2 and a D siloxane unit represented by the general formula: R 1 2SiO 2/2, wherein R 1 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least two R 1 are the alkenyl groups and at least one R 1 is the fluoroalkyl group.
In various embodiments, component (B) has the fluoroalkyl groups in an amount such that a content of fluorine atoms associated with the fluoroalkyl groups in a molecule is at least 15 mass%.
In various embodiments, component (B) is an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 2 3SiO 1/2, a D siloxane unit represented by the general formula: R 2 2SiO 2/2 and a Q siloxane unit represented by the formula: SiO 4/2, wherein R 2 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least one R 2 is the fluoroalkyl group.
In various embodiments, component (C) has the fluoroalkyl groups in an amount such that a content of fluorine atoms associated with the fluoroalkyl groups in a molecule is at least 20 mass%.
In various embodiments, component (C) is an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 3 3SiO 1/2 and a D siloxane unit represented by the general formula: R 3 2SiO 2/2, wherein R 3 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least one R 3 is the fluoroalkyl group.
In various embodiments, the fluorosilicone release coating composition further comprises: (F) a hydrosilylation reaction inhibitor, in an amount of from about 0.01 to about 5 parts by mass with respect to 100 parts by mass of a total mass of components (A) to (C) .
In various embodiments, the fluorosilicone release coating composition further comprises: (G) an arbitrary amount of a solvent.
In various embodiments, the fluorosilicone release coating composition is used for a silicone pressure sensitive adhesive.
The release liner of the present invention is obtained by coating a substrate with the fluorosilicone release coating composition described above.
In various embodiments, the substrate is a plastic film.
Effects of the Invention
The fluorosilicone release coating composition of the present invention can be cured to form a release coating exhibiting a stable and low release force with respect to a silicone pressure-sensitive adhesive having a low glass transition temperature. In especial, the release liner of the present invention has a stable and low release force with  respect to a silicone pressure-sensitive adhesive having a low glass transition temperature.
Definitions
The terms “comprising” or “comprise” are used herein in their broadest sense to mean and encompass the notions of “including, ” “include, ” “consist (ing) essentially of, ” and “consist (ing) of. ” The use of “for example, ” “e.g., ” “such as, ” and “including” to list illustrative examples does not limit to only the listed examples. Thus, “for example” or “such as” means “for example, but not limited to” or “such as, but not limited to” and encompasses other similar or equivalent examples. The term “about” as used herein serves to reasonably encompass or describe minor variations in numerical values measured by instrumental analysis or as a result of sample handling. Such minor variations may be in the order of ±0-25, ±0-10, ±0-5, or ±0-2.5, %of the numerical values. Further, the term “about” applies to both numerical values when associated with a range of values. Moreover, the term “about” may apply to numerical values even when not explicitly stated.
Detailed Description of the Invention
<Fluorosilicone Release Coating Composition>
First, the fluorosilicone release coating composition of the present invention will be described in detail.
<Component (A) >
Component (A) is a linear organopolysiloxane having at least two alkenyl groups and at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom. Examples of the alkenyl groups include alkenyl groups having from 2 to 12 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and so forth, among these, vinyl groups are preferable. Examples of the fluoroalkyl groups include fluoroalkyl groups having from 1 to 12 carbon atoms, such as 3, 3, 3-trifluoropropyl groups, 3, 3, 4, 4, 4-pentafluorobutyl  groups, 3, 3, 4, 4, 5, 5, 5-heptafluoropentyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups, 3,3, 4, 4, 5, 5, 6, 6, 7, 7, 7-undecafluoroheptyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 9, 9, 9-pentadecafluorononyl groups, and so forth, among these, 3, 3, 4, 4, 5, 5, 5-heptafluoropentyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 7-undecafluoroheptyl groups, and 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl groups are preferable. Examples of silicon atom-bonded groups other than the alkenyl groups and fluoroalkyl groups include alkyl groups having from 1 to 12 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, and so forth; aryl groups having from 6 to 12 carbon atoms, such as phenyl, tolyl, xylyl, and so forth; aralkyl groups having from 7 to 12 carbon atoms such as benzyl, phenethyl, and so forth; among these, methyl groups are preferable. Note that the content of fluorine atoms associated with the fluoroalkyl groups in a molecule is preferably at least 30 mass%, alternatively at least 35 mass%, or alternatively at least 40 mass%. This is because when the content of fluorine atoms in component (A) is greater than or equal to the lower limit described above, a release coating obtained by crosslinking the present composition exhibits a good release force with respect to a silicone pressure-sensitive adhesive. Note that the upper limit of the content of fluorine atoms in component (A) is not particularly limited, however, when the content is too high, component (A) itself tends to not dissolve in the solvent, which diminishes the handleability, and the content therefore is preferably at most 60 mass%, alternatively at most 50 mass%. Note that a small amount of hydroxyl groups or alkoxy groups having from 1 to 3 carbon atoms may be bonded to the silicon atoms in component (A) within a range that does not diminish the object of the present invention.
Component (A) is preferably an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 1 3SiO 1/2 and a D siloxane unit represented by the general formula: R 1 2SiO 2/2.
In the formula, R 1 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, examples of which are the same as those described above. Note that, in a molecule, at least two R1 are the alkenyl groups and at least one R 1 is the fluoroalkyl group.
The organopolysiloxane for component (A) may contain small amount of other siloxane units such as a M siloxane unit represented by the general formula: (X) R 1 2SiO 1/2 within a range that does not diminish the object of the present invention. In the formula, X is a hydroxyl group or an alkoxy group having from 1 to 3 carbon atoms.
<Component (B) >
Component (B) is a branched organopolysiloxane having at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom. Examples of the fluoroalkyl groups include the same as those described above, and 3, 3, 3-trifluoropropyl groups are preferable. Examples of silicon atom-bonded groups other than the fluoroalkyl groups include alkyl groups having from 1 to 12 carbon atoms, alkeyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, and aralkyl groups having from 7 to 12 carbon atoms, examples of which are the same as those described above, and methyl groups and vinyl groups are preferable. Note that the content of fluorine atoms associated with the fluoroalkyl groups in a molecule is preferably at least 15 mass%, alternatively at least 20 mass%, or alternatively at least 25 mass%. This is because when the content of fluorine atoms in component (B) is greater than or equal to the lower limit described above, a release coating obtained by crosslinking the present composition exhibits a good release force with respect to a silicone pressure-sensitive adhesive. Note that the upper limit of the content of fluorine atoms in component (B) is not particularly limited, however, when the content is too high, component (B) itself  tends to not dissolve in the solvent, which diminishes the handleability, and the content therefore is preferably at most 60 mass%, alternatively at most 50 mass%. Note that a small amount of hydroxyl groups or alkoxy groups may be bonded to the silicon atoms in component (B) within a range that does not diminish the object of the present invention.
Component (B) is preferably an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 2 3SiO 1/2, a D siloxane unit represented by the general formula: R 2 2SiO 2/2 and a Q siloxane unit represented by the formula: SiO 4/2.
In the formula, R 2 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, examples of which are the same as those described above. Note that, in a molecule, at least one R 2 is the fluoroalkyl group.
The organopolysiloxane for component (B) may contain small amount of other siloxane units such as a M siloxane unit represented by the general formula: (X) R 2 2SiO 1/2 , a T siloxane unit represented by the general formula: R 2SiO 3/2 within a range that does not diminish the object of the present invention. In the formula, X is a hydroxyl group or an alkoxy group having from 1 to 3 carbon atoms.
A viscosity of component (B) at 25℃ is not limited, but in various embodiments is in a range of from about 100 mPa·sto about 100,000 mPa·s, alternatively in the range of from about 200 mPa·sto about 50,000 mPa·s, alternatively in the range of from about 300 mPa·sto about 50,000 mPa·s. This is because when the viscosity of component (B) is greater than or equal to the lower limit of the range described above, the characteristics of the resulting release coating are sufficiently, while when the viscosity is less than or equal to the upper limit of the range described above, the resulting composition has a suitable viscosity in processing and handling. Note that in the present specification,  viscosity is the value measured using a type B viscometer according to ASTM D 1084 at 23 ± 2 ℃.
<Component (C) >
Component (C) is a linear organopolysiloxane having at least one fluoroalkyl group per molecule, and having neither an aliphatic unsaturated group nor a silicon atom-bonded hydrogen atom. Examples of the fluoroalkyl groups include the same as those described above, and 3, 3, 4, 4, 5, 5, 5-heptafluoropentyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 7-undecafluoroheptyl groups, and 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl groups are preferable. Examples of silicon atom-bonded groups other than the fluoroalkyl groups include alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, and aralkyl groups having from 7 to 12 carbon atoms, examples of which are the same as those described above, and methyl groups are preferable. Note that the content of fluorine atoms associated with the fluoroalkyl groups in a molecule is preferably at least 20 mass%, alternatively at least 25 mass%, or alternatively at least 30 mass%. This is because when the content of fluorine atoms in component (C) is greater than or equal to the lower limit described above, a release coating obtained by crosslinking the present composition exhibits a good release force with respect to a silicone pressure-sensitive adhesive. Note that the upper limit of the content of fluorine atoms in component (C) is not particularly limited, however, when the content is too high, component (C) itself tends to not dissolve in the solvent, which diminishes the handleability, and the content therefore is preferably at most 60 mass%, alternatively at most 50 mass%. Note that a small amount of hydroxyl groups or alkoxy groups having from 1 to 3 carbon atoms may be bonded to the silicon atoms in component (C) within a range that does not diminish the object of the present invention.
Component (C) is preferably an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 3 3SiO 1/2 and a D siloxane unit represented by the general formula: R 3 2SiO 2/2.
In the formula, R 3 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, examples of which are the same as those described above. Note that, in a molecule, at least one R 3 is the fluoroalkyl group.
The organopolysiloxane for component (C) may contain small amount of other siloxane units such as a M siloxane unit represented by the general formula: (X) R 3 2SiO 1/2 within a range that does not diminish the object of the present invention. In the formula, X is a hydroxyl group or an alkoxy group having from 1 to 3 carbon atoms.
A viscosity of component (C) at 25℃ is not limited, but in various embodiments is in a range of from about 1,000 mPa·sto about 100,000 mPa·s, alternatively in the range of from about 2,000 mPa·sto about 100,000 mPa·s, alternatively in the range of from about 3,000 mPa·sto about 100,000 mPa·s. This is because when the viscosity of component (C) is greater than or equal to the lower limit of the range described above, the characteristics of the resulting release coating are sufficiently, while when the viscosity is less than or equal to the upper limit of the range described above, the resulting composition has a suitable viscosity in processing and handling. Note that in the present specification, viscosity is the value measured using a type B viscometer according to ASTM D 1084 at 23 ± 2 ℃.
A content of component (A) is in a range of from about 40 to about 90.5 mass%, a content of component (B) is in a range of from about 9 to about 56 mass%, and a content of component (C) is in a range of from about 0.5 to about 4 mass%, pereferably the content of component (A) is in a range of from about 40 to about 85.5  mass%, the content of component (B) is in a range of from about 14 to about 56 mass%, and the content of component (C) is in a range of from about 0.5 to about 4 mass%, alternatively the content of component (A) is in a range of from about 40 to about 80.5 mass%, the content of component (B) is in a range of from about 19 to about 56 mass%, and the content of component (C) is in a range of from about 0.5 to about 4 mass%, each based on a total mass of components (A) to (C) . This is because when the content of component (A) is greater than or equal to the lower limit of the range described above, the release force of the resulting release coating tends to be stable, while when the content is less than or equal to the upper limit of the range described above, comparativity of component (A) tends to be enhanced. On the other hand, when the content of component (B) is greater than or equal to the lower limit of the range described above, the release force of the resulting release coating tends to be good in wet coating and aged release force tends to be stable, while when the content is less than or equal to the upper limit of the range described above, comparativity of component (B) tends to be enhanced. On the other hand, when the content of component (C) is greater than or equal to the lower limit of the range described above, the release force of the resulting release coating tends to be reduced, while when the content is less than or equal to the upper limit of the range described above, the release force of the resulting release coating tends to be stable and aged release force also tends to be stable.
<Component (D) >
Component (D) is an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms per molecule. Examples of groups bonded to silicon atoms in component (D) include alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, and fluoroalkyl groups having from 1 to 12 carbon atoms, examples of which are the same as those described above, among these, methyl groups, 3, 3, 4, 4, 5, 5, 5-heptafluoropentyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl groups, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 7- undecafluoroheptyl groups, and 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-tridecafluorooctyl groups are preferable. Note that the content of fluorine atoms associated with the fluoroalkyl groups in a molecule is not particularly limited but is preferably at least 20 mass%, at least 25 mass%, at least 30 mass%, or at least 35 mass%. This is because when the content of fluorine atoms in component (D) is greater than or equal to the lower limit described above, the compatibility with components (A) to (C) is enhanced, and a release coating obtained by crosslinking the present composition exhibits a good peeling force with respect to a silicone pressure-sensitive adhesive. Note that the upper limit of the content of fluorine atoms in component (D) is not particularly limited, however, when the content is too high, component (D) itself tends to not dissolve in the solvent, which diminishes the handleability, so the content is preferably at most 60 mass%or at most 50 mass%. Note that a small amount of hydroxyl groups or alkoxy groups having from 1 to 3 carbon atoms may be bonded to the silicon atoms in component (D) within a range that does not diminish the object of the present invention.
A molecular structure of component (D) is not limited. Examples thereof include a straight-chain structure, a branched-chain structure, a partially branched straight-chain structure, a resinous structure, and a cyclic structure, and a straight-chain structure or a partially branched straight-chain structure is preferable.
A content of component (D) is in a range of from about 1 to about 15 parts by mass, preferably in a range of from about 1 to about 13 parts by mass, alternatively in a range of from about 2 to about 15 parts by mass, alternatively in a range of from about 3 to about 15 parts by mass, alternatively in a range of from about 2 to about 13 parts by mass, alternatively in a range of from about 3 to about 13 parts by mass, with respect to 100 parts by mass of a total mass of components (A) to (C) . This is because when the content of component (D) is greater than or equal to the lower limit of the range described above, the crosslinking of the present composition progresses sufficiently, while when the  content is less than or equal to the upper limit of the range described above, the characteristics of the resulting release coating are stabilized.
<Component (E) >
Component (E) is a hydrosilylation reaction catalyst for promoting the curing of the present composition. Examples thereof include platinum-based catalysts, rhodium-based catalysts, and palladium-based catalysts, and platinum-based catalysts are preferable. Examples of the platinum-based catalyst include platinum fine powder, platinum black, platinum supporting silica fine powder, platinum supporting activated carbon, chloroplatinic acid, alcohol solutions of chloroplatinic acid, olefin complexes of platinum, and alkenylsiloxane complexes of platinum.
A content of component (E) is an effective amount that promotes the curing of the present composition and is specifically an amount in which the platinum atoms in the catalyst are within a range of from about 0.1 to 1,000 ppm in mass units with respect to the present composition. This is because when the content of component (E) is greater than or equal to the lower limit of the range described above, the curing of the resulting composition progresses, while when the content is less than or equal to the upper limit of the range described above, the resulting cured product becomes less susceptible to discoloration.
<Component (F) >
The present composition may also comprise (F) a hydrosilylation reaction inhibitor in order to control the crosslinking reactions thereof. Examples of component (F) include: alkyne alcohols such as 1-ethynylcyclohexan-1-ol, 2-methyl-3-butyn-2-ol, 3, 5-dimethyl-1-hexyn-3-ol, and 2-phenyl-3-butyn-2-ol; enyne compounds such as 3-methyl-3-penten-1-yne and 3, 5-dimethyl-3-hexen-1-yne; methyl alkenyl siloxane oligomers such as 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetravinylcyclotetrasiloxane and 1, 3, 5, 7-tetramethyl-1, 3, 5, 7-tetrahexenylcyclotetrasiloxane; alkynoxysilanes such as dimethyl bis (3-methyl-1-butyn-3-oxy) silane and methylvinyl bis (3-methyl-1-butyn-3-oxy) silane; alkyneoxysilane  compounds such as methyl tris (1-methyl-1-phenyl-propyneoxy) silane, dimethyl bis (1-methyl-1-phenyl-propyneoxy) silane, methyl tris (1, 1-dimethyl-propyneoxy) silane, dimethyl bis (1, 1-dimethyl-propyneoxy) silane; triazoles, phosphines, mercaptans, hydrazines, sulphoxides, phosphates, nitriles, hydroperoxides, amines, ethylenically unsaturated isocyanates, fumarates (e.g., dialkyl fumarates, dialkenyl fumarates, and/or dialkoxyalkyl fumarates) , maleates (e.g., diallyl maleates) , alkenes, and combinations thereof.
A content of component (F) is not limited, and from the perspective of imparting sufficient pot-life to the present composition, the content is preferably in a range of from about 0.01 to about 5 parts by mass, alternatively in a range of from about 0.05 to about 5 parts by mass, or alternatively in a range of from about 0.05 to about 3 parts by mass, with respect to 100 parts by mass of a total mass of components (A) to (C) . This is because when the content of component (F) is greater than or equal to the lower limit of the range described above, the pot-life of the present composition is sufficiently for use, while when the content is less than or equal to the upper limit of the range described above, the curability of the present composition is good for use.
<Component (G) >
In addition, the present composition may comprise (G) a solvent in order to reduce the viscosity thereof and to improve the application workability or wettability. Examples of component (G) include: hydrocarbon-based solvents such as aromatic hydrocarbon-based solvents such as toluene and xylene, aliphatic hydrocarbon-based solvents such as hexane, heptane, octane, isooctane, decane, cyclohexane, methylcyclohexane, and isoparaffin, industrial gasoline (rubber solvents or the like) , petroleum benzene, and solvent naphtha; ketone-based solvents such as acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, methyl isobutyl ketone, diisobutyl ketone, acetonyl acetone, and cyclohexanone; ester-based solvents such as ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate; ether-based solvents such as diethyl ether, dipropyl ether, diisopropyl  ether, dibutyl ether, 1, 2-dimethoxyethane, and 1, 4-dioxane; solvents having ester and ether components such as 2-methoxyethylacetate, 2-ethoxyethylacetate, propylene glycol monoether acetate, and 2-butoxyethylacetate; siloxane-based solvents such as hexamethyl disiloxane, octamethyl trisiloxane, octamethyl cyclotetrasiloxane, decamethyl cyclopentasiloxane, tris (trimethylsiloxy) methylsilane, and tetrakis (trimethylsiloxy) silane; fluorine-based solvents such as trifluorotoluene, hexafluoroxylene, methyl nonafluorobutyl ether, and ethyl nonafluorobutyl ether; and mixed solvents of two or more types thereof.
A content of component (G) is arbitrary and may be adjusted appropriately as necessary, but the content is typically not greater than aout 2,000 parts by mass with respect to 100 parts by mass of a total mass of components (A) to (C) .
The present composition may comprise an antioxidant, a reactive diluent, a leveling agent, a filler, an antistatic agent, an antifoaming agent, a pigment, or the like within a range that does not impair the object of the present invention.
<Release Liner>
Next, the release liner of the present invention will be described in detail.
The release liner can be produced by applying the present composition to a substrate and curing the composition.
Examples of the substrate may include a paper, a plastic film, a glass, and a metal film. Examples of paper include high-quality paper, coated paper, art paper, glassine paper, polyethylene laminate paper, and craft paper. Examples of plastic films include polyethylene films, polypropylene films, polyester films, polyimide films, polyvinyl chloride films, polyvinylidene chloride films, polyvinyl alcohol films, polycarbonate films, polytetrafluoroethylene films, polystyrene films, ethylene-vinyl acetate copolymer films, ethylene-vinyl alcohol copolymer films, triacetyl cellulose films, polyether ether ketone films, and polyphenylene sulfide films. The glass is not particularly limited in terms of thickness, type, or the like, and may be subjected to chemical reinforcement treatment or the like. In addition, glass fibers may also be applied, and glass fibers may be used alone  or in combination with another resin. Examples of metals include aluminum foil, copper foil, gold foil, silver foil, and nickel foil. When used as a release film, a polyester film is preferable.
A method of applying the present composition to a substrate is not limited, and a known coating method may be used. Examples of the coating method include a wire bar, a comma coater, a lip cpater, a roll coater, a die coater, a knife coater, a blade coater, a rod coater, a kiss coater, a gravure coater, screen coating, immersion coating, and cast coating.
An amount of the present composition applied to the substrate is also not limited and is preferably within a range of from about 0.1 to about 2 g/m 2 or within a range of from about 0.2 to about 1.8 g/m 2 in terms of solid content. Curing conditions are also not limited, however, the composition is preferably heated for about 10 to about 180 seconds or about 15 to about 150 seconds within a range of from about 80 to about 180 ℃ or within a range of from about 90 to about 160 ℃.
A silicone pressure-sensitive adhesive may be applied to the release liner produced in this way. A commercially available composition may be used as the silicone pressure-sensitive adhesive composition.
A method of applying the silicone pressure-sensitive adhesive composition may be a known coating method, examples of which include a comma coater, a lip coater, a roll coater, a die coater, a knife coater, a blade coater, a rod coater, a kiss coater, a gravure coater, screen coating, immersion coating, and cast coating.
An amount of the silicone pressure-sensitive adhesive that is applied may be an amount such that a thickness after curing is from about 0.1 to about 300 μm and is preferably an amount such that a thickness after curing is from about 0.5 to about 200 μm. In addition, in a measurement of the peeling force described above, curing conditions of the silicone pressure-sensitive adhesive composition may be from about 10 seconds to about 10 minutes at about 80 to about 150 ℃.
Examples
The fluorosilicone release coating composition and the release liner of the present invention will be described in further detail hereinafter using Practical and Comparative Examples. However, the present invention is not limited to the Examples that follow. Note that in the formulas, Me, Vi, P f1, and P f2 are respectively a methyl group, a vinyl group, a 3, 3, 4, 4, 5, 5, 6, 6, 6-nonafluorohexyl group, and a 3, 3, 3-trifluoroproplyl group. Viscosity of the organopolysiloxane was measured as follows.
<Viscosity>
Viscosity at 23 ± 2 ℃ was measured by using a type B viscometer (Brookfield HA or HB Type Rotational Viscometer with using Spindle #52 at 5 rpm) according to ASTM D 1084 “Standard Test Methods for Viscosity of Adhesive. ”
<Practical Example 1 and Comparative Examples 1-3>
Fluorosilicone release coating composition shown in Table 1 were prepared using the components mentioned below. Firstly, components (A) , (B) , (C) and (F) were mixed homogeneously, and a suitable solvent, e.g., isopropyl ether, heptane, fluorinated solvent, or a mixture thereof as component (G) was loaded to adjust a non-volatile content. Next, components (D) and (E) were added to produce fluorosilicone release coating compositions. Note each non-volatile content of the fluorosilicone release coating compositions was adjusted to 9 mass%. The compositions were coated on PET substrates by a coater, and then cured under 140 ℃ for 30 seconds. The performances of the compositions were also shown in Table 2.
The following components were used as component (A) . component (a-1) : a mixture of an organopolysiloxane composed of Me 2SiO 2/2, M eR f1SiO 2/2, ViMeSiO 2/2 and ViMe 2SiO 1/2 unites, and having a vinyl group conte nt of 0.16 mass%and a fluoro atom content of 42.1 mass%component (a-2) : an organopolysiloxane composed of Me 2SiO 2/2, MeR f1SiO 2/2, V iMeSiO 2/2 and Me 3SiO 1/2 unites, and having a vinyl group content of 0.20 mass  %and a fluoro atom content of 41.9 mass%
The following component was used as component (B) .
component (b-1) : an organopolysiloxane composed of SiO 4/2, Me 2SiO 2/2, MeR f2SiO 2/2, Me 3SiO 1/2, and ViMe 2SiO 1/2 units, and having a viscosity of about 500 mPa·s, a vinyl group content of 0.44 mass%, a fluoro atom content of 26 mass%
The following component was used as component (C) .
component (c-1) : an organopolysiloxane composed of Me 2SiO 2/2, MeR f1SiO 2/2. an d Me 3SiO 1/2, and having a viscosity of 66,000 mPa·sand a fluoro atom content o f 32.4 mass%
The following component was used as component (D) .
component (d-1) : an oragnohydrogenpolysiloxane composed of MeHSiO 2/2, MeR f1SiO 2/2. and Me 3SiO 1/2, and having a viscosity of 66,000 mPa·s, a fluoro atom content of 38 mass%and silicon atom-bonded hydrogen atom content of 0.50 mass%
The following component was used as component (E) .
component (e-1) : 1.5 mass%of Pt-1, 3-divinyl-1, 1, 3, 3-tetramethyldisiloxane complex in dimethyvinylsiloxy-terminated dimethylpolysiloxane having a viscosity of 450 mPa·s
The following components were used as component (F) .
component (f-1) : 3-methyl-1-butyn-2-ol
component (f-2) : diallyl maleate
<Table 1>
Figure PCTCN2021093762-appb-000001
Figure PCTCN2021093762-appb-000002
<Si-PSAs>
The following silicone presure-sensitive adhesives were used to evaluate the fluorosilicone release coating compositions of Practical and Comparative Examples.
Si-PSA 1: a silicone pressure-sensitive adheseive having a glass transition temperature of -11 ℃.
Si-PSA 2: a silicone pressure-sensitive adheseive having a glass transition temperature of -18 ℃.
Si-PSA 3: a silicone pressure-sensitive adheseive having a glass transition temperature of 30 ℃.
<Measurement of release force (a) >
Dry laminate: laminate cured Si-PSA1 or Si-PSA2 tapes on coated release coating, load weight of 20 g/cm 2 on laminated sample and left under room temperature (RT) or 70 ℃ for 20 hrs. or 3 days. After 20 hrs. or 3 days, remove the load and wait for 30 mins. Then test the release force with liner side by ChemInstruments AR-1500. Refer to FINAT Test Method No. 10 (FINAT Technical Handbook 7 th edition, 2005) .
<Measurement of release force (b) >
Wet coating: the Si-PSA was directly coating on coated release liner and cured and laminate a blank PET on PSA surface and then cut with 1 inch width. Load weight of 20 g/cm 2 on laminated sample and left under RT or 70 ℃ for 20 hrs. or 3 days. After 20 hrs. or 3 days, remove the load and wait for 30 mins. Then test the release force with liner side by ChemInstruments AR-1500. Refer to FINAT Test Method No. 10 (FINAT Technical Handbook 7 th edition, 2005) .
<Table 2>
Figure PCTCN2021093762-appb-000003
Industrial Applicability
The fluorosilicone release coating composition of the present invention can form a release coating exhibiting a low release force with respect to Si-PSAs having a low glass transition temperature, so the composition is effective as F-Si release coating composition for producing a release liner for Si-PSAs for the OCA protection.

Claims (12)

  1. A fluorosilicone release coating composition comprising:
    (A) a linear organopolysiloxane having at least two alkenyl groups and at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom;
    (B) a branched organopolysiloxane having at least one fluoroalkyl group per molecule, and not having a silicon atom-bonded hydrogen atom;
    (C) a linear organopolysiloxane having at least one fluoroalkyl group per molecule, and having neither an aliphatic unsaturated group nor a silicon atom-bonded hydrogen atom;
    (D) an organohydrogenpolysiloxane having at least two silicon atom-bonded hydrogen atoms and at least one fluoroalkyl group per molecule; and
    (E) an effective amount of a hydrosilylation reaction catalyst,
    wherein a content of component (A) is in a range of from about 40 to about 90.5 mass%, a content of component (B) is in a range of from about 9 to about 56 mass%, and a content of component (C) is in a range of from about 0.5 to about 4 mass%, each based on a total mass of components (A) to (C) ; and a content of component (D) is in a range of from about 1 to about 15 parts by mass with respect to 100 parts by mass of a total mass of components (A) to (C) .
  2. The fluorosilicone release coating composition according to claim 1, wherein component (A) has the fluoroalkyl groups in an amount such that a content of fluorine atoms associated with the fluoroalkyl groups in a molecule is at least 30 mass%.
  3. The fluorosilicone release coating composition according to claim 1, wherein component (A) is an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 1 3SiO 1/2 and a D siloxane unit represented by the  general formula: R 1 2SiO 2/2, wherein R 1 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least two R 1 are the alkenyl groups and at least one R 1 is the fluoroalkyl group.
  4. The fluorosilicone release coating composition according to claim 1, wherein component (B) has the fluoroalkyl groups in an amount such that a content of fluorine atoms associated with the fluoroalkyl groups in a molecule is at least 15 mass%.
  5. The fluorosilicone release coating composition according to claim 1, wherein component (B) is an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 2 3SiO 1/2, a D siloxane unit represented by the general formula: R 2 2SiO 2/2 and a Q siloxane unit represented by the formula: SiO 4/2, wherein R 2 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, alkenyl groups having from 2 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least one R 2 is the fluoroalkyl group.
  6. The fluorosilicone release coating composition according to claim 1, wherein component (C) has the fluoroalkyl groups in an amount such that a content of fluorine atoms associated with the fluoroalkyl groups in a molecule is at least 20 mass%.
  7. The fluorosilicone release coating composition according to claim 1, wherein component (C) is an organopolysiloxane consisting essentially of a M siloxane unit represented by the general formula: R 3 3SiO 1/2 and a D siloxane unit represented by the general formula: R 3 2SiO 2/2, wherein R 3 are the same or different, and are alkyl groups having from 1 to 12 carbon atoms, aryl groups having from 6 to 12 carbon atoms, aralkyl groups having from 7 to 12 carbon atoms, or fluoroalkyl groups having from 1 to 12 carbon atoms, providing that, in a molecule, at least one R 3 is the fluoroalkyl group.
  8. The fluorosilicone release coating composition according to claim 1, further comprising: (F) a hydrosilylation reaction inhibitor, in an amount of from about 0.01 to about 5 parts by mass with respect to 100 parts by mass of a total mass of components (A) to (C) .
  9. The fluorosilicone release coating composition according to claim 1, further comprising: (G) an arbitrary amount of a solvent.
  10. The fluorosilicone release coating composition according to claim 1 used for a silicone pressure sensitive adhesive.
  11. A release liner obtained by coating a substrate with the fluorosilicone release coating composition according to any one of claims 1 to 9.
  12. The release liner according to claim 11, wherein the substrate is a plastic film.
PCT/CN2021/093762 2021-05-14 2021-05-14 Fluorosilicone release coating composition and release liner Ceased WO2022236796A1 (en)

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JP2023567182A JP7741201B2 (en) 2021-05-14 2021-05-14 Fluorosilicone release coating composition and release liner
EP21941367.1A EP4337727A4 (en) 2021-05-14 2021-05-14 FLUOROSILICONE-BASED NON-STICK COATING COMPOSITION AND NON-STICK PROTECTIVE LAYER
KR1020237042310A KR20240008331A (en) 2021-05-14 2021-05-14 Fluorosilicone release coating composition and release liner
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CN117178026A (en) 2023-12-05
US20240034916A1 (en) 2024-02-01
KR20240008331A (en) 2024-01-18

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