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WO2025029496A1 - Compositions de siloxane durcissables par rayonnement et leurs procédés de préparation et d'utilisation - Google Patents

Compositions de siloxane durcissables par rayonnement et leurs procédés de préparation et d'utilisation Download PDF

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Publication number
WO2025029496A1
WO2025029496A1 PCT/US2024/038634 US2024038634W WO2025029496A1 WO 2025029496 A1 WO2025029496 A1 WO 2025029496A1 US 2024038634 W US2024038634 W US 2024038634W WO 2025029496 A1 WO2025029496 A1 WO 2025029496A1
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starting material
composition
alternatively
weight
group
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Inventor
Elena MONTOTO-BLANCO
Vikram PRASAD
Christopher Tucker
Dongchan Ahn
Shane MANGOLD
Myoungbae LEE
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Dow Global Technologies LLC
Dow Silicones Corp
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Dow Global Technologies LLC
Dow Silicones Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • 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
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

  • This invention relates to a radiation curable composition including an ethylenically unsaturated polydiorganosiloxane, a siloxane - urethane/urea copolymer, and a reactive diluent.
  • the composition can be cured to form a transparent coating.
  • Polyurethanes possess high cohesive strength and interfacial interactions leading to superior adhesion as well as toughening mechanisms, but typically suffer from high viscosities in absence of solvents.
  • Polyorganosiloxanes possess weatherability, optical clarity, excellent wetting and flowability as well as a wide thermal range of use. Combinations of polyorganosiloxanes and polyurethanes are desirable to provide complimentary properties for use in products such as adhesives and coatings.
  • urethanes and polyorganosiloxanes may suffer from the drawback of being immiscible with each other.
  • solvents can be used to improve the processability of urethane-containing polyorganosiloxanes, it is desirable to reduce the use of solvents, which are classified as volatile organic compounds (VOCs) for sustainability purposes.
  • VOCs volatile organic compounds
  • a base siloxane composition comprises an ethylenically unsaturated polydiorganosiloxane, a radical curable siloxane - urethane/urea copolymer, and a reactive diluent.
  • a crosslinker and a photoinitiator can be combined therewith to form a radiation curable siloxane composition.
  • the radiation curable siloxane composition is useful for forming a transparent cured film, which may be useful as a conformal coating.
  • the base siloxane composition introduced above comprises starting materials (A), (B), and (C), where starting material (A) is the ethylenically unsaturated polydiorganosiloxane, starting material (B) is the radical curable siloxane - urethane/urea copolymer, and starting material (C) is the reactive diluent, which is distinct from starting materials (A) and (B). Additional starting materials, i.e., (D) a crosslinker and (E) a photoinitiator can be combined with the base composition to form a radiation curable siloxane composition comprising starting materials (A), (B), (C), (D), and (E).
  • starting material (A) is the ethylenically unsaturated polydiorganosiloxane
  • starting material (B) is the radical curable siloxane - urethane/urea copolymer
  • starting material (C) is the reactive diluent, which is distinct from starting
  • the base siloxane composition comprising (A), (B), and (C); and/or the radiation curable siloxane composition, may further comprise one or more additional starting materials.
  • the additional starting material may be selected from the group consisting of: (F) a filler, (G) a stabilizer, (H) a UV absorber, (I) an adhesion promoter, (J) an alkenyl functional polyorganosiloxane resin, and a combination of two or more thereof.
  • Starting material (A) in the composition introduced above is an ethylenically unsaturated polydiorganosiloxane.
  • subscript a may be 0 and subscript b may be 2.
  • the quantity (c + d) may be at least 10, alternatively at least 25, alternatively at least 50, alternatively at least 75, alternatively at least 100, and alternatively at least 125; while at the same time the quantity (c + d) may be up to 1,000, alternatively up to 750, alternatively up to 500, alternatively up to 260, alternatively up to 250, alternatively up to 200, and alternatively up to 180.
  • subscript d may be 0 and subscript c may be 10 to 1,000.
  • Suitable monovalent hydrocarbyl groups for R 4 are exemplified by alkyl groups and aryl groups.
  • Suitable alkyl groups for R 4 may be linear, branched, cyclic, or combinations of two or more thereof.
  • the alkyl groups are exemplified by methyl, ethyl, propyl (including n- propyl and/or isopropyl), butyl (including n-butyl, tert-butyl, sec -butyl, and/or isobutyl); pentyl, hexyl, heptyl, octyl, decyl, dodecyl, undecyl, and octadecyl (and branched isomers having 5 to 18 carbon atoms), and the alkyl groups are further exemplified by cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclo
  • the alkyl group for R 4 may be selected from the group consisting of methyl, ethyl, propyl and butyl; alternatively methyl, ethyl, and propyl; alternatively methyl and ethyl.
  • the alkyl group for R 4 may be methyl.
  • each R 4 may be methyl.
  • Suitable aryl groups for R 4 may be monocyclic or polycyclic and may have pendant hydrocarbyl groups.
  • the aryl groups for R 4 include phenyl, tolyl, xylyl, naphthyl, benzyl, 1-phenylethyl and 2-phenylethyl.
  • the aryl group for R 4 may be monocyclic, such as phenyl, tolyl, or benzyl; alternatively the aryl group for R 4 may be phenyl.
  • each R 4 may be independently selected from methyl and phenyl.
  • Each R 5 is an independently selected ethyl enically unsaturated group of 2 to 12 carbon atoms, such as alkenyl or alkynyl. Alternatively, each R 5 may be an independently selected alkenyl group.
  • the alkenyl group for R 5 may have terminal alkenyl functionality, e.g. , R 5 may
  • each R 5 may be independently selected from the group consisting of vinyl, allyl, and hexenyl. Alternatively, each R 5 may be independently selected from the group consisting of vinyl and allyl. Alternatively, each R 5 may be independently selected from the group consisting of vinyl and hexenyl. Alternatively, each R 5 may be vinyl.
  • the ethylenically unsaturated polydiorganosiloxane may comprise formula (A2): subscript c are as described above.
  • each R 4 may be alkyl, alternatively methyl; and each R 5 may be independently selected from the group consisting of vinyl, allyl, and hexenyl, alternatively vinyl.
  • subscript c may be at least 10, alternatively at least 25, alternatively at least 50, alternatively at least 75, alternatively at least 100, and alternatively at least 125; while at the same time subscript c may be up to 1,000, alternatively up to 750, alternatively up to 500, alternatively up to 260, alternatively up to 250, alternatively up to 200, and alternatively up to 180.
  • subscript d may be 0 and subscript c may be 10 to 1,000.
  • Starting material (A) may comprise an alkenyl-functional polydiorganosiloxane such as i) bis-dimethylvinylsiloxy-terminated polydimethylsiloxane, ii) bis-dimethylvinylsiloxy- terminated poly(dimethylsiloxane/methylvinylsiloxane), iii) bis-dimethylvinylsiloxy-terminated polymethylvinylsiloxane, iv) bis-trimethylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane), v) bis-trimethylsiloxy-terminated polymethylvinylsiloxane, vi) bis-dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylphenylsiloxane/methylvinylsiloxane), vii) bis- dimethylvinylsiloxy-terminated poly(dimethylsimethylsi
  • Methods of preparing the ethylenically unsaturated polydiorganosiloxanes described above for starting material (A), such as hydrolysis and condensation of the corresponding organohalosilanes and oligomers or equilibration of cyclic polydiorganosiloxanes, are known in the art, see for example U.S. Patents 3,284,406; 4,772,515; 5,169,920; 5,317,072; and 6,956,087, which disclose preparing polydiorganosiloxanes with alkenyl groups.
  • Examples of polydiorganosiloxanes having alkenyl groups are commercially available from, e.g., Gelest Inc.
  • Starting material (B) is a radical curable siloxane - urethane/urea copolymer.
  • This radical curable siloxane - urethane/urea copolymer may comprise formula (Bl): is an independently selected ethylenically unsaturated monovalent hydrocarbyl group, each R 6 is independently selected from H or R 2 , each X is independently selected from O or NH, each D 1 is a divalent hydrocarbyl group or an oxyhydrocarbyl group, each R 1 is an independently selected monovalent hydrocarbyl group that is free of aliphatic unsaturation, and subscript n > 0.
  • R 1 is as described and exemplified above for R 4 .
  • the ethylenically unsaturated monovalent hydrocarbyl group for R 2 may be an alkenyl group, as described and exemplified above for R 5 .
  • each R 2 may be independently selected from vinyl, allyl or hexenyl; alternatively allyl or hexenyl; and alternatively allyl.
  • R 6 may be R 2 or H.
  • each R 6 may be H.
  • Each X may be O or NH.
  • each X may be O.
  • Each D 1 may be a divalent hydrocarbyl group or an oxyhydrocarbyl group.
  • the divalent hydrocarbyl groups may be alkane-diyls such as ethylene (with empirical formula -C2H4-), propylene (with empirical formula -C3H6-), butylene (with empirical formula -C4H8-), or hexylene (with empirical formula H 2 H 2
  • alkane-diyls may be linear or branched, e.g., D 1 may be
  • D 1 may be an oxyhydrocarbyl group of formula -R 7 -O-R 8 -, where R 7 and R 8 are each independently selected monovalent hydrocarbyl groups, such as those described and exemplified above for R 4 .
  • the oxyhydrocarbyl group for D 1 may be selected from are provided to be exemplary and not limiting.
  • Subscript n has a value > 0.
  • subscript n may be at least 10, alternatively at least 20, alternatively at least 30, alternatively at least 40, alternatively at least 50 and alternatively at least 60, while at the same time, subscript n may have a value up to 150, alternatively up to 110, alternatively up to 100, alternatively up to 90, alternatively up to 80, alternatively up to 70, and alternatively up to 60.
  • each R 6 may be H or allyl
  • each R 2 may be allyl
  • each X may be O
  • each D 1 may be an oxyhydrocarbyl group
  • 20 ⁇ n ⁇ 100 may be an oxyhydrocarbyl group.
  • starting material (B) comprises formula (B2):
  • R 1 and subscript n are as described and exemplified above.
  • each R 2 may be allyl, each X may be O, each D 1 may be an oxyhydrocarbyl group, and 20 ⁇ n ⁇ 100.
  • starting material (B) may comprise a copolymer of formula (B3): where subscript n has a value > 0 and is as described and exemplified above.
  • subscript n may be 50 to 70.
  • the radical curable siloxane - urethane/urea copolymer may be prepared by known methods, such as reaction of a carbinol-functional polyorganosiloxane with an isocyanate compound, e.g., via the reaction described below in Synthesis Example 1 by varying appropriate starting materials.
  • Suitable bis-carbinol-terminated polydimethylsiloxanes are commercially available, e.g., from Gelest, Inc. of Morrisville, Pennsylvania, USA with tradenames DMS-C15, DMS-C16, DMS-C21, and DMS-C23.
  • Suitable isocyanates, such as allyl isocyanate are commercially available from Sigma - Aldrich, Inc. of St. Louis, Missouri, USA.
  • Starting material (C) is a reactive diluent.
  • This reactive diluent comprises, per molecule, at least one radical curable group selected from the group consisting of vinyl, vinyl ether, acrylate, and methacrylate, and this reactive diluent has a solubility parameter 8 ⁇ 19 (MPa) 1/2 when estimated by method of Fedors, described below.
  • the reactive diluent may have a weight average molecular weight (M w ) such that 100 ⁇ M w ⁇ 500.
  • the reactive diluent may have a viscosity ⁇ 1,000 cP.
  • the reactive diluent may be vinyl-functional, e.g., may be a vinyl functional organosilicon compound.
  • the vinyl-functional organosilicon compound may have formula ( 5 are as described above.
  • each R 4 may be an alkyl group, such as methyl.
  • each R 5 may be selected from vinyl, allyl, and hexenyl; alternatively vinyl.
  • the vinyl-functional organosilicon compound of the formula (Cl) is known in the art, e.g., as disclosed in U.S. Patent 6,806,339 to Cray, et al.
  • formula (Cl) is tetrakis(dimethyl(vinyl)silyl) silicate, which is commercially available from Fisher Scientific and TCI America. Tetrakis(dimethyl(vinyl)silyl)silicate has a solubility parameter of 15.1 (MPa) 1/2 measured by the method of Fedors, described below.
  • the reactive diluent may be a vinyl ether-functional compound.
  • the vinyl ether- functional compound may be an alkane substituted with one or two vinyl ether moieties.
  • suitable vinyl ether- functional compounds include 1 ,4-cyclohexanedimethanol di vinyl ether (which has solubility parameter of 17.4), isobutyl vinyl ether (which has solubility parameter of 15.3), dodecyl vinyl ether (which has solubility parameter of 16.6), and a combination of two or more thereof.
  • These vinyl ether-functional compounds are commercially available from various sources, such as Sigma - Aldrich, Inc. of St. Louis, Missouri, USA and TCI America.
  • the reactive diluent may be a (meth)acrylate-functional compound, e.g., an acrylate-functional compound or a methacrylate-functional compound.
  • suitable methacrylate-functional compounds include isobomyl methacrylate (which has solubility parameter of 18.9), lauryl methacrylate (which has solubility parameter of 17.8), 3- methacryloxypropyltrimethoxysilane (which has solubility parameter of 17.7), and a combination of two or more thereof.
  • suitable acrylate-functional compounds include vinyl laurate (which has solubility parameter of 17.8).
  • the base siloxane composition introduced above comprises starting materials (A), (B), and (C); alternatively consists essentially of starting materials (A), (B), and (C); and alternatively consists of starting materials (A), (B), and (C).
  • the base siloxane composition may comprise 35 weight % to ⁇ 50 weight % of starting material (A), 35 weight % to ⁇ 50 weight % of starting material (B) and > 0 to 30 weight % of starting material (C), where combined weights of (A), (B), and (C) total 100 weight %.
  • one or more additional starting materials may be added to the base siloxane composition.
  • the base siloxane composition including (A), (B) and (C) may further comprise an additional starting material, where the additional starting material may be selected from the group consisting of: (F) a filler, (G) a stabilizer, (H) a UV absorber, (I) an adhesion promoter, (J) an alkenyl functional polyorganosiloxane resin, and a combination of two or more thereof.
  • the additional starting material may be selected from the group consisting of: (F) a filler, (G) a stabilizer, (H) a UV absorber, (I) an adhesion promoter, (J) an alkenyl functional polyorganosiloxane resin, and a combination of two or more thereof.
  • the composition including (A), (B), and (C) may be a radiation curable composition further comprising (D) a crosslinker, and (E) a photoinitiator, and optionally an additional starting material that may be selected from the group consisting of: (F) the filler, (G) the stabilizer, (H) the UV absorber, (I) the adhesion promoter, (J) the alkenyl functional polyorganosiloxane resin, and a combination of two or more thereof.
  • Starting material (D) is a crosslinker that may be added to the base siloxane composition described above to form the radiation curable siloxane composition and facilitate cure.
  • Suitable crosslinkers comprise sulfur.
  • suitable poly thiol crosslinkers for use in the present invention include, but are not limited to: glycol dimercaptoacetate (GDMA) (CAS #123-81-9); glycol di(3-mercaptopropionate) (GDMP) (CAS #22504- 50-3); trimethylolpropane tri(3 -mercaptopropionate) (TMPMP) (CAS #33007-83-9); ethoxylated-trimethylolpropane tri(3 - mercaptopropionate) (CAS #345352-19-4); tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate (TEMPIC) (CAS #36196-44-8); pentaerythritol tetramercaptoacetate (PETMA) (
  • crosslinker may be a (mercaptopropyl)methylsiloxane- dimethylsiloxane copolymer.
  • examples of mercaptopropyl terminated polydimethylsiloxane are commercially available e.g., under tradename DMS-SM21 from Gelest, Inc.
  • Starting material (E) is a photoinitiator that may be added to the base siloxane composition described above to form the radiation curable siloxane composition.
  • suitable photoinitiators include 1 -hydroxy cyclohexyl phenyl ketone; 2,2-dimethoxy-2- phenylacetophenone; xanthone; fluorenone; benzaldehyde; fluorene; anthraquinone; triphenylamine; carbazole; 3-methylacetophenone; 4-chlorobenzophenone; 4,4'- dimethoxybenzophenone; 4,4'-diaminobenzophenone; Michler’s ketone; benzoin propyl ether; benzoin ethyl ether; benzyl dimethyl ketal, l-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-l- one; 2-hydroxy-2-methyl-l-phenylpropan-l-one
  • the radiation curable siloxane composition comprises starting materials (A), (B), (C), (D), and (E) described above.
  • the radiation curable siloxane composition may consist essentially of starting materials (A), (B), (C), (D), and
  • the radiation curable composition may consist of (A), (B), (C), (D), and (E). Based on combined weights of starting materials (A), (B), (C), (D), and (E), each starting material may be present in the radiation curable siloxane composition in the following amounts.
  • Starting material (A) the ethylenically unsaturated polydiorganosiloxane may be present in an amount of 30 weight % to 40 weight %.
  • Starting material (B), the radiation curable siloxane - urethane copolymer may be present in an amount of 30 weight % to 40 weight %.
  • Starting material (C) the reactive diluent may be present in an amount of > 0 to 25 weight %, alternatively 1 weight % to 5 weight %.
  • Starting material (D) the crosslinker may be present in an amount of 20 weight % to 35 weight %.
  • starting material (E) the photoinitiator may be present in an amount of > 0 to 2 weight %, alternatively 0.25 weight % to 1.1 weight %.
  • the amounts of starting materials (A), (B), (C), (D), and (E) in the radiation curable siloxane composition may total 100 weight %.
  • the base siloxane composition including starting materials (A), (B), and
  • the additional starting material may be added in an amount that may provide a benefit provided it does not detrimentally impact performance of the composition, e.g., provided the additional starting material does not cause the base siloxane composition including starting materials (A), (B), and (C) to phase separate and/or does not detrimentally impact ability to cure the radiation curable siloxane composition including materials (A), (B), (C), (D), and (E).
  • the type and amount of additional starting material depends on various factors including the type and amount of other starting materials used and the end use of the composition and/or the cured product thereof. However, 0 to 30 weight % of an additional starting material may be added, provided that the combined amounts of starting materials (A), (B), (C), (D), and (E) and the additional starting material total 100 weight %.
  • a filler may be added to the compositions described above, depending on the properties desired in the product to be made (e.g., a conformal coating made by curing the radiation curable siloxane composition).
  • fillers may be solid or liquid, organic or inorganic, and may include reactive and non-reactive siloxanes, and/or acrylonitrile-butadiene rubbers; reactive and non-reactive thermoplastics (including but not limited to: poly(ether imides), maleimide-styrene terpolymers, polyarylates, polysulfones and polyethersulfones) inorganic fillers such as silicates (such as talc, clays, silica, and mica), glass, carbon nanotubes, graphene, and cellulose nanocrystals, including combinations of all of the foregoing.
  • silicates such as talc, clays, silica, and mica
  • a polyorganosiloxane resin may be included as the filler.
  • the polyorganosiloxane resin may comprise monofunctional units (“M” units) of formula R M 3SiOi/2 and tetrafunctional units (“Q” units) of formula SiO4/2, where each R M is an independently selected monovalent hydrocarbyl group.
  • Suitable monovalent hydrocarbyl groups for R M may have 1 to 20 carbon atoms, alternatively 1 to 12 carbon atoms, alternatively 1 to 8 carbon atoms, alternatively 1 to 4 carbon atoms, and alternatively 1 to 2 carbon atoms.
  • the hydrocarbyl groups for R M may be selected from the group consisting of alkyl groups and aryl groups; alternatively alkyl.
  • the alkyl groups are exemplified by methyl, ethyl, propyl e.g. , isopropyl and/or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl, and/or sec-butyl), pentyl (e.g., isopentyl, neopentyl, and/or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as branched saturated monovalent hydrocarbyl groups of 6 or more carbon atoms including cycloalkyl groups such as cyclopentyl and cyclohexyl.
  • the aryl groups are exemplified by cyclopentadienyl, phenyl, tolyl, xylyl, anthracenyl, benzyl, 1 -phenylethyl, 2-phenylethyl, and naphthyl.
  • Monocyclic aryl groups may have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, and alternatively 5 to 6 carbon atoms.
  • Polycyclic aryl groups may have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, and alternatively 12 to 14 carbon atoms.
  • each R M may be selected from methyl and phenyl.
  • the M units may be exemplified by (Me3SiOi/2) and (Me2PhSiOi/2).
  • the resin is soluble in solvents exemplified by liquid hydrocarbons, such as benzene, toluene, xylene, ethyl benzene, heptane, and combinations of two or more thereof; or in liquid organosilicon compounds such as low viscosity linear and cyclic polydiorganosiloxanes.
  • the polyorganosiloxane resin may comprise the M and Q units described above, and further comprises units with silanol (silicon bonded hydroxyl) groups and may comprise neopentamer of formula Si(OSiR M 3)4, where R M is as described above.
  • Si 29 Nuclear Magnetic Resonance (NMR) spectroscopy as described in U.S. Patent 9,593,209 at col.
  • Reference Example 2 may be used to measure molar ratio of M and Q units, where said ratio is expressed as ⁇ M(resin)+(M(neopentamer) ⁇ / ⁇ Q(resin)-i-Q(neopentamer) ⁇ and represents the molar ratio of the total number of triorganosiloxy groups (M units) of the resinous and neopentamer portions of the resin to the total number of silicate groups (Q units) in the resinous and neopen tamer portions.
  • the Mn of the above described resin depends on various factors including the types of hydrocarbyl groups represented by R M that are present.
  • the Mn of the resin refers to the number average molecular weight measured using GPC according to the procedure in U.S. Patent 9,593,209 at col. 31, Reference Example 1, when the peak representing the neopentamer is excluded from the measurement.
  • the Mn of the resin may be greater than 3,000 g/mol, alternatively > 3,000 g/mol to 8,000 g/mol. Alternatively, Mn of the resin may be 4,500 g/mol to 7,500 g/mol.
  • U.S. Patent 8,580,073 at col. 3, line 5 to col. 4, line 31, is hereby incorporated by reference for disclosing silicone resins, which are suitable resins for use herein.
  • the resin can be prepared by any suitable method, such as cohydrolysis of the corresponding silanes or by silica hydrosol capping methods.
  • the resin may be prepared by silica hydrosol capping processes such as those disclosed in U.S. Patent 2,676,182 to Daudt, et al.; U.S. Patent 4,611,042 to Rivers-Farrell et al.; and U.S. Patent 4,774,310 to Butler, et al. The method of Daudt, et al.
  • a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or mixtures thereof, and recovering a copolymer having M-units and Q-units.
  • a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or mixtures thereof
  • the resin may optionally further comprise difunctional units D of formula (R M 2SiO2/2) and/or trifunctional T units of formula (R M SiO3/2).
  • the filler may comprise a polyorganosiloxane resin, such as an MQ resin and/or a T resin, optionally further comprising D units (e.g., the polyorganosiloxane resin may be an MDQ, DT, MDT, or MDTQ resin).
  • Suitable resins for use as fillers in the compositions described herein are known in the art and are commercially available from The Dow Chemical Company of Midland, Michigan, USA, and are exemplified by solvent based resins such as DOWSILTM RSN-0409 HR, RSN-0431, RSN-0804, RSN-0805, RSN-0806, RSN-0808, and RSN-0840; Flake resins such as RSN-0217, RSN-0220, RSN-0233, RSN-0249, RSN-0255, and RSN-6018. Alkoxy-functional resins include DOWSIL US-CF-2403, 2405, 3037, 3074, and 5314.
  • the radiation curable siloxane composition may optionally comprise a stabilizer.
  • a viable free radical scavenger may be present to prevent premature gelation, either in storage or preparation for use, e.g. such as before coating on a substrate.
  • Stabilizers comprising phenolic compounds are one class of such materials that may be used herein, including, for example, 4-methoxyphenol (MEHQ, methyl ether of hydroquinone), hydroquinone, 2- methylhydroquinone, 2-t-butylhydroquinone, t-butyl catechol, butylated hydroxy toluene, and butylated hydroxy anisole, and combinations thereof.
  • Other stabilizers that may be used include potassium hydroxide, phenothiazine and anaerobic inhibitors, such as the NPAL type inhibitors (tris-(N-nitroso-N-phenylhydroxylamine) aluminum salt) from Albemarle Corporation, Baton Rouge, La.
  • Starting material (H) is an optional UV absorber, which may be a dye or pigment, that may be added to the compositions described above.
  • a non-reactive dye or pigment that absorbs light, particularly UV light may be used.
  • Suitable examples of such UV absorbers include, but are not limited to: (i) titanium dioxide (e.g., included in an amount of 0.05 weight % to 1 weight %, alternatively 0.1 weight % to 1 weight %, based on combined weights of all starting materials in the composition, and/or (ii) an organic ultraviolet light absorber such as a hydroxybenzophenone, hydroxyphenyl - benzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, and/or benzotriazole ultraviolet light absorber (e.g., Mayzo BLSTM 1326).
  • the organic ultraviolet light absorber may be present in an amount of 0.001 weight % to 4 weight %, alternatively 0.005 weight
  • the resin described above for use as a filler may alternatively have terminal aliphatically unsaturated groups (e.g., alkenyl groups as described above for R 5 ), which allow the resin to react with starting material (A) and/or (B).
  • terminal aliphatically unsaturated groups e.g., alkenyl groups as described above for R 5
  • a polyorganosiloxane resin e.g., an MQ resin having terminal aliphatically unsaturated groups (e.g., an alkenyl-functional MQ resin) may act as a co-compatibilizer or matrix component in the compositions described above.
  • An MQ resin having terminal aliphatically unsaturated groups may be prepared by reacting the product of Daudt, et al.
  • endblocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblocking agents are known in the art and exemplified in U.S. Patents 4,584,355; 4,591,622; and 4,585,836. A single endblocking agent or a mixture of such agents may be used to prepare such resin.
  • Suitable adhesion promoters for starting material (J) include silane coupling agents such as alkyltrialkoxysilanes such methyltrimethoxysilane and/or methyl triethoxysilane; alkenyltrialkoxysilanes such as vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, and combinations thereof; (meth)acryloxy-functional trialkoxysilanes such as 3-methacryloxypropyltrimethoxysilane and/or 3-methacryloxypropyl triethoxysilane; amino-functional trialkoxysilanes such as 3-aminopropyltrimethoxysilane, 3- aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, and combinations thereof; mercapto-functional silane coupling agents such as alkylt
  • the adhesion promoter may comprise a tetraalkoxysilane such as tetramethoxysilane and/or tetraethoxysilane; and/or a dialkoxy silane such as dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane; or other trialkoxysilane such as phenyltrimethoxysilane.
  • tetraalkoxysilane such as tetramethoxysilane and/or tetraethoxysilane
  • a dialkoxy silane such as dimethyldimethoxysilane, methylphenyldimethoxysilane, methylphenyldiethoxysilane
  • other trialkoxysilane such as phenyltrimethoxysilane.
  • Exemplary adhesion promoters are known in the art and are commercially available.
  • XIAMETERTM OFS-6020 Silane, XIAMETERTM OFS-6040 Silane, XIAMETERTM OFS-6070 Silane, XIAMETERTM OFS-6062 Silane, and XIAMETERTM OFS-6697 Silane are available from Dow.
  • alkoxysilanes may be useful as crosslinkers and as adhesion promoters.
  • One skilled in the art would be able to select suitable additional starting materials for the compositions which are distinct from starting materials (A), (B), and (C), and when present, starting materials (D) and (E).
  • compositions described above may be prepared by any convenient means using any convenient equipment. No special equipment or conditions are required.
  • the composition may be prepared by mixing starting materials (A), (B), and (C); and, when present, (D) and (E) to make the radiation curable siloxane composition at RT and ambient pressure.
  • starting materials A, (B), and (C)
  • D when present, (D) and (E)
  • one or more of the additional starting materials described above may be added by mixing at RT and ambient pressure.
  • the radiation curable siloxane composition described above may be used to form a cured film, such as a coating, e.g., a conformal coating, a release coating, a pressure sensitive adhesive, and/or a topcoat for a laminate article.
  • the cured film may be transparent.
  • a method for preparing the cured film may comprise forming the radiation curable siloxane composition described above into liquid film and exposing the liquid film to UV radiation, thereby forming the cured film.
  • the liquid film may be formed on a surface of a substrate.
  • the method for forming the cured film may optionally comprise treating the surface of the substrate before forming the liquid film of the radiation curable siloxane composition on the surface. Treating the surface may be performed by any convenient means, such as applying a primer, or subjecting the substrate to corona-discharge treatment, etching, or plasma treatment before applying the radiation curable siloxane composition to the surface so treated.
  • Preparing the liquid film e.g., by applying the radiation curable siloxane composition to the surface of the substrate, can be performed by any convenient means.
  • a circular puck or a drawdown film method may be used.
  • composition may be poured onto a Teflon coated aluminum substrate with a stainless steel circular washer. Drawdowns may be done on substrates of Teflon, aluminum or FR4.
  • the radiation curable siloxane composition may be applied onto a substrate by gravure coater, offset coater, offset-gravure coater, roller coater, and reverse-roller coater.
  • applying the radiation curable siloxane composition to the surface of the substrate may be performed by a printing process such as screen printing, pin transfer, stencil printing, or inkjet printing.
  • a printing process such as screen printing, pin transfer, stencil printing, or inkjet printing.
  • use of the radiation curable siloxane composition described above as an ink in an inkjet printing process is contemplated herein.
  • the liquid film applied on the surface of the substrate by any means described herein may be continuous, i.e., uniformly covering all or a portion of the surface of the substrate, which cures to form a continuous layer on the surface of the substrate.
  • the liquid film may be discontinuous, for example when a printing process, such as inkjet printing, is used for applying the radiation curable siloxane composition in a discontinuous layer on the surface of the substrate.
  • a discontinuous film may be applied, for example, when it is desired to form a pattern on the surface of the substrate.
  • Suitable inkjet printing apparatus are known in the art and commercially available, for example, see the apparatus described in U.S. Patent Application Publication 2019/0292394 to Linton et al. at paragraphs [0052] to [0055].
  • the amount of the radiation curable siloxane composition to be applied to the surface substrate depends on various factors including whether a continuous or discontinuous coating layer is desired on the surface, the desired thickness of the film to be formed, and the specific end use application for the substrate having the cured film on its surface, however, the amount may be sufficient such that thickness of the coating may be > 0 up to 3175 micrometers (0.125 inch), alternatively up to 2540 micrometers, and alternatively up to 1575 micrometers; after cure. Forming a liquid film and curing may be repeated one or more times to increase thickness of the cured film.
  • Exposing the liquid film to UV radiation may be performed by any convenient means using a commercially available ultraviolet irradiation apparatus, for example, a face type or a conveyer belt-type ultraviolet irradiation apparatus, where a lamp such as a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh- pressure mercury lamp, a xenon lamp, a metal halide lamp, an electrodeless lamp, an ultraviolet light-emitting diode, or a D-bulb ultraviolet lamp is used as the radiation source.
  • the exact dose may be selected by one skilled in the art depending on various factors including the thickness of the liquid film.
  • the substrate can be any material that can withstand the conditions (described herein) used to cure the radiation curable siloxane composition to form the cured film on the substrate.
  • any substrate that can withstand exposure to UV radiation, and optionally heat treatment at a temperature equal to or greater than 120 °C, alternatively 150 °C is suitable.
  • materials suitable for such substrates including glasses or plastic films such as polyimide (PI), polyetheretherketone (PEEK), polyethylene naphthalate (PEN), liquid-crystal polyarylate, polyamideimide (PAI), polyether sulfide (PES), polyethylene terephthalate (PET).
  • the substrate may be transparent, alternatively, substrates which are not transparent may be used provided that they allow the liquid film to be exposed to UV radiation.
  • the substrate may be a component or layer of an (opto)electronic device.
  • DMS-C21 from Gelest, Inc. has formula where subscript n has a value sufficient to give the carbinol siloxane the viscosity shown in Table 1, above.
  • component (B-l) the terminal Dp60 Si-PU shown above in Table 1 was synthesized as follows: The carbinol siloxane was dried prior to use (using a rotary evaporator at 100 °C, 10 mbar, for 2 hours). A portion of the carbinol siloxane (41.0 grams, 8.56 mmol) was charged into a 250 mL, 4-necked flask equipped with nitrogen inlet, reflux condenser, stirring shaft, and dual thermometer probe connected to higher temperature cutoff unit.
  • Viscosity of the clear fluid was 156 cP determined using an Anton-Paar Physical MCR 301 rheometer fitted with a 25 mm stainless steel cone-in-plate fixture at a temperature of 25 °C at a shear rate of 10s-l.
  • the product was terminal Dp60 Si-PU of formula:
  • starting material (B-2) Hema chain extended Dp60 Si-PU was prepared as follows: The carbinol siloxane was dried at 90 °C overnight in a vacuum oven (0.1 in Hg) prior to reaction. The carbinol siloxane (70.80 g, 15.3 mmol) and isocyanate IPDI (6.75 g, 30.6 mmol) were charged into a 250 mL 4-necked flask fitted with an overhead mechanical stirrer, nitrogen inlet, dual probe thermocouple, heating mantle, and overhead temperature control shut off. The contents were stirred (-300 rpm) at room temperature for 15 minutes to homogenize.
  • Table 2 shows the results using reactive diluents that have allyl, vinyl or acrylate functionality used with combinations of components (A-l ) and (B-l) at 1 : 1 wt ratio.
  • Sample 3-1 the silicone control was component (A-l) by itself.
  • Sample 3-2 the SiPU control was component (B-l) by itself.
  • Sample 3-3 was a mixture of component (A-l) and component (B-l) in a 1:1 weight ratio, without reactive diluent or other components.
  • Sample 3-4 was component (B-2) by itself.
  • Samples 3-1 to 3-4 were comparative.
  • Samples 3-5 to 3-9 each contained component (A-l) and component (B-l) in a 1:1 weight ratio with a reactive diluent added (selection and amount shown below in Table 3.
  • Sample 3-10 contained a mixture of component (A-l) and component (F-l) in a weight ratio 1:1 with component (B-l), and no reactive diluent.
  • N/A means not applicable.
  • the present invention provides a curable composition that is stable (does not phase separate when tested as described in Reference Example 1, above) and can cure to form a transparent film.
  • the transparent film may have a high Shore M hardness, e.g., higher Shore M hardness than when an unstable system (i.e., composition that phase separates when tested as described in Reference Example 1) is prepared.
  • Samples 3-5, 3-6, and 3-7 each cured to form clear films when 2.5% of a reactive diluent corresponding to starting material (C) of this invention was combined with an equal weight mixture of starting materials (A-l) and (B-l) in Table 1.
  • a reactive diluent corresponding to starting material (C) of this invention was combined with an equal weight mixture of starting materials (A-l) and (B-l) in Table 1.
  • the resulting cured film had lower Shore M hardness, as shown by comparative samples 3-8 and 3-9 when compared to working samples 3-5, 3-6, and 3-7.
  • a radiation curable siloxane composition comprises:
  • each R 2 is an independently selected ethylenically unsaturated monovalent hydrocarbyl group
  • each R 6 is independently selected from H or R 2
  • each X is independently selected from O or NH
  • each D 1 is a divalent hydrocarbyl group or an oxyhydrocarbyl group
  • each R 1 is an independently selected monovalent hydrocarbyl group that is free of aliphatic unsaturation, and subscript n > 0, and
  • starting material (A) the ethylenically unsaturated polydiorganosiloxane is present in an amount of 30 weight % to 40 weight %, based on combined weights of starting materials (A), (B), (C), (D), and (E);
  • starting material (B) the siloxane - urethane copolymer is present in an amount of 30 weight % to 40 weight %, based on combined weights of starting materials (A), (B), (C), (D), and (E);
  • starting material (C) the reactive diluent is present in an amount of > 0 to 25 weight %, alternatively 1 weight % to 5 weight %, based on combined weights of starting materials (A), (B), (C), (D), and (E);
  • starting material (D) the crosslinker is present in an amount of 20 weight % to 35 weight %, based on combined weights of starting materials (A), (B), (C), (D
  • the composition of the first embodiment or the second embodiment further comprises an additional starting material in an amount of > 0 to 30 weight %, where the additional starting material is selected from the group consisting of: (F) a filler, (G) a stabilizer, (H) a UV absorber, (I) an adhesion promoter, (J) an alkenyl functional polyorganosiloxane resin, and a combination of two or more thereof, where combined amounts of all starting materials in the composition total 100 weight %.
  • the additional starting material is selected from the group consisting of: (F) a filler, (G) a stabilizer, (H) a UV absorber, (I) an adhesion promoter, (J) an alkenyl functional polyorganosiloxane resin, and a combination of two or more thereof, where combined amounts of all starting materials in the composition total 100 weight %.
  • starting material (A) comprises formula (where each R 4 is alkyl, each R is independently selected from the group consisting of vinyl, allyl, and hexenyl, and
  • each R 4 is methyl, each R 5 is vinyl, and 10 ⁇ c ⁇ 200.
  • starting material (B) comprises formula (B2): each R 2 is an independently selected ethylenically unsaturated monovalent hydrocarbyl group, each X is independently selected from O or NH, each D 1 is a divalent hydrocarbyl group or oxyhydrocarbyl group, each R 1 is an independently selected monovalent hydrocarbyl group that is free of aliphatic unsaturation, and
  • each R 2 is allyl
  • each X is O
  • each D 1 is an oxyhydrocarbyl group
  • starting material (B) comprises a copolymer of formula: where subscript n is 50 to 70.
  • starting material (C) has a viscosity ⁇ 1,000 cP measured at 25 °C using a Cone/Plate viscometer with Spindle CP-52 at 12 RPM.
  • starting material (C) comprises a vinyl functional compound comprising tetrakis(dimethyl(vinyl)silyl) silicate.
  • starting material (C) is a (meth)acrylate-functional compound selected from the group consisting of isobornyl methacrylate, lauryl methacrylate, vinyl laurate, 3- methacryloxypropyltrimethoxysilane, and a combination of two or more thereof.
  • starting material (C) is a vinyl ether-functional compound selected from the group consisting of 1,4-cyclohexanedimethanol divinyl ether, isobutyl vinyl ether, dodecyl vinyl ether, and a combination of two or more thereof.
  • a method for making a transparent cured film comprises:
  • composition into a liquid film
  • the transparent cured film is a coating.
  • the transparent cured film is a conformal coating.

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Abstract

Selon l'invention, une composition durcissable comprend un polydiorganosiloxane à insaturation éthylénique, un copolymère siloxane-uréthane/urée durcissable par voie radicalaire, un diluant réactif, un agent de réticulation et un photo-initiateur. La composition peut être durcie par exposition à un rayonnement UV. La composition peut être utilisée pour former un film transparent de dureté Shore M ≥ 35.
PCT/US2024/038634 2023-08-01 2024-07-19 Compositions de siloxane durcissables par rayonnement et leurs procédés de préparation et d'utilisation Pending WO2025029496A1 (fr)

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