Photocuring silicone composition, method for forming a silicone film on a substrate and articles comprising said composition

Abstract

PHOTOCURABLE SILICONE COMPOSITIONS AND PROCESS FOR MANUFACTURING RELEASE COATINGS. A photocurable silicone composition, a method for forming a coating from such compositions, and an article comprising a coating formed from such compositions and / or methods are shown and described in this report. The photocurable silicone composition comprises (i) a vinyl functional polysiloxane; (ii) a hydride functional polysiloxane; (iii) a photoactive catalyst; and (iv) an acid anhydride functional polysiloxane. The composition and method can be used to process thin coatings on paper and film substrates, followed by exposure to actinic radiation under ambient temperature and atmosphere conditions for the manufacture of release coatings.

Description

"PHOTOCURABLE SILICONE COMPOSITION, METHOD FOR FORMING A SILICONE FILM ON A SUBSTRATE AND ARTICLES COMPRISING SAID COMPOSITION" CROSS-REFERENCE TO RELATED ORDERS

[001] This application claims priority and benefit of U.S. Provisional Application 62 / 978,488, filed February 19, 2020, entitled “PHOTOCURABLE SILICONE COMPOSITIONS AND PROCESS FOR MANUFACTURE OF RELEASE LINERS”, disclosure of which is incorporated in full in this report by reference. FIELD OF THE INVENTION

[002] The present invention relates to curable silicone compositions, to articles comprising cured coatings formed from the compositions, and to processes for manufacturing such coatings and articles. In particular, the present invention relates to silicone compositions that are photocurable, to processes for forming a coating from such compositions, and to articles comprising such coatings. The compositions and processes are particularly useful for forming release coatings comprising silicone coatings. FUNDAMENTALS

[003] Silicone release coatings composed of vinyl-silicone and hydreto-silicone polymers with low levels of silicone-compatible platinum(II) complexes, such as the Karstedt hydrosilylation catalyst disclosed in US Patent 3,715,334, and platinum inhibitors, such as maleate esters disclosed by Eckberg in US Patent 4,256,870, are known and have been used for some time. Such coatings can be applied to paper or film substrates without the use of solvents and cured by applying heat that evaporates the inhibitor. High-speed curing typically requires Petition 870240108444, dated 12 / 19 / 2024, page 11 / 116 2 / 46 Exposure to temperatures exceeding 150 °C for a period of several seconds can dewet the paper and degrade thermally sensitive films such as polyethylene or polyester. A large amount of energy is spent heating the curing ovens, which are too large to allow for the rapid processing of release coatings.

[004] Silicone polymers containing reactive functional groups, including cycloaliphatic epoxy and acrylate groups, are commercially available materials that crosslink when exposed to focused UV light in the presence of iodonium and free radical photocatalysts. These products are used for the manufacture of release coatings (See, for example, US Patents 4,279,717 and 6,548,568, respectively.) Such polymers, however, require multiple processing steps employing various inputs of organic molecules and are much more expensive than platinum-catalyzed hydrosilylated vinyl and hydride functional silicone polymers. Furthermore, the useful cure rate of acrylate functional silicone coatings requires an inert atmosphere with less than 50 ppm of oxygen present in the UV curing chamber.The reactive polar functionality required to enable these silicones to rapidly photocrosslink interferes with the release of aggressive adhesives, such as common types of acrylic emulsion.

[005] Trialkyl cyclopentadiene platinum (IV) photoactive compounds have been described by Robinson and Shaw, J. Chem Soc 1965, 1529, and by Fritz and Shwarzhaus, J. Organometallic Chem 5, 181 (1966), among others. US Patent 4,600,484 describes the use of various cyclopentadienyl (Cp) trialkyl Pt(IV) compounds [abbreviated CpPtR3] for photoactivated hydrosilylation reactions, including the addition of olefins to functional SiH silane and siloxane monomers, as well as crosslinking reactions between functional SiH polydimethylsiloxane and polysiloxanes to convert their liquid mixtures into Petition 870240108444, dated 12 / 19 / 2024, page 12 / 116 3 / 46 Solid adhesive coatings are useful for the release of pressure-sensitive adhesives. These compositions, however, require relatively high concentrations of the photoactive platinum catalyst (Pt 200 ppm or more) to achieve rapid curing of silicone coatings > 2 microns thick when applied to a polyethylene-coated Kraft paper sheet and then exposed to UV emission from a 200 watt / in² mercury vapor UV lamp.

[006] US Patent 4,916,169 describes the addition of various visible light-absorbing polycyclic aromatic hydrocarbon sensitizers, such as anthracenes, thioxanthones, and anthraquinones, to enable the photopolymerization of CpPtR3-photocatalyzed silicone coatings and thick-section silicone elastomeric compositions, such as dental molds. Boardman describes the long light absorption (several minutes of irradiation) of viscous vinyl and functional SiH polydimethylsiloxane compositions, including high catalyst concentrations (Pt > 300 ppm) to produce thick rubber products. It should be noted that some of the polycyclic sensitizers described in patent '169 are poorly soluble in dimethyl silicone matrices.

[007] US Patent 6,451,869 refers to the use of self-sensitized trimethyl dicyclopentadienyl Pt(IV) photoactivated hydrosilylation catalysts for fast crosslinking of vinylsilicone and hydretosilicone blends after exposure to UV light. These catalysts employ the substitution of aromatic UV-absorbing groups, such as naphthyl and phenantryl, in the Cp ring prior to the synthesis of [Ar-Cp]PtMe3 catalysts. However, Butts reports yields of less than 50% of the final self-sensitized photocatalysts, making these compounds expensive and difficult to produce for commercial purposes.

[008] US Patent 8,088,878 describes the modification of CpPtR3 photoactivated hydrosilylation catalysts by replacing hydrolyzable siloxy substituents, such as -Si(OMe)3, on the cyclopentadiene ring, so as to make the Petition 870240108444, dated 12 / 19 / 2024, p. 13 / 116 4 / 46 non-volatile catalyst and allow it to cure into a silicone elastomeric article produced by UV light irradiation of viscous mixtures of polydimethylsiloxane stopped with silanol, vinylsilicone polymers and functional SiH siloxanes with a condensation cocatalyst such as zinc(acac)2. Irradiation times of 10 seconds followed by long post-curing of up to 2 hours are reported to complete crosslinking and subsequent condensation of the platinum catalyst compound. This processing is not suitable for the commercial production of silicone release coatings. SUMMARY

[009] The following is a summary of this disclosure to provide a basic understanding of some aspects. This summary is not intended to identify key or critical elements or to define any limitations on embodiments or claims. In addition, this summary may provide a simplified overview of some aspects that may be described in more detail elsewhere in this disclosure.

[010] The present invention is generally directed to novel addition-curable silicone formulations that can be processed by applying thin coatings of these formulations onto paper and film substrates, followed by exposure to actinic radiation under ambient or slightly elevated ambient temperature and atmosphere conditions to manufacture release coatings. The formulations comprise vinyl hydride functional polysiloxane polymers (e.g., vinyl hydride functional polydimethylsiloxane polymers), acid anhydride functional polysiloxane additives, and cyclopentadienyl platinum(IV) photoactive catalysts capable of initiating crosslinking hydrosilylation reactions after ultraviolet light absorption. The selection of certain UV lamps and combinations of reflectors and filters significantly improves the photopolymerization performance of these systems. Petition 870240108444, dated 12 / 19 / 2024, page 14 / 116 5 / 46 Additionally, exposing curable compositions to low levels of heat prior to UV light exposure may provide enhanced curing of the composition.

[011] Therefore, it is an object of the present invention to provide a commercially viable means for processing addition-curing silicone release coatings by ultraviolet light irradiation of an addition-curing silicone formulation. The present composition, methods and processes provide photocurable silicone release coatings that do not suffer from the disadvantages of previous methods and systems, including those described above. These and other objectives are achieved by formulating silicone coating compositions comprising a polysiloxane with vinyl functionality, a polysiloxane crosslinking polymer with hydride functionality, a catalytic amount of a platinum(IV) cyclopentadienyl trialkyl photohydrosylation catalyst and a low level of acid anhydride functional polydimethylmethylhydride siloxane anchoring and curing additive.

[012] In one aspect, a cyclopentadienyl trialkyl platinum(IV) catalyst can be used in combination with vinyl functional and hydride functional polysiloxanes (e.g., polydimethylsiloxanes) plus some other polysiloxanes with alkyl-acid anhydride functionality to provide a release coating composition capable of high rapid cure on ordinary supercalendered kraft papers and polycoated kraft papers when applied as 1-2 micron coatings and processed with iron-doped mercury vapor ultraviolet curing lamps or (preferred) combinations of gentle preheating followed by UV exposure.

[013] In one aspect, a photocurable silicone composition is provided comprising: (i) a vinyl functional polysiloxane; (ii) a hydride functional siloxane; Petition 870240108444, dated 12 / 19 / 2024, page 15 / 116 6 / 46 (iii) a photoactive catalyst; and (iv) an acid anhydride functional polysiloxane.

[014] In one embodiment, the vinyl functional polysiloxane has formula (I): M1ViaM2bD1VicD2dT1VieT2fQ1g where M1Vi= (R1)(R2)(CH2=CH)SiO1 / 2 M2= (R3)(R4)(R5SíOi / 2 D1Vi= (R6)(CH2=CH)SiO2 / 2 D2= (R7)(R8)SiO2 / 2 T1Vi= (CH2=CH)SiO3 / 2 T2= (R9)SiO3 / 2 Q1 = SiO4 / 2 where R1, R2, R3, R4, R5, R6, R7, R8 and R9 are independently a saturated hydrocarbon radical C1-C10; 50 < a + b + c + d + e + f + g < 10,000, and a + c + e is greater than 0.

[015] In one embodiment, the vinyl functional polysiloxane has the formula (Ia): M1viD1vicD2dM1vi(Ia) where M1vi is (R1)(R2)(CH2=CH)SiO1 / 2; D1vi is (R6)(CH2=CH))SiO2 / 2; D2 is (R7)(R8)SiO2 / 2; R1, R2, R3, R5, R6, R7 and R8 are independently a saturated hydrocarbon radical C1-C10; c is 0 to 10; ed is 50 to 250.

[016] In one embodiment of the composition, in accordance with any previous embodiment, the hydride functional siloxane has formula (II): M3HhM4iD3HjD4kT3HlT4mQ2n(II) where M3H= (R10)(R11)(H)SíOi / 2 M4= (R12)(R13)(R14)SíOi / 2 D3H= (R15)(H)SiO2 / 2 Petition 870240108444, dated 12 / 19 / 2024, p. 16 / 116 7 / 46 D4= (R16)(R17)SiO2 / 2 T3H= (H)SiO3 / 2 T2= (R18)SiO3 / 2 Q2 = SiO4 / 2 where R10, R11, R12, R13, R14, R15, R16, R17 and R18 are independently a saturated C1-C10 hydrocarbon radical; the subscripts h, i, j, k, l, mn are zero or positive subject to the following limitations: 2 < h + i + j + k + l + m + n < 1,000, and h + j + l is greater than 0.

[017] In one embodiment, the hydride functional siloxane has the formula (IIb): M4D3HjM4(IIb) where M4D3H and M4 are defined above, and j is 10 to 40.

[018] In one embodiment, the hydride functional siloxane is a copolymer of formula (IIa): M4D3HjD4kM4Q2(IIa) where M4D3H, D4, M4, and Q2 are defined above, and j + k is 10 to 40.

[019] In one embodiment of the photocurable composition, according to any of the preceding embodiments, the photoactive catalyst is selected from one or more of a platinum-cyclopentadiene complex of formula (i) R19CpPtR203, wherein R19 and R20 are independently selected from a C1-C10 alkyl group, and Cp is a cyclopentadiene group, in which the link between Cp and Pt is an eta linkage; (ii) [(R29)a(R30)bCp]Pt(R31)3 where R29 is a C7-20 aromatic organic radical, R30 and R31 are independently C1-22 aliphatic organic radicals, Cp is a cyclopentadienyl radical, “a” is an integer from 1 to 3 inclusive, “b” is an integer from 0 to 3 inclusive, and the sum of a + b is from 1 to 4 inclusive; and / or (iii) [(R32)c(R33)dCp]PtR34R35Q, where R32 is a C6-20 aromatic radical, R33, R34 and R35 are independently organic radicals Petition 870240108444, dated 12 / 19 / 2024, p. 17 / 116 8 / 46 aliphatic C1-22, Cp is a cyclopentadienyl radical, Q is a silicon-containing organic sensitizing group, “c” and “d” are independently equal integers from 0 to 5 inclusive, and the sum of “c + d” is equal to 0 to 5 inclusive.

[020] In one embodiment, the photoactive catalyst is a Pt(IV) methylcyclopentadienyltrimethylplatinum compound.

[021] In one embodiment of the photocurable composition, according to any of the preceding embodiments, the acid anhydride functional silicone is a compound of the formula M5AD5oD6ApD7HqM5Where M5Ais (R21)(R22) (R23)SíOi / 2 D5é (R24)(R25)SíO2 / 2, D6Aé (R26)(R27)SíO2 / 2 D7H= (R28)(H)SiO2 / 2 where R21, R22, R24, R25, R26 and R28 are independently a saturated C1-C10 hydrocarbon radical; R23 and R2 independently represent an acid anhydride functional group that can be derived from the reaction of allyl succinic anhydride with Si(H) functionality; o + q is 10 to 40, ep is 1 to 20.

[022] In one embodiment of the photocurable composition, according to any of the previous embodiments, the composition further comprises a siloxanol resin.

[023] In one embodiment of the photocurable composition, according to any of the previous embodiments, wherein the ratio of hydride groups to vinyl groups is from about 0.5:1 to about 10:1.

[024] In one embodiment of the photocurable composition, according to any of the previous embodiments, the ratio of hydride groups to vinyl groups is from about 1.5:1 to about 3:1.

[025] In one embodiment of photocurable composition, according Petition 870240108444, dated 12 / 19 / 2024, p. 18 / 116 9 / 46 with any of the above embodiments, the ratio of hydride groups to vinyl groups is about 2:1 to about 2.5:1.

[026] In one embodiment of the photocurable composition, according to any of the foregoing embodiments, the vinyl functional polysiloxane (i) is present in an amount of about 80 to about 99 parts by weight; the hydride functional polysiloxane (ii) is present in an amount of about 1 to about 20 parts by weight; the acid anhydride functional polysiloxane (iv) is present in an amount of about 0.1 to 10 parts by weight, and the photoactive catalyst (iii) is present in an amount sufficient to provide platinum in an amount of about 50 to about 150 ppm; and each of the parts by weight is based on the total weight of the composition.

[027] In another aspect, a method is provided for forming a silicone film on a substrate comprising: (a) applying the photocurable silicone composition, according to any of the previous embodiments, onto the surface of the substrate; and (b) exposing the photocurable silicone composition to a UV light source with a wavelength of about 25 nm to about 500 nm.

[028] In one embodiment, the UV light source is a UV lamp of the H+ mercury vapor type.

[029] In one embodiment, the UV light source is a type D iron-doped mercury vapor UV lamp.

[030] In one embodiment of the method, according to any of the previous embodiments, the substrate carrying the silicone composition is transported at a speed of about 20 feet per minute to about 1,000 feet per minute.

[031] In one embodiment of the method, according to any of the previous embodiments, the method additionally comprises focusing on Petition 870240108444, dated 12 / 19 / 2024, page 19 / 116 10 / 46 UV light source light onto the composition using one or more reflectors.

[032] In one embodiment of the method, according to any of the previous embodiments, the method further comprises exposing the silicone composition and the substrate to which it is applied to a heat source before exposing the composition to the UV light source.

[033] In one embodiment, the heat source is chosen from an oven, an infrared lamp, an LED light source, or a combination thereof.

[034] In one embodiment, the composition and the substrate to which it is applied are heated to a temperature of about 25 °C to about 120 °C.

[035] In one embodiment of the method, according to any of the previous embodiments, the substrate is selected from one or more of glassine, supercalendered Kraft paper (SCK), clay-coated Kraft paper (CCK), polyethylene, polypropylene, polyester, a polyethylene Kraft paper (PK) or a polypropylene Kraft paper (PPK).

[036] In yet another aspect, an article is provided comprising a coating formed from the photocurable composition, according to any of the previous embodiments, arranged on a substrate surface.

[037] In one embodiment, the article is a release coating and the substrate is selected from one or more of glassine, supercalendered Kraft paper (SCK), clay-coated Kraft paper (CCK), polyethylene, polypropylene, polyester, a polyethylene Kraft paper (PK) or a polypropylene Kraft paper (PPK).

[038] In yet another aspect, an adhesive article is provided comprising a releasable adhesive backing substrate in contact with a release layer, the release layer comprising a coating formed from Petition 870240108444, dated 12 / 19 / 2024, page 20 / 116 11 / 46 of the photocurable composition, according to any of the previous embodiments.

[039] In yet another aspect, an article is provided that is formed from the method, according to any of the previous embodiments.

[040] The following description reveals several illustrative aspects. Some improvements and new aspects can be explicitly identified, while others may be evident from the description. DETAILED DESCRIPTION

[041] Reference will now be made to exemplary embodiments, examples of which are described in this report. It should be understood that other embodiments may be used and structural and functional changes may be made. Furthermore, the characteristics of the various embodiments may be combined or altered. As such, the following description is presented for illustrative purposes only and should in no way limit the various alternatives and modifications that may be made to the illustrated embodiments. In this disclosure, several specific details provide a full understanding of the disclosure in question. It should be understood that aspects of this disclosure may be practiced with other embodiments, not necessarily including all aspects described in this report, etc.

[042] As used in this report, the words “example” and “exemplary” mean an example or illustration. The words “example” or “copy” do not indicate a key or aspect or preferred embodiment. The word “or” is intended to be inclusive and not exclusive, unless the context suggests otherwise. As an example, the phrase “A employs B or C” includes any inclusive permutation (e.g., A employs B; A employs C; or A employs both B and C). Conversely, the articles “a” and “an” generally mean “one or more,” unless the context suggests otherwise. Petition 870240108444, dated 12 / 19 / 2024, p. 21 / 116 12 / 46

[043] As used in this application, the term “alkyl” includes linear, branched, and cyclic alkyl groups. Specific and non-limiting examples of alkyl include, but are not limited to, methyl, ethyl, propyl, hexyl, octyl, and isobutyl. In embodiments, the alkyl group is chosen from a C1-C30 alkyl, a C1-C18 alkyl, a C2-C10 alkyl, or even a C4-C6 alkyl. In embodiments, the alkyl is chosen from a C1-C6 alkyl.

[044] As used in this report, the term “aryl” refers to a non-limiting group of any aromatic hydrocarbon from which a hydrogen atom has been removed. An aryl may have one or more aromatic rings, which may be fused or connected by single bonds or other groups. Specific and non-limiting examples of aryls include, but are not limited to, tolyl, xylyl, phenyl, and naphthalenyl. In embodiments, an aryl group may be chosen from a C6-C30 aryl, a C6-C20 aryl, or even a C6-C10 aryl.

[045] Viscosity can be measured in any suitable manner. In one embodiment, viscosity can be measured using an Ostwald viscometer. The Ostwald viscosity is defined by the time required for a viscous fluid to drain through a specified distance of a calibrated tube at 25 °C multiplied by a constant for the tube determined in a liquid of known viscosity, as selected by the user. In one embodiment, the reference liquid is deionized water. Alternatively, the constant for the instrument can be determined and supplied by the instrument manufacturer.

[046] A photocurable silicone composition, a method or process for treating such composition to form a cured coating, and articles comprising such coatings are provided. Photocurable Silicone Composition

[047] The present photocurable silicone compositions comprise: (i) a vinyl functional polysiloxane; (ii) a hydride functional polysiloxane; (iii) a Petition 870240108444, dated 12 / 19 / 2024, p. 22 / 116 13 / 46 photoactive catalyst; and (iv) an acid anhydride functional polysiloxane. The composition may optionally include other additives and materials including, but not limited to, (v) an additional crosslinker and (vi) a silanol-stop fluid. The photocurable silicone composition can be cured by exposure to UV radiation to form a coating on a substrate surface.

[048] Silicone compositions are generally supplied to have a fluid consistency so that they can be applied to a substrate as a coating, for example, by roller coating, spraying and the like. For example, the silicone composition may be an uncured or partially cured liquid with a viscosity low enough that it can be readily applied as a coating to a substrate.

[049] Vinyl functional polysiloxane can be selected, as desired, for a particular purpose or intended application to provide a suitable composition for forming a desired coating or film. Vinyl functional polysiloxane comprises vinyl radicals linked to silicon via carbon-silicon bonds. The vinyl radicals may be in the terminal position (i.e., with the vinyl chain stopped), pendant from a silicon atom in the siloxane polymer structure, or a combination thereof. Typically, vinyl functional polysiloxane has a viscosity ranging from about 50 to about 100,000 centipoise (cPs) at 25 °C, where 1 centipoise (cPs) = 1 millipascal-second (mPa^s). In embodiments, the viscosity may range from about 100 to about 50,000 cPs at 25 °C; from about 500 to about 25,000 cPs at 25°C; from about 1,000 to about 10,000 cPs at 25°C; or from about 2,500 to about 5,000 cPs. at 25°C.In one embodiment, the vinyl functional polysiloxane has a viscosity of about 200 to about 600 cPs at 25 °C. In this report, as in other parts of the descriptive report and claims, numerical values ​​can be combined to form novel and unspecified ranges. Petition 870240108444, dated 12 / 19 / 2024, p. 23 / 116 14 / 46

[050] In one embodiment, the vinyl functional polysiloxane has formula (I): M1ViaM2bD1VicD2dT1VieT2fQ1g(I) where M1Vi= (R1)(R2)(CH2=CH)SiO1 / 2 M2= (R3)(R4)(R5SiO1 / 2 D1Vi= (R6)(CH2=CH)SiO2 / 2 D2= (R7)(R8)SiO2 / 2 T1Vi= (CH2=CH)SiO3 / 2 T2= (R9)SiO3 / 2 Q1 = SiO4 / 2 R1, R2, R3, R4, R5, R6, R7, R8, and R9 are independently a saturated C1-C10 hydrocarbon radical; 50 < a + b + c + d + e + f + g < 10,000, and a + c + e is greater than 1. In embodiments, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are a C1-C10 alkyl, a C2-C8 alkyl, or a C4-C6 alkyl. In one embodiment, R1, R2, R3, R4, R5, R6, R7, R8, and R9 are each methyl. In one embodiment, 100 < a + b + c + d + e + f + g < 7,500; 250 < a + b + c + d + e + f + g < 5,000; or 500 < a + b + c + d + e + f + g < 2,500.

[051] In one embodiment, the vinyl functional polysiloxane has the formula (Ia): M1viD1vicD2dM1vi(Ia)where M1vi is (R1)(R2)(CH2=CH)SiO1 / 2; D1vi is (R6)(CH2=CH))SiO2 / 2; D2 is (R7)(R8)SiO2 / 2; R1, R2, R3, R5, R6, R7 and R8 are independently a saturated C1-C10 hydrocarbon radical; c is 0 to 10; d is 50 to 250. In embodiments, R1, R2, R3, R5, R6, R7 and R8 are a C1-C10 alkyl, a C2-C8 alkyl or a C4-C6 alkyl. In one embodiment, R1, R2, R3, R5, R6, R7 and R8 are each methyl. In one embodiment, c is 1 to 10, 2 to 8, or 4 to 6.

[052] Functional vinyl siloxane is present in the composition in a Petition 870240108444, dated 12 / 19 / 2024, p. 24 / 116 15 / 46 quantity of about 80 to about 99 parts by weight based on the total weight of the composition, from about 85 to about 95 parts or from about 89 to about 92 parts.

[053] A hydride functional polysiloxane is a siloxane polymer comprising Si-H groups in the terminal position, the polymer backbone, or a combination thereof. The hydride functional polysiloxane polymer may be a linear molecule or may be branched. Typically, hydride functional polysiloxane has a viscosity below about 1,500 centipoise (cPs) at 25 °C, more typically in the range of about 20 to about 1,000 cPs at 25 °C, and even more typically in the range of about 30 to about 500 cPs at 25 °C. In this report, as in other parts of the descriptive report and claims, numerical values ​​may be combined to form new and unspecified ranges.

[054] In one embodiment, the hydride functional siloxane has formula (II): M3HhM4iD3HjD4kT3HT4mQ2n(II) where M3H= (R10)(R11)(H)SíOi / 2 M4= (R12)(R13)(R14)SíOi / 2 D3H= (R15)(H)SiO2 / 2 D4= (R16)(R17)SiO2 / 2 T3H= (H)SiO3 / 2 T2= (R18)SiO3 / 2 Q2 = SiO4 / 2 R10, R11, R12, R13, R14, R15, R16, R17, and R18 are independently a saturated C1-C10 hydrocarbon radical; the subscripts h, i, j, k, l, m, n are zero or positive subject to the following limitations: h + i + j + k + l + m + n < 1000, and h + j + l is greater than 0. In embodiments, R10, R11, R12, R13, R14, R15, R16, R17, and R18 are a C1-C10 alkyl, a C2-C8 alkyl, or a C4-C6 alkyl. Petition 870240108444, dated 12 / 19 / 2024, p. 25 / 116 16 / 46 embodiment, R10, R11, R12, R13, R14, R15, R16, R17 and R18 are each methyl.

[055] In one embodiment, the hydride functional polysiloxane is a copolymer of formula (IIa): M4D3HjD4kM4(IIa) where j + k is 10 - 40.

[056] In another embodiment, the hydride functional polysiloxane is a polymer of formula (IIb): M4D3HjM4(IIb) where j is 10 - 40.

[057] In yet another embodiment, the hydride functional polysiloxane has the formula (IIc): M3HhQ2(IIc) where h is 1 to 4.

[058] The functional polysiloxane hydride is present in amounts of about 1 to about 20 parts, about 2 to about 15 parts, or about 5 to about 10 parts based on the total weight of the composition.

[059] It will be evaluated that the hydride functional polysiloxane can be provided as a mixture of hybrid functional silicones of different formulas. The different hydride functional polysiloxanes may be of similar structures but different molecular weight (weighted average molecular weight), or they may be of different structures. In one embodiment, the hydride functional polysiloxane is provided as a mixture of a hydride functional polysiloxane of formula (IIa) and a hydride functional polysiloxane of formula (IIb).

[060] The ratio of hydride groups to vinyl can be selected as desired. In one embodiment, the ratio of hydride groups to vinyl is from about 0.5:1 to about 10:1, from about 1:1 to about 7.5:2, or from about 2.5:1 to about 5:1. In embodiments, the ratio of hydride groups to vinyl is Petition 870240108444, dated 12 / 19 / 2024, p. 26 / 116 17 / 46 approximately 1.5:1 to approximately 3:1. In yet another embodiment, the ratio of hydride groups to vinyl groups is approximately 2:1 to approximately 2.5:1. In one embodiment, the ratio of hydride groups to vinyl groups can be 1:1, 1.2:1, 1.5:1, 1.75:1, 2:1, 2.25:1, 2.5:1, or 3:1. Thus, the variables a, c, e, h, j, l in Formulas (I) and (II) can be selected to provide the desired ratio of hydride groups to vinyl groups.

[061] The composition includes a photoactive platinum catalyst suitable for catalyzing the reaction of vinyl functional siloxane and hydride functional siloxane after exposure to a sufficient wavelength of light. Particularly suitable catalysts are UV-activated Pt catalysts which are inert in the absence of light and which, after irradiation with light of wavelength 250 to 500 nm, can be converted into Pt catalysts that are active at room temperature. Examples of suitable UV-activated Pt catalysts include, but are not limited to, trialphatic (alkylcyclopentadienyl) Pt ​​compounds or their derivatives, as disclosed, for example, in EP 0146307, which is incorporated in its entirety in this report by reference.Particularly suitable are cyclopentadienyltrimethylplatinum, methylcyclopentadienyltrimethylplatinum and their derivatives comprising substituted cyclopentadienyl moieties, which may optionally be linked directly or through other additional moieties to the polymers. Other suitable photoactive hydrosilylation catalysts include, for example, bis(acetylacetonato)platinum compounds and also their corresponding derivatives. A single catalyst or a mixture of at least two catalysts may be used.

[062] In one embodiment, the photoactive catalyst is a platinum-cyclopentadiene complex of formula R19CpPtR203, where R19 and R20 are independently selected from a C1-C10 alkyl group, and Cp is a cyclopentadiene group, where the link between Cp and Pt is an eta linkage. In a Petition 870240108444, dated 12 / 19 / 2024, page 27 / 116 In embodiment 18 / 46, R19 and R20 are independently selected from either a C1-C6 alkyl or a C2-C4 alkyl. In one embodiment, R19 and R20 are each methyl.

[063] Additional catalysts that are suitable for catalyzing the hydrosilylation reaction are those described in U.S. Patent 6,127,446 and EP Patent 1050538, each of which is incorporated herein by reference. In one embodiment, the photoactive catalyst is a compound of the formula [(R29)a(R30)bCp]Pt(R31)3 where R29 is a C7-20 aromatic organic radical, R30 and R31 are independently C1-22 aliphatic organic radicals, Cp is a cyclopentadienyl radical, “a” is an integer equal to 1 to 3 inclusive, “b” is an integer equal to 0 to 3 inclusive, and the sum of a + b is equal to 1 to 4 inclusive.In one embodiment, the photoactive catalyst is a compound of the formula [(R32)c(R33)dCp]PtR34R35Q, where R32 is a C6-20 aromatic radical, R33, R34 and R35 are independently C1-22 aliphatic organic radicals, Cp is a cyclopentadienyl radical, Q is a silicon-containing organic sensitizing group, “c” and “d” are independently integers equal to 0 to 5 inclusive, and the sum of “c + d” is equal to 0 to 5 inclusive.

[064] Some examples of such catalysts include, but are not limited to, aryl(methylcyclopentadienyl)trimethylplatinum and aryl(methylcyclopentadienyl)dimethyl(trimethylsilylmethyl)platinum, where the aryl functionality may be, for example, naphthyl, phenantrile or similar. Some specific examples include, but are not limited to, [(1'-naphthyl)cyclopentadeinyl]trimethylplatinum; [(2'-naphthyl)-cyclopentadienyl]trimethylplatinum; [1-methyl-3-(1'-naphthyl)-cyclopentadienyl]trimethylplatinum; [1-methyl-3-(2'-naphthyl)cyclopentadienyl]trimethylplatinum; [(4'-biphenyl)-cyclopentadienyl]trimethylplatinum; [1-(4'-biphenyl)-3-methyl-cyclopentadienyl]trimethylplatinum; [(9'-phenantryl)-cyclopentadienyl]trimethylplatinum; [1-methyl-3-(9'-phenantryl)-cyclopentadienyl]-trimethylplatinum; [1-(2'Petition 870240108444, of 12 / 19 / 2024, page 28 / 116] 19 / 46 anthracenyl)-3-methyl-cyclopentadienyl]-trimethylplatinum; [(2'-anthracenyl)cyclopentadienyl]trimethylplatinum; [(1 '-pyrenyl)-cyclopentadienyl]trimethylplatinum; [1 -methyl-3(1'-pyrenyl)-cyclopentadienyl]trimethylplatinum; (cyclopentadienyl)dimethyltrimethylsilylmethylplatinum; (cyclopentadienyl)diethyltrimethylsilylmethylplatinum; (cyclopentadienyl)dipropyltrimethylsilylmethylplatinum; (cyclopentadienyl)diisopropyltrimethylsilylmethylplatinum; (cyclopentadienyl)diallyltrimethylsilylmethylplatinum; (cyclopentadienyl)dibenzyltrimethylsilylmethylplatinum; (cyclopentadienyl)dimethyltriethylsilylmethylplatinum; (cyclopentadienyl)dimethyltripropylsilylmethylplatinum; (cyclopentadienyl)dimethyltriisopropylsilylmethylplatinum; (cyclopentadienyl)dimethyltriphenylsilylmethylplatinum; (cyclopentadienyl)dimethyldimethylphenylsilylmethylplatinum; (cyclopentadienyl)dimethylmethylphenylsilylmethylplatinum; (cyclopentadienyl)dimethyldimethyl(trimethylsiloxy)silylmethylplatinum; (cyclopentadienyl)dimethyldimethyl(dimethylvinylsiloxy)silylmethylplatinum; [(1'- naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum; [(2'- naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum; [1-methyl-3-(1'- naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum; [1-methyl-3-(2'- naphthyl)cyclopentadienyl]trimethylsilylmethylplatinum; [(4'- biphenyl)cyclopentadienyl]trimethylsilylmethylplatinum; [1(4'- biphenyl)-3- methylcyclopentadienyl]trimethylsilylmethylplatinum; [(9'- phenanthryl)cyclopentadienyl]trimethylsilylmethylplatinum; [1-methyl-3-(9'- phenanthryl)cyclopentadienyl]trimethylsilylmethylplatinum; [1-(2'- anthracenyl)-3- methylcyclopentadienyl]trimethylsilylmethylplatinum; [(2'- anthracenyl)cyclopentadienyl]trimethylsilylmethylplatinum; [(1'- pyrenyl)cyclopentadienyl]trimethylsilylmethylplatinum; [1-methyl-3-(1'- Petition 870240108444, dated 12 / 19 / 2024, p. 29 / 116 20 / 46 pirenil)cyclopentadienyl]trimethylsilylmethylplatin and similar.

[065] The catalyst may be supplied in any amount sufficient to convert the composition into a non-sticky state. In embodiments, the catalyst is supplied in an amount sufficient to provide platinum in an amount of about 50 to about 150 ppm, about 60 to about 120 ppm, about 75 to about 100 ppm, or about 80 to about 90 ppm.

[066] The acid anhydride-functionalized polysiloxane is, in one embodiment, selected from an acid anhydride-functionalized polysiloxane, as described in International Patent Application PCT / EP2019 / 074418 filed on September 12, 2019, the disclosure of which is incorporated herein by reference. In one embodiment, the acid anhydride-functionalized polysiloxane polymer may be selected from a compound represented by formula (III): M5AD5oD6ApD7HqM5A(III) where M5Ais (R21)(R22) (R23)SiO1 / 2 D5é (R24)(R25)SiO2 / 2, D6Aé (R26)(R27)SiO2 / 2 D7H= (R28)(H)SiO2 / 2 where R21, R22, R24, R25, R26 and R28 are independently a saturated C1-C10 hydrocarbon radical; R23 and R27 independently represent an acid anhydride functional group that can be derived from the reaction of allyl succinic anhydride with Si(H) functionality; o + q is 10 to 40, ep is 1 to 20. In embodiments, R21, R22, R24, R25, R26 and R28 are a C1-C10 alkyl, a C2-C8 alkyl or a C4-C6 alkyl. In one embodiment, R21, R22, R24, R25, R26 and R28 are each methyl. The acid anhydride functional polysiloxane may be referred to in this report as AA polymer.

[067] The functional acid anhydride siloxane is present in an amount Petition 870240108444, dated 12 / 19 / 2024, p. 30 / 116 21 / 46 from about 0.1 parts to about 10 parts, from about 0.5 to about 7.5 parts, or from about 1 to about 5 parts based on the weight of the composition.

[068] The coating composition may optionally include one or more other additives, as desired, for a specific purpose or intended application. Examples of suitable additives include, but are not limited to, for example, inhibitors, stabilizers, inert fillers, resin-like polyorganosiloxanes other than the functional hydride or vinyl functional polysiloxanes described above, non-reinforcing fillers, adhesion promoters, fungicides, fragrances, rheological additives, corrosion inhibitors, antioxidants, light stabilizers, flame retardants, agents to influence electrical properties, dispersing aids, solvents, pigments, dyes, plasticizers, organic polymers, heat stabilizers, etc.

[069] In one embodiment, the composition may include a sensitizer as an additive. The sensitizer is a material that absorbs specific beams of active and excited-state electron energy. Examples of suitable sensitizers that may be used include, but are not limited to, benzophenone, thioxanthone, isopropylthioxanthone, anthraquinone, a 3-acylcoumarin derivative, terphenyl, styryl ketone, 3-(aroylmethylene)thiazolinone, camphorquinone, eosin, rhodamine, and erythrosine.

[070] An example of a suitable resin-like polyorganosiloxane includes a hydroxy functional polysiloxane with an -OH group attached to a silicon atom, which may be referred to as silanols or silanol resins. The silanol functionality may be in the terminal position or attached to a silicon atom in the siloxane chain. Silanol resins may be of the MDTQ type. In one embodiment, the silanol resin is a silanol chain polysiloxane with the silanol functionality in the terminal positions. In one embodiment, silanol resins may have a viscosity of about 25 to about 10,000 cPs Petition 870240108444, dated 12 / 19 / 2024, p. 31 / 116 22 / 46 at 25°C, from about 50 to about 7,500 cPs at 25°C, from about 100 to about 5,000 cPs at 25°C, from about 500 to about 2,500 cPs at 25°C, or from about 1,000 to about 2,000 cPs at 25°C °C.

[071] Some examples of suitable additives may include activated carbon, finely ground quartz, diatomaceous earth, clays, chalk, lithopones, carbon black, graphite, metal oxides, metal carbonates, metal sulfates, metal salts of carboxylic acids, metal powders, fibers, such as, for example, crystal fibers, plastic fibers, plastic powders, metal powders, dyes, pigments, etc. Process for forming a coating from the compositions.

[072] The coating composition can be used to form a coating on a substrate. The coating is formed by applying the coating composition to a substrate surface and exposing the coating to UV radiation to cure the composition.

[073] The photocurable composition can be applied to a substrate by any suitable method, such as, for example, by roller coating or, alternatively, by spraying from a suitable applicator (e.g., a nozzle), wherein the applicator may be stationary or moving relative to the substrate. Although mist or aerosol is often caused predominantly by the movement of the applicator relative to a substrate, mist or aerosol may be caused by factors other than the movement of the applicator or substrate. For example, mist may be caused partly or predominantly by the application method and not by any movement of the applicator relative to the substrate, for example, in a stationary or slow spraying process.

[074] Photocurable compositions can be applied to the substrate in any quantity or thickness, as desired, for a specific purpose or intended application. It will be evaluated whether thicker coatings can Petition 870240108444, dated 12 / 19 / 2024, page 32 / 116 23 / 46 require longer curing times. In one embodiment, the photocurable composition is applied to the substrate with a coating weight of about 0.5 to about 2 grams per square meter (gsm), about 0.75 to about 2 gsm, or about 1 to about 1.75 gsm.

[075] The UV light source can provide light in the wavelength range of about 200 nm to about 400 nm. UV light sources that can be used to cure the composition include, but are not limited to, an electrodeless UV lamp, a type H mercury vapor lamp, a type D iron-doped mercury vapor lamp, a type V lamp, an X-type lamp, etc. The lamp size can be selected as desired for a specific purpose or to provide a desired curing effect.

[076] Additionally, the process and the system for implementing the process may employ one or more reflectors or other suitable devices to focus the UV light. The type and number of such reflectors may be selected, as desired, to focus the light energy to a selected degree during the coating / curing process. In one embodiment, the reflector may be a dichroic reflector.

[077] In one embodiment, the method of curing the composition comprises first exposing the composition and the substrate to which it is applied to heat before exposure to the UV light source. The heat may be provided by any device or method suitable for applying heat. In one embodiment, the heat may be provided by an oven, such as a convection oven or forced-air oven. In another embodiment, the heat may be provided by an infrared light source, such as an LED light source emitting a wavelength greater than 800 nm or a “blackbody” type heat lamp. Such an infrared light source may be focused on the moving coated substrate at a point before where the UV light source is placed so that the Petition 870240108444, dated 12 / 19 / 2024, p. 33 / 116 24 / 46 The coated substrate was heated above ambient temperature to a temperature of about 25 °C to about 120 °C at the time the UV lamp emission is focused on the coating. The temperature of the heat source should be relatively mild. In embodiments, the coated substrate is heated to a temperature of about 25 °C to about 120 °C, about 40 °C to about 105 °C, or about 50 °C to about 90 °C.

[078] The substrate coated with the curable composition is generally moved continuously through the system by means of a conveyor belt or other suitable device for transporting the coated substrate. The coated substrate may be moved through the system and exposed to curing conditions at any speed suitable for exposing the curable composition to UV light (and / or heat source) to effectively promote the curing of the composition. In one embodiment, the substrate carrying the silicone composition is transported through the system at a speed of about 20 feet per minute to about 1,000 feet per minute, about 50 feet per minute to about 750 feet per minute, about 100 feet per minute to about 500 feet per minute, or about 200 to about 400 feet per minute. Articles

[079] Articles formed from the process comprise a substrate with a coating formed from the composition applied to a surface of the substrate. The substrate can be any substrate on which a coating of the above coating formulation is desired. Some examples of suitable substrates include paper, cardboard, wood products, polymer and plastic products, crystal products, and metal products.

[080] Coatings formed from photocurable compositions may be suitable for use in forming a release coating. The coatings exhibit release properties on substrates such as paper. Petition 870240108444, dated 12 / 19 / 2024, page 34 / 116 25 / 46 engineering paper, asphalt packaging paper, double-surface peel-off paper with different release properties, etc., as well as tapes, labels, etc., which require an appropriate level of release properties.

[081] Coatings or release layers, such as those used in the construction of adhesive articles, for example, labels, tapes, etc., are frequently formed from cellulose-based substrates. Examples of substrates that can be coated with the curable silicone composition include, but are not limited to, cellulose-based substrates such as papers, glassine, super calendered Kraft paper (SCK) and clay-coated Kraft paper (CCK), and film substrates including polyethylene, polypropylene and polyester and hybrid substrates such as those comprising polyethylene Kraft paper (PK) or polypropylene Kraft paper (PPK). Examples

[082] In order that those skilled in the art may better practice the invention, the following examples are given by way of illustration and not of limitation. All parts are by weight, unless otherwise indicated. Example 1A

[083] A UV light-curable silicone coating formula A was prepared having 91.6 parts of a vinylsilicone of composition M(vi)D8oM(vi), 8.4 parts of the acid anhydride functional polymer AA, 7.2 parts of a hydride functional silicone crosslinker of composition [M(H)]2Q, and [MeCp]PtMe3 catalyst sufficient to provide about 85 ppm of platinum in the coating bath (not including crosslinker). This coating mixture was manually applied to Verso 40 lb / ream basic weight SCK sheets using a Meyer rod to provide about 2 to 6 g / m2 of deposition. The coated sheets were then passed under a single 13 mm diameter focused H+ lamp (medium pressure mercury vapor type) mounted on top of a Petition 870240108444, dated 12 / 19 / 2024, p. 35 / 116 26 / 46 A laboratory UV processor equipped with an adjustable-speed conveyor belt was used. Curing was qualitatively determined as a function of conveyor belt speed based on smearing, silicone migration to cellophane test tape, and anchoring to the SCK sheet. Excellent curing (no smearing, no silicone migration, and no substrate friction) was found at conveyor speeds up to 30 feet / minute (fpm). Increasing the conveyor speed to 40 fpm resulted in some migration that rapidly diminished as the cured coating aged after UV exposure. Higher conveyor speeds resulted in incomplete curing that slowly improved after a few minutes following exposure. The coating technique in this example led to thicker cured silicone-coated samples than those typically produced in commercial silicone release coating production. Example 1B

[084] Silicone formula A was manually applied to Verso SCK as described in example 1, but in this case a 13 mm, 300-watt Heraeus D lamp (medium-pressure mercury vapor type doped with iron) was replaced by the H+ lamp. An R500 type reflector that does not attenuate the long-wavelength lamp emission was used to focus the UV light onto the coating surface. Coated sheets were passed under the focused D lamp at different transport speeds, with the results observed below: Carrier speed, excellent qualitative curing (fpm); no staining, no migration, good anchoring. 120 well-cured; slight staining, no migration, good anchorage. 150 subcures; some migration observed, post-cures

[085] A dramatic improvement in healing speed (> 3x) was achieved Petition 870240108444, dated 12 / 19 / 2024, page 36 / 116 27 / 46 replacing the H+ lamp with a comparable D lamp. The emission from the D lamp is redshifted for longer wavelengths than the H+ emission, which appears to improve the photopolymerization efficiency of MeCpPtMe3. Example 1C

[086] Silicone formula A was manually applied to the Verso SCK sheet as in previous examples, but in this case a Dichroic + Reflector was replaced by an R500 reflector. Dichroic reflectors reduce the emission of long wavelengths (visible and IR light) focused on the sample compared to conventional R500 type reflectors and increase the relative amounts of shorter wavelength emission. Coated sheets were then passed under the focused lamp D at different conveyor speeds, with observations noted below: Carrier speed, excellent qualitative curing; no migration, no staining, good adhesion. 120 excellent cure 150 good cure; slight migration, coating stain, good anchorage 180 undercured; spot and migration observed, rapid post-cure

[087] Switching to dichroic reflectors unexpectedly provided further improvements in the photopolymerization response of this system. Example 1D

[088] Silicone formula A was applied manually to the Verso SCK sheet samples, as described above, but in this case, the applied coating was passed under two 13 mm diameter focused lamps D mounted in tandem. Observations follow below: Carrier speed, Qualitative Curing fpm 200 excellent cure; no migration, no staining, good anchorage Petition 870240108444, dated 12 / 19 / 2024, page 37 / 116 28 / 46 250 well healed; no migration, no staining, hard smear 275 well healed; slight migration, slight stain, hard smear 300 undercured; some existing staining and migration, rapid post-cure Example 1E

[089] A silicone formula B was formulated as 99.0 parts of M(vi)D8oM(vi) polymer, 1.0 part of acid anhydride functional polymer AA including MeCpPtMe3 catalyst sufficient to provide 85 ppm of platinum and 8.3 parts of [MeH]2 Crosslinker Q. Formula B differed from formula A in that the amount of acid anhydride functional silicone polymer was reduced to ~1% (w / w). Cure studies were conducted using the Verso SCK substrate, as described in previous examples. Carrier speed, Qualitative Curing fpm 150 excellent cure; no migration, no staining, good anchoring 250 excellent cure; no migration, no staining, good adhesion. 300 well cured; slight migration, no blemishes, good anchorage. 350 subcured; observed migration that improved rapidly post-cure.

[090] Further improvement in curing performance was obtained by reducing the concentration of functional silicone additive acid anhydride from 8.5% to 1%. Example 1F

[091] A silicone formula C was prepared that was identical to formula B, except that no acid anhydride functional silicone polymer AA was present. For the purposes of the present technology, Example 1F is considered a comparative example. The cure evaluation was performed in the same manner as Examples 1A-1E. Carrier speed, Qualitative Curing fpm 150 Cured; no migration, no staining, but poor anchorage. 250 Subcured; stained surface and poor anchorage that did not improve in Petition 870240108444, dated 12 / 19 / 2024, page 38 / 116 29 / 46 post-cure. Example 1G

[092] A silicone formula D was prepared that was identical to formula B, except that the concentration of MeCpPtMe3 catalyst was reduced to provide 50 ppm of Pt. The results of the cure evaluation are indicated below. Carrier speed, Qualitative Curing fpm 100 Cured, slight migration and staining. Post-cure observed. 150 Subcure; migration and spotting that improved post-cure 200 Subcure; migration and staining with good anchorage

[093] Examples 1A to 1G demonstrate various ways in which the photo-hydrosilylation curing of vinyl silicone and a hydride-silicone-based coating with R'CpPtR'3 catalyst can be markedly improved. Improved curing and product were observed using iron-doped mercury vapor lamps, such as Heraeus 'D' type, instead of standard 'H' type mercury vapor lamps. Equipping the lamp housing with dichroic reflectors is another option to adjust or improve curing. Finally, optimizing the content of the acid anhydride functional silicone polymer additive also contributed to improving curing speed and stability. Example 2

[094] A series of experiments was conducted in which the photo-hydrosylation curing of different silicone formulations based on the same vinylsilicone polymer M(vi)D8oM(vi), [M(h)]2Q crosslinker and acid anhydride functional silicone polymer AA described in Examples 1A to 1G was studied as a function of the concentration of MeCpPtMe3 catalyst, molar concentration of ITX (2-isopropylthioxanthone) as a % molarity of MeCpPtMe3, lamp type and number of lamps, and coating line speed. 1% acid anhydride functional polymer AA was present in all coatings tested. A quartz shield Petition 870240108444, dated 12 / 19 / 2024, p. 39 / 116 30 / 46 separating the lamps from the samples being cured was either present or absent. These experiments were performed on a pilot coating line equipped with a five-roll film separation silicone coater capable of applying defect-free coatings 1 to 2 microns thick. UV curing radiation was provided by 2 or 4 banks of 600 watt / inch type H or D microwave lamps. Dichroic reflectors were fitted in all experimental runs.

[095] The weight of the silicone coating was evaluated using the XRF technique common to the silicone coating industry. Silicone was applied to the Verso SCK described in Examples 1A to 1G. The qualitative cure of the samples was observed immediately offline, with post-cure also observed. For these experiments, the cure quality was given a numerical rating, with 0 denoting no cure and 4 denoting excellent cure. From a commercial standpoint, a rating of 3 or 4 would be considered acceptable performance. In the table below, only runs that produce a qualitative cure of 3 or better are included for simplicity. It should be noted that 1 micron of coating thickness is ~ 1 g / m2 TABLE 1 Coating % mol Pt ppm Lamps Line speed fpm Ct. By weight, gsm Q Shield Cure ITX 2A 50 4 x D 100 1.20 Yes 3 0 2B 80 4 x D 300 1.10 Yes 3 0 2C 85 4 x D 300 1.20 Yes 4 0 2D 100 4 x D 300 1.27 Yes 4 0 2D 100 4 x D 600 1.33 Yes 3 0 2E 120 4 x D 600 1.35 Yes 4 0 Petition 870240108444, dated 12 / 19 / 2024, p. 40 / 116 31 / 46 Coating % mol Pt ppm Lamps Line speed fpm Ct. By weight, gsm Q Shield Heal ITX 2E 120 2 x D 100 1.27 Yes 3 0 2G 85 4 x D 300 1.26 Yes 4 20 2H 85 4 x D 300 1.26 Yes 4 50 2J 100 4 x D 600 1.27 Yes 3 50 2K 100 2H+2D 300 1.30 Yes 3 50 2K 100 2 x H 200 1.40 Yes 4 50 2K 100 2 x D 200 1.40 Yes 3 50 2K 100 2 x D 300 1.35 No 3 50 2K 100 2 x H 200 1.42 No < 3 50 2K 100 2H+2D 300 1.35 No 3 50 2K 100 4 x D 600 1.40 No 3 50 2L 85 4 x D 500 1.35 No 3 0 2O 85 4 x D 500 1.29 No 3 100 2P* 85 4 x D 500 1.27 No 3 50 *High SiH / Vinyl ratio (normal 2x crosslinking level)

[096] Example 2 is an extensive series of experiments performed in a manner that mimics the commercial production of silicone-coated release coatings. The major difference between Example 1 and Example 2 is the much thicker silicone coating applied by hand using a Meyer #0 rod in the experiments described in Example 1. The high-speed multi-roll silicone coating machiner in the pilot line used for the Example 2 experiments is the same type of coating machiner found in commercial silicone coating manufacturing. Sample coating weights range from 0.8 to 2.0 gsm on Verso SCK. Petition 870240108444, dated 12 / 19 / 2024, page 41 / 116 32 / 46 are representative of the micron-scale silicone thickness of industrial release coatings, and the cure evaluation of these samples provides a realistic assessment of how changes in silicone formulation and processing affect the quality and commercial viability of photoactivated hydrosilylation-cured silicone coatings.

[097] Example 2 shows that a processing line speed of 500-600 fpm under the conditions described above was obtained with a sufficient quantity of MeCpPtMe3 to provide approximately 100 ppm of Pt to the coating formula. The data also show that D lamps may be more suitable for MeCpPtMe3 photochemistry than H lamps in the absence of sensitizer, but the addition of ITX sensitizer marginally improves system performance if H lamps are in use. Good adhesion of the cured silicone to the Verso SCK sheet was observed in all tests. Removal of quartz shields improves curing to some extent, all other things being equal. Example 3

[098] A third set of experiments was performed on the same pilot coating line described above in Example 2. In this case, different silicone crosslinking polymers with SiH functionality were mixed with two different vinyl-terminated linear polydimethylsiloxane-based polymers. Concentrations of MeCpPtMe3 providing 60 to 120 ppm of platinum were mixed with the curable silicone mixture, and between 0 and 0.5% of acid anhydride functional silicone polymer AA was also present in the coating formulations. None of the formulations included ITX sensitizer. The reactive SiH / vinylsiloxane ratio ranged from 2.0 to 2.5. As in Example 2, the line speed and silicone coating weight were varied, and the degree of cure was qualitatively assessed as previously described, and in addition, samples of Petition 870240108444, dated 12 / 19 / 2024, page 42 / 116 33 / 46 cured silicone coatings were quantitatively evaluated for cure by determining the % by weight of extractable silicone present within a few minutes of exposure to focused UV light. Extractions were performed on small, precisely measured areas of the coatings placed in methyl isobutyl ketone solvent for several days before analysis of the extracting liquid by atomic absorption spectroscopy. All experiments were performed with 4 banks of 600 watt / in² microwave-powered Hereau lamps equipped with dichroic reflectors. These experiments varied silicone formulations, substrates, and processing conditions to evaluate different processing conditions of UV-activated addition-cured release coatings.

[099] Formulations, processing conditions, qualitative cure and % of extractable silicone for selected tests resulting in well-cured silicone coatings are presented in the following tables. Vinyl-based polymer 1 has the structure M(vi)Dii4M(vi); Vinyl-based polymer 2 has the structure M(vi)Di49M(vi); a silanol-stopped polymer has the structure HO(Me)2SiOD230OSi(Me2)OH. Crosslinker 3 has a linear structure MD(H)aDbM where D(H) = (CH3)(H)SiO, and where a and b are integers between 10 and 30. Crosslinkers 4, 5 and 6 are mixtures of crosslinker 3 with a homopolymer of structure MD(H)cM, where c is an integer between 20 and 40. Crosslinker 3 includes approximately 0.8% reactive hydride; Crosslinker 4 includes approximately 1.04% hydride; crosslinker 5 includes approximately 0.96% reactive hydride; and crosslinker 6 includes approximately 0.88% reactive hydride.The substrate is Verso SKP sheet (a supercalendered Kraft paper) and the functional polymer level of AA anhydride is maintained at 0.5% by weight in all results summarized in Table 2. TABLE 2 Coating Polymer Base Crosslinker SiH / Vinyl Pt ppm Line speed Ct. By weight, gsm Cure % of Extract Petition 870240108444, dated 12 / 19 / 2024, p. 43 / 116 34 / 46 Revesti mento Polímero Base Reticulador SiH / V inila Pt ppm Velocidade da linha Ct. Em peso, gsm Cu ra % de Extrato 3A 1 3 2.0 100 200 1.64 4 3.0 3A 1 3 2.0 100 400 1.77 3 3.7 3A 1 3 2.0 100 600 1.59 3 5.0 3B 1 3 2.0 120 200 1.77 4 3.0 3B 1 3 2.0 120 400 1.80 4 2.9 3B 1 3 2.0 120 600 1.72 4 3.0 3D 1 3 2.5 80 200 1.79 4 3.4 3D 1 3 2.5 80 400 1.74 3 3.9 3D 1 3 2.5 80 600 1.69 3 4.2 3E 1 3 2.5 100 200 1.77 4 2.9 3E 1 3 2.5 100 400 1.80 4 2.6 3E 1 3 2.5 100 600 1.79 3 2.9 3C 1 3 2.3 100 200 1.79 4 3.1 3C 1 3 2.3 100 400 1.77 4 3.9 3C 1 3 2.3 100 600 1.71 3 4.2 3D 1 3 2.5 80 200 1.79 4 3.3 3D 1 3 2.5 80 400 1.77 4 3.9 3D 1 3 2.5 80 600 1.79 4 4.2

[0100] The data in Table 2 demonstrate that the concentration of MeCpPtMe3 (expressed as Pt ppm) and the relative molar ratio of SiH / reactive vinyl can affect the qualitative and quantitative crosslinking density, as expressed in degree of cure and percentage of extractable siloxane, respectively. For example, a combination of 80 ppm Pt with a SiH / vinyl ratio of 2.5 or 120 ppm Pt with a SiH / vinyl ratio of 2.0 leads to excellent cure and low Petition 870240108444, dated 12 / 19 / 2024, p. 44 / 116 35 / 46 extractables at processing speeds of 200 to 600 fpm. In general, thermally processed solventless addition-cure silicone release agents are considered well-cured and stable in contact with adhesives if the extractable siloxane percentage is 5% or less; in most cases, the post-cure extractable percentage drops below 5% within a short period of time after oven exposure. Thus, on this basis, it is evident that the selection of base polymer 1 and crosslinking polymer 3 combined with 0.5% acid anhydride functional additive polymer provides some flexibility in the concentration of UV-activated catalyst and silicone / vinyl crosslinking base polymer ratio in processing release coatings on a typical SCK substrate.

[0101] A series of experiments was then carried out to determine the effect of crosslinking hydride content on the degree of cure of addition coating formulations activated by UV-catalyzed platinum. Formulations, processing conditions and results are noted in Table 3. The substrate is Verso SKP. TABLE 3 Polymer Coating Base Crosslinker SiH / Vinyl PT ppm Line Speed ​​Ct. By weight., gsm Cure % of Extract 3C 1 3 2.3 100 200 1.79 4 3.1 3C 1 3 2.3 100 400 1.77 4 3.9 3C 1 3 2.3 100 600 1.71 3 4.2 3T 1 4 2.3 100 200 1.80 4 7.2 3T 1 4 2.3 100 400 1.77 4 12.9 3T 1 4 2.3 100 600 1.8 4 14.0 3T 1 4 2.3 100 800 1.77 2.5 22.0 Petition 870240108444, dated 12 / 19 / 2024, page 45 / 116 36 / 46 Polymer Coating Base Crosslinker SiH / Vinyl PT ppm Line Speed ​​Ct. By weight, gsm Cure % of Extract 3D 1 3 2.5 80 200 1.79 4 3.4 3D 1 3 2.5 80 400 1.74 3 3.9 3D 1 3 2.5 80 600 1.69 3 4.2 3J 1 4 2.5 80 200 1.77 4 7.5 3J 1 4 2.5 80 400 1.82 4 13.0 3J 1 4 2.5 80 600 1.75 3 14.4 3J 1 4 2.5 80 800 1.54 2 22.5

[0102] It appears that there is a response of the UV-activated Pt-catalyzed system to the H content of the crosslinker (whether single polymer or mixture). A modest increase in H content from crosslinker 3 (0.8% H) to crosslinker 4 (1.04% H) results in a large increase in the % extractable silicone, regardless of catalyst concentration or H / vinyl ratio. The qualitative cure rating of 3 to 4 is maintained if the extractable silicone is kept < 15%.

[0103] The next set of experiments included two different base polymers and two levels of AA polymer, 0 or 0.5%. The catalyst concentration was 100 ppm and the SiH / vinyl ratio was 2.3:1 throughout. TABLE 4 Coating Polymer Base Crosslinker Polymer AA Line Speed ​​Ct. By weight, gsm Cure % Extract 3H 1 4 0.5% 200 1.80 4 4.7 3H 1 4 0.5% 400 1.84 4 6.8 3H 1 4 0.5% 600 1.79 4 8.9 3L 2 4 0.5% 200 1.82 4 14.4 3L 2 4 0.5% 400 1.77 3 19.9 Petition 870240108444, dated 12 / 19 / 2024, page 46 / 116 37 / 46 Coating Polymer Base Crosslinker Polymer AA Line Speed ​​Ct. By weight, gsm Cure % Extract 3L 2 4 0.5% 600 1.77 3 23.8 3I 1 4 0 200 1.79 4 7.2 3I 1 4 0 400 1.85 4 10.2 3I 1 4 0 600 1.79 3 14 3M 2 4 0 200 1.79 4 12.2 3M 2 4 0 400 1.79 3 23 3M 2 4 0 600 1.71 2 30.5

[0104] In this case, base polymer 2, which is a vinyl-terminated polydimethylsiloxane with a higher MW than base polymer 1, did not provide such complete curing. Furthermore, the presence of 0.5% AA polymer significantly aids cure completeness, as evidenced by lower extractables and higher cure ratings for 3H and 3L coatings versus 3I and 3M, respectively.

[0105] To better define the relationship between the concentration of MeCpPtMe3e and the photocuring effectiveness of vinylsiloxane-hydrididossiloxane crosslinking reactions, a series of tests were performed using base polymer 1 and crosslinker 4 with 0.5% AA polymer included, at 4 different catalyst concentrations with SiH / vinyl 2.3. Coatings were applied to Verso SKP at different line speeds and then exposed to 4 banks of Heraeus D lamps as before. The degree of cure and the % of extractable siloxane were measured. The results are shown in Table 5. TABLE 5 Coating Polymer Base Crosslinker PT ppm Line speed fpm Cure % of Extract Petition 870240108444, dated 12 / 19 / 2024, p. 47 / 116 38 / 46 Coating Polymer Base Crosslinker PT ppm Line speed fpm Cure % Extract 3R 1 4 120 200 4 4 3R 1 4 120 400 4 4.2 3R 1 4 120 600 4 5 3R 1 4 120 800 4 7.2 3S 1 4 100 200 4 4 3S 1 4 100 400 4 5 3S 1 4 100 600 4 7 3S 1 4 100 800 3 9 3T 1 4 80 200 4 7.2 3T 1 4 80 400 4 12.9 3T 1 4 80 600 4 14 3T 1 4 80 800 2 22 3U 1 4 60 200 4 9 3U 1 4 60 400 3.5 15.6 3U 1 4 60 600 3 20 3U 1 4 60 800 2 27.5

[0106] A catalyst concentration of less than 100 ppm coupled with the high SiH crosslinker 4 led to a high extractable siloxane at higher line speeds, consistent with previous examples. Subsequently, the coating with the lowest catalyst concentration (Pt 60 ppm) was used to further study the curing effectiveness of this system applied to Verso SKP paper as a function of the hydride content of the crosslinking agent. Processing conditions, AA polymer loading, and SiH / vinyl 2,3 were maintained in all formulations described in Table 6. Petition 870240108444, dated 12 / 19 / 2024, page 48 / 116 39 / 46 TABLE 6 Coating Polymer Base Crosslinker Xlink % of H Line Speed ​​Cure % of Extract 3U 1 4 1.04 200 4 9 3U 1 4 1.04 400 3.5 15.6 3U 1 4 1.04 600 3 20 3U 1 4 1.04 800 2 27.5 3V 1 3 0.8 200 4 4 3V 1 3 0.8 400 3.5 5.5 3V 1 3 0.8 600 3.5 6 3V 1 3 0.8 800 3 7 3W 1 5 0.96 200 4 5 3W 1 5 0.96 400 3.5 7.7 3W 1 5 0.96 600 3.5 12 3W 1 5 0.96 800 2.5 20.5 3X 1 6 0.88 200 4 6 3X 1 6 0.88 400 3.5 11 3X 1 6 0.88 600 3 17.7 3X 1 6 0.88 800 2.5 21.5

[0107] The cure classification and the % extractable silicone were inversely related to the % reactive hydride (SiH) present in the crosslinker, with the greatest performance difference observed between crosslinkers 3 and 4. The intermediate hydride levels of crosslinkers 5 and 6 led to extractable levels for cured 3W and 3X coatings that were between those of 3U and 3V. After these tests, the photocure of the 3U formulation (60 ppm Pt catalyst load applied at ~ Petition 870240108444, dated 12 / 19 / 2024, p. 49 / 116 40 / 46 The Kruger sheets (1.6 to 1.7 gsm) were examined on several different paper substrates, with results described in Table 7. The Kruger sheets are of the supercalendered Kraft type. TABLE 7 Coating Polymer Base Crosslinker Substrate Line speed fpm Cure % Extract 3U 1 4 Verso SKP 200 4 9.0 3U 1 4 Verso SKP 400 3.5 15.6 3U 1 4 Verso SKP 600 3 20.0 3U 1 4 Verso SKP 800 2 27.5 3U 1 4 Kruger 18121 200 4 7.0 3U 1 4 Kruger 18121 400 4 11.0 3U 1 4 Kruger 18121 600 4 15.6 3U 1 4 Kruger 18121 800 3.5 19.4 3U 1 4 Kruger 18121 200 4 6.8 3U 1 4 Kruger 18121 400 4 10.2 3U 1 4 Kruger 18121 600 4 12.7 3U 1 4 Kruger 18121 800 3.5 16.0 3U 1 4 UPM G58 Glassine 200 4+ 4.0 3U 1 4 UPM G58 Glassine 400 4+ 7.3 3U 1 4 UPM G58 Glassine 600 4+ 10.1 3U 1 4 UPM G58 Glassine 800 4 12.0 Petition 870240108444, dated 12 / 19 / 2024, page 50 / 116 41 / 46

[0108] These data demonstrate that certain paper substrates available from different suppliers are very suitable for use with the UV-activated MeCpPtMe3 photohydrosylation catalyst system. For example, qualitative curing and reduced extractable silicon were obtained with crystal foil at 800 fpm line speed with 60 ppm Pt concentration in irradiation with 4 D lamp banks, as described above.

[0109] A test of an Evergreen poly-coated kraft (low-density polyethylene coated on unbleached kraft paper) with the same 3U silicone formulation applied at 1.5 g / m2 was conducted at a line speed of 400 fpm to produce well-cured silicone coatings with excellent anchorage to the polykraft coating substrate without damaging the polyethylene layer. It should be noted that thermal addition-curing silicone release agents are difficult to cure on the PK coating at temperatures that do not degrade and melt the polyethylene, thus demonstrating that photocurable silicone systems employing vinyl-silicone-based polymers and SiH crosslinkers with MeCpPtMe3 catalyst are particularly suitable for use on polykraft substrates.

[0110] Two coating formulations that included the silanol-stopped polymer were also tested for qualitative cure: 3N employs 90 parts vinyl-stopped polymer 1, 10 parts silanol-stopped polymer HO(Me)2SiOD230-OSi(Me2)OH, 0.5 parts AA Polymer, 100 ppm of Pt as MeCpPtMe3 and crosslinker 4 sufficient to provide a SiH / vinyl ratio of 2.3. 3O is a 75 / 25 / 0.5 analogue of 3N. The cure rating of coating 3N was rated at 4.0 applied to Verso SKP sheet at a line speed of 600 fpm. The cure rating of coating 3O was rated as 3.0 also at a line speed of 600 fpm. These results confirmed that polydimethylsiloxane fluids or gums stopped with silanol can be used as additives to modify the release characteristics, coverage, or other properties of Petition 870240108444, dated 12 / 19 / 2024, page 51 / 116 42 / 46 performance of these photocurable addition-curing formulations. Platinum hydrosilylation catalysts are known to catalyze the condensation of SiOH + SiH -> SiOSi + H2, and MeCpPtMe3 is no exception. Example 4

[0111] The laboratory-scale UV processor described in examples 1A, 1B, 1C, 1D, 1E, 1F, and 1G above was used to provide qualitative cure assessments (rated as in previous examples) of curing lamp combinations that included a 385 nm monochromatic LED source emission. A curable silicone formula consisting of M(vi)Dii5M(vi)+ MD(H)nDmM (0.8% H content) with 100 ppm Pt derived from MeCpPtMe3 and an H / vinyl ratio of 2 was prepared. 0.5 wt% AA polymer was also present. The lamp combinations included the LED curing lamp set alone and in combination with 13 mm and 9 mm diameter microwave D lamps fitted with dichroic reflectors. Manually deburred samples of SKP back-sided sheets with average basis weights around 1.3 g / m² were exposed to curing lamps focused at different conveyor line speeds. Experiments and observations are recorded in Table 8. TABLE 8 Lamps Carrier Speed ​​Qualitative Classification, fpm Curing LED 385 nm 3 x 50 0 (no curing) 13 mm D lamp 50 3.5 LED + 13 mm D 50 4 13 mm D lamp 100 3 LED + 13 mm D 100 4 13 mm D lamp 200 1.5 LED + 13 mm D 200 2.5 Petition 870240108444, dated 12 / 19 / 2024, page 52 / 116 43 / 46 Lamps Speed ​​of Carrier Qualitative Classification, fpm Curing lamp D 9 mm 100 3.5 LED + 9 mm D 100 4 LED + 9 mm D 200 3.5 9 mm D + LED 200 2.5 (reverse lamp order)

[0112] As shown in example 4, manual downlights on the laboratory UV processor, while exposure to 385 nm wavelength LED emission does not initiate photohydrosylation curing of this coating, exposure to 385 nm LED light prior to exposure with an iron-doped mercury vapor (D) lamp provides faster curing than the D lamp alone. The sharper focus of the narrower 9 mm diameter D lamp promotes significantly better coating curing than that observed with the 13 mm diameter lamp. The inferior curing observed when D lamp exposure preceded LED lamp exposure suggests that the thermal output of the LED source is more important for the system's curing than the 385 nm absorption by the catalyst. Example 5

[0113] A series of photo-DSC experiments were performed using a TA Instruments differential scanning calorimeter equipped with a UV lamp for sample irradiation to determine how preheating a curable mixture of vinyl silicone-based polymer 1 and hydride crosslinking polymer 3 prior to UV light exposure would affect the photocuring rate. A programmed experimental sequence was performed consisting of the following steps: 1) equilibration step to establish the target temperature of the samples; 2) Petition 870240108444, dated 12 / 19 / 2024, page 53 / 116 44 / 46 a 30-second dark hold at target temperature; 3) a 0.6-second UV light exposure; 4) a 1-minute hold at target temperature. Steps 3 and 4 were repeated 8 times for 9 separate exposures to UV light passed through a 280-450 nm bandwidth filter, a fairly good facsimile of a Heraeus D lamp. 10 g of a curable mixture of vinylsilicone base polymer 1 and functional silicone hydride crosslinker 3 were mixed with 0.05 g of AA anhydride functional polymer with sufficient MeCpPtMe3 catalyst to provide 50 or 25 ppm of Pt. The H / vinyl ratio was maintained at 2.0. Samples of 14 to 18 mg of catalyzed formula were placed in sample containers mounted on the instrument along with reference containers. An exothermic hydrosilylation reaction was observed for each sequential UV light pulse by calorimetric response and expressed as a percentage of the total exotherm resulting from all 9 UV pulse exposures.The sample temperature was limited to the range of 25 to 80 °C. The results are tabulated below: TABLE 9: Pt formulation of 50 ppm Isothermal Temp., C 1st exposure, % exothermic 2nd exposure, % exothermic 4th exposure, % exothermic 6th exposure, % exothermic 25 49.8 75.7 84.0 90.4 50 74.7 81 86.2 95.0 60 80.7 87.6 93.3 97.0 70 85.4 88.3 92.3 95.3 80 75.8 83.3 88.0 92.0 TABLE 10: 25 ppm Pt formulation Isothermal Temp., C 1st exposure, % exothermic 2nd exposure, % exothermic 4th exposure, % exothermic 6th exposure, % exothermic 25 66.8 83.8 89.6 93.3 50 83.2 88.2 93.3 98.1 Petition 870240108444, dated 12 / 19 / 2024, page 54 / 116 45 / 46 Isothermal Temp., C 1st exposure, % exothermic 2nd exposure, % exothermic 4th exposure, % exothermic 6th exposure, % exothermic 80 84.3 87.4 91.9 95.1

[0114] An ideal photo-DSC response would be that the initial exposure of 0.6 seconds would result in the complete reaction of vinyl and SiH available in the formulation (100% exotherm). What this experiment demonstrated was that gentle heating of the curable formulation before UV light exposure unequivocally accelerates the photoresponse and therefore reduces post-curing. In all cases, the reaction is essentially complete (>90%) after 6 x 0.6 seconds of UV light exposure, but preheating the curable sample to 70 °C (with 50 ppm of Pt present) results in an increase in the % reaction with an exposure from about 50% to about 85%. The anomalous result of 80 °C is probably caused by the heat promoting the dark thermal reaction before the initial UV exposure, thus limiting the crosslinking available through photoactivation. Similar effects were observed when the catalyst concentration was reduced to 25 ppm Pt.

[0115] Thus, MeCpPtMe3 catalyzed light-curing silicone coatings can be crosslinked more effectively and quickly by passing the coated substrate through gentle heat from an oven or IR lamp radiation immediately before passing the heated coating under UV curing lamps; a double curing process. Heating the coated formulation and the substrate to which it is applied to 60 °C to 120 °C should prevent or minimize dewetting of paper substrates or damage to the film or plastic-coated paper substrates, and the subsequent UV curing should be faster and more complete than exposure to UV rays alone.

[0116] What has been described above includes examples from this report. Petition 870240108444, dated 12 / 19 / 2024, p. 55 / 116 46 / 46 Descriptive. Obviously, it is not possible to describe all conceivable combinations of components or methodologies for the purposes of describing this descriptive report, but a person skilled in the art may recognize that many other combinations and permutations of this descriptive report are possible. Consequently, this descriptive report is intended to encompass all alterations, modifications, and variations that fall within the spirit and scope of the appended claims. Furthermore, to the extent that the term “includes” is used in the detailed description or claims, such term is intended to be inclusive in a manner similar to the term “comprising,” as “comprising” is interpreted when employed as a transitional word in a claim.

[0117] The preceding description identifies various non-limiting embodiments of a photocurable silicone composition, coatings formed from such compositions, articles comprising such coatings, and methods of forming such coatings and articles. Modifications may occur for those skilled in the art and for those who may make and use the invention. The embodiments disclosed are merely for illustrative purposes and are not intended to limit the scope of the invention or the subject matter set forth in the claims.

Claims

1. Photocurable silicone composition CHARACTERIZED by the suit comprising: (i) a vinyl functional polysiloxane; (ii) a hydride functional siloxane; (iii) a photoactive catalyst; and (iv) an acid anhydride functional polysiloxane.

2. Photocurable silicone composition, according to claim 1, CHARACTERIZED in that the vinyl functional polysiloxane is of formula (I): M1ViaM2bD1VicD2dT1VieT2fQ1g where M1Vi = (R1)(R2)(CH2=CH)SiO1 / 2 M2 = (R3)(R4)R5SiO1 / 2 D1Vi = (R6)(CH2=CH)SiO2 / 2 D2 = (R7)(R8)SiO2 / 2 T1Vi = (CH2=CH)SiO3 / 2 T2 = (R9)SiO3 / 2 Q1 = SiO4 / 2 where R1, R2, R3, R4, R5, R6, R7, R8 and R9 are each independently a C1-C10 saturated hydrocarbon radical; 50 < a + b + c + d + e + f + g < 10,000, and a + c + e is greater than 0.

3. Photocurable silicone composition, according to claim 1, CHARACTERIZED in that the vinyl functional polysiloxane is of formula (Ia): M1viD1vicD2dM1vi (Ia) where M1vi is (R1)(R2)(CH2=CH)SiO1 / 2; D1vi is (R6)(CH2=CH))SiO2 / 2; D2 is (R7)(R8)SiO2 / 2; R1, R2, R3, R5, R6, R7 and R8 are each independently a C1-C10 saturated hydrocarbon radical; c is 0 to 10; ed is 50 to 250.

4. Photocurable silicone composition, according to any one of claims 1 to 3, CHARACTERIZED in that the hydride functional siloxane is of formula (II): M3HhM4iD3HjD4kT3HlT4mQ2n (||) where M3H = (R10)(R11)(H)SiO1 / 2 M4 = (R12)(R13)(R14)SiO1 / 2 D3H = (R15)(H)SiO2 / 2 D4 = (R16)(R17)SiO2 / 2 T3H = (H)SiO3 / 2 T2 = (R18)SiO3 / 2 Q2 = SiO4 / 2 where R10, R11, R12, R13, R14, R15, R16, R17 and R18 are each independently a saturated hydrocarbon radical C1-C10; the subscripts h, i, j, k, l, men are zero or positive subject to the following limitations: 2 < h + i + j + k + l + m + n < 1,000, and h + j + l is greater than 0.

5. Photocurable silicone composition, according to claim 4, CHARACTERIZED in that the hydride functional siloxane is of formula (IIb): M4D3HjM4 (IIb) where M4 D3H and M4 are defined above and j is 10 to 40.

6. Photocurable silicone composition, according to claim 4, CHARACTERIZED in that the hydride functional siloxane is a copolymer of formula (IIa): M4D3HjD4kM4Q2 (IIa) where M4 D3H, D4, M4 and Q2 are defined above and j + k is 10 to 40.

7. Photocurable silicone composition, according to any of claims 1 to 6, CHARACTERIZED in that the photoactive catalyst is selected from one or more of a platinum-cyclopentadiene complex of formula (i) R19CpPtR203, where R19 and R20 are each independently selected from a C1-C10 alkyl group, and Cp is a cyclopentadiene group, in which the link between Cp and Pt is an eta link; (ii) [(R29)a(R30)bCp]Pt(R31)3 where R29 is a C7-20 aromatic organic radical, R30 and R31 are each independently a C1-22 aliphatic organic radical, Cp is a cyclopentadienyl radical, “a” is an integer equal to 1 to 3 inclusive, “b” is an integer equal to 0 to 3 inclusive, and the sum of a + b is equal to 1 to 4 inclusive;and / or (iii) [(R32)c(R33)dCp]PtR34R35Q, where R32 is a C6-20 aromatic radical, R33, R34 and R35 are each independently a C1-22 aliphatic organic radical, Cp is a cyclopentadienyl radical, Q is a silicon-containing organic sensitizer group, “c” and “d” are independently integers equal to 0 to 5 inclusive, and the sum of “c + d” is equal to 0 to 5 inclusive.

8. Photocurable silicone composition, according to claim 7, CHARACTERIZED in that the photoactive catalyst is a Pt(IV) methylcyclopentadienyltrimethylplatinum compound.

9. Photocurable silicone composition, according to any one of claims 1 to 8, CHARACTERIZED in that the acid anhydride functional silicone is a compound of the formula: M5AD5oD6ApD7HqM5A where M5A is (R21)(R22)(R23)SiO1 / 2, D5 is (R24)(R25)SiO2 / 2, D6A is (R26)(R27)SiO2 / 2, D7H = (R28)(H)SiO2 / 2 where R21, R22, R24, R25, R26 and R28 are each independently a saturated C1-C10 hydrocarbon radical; R23 and R27 each represent Petition 870240108444, dated 12 / 19 / 2024, p. 59 / 116 4 / 6 independently, an acid anhydride functional group that can be derived from the reaction of allyl succinic anhydride with Si(H) functionality; o + q is 10 to 40, ep is 1 to 20.

10. Photocurable silicone composition, according to any one of claims 1 to 9, CHARACTERIZED by the suit further comprising a siloxanol resin.

11. Photocurable silicone composition, according to any one of claims 1 to 10, CHARACTERIZED in that the ratio of hydride groups to vinyl groups is from about 0.5:1 to about 10:

1.

12. Photocurable composition, according to any one of claims 1 to 11, CHARACTERIZED in that the ratio of hydride groups to vinyl groups is from about 1.5:1 to about 3:

1.

13. Photocurable composition, according to any one of claims 1 to 11, CHARACTERIZED in that the ratio of hydride groups to vinyl groups is from about 2:1 to about 2.5:

1.

14. Photocurable composition, according to any one of claims 1 to 13, CHARACTERIZED in that the vinyl functional polysiloxane (i) is present in an amount of about 80 to about 99 parts by weight; the hydride functional polysiloxane (ii) is present in an amount of about 1 to about 20 parts by weight; the acid anhydride functional polysiloxane (iv) is present in an amount of about 0.1 to 10 parts by weight and the photoactive catalyst (iii) is present in an amount sufficient to provide platinum in an amount of about 50 to about 150 ppm; and each of the parts by weight is based on the total weight of the composition.

15. Method for forming a silicone film on a substrate CHARACTERIZED in that it comprises: (a) applying the photocurable silicone composition, as defined in any one of claims 1 to 14, onto the surface of the substrate; and (b) exposing the photocurable silicone composition to a UV light source having a wavelength of about 25 nm to about 500 nm; and exposing the silicone composition and the substrate to which it is applied to a heat source before exposing the composition to the UV light source.

16. Method according to claim 15, CHARACTERIZED in that the UV light source is a mercury vapor type H+ UV lamp.

17. Method according to claim 15, CHARACTERIZED in that the UV light source is a type D iron-doped mercury vapor UV lamp.

18. Method, according to any one of claims 15 to 17, CHARACTERIZED in that the substrate carrying the silicone composition is transported at a speed of about 20 feet per minute to about 1,000 feet per minute.

19. A method, according to any one of claims 15 to 18, CHARACTERIZED in that it further comprises focusing the light from the UV light source onto the composition using one or more reflectors.

20. Method according to claim 15, CHARACTERIZED in that the heat source is chosen from an oven, an infrared lamp, an LED light source or a combination thereof.

21. Method, according to claim 15 or 20, CHARACTERIZED in that the composition and the substrate to which it is applied are heated to a temperature of about 25 °C to about 120 °C.

22. Method, according to any one of claims 15 to 21, CHARACTERIZED in that the substrate is selected from one or more of glassine, supercalendered Kraft paper (SCK), clay-coated Kraft paper (CCK), polyethylene, polypropylene, polyester, a polyethylene Kraft paper (PK) Petition 870240108444, dated 12 / 19 / 2024, page 61 / 116 6 / 6 or a polypropylene Kraft paper (PPK).

23. Article CHARACTERIZED by the fact that it comprises a coating formed from the photocurable composition, as defined in any of claims 1 to 14, disposed on the surface of a substrate.

24. Article according to claim 23, CHARACTERIZED in that the article is a release coating and the substrate is selected from one or more of glassine, supercalendered Kraft paper (SCK), clay-coated Kraft paper (CCK), polyethylene, polypropylene, polyester, a polyethylene Kraft paper (PK) or a polypropylene Kraft paper (PPK).

25. Adhesive article CHARACTERIZED in that it comprises a releasable adhesive backing substrate in contact with a release layer, the release layer comprising a coating formed from the photocurable composition, as defined in any one of claims 1 to 14.

26. Article CHARACTERIZED by the fact that it is formed from the method as defined in any one of claims 15 to 22.