Composition for preparing anti-sticking coating and method for preparing coated substrate

Abstract

A composition for forming a release coating includes (A) an organopolysiloxane having an average of at least two methanol functional groups per molecule. The composition also includes (B) a polyisocyanate component. Component (B) comprises (b1) an isocyanate-functional copolymer and (b2) a polyisocyanate different from component (b1). The release coating formed with the composition is not a foam. An anti-sticking coating formed with the composition is also disclosed. In addition, a method of preparing a coated substrate comprising an anti-sticking coating disposed on a substrate, and a coated substrate formed according to the method are disclosed.

Description

[0001] Cross - reference to related applications

[0002] None. Technical field

[0003] The present disclosure generally relates to a composition, and more particularly to a composition for preparing an anti - sticking coating and related methods. Background art

[0004] Silicone compositions are known in the art and are used in numerous industries and end - use applications. One such end - use application is to form anti - sticking coatings or liners from which adhesives can be removed. For example, silicone compositions can be used to coat various substrates, such as paper, to obtain anti - sticking liners for laminating pressure - sensitive adhesives (e.g., tapes). Such silicone compositions are typically addition - curable.

[0005] Conventional anti - sticking liners are typically formed by subjecting an organopolysiloxane having unsaturated hydrocarbon groups to an addition reaction (or hydrosilylation) with an organohydrogenpolysiloxane in the presence of a hydrosilylation reaction catalyst at an elevated temperature. In certain applications, anti - sticking liners are formed at high speed via a coating process. The cure rate for forming conventional anti - sticking liners is particularly important. Additionally, many conventional anti - sticking liners are formed on substrates that are susceptible to softening or other undesirable effects attributable to the elevated temperatures required for curing, which limits the types of substrates that can be used. Summary of the invention

[0006] Disclosed is a composition for forming an anti - sticking coating. The composition comprises (A) an organopolysiloxane having an average of at least two methoxy functional groups per molecule. The composition further comprises (B) a polyisocyanate component. Component (B) comprises (b1) an isocyanate - functional copolymer and (b2) a polyisocyanate different from component (b1). The anti - sticking coating formed with this composition is not a foam. Also disclosed is an anti - sticking coating formed with this composition.

[0007] Additionally, disclosed is a method of preparing a coated substrate comprising an anti - sticking coating disposed on a substrate, and a coated substrate formed according to the method. Detailed description

[0008] Disclosed is a composition for forming an anti - sticking coating. The composition comprises (A) an organopolysiloxane having an average of at least two methoxy functional groups per molecule. The methoxy functional groups on the organopolysiloxane are different from silanol groups, wherein the methoxy functional groups include carbon - bonded hydroxyl groups, while the silanol functional groups include silicon - bonded hydroxyl groups. In other words, the methoxy functional groups include a moiety of the formula –COH, while the silanol functional groups have the formula –SiOH. These functional groups behave differently; for example, silanol functional groups can readily condense to form siloxane (-SiOSi-) bonds, which generally does not occur with methoxy functional groups (at least under the same catalysis as silanol functional group condensation). The methoxy functional groups of component (A) can be the same or different from each other. In certain embodiments, the organopolysiloxane (A) includes an average of at least three, alternatively at least four methoxy functional groups per molecule. For example, the organopolysiloxane (A) can include an average of 2 to 8, alternatively 3 to 8, alternatively 3 to 7, alternatively 3 to 6, alternatively 3 to 5 methoxy functional groups per molecule. In other embodiments, the organopolysiloxane (A) can include an average of 4 to 12, alternatively 6 to 10 methoxy functional groups per molecule.

[0009] In certain embodiments, the methoxy functional groups independently have the general formula -D - O a -(C b H 2b O) c -H, where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each moiety indicated by subscript c, and subscript c is 0 to 500, provided that subscripts a and c are not both 0.

[0010] In one embodiment, subscript c and the moieties indicated by subscript c are selected such that at least one of the methoxy functional groups in the methoxy functional groups has the general formula:

[0011] –D–O a –[C 2 H 4 O] d [C 3 H 6 O] e [C 4 H 8 O] f –H;

[0012] where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, 0 ≤ d ≤ 500, 0 ≤ e ≤ 500, and 0 ≤ f ≤ 500, provided that 1 ≤ d + e + f ≤ 500. In these embodiments, the methoxy functional groups can alternatively be referred to as polyether groups or moieties, but the polyether groups or moieties are of the form –COH rather than –COR0 End-capping, where R 0 is a monovalent hydrocarbon group, which is the case for certain conventional polyether groups or moieties. As understood in the art, the moiety indicated by the subscript d is an ethylene oxide (EO) unit, the moiety indicated by the subscript e is a propylene oxide (PO) unit, and the moiety indicated by the subscript f is a butylene oxide (BO) unit. The EO, PO, and BO units (if present) can be in block or random form in the polyether group or moiety. The relative amounts of the EO, PO, and BO units (if present) can be selectively controlled based on the desired properties of the organopolysiloxane (A), the composition, and the resulting anti-stick coating. For example, the molar ratio of such alkylene oxide units can affect hydrophilicity and other properties.

[0013] Each methanol functional group of component (A) can include more than one -COH moiety per methanol functional group. In other words, a single methanol functional group substituent can include more than one methanol functional moiety. For example, any of the EO, PO, or BO units in the methanol functional group can include a side group OH group, i.e., a hydrogen atom of the EO, PO, or BO group can be replaced by an OH group. Merely as an example, the methanol functional group can have the formula –D–O–CH 2 CH(OH)CH 2 OH.

[0014] In one embodiment, component (A) is substantially linear. Substantially linear means that component (A) contains M and D siloxane units, consists essentially of M and D siloxane units, or consists only of M and D siloxane units. As is readily understood in the art, the M siloxane unit has the formula [R 3 SiO 1 / 2 and the D siloxane unit has the formula [R 2 SiO 2 / 2 . Traditionally, the M and D siloxane nomenclature has been used only in combination with methyl substitution. However, for the purposes of the present disclosure, in the above M and D siloxane units, R is independently selected from substituted or unsubstituted hydrocarbon groups or methanol functional groups, provided that at least two of the Rs are independently selected from methanol functional groups. When the M siloxane unit includes at least one methanol functional group, the methanol functional group is a terminal group. When the D siloxane unit includes at least one methanol functional group, the methanol functional group is a side group. The substantially linear organopolysiloxane can have the average formula: R a' SiO (4-a') / 2 , where each R is independently selected and as defined above, including the condition that at least two of the Rs are independently selected methanol functional groups, and where the subscript a' is selected such that 1.9 ≤ a' ≤ 2.2.

[0015] Typically, the hydrocarbyl groups suitable for R can independently be straight-chain, branched-chain, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. The cyclic hydrocarbyl groups can independently be monocyclic or polycyclic. The straight-chain and branched-chain hydrocarbyl groups can independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. General examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as their derivatives, modifications, and combinations. Examples of suitable alkyl groups include 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, hexadecyl, octadecyl, and branched saturated hydrocarbon groups having 6 to 18 carbon atoms. Examples of suitable non-conjugated cyclic groups include cyclobutyl, cyclohexyl, and cycloheptyl groups. Examples of suitable aryl groups include phenyl, tolyl, xylyl, naphthyl, benzyl, and dimethylphenyl. Examples of suitable alkenyl groups include vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, heptenyl, hexenyl, hexadecenyl, octadecenyl, and cyclohexenyl groups. Examples of suitable monovalent halohydrocarbon groups (i.e., halocarbon groups or substituted hydrocarbon groups) include haloalkyl groups, aryl groups, and combinations thereof. Examples of haloalkyl groups include alkyl groups in which one or more of the above hydrogen atoms are replaced by halogen atoms such as F or Cl. Specific examples of haloalkyl groups include fluoromethyl, 2-fluoropropyl, 3,3,3-trifluoropropyl, 4,4,4-trifluorobutyl, 4,4,4,3,3-pentafluorobutyl, 5,5,5,4,4,3,3-heptafluoropentyl, 6,6,6,5,5,4,4,3,3-nonafluorohexyl, and 8,8,8,7,7-pentafluorooctyl, 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, chloromethyl, chloropropyl, 2-dichlorocyclopropyl, and 2,3-dichlorocyclopentyl groups, as well as their derivatives. Examples of haloaryl groups include aryl groups in which one or more of the above hydrogen atoms are replaced by halogen atoms such as F or Cl. Specific examples of haloaryl groups include chlorobenzyl and fluorobenzyl groups.

[0016] In a specific embodiment, each R that is not a methanol functional group is independently selected from alkyl groups having 1 to 32, alternatively 1 to 28, alternatively 1 to 24, alternatively 1 to 20, alternatively 1 to 16, alternatively 1 to 12, alternatively 1 to 8, alternatively 1 to 4, alternatively 1 carbon atom.

[0017] In an embodiment where component (A) is linear, component (A) can have the following general formula:

[0018]

[0019] Each R is independently selected and defined as above, with the proviso that at least two of the Rs independently contain a methanol functional group, and the subscript n is from 0 to 1,000, alternatively from 1 to 800, alternatively from 5 to 500. The subscript n may alternatively be referred to as the degree of polymerization (DP) of component (A). Generally, the DP is inversely proportional to the viscosity, all other things (such as substituents) being equal. The subscript n is alternatively greater than 0 to 95, alternatively greater than 0 to 90, alternatively greater than 0 to 85, alternatively greater than 0 to 80, alternatively greater than 0 to 75, alternatively greater than 0 to 70, alternatively greater than 0 to 65. Alternatively, the subscript n is from 5 to 70, alternatively from 10 to 65.

[0020] In a specific embodiment, when component (A) is linear, each methanol functional group is a side group, such that the organopolysiloxane (A) has the following general formula:

[0021]

[0022] where each R 1 is an independently selected substituted or unsubstituted hydrocarbon group, each X is –D–O a –(C b H 2b O) c –H, where D and the subscripts a-c are defined as above, each subscript R 2 is independently selected from R 1 and X, and the subscripts p and q are each from 1 to 99, with the proviso that p + q ≤ 100, alternatively 5 < (p + q) < 70, alternatively 10 < (p + q) < 65. In these or other embodiments, the subscript q is from 1 to 99, alternatively from 5 to 85, alternatively from 10 to 70, alternatively from 20 to 60, alternatively from 30 to 50. In these or other embodiments, the subscript p is from 1 to 99, alternatively from 1 to 60, alternatively from 1 to 30, alternatively from 2 to 20, alternatively from 2 to 10. In the general formula above, the siloxane units indicated by the subscripts q and p can be random or in block form. The general formula above is intended to represent the average unit formula of component (A) in this embodiment, based on the number of R 1 2 SiO 2 / 2 units represented by the subscript q and the number of R 2 XSiO 2 / 2 units represented by the subscript p, without requiring their specific order. Thus, the general formula can alternatively be written as [(R 1 ) 3 SiO 1 / 2 2 [(R 1 ) 2 SiO​2 / 2 q [(R 1 )XSiO 2 / 2 p , where the subscripts q and p are defined as above. In these embodiments, the methoxy functional group is a polyether group, and the polyether group is a side group in component (A). When each R 1 is methyl, this embodiment of component (A) is trimethylsilyloxy-terminated and includes dimethylsilyloxy units (indicated by subscript q).

[0023] In other specific embodiments, when component (A) is linear, each methoxy functional group is a terminal group, such that the organopolysiloxane (A) has the following general formula:

[0024]

[0025] In each case where R 1 is independently selected and defined as above, each X is independently selected and defined as above, and q' is from 1 to 100, alternatively from 5 to 70, alternatively from 10 to 65. In still other embodiments, component (A) is linear, and the methoxy functional groups are in linear and side group positions.

[0026] In still other specific embodiments, when component (A) is linear, each methoxy functional group is a side group, such that the organopolysiloxane (A) has the following general formula:

[0027] R 1 3 O[SiR 1 2 O] w' [SiR 1 XO] x' R 1 3 , where each R 1 and each X are independently selected and defined as above; the subscript w' is from 10 to 1000, alternatively from 10 to 800, alternatively from 10 to 600, alternatively from 10 to 400, alternatively from 10 to 200, and the subscript x' is from 4 to 200, alternatively from 4 to 180, alternatively from 4 to 160, alternatively from 4 to 140, alternatively from 4 to 120, alternatively from 4 to 100, alternatively from 4 to 80, alternatively from 4 to 60, alternatively from 4 to 40, alternatively from 4 to 20. The portions indicated by the subscripts w' and x' can be random or in block form in component (A).

[0028] ​​D is typically a function of the preparation of the organopolysiloxane (A). For example, the organopolysiloxane (A) can be formed by a hydrosilylation reaction between an organohydrogenpolysiloxane and an unsaturated methanol compound (which may be referred to herein as an alcohol compound or an unsaturated alcohol compound). In such an embodiment, the organohydrogenpolysiloxane includes silicon-bonded hydrogen atoms at positions where a methanol functionality is desired (such as end groups and / or side groups). The unsaturated alcohol compound can have the formula Z–O a –(C b H 2b O) c –H, where Z is an ethylenically unsaturated group and the subscripts a, b, and c are as defined above. Suitable examples of the hydrocarbon groups are as defined above for R.

[0029] In the above hydrosilylation reaction, the ethylenically unsaturated group represented by Z can be an alkenyl and / or alkynyl group having 2 to 18, alternatively 2 to 16, alternatively 2 to 14, alternatively 2 to 12, alternatively 2 to 8, alternatively 2 to 4, alternatively 2 carbon atoms. "Alkenyl" means an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples thereof include vinyl group, allyl group, hexenyl group, and octenyl group. "Alkynyl" means an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples thereof include ethynyl, propynyl, and butynyl groups. Various examples of the ethylenically unsaturated group include CH 2 =CH-, CH 2 =CHCH 2 -, CH 2 =CH(CH 2 ) 4 -, CH 2 =CH(CH 2 ) 6 -, CH 2 =C(CH 3 )CH 2 -, H 2 C=C(CH 3 )-, H 2 C=C(CH 3 )-, H 2 C=C(CH 3 )CH 2 -, H 2 C=CHCH 2 CH 2 -, H 2 C=CHCH 2 CH 2 CH 2 -, HC≡C-, HC≡CCH 2 -, HC≡CCH(CH3 )-, HC≡CC(CH 3 ) 2 - and HC≡CC(CH 3 ) 2 CH 2 -. Generally, the ethylenic unsaturation is at the end group of Z. As understood in the art, ethylenic unsaturation may be referred to as aliphatic unsaturation. Thus, when D is -CH 2 CH 2 -, for example, the unsaturated methanol compound may have the formula CH 2 =CH-O a -(C b H 2b O) c -H. The number of carbon atoms in D is a function of the number of carbon atoms in the ethylenic unsaturated group, which remains constant even after the hydrosilylation reaction for preparing component (A).

[0030] For example, the unsaturated alcohol compounds may include alkenyl alkoxylates such as allyl ethoxylate, vinyloxybutyl ethoxylate, isoprenyl ethoxylate, vinyl butyl propoxylate, and / or polyethylene glycol monoallyl ether.

[0031] In certain embodiments, the hydrosilylation reaction catalyst for forming component (A) comprises Group VIII to Group XI transition metals. The reference to Group VIII to Group XI transition metals is based on the modern IUPAC nomenclature. Group VIII transition metals are iron (Fe), ruthenium (Ru), osmium (Os), and hassium (Hs); Group IX transition metals are cobalt (Co), rhodium (Rh), and iridium (Ir); Group X transition metals are nickel (Ni), palladium (Pd), and platinum (Pt); and Group XI transition metals are copper (Cu), silver (Ag), and gold (Au). Their combinations, their complexes (e.g., organometallic complexes), and other forms of such metals can be used as the hydrosilylation reaction catalyst.

[0032] Additional examples of catalysts suitable for the hydrosilylation reaction catalyst include rhenium (Re), molybdenum (Mo), Group IV transition metals (i.e., titanium (Ti), zirconium (Zr), and / or hafnium (Hf)), lanthanides, actinides, and Group I and Group II metal complexes (e.g., complexes including calcium (Ca), potassium (K), strontium (Sr), etc.). Their combinations, their complexes (e.g., organometallic complexes), and other forms of such metals can be used as the hydrosilylation reaction catalyst.

[0033] The hydrosilylation reaction catalyst can be in any suitable form. For example, the hydrosilylation reaction catalyst can be a solid, examples of which include platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, as well as nickel-based catalysts. Specific examples thereof include nickel, palladium, platinum, rhodium, cobalt, and similar elements, as well as catalysts such as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts including combinations of multiple metals. Additional examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-Al, Cu-Zn-Ti, and similar copper-containing catalysts, etc.

[0034] The hydrosilylation reaction catalyst can be located within the solid support or on top of the solid support. Examples of the support include activated carbon, silica, silica-alumina, alumina, zeolite, and other inorganic powders / granules (e.g., sodium sulfate), etc. The hydrosilylation reaction catalyst can also be disposed in a medium, such as a solvent that dissolves the hydrosilylation reaction catalyst, or alternatively, a medium that only carries but does not dissolve the hydrosilylation reaction catalyst. Such media are known in the art.

[0035] In a specific embodiment, the hydrosilylation reaction catalyst includes platinum. In these embodiments, the hydrosilylation reaction catalyst is exemplified by, for example, platinum black, compounds (such as chloroplatinic acid, chloroplatinic acid hexahydrate, the reaction product of chloroplatinic acid and a monohydric alcohol, bis(ethyl acetoacetato)platinum, bis(acetylacetone)platinum, platinum chloride), and complexes of such compounds with olefins or organopolysiloxanes, as well as platinum compounds microencapsulated in a matrix or core-shell type compound. Microencapsulated hydrosilylation catalysts and their preparation methods are also known in the art.

[0036] The complex of platinum and organopolysiloxane suitable for use as a hydrosilylation reaction catalyst includes the complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and platinum. These complexes can be microencapsulated in a resin matrix. Alternatively, the hydrosilylation reaction catalyst can include the complex of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane and platinum. The hydrosilylation reaction catalyst can be prepared by a method including reacting chloroplatinic acid with an aliphatic unsaturated organosilicon compound such as divinyltetramethyldisiloxane or an olefin-platinum-silyl complex. The olefin-platinum-silyl complex can be prepared, for example, by mixing 0.015 moles of (COD)PtCl 2 with 0.045 moles of COD and 0.0612 moles of HMeSiCl 2 where COD is cyclooctadiene.

[0037] The hydrosilylation reaction catalyst is used in the composition in a catalytic amount (i.e., an amount or quantity sufficient to promote its curing under the desired conditions). The hydrosilylation reaction catalyst can be a single hydrosilylation reaction catalyst or a mixture comprising two or more different hydrosilylation reaction catalysts.

[0038] Alternatively, when component (A) is formed by a reaction other than hydrosilylation, such as a condensation reaction or a ring-opening reaction, D can be a covalent bond.

[0039] As described above, in other embodiments, the organopolysiloxane (A) is branched, i.e., component (A) includes at least one T and / or Q siloxane unit. In one specific embodiment, the organopolysiloxane (A) is a Q-branched polymer, i.e., the organopolysiloxane (A) includes a single Q siloxane unit. In other embodiments, the organopolysiloxane (A) includes two or more Q units. In still other embodiments, the organopolysiloxane (A) includes one or more T units, or a combination of T units and Q units. Even when the organopolysiloxane (A) includes branching attributable to T and / or Q units, the organopolysiloxane (A) is generally flowable at 25 °C. By "flowable" is meant that the organopolysiloxane (A) is flowable at 25 °C and / or has a viscosity that can be measured at 25 °C. In certain embodiments, the organopolysiloxane (A) is flowable in the absence of any solvent (e.g., an organic solvent). In a specific embodiment, the organopolysiloxane (A) is a liquid at 25 °C in the absence of any solvent. In contrast, an MQ resin, which can be distinguished from a Q-branched polymer, is generally a solid at room temperature unless dissolved in a solvent. When component (A) is a Q-branched polymer, all other conditions being the same, the composition generally cures faster than when component (A) is linear. However, using a linear component (A) does not sacrifice the performance characteristics of the resulting anti-stick coating.

[0040] In certain embodiments in which the organopolysiloxane (A) is branched, the organopolysiloxane (A) has the following average formula:

[0041] [Z 1 v [R 1 3 SiO 1 / 2 w [R 1 2 XSiO 1 / 2 x [R 1 2 SiO 2 / 2 y [R 1 XSiO 2 / 2 ​​​​​z [SiO 4 / 2 1.0

[0042] where 0 ≤ v ≤ 12, 0 ≤ w ≤ 8, 0 ≤ x ≤ 8, 40 ≤ y ≤ 1,000 and 0 ≤ z ≤ 8, provided that 2 ≤ (x + z) ≤ 8; each R 1 is independently selected and defined as above; each X is an independently selected methanol functional group; and Z 1 is independently of the formula (O 1 / 2 SiR 1 2 -D 1 -R 1 SiO 2 / 2 ) or (O 1 / 2 SiR 1 2 -D 1 -R 1 2 SiO 1 / 2 ) moiety, where each R 1 is independently selected and defined as above, and each D 1 is an independently selected divalent linking group. In the moiety indicated by the subscript v, the silicon atom is linked via D 1 , which is typically a divalent hydrocarbon group from hydrosilylation. The subscripts v, w, x, y and z represent the molar number of each particular siloxy unit of each Q siloxy unit, which is normalized to one. In the above average formula, the subscripts v, w, x, y and z are normalized based on the presence of one Q siloxy unit. However, this does not mean that the organopolysiloxane (A) only includes one Q siloxy unit. In certain embodiments, the organopolysiloxane (A) only includes one Q siloxy unit. In other embodiments, the organopolysiloxane (A) includes two or more Q siloxy units, i.e., a plurality of Q siloxy units, which may aggregate together in the component (A).

[0043] ​In a specific embodiment, the subscript v is 0. In another specific embodiment, the subscript v is from 2 to 12, alternatively from 2 to 11, alternatively from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 7, alternatively from 2 to 6, alternatively from 3 to 6, alternatively from 3 to 5. In these or other embodiments, the subscript w is from 0 to 8, alternatively from 2 to 8, alternatively from 3 to 8, alternatively from 4 to 8, alternatively from 5 to 8, alternatively from 6 to 8, alternatively 7 or 8, alternatively 8. In these or other embodiments, the subscript x is from 0 to 8, alternatively from 0 to 6, alternatively from 0 to 4, alternatively from 0 to 3, alternatively from 0 to 2, alternatively 0 or 1, alternatively 0. In these or other embodiments, the subscript y is from 40 to 500, alternatively from 40 to 400, alternatively from 40 to 300, alternatively from 40 to 200, alternatively from 50 to 150, alternatively from 60 to 125. In these or other embodiments, the subscript z is from 1 to 8, alternatively from 2 to 7, alternatively from 3 to 6, alternatively from 3 to 5, alternatively 4. D 1 is typically a divalent hydrocarbon group and has 2 to 12, alternatively 2 to 10, alternatively 2 to 8, alternatively 2 to 6, alternatively 2 to 4, alternatively 2 carbon atoms. For example, when the hydrosilylation reaction involves a silicon-bonded vinyl group, D 1 has two carbon atoms.

[0044] When the organopolysiloxane (A) is branched, the organopolysiloxane (A) can be prepared in various ways. For example, the organopolysiloxane (A) can be prepared as described above, for example, via the hydrosilylation of an unsaturated alcohol compound and an organohydrogenpolysiloxane, where in this embodiment, the organohydrogenpolysiloxane itself is branched.

[0045] In other embodiments, the organopolysiloxane (A) is prepared via the hydrosilylation of an initial organosiloxane, an organohydrogenpolysiloxane, and an alcohol compound. The alcohol compound typically includes a terminal unsaturated group with a methanol functional group for participating in the hydrosilylation reaction to produce the organopolysiloxane (A), examples of which were described above with respect to the methanol functional group. When the organopolysiloxane (A) includes a single Q silanoxy unit, the initial organosiloxane can have the formula M Vi 4 Q, where M Vi has the formula (CH 3 ) 2 (CH 2 =CH)SiO 1 / 2 , and Q has the formula SiO 4 / 2 . When the organopolysiloxane (A) includes two Q silanoxy units, the initial organosiloxane can have the formula M Vi 3 Q-QM Vi 3。The vinyl groups exemplified herein can be replaced by any silicon-bonded alkenyl or alkynyl group.

[0046] The organohydrogensiloxane can include side and / or terminal silicon-bonded hydrogen atoms, which affect the structure of the resulting organopolysiloxane (A). In one embodiment, an initial siloxane and an organohydrogensiloxane are first reacted to obtain a reaction intermediate comprising residual silicon-bonded hydrogen atoms (or silane hydride functionality), and then the reaction intermediate is reacted with an alcohol compound to obtain the organopolysiloxane (A). In other embodiments, the initial siloxane, organohydrogensiloxane, and alcohol compound are reacted simultaneously.

[0047] When the organohydrogensiloxane includes only terminal silicon-bonded hydrogen atoms, the organohydrogensiloxane forms a linear organosiloxane chain extending from each M siloxy unit of the initial siloxane after hydrosilylation of the ethylenically unsaturated group of each M siloxy unit, and is then capped (also via hydrosilylation) with an alcohol compound, which gives a methanol functionality. For example, in these embodiments, and when the organopolysiloxane (A) includes a single Q siloxy unit, the organopolysiloxane (A) can have the formula: Si-([OSiR 2 -D 1 -[-SiR 2 O 1 / 2 [R 2 SiO 2 / 2 m’ [XR 2 SiO 1 / 2 ) 4 , where each R is independently selected and defined as above, each D 1 is independently selected and defined as above, each subscript m' is independently from 10 to 250, and each X is a methanol functionality independently selected. When forming the organopolysiloxane (A) with an organohydrogensiloxane that includes only terminal silicon-bonded hydrogen atoms, Z 1 is typically (O 1 / 2 SiR 1 2 -D 1 -R 1 2 SiO 1 / 2 ), where R 1 and D 1 are independently selected and defined as above.

[0048] In certain embodiments, when the organohydrogensiloxane includes only terminal silicon-bonded hydrogen atoms, the organopolysiloxane (A) has the formula:

[0049] [O 1 / 2 SiR 1 2 ​-D 1 -R 1 2 SiO 1 / 2 v [R 1 2 XSiO 1 / 2 x [R 1 2 SiO 2 / 2 y [SiO 4 / 2 1.0 ,

[0050] wherein R 1 、D 1 、X, v, x and y are as defined above.

[0051] As described in the average formula for an exemplary embodiment of the organopolysiloxane (A) above, although there is a single Q silanolate unit, there can be more than 4 terminal M silanolate units. In contrast, in a conventional organopolysiloxane, the ratio of M units to Q units is typically 4:1 or less. The ratio of M units to Q units is a function of the additional branching that can be imparted in forming the organopolysiloxane (A) described below.

[0052] For example, when the organohydrogensiloxane includes only hydrogen atoms bonded to silicon in the side groups, the organopolysiloxane (A) includes additional branching. For example, in this embodiment, when the organopolysiloxane (A) includes a single Q unit, the organopolysiloxane (A) includes eight terminal M units instead of four (as in the above embodiment). In these embodiments, the moiety Z represented by the subscript v 1 is generally greater than 0, and most typically the subscript v is 4.

[0053] As a specific example of an organohydrogensiloxane that includes only hydrogen atoms bonded to silicon in the side groups, the organopolysiloxane (A) can have the formula Si-Y 4 , wherein each Y independently has the following structure:

[0054]

[0055] wherein each R 1 、each D 1 、each m' and each X are independently selected and as defined above. It should be understood that the SiR 2 O 2 / 2 and SiRXO 2 / 2 units in Y can be in any position within the moiety represented by Y. For example, the SiRXO 2 / 2 unit can be separated from the M unit by another SiR 2 O 2 / 2 ​​​​Unit. In these embodiments, the organopolysiloxane (A) may alternatively be represented by Si-[OSiR 2 -D 1 -Y 1 , where each Y 1 comprises two R 3 SiO 1 / 2 units, one SiRXO 2 / 2 unit, and 1 to 250 SiR 2 O 2 / 2 units, as well as the -SiRO 1 unit that connects Y 1 to D 2 / 2 .

[0056] When the organohydrogensiloxane only comprises hydrogen atoms bonded to silicon in the side groups, the organohydrogensiloxane forms a linear organosiloxane chain upon hydrosilylation with an ethylenically unsaturated group, which caps each M siloxane unit of the initial organosiloxane but does not extend beyond the Q siloxane units of the initial organosiloxane. When forming the organopolysiloxane (A) with an organohydrogensiloxane that only comprises hydrogen atoms bonded to silicon in the side groups, Z 1 is typically (O 1 / 2 SiR 1 2 -D 1 -R 1 SiO 2 / 2 ), where R 1 and D 1 are independently selected and defined as above. Z 1 represents the M siloxane units of the initial organosiloxane and the siloxane units of the organohydrogensiloxane hydrosilylated therewith.

[0057] In certain embodiments, when the organohydrogensiloxane only comprises hydrogen atoms bonded to silicon in the side groups, the organopolysiloxane (A) has the following formula:

[0058] [O 1 / 2 SiR 1 2 -D 1 -R 1 SiO 2 / 2 v [R 1 3 SiO 1 / 2 w [R 1 2 SiO 2 / 2 y [R 1 XSiO 2 / 2 z [SiO 4 / 2 ​​​​​1.0

[0059] wherein R 1 , D 1 , X, v, w, y and z are as defined above.

[0060] In other embodiments, the organohydrogensiloxane has both hydrogen atoms bonded to silicon in side groups and end groups. In these embodiments, the organopolysiloxane (A) may include XR 2 SiO 1 / 2 and XRSiO 2 / 2 silyloxy units, wherein X and R are independently selected and as defined above.

[0061] In another specific embodiment, the organopolysiloxane (A) is prepared by the reaction of an initial organosiloxane, a cyclic organohydrogensiloxane, and an alcohol compound. In these embodiments, the cyclic organohydrogensiloxane undergoes a ring-opening polymerization reaction and causes the formation of D silyloxy units in the organopolysiloxane (A). In this embodiment, the initial organosiloxane does not require silicon-bonded ethylenically unsaturated groups because it does not undergo any hydrosilylation reactions. Thus, the initial organosiloxane may have the formula Si-[OSiR 3 4 , wherein each R is independently selected and as defined above. When each R is methyl, the initial organosiloxane is M 4 Q or Si-[OSi(CH 3 ) 3 4 . However, the initial organosiloxane may be the same as the organosiloxane involved in hydrosilylation described above, such that the M silyloxy units include silicon-bonded ethylenically unsaturated groups, such as vinyl groups.

[0062] The cyclic organohydrogensiloxane has the formula (RHSiO 2 / 2 ) n , wherein R is independently selected and as defined above, and n is an integer from 3 to 15. In the cyclic organohydrogensiloxane, each R is typically an independently selected alkyl group, and most typically, each R is a methyl group.

[0063] The subscript n is from 3 to 15, alternatively from 3 to 12, alternatively from 3 to 10, alternatively from 3 to 8, alternatively from 3 to 6, alternatively from 4 to 5. Additionally, (ii) the cyclic organohydrogensiloxane may include a blend of different cyclic siloxanes, such as a blend of those cyclic siloxanes wherein n is 4 and those wherein n is 5. In a specific embodiment, (ii) the cyclic organohydrogensiloxane is selected from the group consisting of cyclotrisiloxane, cyclotetrasiloxane (such as octamethylcyclotetrasiloxane), cyclopentasiloxane (such as decamethylcyclopentasiloxane), cyclohexasiloxane, and combinations thereof. ​​

[0064] Typically, a cyclic organohydrogensiloxane is used together with a cyclic siloxane that does not contain silicon-bonded hydrogen atoms to selectively control the number of silicon-bonded hydrogen atoms present in the reaction intermediate formed by the ring-opening polymerization of the cyclic organohydrogensiloxane in the initial organosiloxane. The cyclic siloxane has the formula (R 2 SiO 2 / 2 ) n , where R is independently selected and as defined above, and n is an integer from 3 to 15. In the cyclic siloxane, each R is typically an independently selected alkyl group, and most typically, each R is a methyl group. The subscript n is from 3 to 15, alternatively from 3 to 12, alternatively from 3 to 10, alternatively from 3 to 8, alternatively from 3 to 6, alternatively from 4 to 5.

[0065] One of ordinary skill in the art can optimize the number of silicon-bonded hydrogen atoms in the reaction intermediate based on the molar ratio of the cyclic organohydrogensiloxane to the cyclic siloxane. For example, in certain embodiments, it may be desirable for the reaction intermediate to include four silicon-bonded hydrogen atoms such that the organopolysiloxane (A) includes four silicon-bonded methanol functional groups. In one embodiment, the molar ratio of the cyclic organohydrogensiloxane to the cyclic siloxane can be from 1:1 to 1:20, alternatively from 1:2 to 1:19, alternatively from 1:3 to 1:18, alternatively from 1:4 to 1:17, alternatively from 1:5 to 1:15, alternatively from 1:6 to 1:14, alternatively from 1:6 to 1:13, alternatively from 1:7 to 1:12, alternatively from 1:7 to 1:11.

[0066] The initial organosiloxane and the cyclic organohydrogensiloxane (and any cyclic organosiloxane) react in the presence of a polymerization catalyst. Typically, the polymerization catalyst is an acid or a base such that the reaction between the initial organosiloxane and the cyclic organohydrogensiloxane (and any cyclic organosiloxane) is either an acid-catalyzed reaction or a base-catalyzed reaction. Thus, in certain embodiments, the polymerization catalyst can be selected from the group consisting of strong acid catalysts, strong base catalysts, and combinations thereof. The strong acid catalyst can be trifluoromethanesulfonic acid, etc. The polymerization catalyst is typically a strong base catalyst. Typically, the strong base catalyst is a phosphazene catalyst, although other strong base catalysts (such as KOH) can be utilized in place of the phosphazene base catalyst.

[0067] The phosphazene catalyst typically contains at least one -(N=P<)- unit (i.e., a phosphazene unit) and is typically an oligomer having up to 10 such phosphazene units (e.g., having an average of 1.5 to up to 5 phosphazene units). The phosphazene catalyst can be, for example, a halogenated phosphazene, such as chlorophosphazene (phosphazene chloride), an oxohalogenated phosphazene, an ionic derivative of a phosphazene, such as a phosphazene salt, especially an ionic derivative of a phosphazene halide, such as a perchlorinated oligophosphazene salt or a partially hydrolyzed form thereof.

[0068] In a specific embodiment, the polymerization catalyst includes a phosphazene base catalyst. The phosphazene base catalyst can be any known in the art, but generally has the following chemical formula:

[0069] ((R 3 2 N) 3 P=N) t (R 3 2 N) 3-t P=NR 3

[0070] where each R 3 is independently selected from the group consisting of: a hydrogen atom, R 1 , and combinations thereof, and t is an integer from 1 to 3. If R 3 is R 1 , then R 3 is generally an alkyl group having from 1 to 20, alternatively from 1 to 10, alternatively from 1 to 4 carbon atoms. In any (R 3 2 N) moiety, two R 3 groups can be bonded to the same nitrogen (N) atom and linked to complete a heterocycle usually having 5 or 6 members.

[0071] Alternatively, the phosphazene base catalyst can be a salt and have one of the following alternative chemical formulas:

[0072] [((R 3 2 N) 3 P=N) t (R 3 2 N) 3-t P=N(H)R 3 + [A - ; or

[0073] [((R 3 2 N) 3 P=N) s (R 3 2 N) 4-s P] + [A -

[0074] where each R 3 ​​are independently selected and as defined above, subscript t is as defined above, subscript s is an integer from 1 to 4, and [A] is an anion and is generally selected from the group consisting of: fluoride, hydroxide, silanolate, alkoxide, carbonate, and bicarbonate. In one embodiment, the phosphazene base is aminophosphazene hydroxide.

[0075] The reaction of the initial organosiloxane and the cyclic organohydrogensiloxane (and any cyclic siloxane) in the presence of a polymerization catalyst causes ring-opening of the cyclic organohydrogensiloxane (and any cyclic siloxane) and incorporation of D-silyloxy units into the reaction intermediate. The relative amounts of the cyclic organohydrogensiloxane (and any cyclic siloxane) used are a function of the desired content of D-silyloxy units in the reaction intermediate.

[0076] In certain embodiments, in the presence of a solvent, the initial organosiloxane and the cyclic organohydrogensiloxane (and any cyclic siloxane) are reacted at an elevated temperature (e.g., 125 °C to 175 °C). Suitable solvents can be hydrocarbons. Suitable hydrocarbons include aromatic hydrocarbons such as benzene, toluene, or xylene; and / or aliphatic hydrocarbons such as heptane, hexane, or octane. Alternatively, the solvent can be a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride. A complexing agent such as bis(trimethylsilyl) hydrogen phosphate can be utilized after the reaction to inhibit the activity of the polymerization catalyst. Those skilled in the art can readily determine the catalytic amount of the polymerization catalyst to be utilized, which is a function of its selection and the reaction conditions. For example, in these embodiments, the reaction intermediate can have the following formula: [R 3 SiO 1 / 2 4 [RHSiO 2 / 2 v' [R 2 SiO 2 / 2 y [SiO 4 / 2 1.0 , where each R is independently selected and as defined above, y is as defined above, and v' is from 2 to 10, alternatively from 2 to 8, alternatively from 2 to 6, alternatively from 3 to 5.

[0077] The reaction intermediate formed via the initial organosiloxane and the cyclic organohydrogensiloxane (and any cyclic siloxane) can then be hydrosilylated with an alcohol compound to obtain the organopolysiloxane (A). Examples of the alcohol compound, together with suitable hydrosilylation reaction catalysts, are described above. When the reaction intermediate has the above formula, the organopolysiloxane (A) thus formed has the following formula: [R 3 SiO 1 / 2 4 [RXSiO 2 / 2 v’ ​​​​​​[R 2 SiO 2 / 2 y [SiO 4 / 2 1.0 , where each R is independently selected and defined as above, y is defined as above, and v' is defined as above, and each X is independently selected and defined as above.

[0078] In certain embodiments, the capillary viscosity (kinematic viscosity via a glass capillary) of component (A) at 25 °C is from 1 mPa·s to 1,000 mPa·s, alternatively from 1 mPa·s to 900 mPa·s, alternatively from 10 mPa·s to 700 mPa·s, alternatively from 10 mPa·s to 600 mPa·s. The capillary viscosity can be measured according to Dow Corning Corporate Test Method CTM0004 of July 20, 1970. CTM0004 is known in the art and is based on ASTM D445, IP 71. Generally, when component (A) has a polyether side group as a methanol functional group, component (A) has a higher viscosity than when component (A) contains a terminal methanol functional group that is not a polyether group (as shown in the exemplary structures above). For example, when component (A) contains a polyether side group, the capillary viscosity at 25 °C is typically from 200 mPa·s to 900 mPa·s, alternatively from 300 mPa·s to 800 mPa·s, alternatively from 400 mPa·s to 700 mPa·s, alternatively from 500 mPa·s to 600 mPa·s. In contrast, when component (A) contains only a terminal methanol functional group that is not a polyether group, the capillary viscosity of component (A) at 25 °C can be greater than 0 mPa·s to 250 mPa·s, alternatively greater than 0 mPa·s to 100 mPa·s, alternatively greater than 0 mPa·s to 75 mPa·s, alternatively from 10 mPa·s to 75 mPa·s, alternatively from 25 mPa·s to 75 mPa·s. In a specific embodiment, the capillary viscosity of component (A) at 25 °C is from 25 mPa·s to 1,000 mPa·s, alternatively from 50 mPa·s to 800 mPa·s, alternatively from 60 mPa·s to 700 mPa·s, alternatively from 70 mPa·s to 600 mPa·s, alternatively from 80 mPa·s to 500 mPa·s, alternatively from 90 mPa·s to 400 mPa·s.

[0079] ​​In these or other embodiments, the OH equivalent weight of component (A) can be from 100 g / mol to 2,000 g / mol, alternatively from 200 g / mol to 1,750 g / mol, alternatively from 300 g / mol to 1,500 g / mol, alternatively from 400 g / mol to 1,200 g / mol. Methods for determining the OH equivalent weight based on functionality and molecular weight are known in the art.

[0080] Based on the total weight of the composition, the composition comprises the following amounts of organopolysiloxane (A): 50 wt% to 99 wt%, alternatively 55 wt% to 99 wt%, alternatively 60 wt% to 99 wt%, alternatively 65 wt% to 99 wt%, alternatively 70 wt% to 99 wt%, alternatively 75 wt% to 99 wt%.

[0081] The composition further comprises (B) a polyisocyanate component. The polyisocyanate component comprises (b1) an isocyanate-functional copolymer; and (b2) a polyisocyanate different from component (b1). Surprisingly, it has been found that by using the polyisocyanate (B) component, the compositions of the present invention have excellent cure times attributable to the polyisocyanate (b2), while maintaining the desired compatibility between the organopolysiloxane (A) and the polyisocyanate (b2) due to the isocyanate-functional copolymer (b1). In the absence of the isocyanate-functional copolymer (b1), the polyisocyanate (b2) is generally not miscible with the organopolysiloxane (A).

[0082] The isocyanate-functional copolymer (b1) generally comprises a siloxane moiety and an organic moiety and can be random, block, branched, grafted, alternating, and / or periodic. When the isocyanate-functional copolymer (b1) comprises a siloxane moiety and an organic moiety, the isocyanate-functional copolymer (b1) is generally prepared by reacting a siloxane and a polyisocyanate. The structure of the isocyanate-functional copolymer (b1) can be selected based on the siloxane and polyisocyanate utilized.

[0083] In one embodiment, (b1) the isocyanate-functional copolymer is prepared by reacting (b1a) a siloxane having at least two methanol functional groups and (b1b) a polyisocyanate having at least two isocyanate functional groups. Since the isocyanate-functional copolymer (b1) is isocyanate-functional, component (b1) is prepared with a molar excess of isocyanate functional groups in component (b1b) compared to the methanol functional groups of component (b1a). The siloxane (b1a) can be the same as or different from the above-described organopolysiloxane (A). The methanol groups of component (b1a) can be only those described above for component (A).

[0084] The branched or grafted form of the isocyanate-functional copolymer (b1) can be prepared based on the position of the methoxy-functional groups of the siloxane (b1a) and its overall structure. For example, the siloxane (b1a) can include branching attributable to T and / or Q siloxy units, or can be linear and consist only of D and M siloxy units. Similarly, even when the siloxane (b1a) is linear, the methoxy-functional groups can be side groups, end groups, or in two positions, which affects whether the resulting isocyanate-functional copolymer (b1) is branched.

[0085] In one embodiment, the siloxane (b1a) used to prepare the isocyanate-functional copolymer (b1) is linear. In a specific embodiment, the methoxy-functional group of component (b1a) is an end group. When the siloxane (b1a) is linear with end-group methoxy-functional groups, the resulting isocyanate-functional copolymer (b1) can also be linear. In a specific embodiment, component (b1a) has the average formula R 1 2 XO[SiR 1 2 O] n' XR 1 2 , where each R 1 is independently selected substituted or unsubstituted hydrocarbyl group; each X is independently selected methoxy-functional group, and the subscript n' is from 1 to 100. Suitable hydrocarbyl groups for R 1 are as described above. In a specific embodiment, the subscript n' is from 1 to 100, alternatively 2 to 80, alternatively 2 to 60, alternatively 2 to 40, alternatively 2 to 30, alternatively 5 to 25, alternatively 10 to 20. Blends of different siloxanes can be used together as component (b1a).

[0086] Suitable polyisocyanates for component (b1b) have two or more isocyanate functional groups and include conventional aliphatic, alicyclic, araliphatic, and aromatic isocyanates. The polyisocyanate (b1b) is optionally selected from the group consisting of diphenylmethane diisocyanate (“MDI”), polymeric diphenylmethane diisocyanate (“pMDI”), hydrogenated MDI (H12MDI), toluene diisocyanate (“TDI”), hexamethylene diisocyanate (“HDI”), dicyclohexylmethane diisocyanate (“HMDI”), isophorone diisocyanate (“IPDI”), cyclohexyl diisocyanate (“CHDI”), naphthalene diisocyanate (“NDI”), phenyl diisocyanate (“PDI”), and combinations thereof. In one embodiment, the polyisocyanate (B) has the formula OCN-R'-NCO, where R' is an alkyl moiety, an aryl moiety, or an aralkyl moiety. In this embodiment, the polyisocyanate (b1b) can include any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0087] Suitable polyisocyanates for component (b1b) have two or more isocyanate functional groups and include conventional aliphatic, cycloaliphatic, araliphatic and aromatic isocyanates. The polyisocyanate (b1b) is optionally selected from the group consisting of diphenylmethane diisocyanate ("MDI"), polymeric diphenylmethane diisocyanate ("pMDI"), hydrogenated MDI (H12MDI), toluene diisocyanate ("TDI"), hexamethylene diisocyanate ("HDI"), dicyclohexylmethane diisocyanate ("HMDI"), isophorone diisocyanate ("IPDI"), cyclohexyl diisocyanate ("CHDI"), naphthalene diisocyanate ("NDI"), phenyl diisocyanate ("PDI") and combinations thereof. In one embodiment, the polyisocyanate (B) has the formula OCN-R'-NCO, where R' is an alkyl moiety, an aryl moiety or an aralkyl moiety. In this embodiment, the polyisocyanate (b1b) can include any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0088] In a specific embodiment, component (b1b) is not a polymer. In these or other embodiments, component (b1b) comprises, alternatively is an aliphatic or cycloaliphatic isocyanate. In one embodiment, component (b1b) has two isocyanate functional groups. In different embodiments, component (b1b) has three functional groups. Blends of different polyisocyanates can be used together as component (b1b). In a specific embodiment, the polyisocyanate (b1b) is selected from hydrogenated MDI (H12MDI), hexamethylene diisocyanate ("HDI"), dicyclohexylmethane diisocyanate ("HMDI"), isophorone diisocyanate ("IPDI"), cyclohexyl diisocyanate ("CHDI") and combinations thereof. When component (b1b) is not a polymer, component (b1b) can still be an oligomer. For example, component (b1b) can comprise trimers of HDI or IPDI.

[0089] (b1) The isocyanate-functional copolymer can be formed in the absence of any catalyst and at room temperature. If desired, a catalyst and a solvent can be utilized to accelerate the reaction to prepare the (b1) isocyanate-functional copolymer. However, since components (b1a) and (b1b) are liquids at room temperature, a solvent is generally not used or is not required. Similarly, the environmental conditions can be selectively controlled, for example, an elevated temperature such as 60 °C to 120 °C can be utilized. Component (b1) is prepared with a molar excess of isocyanate functional groups in component (b1b) compared to the methanol functional groups of component (b1a). Generally, the relative amounts of components (b1a) and (b1b) are selected such that no residual amount of component (b1a) remains and such that component (b1) contains at least two, alternatively two isocyanate functional groups. Those skilled in the art can readily understand how to select their relative amounts based on the properties of components (b1a) and (b1b), including the number and structure of the functional groups).

[0090] In a specific embodiment, when the (b1) isocyanate-functional copolymer is formed from components (b1a) and (b1b) and when each of components (b1a) and (b1b) is bifunctional, the (b1) isocyanate-functional copolymer has the average formula: Y-([SiR 1 2 O] n' -Y'--[SiR 1 2 O] n' ) m' -Y, where Y is an isocyanate moiety, Y is a residue from a polyisocyanate, each n' is independently selected from 1 to 100, each R 1 is an independently selected substituted or unsubstituted hydrocarbon group, and the subscript m' is from 1 to 50.

[0091] Suitable polyisocyanates for component (b2) can be the same as or different from component (b1b). Component (b2) is different from component (b1). Generally, component (b2) is a conventional polyisocyanate and does not include any siloxane segments, which is different from component (b1).

[0092] The polyisocyanate (b2) can be optionally selected from the group consisting of diphenylmethane diisocyanate (“MDI”), polymeric diphenylmethane diisocyanate (“pMDI”), hydrogenated MDI (H12MDI), toluene diisocyanate (“TDI”), hexamethylene diisocyanate (“HDI”), dicyclohexylmethane diisocyanate (“HMDI”), isophorone diisocyanate (“IPDI”), cyclohexyl diisocyanate (“CHDI”), naphthalene diisocyanate (“NDI”), phenyl diisocyanate (“PDI”), and combinations thereof. In one embodiment, the polyisocyanate (b2) has the formula OCN-R'-NCO, where R' is an alkyl moiety, an aryl moiety, or an aralkyl moiety. In this embodiment, the polyisocyanate (b2) can include any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0093] Specific examples of suitable polyisocyanates of component (b2) include: alkylene diisocyanates having 4 to 12 carbons in the alkylene moiety, such as 1,12-dodecane diisocyanate, 2-ethyl-1,4-tetramethylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 1,4-tetramethylene diisocyanate, and 1,6-hexamethylene diisocyanate; cycloaliphatic diisocyanates, such as 1,3- and 1,4-cyclohexane diisocyanate and any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4- and 2,6-hexahydrotoluene diisocyanate and corresponding isomer mixtures, 4,4'-, 2,2'- and 2,4'-dicyclohexylmethane diisocyanate and corresponding isomer mixtures; and aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate and corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2'-diphenylmethane diisocyanate and corresponding isomer mixtures, 4,4'-, 2,4'- and 2,2-diphenylmethane diisocyanate and mixtures of polyphenylpolymethylene polyisocyanates, and mixtures of MDI and toluene diisocyanate (TDI).

[0094] The polyisocyanate (b2) can include or be a modified polyvalent isocyanate, i.e., a product obtained by partial chemical reaction of organic diisocyanates and / or polyisocyanates. Examples of suitable modified polyvalent isocyanates include diisocyanates and / or polyisocyanates containing ester groups, urea groups, biuret groups, urethane groups, carbodiimide groups, isocyanurate groups, and / or urethane groups.

[0095] It should be understood that the polyisocyanate (b2) can include any combination of two or more polyisocyanates that differ from each other based on functionality, molecular weight, viscosity, or structure.

[0096] The functionality of the polyisocyanate (b2) is typically from 2.0 to 5.0, alternatively from 2.0 to 4.5, alternatively from 2.0 to 4.0. In one specific embodiment, the polyisocyanate (b2) is a polyisocyanate trimer such as an HDI trimer.

[0097] In these or other embodiments, the polyisocyanate (b2) has an NCO weight of from 15 wt% to 60 wt%, alternatively from 15 wt% to 55 wt%, alternatively from 20 wt% to 48.5 wt%. Methods for determining the NCO weight content are known in the art based on the functionality and molecular weight of the specific isocyanate.

[0098] Component (B) is typically used in the composition as a pre - blend, i.e., components (b1) and (b2) are mixed together before combining components (A) and (B). Components (b1) and (b2) can be mixed via any order of addition, optionally with shearing or blending. In certain embodiments, component (B) contains from 10 wt% to 90 wt% of component (b1). In these or other embodiments, component (B) contains from 90 wt% to 10 wt% of component (b2).

[0099] Component (B) is typically present in the composition in an amount providing an isocyanate index of from 75 to 200, alternatively from 75 to 130, alternatively from 75 to 125, alternatively from 85 to 125, alternatively from 90 to 120, alternatively from 95 to 120, alternatively from 100 to 120, alternatively from 80 to 120, alternatively from 85 to 115, alternatively from 90 to 110, alternatively from 90 to 105, alternatively from 90 to 100. In one embodiment, the isocyanate index is from 70 to 110, alternatively from 72 to 100. The isocyanate index is the molar ratio of NCO to isocyanate - reactive hydrogen functional groups multiplied by 100. The isocyanate index and its calculation method are well - known in the art.

[0100] In certain embodiments, the composition additionally contains (C) a catalyst. Typically, the composition contains the catalyst (C). However, components (A) and (B) are generally reactive in the absence of the catalyst (C), such that the catalyst (C) is used to accelerate the reaction at lower temperatures, which is generally desired in the preparation of anti - sticking coatings.

[0101] In one embodiment, catalyst (C) includes a tin catalyst. Suitable tin catalysts include tin(II) salts of organic carboxylic acids, such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate, and tin(II) laurate. In one embodiment, catalyst (C) includes dibutyltin dilaurate, which is a dialkyltin(IV) salt of an organic carboxylic acid. Specific examples of suitable organometallic catalysts (such as dibutyltin dilaurate) are available from Air Products and Chemicals, Inc., Allentown, PA under the trademark and can be purchased. The organometallic catalyst may also include other dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin maleate, and dioctyltin diacetate.

[0102] Examples of other suitable catalysts include iron(II) chloride; zinc chloride; lead octoate; tris(dialkylaminoalkyl)-s-hexahydrotriazines, including tris(N,N-dimethylaminopropyl)-hexahydrotriazine; tetraalkylammonium hydroxides, including tetramethylammonium hydroxide; alkali metal hydroxides, including sodium hydroxide and potassium hydroxide; alkali metal alkoxides, including sodium methoxide and potassium isopropoxide; and alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms and / or side OH groups.

[0103] Other examples of other suitable catalysts, particularly trimerization catalysts, include N,N,N-dimethylaminopropylhexahydrotriazine, potassium, potassium acetate, N,N,N-trimethylisopropylamine / formate, and combinations thereof.

[0104] Other suitable catalysts, particularly other examples of tertiary amine catalysts, include dimethylaminoethanol, dimethylaminoethoxyethanol, triethylamine, N,N,N',N'-tetramethylethylenediamine, triethylenediamine (also known as 1,4-diazabicyclo[2.2.2]octane), N,N-dimethylaminopropylamine, N,N,N',N',N”-pentamethyldipropylenetriamine, tris(dimethylaminopropyl)amine, N,N-dimethylpiperazine, tetramethyliminobis(propylamine), dimethylbenzylamine, trimethylamine, triethanolamine, N,N-diethylethanolamine, N-methylpyrrolidone, N-methylmorpholine, N-ethylmorpholine, bis(2-dimethylamino-ethyl)ether, N,N-dimethylcyclohexylamine (“DMCHA”), N,N,N',N',N”-pentamethyldiethylenetriamine, 1,2-dimethylimidazole, 3-(dimethylamino)propylimidazole, 2,4,6-tris(dimethylaminomethyl)phenol, and combinations thereof. Catalyst (C) may include a delayed-action tertiary amine based on 1,8-diazabicyclo[5.4.0]undec-7-ene (“DBU”). Alternatively or additionally, catalyst (C) may include N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether and / or ethylenediamine. Tertiary amine catalysts can be further modified to act as delayed-action catalysts by adding approximately stoichiometric amounts of acids containing acidic protons such as phenol or formic acid. Such delayed-action catalysts are commercially available from Air Products and Evonik.

[0105] Additional examples of other suitable catalysts include metal chelates such as aluminum acetylacetonate, TiCH, titanium(IV) acetylacetonate oxide, bismuth(III) acetate, bis(isopropanol)aluminum acetoacetate, and combinations thereof.

[0106] Catalyst (C) can be used alone or placed in a vehicle. Vehicles are known in the art and are further described below as optional components of the composition. If a vehicle is used and catalyst (C) is dissolved, the vehicle may be referred to as a solvent. The vehicle can be isocyanate-reactive, for example an alcohol-functional vehicle such as dipropylene glycol.

[0107] Catalyst (C) can be used in various amounts. Catalyst (C) can include any combination of different catalysts.

[0108] The composition may optionally comprise at least one additive selected from the following: (D) inhibitors, (E) chain extenders, (F) mediators, (G) fixing additives, (H) anti-fogging additives, and / or (I) anti-sticking modifiers. In certain embodiments, the composition is substantially free of conventional organic polyols, such as polyether and / or polyester polyols. Different from component (A), conventional organic polyols do not include a siloxane backbone. With respect to the composition being substantially free of conventional polyols, "substantially free" means that based on the total weight of the composition, the composition contains less than 4% by weight, alternatively less than 3% by weight, alternatively less than 2% by weight, alternatively less than 1% by weight, alternatively 0% by weight of conventional organic polyols.

[0109] In certain embodiments, the composition further comprises an inhibitor (D). The inhibitor (D) can be used to change the reaction rate or curing rate of the composition compared to a composition that contains the same starting materials but omits the inhibitor (D). The inhibitor (D) is exemplified by acetylenic alcohols, such as methyl butynol, ethynylcyclohexanol, dimethylhexynol, and 3,5-dimethyl-1-hexyn-3-ol, 1-butyn-3-ol, 1-propyn-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-ol, 3-phenyl-1-butyn-3-ol, 4-ethyl-1-octyn-3-ol, and 1-ethynyl-1-cyclohexanol and combinations thereof; cycloalkenyl siloxanes, such as methyl vinyl cyclo siloxanes, examples of which are 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetrahexenylcyclotetrasiloxane and combinations thereof; enyne compounds, such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; triazoles, such as benzotriazole; phosphines; thiols; hydrazines; amines, such as tetramethylethylenediamine; dialkyl fumarates, diene fumarates, dialkoxyalkyl fumarates; maleates, such as diallyl maleate; nitriles; ethers; carbon monoxide; olefins, such as cyclooctadiene, divinyltetramethyldisiloxane; alcohols, such as benzyl alcohol; and combinations thereof. Alternatively, the inhibitor (D) may be selected from the group consisting of: acetylenic alcohols (e.g., 1-ethynyl-1-cyclohexanol) and maleates (e.g., diallyl maleate, bismaleate or n-propyl maleate) and combinations of two or more of them. Another example of the inhibitor (D) is acetylacetone.

[0110] Alternatively, the inhibitor (D) may be a silylated acetylenic compound. Without wishing to be bound by theory, it is believed that the addition of a silylated acetylenic compound reduces the yellowing of the reaction product prepared by the hydrosilylation reaction of the composition compared to the reaction product obtained by hydrosilylation of a composition that does not contain a silylated acetylenic compound or contains an organic acetylenic alcohol inhibitor (such as those described above).

[0111] Examples of silylated alkynyl compounds include (3-methyl-1-butyn-3-yloxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-yloxy)dimethylsilane, bis(3-methyl-1-butyn-3-yloxy)silane methylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tri(1,1-dimethyl-2-propynyloxy))silane, methyl(tri(3-methyl-1-butyn-3-yloxy))silane, (3-methyl-1-butyn-3-yloxy)dimethylphenylsilane, (3-methyl-1-butyn-3-yloxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-yloxy)triethylsilane, bis(3-methyl-1-butyn-3-yloxy)methyltrifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-yloxy)trimethylsilane, (3-phenyl-1-butyn-3-yloxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-yloxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-yloxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-yloxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-yloxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-yloxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-yloxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-yloxy)trimethylsilane, and combinations thereof. Alternatively, examples of inhibitor (D) are methyl(tri(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or combinations thereof. The silylated alkynyl compounds useful as inhibitor (D) can be prepared by methods known in the art, such as by reacting the above-mentioned alkynols with chlorosilanes in the presence of an acid acceptor to silylate the above-mentioned alkynols.

[0112] In a specific embodiment, inhibitor (D) comprises or is selected from alkynols, silylated alkynols, enyne compounds, triazoles, phosphines, thiols, hydrazines, amines, fumarates, maleates, ethers, carbon monoxide, and combinations of two or more thereof.

[0113] The amount of inhibitor (D) present in the composition will depend on various factors, including the desired pot life of the composition, whether the composition will be a one-component or multi-component composition, the specific inhibitor used, and the selection and amount of components (A) to (C). However, when inhibitor (D) is present, based on the total weight of the composition, the amount of inhibitor (D) can be 0% to 1%, alternatively 0% to 5%, alternatively 0.001% to 1%, alternatively 0.01% to 0.5%, and alternatively 0.0025% to 0.025%.

[0114] In certain embodiments, the composition further comprises a chain extender (E). In certain embodiments, the chain extender (E) comprises an organopolysiloxane chain extender. When used, the organopolysiloxane chain extender is different from component (A). In a specific embodiment, the organopolysiloxane chain extender is a linear organopolysiloxane comprising two terminal silicon-bonded methanol functional groups. When an organopolysiloxane chain extender is used and comprises a linear organopolysiloxane comprising two terminal silicon-bonded methanol functional groups, and component (A) is branched per molecule and component (A) comprises on average at least three silicon-bonded methanol functional groups per molecule, etc., component (A) can be different from component (E).

[0115] In certain embodiments, the composition further comprises an organopolysiloxane chain extender, and the organopolysiloxane chain extender has the formula R 2 XSiO(SiR 2 O 2 / 2 ) n’ SiR 2 X, where each R is independently selected and as defined above, X is independently selected and as defined above, and the subscript n' is from 3 to 250, alternatively from 5 to 200, alternatively from 5 to 150, alternatively from 5 to 100, alternatively from 5 to 50. However, the organopolysiloxane chain extender can comprise side-chain silicon-bonded methanol functional groups or both side-chain and terminal silicon-bonded methanol functional groups.

[0116] In other embodiments, the chain extender (E) can be organic or free of siloxane bonds. In such embodiments, the chain extender (E) can be any conventional chain extender (E) from polyurethane and / or polyisocyanurate compositions. Generally, in such embodiments, the chain extender (E) comprises two hydroxyl groups per molecule. The initiator can be selected from, for example, neopentyl glycol; 1,2-propanediol; alkane diols such as 1,6-hexanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,3-propanediol, 1,2-propanediol, 1,5-pentanediol, 2-methylpropane-1,3-diol, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,5-hexanediol; ethylene glycol; diethylene glycol; triethylene glycol; and combinations thereof.

[0117] Generally, when the composition further comprises a chain extender (E), for the purpose of miscibility with component (A), the chain extender (E) comprises an organopolysiloxane chain extender. However, depending on the presence of component (F) described below, the miscibility between component (A) and other forms of chain extender (E) (including the organic chain extenders described above) can be improved. Combinations of different chain extenders can be used.

[0118] When in use, based on 100 parts by weight of component (A), the chain extender (E) can be used in an amount greater than 0 parts by weight to 50 parts by weight, alternatively 10 parts by weight to 50 parts by weight, alternatively 20 parts by weight to 40 parts by weight.

[0119] In certain embodiments, the composition further comprises a vehicle (F), which may also be referred to as a carrier vehicle. The vehicle (F) generally dissolves the components of the composition, and if the components are dissolved, the vehicle (F) may be referred to as a solvent. Suitable vehicles include silicones (both linear and cyclic), organic oils, organic solvents, and mixtures thereof.

[0120] Typically, the vehicle (F), if present in the composition, is an organic liquid. Organic liquids include those regarded as oils or solvents. Organic liquids are exemplified by, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having more than 3 carbon atoms, aldehydes, ketones, amines, esters, ethers, diols, diol ethers, alkyl halides, and aromatic halides. Hydrocarbons include isododecane, isocetane, Isopar L (C11 to C13), Isopar H (C11 to C12), hydrogenated polydecene, aromatic hydrocarbons, and halogenated hydrocarbons. Ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, diol distearate, dioctyl carbonate, diethylhexyl carbonate, propylene glycol n-butyl ether, ethyl-3-ethoxypropionate, propylene glycol methyl ether acetate, tridecyl neopentanoate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether (PGME), diethylene glycol butyl ether, octyldodecyl neopentanoate, diisobutyl adipate, diisopropyl adipate, propylene glycol dicaprylate / dicaprate, octyl ether, and octyl palmitate. Additional organic fluids suitable as individual compounds or as components of the vehicle (F) include fats, oils, fatty acids, and fatty alcohols. The vehicle (F) may also be a low-viscosity organopolysiloxane or a volatile methylsiloxane or a volatile ethylsiloxane or a volatile methyl ethylsiloxane having a viscosity at 25 °C in the range of 1 square millimeter per second to 1,000 square millimeters per second, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{ (trimethylsilyl)oxy} trisiloxane, hexamethyl-3,3-bis{ (trimethylsilyl)oxy} trisiloxane, pentamethyl{ (trimethylsilyl)oxy} cyclotrisiloxane, and polydimethylsiloxane, polyethylsiloxane, polymethyl ethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, octanoyl polymethylsiloxane, and any mixture thereof.

[0121] In a specific embodiment, the vehicle (F) is selected from polyalkylsiloxanes; tetrahydrofuran; solvent naphtha; naphtha; alcohols such as methanol, ethanol, isopropanol, butanol or n-propanol; ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone; aromatic hydrocarbons such as benzene, toluene or xylene; aliphatic hydrocarbons such as heptane, hexane or octane; diol ethers such as propylene glycol methyl ether, dipropylene glycol methyl ether, propylene glycol n-butyl ether, propylene glycol n-propyl ether or ethylene glycol n-butyl ether; or combinations thereof.

[0122] In one embodiment, the vehicle (F) is a polar vehicle. In a specific embodiment, when the vehicle (F) is polar, the vehicle (F) comprises, alternatively is, acetone.

[0123] The amount of the vehicle (F) will depend on various factors including the type of vehicle selected and the amounts and types of the other components present in the composition. However, based on the total weight of the composition, the amount of the vehicle (F) in the composition can be from 0 wt% to 80 wt%, alternatively from 1 wt% to 50 wt%, alternatively from 1 wt% to 40 wt%, alternatively from 1 wt% to 35 wt%, alternatively from 1 wt% to 30 wt%, alternatively from 5 wt% to 30 wt%, alternatively from 10 wt% to 30 wt%, alternatively from 15 wt% to 25 wt%. The vehicle (F) can be added during the preparation of the composition, for example to aid in mixing and delivery. After the composition is prepared, including before and / or simultaneously with the preparation of the anti-stick coating from the composition, all or a portion of the vehicle (F) can optionally be removed.

[0124] In certain embodiments, the composition further comprises an adhesion additive (G). Examples of suitable adhesion additives are reaction products of vinylalkoxysilanes with epoxy-functionalized alkoxysilanes; reaction products of vinylacetoxysilanes with epoxy-functionalized alkoxysilanes; and combinations (e.g., physical blends and / or reaction products) of polyorganosiloxanes having at least one aliphatic unsaturated hydrocarbon group and at least one hydrolysable group per molecule (e.g., a combination of a hydroxy-terminated vinyl-functionalized polydimethylsiloxane and glycidoxypropyltrimethoxysilane). Alternatively, the adhesion additive can comprise a polyorganosilicate resin. Suitable adhesion additives and methods for their preparation are disclosed, for example, in U.S. Patent 9,562,149, U.S. Patent Application Publication Nos. 2003 / 0088042, 2004 / 0254274 and 2005 / 0038188 and European Patent 0 556 023.

[0125] Other examples of suitable anchoring additives may include transition metal chelates, alkoxysilanes (such as alkoxysilanes), combinations of alkoxysilanes and hydroxy-functionalized polyorganosiloxanes, or combinations thereof. The anchoring additive (G) may be a silane having at least one substituent having an adhesion promoting group such as an epoxy group, an acetoxy group, or an acrylate group. The adhesion promoting group may additionally or alternatively be any hydrolyzable group. Alternatively, the anchoring additive (G) may comprise a partial condensate of such silanes, such as an organopolysiloxane having an adhesion promoting group. Still alternatively, the anchoring additive (G) may comprise a combination of an alkoxysilane and a hydroxy-functionalized polyorganosiloxane.

[0126] Alternatively, the anchoring additive (G) may include an unsaturated compound or an epoxy-functionalized compound, such as an unsaturated or epoxy-functionalized silane. The anchoring additive (G) may include an unsaturated alkoxysilane or an epoxy-functionalized alkoxysilane. For example, the functionalized alkoxysilane may comprise at least one unsaturated organic group or an epoxy-functionalized organic group. Examples of epoxy-functionalized organic groups are 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. Unsaturated organic groups are, for example, 3-methacryloxypropyl, 3-acryloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, undecenyl. A specific example of an unsaturated compound is vinyltriacetoxysilane.

[0127] Specific examples of suitable epoxy-functional alkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, (epoxycyclohexyl)ethyldimethoxysilane, (epoxycyclohexyl)ethyldiethoxysilane, and combinations thereof. Examples of suitable unsaturated alkoxysilanes include vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hexenyltrimethoxysilane, undecenyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropyltriethoxysilane, and combinations thereof.

[0128] The anchoring additive (G) may also include reaction products or partial reaction products of one or more of these compounds. For example, in a specific embodiment, the anchoring additive (G) may include a reaction product or partial reaction product of vinyltriacetoxysilane and 3-glycidoxypropyltrimethoxysilane. Alternatively or additionally, the anchoring additive (G) may include alkoxy- or alkenyl-functionalized siloxanes.

[0129] Alternatively, the fixing additive (G) may include an epoxy-functionalized siloxane, such as the reaction product of a hydroxyl-terminated polyorganosiloxane as described above and an epoxy-functionalized alkoxysilane, or a physical blend of a hydroxyl-terminated polyorganosiloxane and an epoxy-functionalized alkoxysilane. The fixing additive (G) may include a combination of an epoxy-functionalized alkoxysilane and an epoxy-functionalized siloxane. For example, the fixing additive (G) is exemplified by: a mixture of 3-glycidoxypropyltrimethoxysilane and the reaction product of a hydroxyl-terminated methylvinylsiloxane and 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxyl-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxyl-terminated methylvinyl / dimethylsiloxane copolymer.

[0130] Examples of acetoxysilanes suitable for use as the fixing additive (G) include tetraacetoxysilane, organotriacetoxysilane, diorganodiacetoxysilane, and combinations thereof. The acetoxysilane may contain: alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tert-butyl; alkenyl groups such as vinyl, allyl, or hexenyl; aryl groups such as phenyl, tolyl, or xylyl; aralkyl groups such as benzyl or 2-phenylethyl; and fluorinated alkyl groups such as 3,3,3-trifluoropropyl. Exemplary acetoxysilanes include tetraacetoxysilane, methyltriacetoxysilane, ethyltriacetoxysilane, vinyltriacetoxysilane, propyltriacetoxysilane, butyltriacetoxysilane, phenyltriacetoxysilane, octyltriacetoxysilane, dimethyldiacetoxysilane, phenylmethyldiacetoxysilane, vinylmethyldiacetoxysilane, diphenyldiacetoxysilane, tetraacetoxysilane, and combinations thereof. In some embodiments, the fixing additive (G) includes an organotriacetoxysilane, for example, a mixture including methyltriacetoxysilane and ethyltriacetoxysilane.

[0131] Examples of amino-functional alkoxysilanes suitable for or used as the fixing additive (G) are exemplified by: H 2 N(CH 2 ) 2 Si(OCH 3 ) 3 、H 2 N(CH 2 ) 2 Si(OCH 2 CH 3 ) 3 、H 2 N(CH 2 ) 3 Si(OCH 3 ) 3 、H2 N(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 、CH 3 NH(CH 2 ) 3 Si(OCH 3 ) 3 、CH 3 NH(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 、 CH 3 NH(CH 2 ) 5 Si(OCH 3 ) 3 、CH 3 NH(CH 2 ) 5 Si(OCH 2 CH 3 ) 3 、 H 2 N(CH 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 、H 2 N(CH 2 ) 2 NH(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 、CH 3 NH(CH 2 ) 2 NH(CH 2 ) 3 Si(OCH 3 ) 3 、CH 3 NH(CH 2 ) 2 NH(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 、C 4 H 9 NH(CH 2 ) 2 NH(CH2 ) 3 Si(OCH 3 ) 3 、C 4 H 9 NH(CH 2 ) 2 NH(CH 2 ) 3 Si(OCH 2 CH 3 ) 3 、 H 2 N(CH 2 ) 2 SiCH 3 (OCH 3 ) 2 、H 2 N(CH 2 ) 2 SiCH 3 (OCH 2 CH 3 ) 2 、 H 2 N(CH 2 ) 3 SiCH 3 (OCH 3 ) 2 、H 2 N(CH 2 ) 3 SiCH 3 (OCH 2 CH 3 ) 2 、 CH 3 NH(CH 2 ) 3 SiCH 3 (OCH 3 ) 2 、CH 3 NH(CH 2 ) 3 SiCH 3 (OCH 2 CH 3 ) 2 、 CH 3 NH(CH 2 ) 5 SiCH 3 (OCH 3 ) 2 、CH 3 NH(CH 2 ) 5 SiCH 3 (OCH 2 CH3 ) 2 、H 2 N(CH 2 ) 2 NH(CH 2 ) 3 SiCH 3 (OCH 3 ) 2 、H 2 N(CH 2 ) 2 NH(CH 2 ) 3 SiCH 3 (OCH 2 CH 3 ) 2 、CH 3 NH(CH 2 ) 2 NH(CH 2 ) 3 SiCH 3 (OCH 3 ) 2 、CH 3 NH(CH 2 ) 2 NH(CH 2 ) 3 SiCH 3 (OCH 2 CH 3 ) 2 、C 4 H 9 NH(CH 2 ) 2 NH(CH 2 ) 3 SiCH 3 (OCH 3 ) 2 、C 4 H 9 NH(CH 2 ) 2 NH(CH 2 ) 3 SiCH 3 (OCH 2 CH 3 ) 2 and their combinations.

[0132] Examples of oxime-based silanes suitable for the anchoring additive (G) include alkyltrioxime silanes such as methyltrioxime silane, ethyltrioxime silane, propyltrioxime silane, and butyltrioxime silane; alkoxytrioxime silanes such as methoxytrioxime silane, ethoxytrioxime silane, and propoxytrioxime silane; or alkenyltrioxime silanes such as allyltrioxime silane or butenyltrioxime silane; alkenyl oxime silanes such as vinyl oxime silane; alkenylalkyl dioxime silanes such as vinylmethyl dioxime silane, vinylethyl dioxime silane, vinylmethyl dioxime silane, or vinylethyl dioxime silane; or combinations thereof.

[0133] Examples of ketoxime-based silanes suitable for the anchoring additive (G) include methyltris(dimethylketoxime)silane, methyltris(methylethylketoxime)silane, methyltris(methylpropylketoxime)silane, methyltris(methylisobutylketoxime)silane, ethyltris(dimethylketoxime)silane, ethyltris(methylethylketoxime)silane, ethyltris(methylpropylketoxime)silane, ethyltris(methylisobutylketoxime)silane, vinyltris(dimethylketoxime)silane, vinyltris(methylethylketoxime)silane, vinyltris(methylpropylketoxime)silane, vinyltris(methylisobutylketoxime)silane, tetrakis(dimethylketoxime)silane, tetrakis(methylethylketoxime)silane, tetrakis(methylpropylketoxime)silane, tetrakis(methylisobutylketoxime)silane, methylbis(dimethylketoxime)silane, methylbis(cyclohexylketoxime)silane, triethoxy(ethylmethylketoxime)silane, diethoxybis(ethylmethylketoxime)silane, ethoxytri(ethylmethylketoxime)silane, methylvinylbis(methylisobutylketoxime)silane, or combinations thereof.

[0134] Alternatively, the anchoring additive (G) may include transition metal chelates. Suitable transition metal chelates include titanates, zirconates such as zirconium acetylacetonate, aluminum chelates such as aluminum acetylacetonate, and combinations thereof. Alternatively, the anchoring additive (G) may include a combination of a transition metal chelate and an alkoxysilane, such as a combination of glycidoxypropyltrimethoxysilane and an aluminum chelate or a zirconium chelate.

[0135] If utilized, the specific amount of the anchoring additive (G) present in the composition depends on various factors, including the type of substrate and whether a primer is used. In certain embodiments, the anchoring additive (G) is present in the composition in an amount of from 0 parts by weight / 100 parts by weight to 2 parts by weight / 100 parts by weight of component (B). Alternatively, the anchoring additive (G) is present in the composition in an amount of from 0.01 parts by weight / 100 parts by weight to 2 parts by weight / 100 parts by weight of component (B).

[0136] In certain embodiments, the composition further comprises an anti-fog additive (H). The anti-fog additive (H) can be used in the composition to reduce or inhibit the formation of silicone fog during the coating process, especially in high-speed coating equipment. The anti-fog additive (H) can be any compound or component suitable for reducing, minimizing, or eliminating atomization during the application of the composition. In one embodiment, the anti-fog additive (H) comprises or is a reaction product of an organohydrogensilicon compound, an alkylene oxide compound, or an organovinylsiloxane having at least three silicon-bonded alkenyl groups per molecule with a suitable catalyst. In a specific embodiment, the anti-fog additive (H) comprises a Q-branched dimethyl vinyl-terminated organopolysiloxane. In another specific embodiment, the anti-fog additive (H) comprises an MDQ resin. The anti-fog additive (H) can have a viscosity at 25 °C of from 30,000 centipoise to 50,000 centipoise or from 35,000 centipoise to 45,000 centipoise. Suitable anti-fog additives are disclosed, for example, in U.S. Patent Application 2011 / 0287267, U.S. Patent 8,722,153, U.S. Patent 6,586,535, and U.S. Patent 5,625,023.

[0137] The amount of the anti-fog additive (H) used in the composition and its selection will depend on various factors, including the amount and type of other starting materials selected for the composition. For example, when component (A) is linear or only slightly branched, the anti-fog additive (H) can be used and it can have a highly branched or resinous structure. However, when component (A) is branched or resinous, the anti-fog additive (H) can be used and it can be linear or only partially branched. Based on the total weight of the composition, the anti-fog additive (H) is typically used in an amount of from 0% to 10%, alternatively from 0.1% to 3%. This amount does not include the amount associated with component (A) and only relates to the anti-fog additive (H) that is separate and distinct from component (A).

[0138] In certain embodiments, the composition further comprises an anti-tack modifier (I), which can be used in the composition to control (reduce) the level of anti-tack force (the adhesive force between the anti-tack coating formed from the composition and its adherend, such as a label containing a pressure-sensitive adhesive). By adjusting the level or concentration of the anti-tack modifier (I), an anti-tack coating having a desired or expected anti-tack force can be formulated from a composition without the modifier. Examples of suitable anti-tack modifiers for component (I) include trimethylsiloxy-terminated dimethyl, phenylmethylsiloxane. Alternatively, the anti-tack modifier (I) can be a condensation reaction product of an organopolysiloxane resin having a hydroxyl or alkoxy group and a diorganopolysiloxane having at least one hydroxyl or hydrolyzable group. Examples of suitable anti-tack modifiers are disclosed, for example, in U.S. Patent 8,933,177 and U.S. Patent Application Publication 2016 / 0053056.

[0139] The anti-stick coating formed with the composition is not a foam. As understood in the art, conventional reactions between isocyanates and isocyanate-reactive components can be carried out in the presence of a blowing agent to obtain a foam. Blowing agents can be classified as physical and chemical blowing agents. Physical blowing agents undergo a phase change from liquid to gas during exposure to atmospheric pressure and elevated temperatures associated with curing (e.g., ≥100 °C). The phase change is typically related to the boiling point temperature of the physical blowing agent. In contrast, chemical blowing agents react with one or more other components in the composition or with other molecules of the chemical blowing agent to release gaseous by-products. Such blowing agents are typically used to form polyurethane and / or polyisocyanurate foams. However, the anti-stick coating formed with the composition is not a foam, and in certain embodiments, the composition does not contain a physical blowing agent, a chemical blowing agent, or both a physical blowing agent and a chemical blowing agent. As understood in the art, determining whether a component constitutes a physical blowing agent is related to the processing parameters (including temperature) during the formation of the anti-stick coating with the composition (i.e., based on the physical properties of the component and whether the component will boil or volatilize during the formation of the anti-stick coating). For example, certain components of the composition may volatilize at particularly high processing temperatures (e.g., >120 °C) but not at the processing temperatures used to prepare the anti-stick coating with the composition, such that the composition does not contain a blowing agent. As described above, the composition typically does not contain a chemical blowing agent. Chemical blowing agents are different from components (A), (B), and optional components (C)-(I). Depending on the selection of these components, gas can be at least a by-product of the reaction to form the anti-stick coating. However, if any gas is formed as a by-product in the preparation of the anti-stick coating, the level of the gas produced is much less than the level of gas formed with a conventional chemical blowing agent, such that the anti-stick coating is not a foam.

[0140] Other optional components may be present in the composition, including, for example, reactive diluents, fragrances, preservatives, colorants, dyes, pigments, antioxidants, heat stabilizers, flame retardants, flow control additives, biocides, fillers (including extender and reinforcing fillers), surfactants, thixotropic agents, pH buffers, etc. The composition can be in any form and can be incorporated into other compositions.

[0141] Alternatively, the composition and the anti-stick coating formed therefrom can be free of particles or contain only a limited amount of particles (e.g., fillers and / or pigments), such as from 0 wt% to 30 wt% of the composition. The particles can agglomerate or otherwise adhere to the coating machine equipment used to form the anti-stick coating. Additionally, if optical transparency is desired, the particles can hinder the optical properties of the anti-stick coating and the anti-stick liner formed therefrom, such as transparency. The particles may be disadvantageous for adhesion to the adherend.

[0142] In certain embodiments, the composition is free of fluorinated organosiloxane compounds. It is believed that during curing, fluorinated compounds, due to their low surface tension, can rapidly migrate to the interface between the composition or the anti-stick coating formed therefrom and the substrate to which the composition is applied and the anti-stick coating is formed, such as the composition / PET film interface. Such migration can prevent the anti-stick coating (prepared by curing the composition) from adhering to the substrate by forming a fluorinated barrier. By forming the barrier, the fluorinated organosiloxane compound can prevent any components of the composition from reacting at the interface, thereby affecting curing and related properties. Additionally, fluorinated organosiloxane compounds are generally expensive.

[0143] The composition in its curable form can be prepared by combining components (A) through (B) and any optional components (as described above) in any order of addition, optionally with a masterbatch, and optionally under shear. As described in more detail below, the composition can be a one-component composition, a two-component or 2K composition, or a multi-component composition. For example, the composition can comprise an isocyanate-reactive component and an isocyanate component. Component (A) is present in the isocyanate-reactive component, and component (B) is present in the isocyanate component. Catalyst (C) is generally present in the isocyanate-reactive component, but can alternatively be present in a third component separate from the isocyanate-reactive component and the isocyanate component. In certain embodiments, the isocyanate component consists of polyisocyanate (B), and the remaining components are present in the isocyanate-reactive component. When forming an anti-stick coating therewith, these components are generally combined to obtain the composition in solvent form.

[0144] The method of preparing a coated substrate with the composition includes applying (i.e., disposing) the composition on the substrate. The method further includes curing the composition on the substrate, which results in forming an anti-stick coating on the substrate to obtain a coated substrate. Curing can be carried out by heating at an elevated temperature (e.g., 50 °C to 180 °C, alternatively 50 °C to 120 °C, alternatively 50 °C to 90 °C, alternatively 70 °C to 90 °C, alternatively 70 °C to 85 °C, alternatively 75 °C to 85 °C) to obtain a coated substrate. Those skilled in the art will be able to select an appropriate temperature based on various factors, including the composition and the choice of the substrate composition or material of construction. Compared to conventional compositions used to prepare conventional anti-stick coatings, the composition cures at a lower temperature, thus allowing reduced energy consumption and the use of different types of substrates that can soften or deform at elevated temperatures.

[0145] The composition can be set or dispensed on the substrate in any suitable manner. Generally, the composition is applied in wet form by wet coating techniques. The composition can be applied by: i) spin coating; ii) brush coating; iii) drop coating; iv) spraying; v) dip coating; vi) roll coating; vii) flow coating; viii) slot coating; ix) concave coating; x) Mayer rod coating; or xi) a combination of any two or more of i) to x). Generally, setting the composition on the substrate results in a wet deposit on the substrate, which is subsequently cured to obtain a coated substrate that includes a cured film (i.e., an anti-stick coating) formed from the composition on the substrate.

[0146] The substrate is not limited and can be any substrate. The cured film can be separated from the substrate or can be physically and / or chemically bonded to the substrate depending on its choice. The substrate can have an integrated hot plate or an integrated or separate furnace for curing the wet deposit. The substrate can optionally have continuous or discontinuous shapes, sizes, dimensions, surface roughnesses, and other properties. Alternatively, the substrate has a softening point temperature at an elevated temperature. However, the composition and method are not limited by this.

[0147] Alternatively, the substrate can include plastics, which can be thermosetting and / or thermoplastic. However, alternatively, the substrate can be or include glass, metal, cellulose (e.g., paper), wood, cardboard, paperboard, silicone, or polymeric materials or combinations thereof.

[0148] Specific examples of suitable substrates include paper blanks such as kraft paper, polyethylene-coated kraft paper (PEK-coated paper), thermal paper, and conventional paper; polymer substrates such as polyamide (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutene; styrenic resins; polyoxymethylene (POM); polycarbonate (PC); polymethyl methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); polyphenylene ether (PPE); polyimide (PI); polyamideimide (PAI); polyetherimide (PEI); polysulfone (PSU); polyethersulfone; polyketone (PK); polyetherketone; polyvinyl alcohol (PVA); polyetheretherketone (PEEK); polyetherketoneketone (PEKK); polyarylate (PAR); polyethernitrile (PEN); phenolic resins; phenoxy resins; cellulose such as triacetyl cellulose, diacetyl cellulose, and cellophane; fluorinated resins such as polytetrafluoroethylene; thermoplastic elastomers such as polystyrene type, polyolefin type, polyurethane type, polyester type, polyamide type, polybutadiene type, polyisoprene type, and fluorine type; and copolymers and combinations thereof.

[0149] The composition or wet deposit is typically cured at an elevated temperature for a period of time. This period of time is typically sufficient to effect curing of the composition, i.e., crosslinking. This period of time can be greater than 0 hours to 8 hours, alternatively greater than 0 hours to 2 hours, alternatively greater than 0 hours to 1 hour, alternatively greater than 0 minutes to 30 minutes, alternatively greater than 0 minutes to 15 minutes, alternatively greater than 0 minutes to 10 minutes, alternatively greater than 0 minutes to 5 minutes, alternatively greater than 0 minutes to 2 minutes, alternatively greater than 0 seconds to 90 seconds, alternatively greater than 0 seconds to 80 seconds, alternatively greater than 0 seconds to 70 seconds, alternatively greater than 0 seconds to 60 seconds. This period of time depends on various factors including the elevated temperature utilized, the temperature selected, the desired film thickness, and the presence or absence of any vehicle in the composition.

[0150] The cured composition typically has a dwell time of from 0.1 second to 50 seconds, alternatively from 0.5 second to 30 seconds, alternatively from 1 second to 20 seconds, alternatively from 1 second to 15 seconds, alternatively from 1 second to 10 seconds. The dwell time selected can depend on substrate selection, the temperature selected, and the line speed. As used herein, the dwell time is the time that the composition or wet deposit is subjected to the elevated temperature. The dwell time is different from the cure time because curing may be ongoing even after the composition, wet deposit, or partially cured reaction intermediate thereof is no longer subjected to the elevated temperature (i.e., that which typically initiates curing). Alternatively, the coated article can be prepared on a conveyor belt in an oven and the dwell time can be calculated by dividing the length of the oven (e.g., in meters) by the line speed of the conveyor belt (e.g., in meters per second). In fact, even at relatively low temperatures of 75 °C to 85 °C, the compositions of the present invention can be cured at these dwell times to give non-stick coatings.

[0151] This period of time can be broken down into cure iterations, e.g., a first cure and a post-cure, where the first cure is, for example, 1 hour and the post-cure is, for example, 3 hours. The elevated temperature can be independently selected from any temperature above room temperature in such iterations and can be the same in each iteration.

[0152] Depending on the optional presence and selection of vehicle (F), the cured composition can further include a drying step. For example, when the composition contains vehicle (F), the curing step typically also dries or removes vehicle (F) from the composition. Drying can be carried out simultaneously with curing or can be carried out separately from curing.

[0153] Depending on the thickness and other dimensions of the film and the coated substrate, the coated substrate can be formed by an iterative process. For example, a first deposit can be formed and the first deposit can be subjected to a first elevated temperature for a first period of time to obtain a partially cured deposit. Then, a second deposit can be disposed on the partially cured deposit and the second deposit can be subjected to a second elevated temperature for a second period of time to obtain a second partially cured deposit. The partially cured deposit will also further cure for the second period of time during exposure to the second elevated temperature. A third deposit can be disposed on the second partially cured deposit and subjected to a third elevated temperature for a third period of time to obtain a third partially cured deposit. The second partially cured deposit will also further cure for the second period of time during exposure to the second elevated temperature. The process can be repeated, for example, 1 to 50 times to construct the coated article as desired. The composite has a partially cured layer that can be subjected to a final post-cure, for example, at the elevated temperatures and time periods described above. Each elevated temperature and time period can be independently selected and can be the same as or different from each other. When the article is formed by an iterative process, each deposit can also be independently selected and can differ in terms of the composition selected in the composition, their amounts, or both. Still alternatively, in such an iterative process, each iterative layer can be fully cured rather than only partially cured.

[0154] Alternatively, the deposit can comprise a wet film. Alternatively, depending on the curing state of the partially cured layer, the iterative process can be wet-on-wet. Alternatively, the iterative process can be wet-on-dry.

[0155] The coated substrate (which includes a film formed from a composition on the substrate) can have different dimensions, including the relative thickness of the film and the substrate. The thickness of the film can vary depending on its end-use application. The thickness of the film can be greater than 0 μm to 4,000 μm, alternatively greater than 0 μm to 3,000 μm, alternatively greater than 0 μm to 2,000 μm, alternatively greater than 0 μm to 1,000 μm, alternatively greater than 0 μm to 500 μm, alternatively greater than 0 μm to 250 μm. However, other thicknesses can be envisioned, for example, 0.1 μm to 200 μm. For example, the thickness of the film can be 0.2 μm to 175 μm; alternatively 0.5 μm to 150 μm; alternatively 0.75 μm to 100 μm; alternatively 1 μm to 75 μm; alternatively 2 μm to 60 μm; alternatively 3 μm to 50 μm; and alternatively 4 μm to 40 μm. Alternatively, when the substrate is plastic, the thickness of the film can be greater than 0 μm to 200 μm, alternatively greater than 0 μm to 150 μm, and alternatively greater than 0 μm to 100 μm.

[0156] If desired, the film can be subjected to further processing depending on the end use application of the film. For example, the film can be subjected to oxidative deposition (e.g., SiO 2 deposition), resist deposition, and patterning, etching, chemical, corona, or plasma stripping, metallization, or metal deposition processes. Such further processing techniques are generally known. Such depositions can be chemical vapor deposition (including low pressure chemical vapor deposition, plasma enhanced chemical vapor deposition, and plasma assisted chemical vapor deposition), physical vapor deposition, or other vacuum deposition techniques. Many such further processing techniques involve elevated temperatures, particularly vacuum deposition, and the film is well suited for such techniques given its excellent thermal stability. However, depending on the end use of the film, the film can be used with such further processing.

[0157] The coated substrate can be used in a variety of end use applications. For example, the coated substrate can be used in coating applications, packaging applications, adhesive applications, fiber applications, fabric or textile applications, building applications, transportation applications, electronic device applications, or electrical applications. However, the composition can be used in end use applications other than the preparation of the coated substrate, such as in the preparation of articles such as silicone rubber.

[0158] Alternatively, the coated substrate can be used as a release liner, for example, for tapes or adhesives, including any pressure sensitive adhesive, including acrylic type pressure sensitive adhesives, rubber type pressure sensitive adhesives, and silicone type pressure sensitive adhesives, as well as acrylic type adhesives, synthetic rubber type adhesives, silicone type adhesives, epoxy resin type adhesives, and polyurethane type adhesives. For double-sided tapes or adhesives, each major surface of the substrate can have a film disposed thereon.

[0159] Alternatively, when the composition is to be formulated as a release coating composition (e.g., for forming a release coating or liner), the release coating composition can be prepared by mixing the components together, for example, to prepare a one-component composition. However, it may be desirable to prepare the release coating composition as a multi-part composition, where the component having a methanol functional group (e.g., component (A)) and the component having an isocyanate functional group (e.g., component (B)) are stored in separate parts until these parts are combined at the time of use (e.g., immediately prior to application to the substrate). As described above, when the composition is a release coating composition, the release coating composition can be used to form a coated substrate, and the release coating is formed by applying and curing the release coating composition on the substrate (e.g., the surface of the substrate).

[0160] The release coating composition can be applied to the substrate, for example, by any convenient means such as spraying, knife coating, dipping, screen printing, or by a roll coater such as an offset web coater, kiss coater, or gravure roll coater).

[0161] The anti-stick coating composition of the present invention can be applied to any substrate, such as those described above. Alternatively, the anti-stick coating composition can be applied to a polymer film substrate, such as polyester, particularly polyethylene terephthalate (PET), polyethylene, polypropylene, or polystyrene film. Alternatively, the anti-stick coating composition can be applied to a paper web, including plastic-coated paper (e.g., paper coated with polyethylene), cellophane, supercalendered paper, or clay-coated kraft paper. Alternatively, the release coating composition can be applied to a metal foil substrate, such as aluminum foil.

[0162] In certain embodiments, the method of preparing the coated substrate may further include treating the substrate before applying or disposing the anti-stick coating composition on the substrate. Treating the substrate can be carried out by any convenient means, such as plasma treatment or corona discharge treatment. Alternatively, the substrate can be treated by applying a primer. In some cases, the adhesion of the anti-stick coating can be improved if the substrate is treated before the anti-stick coating is formed on the substrate by the anti-stick coating composition.

[0163] When the anti-stick coating composition contains the vehicle (F), the method may further include: removing the vehicle (F), which can be carried out by any conventional means, such as heating at 50 °C to 100 °C for a time sufficient to remove all or a part of the vehicle (F). The method may further include curing the anti-stick coating composition to form an anti-stick coating on the surface of the substrate. Curing can be carried out by any conventional means, such as heating at 100 °C to 200 °C.

[0164] Under production coater conditions, curing can be achieved at an air temperature of 120 °C to 150 °C with a dwell time of 1 second to 6 seconds, alternatively 1.5 seconds to 3 seconds. Heating can be carried out in an oven, such as an air-circulation oven or a tunnel furnace, or by passing the coated film around a heated cylinder.

[0165] The following examples are intended to illustrate the present invention and should not be construed in any way as limiting the scope of the present invention. Certain components used in the examples are shown in Table 1 below, followed by the characterization and evaluation procedures also used in the examples.

[0166] The following examples illustrating embodiments of the disclosure are intended to illustrate and not limit the invention. Unless otherwise noted, all reactions are carried out under air, and all solvents, substrates, and reagents are purchased from various commercial suppliers (e.g., Evonik, TCI, Sigma-Aldrich, etc.) or otherwise obtained and used as received.

[0167] Materials

[0168] A summary is provided in Table 1 below, setting forth information regarding certain abbreviations, symbols, and components used in the examples.

[0169] Table 1: Materials Used

[0170]

[0171]

[0172] Equipment and Characterization Parameters

[0173] The following equipment and characterization procedures / parameters are used to evaluate the various physical properties of the compounds prepared in the following examples.

[0174] Hydroxyl Number Calculation

[0175] An automatic titrator is used to obtain the hydroxyl number or value. An esterification reagent is prepared using phthalic anhydride, pyridine, and imidazole. Weigh 63 g to 66 g of phthalic anhydride into a 500 mL brown reagent bottle. Add 400 mL of fresh pyridine and shake the bottle vigorously until the solution is complete. Then add 9 g to 10 g of imidazole and vortex carefully to dissolve. Then let the reagent stand overnight. Avoid long-term exposure of the reagent to moisture in the air. Then weigh approximately 1.0 g of the sample into a 40 mL glass bottle and add 4.00 mL of the esterification reagent. Stir the solution on a magnetic stirrer until the sample is completely dissolved in the esterification reagent. Then heat the bottle in a water bath at 90 °C ± 2 °C for 2 hours. After cooling to room temperature, open the lid of the bottle and rinse the rubber gasket with 8 mL of pyridine and 4 mL of deionized water. To increase the solubility of the methanol siloxane, add 4 mL of THF to the solution. Let the solution stand for 2 minutes and then titrate with 1.000 mol / L sodium hydroxide solution. A blank test is carried out in the same manner, but without adding the sample to the esterification reagent. The hydroxyl number in the sample is calculated as follows:

[0176]

[0177] Where: OHsample = hydroxyl number of the sample (mg KOH / g sample); Vblank = volume of sodium hydroxide solution required for the blank (mL); Vsample = volume of sodium hydroxide solution required for the sample (mL); N = normality of the sodium hydroxide solution, in meq / mL (eq / L); 56.1 = equivalent weight of KOH, in mg / meq (g / eq); and Wsample = sample weight (g).

[0178] NCO Content Calculation

[0179] To measure the NCO content, weigh the sample into a beaker to an accuracy of 0.0001 g, and then dissolve it in toluene (previously dried with molecular sieves). Then add an appropriate amount of DBA / DMF solution (a di-n-butylamine / dimethylformamide solution prepared by dissolving 155 mL of DBA in 350 mL of DMF, adding 15 g of molecular sieves, and allowing the solution to stand and dry overnight before use) using a precision pipette. Add a stir bar to the solution and cover the beaker with aluminum foil. Stir the solution for at least 5 minutes. Then use 25 ml of isopropanol to wash the inner wall of the beaker and the aluminum foil, and collect the washing solvent in the beaker. Titrate the final solution with 0.5 mol / L HCl. Analyze the blank sample in the same manner without adding the sample. Calculate according to the following formula:

[0180]

[0181] Where: NCO% = NCO content of the sample; NHCl (mol / L) = equivalent concentration of the HCl solution; Vblank (mL) = volume of HCl consumed in the blank test; and Vsample (mL) = volume of HCl consumed in the sample test. Wsample (g) is the sample weight.

[0182] Performance Evaluation

[0183] Extractables: The curing characteristics of the coating are evaluated by measuring the percentage of extractables in the coating after curing. This measurement is carried out by first determining the coating weight of a substrate sample of standard size with a cured coating by X-ray fluorescence using an X-ray fluorescence spectrometer. Then place the coated sample in a solution of methyl isobutyl ketone solvent to extract any unreacted siloxanes that have not crosslinked into the coating matrix or have adhered to the substrate. After a predetermined time (immersed in MIBK for 1 day), remove the sample from the solvent, dry it, and re-measure the coating weight.

[0184] Release Force (RF-RT)

[0185] To measure the anti-sticking force at room temperature, use a 180° peel test. Specifically, laminate a Tesa7475 standard tape onto each anti-sticking coating to obtain a laminated sample, and place a load weight of 20 g / cm 2 on each laminated sample at room temperature for 20 hours. After 20 hours, remove the load weight. After 30 minutes, measure the anti-sticking force using a ChemInstruments AR-1500 according to FINAT Test Method No. 10 (FINAT Technical Handbook, 7th Edition, 2005).

[0186] Release Force after Aging (RF-70°C)

[0187] To measure the anti-sticking force of the aged product at 70 °C, an 180° peel test was used. Specifically, a Tesa 7475 standard tape was laminated onto each anti-sticking coating to obtain a laminated sample, and a load weight of 20 g / cm 2 was placed on each laminated sample at 70 °C for 20 hours. After 20 hours, the load weight was removed. After 30 minutes at room temperature, the anti-sticking force was measured by ChemInstruments AR-1500 according to FINAT Test Method No. 10 (FINAT Technical Handbook, 7th Edition, 2005).

[0188] Subsequent Adhesion Strength (SAS)

[0189] SAS is an indicator of migration and was measured by first laminating a Nitto Denko 31B tape onto each anti-sticking coating to obtain a laminated sample, and placing a load weight of 20 g / cm 2 on each laminated sample at 70 °C for 20 hours. After 20 hours, the load weight was removed. After 30 minutes at room temperature, each laminated sample was placed on a PET substrate for 1 hour. Then, the anti-sticking force was measured by ChemInstruments AR-1500 to obtain an RF 防粘 value. The same procedure was performed for each anti-sticking coating, but using a PTFE substrate instead of a PET substrate, and the resulting anti-sticking force was called RF PTFE value. According to FINAT Test Method No. 11 (FINAT Technical Handbook, 7th Edition, 2005), SAS was calculated by the formula RF 防粘 / RF PTFE × 100%.

[0190] Preparation Example 1: Synthesis of Isocyanate-Functional Copolymer (b1-1)

[0191] 374 g (b1a-1) siloxane (0.2 mol) and 89 g (b1b) polyisocyanate (0.38 mol) were placed into a dry 1000 mL three-necked flask equipped with a condenser and a mechanical stirrer. The system was purged with nitrogen for 10 minutes, and the temperature was gradually increased to 80 °C within 30 minutes. The reaction was carried out for 3 hours to obtain a (b1-1) isocyanate-functional copolymer. The (b1-1) isocyanate-functional copolymer was cooled to room temperature and then transferred to a container. Then the container was placed in a desiccator for storage. Based on the above titration method, the titrated NCO% was determined to be 3.42%.

[0192] Preparation Example 2: Synthesis of Isocyanate-Functional Copolymer (b1-2)

[0193] Into a 1000 mL three-necked flask equipped with a condenser and a mechanical stirrer, 200 g of (b1a-2) siloxane (0.21 mol) and 94 g of (b1b) polyisocyanate (0.42 mol) were placed. The system was purged with nitrogen for 10 minutes, and the temperature was gradually increased to 80 °C within 30 minutes. The reaction was carried out for 3 hours to obtain a (b1-2) isocyanate-functional copolymer. The (b1-2) isocyanate-functional copolymer was cooled to room temperature and then transferred to a container. The container was placed in a desiccator for storage. Based on the above titration method, the titrated NCO% was determined to be 6.±0.1%.

[0194] Table 2 below shows the relationship between the theoretical NCO content of the (b1-1) isocyanate-functional copolymer and the (b1-2) isocyanate-functional copolymer and the actual titrated NCO values measured in Preparation Examples 1 and 2.

[0195] Table 2: NCO Content (%)

[0196] Isocyanate-Functional Copolymer: Theoretical NCO Content (%) Measured NCO Content (%) (b1-1) Isocyanate-Functional Copolymer 3.6 3.42±0.02 (b1-2) Isocyanate-Functional Copolymer 6.1 6.1±0.1

[0197] Preparation Example 3: Synthesis of Organopolysiloxane (A-1)

[0198] Into a 2000 mL three-necked flask, cyclic siloxane (800 g) (2.74 mol), cyclic organohydrogensiloxane (45 g), and a capping agent (14.6 g) were placed. Then, 0.68 mL of trifluoromethanesulfonic acid was placed in the flask as a catalyst. The system was purged with nitrogen for 10 minutes and gradually heated to 60 °C within 30 minutes. The reaction was carried out for 3 hours, and then the system was cooled to room temperature. Then, 700 mesh CaCO 3 (12 g) was added to the flask and stirred at room temperature for 2 hours to obtain a mixture. Then the mixture was centrifuged to remove most of the CaCO 3 , and then filtered through silica gel on a Buchi funnel to obtain a filtered mixture. Then the filtered mixture was rotary evaporated at 70 °C under maximum vacuum, and then rotary evaporated at 120 °C and maximum vacuum using a vacuum pump to obtain a linear organopolysiloxane having the following average formula: MD 120 D H 8 M.

[0199] 500 g of the linear organopolysiloxane just prepared above was placed together with 86 g of an alcohol compound, 200 g of a solvent, 0.48 g of a pH control, and 1.20 g of a hydrosilylation catalyst in a device equipped with a mechanical stirrer, N 2Into a 1000 mL three-necked flask of the inlet and condenser. Under nitrogen purge, the flask was stirred at 400 rpm for 10 minutes at room temperature. The system was gradually heated to 70 °C over 30 minutes and held at this temperature for 2.5 hours to obtain a crude product. The crude product was filtered through a 0.45 μm pipette tip. A solution of 17.2 g of antioxidant in solvent (1 wt%) was added to the crude product to obtain a mixture, and then the mixture was rotary evaporated at 70 °C under maximum vacuum and then at 115 °C and maximum vacuum by WIFI for 2 hours to obtain (A-1) organopolysiloxane. The (A-1) organopolysiloxane was obtained and its average hydroxyl number was calculated to be 42.0 mg KOH / g (based on the above titration method).

[0200] Preparation Example 4: Synthesis of Organopolysiloxane (A-2)

[0201] Acetic acid (268 g), a capping agent (696 g), and an equilibration catalyst (150 g) were placed into a 2000 mL flask. The system was purged with nitrogen for 10 minutes. Then the nitrogen flow was reduced to a minimum and the temperature of the flask was raised to 45 °C. TEOS (232 g) was added dropwise to the flask through a constant pressure funnel and the addition was completed after 30 minutes. The temperature was maintained for another 120 minutes. Then acetic anhydride (228 g) was added dropwise through the constant pressure funnel with stirring and the addition was completed after 15 minutes. The temperature was maintained for another 150 minutes. Then stirring was stopped and the temperature of the system was lowered to room temperature.

[0202] Then the system was centrifuged to remove most of the equilibration catalyst and a preliminary mixture was obtained. Then the preliminary mixture was rotary evaporated at room temperature at 66.5 mbar (50 Torr). Then the temperature was gradually raised to 60 °C to remove by-products and unreacted reagents to obtain a purified mixture. Then 300 mL of ethyl acetate was added to the purified mixture, followed by washing with deionized water (200 mL in total), washing twice with 4% NaHCO 3 (150 mL in total), and then an additional washing step with deionized water (50 mL) to obtain a product mixture. By test paper measurement, the pH of the product mixture was neutral. Then the organic phase of the product mixture was dried with anhydrous sodium sulfate Na 2 SO 4 to obtain a preliminary mixture product. Then the preliminary mixture product was rotary evaporated at room temperature at 13 mbar (10 Torr). Then the temperature was gradually raised to 50 °C and maintained for at least 1 hour. Then M 4 Q was collected and its purity was determined to be 65%.

[0203] Add the M 4Q (60 g), cyclic siloxane (1380 g), cyclic organohydrogensiloxane (75 g), and trifluoromethanesulfonic acid (1.4 mL). The system was purged with nitrogen for 10 minutes. Then the system was heated to 60 °C and held at that temperature for 3 hours. Then, 700-mesh CaCO 3 (20 g) was added to the flask to obtain a precursor mixture, and the system was stirred at room temperature for 2 hours. Then the precursor mixture was filtered through cotton and then through silica gel on a Buchi funnel. Then the precursor mixture was rotary evaporated at 70 °C under maximum vacuum for 1 hour, followed by stripping at 110 °C for 2 hours. An organopolysiloxane with an average formula QD 120 D H 4 M 4 was obtained.

[0204] The QD 120 D H 4 M 4 (1000 g) just prepared above, an alcohol compound (224 g), a solvent (400 g), an inhibitor (D) (0.96 g), and a hydrosilylation catalyst (2.4 g) were placed in a 2000 mL three-necked flask. The system was stirred at 400 rpm for 10 minutes at room temperature under a nitrogen blanket. The system was heated to 70 °C and held at that temperature for 2.5 hours to obtain a crude product. Then the crude product was filtered through silica gel on a Buchi funnel. A 1 wt% solution of an antioxidant (20 g) in a solvent was added to the crude product, and then it was rotary evaporated at 70 °C under maximum vacuum for 1 hour, followed by heating and stripping at 115 °C. An (A-2) organopolysiloxane was obtained and its average hydroxyl number was calculated to be 41.4 ± 0.003 mg KOH / g (based on the above titration method).

[0205] Preparation Example 5: Synthesis of Organopolysiloxane (A-3)

[0206] 133.5 g of cyclic siloxane, 11.1 g of organohydrogensiloxane, 7.25 g of a capping agent, and 24 g of an equilibration catalyst were placed in a 250 mL three-necked flask. The system was purged with nitrogen for 10 minutes, the nitrogen was reduced, and the system was gradually heated to 65 °C. The reaction was allowed to proceed for 48 hours, and then the system was cooled to room temperature. Then the crude product was centrifuged to remove most of the equilibration catalyst and then filtered through silica gel on a Buchi funnel to obtain a filtered mixture. Then the filtered mixture was rotary evaporated at 70 °C under maximum vacuum and then rotary evaporated at 110 °C and maximum vacuum using a vacuum pump to obtain a linear organopolysiloxane with the following average formula: MD 40 D H 4 M.

[0207] Place 140 g of the linear organopolysiloxane just prepared above together with 32.3 g of an alcohol compound, 70 g of a solvent, 0.14 g of a pH control and 0.35 g of a hydrosilylation catalyst in a 500 mL three-necked flask equipped with a mechanical stirrer, N 2 inlet and a condenser. Purge the flask with nitrogen for 10 minutes. Gradually heat the system to 70 °C and hold at this temperature for 2 hours to obtain a crude product. Filter the crude product through a 0.45 μm pipette filter. Add a solution of 2 g of an antioxidant in a solvent (1 wt%) to the crude product to obtain a mixture, and then rotary evaporate the mixture at 70 °C under maximum vacuum, and then rotary evaporate at 110 °C under maximum vacuum using a vacuum pump for 2 hours to obtain the (A-3) organopolysiloxane.

[0208] Preparation Example 6: Synthesis of Organopolysiloxane (A-4)

[0209] Charge M 4 Q (60 g), cyclic siloxane (1150 g), cyclic organohydrogensiloxane (75 g) and trifluoromethanesulfonic acid (1.4 mL) into a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet and a condenser. Purge the system with nitrogen for 10 minutes and gradually heat to 60 °C over 30 minutes. Allow the reaction to proceed for 3 hours, then cool the system to room temperature. Then add 700 mesh CaCO 3 (20 g) to the flask and stir at room temperature for 2 hours to obtain a precursor mixture. Filter the precursor mixture through a 0.45 μm pipette filter. Then rotary evaporate the precursor mixture at 70 °C under maximum vacuum. Then subject the precursor mixture to vacuum pumping at 110 °C and maximum vacuum to obtain an organohydrogensiloxane having an average formula QD 57 D H 5.7 M 4 .

[0210] Charge the organohydrogensiloxane (484 g), alcohol compound (118 g), solvent (242 g), pH control (0.484 g) and hydrosilylation catalyst (1.21 g) just prepared above into a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet and a condenser. Stir the system at 400 rpm for 10 minutes at room temperature under nitrogen purge. Gradually heat the system to 70 °C over 30 minutes and hold at this temperature for 2.5 hours to obtain a precursor mixture. Then filter the precursor mixture through a 0.45 μm pipette filter. Add a solution of 10 g of an antioxidant in a solvent (1 wt%) to the precursor mixture, and then rotary evaporate it at 70 °C under maximum vacuum. Then subject the precursor mixture to vacuum pumping at 110 °C and maximum vacuum to obtain the (A-4) organopolysiloxane.

[0211] Preparation Example 7: Synthesis of Organopolysiloxane (A-5)

[0212] Charge M into a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a condenser. 4 Q (60 g), cyclic siloxane (1380 g), cyclic organohydrogensiloxane (75 g), and trifluoromethanesulfonic acid (1.4 mL). Purge the system with nitrogen for 10 minutes and gradually heat it to 60 °C over 30 minutes. Allow the reaction to proceed for 3 hours, then cool the system to room temperature. Next, add 700-mesh CaCO 3 (20 g) to the flask and stir at room temperature for 2 hours to obtain a precursor mixture. Filter the precursor mixture through a 0.45 μm pipette filter. Then rotary evaporate the precursor mixture at 70 °C under maximum vacuum. Then subject the precursor mixture to a vacuum pump treatment at 110 °C and maximum vacuum to obtain an organohydrogensiloxane having the average formula QD 120 D H 8 M 4 .

[0213] Charge the organohydrogensiloxane (968 g) just prepared above, an alcohol compound (224 g), a solvent (424 g), a pH control agent (1.12 g), and a hydrosilylation catalyst (2.78 g) into a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a condenser. Stir the system at 400 rpm for 10 minutes at room temperature under nitrogen purge. Gradually heat the system to 70 °C over 30 minutes and hold at this temperature for 2.5 hours to obtain a precursor mixture. Then filter the precursor mixture through a 0.45 μm pipette filter. Add a 1 wt% solution of an antioxidant (20 g) in a solvent to the precursor mixture, then rotary evaporate it at 70 °C under maximum vacuum. Then subject the precursor mixture to a vacuum pump treatment at 110 °C and maximum vacuum to obtain (A-5) organopolysiloxane.

[0214] Preparation Example 8: Synthesis of Organopolysiloxane (A-6)

[0215] Charge M into a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a condenser. 4 Q (60 g), cyclic siloxane (416 g), cyclic organohydrogensiloxane (37.5 g), and trifluoromethanesulfonic acid (1.4 mL). Purge the system with nitrogen for 10 minutes and gradually heat it to 60 °C over 30 minutes. Allow the reaction to proceed for 3 hours, then cool the system to room temperature. Next, add 700-mesh CaCO 3(20 g) was added to a flask and stirred at room temperature for 2 hours to obtain a precursor mixture. The precursor mixture was filtered through a 0.45 μm pipette filter. Then the precursor mixture was rotary evaporated at 70 °C under maximum vacuum. Then the precursor mixture was vacuum pumped at 110 °C and maximum vacuum to obtain an organohydrogensiloxane having the average formula QD 36 D H 4 M 4 .

[0216] Into a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a condenser were charged the organohydrogensiloxane (900 g), alcohol compound (167 g), solvent (533 g), pH control (1.12 g), and hydrosilylation catalyst (2.78 g) just prepared above. The system was stirred at 400 rpm for 10 minutes at room temperature under a nitrogen purge. The system was gradually heated to 70 °C over 30 minutes and held at that temperature for 2.5 hours to obtain a precursor mixture. Then the precursor mixture was filtered through a 0.45 μm pipette filter. A 1 wt% solution of antioxidant (20 g) in solvent was added to the precursor mixture, which was then rotary evaporated at 70 °C under maximum vacuum. Then the precursor mixture was vacuum pumped at 110 °C and maximum vacuum to obtain (A-6) organopolysiloxane.

[0217] Preparation Example 9: Synthesis of Organopolysiloxane (A-7)

[0218] Into a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a condenser were charged M 4 Q (60 g), cyclic siloxane (369 g), cyclic organohydrogensiloxane (75 g), and trifluoromethanesulfonic acid (1.4 mL). The system was purged with nitrogen for 10 minutes and gradually heated to 60 °C over 30 minutes. The reaction was allowed to proceed for 3 hours, and then the system was cooled to room temperature. Subsequently, 700 mesh CaCO 3 (20 g) was added to the flask and stirred at room temperature for 2 hours to obtain a precursor mixture. The precursor mixture was filtered through a 0.45 μm pipette filter. Then the precursor mixture was rotary evaporated at 70 °C under maximum vacuum. Then the precursor mixture was vacuum pumped at 110 °C and maximum vacuum to obtain an organohydrogensiloxane having the average formula QD 32 D H 8 M 4 .

[0219] Charge an organic hydrogen siloxane (600 g), an alcohol compound (224 g), a solvent (300 g), a pH control substance (1.22 g), and a hydrosilylation catalyst (1.44 g), which were just prepared above, into a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a condenser. Stir the system at 400 rpm for 10 minutes at room temperature under a nitrogen purge. Gradually heat the system to 70 °C within 30 minutes and hold at this temperature for 2.5 hours to obtain a precursor mixture. Then filter the precursor mixture through a 0.45 μm pipette filter. Add a 1 wt% solution of an antioxidant (20 g) in a solvent to the precursor mixture, and then rotary evaporate it at 70 °C under the highest vacuum. Then subject the precursor mixture to a vacuum pump treatment at 110 °C and the highest vacuum to obtain the (A-7) organopolysiloxane.

[0220] Preparation Example 10: Synthesis of Organopolysiloxane (A-8)

[0221] Charge M 4 Q (60 g), a cyclic siloxane (184.8 g), a cyclic organic hydrogen siloxane (37.5 g), and trifluoromethanesulfonic acid (1.4 mL) into a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a condenser. Purge the system with nitrogen for 10 minutes and gradually heat it to 60 °C within 30 minutes. Allow the reaction to proceed for 3 hours, and then cool the system to room temperature. Then, add 700-mesh CaCO 3 (20 g) to the flask and stir at room temperature for 2 hours to obtain a precursor mixture. Filter the precursor mixture through a 0.45 μm pipette filter. Then rotary evaporate the precursor mixture under the highest vacuum at 70 °C. Then subject the precursor mixture to a vacuum pump treatment at 110 °C and the highest vacuum to obtain an organic hydrogen siloxane having an average formula QD 16 D H 4 M 4 .

[0222] Charge a 2000 mL three-necked flask equipped with a mechanical stirrer, a nitrogen inlet, and a condenser with the organohydrogensiloxane (460 g), alcohol compound (100 g), solvent (200 g), pH control agent (0.60 g), and hydrosilylation catalyst (1.44 g) just prepared above. Stir the system at 400 rpm for 10 minutes at room temperature under a nitrogen purge. Gradually heat the system to 70 °C over 30 minutes and hold at this temperature for 2.5 hours to obtain a precursor mixture. Then filter the precursor mixture through a 0.45 μm pipette filter. Add a 1 wt% solution of the antioxidant (20 g) in solvent to the precursor mixture and then rotary evaporate it at 70 °C under maximum vacuum. Then subject the precursor mixture to a vacuum pump treatment at 110 °C and maximum vacuum to obtain the (A-8) organopolysiloxane.

[0223] Table 3 below shows the theoretical hydroxyl numbers of the organopolysiloxanes (A3)-(A8) and the actual average hydroxyl numbers measured according to the above titration method.

[0224] Table 3: Hydroxyl Number

[0225] Organopolysiloxane: Average Hydroxyl Number (mgKOH / g) Theoretical Hydroxyl Number (mgKOH / g) (A-3) 55.8±0.08 60.1 (A-4) 58.2±0.03 57.8 (A-5) 41.4±0.03 42.4 (A-6) 55.85±0.05 60.6 (A-7) 110.3±0.04 110.7 (A-8) 92.4±0.08 101.0

[0226] Examples 1-10: Compositions

[0227] Prepare a composition for preparing an anti-stick coating. The composition is a two-part composition: (1) Part (A) comprises (b1-1) an isocyanate-functional prepolymer and (b2) a polyisocyanate; and (2) Part (B) comprises the remaining components. Table 4 shows the relative amounts of the components in each of the compositions of Examples 1-5. Table 5 shows the relative amounts of the components in each of the compositions of Examples 6-10. The values in Tables 4 and 5 are in grams (except for the NCO / OH index, which is a unitless molar ratio).

[0228] Thoroughly blend each composition at 1000 rpm using a mechanical stirrer for 1 minute. After mixing, coat each mixture onto a substrate with a controlled thickness of about 1 μm at room temperature using a coater to obtain a wet deposit on the substrate. Then, place the wet deposit on the substrate in an oven set at a predetermined temperature (80 °C) to determine whether the wet deposit will cure within 30 seconds to obtain an anti-stick coating. Hold the remaining volume of each composition at room temperature for gel time determination based on visual inspection (based on when the composition is no longer flowable). The results are also listed in Tables 4 and 5 below.

[0229] Table 4: Examples 1-5

[0230] Formulations Example 1 Example 2 Example 3 Example 4 Example 5 (A-2) Organopolysiloxane (g) 8.5 7.9 7.06 7.37 6.67 (b1-1) Isocyanate-Functional Copolymer (g) 1.13 1.58 1 1.3 1.66 (b2) Polyisocyanate (g) 0.37 0.52 0.8 1.3 1.66 (D) Inhibitor (g) 0.2 0.2 0.25 0.2 0.2 (C) Catalyst (g) 0.04 0.04 0.04 0.04 0.04 NCO / OH Ratio 0.48 0.72 1.0 1.33 1.87 Curing Rate (80°C, 30 s) Curing Curing Curing Curing Curing Gel Time (hours) >24 >24 >24 >24 >24

[0231] Table 5: Examples 6-10

[0232] Formulations Example 6 Example 7 Example 8 Example 9 Example 10 (A-1) Organopolysiloxane (g) 8.5 7.9 7.06 7.37 6.67 (b1-1) Isocyanate-Functional Copolymer (g) 1.13 1.58 1 1.3 1.66 (b2) Polyisocyanate (g) 0.37 0.52 0.8 1.3 1.66 (D) Inhibitor (g) 0.2 0.2 0.25 0.2 0.2 (C) Catalyst (g) 0.04 0.04 0.04 0.04 0.04 NCO / OH Ratio 0.48 0.72 1.0 1.33 1.87 Curing Rate (80°C, 30 s) Curing Curing Curing Curing Curing Gel Time (hours) >24 >24 >24 >24 >24

[0233] Examples 1-10: Release Coatings

[0234] Anti - sticking coatings are formed using the compositions of Examples 1 - 10. The composition of Example 1 is used to prepare the anti - sticking coating in Example 1, and so on. In each example, Part B of each composition is placed in a container, and then Part A is placed to obtain a mixture. The mixture is thoroughly blended for 1 minute at 1000 rpm using a mechanical stirrer. After mixing, each mixture is coated onto a substrate with a controlled thickness of about 1 μm at room temperature by means of a coater to obtain a wet deposit on the substrate. Then, the wet deposit on the substrate is placed in an oven set at a predetermined temperature (80 °C) for 30 seconds to determine whether the wet deposit will cure to obtain an anti - sticking coating. The remaining volume of each composition is kept at room temperature for gel time determination (based on when the composition is no longer flowable). The anti - sticking coatings are evaluated as described above, and the results are listed in Tables 6 and 7 below.

[0235] Table 6: Release Coatings of Examples 1-5

[0236] Properties: Example 1 Example 2 Example 3 Example 4 Example 5 Release Force RT (g / in) 7.9 10.3 9.05 12.15 24.25 Release Force 70°C (g / in) 24 33 44.5 105.5 250.5 SAS % 80 90 94 100 100 Extractable % 6 3 3 2 3

[0237] Table 7: Release Coatings of Examples 6-10

[0238] Properties: Example 6 Example 7 Example 8 Example 9 Example 10 Release Force RT (g / in) 7.7 11.05 10.75 14.1 25.25 Release Force 70°C (g / in) 21.9 27.9 41.2 95.1 292.0 SAS % 82 89 99 102 99 Extractable % 10 3 3 2 3

[0239] Example 11: Curing Rate Measurement

[0240] The composition of Example 7 is used to determine how fast the composition cures at 80 °C to obtain an anti - sticking coating. Conventional compositions for preparing anti - sticking coatings cure at temperatures greater than 80 °C and require long cure times (e.g., more than one minute) at low temperatures such as 80 °C. Table 8 below shows the properties of the anti - sticking coatings prepared in Example 11 based on different cure times at a cure temperature of 80 °C. The quality of the anti - sticking coatings is analyzed by visual inspection and touch to determine whether a particular anti - sticking coating is fully cured.

[0241] Table 8: Curing Rate Measurement of Example 11

[0242] Curing Time (s): 30 15 10 7 Release Coating Quality Good Good Good Stained Release Force RT (g / in) 15.5 n / a 13.4 n / a Release Force 70°C (g / in) 27.2 n / a 23.3 n / a SAS % 88 n / a 80 n / a Extractable % 4 n / a 3 n / a

[0243] As shown in Table 8 above, the compositions of the present invention can cure at 80 °C in only 10 seconds, obtaining anti - sticking coatings with excellent performance characteristics.

[0244] Examples 12-15 and Comparative Examples 1-5: Compositions and Release Coatings

[0245] A composition for preparing an anti-stick coating, and a corresponding anti-stick coating. The composition is a two-part composition: (1) Part (A) includes (b1-1) an isocyanate-functional prepolymer and (b2) a polyisocyanate; and (2) Part (B) includes the remaining components. Tables 9 and 10 show the relative amounts of the components in each composition of Examples 12-15 and Comparative Examples 1-5. The values in Tables 9 and 10 are in grams (except for the NCO / OH index, which is a unitless molar ratio).

[0246] Using a mechanical stirrer, each composition was thoroughly blended at 1000 rpm for 1 minute. After mixing, each mixture was coated onto a substrate with a controlled thickness of about 1 μm at room temperature by means of a coater to obtain a wet deposit on the substrate. Then, the wet deposit on the substrate was placed in an oven set at a predetermined temperature (90 °C) to determine whether the wet deposit would cure within a predetermined time to obtain an anti-stick coating. The remaining volume of each composition was kept at room temperature for gel time determination based on visual inspection (based on when the composition was no longer flowable).

[0247] Table 9: Examples 12-15

[0248] Formulations Example 12 Example 13 Example 14 Example 15 (A-6) Organopolysiloxane (g) 5 5 5 0 (A-4) Organopolysiloxane (g) 0 0 0 5 (b1-1) Isocyanate-functional copolymer (g) 2 2 3 0 (b1-2) Isocyanate-functional copolymer (g) 0 0 0 2 (b2) Polyisocyanate (g) 0.4 0.4 0.3 0.4 (D) Inhibitor (g) 0.5 0.5 0.5 0.25 (C) Catalyst (g) 0 0 0 0.033 A blend of (C) and (D), with 20 wt% being component (C). 0.2 0.2 0.2 0 NCO / OH ratio 0.95 0.95 1.11 1.0 Curing rate (80 °C) Not tested Not tested Not tested 30 seconds Curing rate (90 °C) <30 seconds <30 seconds <30 seconds Not tested Gel time (hours) > 16 hours > 16 hours > 16 hours > 16 hours Appearance Transparent Transparent Transparent Transparent

[0249] Table 10: Comparative Examples 1-5

[0250]

[0251] Examples 20-22: Compositions and Anti-stick Coatings

[0252] A composition for preparing an anti-stick coating, and a corresponding anti-stick coating. The composition is a two-part composition: (1) Part (A) includes (b1-1) an isocyanate-functional prepolymer and (b2) a polyisocyanate; and (2) Part (B) includes the remaining components. Tables 11 and 12 show the relative amounts of the components in each composition of Examples 16-22. The values in Tables 11 and 12 are in grams (except for the NCO / OH index, which is a unitless molar ratio).

[0253] Each composition was thoroughly blended for 1 minute at 1000 rpm using a mechanical stirrer. After mixing, each mixture was coated onto a substrate with a controlled thickness of approximately 1 μm at room temperature by means of a coater to obtain a wet deposit on the substrate. Then, the wet deposit on the substrate was placed in an oven set at a predetermined temperature (80 °C) to determine whether the wet deposit would cure within a predetermined time (30 seconds) to obtain an anti-stick coating, except for Example 18, which was cured at 90 °C for 30 seconds. The anti-stick coating was analyzed after standing at room temperature (RT) for 24 hours. The remaining volume of each composition was kept at room temperature for gelation time determination based on visual inspection, and for each example, the gelation time exceeded 8 hours.

[0254] Table 11: Examples 16-19

[0255] Formulation Example 16 Example 17 Example 18 Example 19 (A-6) Organopolysiloxane (g) 5 0 0 0 (A-7) Organopolysiloxane (g) 0 5 0 0 (A-3) Organopolysiloxane (g) 0 0 5 0 (A-8) Organopolysiloxane (g) 0 0 0 5 (b1-1) Isocyanate-functional copolymer (g) 2 3.7 2 3.34 (b2) Polyisocyanate (g) 0.4 0.73 0.4 0.67 (D) Inhibitor (g) 0.5 0.5 0.5 0.25 A blend of (C) and (D), with 20 wt% being component (C). 0.2 0.2 0.2 0.2 NCO / OH ratio 0.95 0.96 0.95 0.96 Anti-stick force RT (g / in) 38.6±0.5 215.5±2.5 29.6±4 239.5±4.5 SAS % 76 77 76 76 Extractable % 12 1 10 2

[0256] Table 12: Examples 20-22

[0257] Formulation Example 20 Example 21 Example 22 (A-5) Organopolysiloxane (g) 7.06 7.37 6.67 (b1-1) Isocyanate-functional copolymer (g) 1.0 1.3 1.66 (b2) Polyisocyanate (g) 0.8 1.3 1.66 (D) Inhibitor (g) 0.25 0.2 0.2 (C) Catalyst (g) 0.041 0.041 0.041 NCO / OH ratio 1.0 1.5 2.1 Anti-stick force RT (g / in) 25.4±0.6 27.6±1.7 32.1±1.8 SAS % 78 93 91 Extractable % 4 4 5

Claims

1. A composition for forming an anti - sticking coating, the composition comprising: (A) an organopolysiloxane having an average of at least two methoxy functional groups per molecule, and (B) a polyisocyanate component, the polyisocyanate component comprising: (b1) an isocyanate - functional copolymer; and (b2) a polyisocyanate different from component (b1); wherein the anti - sticking coating formed with the composition is not a foam.

2. The composition according to claim 1, wherein component (b1) is prepared by reacting (b1a) a siloxane having at least two methoxy functional groups with (b1b) a polyisocyanate having at least two isocyanate functional groups, and wherein component (b1) is prepared with a molar excess of isocyanate functional groups in component (b1b) compared to the methoxy functional groups in component (b1a).

3. The composition according to claim 2, wherein: (i) The component (b1a) has the average formula R 1 2 XO[SiR 1 2 O] n' XR 1 2 , where each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group; each X is an independently selected methanol functional group, and the subscript n' is from 1 to 100; (ii) the methanol functional groups in the component (b1a) are at opposite ends; or (iii) both (i) and (ii).

4. The composition according to claim 2 or 3, wherein: (i) component (b1b) comprises an aliphatic isocyanate; (ii) component (b2) comprises at least three isocyanate functional groups; or (iii) both (i) and (ii).

5. The composition according to any one of the preceding claims, wherein: (i) the composition further comprises (C) a catalyst; (ii) the composition does not contain a physical blowing agent; (iii) the composition does not contain a chemical blowing agent; (iv) component (b1) comprises two isocyanate functional groups; (v) component (B) is prepared by combining component (b1) and (b2) before combining component (A) and (B) to obtain the composition; (vi) component (B) comprises an amount of component (b2) greater than 10 wt% to 90 wt% based on the total weight of component (B); or (vii) any combination of (i) to (vi).

6. The composition according to any one of the preceding claims, wherein the organopolysiloxane (A): (i) comprises at least one SiO 4 / 2 unit; (ii) comprises on average three or more methoxy functional groups; (iii) comprises at least one side-chain methoxy functional group; (iv) comprises at least one terminal methoxy functional group; or (v) any combination of (i) to (iv).

7. The composition according to any one of the preceding claims, wherein: (i) The methanol functional groups are identical to each other; (ii) The methanol functional groups independently have the general formula –D–O a –(C b H 2b O) c –H, where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each part indicated by subscript c, and subscript c is from 0 to 500, provided that subscripts a and c are not both 0; or (iii) both (i) and (ii).

8. The composition according to any one of the preceding claims, wherein: (i) the methoxy functional group has the general formula: –D–O a –[C 2 H 4 O] d [C 3 H 6 O] e [C 4 H 8 O] f –H; where D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, subscript a is 0 or 1, 0 ≤ d ≤ 500, 0 ≤ e ≤ 500, and 0 ≤ f ≤ 500, provided that 1 ≤ d + e + f ≤ 500; (ii) the methoxy functional group is a side group; or (iii) both (i) and (ii).

9. The composition according to any one of the preceding claims, wherein the organopolysiloxane (A): (i) has the following average formula: [Z 1 v [R 1 3 SiO 1 / 2 w [R 1 2 XSiO 1 / 2 x [R 1 2 SiO 2 / 2 y [R 1 XSiO 2 / 2 z [SiO 4 / 2 1.0 ​​​​​​ where 0 ≤ v ≤ 12, 0 ≤ w ≤ 8, 0 ≤ x ≤ 8, 40 ≤ y ≤ 1,000 and 0 ≤ z ≤ 8, provided that 2 ≤ (x + z) ≤ 8; each R 1 is an independently selected substituted or unsubstituted hydrocarbon group; each X is an independently selected methanol functional group; and Z 1 is independently (O 1 / 2 SiR 1 2 -D 1 -R 1 SiO 2 / 2 ), or (O 1 / 2 SiR 1 2 -D 1 -R 1 2 SiO 1 / 2 ), where each R 1 is independently selected and as defined above, and each D 1 is an independently selected divalent linking group; or (ii) having an average formula R 1 3 O[SiR 1 2 O] w' [SiR 1 XO] x' R 1 3 , where each R 1 and each X are independently selected and defined as above; the subscript w' is from 10 to 1000, and the subscript x' is from 4 to 200.

10. The composition according to any one of claims 1 to 8, wherein the organopolysiloxane (A) has the following average formula: SiY 4 , where each Y independently has the following formula: where each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group; each X is an independently selected methanol functional group; each D 1 is an independently selected divalent linking group; and each subscript m' is independently 10 to 250.

11. The composition according to any one of the preceding claims, wherein: (i) the composition does not contain an organic polyol; (ii) the composition comprises at least one of the following: (D) an inhibitor; (E) a chain extender; and / or (F) a carrier medium; (iii) the composition is capable of curing to obtain the anti - sticking coating in less than 30 seconds when exposed to a temperature of 80 °C; or (iv) any combination of (i) to (iii).

12. An anti - sticking coating formed from the composition according to any one of the preceding claims.

13. A method of forming a coated substrate, the method comprising: applying a composition onto the substrate; and curing the composition to obtain an anti - sticking coating on the substrate, thereby forming the coated substrate; wherein the composition is the composition according to any one of claims 1 to 11.

14. The method according to claim 13, wherein applying the composition onto the substrate forms a wet deposit on the substrate, and curing the composition comprises exposing the wet deposit to an elevated temperature for a period of time.

15. A coated substrate comprising an anti - sticking coating disposed on a substrate formed by the method according to claim 13 or 14.

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