Composition for preparing a release coating and method for preparing a coated substrate - Patent Application 20070122997

Abstract

A composition for forming a release coating includes (A) an organopolysiloxane having an average of at least two carbinol functional groups per molecule. The composition also includes (B) a polyisocyanate component. Component (B) includes (b1) an isocyanate-functional copolymer and (b2) a polyisocyanate different from component (b1). The release coating formed using the composition is not a foam. Release coatings formed using this composition are also disclosed. Additionally, a method for preparing a coated substrate comprising a release coating disposed on a substrate, as well as the coated substrate formed according to the method, are disclosed.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) none.

[0002] FIELD OF THE INVENTION The subject disclosure relates generally to compositions, and more particularly to compositions and related methods for preparing release coatings. [Background technology]

[0003] Silicone compositions are known in the art and are used in countless industries and end uses.One of these end uses is to form a release coating or release liner that can remove adhesive.For example, silicone compositions can be used to coat various substrates, such as paper, to obtain a release liner for laminating pressure-sensitive adhesives (e.g., tapes).Such silicone compositions are typically addition-cured.

[0004] Conventional release liners are typically formed by the addition reaction (or hydrosilylation) of an organopolysiloxane having unsaturated hydrocarbon groups with an organohydrogenpolysiloxane at high temperatures in the presence of a hydrosilylation catalyst. In certain applications, release liners are formed at high speeds via a coating process. The cure speed in forming conventional release liners is particularly important. In addition, many conventional release liners are formed on substrates that are susceptible to softening or other undesirable effects due to the high temperatures required for curing, which limits the types of substrates that can be used. Summary of the Invention

[0005] A composition for forming a release coating is disclosed. The composition includes (A) an organopolysiloxane having an average of at least two carbinol functional groups per molecule. The composition also includes (B) a polyisocyanate component. Component (B) includes (b1) an isocyanate-functional copolymer and (b2) a polyisocyanate different from component (b1). The release coating formed using the composition is not a foam. The release coating formed using this composition is also disclosed.

[0006] Additionally, methods of preparing a coated substrate that includes a release coating disposed on a substrate, as well as coated substrates formed according to the methods, are disclosed. DETAILED DESCRIPTION OF THE INVENTION

[0007] A composition for forming a release coating is disclosed. The composition includes (A) an organopolysiloxane having an average of at least two carbinol functional groups per molecule. The carbinol functional groups on the organopolysiloxane are distinct from silanol groups; the carbinol functional groups contain carbon-bonded hydroxyl groups, while the silanol functional groups contain silicon-bonded hydroxyl groups. Stated differently, the carbinol functional groups contain moieties of the formula -COH, while the silanol functional groups are of the formula -SiOH. These functional groups function differently; for example, the silanol functional groups can readily condense to provide siloxane (-SiOSi-) bonds, whereas the carbinol functional groups generally do not (at least under the same catalytic action as the hydrolysis of the silanol functional groups). The carbinol functional groups of component (A) can be the same or different from each other. In certain embodiments, organopolysiloxane (A) contains an average of at least three, alternatively at least four, carbinol functional groups per molecule. For example, organopolysiloxane (A) can contain an average of 2 to 8, alternatively 3 to 8, alternatively 3 to 7, alternatively 3 to 6, or alternatively 3 to 5, carbinol functional groups per molecule. In other embodiments, organopolysiloxane (A) can contain an average of 4 to 12, alternatively 6 to 10, carbinol functional groups per molecule.

[0008] In certain embodiments, the carbinol functional groups are independently represented by the general formula -DO 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 designated by subscript c, and subscript c is 0 to 500, provided that subscripts a and c are not simultaneously 0.

[0009] In one embodiment, the moieties designated by subscript c and subscript c are selected so that at least one of the carbinol functional groups has the general formula: -DO a -[C2H4O] d [C3H6O] e [C4H8O] f -H wherein D is a covalent bond or a divalent hydrocarbon linking group having 2 to 18 carbon atoms, the subscript a is 0 or 1, and 0≦d≦500, 0≦d≦500, and 0≦f≦500, with the proviso that 1≦d+e+f≦500. In these embodiments, the carbinol functionality may alternatively be referred to as a polyether group or moiety, and the polyether group or moiety may be a -COR 0 terminated with -COH, but not R 0 is a monovalent hydrocarbon radical, as is the case for certain conventional polyether groups or moieties. As understood in the art, moieties designated by subscript d are ethylene oxide (EO) units, moieties designated by subscript e are propylene oxide (PO) units, and moieties designated by subscript f are butylene oxide (BO) units. EO, PO, and BO units, when present, can be in block or randomized form in the polyether group or moiety. The relative amounts of EO, PO, and BO units, when present, can be selectively controlled based on the desired properties of the organopolysiloxane (A), the composition, and the resulting release coating. For example, the molar ratio of such alkylene oxide units can affect hydrophilicity and other properties.

[0010] Each carbinol functional group of component (A) may contain more than one -COH moiety per carbinol functional group. Stated another way, a single carbinol functional group substituent may contain more than one carbinol functional moiety. By way of example, any of the EO, PO, or BO units in the carbinol functional group may contain a pendant OH group, i.e., a hydrogen atom of the EO, PO, or BO group may be replaced with an OH group. By way of example only, the carbinol functional group may be of the formula -DO-CHCH(OH)CHOH.

[0011] In one embodiment, component (A) is substantially linear. By substantially linear, it is meant that component (A) comprises, consists essentially of, or consists only of M and D siloxy units. As is readily understood in the art, M siloxy units are those having the formula [RSiO 1 / 2 ], and the D siloxy units are of the formula [RSiO 2 / 2

[0033] Conventionally, the M and D siloxy nomenclature has been utilized in connection with methyl substitution only. However, for purposes of this disclosure, in the above M and D siloxy units, R is independently selected from substituted or unsubstituted hydrocarbyl groups or carbinol functional groups, provided that at least two of the R's are independently selected carbinol functional groups. When the M siloxy unit contains at least one carbinol functional group, the carbinol functional group is terminal. When the D siloxy unit contains at least one carbinol functional group, the carbinol functional group is pendant. Substantially linear organopolysiloxanes have the average formula: R a’ SiO (4-a’) / 2 wherein each R is independently selected and defined above, including the proviso that at least two of the R's are independently selected carbinol functional groups, and the subscript a' is selected such that 1.9≦a'≦2.2.

[0012] Generally, suitable hydrocarbyl groups for R can be independently linear, branched, cyclic, or a combination thereof. Cyclic hydrocarbyl groups include aryl groups and saturated or non-conjugated cyclic groups. Cyclic hydrocarbyl groups can independently be monocyclic or polycyclic. Linear and branched hydrocarbyl groups can independently be saturated or unsaturated. An example of a combination of linear and cyclic hydrocarbyl groups is an aralkyl group. Common examples of hydrocarbyl groups include alkyl groups, aryl groups, alkenyl groups, halocarbon groups, etc., as well as derivatives, variants, and combinations thereof. 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. 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. Examples of suitable monovalent halogenated hydrocarbon groups (i.e., halocarbon or substituted hydrocarbon groups) include halogenated alkyl groups, aryl groups, and combinations thereof. Examples of halogenated alkyl groups include the alkyl groups described above in which one or more hydrogen atoms have been replaced with a halogen atom, such as F or Cl.Specific examples of halogenated alkyl 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, and derivatives thereof. Examples of halogenated aryl groups include the aryl groups described above, in which one or more hydrogen atoms are replaced with halogen atoms such as F or Cl. Specific examples of halogenated aryl groups include chlorobenzyl and fluorobenzyl groups.

[0013] In specific embodiments, each R that is not a carbinol functional group is independently selected from an alkyl group 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, or alternatively 1 carbon atom.

[0014] In embodiments where component (A) is linear, component (A) may have the general formula:

[0015] [ka] wherein each R is independently selected and defined above, with the proviso that at least two of R independently comprise a carbinol functional group, and the subscript n is 0 to 1,000, alternatively 1 to 800, alternatively 5 to 500. The subscript n may alternatively be referred to as the degree of polymerization (DP) of component (A). Typically, DP is inversely proportional to viscosity, all else (e.g., 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 5 to 70, alternatively 10 to 65.

[0016] In a specific embodiment, when component (A) is linear, each carbinol functional group is pendant, such that organopolysiloxane (A) has the general formula:

[0017] [ka] In the formula, each R 1 are independently selected substituted or unsubstituted hydrocarbyl groups, and each X is -DO a -(C b H 2b O) c -H, where D and subscripts a-c are defined above, and each subscript R 2 is R 1and X, and the subscripts p and q are each 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 1 to 99, alternatively 5 to 85, alternatively 10 to 70, alternatively 20 to 60, alternatively 30 to 50. In these or other embodiments, the subscript p is 1 to 99, alternatively 1 to 60, alternatively 1 to 30, alternatively 2 to 20, alternatively 2 to 10. In the above general formula, the siloxy units denoted by the subscripts q and p can be randomized or can be in block form. The above general formula can be used to represent the R groups denoted by the subscript q without requiring a particular order thereof. 1 2SiO 2 / 2 Units and R denoted by the subscript p 2 XSiO 2 / 2 Based on the number of units, this is intended to represent the average unit formula of component (A) in this embodiment. Thus, this general formula may alternatively be written as [(R 1 )3SiO 1 / 2 ]2[(R 1 )2SiO 2 / 2 ] q [(R 1 )XSiO 2 / 2 ] p where the subscripts q and p are defined above. In these embodiments, the carbinol functional group is a polyether group, and the polyether group is pendant in component (A). Each R 1 When is methyl, this embodiment of component (A) is trimethylsiloxy endblocked and includes dimethylsiloxy units (denoted by the subscript q).

[0018] In another specific embodiment, when component (A) is linear, each carbinol functional group is terminal, such that organopolysiloxane (A) has the following general formula:

[0019] [ka] Each R1 is independently selected and defined above, each X is independently selected and defined above, and q' is from 1 to 100, alternatively from 5 to 70, alternatively from 10 to 65. In yet other embodiments, component (A) is linear and the carbinol functional groups are in both linear and pendant positions.

[0020] In yet another specific embodiment, when component (A) is linear, each carbinol functional group is pendant, such that organopolysiloxane (A) has the following general formula: R 1 3O[SiR 1 2O] w [SiR 1 XO] x R 1 3, wherein each R 1 and each X is independently selected and defined above, wherein 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 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 moieties denoted by subscripts w' and x' can be randomized or in block form in component (A).

[0021] D is typically a functional group that prepares the organopolysiloxane (A). For example, the organopolysiloxane (A) can be formed by a hydrosilylation reaction between an organohydrogenpolysiloxane and an unsaturated carbinol compound (sometimes referred to herein as an alcohol compound or an unsaturated alcohol compound). In such embodiments, the organohydrogenpolysiloxane contains silicon-bonded hydrogen atoms where carbinol functionality is desired (e.g., terminal and / or pendant). The unsaturated alcohol compound can be represented by the formula ZO 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 hydrocarbyl groups are defined above for R.

[0022] In the above hydrosilylation reaction, the ethylenically unsaturated group represented by Z can be an alkenyl and / or alkynyl group having 2 to 18 carbon atoms, alternatively 2 to 16, alternatively 2 to 14, alternatively 2 to 12, alternatively 2 to 8, alternatively 2 to 4, or alternatively 2 carbon atoms. "Alkenyl" refers to an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon double bonds. Specific examples include vinyl, allyl, hexenyl, and octenyl. "Alkynyl" refers to an acyclic, branched or unbranched monovalent hydrocarbon group having one or more carbon-carbon triple bonds. Specific examples include ethynyl, propynyl, and butynyl. Various examples of ethylenically unsaturated groups include CH2=CH-, CH2=CHCH2-, CH2=CH(CH2)4-, CH2=CH(CH2)6-, CH2=C(CH3)CH2-, H2C=C(CH3)-, H2C=C(CH3)-, H2C=C(CH3)CH2-, H2C=CHCH2CH2-, H2C=CHCH2CH2CH2-,

[0023] [ka] Typically, the ethylenic unsaturation is at the terminal end of Z. As is understood in the art, ethylenic unsaturation may be referred to as aliphatic unsaturation. Thus, when D is -CHCH-, for example, the unsaturated carbinol compound may have the formula CH=CH-O a -(C b H 2b O) c The number of carbon atoms in D is a function of the number of carbon atoms in the ethylenically unsaturated group, which remains constant even after the hydrosilylation reaction to prepare component (A).

[0024] By way of example, the unsaturated alcohol compound may include alkenyl alkoxylates such as allyl ethoxylate, vinyloxybutyl ethoxylate, isoprenyl ethoxylate, vinyl butyl propoxylate, and / or polyethylene glycol monoallyl ether.

[0025] In certain embodiments, the hydrosilylation catalyst utilized to form component (A) comprises a Group VIII-Group XI transition metal. References to Group VIII-Group XI transition metals are based on the latest 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). Combinations thereof, complexes thereof (e.g., organometallic complexes), and other forms of such metals may be utilized as hydrosilylation catalysts.

[0026] Additional examples of catalysts suitable for hydrosilylation reaction catalysis 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 II metal complexes (e.g., those containing calcium (Ca), potassium (K), strontium (Sr), etc.). Combinations thereof, complexes thereof (e.g., organometallic complexes), and other forms of such metals can be utilized as hydrosilylation reaction catalysts.

[0027] The hydrosilylation catalyst may be in any suitable form. For example, the hydrosilylation catalyst may be solid, including platinum-based catalysts, palladium-based catalysts, and similar noble metal-based catalysts, as well as nickel-based catalysts. Specific examples include nickel, palladium, platinum, rhodium, cobalt, and similar elements, as well as platinum-palladium, nickel-copper-chromium, nickel-copper-zinc, nickel-tungsten, nickel-molybdenum, and similar catalysts containing multiple metal combinations. Further examples of solid catalysts include Cu-Cr, Cu-Zn, Cu-Si, Cu-Fe-AI, Cu-Zn-Ti, and similar copper-containing catalysts.

[0028] The hydrosilylation catalyst can be in or on a solid support. Examples of supports include activated carbon, silica, silica alumina, alumina, zeolites, and other inorganic powders / particles (e.g., sodium sulfate). The hydrosilylation catalyst can also be placed in a vehicle, such as a solvent that solubilizes the hydrosilylation catalyst, or alternatively, a vehicle that simply carries but does not solubilize the hydrosilylation catalyst. Such vehicles are known in the art.

[0029] In specific embodiments, the hydrosilylation catalyst comprises platinum. In these embodiments, the hydrosilylation catalyst is exemplified by compounds such as platinum black, chloroplatinic acid, chloroplatinic acid hexahydrate, reaction products of chloroplatinic acid with monohydric alcohols, platinum bis(ethylacetoacetate), platinum bis(acetylacetonate), platinum chloride, and complexes of such compounds with olefins or organopolysiloxanes, as well as platinum compounds microencapsulated in matrices or core-shell compounds. Microencapsulated hydrosilylation catalysts and methods for their preparation are also known in the art.

[0030] Platinum complexes with organopolysiloxanes suitable for use as hydrosilylation catalysts include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. These complexes can be microencapsulated in a resin matrix. Alternatively, the hydrosilylation catalyst can include 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane platinum complexes. The hydrosilylation catalyst can be prepared by a method comprising reacting chloroplatinic acid with an aliphatically unsaturated organosilicon compound, such as divinyltetramethyldisiloxane, or an alkene-platinum-silyl complex. The alkene-platinum-silyl complex can be prepared, for example, by mixing 0.015 moles of (COD)PtCl with 0.045 moles of COD and 0.0612 moles of HMeSiCl, where COD is cyclooctadiene.

[0031] The hydrosilylation catalyst is utilized in the composition in a catalytic amount, i.e., an amount or quantity sufficient to promote its cure under the desired conditions. The hydrosilylation catalyst can be a single hydrosilylation catalyst or a mixture comprising two or more different hydrosilylation catalysts.

[0032] Alternatively, D can be a covalent bond when component (A) is formed via a reaction other than hydrosilylation, such as a condensation reaction or a ring-opening reaction.

[0033] As introduced above, in other embodiments, the organopolysiloxane (A) is branched, i.e., component (A) contains at least one T and / or Q siloxy unit. In one specific embodiment, the organopolysiloxane (A) is a Q-branched polymer, i.e., the organopolysiloxane (A) contains a single Q siloxy unit. In other embodiments, the organopolysiloxane (A) contains two or more Q units. In yet other embodiments, the organopolysiloxane (A) contains one or more T units, or T units in combination with Q units. Even when the organopolysiloxane (A) contains branched chains due to T units and / or Q units, the organopolysiloxane (A) is typically flowable at 25°C. By "flowable," it is meant that the organopolysiloxane (A) is flowable at 25°C and / or has a measurable viscosity at 25°C. In certain embodiments, the organopolysiloxane (A) is flowable in the absence of any solvent, for example, an organic solvent. In a specific embodiment, the organopolysiloxane (A) is liquid at 25°C in the absence of any solvent. In contrast, MQ resins, which can be distinguished from Q-branched polymers, are typically solid at room temperature unless dissolved in a solvent. When component (A) is a Q-branched polymer, the composition typically cures more quickly than when component (A) is linear, all else being equal. However, the use of a linear component (A) does not sacrifice the performance properties of the resulting release coating.

[0034] In certain embodiments where the organopolysiloxane (A) is branched, the organopolysiloxane (A) has the average formula: [Z 1 ] v [R 1 3SiO 1 / 2 ] w [R 1 2XSiO 1 / 2 ] x [R 1 2SiO 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; 1 are independently selected and defined above, each X is an independently selected carbinol functional group, and Z 1 are independently expressed by 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 2SiO 1 / 2 ) where each R 1 are independently selected and defined above, and each D 1 are independently selected divalent linking groups. In the moiety denoted by the subscript v, the silicon atom is bonded to D, a divalent hydrocarbon group, typically from hydrosilylation. 1 The subscripts v, w, x, y, and z represent the moles of each specific siloxy unit per Q siloxy unit, normalized to 1. 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 organopolysiloxane (A) contains only one Q siloxy unit. In certain embodiments, organopolysiloxane (A) contains only one Q siloxy unit. In other embodiments, organopolysiloxane (A) contains two or more Q siloxy units, i.e., multiple Q siloxy units, which may be clustered together in component (A).

[0035] In a specific embodiment, the subscript v is 0. In another specific embodiment, the subscript v is 2 to 12, alternatively 2 to 11, alternatively 2 to 10, alternatively 2 to 8, alternatively 2 to 7, alternatively 2 to 6, alternatively 3 to 6, alternatively 3 to 5. In these or other embodiments, the subscript w is 0 to 8, alternatively 2 to 8, alternatively 3 to 8, alternatively 4 to 8, alternatively 5 to 8, alternatively 6 to 8, alternatively 7 or 8, alternatively 8. In these or other embodiments, the subscript x is 0 to 8, alternatively 0 to 6, alternatively 0 to 4, alternatively 0 to 3, alternatively 0 to 2, alternatively 0 or 1, alternatively 0. In these or other embodiments, the subscript y is 40 to 500, alternatively 40 to 400, alternatively 40 to 300, alternatively 40 to 200, alternatively 50 to 150, alternatively 60 to 125. In these or other embodiments, the subscript z is 1 to 8, alternatively 2 to 7, alternatively 3 to 6, alternatively 3 to 5, alternatively 4. 1 is typically a divalent hydrocarbon group having 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.

[0036] When the organopolysiloxane (A) is branched, it can be prepared in various ways. For example, the organopolysiloxane (A) can be prepared by the hydrosilylation of an unsaturated alcohol compound with an organohydrogenpolysiloxane, as described above, and in this embodiment, the organohydrogenpolysiloxane itself is branched.

[0037] In another embodiment, organopolysiloxane (A) is prepared by hydrosilylation of an initial organosiloxane, an organohydrogensiloxane, and an alcohol compound. The alcohol compound generally contains a terminal unsaturated group for participating in the hydrosilylation reaction to provide the carbinol functionality of organopolysiloxane (A), examples of which are described above with respect to the carbinol functionality. When organopolysiloxane (A) contains a single Q siloxy unit, the initial organosiloxane has the formula M Vi 4Q, wherein M Vi is the formula (CH 3)2 (CH2=CH)SiO 1 / 2 and Q is of the formula SiO 4 / 2 When the organopolysiloxane (A) contains two Q siloxy units, the initial organosiloxane has the formula M Vi 3Q-QM Vi 3. The vinyl groups exemplified here can be replaced with any silicon-bonded alkenyl or alkynyl group.

[0038] The organohydrogensiloxane may contain pendant and / or terminal silicon-bonded hydrogen atoms, which affects the structure of the resulting organopolysiloxane (A). In one embodiment, the initial organosiloxane and organohydrogensiloxane are first reacted to obtain a reaction intermediate containing residual silicon-bonded hydrogen atoms (or silicon hydride functional groups), and this reaction intermediate is then reacted with an alcohol compound to obtain organopolysiloxane (A). In another embodiment, the initial organosiloxane, organohydrogensiloxane, and alcohol compound are reacted simultaneously.

[0039] When the organohydrogensiloxane contains only terminal silicon-bonded hydrogen atoms, the organohydrogensiloxane, after hydrosilylation with the ethylenically unsaturated group of each M siloxy unit, forms a linear organosiloxane chain extending from each M siloxy unit of the initial organosiloxane, which is then protected (also via hydrosilylation) with an alcohol compound, thereby providing a carbinol functionality. For example, in these embodiments, when organopolysiloxane (A) contains a single Q siloxy unit, organopolysiloxane (A) can be represented by the following formula: Si-([OSiR2]-D 1 -[-SiRO 1 / 2 ][R2SiO 2 / 2 ] m’ [XR2SiO 1 / 2 ])4, wherein each R is independently selected and defined above, and each D 1 is independently selected and defined above, each subscript m' is independently 10 to 250, and each X is an independently selected carbinol functional group. When organopolysiloxane (A) is formed using an organohydrogensiloxane containing only terminal silicon-bonded hydrogen atoms, Z 1 is typically expressed as (O 1 / 2 SiR 1 2-D 1 -R 1 2SiO 1 / 2 ) where R 1 and D 1 are independently selected and defined above.

[0040] In certain embodiments where the organohydrogensiloxane contains only terminal silicon-bonded hydrogen atoms, the organopolysiloxane (A) has the formula: [O 1 / 2 SiR 1 2-D 1 -R 1 2SiO 1 / 2 ] v [R 1 2XSiO 1 / 2 ] x [R 1 2SiO 2 / 2 ] y [SiO 4 / 2] 1.0, and In the formula, R 1 , D 1 , X, v, x, and y are defined above.

[0041] Although there is a single Q siloxy unit, as set forth in the average formula above for one exemplary embodiment of organopolysiloxane (A), there may be more than four terminal M siloxy units. In contrast, in conventional organopolysiloxanes, 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 may be imparted in forming organopolysiloxane (A), as described below.

[0042] For example, if the organohydrogensiloxane contains only pendant silicon-bonded hydrogen atoms, the organopolysiloxane (A) may contain additional branching. For example, in this embodiment, if the organopolysiloxane (A) contains a single Q unit, the organopolysiloxane (A) may contain eight terminal M units instead of four (as in the above embodiment). In these embodiments, the moiety Z, denoted by the subscript v, may be 1 is typically greater than 0, and most typically the subscript v is 4.

[0043] Specific examples of organohydrogensiloxanes include those containing only pendant silicon-bonded hydrogen atoms, where organopolysiloxane (A) can have the formula Si-Y4, where each Y independently has the following structure:

[0044] [ka] In the formula, each R 1 , each D 1 , each m', and each X are independently selected and defined above. 2 / 2 and SiRXO 2 / 2 It should be understood that the unit can be at any position within the moiety represented by Y. For example, SiRXO 2 / 2The unit is another SiR2O 2 / 2 In these embodiments, the organopolysiloxane (A) may alternatively be a Si—[OSiR2-D 1 -Y 1 wherein each Y 1 is two R3SiO 1 / 2 Unit, 1 SiRXO 2 / 2 units, and 1 to 250 SiR2O 2 / 2 Units: Y 1 D 1 Connect to -SiRO 2 / 2 Included with units.

[0045] When the organohydrogensiloxane contains only pendant silicon-bonded hydrogen atoms, the organohydrogensiloxane forms a linear organosiloxane chain after hydrosilylation with the ethylenically unsaturated group, protecting each M siloxy unit of the initial organosiloxane but not extending away from the Q siloxy units of the initial organosiloxane. When organopolysiloxane (A) is formed from organohydrogensiloxanes containing only pendant silicon-bonded hydrogen atoms, Z 1 is typically expressed as (O 1 / 2 SiR 1 2-D 1 -R 1 SiO 2 / 2 ) where R 1 and D 1 are independently selected and defined above. Z 1 represents the M siloxy unit of the initial organosiloxane and the siloxy unit of the organohydrogensiloxane that is to be hydrosilylated therewith.

[0046] In certain embodiments where the organohydrogensiloxane contains only pendant silicon-bonded hydrogen atoms, the organopolysiloxane (A) has the formula: [O 1 / 2 SiR 1 2-D 1 -R 1 SiO 2 / 2 ] v [R 13SiO 1 / 2 ] w [R 1 2SiO 2 / 2 ] y [R 1 XSiO 2 / 2 ] z [SiO 4 / 2 ] 1.0 and In the formula, R 1 , D 1 , X, v, w, y, and z are defined above.

[0047] In other embodiments, the organohydrogensiloxane has both pendant and terminal silicon-bonded hydrogen atoms. In these embodiments, the organopolysiloxane (A) is XRSiO 1 / 2 and XRSiO 2 / 2 The siloxy units may comprise both X and R, and the siloxy units may comprise both X and R, and the siloxy units may comprise both X and R, and the siloxy units may comprise both X and R.

[0048] In another specific embodiment, organopolysiloxane (A) is prepared by reacting an initial organosiloxane, a cyclic organohydrogensiloxane, and an alcohol compound. In these embodiments, the cyclic organohydrogensiloxane undergoes a ring-opening polymerization reaction, resulting in the formation of D siloxy units in organopolysiloxane (A). In this embodiment, the initial organosiloxane does not require silicon-bonded ethylenically unsaturated groups because it does not undergo any hydrosilylation reaction. Thus, the initial organosiloxane can be of the formula Si-[OSiR3]4, where each R is independently selected and defined above. When each R is methyl, the initial organosiloxane is M4Q, or Si-[OSi(CH3)3]4. However, the initial organosiloxane can be the same as described above, including hydrosilylation, such that the M siloxy units contain silicon-bonded ethylenically unsaturated groups, such as vinyl groups.

[0049] Cyclic organohydrogensiloxanes are represented by the formula (RHSiO 2 / 2 ) nwhere R is independently selected and defined above, and n is an integer from 3 to 15. In cyclic organohydrogensiloxanes, each R is typically an independently selected alkyl group, and most typically, each R is a methyl group.

[0050] The subscript n is 3 to 15, alternatively 3 to 12, alternatively 3 to 10, alternatively 3 to 8, alternatively 3 to 6, alternatively 4 to 5. Additionally, (ii) the cyclic organohydrogensiloxane can include a blend of different cyclic siloxanes, for example, a blend of one where n is 4 and one where n is 5. In specific embodiments, (ii) the cyclic organohydrogensiloxane is selected from the group of cyclotrisiloxane, cyclotetrasiloxanes such as octamethylcyclotetrasiloxane, cyclopentasiloxanes such as decamethylcyclopentasiloxane, cyclohexasiloxane, and combinations thereof.

[0051] Typically, cyclic organohydrogensiloxanes are utilized in conjunction with cyclic siloxanes that do not contain silicon-bonded hydrogen atoms to selectively control the number of silicon-bonded hydrogen atoms present in the reaction intermediate formed from the ring-opening polymerization of the cyclic organohydrogensiloxane in the initial organosiloxane. Cyclic siloxanes have the formula (RSiO 2 / 2 ) n where R is independently selected and defined above, and n is an integer from 3 to 15. In cyclic siloxanes, each R is typically an independently selected alkyl group, and most typically, each R is a methyl group. The subscript n is 3 to 15, alternatively 3 to 12, alternatively 3 to 10, alternatively 3 to 8, alternatively 3 to 6, or alternatively 4 to 5.

[0052] Those skilled in the art can optimize the number of silicon-bonded hydrogen atoms in the reaction intermediate based on the molar ratio of cyclic organohydrogensiloxane to cyclic siloxane. For example, in certain embodiments, it may be desirable for the reaction intermediate to contain four silicon-bonded hydrogen atoms so that the organopolysiloxane (A) contains four silicon-bonded carbinol functional groups. In one embodiment, the molar ratio of cyclic organohydrogensiloxane to cyclic siloxane can be 1:1 to 1:20, alternatively 1:2 to 1:19, alternatively 1:3 to 1:18, alternatively 1:4 to 1:17, alternatively 1:5 to 1:15, alternatively 1:6 to 1:14, alternatively 1:6 to 1:13, alternatively 1:7 to 1:12, or alternatively 1:7 to 1:11.

[0053] The initial organosiloxane and cyclic organohydrogensiloxane (and any cyclic organosiloxanes) are reacted 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 organosiloxanes) is either an acid-catalyzed 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, for example, trifluoromethanesulfonic acid. 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 used in place of the phosphazene base catalyst.

[0054] Phosphazene catalysts generally contain at least one -(N=P<)- unit (i.e., a phosphazene unit) and are usually oligomers having up to 10 such phosphazene units, for example, an average of 1.5 to 5 phosphazene units. The phosphazene catalyst may be, for example, a halophosphazene such as a chlorophosphazene (phosphonitrile chloride), an oxygen-containing halophosphazene, an ionic derivative of a phosphazene such as a phosphazenium salt, particularly an ionic derivative of a phosphonitrile halide such as a perchlorooligophosphazenium salt, or a partially hydrolyzed form thereof.

[0055] In a specific embodiment, the polymerization catalyst comprises a phosphazene base catalyst. The phosphazene base catalyst can be any known in the art, but typically has the following chemical formula: ((R 3 2N)3P=N) t (R 3 2N) 3-t P=NR 3 [In the formula, each R 3 is a hydrogen atom, R 1 and combinations thereof, and t is an integer of 1 to 3. 3 R 1 If R 3 is typically an alkyl group having 1 to 20, alternatively 1 to 10, alternatively 1 to 4 carbon atoms. 3 2N) two R 3 The groups can be attached to the same nitrogen (N) atom and linked to complete a heterocyclic ring, typically having 5 or 6 members.

[0056] Alternatively, the phosphazene base catalyst may be a salt, having the following alternative formula: [((R 3 2N)3P=N) t (R 3 2N) 3-t P=N(H)R 3 ] + [A - ], or [((R3 2N)3P=N) s (R 3 2N) 4-s P] + [A - ] [In the formula, each R 3 are independently selected and defined above, the subscript t is defined above, the subscript s is an integer from 1 to 4, and [A] is an anion, typically selected from the group consisting of fluoride, hydroxide, silanolate, alkoxide, carbonate, and bicarbonate. In one embodiment, the phosphazene base is an aminophosphazenium hydroxide.

[0057] The reaction of the initial organosiloxane with the cyclic organohydrogensiloxane (and any cyclic organosiloxanes) in the presence of a polymerization catalyst results in the ring-opening of the cyclic organohydrogensiloxane (and any cyclic organosiloxanes) and the incorporation of D siloxy units into the reaction intermediate. The relative amount of cyclic organohydrogensiloxane (and any cyclic organosiloxanes) utilized is a function of the desired content of D siloxy units in the reaction intermediate.

[0058] In certain embodiments, the initial organosiloxane and cyclic organohydrogensiloxane (and any cyclic organosiloxane) are reacted in the presence of a solvent at elevated temperatures, e.g., 125-175°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. Complexing agents, such as bis(trimethylsilyl) hydrogen phosphate, may 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 polymerization catalyst utilized, which is a function of its selection and reaction conditions. For example, in these embodiments, the reaction intermediate can be represented by the following formula: [RSiO 1 / 2 ]4[RHSiO 2 / 2 ]v’ [R2SiO 2 / 2 ] y [SiO 4 / 2 ] 1.0 wherein each R is independently selected and defined above, y is defined above, and v' is 2 to 10, alternatively 2 to 8, alternatively 2 to 6, alternatively 3 to 5.

[0059] The reaction intermediate formed via the initial organosiloxane and cyclic organohydrogensiloxane (and any cyclic organosiloxane) can then be hydrosilylated with an alcohol compound to obtain organopolysiloxane (A). Examples of alcohol compounds are described above, along with suitable hydrosilylation reaction catalysts. When the reaction intermediate has the formula described immediately above, the organopolysiloxane (A) formed therefrom can have the formula: [RSiO 1 / 2 ]4[RXSiO 2 / 2 ] v’ [R2SiO 2 / 2 ] y [SiO 4 / 2 ] 1.0 wherein each R is independently selected and defined above, y is defined above, v' is defined above, and each X is independently selected and defined above.

[0060] In certain embodiments, component (A) has a capillary viscosity (dynamic viscosity through a glass capillary) at 25°C of 1 to 1,000 mPa·s, alternatively 1 to 900 mPa·s, alternatively 10 to 700 mPa·s, or alternatively 10 to 600 mPa·s. Capillary viscosity may be measured according to Dow Corning Corporate Test Method CTM 0004, dated July 20, 1970. CTM 0004 is known in the art and is based on ASTM D445, IP 71. Typically, when component (A) has pendant polyether groups as carbinol functional groups, component (A) has a higher viscosity than when component (A) contains a terminal carbinol functional group that is not a polyether group (as depicted in the exemplary structure above). For example, when component (A) includes pendant polyether groups, the capillary viscosity at 25° C. is typically from 200 to 900, alternatively from 300 to 800, alternatively from 400 to 700, or alternatively from 500 to 600 mPa·s. In contrast, when component (A) includes only terminal carbinol functional groups that are not polyether groups, component (A) may have a capillary viscosity at 25° C. of greater than 0 mPa·s to 250 mPa·s, alternatively from greater than 0 mPa·s to 100 mPa·s, alternatively from greater than 0 mPa·s to 75 mPa·s, alternatively from 10 mPa·s to 75 mPa·s, or alternatively from 25 mPa·s to 75 mPa·s. In specific embodiments, component (A) has a capillary viscosity at 25°C from 25 to 1,000, alternatively from 50 to 800, alternatively from 60 to 700, alternatively from 70 to 600, alternatively from 80 to 500, alternatively from 90 to 400 mPa·s.

[0061] In these or other embodiments, component (A) may have an OH equivalent weight from 100 to 2,000, alternatively from 200 to 1,750, alternatively from 300 to 1,500, alternatively from 400 to 1,200 g / mole. Methods for determining OH equivalent weight based on functionality and molecular weight are known in the art.

[0062] The composition comprises organopolysiloxane (A) in an amount from 50 to 99, alternatively from 55 to 99, alternatively from 60 to 99, alternatively from 65 to 99, alternatively from 70 to 99, alternatively from 75 to 99 weight percent, based on the total weight of the composition.

[0063] The composition further comprises a polyisocyanate component (B). The polyisocyanate component comprises an isocyanate-functional copolymer (b1) and a polyisocyanate (b2) different from component (b1). Surprisingly, it has been found that by using the polyisocyanate (B) component, the composition of the present invention has an excellent cure time attributable to the polyisocyanate (b2), while maintaining desirable compatibility between the organopolysiloxane (A) and the polyisocyanate (b2) through the isocyanate-functional copolymer (b1). The polyisocyanate (b2) is generally immiscible with the organopolysiloxane (A) in the absence of the isocyanate-functional copolymer (b1).

[0064] The isocyanate-functional copolymer (b1) typically contains siloxane moieties and organic moieties, and may be randomized, block, branched, grafted, alternating, and / or periodic. When the isocyanate-functional copolymer (b1) contains siloxane moieties and organic moieties, the isocyanate-functional copolymer (b1) is typically prepared by reacting a siloxane with a polyisocyanate. The structure of the isocyanate-functional copolymer (b1) can be selected based on the siloxane and polyisocyanate used.

[0065] In one embodiment, (b1) the isocyanate-functional copolymer is prepared by reacting (b1a) a siloxane having at least two carbinol functional groups with (b1b) a polyisocyanate having at least two isocyanate functional groups. Because 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 carbinol functional groups of component (b1a). The siloxane (b1a) can be the same as or different from the organopolysiloxane (A) described above. The carbinol groups of component (b1a) can be only those described above for component (A).

[0066] Branched or grafted forms of the isocyanate-functional copolymer (b1) can be prepared based on the location of the carbinol functional group of the siloxane (b1a) and its overall structure. For example, the siloxane (b1a) can contain branched chains resulting from T and / or Q siloxy units, or it can be linear and consist solely of D and M siloxy units. Similarly, even when the siloxane (b1a) is linear, the carbinol functional groups can be present at pendant, terminal, or both positions, which affects whether the resulting isocyanate-functional copolymer (b1) is branched.

[0067] In one embodiment, the siloxane (b1a) used to prepare the isocyanate-functional copolymer (b1) is linear. In a specific embodiment, the carbinol functionality of component (b1a) is terminal. When the siloxane (b1a) is linear with terminal carbinol functionality, the resulting isocyanate-functional copolymer (b1) can be linear as well. In a specific embodiment, component (b1a) has the average formula R 1 2XO[SiR 1 2O] n’ XR 1 2, wherein each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group, each X is an independently selected carbinol functional group, and the subscript n' is 1 to 100.1 Suitable hydrocarbyl groups in are those described above. In specific embodiments, subscript n' is 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 may be utilized together as component (b1a).

[0068] Suitable polyisocyanates for component (b1b) have an isocyanate functionality of two or more and include conventional aliphatic, cycloaliphatic, araliphatic, and aromatic isocyanates. Polyisocyanates (b1b) include 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"), and phenyl diisocyanate. diisocyanate, "PDI"), and combinations thereof. In one embodiment, polyisocyanate (B) is of the formula OCN-R'-NCO, where R' is an alkyl, aryl, or arylalkyl moiety. In this embodiment, polyisocyanate (b1b) can contain any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0069] Suitable polyisocyanates for component (b1b) have two or more isocyanate functional groups and include conventional aliphatic, cycloaliphatic, araliphatic, and aromatic isocyanates. Polyisocyanates (b1b) may be 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, polyisocyanate (B) is of the formula OCN-R'-NCO, where R' is an alkyl, aryl, or arylalkyl moiety. In this embodiment, polyisocyanate (b1b) can contain any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0070] In specific embodiments, component (b1b) is not a polymer. In these or other embodiments, component (b1b) includes, or alternatively is, an aliphatic or cycloaliphatic isocyanate. In one embodiment, component (b1b) has two isocyanate functional groups. In a different embodiment, component (b1b) has three functional groups. Blends of different polyisocyanates may be utilized together as component (b1b). In specific embodiments, polyisocyanate (b1b) is selected from hydrogenated MDI (H12MDI), hexamethylene diisocyanate ("HDI"), dicyclohexylmethane diisocyanate ("HMDI"), isophorone diisocyanate ("IPDI"), cyclohexyl diisocyanate ("CHDI"), and combinations thereof. If component (b1b) is not a polymer, it can still be an oligomer, for example, it can comprise a trimer of HDI or IPDI.

[0071] The (b1) isocyanate-functional copolymer can be formed at room temperature in the absence of a catalyst. If desired, a catalyst and solvent can be utilized to accelerate the reaction to prepare the (b1) isocyanate-functional copolymer. However, because components (b1a) and (b1b) are liquids at room temperature, a solvent is generally not utilized or required. Similarly, ambient conditions can be selectively controlled; for example, elevated temperatures, such as 60-120°C, can be utilized. Component (b1) is prepared with a molar excess of isocyanate functional groups in component (b1b) compared to the carbinol functional groups of component (b1a). Typically, the relative amounts of components (b1a) and (b1b) are selected so that no residual amounts of component (b1a) remain and so that component (b1) contains at least two, alternatively two, isocyanate functional groups. Those skilled in the art will readily understand how to select the relative amounts of components (b1a) and (b1b) based on their attributes, including the number and structure of functional groups.

[0072] In a specific embodiment, when the (b1) isocyanate-functional copolymer is formed from components (b1a) and (b1b), and when components (b1a) and (b1b) are each difunctional, the (b1) isocyanate-functional copolymer has the average formula: Y-([SiR 1 2O] n’ -Y'--[SiR 1 2O] n’ ) m’ -Y, where Y is an isocyanate moiety, Y is a residue from a polyisocyanate, each n' is independently selected and is 1 to 100, and each R 1 is an independently selected substituted or unsubstituted hydrocarbyl group, and the subscript m' is 1 to 50.

[0073] Suitable polyisocyanates for component (b2) may be the same as or different from component (b1b). Component (b2) is different from component (b1). Generally, component (b2) is a conventional polyisocyanate and, unlike component (b1), does not contain siloxane segments.

[0074] Polyisocyanate (b2) may be 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, polyisocyanate (b2) is of the formula OCN-R'-NCO, where R' is an alkyl, aryl, or arylalkyl moiety. In this embodiment, the polyisocyanate (b2) can contain any number of carbon atoms, typically from 4 to 20 carbon atoms.

[0075] Specific examples of polyisocyanates suitable for component (b2) include alkylene diisocyanates having 4 to 12 carbon atoms 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, alicyclic 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-hexamethylene diisocyanate, and the like. and the corresponding isomeric mixtures, 4,4'-2,2'- and 2,4'-dicyclohexylmethane diisocyanate and the corresponding isomeric mixtures, and aromatic diisocyanates and polyisocyanates, such as 2,4- and 2,6-toluene diisocyanate and the corresponding isomeric mixtures, 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate and the corresponding isomeric mixtures, mixtures of 4,4'-, 2,4'-, and 2,2-diphenylmethane diisocyanate and polyphenylene polymethylene polyisocyanates, and mixtures of MDI and toluene diisocyanate (TDI).

[0076] Polyisocyanate (b2) may comprise or be a modified polyisocyanate, i.e., a product obtained by partial chemical reaction of organic diisocyanates and / or polyisocyanates. Examples of suitable modified polyisocyanates include diisocyanates and / or polyisocyanates containing ester groups, urea groups, biuret groups, allophanate groups, carbodiimide groups, isocyanurate groups, and / or urethane groups.

[0077] It is understood that polyisocyanate (b2) can include any combination of two or more polyisocyanates that differ from one another based on functionality, molecular weight, viscosity, or structure.

[0078] Polyisocyanate (b2) typically has a functionality of 2.0 to 5.0, alternatively 2.0 to 4.5, alternatively 2.0 to 4.0. In one specific embodiment, polyisocyanate (b2) is a polyisocyanate trimer, for example, an HDI trimer.

[0079] In these or other embodiments, polyisocyanate (b2) has an NCO weight of 15 to 60, alternatively 15 to 55, alternatively 20 to 48.5 wt %. Methods for determining NCO content by weight are known in the art, based on the functionality and molecular weight of the particular isocyanate.

[0080] Component (B) is generally utilized in the composition as a preblend, i.e., components (b1) and (b2) are mixed together prior to combining components (A) and (B). Components (b1) and (b2) can be mixed via any order of addition, optionally with shear or blending. In certain embodiments, component (B) comprises component (b1) in an amount of 10 to 90 weight percent. In these or other embodiments, component (B) comprises component (b2) in an amount of 90 to 10 weight percent.

[0081] Component (B) is typically present in the composition in an amount to provide 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. Isocyanate index and methods for calculating it are well known in the art.

[0082] In certain embodiments, the composition further comprises a catalyst (C). Typically, the composition comprises a catalyst (C). However, components (A) and (B) are typically reactive in the absence of catalyst (C). As a result, catalyst (C) is utilized to accelerate the reaction at lower temperatures, which is typically desired when preparing release coatings.

[0083] In one embodiment, catalyst (C) comprises 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) comprises dibutyltin dilaurate, a dialkyltin(IV) salt of an organic carboxylic acid. Specific examples of suitable organometallic catalysts, such as dibutyltin dilaurate, are commercially available from Air Products and Chemicals, Inc. (Allentown, PA) under the trademark DABCO®. Organometallic catalysts may also include other dialkyltin(IV) salts of organic carboxylic acids, such as dibutyltin diacetate, dibutyltin maleate, and dioctyltin diacetate.

[0084] Examples of other suitable catalysts include iron(II) chloride; zinc chloride; lead octoate; tris(dialkylaminoalkyl)-s-hexahydrotriazines, including tris(N,N-dimethylaminopropyl)-hexahydrotriazone, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as sodium methoxide and potassium isopropoxide; and alkali metal salts of long-chain fatty acids having 10 to 20 carbon atoms and / or OH pendant groups.

[0085] Further examples of other suitable catalysts, specifically trimerization catalysts, include N,N,N-dimethylaminopropylhexahydrotriazine, potassium, potassium acetate, N,N,N-trimethylisopropylamine / formate, and combinations thereof.

[0086] Still further examples of other suitable catalysts, particularly 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, tetramethylimino-bis(propylamine), dimethylbenzylamine, trimethylamine, triethanolamine, Examples of suitable catalysts include amines such as methyl ether, 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) can include a delayed action tertiary amine based on 1,8-diazabicyclo[5.4.0]undec-7-ene ("DBU"). Alternatively or additionally, catalyst (C) can include N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether and / or ethylenediamine. The tertiary amine catalysts can be further modified for use as delayed action catalysts by adding approximately the same stoichiometric amount of phenol or an acidic proton-containing acid such as formic acid. Such delayed action catalysts are commercially available from Air Products and Evonik.

[0087] Further examples of other suitable catalysts include metal chelates, such as aluminum acetylacetonate, TiCH, titanium(IV) oxide acetylacetonate, bismuth(III) acetate, aluminum di(isopropoxide) acetoacetate, and combinations thereof.

[0088] The catalyst (C) can be used as is or can be placed in a vehicle. Vehicles are known in the art and are further described below as optional components of the composition. When a vehicle is used to dissolve the catalyst (C), the vehicle can be referred to as a solvent. The vehicle can be an isocyanate-reactive, for example, an alcohol-functional vehicle such as dipropylene glycol.

[0089] Catalyst (C) can be utilized in various amounts. Catalyst (C) can include any combination of different catalysts.

[0090] The composition may optionally include at least one additive selected from (D) inhibitors, (E) chain extenders, (F) vehicles, (G) fixatives, (H) anti-mist additives, and / or (I) release modifiers. In certain embodiments, the composition is substantially free of conventional organic polyols, such as polyether and / or polyester polyols. Unlike 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 the composition includes conventional organic polyols in an amount of less than 4 wt%, alternatively less than 3 wt%, alternatively less than 2 wt%, alternatively less than 1 wt%, or alternatively 0 wt%, based on the total weight of the composition.

[0091] In certain embodiments, the composition further comprises an inhibitor (D), which can be used to modify the reaction rate or cure rate of the composition compared to a composition containing the same starting materials but omitting inhibitor (D). The inhibitor (D) may be an acetylenic alcohol such as methylbutynol, 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; a cycloalkenylsiloxane, for example, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, 1,3,5,7-tetramethyl-1,3 methylvinylcyclosiloxanes exemplified by 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, and combinations thereof; ene-yne ​​compounds such as 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne; triazoles such as benzotriazole; phosphines; mercaptans; hydrazines; amines such as tetramethylethylenediamine; dialkyl fumarates, dialkenyl fumarates, dialkoxyalkyl fumarates, maleates such as diallyl maleate; nitriles; ethers; carbon monoxide; alkenes 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 thereof. Another example of the inhibitor (D) is acetylacetone.

[0092] Alternatively, inhibitor (D) can be a silylated acetylenic compound. Without being bound by theory, it is believed that the addition of the silylated acetylenic compound reduces yellowing of the reaction product prepared from the hydrosilylation reaction of the composition when compared to the reaction product from the hydrosilylation of a composition that does not contain the silylated acetylenic compound or a composition that contains an organic acetylenic alcohol inhibitor such as those described above.

[0093] The silylated acetylene compounds are (3-methyl-1-butyn-3-oxy)trimethylsilane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, bis(3-methyl-1-butyn-3-oxy)dimethylsilane, bis(3-methyl-1-butyn-3-oxy)silanemethylvinylsilane, bis((1,1-dimethyl-2-propynyl)oxy)dimethylsilane, methyl(tris(1,1-dimethyl-2-propynyloxy))silane, methyl(tris(3-methyl-1-butyn-3-oxy))silane, (3-methyl-1-butyn-3-oxy)dimethylphenylsilane, (3-methyl-1-butyn-3-oxy)dimethylhexenylsilane, (3-methyl-1-butyn-3-oxy)triethylsilane, bis(3-methyl-1- cyclohexyl-1-ethyn-1-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, (cyclohexyl-1-ethyn-1-oxy)trifluoropropylsilane, (3,5-dimethyl-1-hexyn-3-oxy)trimethylsilane, (3-phenyl-1-butyn-3-oxy)diphenylmethylsilane, (3-phenyl-1-butyn-3-oxy)dimethylphenylsilane, (3-phenyl-1-butyn-3-oxy)dimethylvinylsilane, (3-phenyl-1-butyn-3-oxy)dimethylhexenylsilane, (cyclohexyl-1-ethyn-1-oxy)dimethylvinylsilane, (cyclohexyl-1-ethyn-1-oxy)diphenylmethylsilane, (cyclohexyl-1-ethyn-1-oxy)trimethylsilane, and combinations thereof. Alternatively, inhibitor (D) is exemplified by methyl(tris(1,1-dimethyl-2-propynyloxy))silane, ((1,1-dimethyl-2-propynyl)oxy)trimethylsilane, or a combination thereof. Silylated acetylenic compounds useful as inhibitor (D) can be prepared by methods known in the art, for example, by silylation of the acetylenic alcohols described above with chlorosilanes in the presence of an acid acceptor.

[0094] In specific embodiments, the inhibitor (D) comprises or is selected from acetylenic alcohols, silylated acetylenic alcohols, ene-yne ​​compounds, triazoles, phosphines, mercaptans, hydrazines, amines, fumarates, maleates, ethers, carbon monoxide, and combinations of two or more thereof.

[0095] 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 is a one-part or multi-part composition, the particular inhibitor used, and the selection and amounts of components (A)-(C). However, the amount of inhibitor (D), if present, may be from 0% to 1%, alternatively from 0% to 5%, alternatively from 0.001% to 1%, alternatively from 0.01% to 0.5%, or alternatively from 0.0025% to 0.025%, based on the total weight of the composition.

[0096] In certain embodiments, the composition further comprises a chain extender (E). In certain embodiments, the chain extender (E) comprises an organopolysiloxane chain extender. When utilized, the organopolysiloxane chain extender is distinct from component (A). In a specific embodiment, the organopolysiloxane chain extender is a linear organopolysiloxane containing two terminal silicon-bonded carbinol functional groups. When an organopolysiloxane chain extender is utilized and comprises a linear organopolysiloxane containing two terminal silicon-bonded carbinol functional groups, component (A) can differ from component (E) by, for example, being branched, containing an average of at least three silicon-bonded carbinol functional groups per molecule, or the like.

[0097] In certain embodiments, the composition further comprises an organopolysiloxane chain extender, the organopolysiloxane chain extender having the formula R2XSiO(SiR2O 2 / 2 ) n’The organopolysiloxane chain extender has the formula SiR2X, where each R is independently selected and defined above, X is independently selected and defined above, and 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 may contain pendant silicon-bonded carbinol functional groups, or both pendant and terminal silicon-bonded carbinol functional groups.

[0098] In other embodiments, the chain extender (E) may be organic or may not contain siloxane bonds. In such embodiments, the chain extender (E) may be any conventional chain extender (E) from polyurethane and / or polyisocyanurate compositions. Typically, in such embodiments, the chain extender (E) contains two hydroxyl groups per molecule. The initiator may be selected from, for example, neopentyl glycol; 1,2-propylene glycol; alkanediols 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, and 2,5-hexanediol; ethylene glycol; diethylene glycol; triethylene glycol; and combinations thereof.

[0099] Typically, when the composition further comprises a chain extender (E), the chain extender (E) comprises an organopolysiloxane chain extender for compatibility with component (A). However, depending on the presence of component (F), described below, compatibility may be improved between component (A) and other forms of chain extender (E), including the organic chain extenders described above. Combinations of different chain extenders may be utilized.

[0100] If utilized, the chain extender (E) may be utilized in an amount of from greater than 0 to 50 parts by weight, alternatively from 10 to 50 parts by weight, alternatively from 20 to 40 parts by weight, based on 100 parts by weight of component (A).

[0101] In certain embodiments, the composition further comprises a vehicle (F), which may also be referred to as a carrier vehicle. The vehicle (F) typically solubilizes the components of the composition, and when the components are solubilized, the vehicle (F) can be referred to as a solvent. Suitable vehicles include both linear and cyclic silicones, organic oils, organic solvents, and mixtures thereof.

[0102] Typically, the vehicle (F), when present in the composition, is an organic liquid. Organic liquids include those considered oils or solvents. Organic liquids are exemplified by, but not limited to, aromatic hydrocarbons, aliphatic hydrocarbons, alcohols having more than three carbon atoms, aldehydes, ketones, amines, esters, ethers, glycols, glycol ethers, alkyl halides, and halogenated aromatics. Hydrocarbons include isododecane, isohexadecane, Isopar L (C11-C13), Isopar H (C11-C12), hydrogenated polydecene, aromatic hydrocarbons, and halogenated hydrocarbons. Ethers and esters include isodecyl neopentanoate, neopentyl glycol heptanoate, glycol distearate, dicaprylyl 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 independent compounds or as components of the vehicle (F) include fats, oils, fatty acids, and fatty alcohols.The vehicle (F) may also be a 1 to 1,000 mm at 25°C solvent such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, tetradecamethylhexasiloxane, hexadecamethylheptasiloxane, heptamethyl-3-{(trimethylsilyl)oxy}trisiloxane, hexamethyl-3,3,bis{(trimethylsilyl)oxy}trisiloxanepentamethyl{(trimethylsilyl)oxy}cyclotrisiloxane, as well as polydimethylsiloxane, polyethylsiloxane, polymethylethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, caprylyl methicone, and any mixture thereof. 2 The organopolysiloxane may be a low viscosity organopolysiloxane or a volatile methyl siloxane or a volatile ethyl siloxane or a volatile methylethyl siloxane having a viscosity in the range of 1 / 2 s. / sec.

[0103] In specific embodiments, the vehicle (F) is selected from polyalkylsiloxanes; tetrahydrofuran; mineral spirits; 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; glycol 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.

[0104] In one embodiment, the vehicle (F) is a polar vehicle. In one specific embodiment, when the vehicle (F) is polar, the vehicle (F) comprises or is alternatively acetone.

[0105] The amount of vehicle (F) depends on various factors, including the type of vehicle selected and the amount and type of other ingredients present in the composition. However, the amount of vehicle (F) in the composition may be 0 to 80, alternatively 1 to 50, alternatively 1 to 40, alternatively 1 to 35, alternatively 1 to 30, alternatively 5 to 30, alternatively 10 to 30, or alternatively 15 to 25 weight percent, based on the total weight of the composition. Vehicle (F) may be added during preparation of the composition, for example, to aid in mixing and delivery. All or a portion of vehicle (F) may optionally be removed after the composition is prepared, including before and / or simultaneously with preparing a release coating from the composition.

[0106] In certain embodiments, the composition further comprises a fixing additive (G).Suitable fixing additives are exemplified by the reaction product of vinylalkoxysilane and epoxy-functional alkoxysilane; the reaction product of vinylalkoxysilane and epoxy-functional alkoxysilane; and the combination (e.g., physical blend and / or reaction product) of polyorganosiloxane having at least one aliphatic unsaturated hydrocarbon group and at least one hydrolyzable group per molecule with epoxy-functional alkoxysilane (e.g., the combination of hydroxy-terminated vinyl-functional polydimethylsiloxane and glycidoxypropyltrimethoxysilane).Alternatively, the fixing additive can comprise a polyorganosilicate resin. Suitable solid additives and methods for their preparation are disclosed, for example, in U.S. Pat. No. 9,562,149, U.S. Patent Application Publication No. 2003 / 0088042, U.S. Patent Application Publication No. 2004 / 0254274, and U.S. Patent Application Publication No. 2005 / 0038188, and European Patent No. 0 556 023.

[0107] Further examples of suitable anchoring additives include transition metal chelates, hydrocarbonoxysilanes such as alkoxysilanes, combinations of alkoxysilanes with hydroxy-functional polyorganosiloxanes, or combinations thereof. The anchoring additive (G) can be a silane having at least one substituent with an adhesion-promoting group such as an epoxy group, an acetoxy group, or an acrylate group. The adhesion-promoting group can additionally or alternatively be any hydrolyzable group. Alternatively, the anchoring additive (G) can include such a silane, for example, a partial condensate of an organopolysiloxane with an adhesion-promoting group. Alternatively, the anchoring additive (G) can include a combination of an alkoxysilane with a hydroxy-functional polyorganosiloxane.

[0108] Alternatively, the anchoring additive (G) may comprise an unsaturated or epoxy-functional compound, such as an unsaturated or epoxy-functional silane. The anchoring additive (G) may comprise an unsaturated or epoxy-functional alkoxysilane. For example, the functional alkoxysilane may comprise at least one unsaturated organic group or an epoxy-functional organic group. Epoxy-functional organic groups are exemplified by 3-glycidoxypropyl and (epoxycyclohexyl)ethyl. Unsaturated organic groups are exemplified by 3-methacryloyloxypropyl, 3-acryloyloxypropyl, and unsaturated monovalent hydrocarbon groups such as vinyl, allyl, hexenyl, and undecylenyl. One specific example of an unsaturated compound is vinyltriacetoxysilane.

[0109] 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, undecylenyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, and combinations thereof.

[0110] The fixed additive (G) may also include a reaction product or partial reaction product of one or more of these compounds. For example, in a specific embodiment, the fixed additive (G) may include a reaction product or partial reaction product of vinyltriacetoxysilane and 3-glycidoxypropyltrimethoxysilane. Alternatively or additionally, the fixed additive (G) may include an alkoxy- or alkenyl-functional siloxane.

[0111] Alternatively, the fixing additive (G) may comprise an epoxy-functional siloxane, such as the reaction product of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane, as described above, or a physical blend of a hydroxy-terminated polyorganosiloxane and an epoxy-functional alkoxysilane. The fixing additive (G) may comprise a combination of an epoxy-functional alkoxysilane and an epoxy-functional siloxane. For example, the fixing additive (G) may be exemplified by a mixture of 3-glycidoxypropyltrimethoxysilane and the reaction product of a hydroxy-terminated methylvinylsiloxane with 3-glycidoxypropyltrimethoxysilane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinylsiloxane, or a mixture of 3-glycidoxypropyltrimethoxysilane and a hydroxy-terminated methylvinyl / dimethylsiloxane copolymer.

[0112] Examples of acetoxysilanes suitable for use as the solid additive (G) include tetraacetoxysilane, organotriacetoxysilane, diorganodiacetoxysilane, and combinations thereof. The acetoxysilane may contain alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, and tertiary 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 solid additive (G) comprises an organotriacetoxysilane, for example, a mixture comprising methyltriacetoxysilane and ethyltriacetoxysilane.

[0113] Examples of amino-functional alkoxysilanes suitable for use in or as the fixed additive (G) are HN(CH)Si(OCH), HN(CH)Si(OCHCH), HN(CH)Si(OCH), HN(CH)Si(OCHCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH(CH)Si(OCH), CHNH (CH2)5Si(OCH2CH3)3, H2N(CH2)2NH(CH2)3Si(OCH3)3, H2N(CH2)2NH(CH2)3Si(OCH2CH3)3, CH3NH(CH2)2NH(CH2)3Si(OCH3 )3, CH3NH(CH2)2NH(CH2)3Si(OCH2CH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH3)3, C4H9NH(CH2)2NH(CH2)3Si(OCH2CH3)3, H2N(C H2)2SiCH3(OCH3)2, H2N(CH2)2SiCH3(OCH2CH3)2, H2N(CH2)3SiCH3(OCH3)2, H2N(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)3Si CH3(OCH3)2, CH3NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)5SiCH3(OCH3)2, CH3NH(CH2)5SiCH3(OCH2CH3)2, H2N(CH2)2NH(CH 2)3SiCH3(OCH3)2, H2N(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, CH3NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH3)2, C4H9NH(CH2)2NH(CH2)3SiCH3(OCH2CH3)2, and combinations thereof.

[0114] Examples of oximosilanes suitable for the solid additive (G) include structural units selected from alkyltrioximosilanes such as methyltrioximosilane, ethyltrioximosilane, propyltrioximosilane, and butyltrioximosilane; alkoxytrioximosilanes such as methoxytrioximosilane, ethoxytrioximosilane, and propoxytrioximosilane; or alkenyltrioximosilanes such as propenyltrioximosilane or butenyltrioximosilane; alkenyloximosilanes such as vinyloximosilane; alkenylalkyldioximosilanes such as vinylmethyldioximosilane, vinylethyldioximosilane, vinylmethyldioximosilane, or vinylethyldioximosilane; or combinations thereof.

[0115] Examples of ketoximo silane crosslinkers suitable for the fixing additive (G) include methyl tris(dimethyl ketoximo) silane, methyl tris(methyl ethyl ketoximo) silane, methyl tris(methyl propyl ketoximo) silane, methyl tris(methyl isobutyl ketoximo) silane, ethyl tris(dimethyl ketoximo) silane, ethyl tris(methyl ethyl ketoximo) silane, ethyl tris(methyl propyl ketoximo) silane, ethyl tris(methyl isobutyl ketoximo) silane, vinyl tris(dimethyl ketoximo) silane, vinyl tris(methyl ethyl ketoximo) silane, vinyl tris(methyl propyl ketoximo) silane, tetrakis(dimethylketoximo)silane, tetrakis(methylethylketoximo)silane, tetrakis(methylpropylketoximo)silane, tetrakis(methylisobutylketoximo)silane, methylbis(dimethylketoximo)silane, methylbis(cyclohexylketoximo)silane, triethoxy(ethylmethylketoxime)silane, diethoxydi(ethylmethylketoxime)silane, ethoxytri(ethylmethylketoxime)silane, methylvinylbis(methylisobutylketoximo)silane, or a combination thereof.

[0116] Alternatively, the solid additive (G) may comprise a transition metal chelate. Suitable transition metal chelates include titanates, zirconates such as zirconium acetylacetonate, aluminum chelates such as aluminum acetylacetonate, and combinations thereof. Alternatively, the solid additive (G) may comprise a combination of a transition metal chelate and an alkoxysilane, for example, a combination of glycidoxypropyltrimethoxysilane and an aluminum chelate or a zirconium chelate.

[0117] The specific amount of anchoring additive (G), if utilized, present in the composition depends on various factors, including the type of substrate and whether a primer is used. In certain embodiments, anchoring additive (G) is present in the composition in an amount of 0 to 2 parts by weight per 100 parts by weight of component (B). Alternatively, anchoring additive (G) is present in the composition in an amount of 0.01 to 2 parts by weight per 100 parts by weight of component (B).

[0118] In certain embodiments, the composition further comprises an anti-mist additive (H). The anti-mist additive (H) can be utilized in the composition to reduce or inhibit silicone mist formation during coating processes, particularly those using high-speed coating equipment. The anti-mist additive (H) can be any compound or component suitable for reducing, minimizing, or eliminating misting during application of the composition. In one embodiment, the anti-mist additive (H) comprises or is the reaction product of an organohydrogensilicon compound, an oxyalkylene compound, or an organoalkenylsiloxane having at least three silicon-bonded alkenyl groups per molecule, and a suitable catalyst. In a specific embodiment, the anti-mist additive (H) comprises a Q-type branched dimethylvinyl-terminated organopolysiloxane. In another specific embodiment, the anti-mist additive (H) comprises an MDQ resin. The anti-mist additive (H) may have a viscosity of 30,000 to 50,000, alternatively 35,000 to 45,000 centipoise at 25° C. Suitable anti-mist additives are disclosed, for example, in U.S. Patent Application Publication No. 2011 / 0287267, U.S. Patent No. 8,722,153, U.S. Patent No. 6,586,535, and U.S. Patent No. 5,625,023.

[0119] The amount and selection of the anti-mist additive (H) utilized in the composition will depend on various factors, including the amount and type of other starting materials selected for the composition. For example, if component (A) is linear or slightly branched, then anti-mist additive (H) may be utilized, which may have a highly branched or resinous structure. However, if component (A) is branched or resinous, then anti-mist additive (H) may be utilized, which may be linear or only partially branched. Anti-mist additive (H) is typically utilized in an amount of 0% to 10%, alternatively 0.1% to 3%, based on the total weight of the composition. This amount excludes the amount associated with component (A) and relates only to the anti-mist additive (H), which is separate and distinct from component (A).

[0120] In certain embodiments, the composition further comprises a release modifier (I) that can be utilized in the composition to control (reduce) the level of release force (the adhesive force between a release coating formed from the composition and an item adhered to the release coating, such as a label containing a pressure-sensitive adhesive). A release coating having the required or desired release force can be formulated from a modifier-free composition by adjusting the level or concentration of the release modifier (I). Examples of suitable release modifiers for component (I) include trimethylsiloxy-terminated dimethyl, phenylmethyl siloxanes. Alternatively, the release modifier (I) can be a condensation reaction product of an organopolysiloxane resin having hydroxyl or alkoxy groups and a diorganopolysiloxane having at least one hydroxyl or hydrolyzable group. Examples of suitable release modifiers are disclosed, for example, in U.S. Pat. No. 8,933,177 and U.S. Patent Application Publication No. 2016 / 0053056.

[0121] The release coating formed using 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 produce a foam. Blowing agents can be classified as physical and chemical blowing agents. Physical blowing agents undergo a phase change from a liquid to a gaseous state when subjected to atmospheric pressure and the elevated temperatures associated with curing (e.g., 100°C or higher). 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 a gas as a by-product. Such blowing agents are typically utilized in forming polyurethane and / or polyisocyanurate foams. However, the release coating formed using the composition is not a foam, and in certain embodiments, the composition does not include a physical blowing agent, a chemical blowing agent, or both a physical and a chemical blowing agent. As understood in the art, the determination of whether a component constitutes a physical blowing agent is a function of processing parameters, including the temperature at which the composition is used to form the release coating (i.e., based on the component's physical properties and whether the component boils or volatilizes during the formation of the release coating). For example, certain components of the composition may volatilize at particularly high processing temperatures (e.g., above 120°C), but not at the processing temperatures utilized to prepare the release coating using the composition such that the composition does not contain a blowing agent. As noted above, the composition typically does not contain a chemical blowing agent. Chemical blowing agents are distinct from components (A), (B), and optional components (C) through (I). Depending on the selection of these components, gas may at least be a by-product of the reaction during the formation of the release coating. However, if any gas is formed as a by-product in the preparation of the release coating, the gas is generated at levels significantly greater than those formed using conventional chemical blowing agents such that the release coating is not a foam.

[0122] Other optional ingredients 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 extending and reinforcing fillers), surfactants, thixotropic agents, pH buffers, etc. The composition may be in any form and may be incorporated into further compositions.

[0123] Alternatively, the composition and the release coating formed therefrom may be free of particulates or may contain only limited amounts of particulates (e.g., fillers and / or pigments), such as 0-30% by weight of the composition. Particulates may clump or otherwise stick to the coating equipment used to form the release coating. Additionally, if optical transparency is desired, particulates may interfere with the optical properties, e.g., transparency, of the release coating and the release liner formed therefrom. Particulates may be detrimental to adherend adhesion.

[0124] In certain embodiments, the composition does not contain a fluoroorganosilicone compound. It is believed that during curing, fluorocompounds, due to their low surface tension, can rapidly migrate to the interface of the composition or the release coating formed using the composition, and to the substrate to which the composition is applied and the release coating is formed, such as the composition / PET film interface. Such migration can prevent adhesion of the release coating (prepared by curing the composition) to the substrate by creating a fluorine-containing barrier. By creating a barrier, the fluoroorganosilicone compound can prevent components of the composition from reacting at the interface, which can affect curing and related properties. Furthermore, fluoroorganosilicone compounds are typically expensive.

[0125] The curable form of the composition can be prepared by combining components (A)-(B), as well as any optional components described above, in any order of addition, optionally in a masterbatch, and optionally under shear. As described in more detail below, the composition can be a one-part, two-part, or 2K composition, or a multi-part composition. For example, the composition can include 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. The catalyst (C) is typically 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. The components are typically combined to provide the composition as a bath when used to form a release coating.

[0126] A method for preparing a coated substrate with the composition includes applying, i.e., disposing, the composition on a substrate. The method further includes curing the composition on the substrate, thereby forming a release coating on the substrate, to obtain a coated substrate. Curing can be accomplished by heating at an elevated temperature, for example, 50-180°C, alternatively 50-120°C, alternatively 50-90°C, alternatively 70-90°C, alternatively 70-85°C, or alternatively 75-85°C, to obtain a coated substrate. One skilled in the art will be able to select an appropriate temperature depending on various factors, including the components of the composition and the selection of materials for the substrate composition or structure. The composition cures at a lower temperature than conventional compositions used to prepare conventional release coatings, thereby reducing energy consumption and allowing for the use of different types of substrates that may soften or deform at elevated temperatures.

[0127] The composition can be disposed or distributed on the substrate in any suitable manner. Typically, the composition is applied in wet form by a wet coating technique. The composition can be applied by i) spin coating, ii) brush coating, iii) drop coating, iv) spray coating, v) dip coating, vi) roll coating, vii) flow coating, viii) slot coating, ix) gravure coating, x) Mayer bar coating, or xi) a combination of any two or more of i)-x). Typically, disposing the composition on the substrate results in a wet deposit on the substrate, which is then cured to obtain a cured film, i.e., a coated substrate including a release coating formed from the composition on the substrate.

[0128] The substrate is not limited and can be any substrate. The cured film can be separable from the substrate or can be physically and / or chemically bonded to the substrate, depending on the choice. The substrate can have an integrated hotplate or an integrated or stand-alone oven for curing the wet deposit. The substrate can optionally have continuous or discontinuous shapes, sizes, dimensions, surface roughness, and other properties. Alternatively, the substrate can have an elevated softening point temperature. However, the compositions and methods are not so limited.

[0129] Alternatively, the substrate may comprise a plastic, which may be thermoset and / or thermoplastic. However, the substrate may alternatively be or comprise glass, metal, cellulose (e.g., paper), wood, cardboard, paperboard, silicone, or a polymeric material, or a combination thereof.

[0130] Specific examples of suitable substrates include paper substrates such as kraft paper, polyethylene-coated kraft paper (PEK-coated paper), thermal paper, and plain paper; polymer substrates such as polyamide (PA); polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PET), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), and liquid crystal polyester; polyolefins such as polyethylene (PE), polypropylene (PP), and polybutylene; styrene resins; polyoxymethylene (POM); polycarbonate (PC); polymethylene methacrylate (PMMA); polyvinyl chloride (PVC); polyphenylene sulfide (PPS); polyphenylene ether (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; celluloses such as triacetyl cellulose, diacetyl cellulose, and cellophane; fluorinated resins such as polytetrafluoroethylene;Thermoplastic elastomers such as polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, and fluoropolymers; and copolymers and combinations thereof.

[0131] The composition, or wet deposit, is typically cured at elevated temperature for a period of time. The time is typically sufficient to effect cure, i.e., crosslinking, of the composition. The time can be from greater than 0 to 8 hours, alternatively from greater than 0 to 2 hours, alternatively from greater than 0 to 1 hour, alternatively from greater than 0 to 30 minutes, alternatively from greater than 0 to 15 minutes, alternatively from greater than 0 to 10 minutes, alternatively from greater than 0 to 5 minutes, alternatively from greater than 0 to 2 minutes, alternatively from greater than 0 to 90 seconds, alternatively from greater than 0 to 80 seconds, alternatively from greater than 0 to 70 seconds, or alternatively from greater than 0 to 60 seconds. The 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.

[0132] Curing the composition typically has a residence time of 0.1 seconds to 50 seconds, alternatively 0.5 seconds to 30 seconds, alternatively 1 to 20 seconds, alternatively 1 to 15 seconds, or alternatively 1 to 10 seconds. The residence time selected can vary depending on the substrate selection, the selected temperature, and the line speed. As used herein, residence time refers to the time the composition or wet deposit is subjected to elevated temperatures. Residence time is distinct from cure time, as there may be ongoing curing even after the composition, wet deposit, or its partially cured reaction intermediate is no longer subjected to elevated temperatures that typically initiate curing. Alternatively, the coated article may be prepared on a conveyor belt in an oven, and the residence time may be calculated by dividing the length of the oven (e.g., in meters) by the line speed of the conveyor belt (e.g., meters / second). In fact, the compositions of the present invention can be cured to obtain a release coating with these residence times, even at relatively low temperatures of 75 to 85°C.

[0133] The period can be subdivided into cure iterations, e.g., a first cure and a post cure, e.g., 1 hour for the first cure and 3 hours for the post cure. The elevated temperature can be independently selected in such iterations from any temperature above room temperature and can be the same in each iteration.

[0134] Depending on the optional presence and selection of a vehicle (F), curing the composition may also include a drying step. For example, if the composition includes a vehicle (F), the curing step typically also involves drying or removing the vehicle (F) from the composition. Drying may occur simultaneously with curing or may be separate from curing.

[0135] Depending on the thickness and other dimensions of the film and coated substrate, the coated substrate can be formed through an iterative process. For example, a first deposit can be formed and subjected to a first elevated temperature for a first period of time to obtain a partially cured deposit. A second deposit can then be placed on the partially cured deposit and subjected to a second elevated temperature for a second period of time to obtain a second partially cured deposit. This partially cured deposit can also be further cured while subjected to a second elevated temperature for a second period of time. A third deposit can be placed 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 can also be further cured while subjected to a second elevated temperature for a second period of time. This process can be repeated, for example, 1 to 50 times, to construct the coated article as desired. The composite of partially cured layers can be subjected to a final post-cure, for example, to the elevated temperature and period described above. Each elevated temperature and period of time can be independently selected and can be the same or different from each other. When an article is formed via an iterative process, each deposit may be independently selected and the components selected in the composition, their amounts, or both may vary. Alternatively, or even further, each repeating layer may be fully cured, rather than only partially cured, in such an iterative process.

[0136] Alternatively, the deposition may include a wet film. Alternatively, the iterative process may be wet-on-wet, depending on the cure state of the partially cured layer. Alternatively, the iterative process may be wet-on-dry.

[0137] The coated substrate, comprising a film formed from the composition on a substrate, can have a variety of dimensions, including the relative thicknesses of the film and the substrate. The film has a thickness that can vary depending on the end use. The film can have a thickness of greater than 0 to 4,000 μm, alternatively greater than 0 to 3,000 μm, alternatively greater than 0 to 2,000 μm, alternatively greater than 0 to 1,000 μm, alternatively greater than 0 to 500 μm, or alternatively greater than 0 to 250 μm. However, other thicknesses, such as 0.1 to 200 μm, are also contemplated. For example, the film thickness can be 0.2 to 175 μm, alternatively 0.5 to 150 μm, alternatively 0.75 to 100 μm, alternatively 1 to 75 μm, alternatively 2 to 60 μm, alternatively 3 to 50 μm, or alternatively 4 to 40 μm. Alternatively, when the substrate is plastic, the film may have a thickness of from greater than 0 to 200 μm, alternatively from greater than 0 to 150 μm, alternatively from greater than 0 to 100 μm.

[0138] If desired, the film can be subjected to further processing depending on its end use. For example, the film can be subjected to oxide deposition (e.g., SiO deposition), resist deposition and patterning, etching, chemical stripping, corona or plasma stripping, metallization, or metal deposition. Such further processing techniques are generally known. Such deposition can be chemical vapor deposition (such as 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 high temperatures, particularly vacuum deposition, for which the film is well suited given its excellent thermal stability. However, depending on the end use of the film, the film can be utilized after such further processing.

[0139] The coated substrates can be utilized in a variety of end uses. For example, the coated substrates can be utilized in coating applications, packaging applications, adhesive applications, fiber applications, fabric or textile applications, construction applications, transportation applications, electronics applications, or electrical applications. However, the compositions can be utilized for end uses other than preparing coated substrates, such as preparing articles such as silicone rubber.

[0140] Alternatively, the coated substrate may be utilized as a release liner for a tape or adhesive, including any pressure-sensitive adhesive, such as, for example, 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-type adhesives, and polyurethane-type adhesives. Each major surface of the substrate may have a film disposed thereon for double-sided tape or adhesive.

[0141] Alternatively, if the composition is formulated as a release coating composition, e.g., to form a release coating or liner, the release coating composition can be prepared, for example, by mixing the components together to form a one-part composition. However, it may be desirable to prepare the release coating composition as a multi-part composition in which the component having carbinol functionality (e.g., component (A)) and the component having isocyanate functionality (e.g., component (B)) are stored in separate parts until the parts are combined at the time of use (e.g., immediately before application to a substrate). When the composition is a release coating composition, the release coating composition can be utilized to form a coated substrate as described above, and the release coating is formed by applying the release coating composition to the substrate, e.g., the surface of the substrate, and curing.

[0142] The release coating composition can be applied to the substrate by any convenient means such as spraying, doctor blading, dipping, screen printing, or by a roll coater, for example, an offset web coater, kiss coater, or etched cylinder coater.

[0143] The release coating composition of the present invention can be applied to any substrate, such as those described above. Alternatively, the release coating composition can be applied to a polymer film substrate, such as a polyester film, particularly a polyethylene terephthalate (PET) film, a polyethylene film, a polypropylene film, or a polystyrene film. Alternatively, the release coating composition can be applied to a paper substrate, including a plastic-coated paper, such as polyethylene-coated paper, glassine, supercalendered paper, or clay-coated kraft paper. Alternatively, the release coating composition can be applied to a metal foil substrate, such as aluminum foil.

[0144] In certain embodiments, the method for preparing a coated substrate can further include treating the substrate before applying or disposing the release coating composition on the substrate. The treatment of 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 certain examples, if the substrate is treated before forming the release coating on the substrate from the release coating composition, the anchorage of the release coating can be improved.

[0145] When the release coating composition includes a vehicle (F), the method can further include removing the vehicle (F), which can be done by any conventional means, such as by heating at 50°C to 100°C for a time sufficient to remove all or a portion of the vehicle (F). The method can further include curing the release coating composition to form a release coating on the surface of the substrate. Curing can be done by any conventional means, such as by heating at 100°C to 200°C.

[0146] Under production coater conditions, curing can be carried out at air temperatures of 120° C. to 150° C. with residence times of 1 to 6 seconds, alternatively 1.5 to 3 seconds. Heating can be carried out in an oven, such as an air circulating oven or tunnel furnace, or by passing the coated film around a heated cylinder.

[0147] The following examples are intended to illustrate the present invention and should not be construed as limiting the scope of the invention in any way. Certain components utilized in the examples are set forth in Table 1 below, followed by characterization and evaluation procedures also used in the examples.

[0148] The following examples illustrating embodiments of the present disclosure are intended to illustrate, but not limit, the invention. Unless otherwise specified, all reactions were conducted under air, and all solvents, substrates, and reagents were purchased from various commercial sources (e.g., Evonik, TCI, Sigma-Aldrich, etc.) or otherwise obtained and utilized as received.

[0149] material Table 1 below provides a brief summary and provides information regarding certain abbreviations, shorthand notations, and components utilized in the examples.

[0150] [Table 1-1]

[0151] [Table 1-2]

[0152] Instrumentation and Characterization Parameters The following instruments and characterization procedures / parameters were used to evaluate various physical properties of the compounds prepared in the examples below.

[0153] Hydroxyl Number Calculation The hydroxyl value was obtained using an automatic titrator. The esterification reagent was prepared using phthalic anhydride, pyridine, and imidazole. 63-66 g of phthalic anhydride was weighed into a 500 mL amber reagent bottle. 400 mL of fresh pyridine was added, and the bottle was vigorously shaken until a solution was formed. 9-10 g of imidazole was then added and carefully vortexed until dissolved. The reagent was then left overnight. Prolonged exposure of the reagent to moisture in the air was avoided. Approximately 1.0 g of sample was then weighed into a 40 mL glass bottle, and 4.00 mL of esterification reagent was added. The solution was stirred with a magnetic stirrer until the sample was completely dissolved in the esterification reagent. The bottle was then heated in a 90°C ± 2°C water bath for 2 hours. After cooling to room temperature, the bottle cap was removed, and the rubber gasket was rinsed with 8 mL of pyridine and 4 mL of DI water. To improve the solubility of the carbinol silicone, 4 mL of THF was added to the solution. The solution was allowed to stand for 2 minutes and then titrated with 1.000 mol / L sodium hydroxide solution. A blank test was performed similarly, but without adding the sample to the esterification reagent. The hydroxyl number was calculated in the sample as follows:

[0154]

number

[0155] Calculating NCO content To measure the NCO content, the sample was weighed to the nearest 0.0001 g into a beaker and then dissolved in toluene (previously dried over molecular sieves). An appropriate amount of DBA / DMF solution (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 dry overnight before use) was then added using a precision pipette. A stir bar was added to the solution, and the beaker was covered with aluminum foil. The solution was left stirring for at least 5 minutes. Then, 25 mL of isopropanol was used to wash the inner walls of the beaker and the aluminum foil, and the washing solvent was collected in the beaker. The final solution was titrated with 0.5 mol / L HCl. A blank sample was analyzed in the same way without adding any sample. Calculations were performed according to the following formula:

[0156]

number

[0157] Performance evaluation Extractables: The cured properties of the coatings were evaluated by measuring the percentage of extractables in the cured coating. This was done by first determining the coating weight of a standard-sized substrate sample bearing the cured coating by X-ray fluorescence using an X-ray fluorescence spectrometer. The coating sample was then placed in a solution of methyl isobutyl ketone solvent to extract any unreacted siloxane that was not crosslinked within the coating matrix or adhered to the substrate. After a predetermined time (1 day of MIBK immersion), the sample was removed from the solvent, dried, and the coating weight was remeasured.

[0158] Peeling force (RF-RT) To measure the peel force at room temperature, a 180° peel test was used. Specifically, Tesa 7475 standard tape was laminated onto each release coating to obtain laminated samples, and a peel strength of 20 g / cm was applied. 2 A weight was placed on each laminate sample at room temperature for 20 hours. After 20 hours, the weight was removed. After 30 minutes, the peel force was measured according to FINAT Test Method No. 10 (FINAT Technical Handbook 7). th The measurements were carried out using a ChemInstruments AR-1500 according to the ChemInstruments AR-1500 (European Chemistry Association, 2005).

[0159] Peel strength over time (RF-70℃) To measure the peel strength over time at 70°C, a 180° peel test was used. Specifically, Tesa 7475 standard tape was laminated onto each release coating to obtain a laminated sample, and a peel strength of 20 g / cm 2 A weight of 1.5 mm was placed on each laminate sample for 20 hours at 70°C. After 20 hours, the weight was removed. After 30 minutes at room temperature, the peel force was measured according to FINAT Test Method No. 10 (FINAT Technical Handbook 7). th The measurements were carried out using a ChemInstruments AR-1500 according to the ChemInstruments AR-1500 (European Chemistry Association, 2005).

[0160] Subsequent Adhesive Strength (SAS) SAS is a measure of migration and was obtained by first laminating Nitto Denko 31B tape onto each release coating to obtain laminate samples, and then applying a 20 g / cm 2 The peel force was measured by placing a weight of 1000 kJ on each laminated sample at 70°C for 20 hours. After 20 hours, the weight was removed. After 30 minutes at room temperature, each laminated sample was placed on a PET substrate for 1 hour. The peel force was then measured by a ChemInstruments AR-1500 and was calculated as RF 剥離 The same procedure was carried out for each release coating using a PTFE substrate instead of a PET substrate, and the resulting release force was measured using RF PTFE SAS is based on FINAT Test Method No. 11 (FINAT Technical Handbook 7th According to the (2005 edition) formula RF 剥離 / RF PTFE Calculated by multiplying by 100%.

[0161] Preparation Example 1: (b1-1) Synthesis of isocyanate-functional copolymer A dry 1000 mL three-neck flask equipped with a condenser and mechanical stirrer was charged with 374 g of (b1a-1) siloxane (0.2 mol) and 89 g of (b1b) polyisocyanate (0.38 mol). The system was purged with nitrogen for 10 minutes, and the temperature was gradually increased to 80°C over 30 minutes. The reaction was allowed to proceed for 3 hours to yield the (b1-1) isocyanate-functional copolymer. The (b1-1) isocyanate-functional copolymer was cooled to room temperature and then transferred to a container. The container was then placed in a desiccator for storage. The titrated NCO% was determined to be 3.42% based on the titration method described above.

[0162] Preparation Example 2: (b1-2) Synthesis of isocyanate-functional copolymer A dry 1000 mL three-neck flask equipped with a condenser and mechanical stirrer was charged with 200 g of (b1a-2) siloxane (0.21 mol) and 94 g of (b1b) polyisocyanate (0.42 mol). The system was purged with nitrogen for 10 minutes, and the temperature was gradually increased to 80°C over 30 minutes. The reaction was allowed to proceed for 3 hours to yield the (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. The titrated NCO% was determined to be 6±0.1% based on the titration method described above.

[0163] Table 2 below shows the theoretical NCO content of (b1-1) isocyanate-functional copolymer and (b1-2) isocyanate-functional copolymer versus the actual titrated NCO values ​​measured from Preparative Examples 1 and 2.

[0164] [Table 2]

[0165] Preparation Example 3: (A-1) Synthesis of organopolysiloxane A 2000 mL three-neck flask was charged with 800 g (2.74 mol) of cyclic siloxane, 45 g of cyclic organohydrogenpolysiloxane, and 14.6 g of endblocker. 0.68 mL of triflic acid was then added to the flask as a catalyst. 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, after which the system was cooled to room temperature. 12 g of 700 mesh CaCO3 was then added to the flask and stirred at room temperature for 2 hours to obtain a mixture. The mixture was then centrifuged to remove most of the CaCO3, and then filtered through silica gel on a Buchi funnel to obtain a filtered mixture. The filtered mixture was then subjected to a rotary evaporator at full vacuum at 70°C, then at 120°C and full vacuum using a vacuum pump to obtain the following average formula: MD 120 D H A linear organopolysiloxane having 8M was obtained.

[0166] 500 g of the newly prepared linear organopolysiloxane was added to a 1000 mL three-neck flask equipped with a mechanical stirrer, N2 inlet, and condenser along with 86 g of an alcohol compound, 200 g of solvent, 0.48 g of a pH control agent, and 1.20 g of a hydrosilylation catalyst. Under a nitrogen purge, the flask was stirred at 400 rpm at room temperature for 10 minutes. The system was gradually heated to 70°C over 30 minutes and maintained at that temperature for 2.5 hours to obtain a crude product. The crude product was filtered through a 0.45 μm mesh pipette. 17.2 g of antioxidant (1 wt%) in solvent was added to the crude product to obtain a mixture, which was then subjected to rotary evaporation at full vacuum at 70°C, then at 115°C and full vacuum for 2 hours with Wi-Fi to obtain organopolysiloxane (A-1). (A-1) An organopolysiloxane was obtained that was calculated (based on the titration method described above) to have an average hydroxyl number of 42.0 mg KOH / g.

[0167] Preparation Example 4: Synthesis of (A-2) organopolysiloxane A 2000 mL flask was charged with acetic acid (268 g), end-capping agent (696 g), and equilibration catalyst (150 g). The system was purged with nitrogen for 10 minutes. The nitrogen flow was then reduced to a minimum, and the temperature of the flask was increased to 45°C. TEOS (232 g) was added dropwise to the flask through a constant pressure funnel, with the addition completed after 30 minutes. The temperature was maintained for an additional 120 minutes. Acetic anhydride (228 g) was then added dropwise through a constant pressure funnel with stirring, with the addition completed after 15 minutes. The temperature was maintained for an additional 150 minutes. The stirring was then stopped, and the temperature of the system was allowed to decrease to room temperature.

[0168] The system was then centrifuged to remove most of the equilibrated catalyst, yielding a premixture. The premixture was then rotary evaporated at room temperature under 66.5 mbar (50 torr). The temperature was then gradually increased to 60°C to remove by-products and unreacted reagents, yielding a purified mixture. 300 mL of ethyl acetate was then added to the purified mixture, followed by washing with deionized water (200 mL total), two washes with 4% NaHCO3 (150 mL total), and one additional wash with deionized water (50 mL) to yield a product mixture. The pH of the product mixture was neutral as determined by test paper. The organic phase of the product mixture was then dried over anhydrous sodium sulfate, Na2SO4, yielding a premixture product. The premixture product was then rotary evaporated at room temperature under 13 mbar (10 torr). The temperature was then gradually increased to 50°C over at least 1 hour. M4Q was then collected, and its purity was determined to be 65%.

[0169] A 2000 mL three-neck flask was charged with freshly prepared M4Q (60 g), cyclic siloxane (1380 g), cyclic organohydrogensiloxane (75 g), and triflic acid (1.4 mL). The system was purged with nitrogen for 10 minutes. The system was then heated to 60°C and held at that temperature for 3 hours. 700 mesh CaCO3 (20 g) was then added to the flask to obtain a precursor mixture, and the system was stirred at room temperature for 2 hours. The precursor mixture was then filtered through cotton and then filtered through silica gel on a Buchi funnel. The precursor mixture was then rotary evaporated at full vacuum at 70°C for 1 hour, followed by stripping at 110°C for 2 hours. Average Formula QD 120 D H Organopolysiloxane 4M4 was obtained.

[0170] Freshly prepared QDs 120 D H 4M4 (1000 g), alcohol compound (224 g), solvent (400 g), inhibitor (D) (0.96 g), and hydrosilylation catalyst (2.4 g) were charged to a 2000 mL three-neck flask. Under a nitrogen blanket, the system was stirred at 400 rpm at room temperature for 10 minutes. The system was heated to 70°C and held at that temperature for 2.5 hours to obtain a crude product. The crude product was then filtered through silica gel on a Buchi funnel. 20 g of antioxidant (1 wt%) in solvent was added to the crude product, which was then rotary evaporated at full vacuum at 70°C for 1 hour, followed by heating and stripping at 115°C. (A-2) organopolysiloxane was obtained and calculated (based on the titration method described above) to have an average hydroxyl number of 41.4 ± 0.003 mg KOH / g.

[0171] Preparation Example 5: Synthesis of (A-3) organopolysiloxane A 250 mL three-neck flask was charged with 133.5 g of cyclic siloxane, 11.1 g of organohydrogenpolysiloxane, 7.25 g of endblocker, and 24 g of equilibration catalyst. 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, after which the system was cooled to room temperature. The crude product was then centrifuged to remove most of the equilibration catalyst, and then filtered through silica gel on a Buchi funnel to obtain a filtered mixture. The filtered mixture was then subjected to a rotary evaporator at full vacuum at 70°C, then at 110°C and full vacuum with a vacuum pump to obtain a product of the following average formula: MD 40 D H A linear organopolysiloxane having 4M was obtained.

[0172] 140 g of the newly prepared linear organopolysiloxane was placed in a 500 mL three-neck flask equipped with a mechanical stirrer, N2 inlet, and condenser along with 32.3 g of an alcohol compound, 70 g of solvent, 0.14 g of a pH control agent, and 0.35 g of a hydrosilylation catalyst. The flask was purged with nitrogen for 10 minutes. The system was gradually heated to 70°C and maintained at that temperature for 2 hours to obtain a crude product. The crude product was filtered through a 0.45 μm mesh pipette. 2 g of an antioxidant (1 wt%) in solvent was added to the crude product to obtain a mixture, which was then subjected to rotary evaporation at full vacuum at 70°C and then at full vacuum at 110°C using a vacuum pump for 2 hours to obtain organopolysiloxane (A-3).

[0173] Preparation Example 6: Synthesis of (A-4) organopolysiloxane A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with M4Q (60 g), cyclic siloxane (1150 g), cyclic organohydrogenpolysiloxane (75 g), and triflic 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, after which the system was cooled to room temperature. Next, 700 mesh CaCO3 (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 with a 0.45 μm mesh pipette. The precursor mixture was then subjected to a rotary evaporator at full vacuum at 70 °C. The precursor mixture was then subjected to a vacuum pump at 110 °C and full vacuum to obtain the average formula QD. 57 D H 5.7 An organohydrogenpolysiloxane having M4 was obtained.

[0174] A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with the freshly prepared organohydrogenpolysiloxane (484 g), alcohol compound (118 g), solvent (242 g), pH control agent (0.484 g), and hydrosilylation catalyst (1.21 g). Under a nitrogen purge, the system was stirred at 400 rpm at room temperature for 10 minutes. 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. The precursor mixture was then filtered through a 0.45 μm mesh pipette. 10 g of antioxidant (1 wt%) in solvent was added to the precursor mixture, which was then rotary evaporated at 70°C under full vacuum. The precursor mixture was then subjected to a vacuum pump at 110°C and full vacuum to obtain organopolysiloxane (A-4).

[0175] Preparation Example 7: Synthesis of (A-5) organopolysiloxane A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with M4Q (60 g), cyclic siloxane (1380 g), cyclic organohydrogenpolysiloxane (75 g), and triflic 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, after which the system was cooled to room temperature. Next, 700 mesh CaCO3 (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 with a 0.45 μm mesh pipette. The precursor mixture was then subjected to a rotary evaporator at full vacuum at 70 °C. The precursor mixture was then subjected to a vacuum pump at 110 °C and full vacuum to obtain the average formula QD. 120 D H An organohydrogenpolysiloxane containing 8M4 was obtained.

[0176] A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with the freshly prepared organohydrogenpolysiloxane (968 g), alcohol compound (224 g), solvent (424 g), pH control agent (1.12 g), and hydrosilylation catalyst (2.78 g). Under a nitrogen purge, the system was stirred at 400 rpm at room temperature for 10 minutes. 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. The precursor mixture was then filtered through a 0.45 μm mesh pipette. 20 g of antioxidant (1 wt%) in solvent was added to the precursor mixture, which was then rotary evaporated at 70°C under full vacuum. The precursor mixture was then subjected to a vacuum pump at 110°C and full vacuum to obtain (A-5) organopolysiloxane.

[0177] Preparation Example 8: Synthesis of (A-6) organopolysiloxane A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with M4Q (60 g), cyclic siloxane (416 g), cyclic organohydrogenpolysiloxane (37.5 g), and triflic 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, after which the system was cooled to room temperature. Next, 700 mesh CaCO3 (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 with a 0.45 μm mesh pipette. The precursor mixture was then subjected to a rotary evaporator at full vacuum at 70 °C. The precursor mixture was then subjected to a vacuum pump at 110 °C and full vacuum to obtain the average formula QD. 36 D H An organohydrogenpolysiloxane containing 4M4 was obtained.

[0178] A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with the freshly prepared organohydrogenpolysiloxane (900 g), alcohol compound (167 g), solvent (533 g), pH control agent (1.12 g), and hydrosilylation catalyst (2.78 g). Under a nitrogen purge, the system was stirred at 400 rpm at room temperature for 10 minutes. 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. The precursor mixture was then filtered through a 0.45 μm mesh pipette. 20 g of antioxidant (1 wt%) in solvent was added to the precursor mixture, which was then rotary evaporated at 70°C under full vacuum. The precursor mixture was then subjected to a vacuum pump at 110°C and full vacuum to obtain (A-6) organopolysiloxane.

[0179] Preparation Example 9: (A-7) Synthesis of organopolysiloxane A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with M4Q (60 g), cyclic siloxane (369 g), cyclic organohydrogenpolysiloxane (75 g), and triflic 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, after which the system was cooled to room temperature. Next, 700 mesh CaCO3 (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 with a 0.45 μm mesh pipette. The precursor mixture was then subjected to a rotary evaporator at full vacuum at 70 °C. The precursor mixture was then subjected to a vacuum pump at 110 °C and full vacuum to obtain the average formula QD. 32 D H An organohydrogenpolysiloxane containing 8M4 was obtained.

[0180] A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with the freshly prepared organohydrogenpolysiloxane (600 g), alcohol compound (224 g), solvent (300 g), pH control agent (1.22 g), and hydrosilylation catalyst (1.44 g). Under a nitrogen purge, the system was stirred at 400 rpm at room temperature for 10 minutes. 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. The precursor mixture was then filtered through a 0.45 μm mesh pipette. 20 g of antioxidant (1 wt%) in solvent was added to the precursor mixture, which was then rotary evaporated at 70°C under full vacuum. The precursor mixture was then subjected to a vacuum pump at 110°C and full vacuum to obtain (A-7) organopolysiloxane.

[0181] Preparation Example 10: Synthesis of (A-8) organopolysiloxane A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with M4Q (60 g), cyclic siloxane (184.8 g), cyclic organohydrogenpolysiloxane (37.5 g), and triflic 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, after which the system was cooled to room temperature. Next, 700 mesh CaCO3 (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 with a 0.45 μm mesh pipette. The precursor mixture was then subjected to a rotary evaporator at full vacuum at 70 °C. The precursor mixture was then subjected to a vacuum pump at 110 °C and full vacuum to obtain the average formula QD. 16 D H An organohydrogenpolysiloxane containing 4M4 was obtained.

[0182] A 2000 mL three-neck flask equipped with a mechanical stirrer, nitrogen inlet, and condenser was charged with the freshly prepared organohydrogenpolysiloxane (460 g), alcohol compound (100 g), solvent (200 g), pH control agent (0.60 g), and hydrosilylation catalyst (1.44 g). Under a nitrogen purge, the system was stirred at 400 rpm at room temperature for 10 minutes. 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. The precursor mixture was then filtered through a 0.45 μm mesh pipette. 20 g of antioxidant (1 wt%) in solvent was added to the precursor mixture, which was then rotary evaporated at 70°C under full vacuum. The precursor mixture was then subjected to a vacuum pump at 110°C and full vacuum to obtain organopolysiloxane (A-8).

[0183] Table 3 below shows the theoretical hydroxyl numbers of organopolysiloxanes (A3)-(A8), as well as the actual average hydroxyl numbers measured according to the titration method described above.

[0184] [Table 3]

[0185] Examples 1 to 10: Compositions Compositions for preparing release coatings were prepared. The compositions were two-part compositions, with (1) part (A) including (b1-1) an isocyanate-functional prepolymer and (b2) a polyisocyanate, and (2) part (B) including the remaining ingredients. Table 4 shows the relative amounts of the ingredients in each of the compositions of Examples 1-5. Table 5 shows the relative amounts of the ingredients in each of the compositions of Examples 6-10. Values ​​in Tables 4 and 5 are in grams (except for the NCO / OH Index, which is a unitless molar ratio).

[0186] Each composition was thoroughly blended using a mechanical stirrer at 1000 rpm for 1 minute. After mixing, each mixture was coated onto a substrate at room temperature with the aid of a coater at a controlled thickness of approximately 1 μm to obtain a wet deposit on the substrate. The wet deposit on the substrate was then placed in an oven set at a predetermined temperature (80° C.) for 30 seconds to determine whether the wet deposit had cured to obtain a release coating. The remaining volume of each composition was kept at room temperature for gel time determination based on visual inspection (based on the point at which the composition was no longer flowable). The results are also shown in Tables 4 and 5 below.

[0187] [Table 4]

[0188] [Table 5]

[0189] Examples 1-10: Release Coatings Release coatings were formed using the compositions of Examples 1-10. The release coating of Example 1 was prepared using the composition of Example 1, and so on. In each example, Part B of each composition was added to a container, followed by Part A, to obtain a mixture. The mixture was thoroughly blended using a mechanical stirrer at 1000 rpm for 1 minute. After mixing, each mixture was coated onto a substrate at room temperature with the aid of a coater at a controlled thickness of approximately 1 μm to obtain a wet deposit on the substrate. The wet deposit on the substrate was then placed in an oven set at a predetermined temperature (80°C) for 30 seconds to determine whether the wet deposit had cured to obtain a release coating. The remaining volume of each composition was kept at room temperature for gel time determination (based on when the composition was no longer flowable). The release coatings were evaluated as described above, and the results are shown in Tables 6 and 7 below.

[0190] [Table 6]

[0191] [Table 7]

[0192] Example 11: Determination of cure rate The composition of Example 7 was utilized to determine how quickly the composition could cure at 80°C to yield a release coating. Conventional compositions for preparing release coatings cure at temperatures above 80°C and require long cure times (e.g., greater than 1 minute) at temperatures as low as 80°C. Table 8 below shows the properties of the release coatings prepared in Example 11 based on different cure times at a cure temperature of 80°C. The quality of the release coatings was analyzed via visual inspection and touch to determine whether a particular release coating had sufficiently cured.

[0193] [Table 8]

[0194] As demonstrated in Table 8 above, the compositions of the present invention were able to cure in as little as 10 seconds at 80° C. to yield release coatings with excellent performance properties.

[0195] Examples 12-15 and Comparative Examples 1-5: Compositions and Release Coatings Compositions for preparing release coatings were prepared similarly to the corresponding release coatings. The compositions were two-part compositions, with (1) part (A) containing (b1-1) an isocyanate-functional prepolymer and (b2) a polyisocyanate, and (2) part (B) containing the remaining ingredients. Tables 9 and 10 show the relative amounts of the components in each of the compositions 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).

[0196] Each composition was thoroughly blended using a mechanical stirrer at 1000 rpm for 1 minute. After mixing, each mixture was coated onto a substrate at room temperature with the aid of a coater at a controlled thickness of approximately 1 μm to obtain a wet deposit on the substrate. The wet deposit on the substrate was then placed in an oven set at a predetermined temperature (90° C.) to determine whether the wet deposit had cured to obtain a release coating over a predetermined time. The remaining volume of each composition was kept at room temperature for gel time determination based on visual inspection (based on the point at which the composition was no longer flowable).

[0197] [Table 9]

[0198] [Table 10]

[0199] Examples 20-22: Compositions and Release Coatings Compositions for preparing release coatings were prepared similarly to the corresponding release coatings. The compositions were two-part compositions, with (1) part (A) containing (b1-1) an isocyanate-functional prepolymer and (b2) a polyisocyanate, and (2) part (B) containing the remaining ingredients. Tables 11 and 12 show the relative amounts of the components in each of the compositions 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).

[0200] Each composition was thoroughly blended using a mechanical stirrer at 1000 rpm for 1 minute. After mixing, each mixture was coated onto a substrate at room temperature with the aid of a coater at a controlled thickness of approximately 1 μm to obtain a wet deposit on the substrate. The wet deposit on the substrate was then placed in an oven set at a predetermined temperature (80° C.) for a predetermined time (30 seconds) to determine whether the wet deposit cured to obtain a release coating, with the exception of Example 18, which was cured at 90° C. for 30 seconds. The release 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, which lasted for 8 hours for each example.

[0201] [Table 11]

[0202] [Table 12]

Claims

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

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

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

4. 4. The composition of 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. 5. The composition of any one of claims 1 to 4, wherein: (i) the composition further comprises (C) a catalyst; (ii) the composition does not comprise a physical blowing agent; (iii) the composition does not comprise a chemical blowing agent; (iv) component (b1) comprises two isocyanate functional groups; (v) component (B) is prepared by combining components (b1) and (b2) prior to combining components (A) and (B) to obtain the composition; (vi) component (B) comprises component (b2) in an amount of greater than 10% to 90% by weight, based on the total weight of component (B); or (vii) any combination of (i) to (vi).

6. The organopolysiloxane (A) comprises: (i) at least one SiO ４／２ units, (ii) an average of three or more carbinol functional groups, (iii) at least one pendant carbinol functional group, (iv) at least one terminal carbinol functional group, or (v) any combination of (i)-(iv).

7. (i) the carbinol functional groups are the same as each other, or (ii) the carbinol functional groups are independently of each other and have the general formula -D-O ａ -(C ｂ H ２ｂ O) ｃ 7. The composition of any one of claims 1-6, having -H, wherein D is a covalent bond or a divalent hydrocarbon linking group having from 2 to 18 carbon atoms, subscript a is 0 or 1, subscript b is independently selected from 2 to 4 in each moiety designated by subscript c, and subscript c is 0 to 500, with the proviso that subscripts a and c are not simultaneously 0; or (iii) both (i) and (ii).

8. (i) the carbinol functional group is represented by 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 wherein D is a covalent bond or a divalent hydrocarbon linking group having from 2 to 18 carbon atoms, and the subscript a is 0 or 1, and 0≦d≦500, 0≦e≦500, and 0≦f≦500, with the proviso that 1≦d+e+f≦500; (ii) the carbinol functional group is pendant; or (iii) both (i) and (ii).

9. The organopolysiloxane (A) is (i) has the 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 wherein 0≦v≦12, 0≦w≦8, 0≦x≦8, 40≦y≦1,000, and 0≦z≦8, with the proviso that 2≦(x+z)≦8; １ are independently selected substituted or unsubstituted hydrocarbyl groups, each X is an independently selected carbinol functional group, and Z １ But 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 ) wherein each R １ are independently selected and defined above, and each D １ are independently selected divalent linking groups; or (ii) is the average formula R １ ３ O[SiR １ ２ O] ｗ [SiR １ XO] ｘ R １ ３ wherein each R １ and each X is independently selected and defined above, subscript w' is from 10 to 1000, and subscript x' is from 4 to 200.

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

11. 11. The composition of any one of claims 1-10, wherein (i) the composition does not include an organic polyol, (ii) the composition includes at least one of (D) an inhibitor, (E) a chain extender, and / or (F) a carrier vehicle, (iii) the composition is capable of curing to provide the release coating in less than 30 seconds when exposed to a temperature of 80°C, or (iv) any combination of (i)-(iii).

12. A release coating formed from the composition of any one of claims 1 to 11.

13. 1. A method of forming a coated substrate, the method comprising: applying a composition onto the substrate; and curing the composition to provide a release coating on the substrate, thereby forming the coated substrate; The method, wherein the composition is a composition according to any one of claims 1 to 11.

14. 14. The method of 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. 15. A coated substrate comprising a release coating disposed on a substrate, formed according to the method of claim 13 or 14.

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