Polyorganosiloxane hybrid pressure-sensitive adhesives and methods for preparing and using same

Abstract

The polydiorganosiloxanes having silicon-bonded poly(meth)acrylate polymers or copolymers are useful in polyorganosiloxane hybrid pressure-sensitive adhesive compositions that cure to form polyorganosiloxane hybrid pressure-sensitive adhesives. Adhesive articles comprising the polyorganosiloxane hybrid pressure-sensitive adhesives are also disclosed.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims the benefit under 35 U.S.C. §119(e) of U.S. Provisional Patent Application No. 63 / 012293, filed April 20, 2020. U.S. Provisional Patent Application No. 63 / 012293 is incorporated herein by reference.

[0002] FIELD OF THE INVENTION Polyorganosiloxanes having silicon-bonded poly(meth)acrylate groups (hereinafter "poly(meth)acrylate-grafted polyorganosiloxanes") are useful in radical-reaction-curable polyorganosiloxane hybrid pressure-sensitive adhesive (hybrid PSA) compositions. Methods for preparing and using hybrid PSAs from the compositions are also disclosed. [Background technology]

[0003] Polyorganosiloxanes and acrylates have been used as bases for pressure sensitive adhesives, and there is a need in the industry to provide pressure sensitive adhesives that have the properties of both polyorganosiloxanes and acrylates.

[0004] Acrylic chains can be incorporated into the polydimethylsiloxane backbone using free radical polymerization by conducting the polymerization in the presence of a mercapto-functional polydimethylsiloxane. The mercapto group acts as a chain transfer agent, allowing acrylic chains to be grafted onto the polydimethylsiloxane chain as pendant and / or terminal groups. However, if the mercapto-functional polydimethylsiloxane also contains vinyl or other aliphatically unsaturated monovalent hydrocarbyl functional groups, the reaction of the aliphatic unsaturated groups during free radical polymerization can saturate or crosslink the system. Furthermore, because chain transfer is a kinetically controlled process, low levels of mercapto functionality can result in low grafting efficiency. Therefore, an improved process for fabricating poly(meth)acrylate-grafted polyorganosiloxanes is desirable. Summary of the Invention

[0005] The polyorganosiloxane hybrid pressure sensitive adhesive (hybrid PSA) composition comprises: (I) a pressure-sensitive adhesive base comprising a physical mixture of starting materials (IA) and (IB), a reaction product of starting materials (IA) and (IB), or a combination of both the physical mixture and the reaction product, in an amount sufficient to provide 15% to 40% by weight of starting material (IA) and 5% to 60% by weight of starting material (IB), wherein: The starting material (IA) is a functional polyorganosiloxane having poly(meth)acrylate groups, said functional polyorganosiloxane having the unit formula: [R 3 w (R 5 -SR")(OR 4 ) (2-w) Si-O 1 / 2 ] p [R 3 v (R 5 -SR")(OR 4 ) (1-v) Si-O 2 / 2 ] q [(R 5-SR”)Si-O 3 / 2 ] k (R 6 R 7 2SiO 1 / 2 ) r (R 7 2SiO 2 / 2 ) s (R 6 R 7 SiO 2 / 2 ) t (R 7 3SiO 1 / 2 ) u wherein each subscript w is independently 0, 1, or 2; each subscript v is independently 0 or 1; and each R 3 are independently selected monovalent hydrocarbon groups, and each R 4 are independently selected alkyl groups, and each R 5 are independently selected divalent hydrocarbon groups, each R″ is independently a (meth)acrylate polymer or copolymer, and each R 6 is selected from the group consisting of hydroxyl groups and aliphatic unsaturated monovalent hydrocarbon groups, and each R 7 are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation, with subscript p≧0, subscript q≧0, subscript k≧0, the numbers (p+q+k)≧1, subscript r≧0, subscript s≧0, subscript t≧0, subscript u≧0, the numbers (r+t)≧1, and the numbers (p+q+k+r+s+t+u) are sufficient to provide the polyorganosiloxane with a molecular weight of at least 50 kDa; The starting material (IB) is a polyorganosilicate resin having the unit formula (R 15 2nd Round 16 SiO 1 / 2 ) x (R 15 3SiO 1 / 2 ) y (SiO 4 / 2 ) z [In the formula, R 15 is an alkyl group, an aryl group, or an aralkyl group, such as methyl and phenyl, and R 16is an alkenyl group of 2 to 18 carbon atoms, e.g., vinyl, allyl, or hexenyl; and the subscripts x, y, and z are mole fractions, where subscript x≧0, subscript y≧0, subscript z>0, the numbers (x+y)>0, the numbers (x+y+z)≦1, and the subscripts x, y, and z have values ​​such that 0.9≦(x+y) / z≦1.3; wherein the polyorganosilicate resin further comprises a hydroxyl group content of up to 5 wt. %, based on the weight of the polyorganosilicate resin; and the polyorganosilicate resin has a number average molecular weight of >1,500 Da as measured by gel permeation chromatography; (II) a peroxide catalyst, 6 is hydroxyl, the peroxide catalyst is present in an amount of 2% to 4% by weight, and each R 6 is an aliphatic unsaturated monovalent hydrocarbon group, the peroxide catalyst is present in an amount of 3% by weight to 4% by weight; and 0 to 70 wt. % of (III) a solvent, all percentages being by weight based on the total weight of all starting materials in the polyorganosiloxane hybrid pressure-sensitive adhesive composition.

[0006] Using the hybrid PSA composition described above, 1) coating a hybrid PSA composition onto the surface of a substrate; 2) curing the hybrid PSA composition to form a hybrid PSA on the surface of the substrate. [Brief explanation of the drawings]

[0007] [Figure 1]Scheme 1 shows a representative example of a (meth)acrylate polymer generated from a thiol functional group after a hydrogen atom is abstracted from either the free radical initiator fragment or the growing chain. The (meth)acrylate oligomer is then end-capped with a hydrogen atom from a different thiol molecule, thereby forming an alkoxysilyl-functional (meth)acrylate macromonomer. This is described below in Reference Example A. [Figure 2] A representative example of Scheme 2 for preparing a bis-vinyl terminated poly(meth)acrylate grafted polyorganosiloxane is shown below in Reference Example D. In Figure 2, a bis-vinyl terminated polydimethylsiloxane, a bis-hydroxyl terminated polydimethylsiloxane, and the alkoxysilyl functional (meth)acrylate macromonomer prepared in Scheme 1 in Figure 1 are reacted in the presence of a phosphazene catalyst and a solvent (toluene) to form a bis-vinyl terminated poly(meth)acrylate grafted polyorganosiloxane having the unit formula shown in the figure. [Figure 3] A representative example of Scheme 3 for preparing a bis-hydroxyl terminated poly(meth)acrylate grafted polyorganosiloxane is shown below in Reference Example C. In Figure 3, a bis-hydroxyl terminated polydimethylsiloxane and the alkoxysilyl functional (meth)acrylate macromonomer prepared in Scheme 1 in Figure 1 are reacted in the presence of a phosphazene catalyst and a solvent (toluene) to form a bis-hydroxyl functional grafted poly(meth)acrylate grafted polyorganosiloxane having the unit formula shown in the figure. DETAILED DESCRIPTION OF THE INVENTION

[0008] A method for producing a product comprising a poly(meth)acrylate-grafted polyorganosiloxane is disclosed. The method comprises: I) A) an alkoxysilyl-functional (meth)acrylate macromonomer; B) a polydiorganosiloxane, B1) an unsaturated polydiorganosiloxane having at least one silicon-bonded aliphatic unsaturated group per molecule; B2) a hydroxyl-functional polydiorganosiloxane having at least two silicon-bonded hydroxyl groups per molecule, and B3) a polydiorganosiloxane selected from the group consisting of a combination of B1) and B2); C) a condensation reaction catalyst; optionally, D) a polydialkylsiloxane; and optionally, E) a solvent; and combining starting materials, thereby producing a product and by-products comprising a poly(meth)acrylate-grafted polyorganosiloxane; II) removing all or part of the by-products during and / or after step I); Optionally, III) neutralizing the product; and Optionally, IV), recovering the poly(meth)acrylate-grafted polyorganosiloxane; Includes:

[0009] Step I) in the present process can be carried out by any convenient means, such as by mixing. Step I) can be carried out under inert conditions, such as under nitrogen or other inert gas. Combining the starting materials can be carried out by heating at an elevated temperature, for example, 80°C to 120°C. A solvent can be optionally added, for example, to facilitate the combining of the starting materials. Combining the starting materials can be carried out, for example, by combining A) an alkoxysilyl-functional (meth)acrylate macromonomer with B) a polydiorganosiloxane (e.g., B1) an unsaturated polydiorganosiloxane and / or B2) a hydroxyl-functional polydiorganosiloxane) and / or D) a polydialkylsiloxane in any order. The resulting mixture is then heated, after which C) a condensation reaction catalyst can be added, optionally dissolved in E) a solvent. Without being bound by theory, it is believed that adding E) a solvent can be beneficial for producing poly(meth)acrylate-grafted polyorganosiloxanes with high MW. When the starting materials react, by-products are generated. These by-products may include water and / or alcohol (e.g., methanol). All or a portion of the by-products can be removed during and / or after step I). Without being bound by theory, it is believed that removing the by-products can drive the reaction to completion and / or facilitate an increase in MW. The by-products can be removed by any convenient means, such as stripping.

[0010] Step III) in the present process is neutralization of the product. Neutralization can be carried out during or after step II) by adding F) a neutralizing agent to the product. Neutralization can be carried out at ambient temperature or at an elevated temperature. Step IV) in the present process is recovery of the poly(meth)acrylate-grafted polyorganosiloxane. Recovery of the poly(meth)acrylate-grafted polyorganosiloxane can be carried out by any convenient means, such as filtration, stripping, and / or distillation. The starting materials used in the above process are as follows:

[0011] The starting material A), i.e., the alkoxysilyl-functional (meth)acrylate macromonomer used in the above process, is represented by the formula A-1)

[0012] [ka] [In the formula, each R 3 are independently selected monovalent hydrocarbon groups, and each R 4 are independently selected alkyl groups, and R 5 is a divalent hydrocarbon group; R" is a (meth)acrylate polymer or copolymer; and subscript a is 0, 1, or 2. R" may have a DP of 1 to 1,000, alternatively 5 to 600. Alternatively, the alkoxysilyl-functional (meth)acrylate macromonomer may have the formula A-2)

[0013] [ka] [In the formula, each R 1 are independently selected from the group consisting of hydrogen and alkyl groups; R 2 are independently selected from the group consisting of hydrogen, alkyl groups, aryl groups, and aralkyl groups; the subscript n is 1 to 1,000; R 3 , R 4 , and R 5 is as above].

[0014] Alternatively, in formula A-2), the subscript n may be 5 to 600. 1 Suitable alkyl groups for R may be alkyl groups having 1 to 4 carbon atoms, or may be methyl or ethyl. Alternatively, each R 1 R may be methyl. 2 Suitable alkyl groups for R may have 1 to 18 carbon atoms, alternatively 1 to 8 carbon atoms. 2 Suitable alkyl groups for R include methyl, ethyl, propyl, and butyl. 2 Suitable aryl groups for R have 6 to 18 carbon atoms and include phenyl; 2Suitable aralkyl groups for have 6 to 18 carbon atoms and include styryl. Alternatively, in formula A-2), each R 2 may be an independently selected alkyl group having 1 to 18 carbon atoms, alternatively 1 to 8 carbon atoms.

[0015] Alternatively, in formulae A-1) and A-2), the subscript a may be 1 or 2, alternatively 1 or 2. Each R 3 R may be an independently selected monovalent hydrocarbon group having 1 to 18 carbon atoms. 3 Suitable monovalent hydrocarbon groups for include alkyl groups (e.g., methyl, ethyl, propyl, and butyl), and alkenyl groups (e.g., vinyl, allyl, and hexenyl), aryl groups such as phenyl, and aralkyl groups such as benzyl, tolyl, xylyl, and phenylethyl. Alternatively, each R 3 may be independently selected from the group consisting of alkyl and alkenyl. Alternatively, each R 3 may be an alkyl group having 1 to 8 carbon atoms. Alternatively, each R 3 may be selected from the group consisting of methyl and vinyl.

[0016] Each R 4 R may be an independently selected alkyl group having 1 to 6 carbon atoms. 4 Suitable alkyl groups for may be methyl, ethyl, propyl and butyl, alternatively methyl.

[0017] Each R 5 may be a divalent hydrocarbon group having 1 to 18 carbon atoms. R 5 Suitable divalent hydrocarbon groups include alkylene groups such as ethylene (-CH-CH-), propylene (e.g., -CH-CH-CH- or -CH(CH)CH-), butylene, or hexylene, arylene groups such as phenylene, or alkarylene groups such as

[0018] [ka] Alternatively, R 5 may be an alkylene group having 2 to 6 carbon atoms, for example, propylene.

[0019] The starting material (A), ie, the alkoxysilyl-functional (meth)acrylate macromonomer, may have a glass transition temperature (Tg) greater than -52°C as calculated using the Fox equation.

[0020]

number

[0021] The amount of starting material A) used in the process for producing the above-described poly(meth)acrylate-grafted polyorganosiloxane-containing product depends on various factors, however, starting material A) may be used in an amount of 4% to 11%, based on the combined weight of starting materials A) and B) of the process. Alternatively, the amount of starting material A) may be 1% to 50%, alternatively 5% to 10%, alternatively 5% to 9%, on the same basis.

[0022] Alkoxysilyl-functional (meth)acrylate monomers suitable for use as starting material A) can be prepared by known methods, for example, by the method disclosed in U.S. Patent No. 6,733,884 (Brown). Alternatively, the alkoxysilyl-functional (meth)acrylate can be prepared by the method 1) i) Formula (where R 1 and R 2 as defined above), i) a (meth)acrylate monomer of the formula

[0023] [ka] wherein R1 and R2 are as defined above; and ii) Equation

[0024] [ka] [In the formula, R 3 , R 4 , R 5 and subscript a is as defined above; optionally, iii) a free radical initiator; and combining the starting materials, optionally including iv) a solvent, thereby producing a product comprising an alkoxysilyl-functional (meth)acrylate macromonomer; Optionally, 2) A) recovering the alkoxysilyl-functional (meth)acrylate macromonomer.

[0025] In this method, i) (meth)acrylate monomer can be combined with iv) solvent, if present, before step 1). The solvent can be optionally dried and then combined with starting material i) and / or any other starting materials. Alternatively, i) (meth)acrylate monomer, ii) mercapto-functional alkoxysilane, and iv) solvent, if present, can be combined before step 1). The resulting combination can be heated, for example, to 50°C or 150°C in a reactor. The reaction of starting materials i) and ii) can be driven by heating sufficient to generate free radicals. Alternatively, iii) free radical initiator can be dissolved, optionally, in iv) solvent and added to the reaction vessel. Step 1) can be carried out under inert conditions, for example, by purging the reactor with nitrogen. The starting materials in step 1) can be combined by mixing, heating, or both. For example, mixing and heating can be performed by heating from 50°C to the reflux temperature of the starting materials, or from 50°C to 150°C, or from 50°C to 110°C, or from 50°C to 100°C, or from 75°C to 85°C, for 1 to 6 hours. The starting materials can be added in any order; however, iii) the free radical initiator can be dissolved in iv) a solvent and optionally combined with i) the (meth)acrylate monomer, and then the resulting combination can be added to a reactor containing ii) the mercapto-functional alkoxysilane. Alternatively, i) the (meth)acrylate monomer and ii) the mercapto-functional alkoxysilane can be combined to form a mixture, and then iii) the free radical initiator can be added to the mixture. Without being bound by theory, it is believed that the resulting alkoxysilyl-functional (meth)acrylate macromonomer (produced using this addition order) has a different molecular weight distribution than when a different addition order is used.

[0026] Step 2) Recovering the alkoxysilyl-functional (meth)acrylate macromonomer can be carried out by any convenient means, such as by cooling the reaction product prepared in step 1) to RT and precipitating in a non-solvent (alkane such as hexane or an alcohol such as methanol) to precipitate the alkoxysilyl-functional (meth)acrylate macromonomer. Optionally, recovering may further comprise drying the precipitate, for example, by heating at atmospheric or reduced pressure, e.g., to 80°C to 100°C, to remove residual monomer, solvent, or both.

[0027] In the method for preparing the alkoxysilyl-functional (meth)acrylate macromonomer, the starting material i) is a (meth)acrylate monomer. A suitable (meth)acrylate monomer is represented by the formula i-1):

[0028] [ka] [In the formula, R 1 and R 2 are as described above. Suitable (meth)acrylate monomers are known in the art and commercially available, and some examples are shown in Table 1. The amount of starting material i) can be 20% to 99.8%, alternatively 30% to 90%, alternatively 70% to 75%, based on the combined weight of starting materials i), ii), iii), and iv).

[0029] [Table 1] a T from the Polymer Properties Database (polymerdatabase.com) g .

[0030] In the method for preparing the alkoxysilyl-functional (meth)acrylate macromonomer, the starting material ii) is a mercapto-functional alkoxysilane. The mercapto-functional alkoxysilane is represented by the formula ii-1):

[0031] [ka] [wherein the subscript a and R 3 , R 4 , and R 5 wherein R is as defined above. Suitable mercapto-functional alkoxysilanes are known in the art and commercially available. These include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 11-mercaptoundecyltrimethoxysilane, (mercaptomethyl)methyldiethoxysilane, and 3-mercaptopropylmethyldimethoxysilane, all of which are commercially available from Gelest, Inc. (Morrisville, Pennsylvania, USA). Alternatively, mercapto-functional alkoxysilanes such as those described above, as well as mercapto-functional monoalkoxysilanes, such as 3-mercaptopropyldimethylmethoxysilane and 3-mercaptopropyldimethylethoxysilane, can be synthesized by known methods, such as those disclosed in U.S. Patent Application Publication No. 2005 / 0124821 and Agina, EV, ACS Applied Materials & Interfaces, 2015, 22, 11755-11764. The amount of starting material ii) can be 0.1% to 50%, alternatively 1% to 10%, alternatively 1% to 8%, based on the combined weight of starting materials i), ii), iii), and iv).

[0032] The starting material iii) for preparing the alkoxysilyl-functional (meth)acrylate macromonomer is a free radical initiator. The free radical initiator may be selected from the group consisting of iii-1) azo compounds, iii-2) peroxides (e.g., hydroxyperoxides, peracids, and peresters (e.g., tert-alkylperoxypivalates), and iii-3) combinations thereof. Suitable free radical initiators are known in the art; see, for example, U.S. Pat. No. 8,258,243 (column 2, lines 9-34). Alternatively, suitable free radical initiators are commercially available. For example, tert-alkylperoxypivalates are commercially available from Akzo Nobel; for example, tert-amylperoxypivalate is available as Trigonox 125-C75, and tert-butylperoxypivalate is available as Trigonox 25-C75. The amount of starting material iii) can be 0 to 5%, alternatively 0.1% to 2%, alternatively 1% to 2%, based on the combined weight of starting materials i), ii), iii), and iv).

[0033] A solvent can be used in the above process. One or more of the starting materials for use in producing the alkoxysilyl-functional (meth)acrylate macromonomer can be dissolved in iv) a solvent and then combined with other starting materials. For example, a free radical initiator can be dissolved in mineral spirits. Alternatively, the solvent can be selected from the group consisting of iv-1) hydrocarbons having a boiling point above 100°C (e.g., aromatic hydrocarbons such as toluene or xylene), iv-2) polar solvents (acetone, methyl ethyl ketone, methyl acetate, ethyl acetate, acetonitrile, methanol, isopropanol, or tert-butanol), iv-3) silicone oils (e.g., the silicone oil can be a polydialkylsiloxane, as described below), and iv-4) combinations of two or more thereof. Alternatively, the solvent can be toluene, which, for example, can facilitate the combination of starting material A) with other starting materials to produce a poly(meth)acrylate-grafted polyorganosiloxane. When polydialkylsiloxane is used as a solvent, the polydialkylsiloxane can serve as a starting material in a process for producing a product comprising poly(meth)acrylate-grafted polyorganosiloxane. When toluene is used, a solvent exchange need not be included in the process for producing a product comprising poly(meth)acrylate-grafted polyorganosiloxane. The amount of starting material iv) can be 0 to 70%, alternatively 0 to 25%, based on the combined weight of starting materials i), ii), iii), and iv).

[0034] In a method for producing a product comprising a poly(meth)acrylate-grafted polyorganosiloxane, starting material B) is a polydiorganosiloxane. The polydiorganosiloxane is selected from the group consisting of B1) unsaturated polydiorganosiloxanes having at least one silicon-bonded aliphatic unsaturated group per molecule, B2) hydroxyl-functional polydiorganosiloxanes having at least two silicon-bonded hydroxyl groups per molecule, and B3) a combination of both B1) and B2). When starting material B1) is used, the poly(meth)acrylate-grafted polyorganosiloxane has both silicon-bonded aliphatic unsaturated groups and silicon-bonded poly(meth)acrylate groups.

[0035] The starting material B1) is an unsaturated polydiorganosiloxane having at least one silicon-bonded aliphatic unsaturated group per molecule, which may be in terminal, pendant, or both terminal and pendant positions.

[0036] The starting material B1), i.e. the unsaturated polydiorganosiloxane, has the unit formula B1-1):(R 6 R 7 2SiO 1 / 2 ) b (R 7 2SiO 2 / 2) c (R 6 R 7 SiO 2 / 2 ) d (R 7 3SiO 1 / 2 ) e (R'OR 7 2SiO 1 / 2 ) f (R'OR7SiO 2 / 2 ) g [In the formula, each R 6 are independently selected aliphatic unsaturated hydrocarbon groups, and each R 7 is an independently selected monovalent hydrocarbon group free of aliphatic unsaturation, and each R' is selected from H and R 7and wherein subscript b is 0, 1, or 2, subscript c≧1, subscript d≧0, subscript e is 0, 1, or 2, subscript f is 0, 1, or 2, and subscript g≧0, with the proviso that the numbers (b+d)≧1, the numbers (b+e+f)=2, and the numbers (b+c+d+e+f+g) are at least 3, alternatively 3-250.

[0037] R 6 The aliphatic unsaturated hydrocarbon group may have 2 to 18 carbon atoms and is exemplified by alkenyl, such as vinyl, allyl, or hexenyl, and alkynyl, such as propynyl, butynyl, or hexynyl. Alternatively, each R 6 may be an alkenyl group. Alternatively, each R 6 may be a vinyl group.

[0038] R 7 The monovalent hydrocarbon groups free of aliphatic unsaturation may have 1 to 18 carbon atoms and include alkyl, aryl, and aralkyl groups, or alkyl and aryl groups. Suitable alkyl groups may be methyl, ethyl, and propyl, or methyl. Suitable aryl groups include phenyl. Alternatively, each R 7 may be an alkyl group, for example methyl.

[0039] Alternatively, in unit formula B1-1), subscript b may be 0 or 2, subscript e may be 0 or 2, and subscript g may be 0. Alternatively, subscript c may be 1 to 250, subscript d may be 0 to 1, subscript g may be 0 to 1, and the numerical value (c + d + g) may be 1 to 250. Alternatively, the numerical value (b + e) ​​may be 2. Alternatively, subscript c may be 1 to 100, or 10 to 75, or 25 to 75, or 30 to 60. Alternatively, subscript d may be 0 to 50, or 0 to 25, or 0 to 10, or 0 to 5. Alternatively, subscript g may be 0 to 50, or 0 to 25, or 0 to 10, or 0 to 5. Subscript b is 0 to 2, or subscript b can be 0, or subscript b can be 2. Subscript e is 0 to 2, or subscript e can be 0, or subscript e can be 2. Subscript f is 0 to 2, or subscript f can be 0, or subscript f can be 2.

[0040] Starting material B1) may contain both silicon-bonded aliphatic unsaturated hydrocarbon groups and silicon-bonded hydroxyl groups. Examples of starting material B1) containing both silicon-bonded aliphatic unsaturated groups and silicon-bonded hydroxyl groups include OH-terminated polymethylvinylsiloxane and OH-terminated poly(dimethyl / methylvinyl)siloxane copolymer, both commercially available from Gelest. See, for example, "Gelest Reactive Silicones: Forging New Polymer Links," 2016, https: / / www.gelest.com / wp-content / uploads / Reactive-SIlicones-No-Price-2016.pdf, page 11. Alternatively, starting material B1) may have silicon-bonded aliphatic unsaturated hydrocarbon groups, silicon-bonded hydroxyl groups, and silicon-bonded alkoxy groups. An example of such a material is DOWSIL™ 4-7042, commercially available from Dow Silicones Corporation (Midland, Michigan, USA), which is a mixture of hydroxyl-terminated poly(dimethyl,methylvinylsiloxane) and α-hydroxyl-terminated, ω-methoxy-terminated poly(dimethyl,methylvinylsiloxane). When starting material B1) contains both silicon-bonded aliphatically unsaturated hydrocarbon groups and sufficient silicon-bonded hydroxyl groups, starting material B2), a hydroxyl-functional polydiorganosiloxane, is optional.

[0041] Alternatively, in the above unit formula B1-1), the number (f+g) may be less than 2 (thereby, starting material B1) may have less than two silicon-bonded hydroxyl groups per molecule). Examples of suitable unsaturated polydiorganosiloxanes include: Bi) dimethylvinylsiloxy-terminated polydimethylsiloxane, B-ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), B-iii) dimethylvinylsiloxy-terminated polymethylvinylsiloxane, B-iv) trimethylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), Bv) trimethylsiloxy-terminated polymethylvinylsiloxane, B-vi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylvinylsiloxane), B-vii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylphenylsiloxane), B-viii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / diphenylsiloxane), B-ix) phenyl, methyl, vinyl-siloxy terminated polydimethylsiloxane; Bx) dimethylhexenylsiloxy-terminated polydimethylsiloxane, B-xi) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), B-xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane, B-xiii) trimethylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), B-xiv) trimethylsiloxy-terminated polymethylhexenylsiloxane, B-xv) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), B-xvi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane / methylhexenylsiloxane), B-xvii) Combinations thereof. Vinyl-functional polydiorganosiloxanes are available; see, for example, "Gelest Reactive Silicones: Forging New Polymer Links," 2016, https: / / www.gelest.com / wp-content / uploads / Reactive-SIlicones-No-Price-2016.pdf, pages 8-11 and 15-16. If starting material B1) does not contain sufficient silicon-bonded hydroxyl groups, starting material B2) is used in the above method. The amount of starting material B1) used in the method depends on various factors, including whether B1) has terminal, pendant, or both terminal and pendant aliphatic unsaturation. However, the amount of starting material B1) is sufficient to provide 0.1% to 10%, or alternatively 0.1% to 2%, of aliphatic unsaturation in all of the starting materials in step I) of the method for producing a product comprising a poly(meth)acrylate-grafted polyorganosiloxane. Alternatively, the amount of starting material B1) may be from 0.5% to 5%, alternatively from 1% to 4%, alternatively from 1% to 3%, based on the combined weight of starting materials A) and B). Alternatively, if B1) has a hydroxyl function and no starting material B2) is used, starting material B1) may be present in a higher amount, for example up to 90%.

[0042] In the process for preparing a product comprising a poly(meth)acrylate-grafted polyorganosiloxane, starting material B2) is a hydroxyl-functional polydiorganosiloxane having at least two silicon-bonded hydroxyl groups per molecule. The hydroxyl groups may be in terminal positions, pendant positions, or both. Starting material B2) is a polydiorganosiloxane having the unit formula B2-1):(R 8 2SiO 2 / 2 ) h (R 8 3SiO 1 / 2 )i(HOR 8 2SiO 1 / 2 ) j [In the formula, each R 8is an independently selected monovalent hydrocarbon radical free of aliphatic unsaturation, subscript j is 1 or 2, subscript i is 0 or 1, the number (j+i)=2, subscript h≧1, and the number (h+i+j) is at least 3, alternatively from 3 to 250, alternatively from 3 to 100. Alternatively, subscript h may be from 1 to 250, alternatively from 1 to 100. Alternatively, i may be 0 and j may be 2. R 8 The monovalent hydrocarbon groups include alkyl, aryl, and aralkyl groups, or alkyl and aryl groups. Suitable alkyl groups may be methyl, ethyl, and propyl, or methyl. Suitable aryl groups include phenyl. Alternatively, each R 8 may be an alkyl group, such as methyl. Examples of starting materials B2) include hydroxyl-terminated polydimethylsiloxane, hydroxyl-terminated poly(dimethyl / diphenyl)siloxane copolymer, and hydroxyl-terminated poly(dimethyl / methylphenyl)siloxane copolymer. Alternatively, suitable bishydroxyl-terminated polydimethylsiloxanes are commercially available from Dow Silicones Corporation (Midland, Michigan, USA). Exemplary hydroxyl-functional polydiorganosiloxanes are commercially available, including the silanol-functional polymers in "Gelest Reactive Silicones: Forging New Polymer Links," 2016, https: / / www.gelest.com / wp-content / uploads / Reactive-SIlicones-No-Price-2016.pdf, pages 22 and 24-25. Starting material B2) can be used in an amount of 80% to 95% by weight, alternatively 85% to 95% by weight, alternatively 87% to 94% by weight, alternatively 89% to 94% by weight on the same basis, based on the total weight of starting materials A) and B).

[0043] In the method for producing a product comprising a poly(meth)acrylate-grafted polyorganosiloxane, starting material C) is a phosphazene condensation catalyst, such as a phosphonitrile halide. Without being bound by theory, it is believed that when a phosphazene condensation catalyst is used in the method, the formation of cyclic siloxane by-products (such as octamethylcyclotetrasiloxane) can be minimized.

[0044] Phosphazene condensation catalysts are exemplified by those disclosed in U.S. Patent No. 9,051,428. Exemplary phosphazene condensation catalysts may contain at least one -(N=P<)- unit per molecule and may be oligomers having up to 10 such phosphazene units, e.g., an average of 1.5 to 5 phosphazene units. The phosphazene condensation catalyst may be, for example, a halophosphazene, e.g., a chlorophosphazene (phosphonitrile chloride), an oxygen-containing halophosphazene, or an ionic derivative of a phosphazene, e.g., a phosphazenium salt, e.g., an ionic derivative of a phosphonitrile halide, e.g., a perchlorooligophosphazenium salt.

[0045] One suitable class of phosphazene condensation reaction catalysts are oxygen-containing chlorophosphazenes, such as oxygen-containing chlorophosphazenes, such as those represented by the formula C-1:

[0046] [ka] , or C-2):

[0047] [ka] In formulae C-1) and C-2), the subscript p may have an average value of 1 to 10, alternatively 1 to 5. The catalyst may also include tautomers of the catalyst of formula C-2). Another class of suitable oxygen-containing chlorophosphazenes is represented by formula C-3):

[0048] [ka] [In the formula, R 9 but an organosilicon moiety bonded to phosphorus through oxygen, e.g., formula C-4):

[0049] [ka] (In the formula, each R 10 represents a monovalent hydrocarbon group having 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group having 1 to 18 carbon atoms, and the subscript q has an average value of 1 to 10, alternatively 1 to 5. The catalyst may also include condensation products of such organosilicon-containing phosphazenes. All or a portion of the chlorine atoms in any of the above oxygen-containing phosphazenes can be replaced with a group Q, where Q represents a moiety selected from the group consisting of a hydroxyl group, a monovalent organic group such as an alkoxy or aryloxy, a halogen atom other than chlorine, an organosilicon group, and a phosphorus-containing group.

[0050] Another suitable class of phosphazene catalysts is represented by formula C-5):

[0051] [ka] wherein the subscript o has an average value of 1 to 10, and Z - represents an anion. Alternatively, the subscript o may have an average value of 1 to 6, or the subscript o may have an average value of 2. The anion may be a complex anion, for example, a perchlorooligophosphazenium salt of the formula MX (v+1) [wherein M is an element having an electronegativity on the Pauling scale of 1.0 to 2.0 and a valence v, and X is a halogen atom]. The element M may be, for example, phosphorus or antimony, or phosphorus. The halogen atom of X may be Cl. Alternatively, the anion Z - is expressed as [MX (v-y+1) R11 y ] - [In the formula, each R 11 is an independently selected alkyl group having 1 to 12 carbon atoms, and the subscript y has a value from 0 to v. Alternatively, in formula C-5), the subscript o may have an average value of 2, and the anion Z - But PCl6 - may be.

[0052] The phosphazene condensation reaction catalyst may be present in an amount of from 1 to 200, alternatively from 2 to 200 parts per million, such as from 5 to 50 parts per million, based on the combined weight of starting materials A) and B).

[0053] Starting material D) is an optional polydialkylsiloxane that can be added in step I) of the process for producing a product comprising a poly(meth)acrylate-grafted polyorganosiloxane. The polydialkylsiloxane has the unit formula D-1):(R 12 2SiO 2 / 2 ) m (R 12 3SiO 1 / 2 )2[where each R 12 are independently selected alkyl groups, and the subscript m is 1 to 250, alternatively 1 to 50. 12Suitable alkyl groups for may be methyl, ethyl, and propyl, or alternatively methyl. Examples of starting materials D) include Di) trimethylsiloxy-terminated polydimethylsiloxane, Dii) triethylsiloxy-terminated polydiethylsiloxane, and Diii) a combination of Di) and Dii). Polydialkylsiloxanes are known in the art and commercially available. For example, methylsilicone fluids, such as trimethylsiloxy-terminated polydimethylsiloxane, are commercially available from Gelest, see, for example, "Gelest Silicone Fluids," https: / / www.gelest.com / themencode-pdf-viewer / ?file=https: / / www.gelest.com:443 / wp-content / uploads / Inert_Silicones.pdf, 2012, pages 8-9, and are available from Dow Silicones Corporation (Midland, Michigan, USA) under the trade name DOWSIL™ 200 fluid. Trimethylsiloxy-terminated polydimethylsiloxane and triethylsiloxy-terminated polydiethylsiloxane are available from Power Chemical Corporation (Jiangsu, China). The amount of starting material D) depends on various factors, including the molecular weight of the selected polydialkylsiloxane; however, if used, the amount may be 1% to 10% based on the weight of starting materials A) to D) used in the process.

[0054] Starting material E) is a solvent that can be used in the above process. The solvent can be an aromatic hydrocarbon such as toluene or xylene, or ethyl acetate. The amount and type of solvent is selected to solubilize both the polyorganosiloxane and the (meth)acrylate polymer or copolymer. However, when present, the solvent can be used in an amount of 30% to 80%, or alternatively 40% to 70%, based on the combined weight of starting materials A), B), C), D), and E).

[0055] Starting material F) is a neutralizing agent that can be optionally used in step III) of the method for producing a product comprising the above-mentioned poly(meth)acrylate-grafted polyorganosiloxane. Starting material F) can be used to neutralize the product after the formation of the poly(meth)acrylate-grafted polyorganosiloxane. When a neutralizing agent is used, any neutralizing agent suitable for the selected catalyst can be used, see, for example, the neutralizing agents disclosed in U.S. Pat. No. 8,580,862. Without being bound by theory, it is believed that the selection of the neutralizing agent depends on the pKa and solubility. Suitable neutralizing agents for phosphazene-based condensation catalysts include, but are not limited to, alkylamines such as trioctylamine, trimethylamine, triethylamine, trihexylamine, and triisononylamine. Neutralizing agents are known in the art and are commercially available, for example, from Millipore Sigma (St. Louis, Missouri, USA). The amount of neutralizing agent will vary depending on various factors, including the amount of starting material C), condensation catalyst, but starting material F) may be present in an amount sufficient to provide a molar ratio of neutralizing agent to catalyst (F:C ratio) of from 1:1 to 100:1, alternatively from 1:1 to 30:1, alternatively from 1:1 to 20:1.

[0056] Poly(meth)acrylate-grafted polyorganosiloxane The above method produces a poly(meth)acrylate-grafted polyorganosiloxane having the unit formula: [R 3 w (R 5 -SR")(OR 4 ) (2-w) Si-O 1 / 2 ] p [R 3 v (R 5 -SR")(OR 4 ) (1-v) Si-O 2 / 2 ] q [(R 5 -SR”)Si-O3 / 2 ] k (R 6 R 7 2SiO 1 / 2 ) r (R 7 2SiO 2 / 2 ) s (R 6 R 7 SiO 2 / 2 ) t (R 7 3SiO 1 / 2 ) u wherein each subscript w is independently 0, 1, or 2; each subscript v is independently 0 or 1; and each R 3 are independently selected monovalent hydrocarbon groups, and each R 4 are independently selected alkyl groups, and each R 5 are independently selected divalent hydrocarbon groups, each R″ is independently a (meth)acrylate polymer or copolymer, and each R 6 are independently selected from the group consisting of hydroxyl groups and aliphatic unsaturated monovalent hydrocarbon groups, and each R 7 are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation, wherein subscript p≧0, subscript q≧0, subscript k≧0, the numbers (p+q+k)≧1, subscript r≧0, subscript s≧0, subscript t≧0, subscript u≧0, the numbers (r+t)≧2, and the numbers (p+q+k+r+s+t+u) are sufficient to provide the poly(meth)acrylate-grafted polyorganosiloxane with a molecular weight of at least 50 kDa.

[0057] Alternatively, the subscript w is 1 or 2. Alternatively, the subscript p is 0 to 2, or 1 or 2. Alternatively, the subscript q is 0 to 100. Alternatively, the subscript k is < 5. Alternatively, k may be 0, 1, or 2, or k = 0. Alternatively, the number (p + q + k) is 1 to 100. Alternatively, the subscript r is 0 to 2. Alternatively, the subscript s is 0 to 100. Alternatively, the subscript t is 0 to 100. Alternatively, the subscript u is 0 to 2. Alternatively, the numbers (p+q+r+s+t+u) are sufficient to provide a molecular weight of from 50 kDa to 1,000 kDa for the poly(meth)acrylate-grafted polyorganosiloxane, alternatively from 60 kDa to 1,000 kDa, alternatively from 50 kDa to 600 kDa, alternatively from 60 kDa to 300 kDa. Alternatively, the numbers (p+r+u)=2. Alternatively, the numbers (p+q) are from 1 to 100. Alternatively, the numbers (r+t) are from 1 to 100. Alternatively, the numbers (p+q+r+s+t+u) are sufficient to provide a molecular weight of from 50 kDa to 1,000 kDa for the functionalized polyorganosiloxane.

[0058] Alternatively, in the above poly(meth)acrylate-grafted polyorganosiloxane unit formula, each R 3 may have 1 to 18 carbon atoms. Alternatively, each R 3 may be an alkyl group of 1 to 6 carbon atoms. Alternatively, each R 4 may have 1 to 6 carbon atoms. Alternatively, each R 4 may be an alkyl group of 1 to 6 carbon atoms. Alternatively, each R 5 may have 1 to 18 carbon atoms. Alternatively, each R 5 may be an alkenyl group of 2 to 8 carbon atoms. Alternatively, each R 6 may be a hydroxyl group or an alkenyl group of 2 to 18 carbon atoms. Alternatively, each R 6 may be a hydroxyl group or an alkenyl group selected from vinyl, allyl, and hexenyl. Alternatively, R 6There may be two or more instances of R per molecule. 6 Two or more instances of R are aliphatically unsaturated monovalent hydrocarbon groups. Alternatively, each R 6 may be a hydroxyl group. Alternatively, each R 7 may have 1 to 18 carbon atoms. Alternatively, each R 7 may be an alkyl group of 1 to 6 carbon atoms. Alternatively, each R" may have a DP of 1 to 1,000, alternatively 5 to 600.

[0059] Radical reaction curable hybrid pressure-sensitive adhesive composition The poly(meth)acrylate-grafted polyorganosiloxanes described above are useful starting materials (IA) in radical-reaction-curable hybrid PSA compositions (hybrid PSA compositions). (I) A pressure-sensitive adhesive base may include a physical mixture of starting materials (IA) and (IB), a reaction product of starting materials (IA) and (IB), or a combination of both the physical mixture and the reaction product, in an amount sufficient to provide 15% to 40% by weight of starting material (IA) and 5% to 60% by weight of starting material (IB), wherein starting material (IA) is the poly(meth)acrylate-grafted polyorganosiloxane described above and starting material (IB) is a polyorganosilicate resin. Alternatively, starting material (IA) may be present in an amount of 17% to 25% by weight. Alternatively, starting material (IB) may be present in an amount of 25% to 40% by weight. Alternatively, the base may include a reaction product of starting materials (IA) and (IB). Alternatively, starting material (IA) may include R as the hydroxyl group. 6 The hybrid PSA composition may comprise all or a portion of (IA) and (IB), and the base may comprise the reaction product of starting materials (IA) and (IB). The hybrid PSA composition may further comprise (II) a peroxide catalyst. The hybrid PSA composition may optionally further comprise (III) a solvent.

[0060] (IB) Polyorganosilicate resin Polyorganosilicate resins for use as starting materials (IB) in hybrid PSA compositions are R 14 3SiO 1 / 2 Units and SiO 4 / 2 Units [wherein, each R 14 are independently selected from the group consisting of hydroxyl groups and monovalent hydrocarbon groups. 14 The monovalent hydrocarbon group may be selected from the group consisting of alkyl groups of 1 to 18 carbon atoms, alkenyl groups of 2 to 18 carbon atoms, and aryl or aralkyl groups of 6 to 18 carbon atoms. Suitable alkyl, alkenyl, aryl, and aralkyl groups are as defined below. Alternatively, each R 14 may be a hydroxyl group or an alkyl group, such as methyl.

[0061] Alternatively, the polyorganosilicate resin may be a polyorganosilicate having the unit formula: (R 15 2nd Round 16 SiO 1 / 2 ) x (R 15 3SiO 1 / 2 ) y (SiO 4 / 2 ) z [In the formula, R 15 is an alkyl group, an aryl group, or an aralkyl group, such as methyl and phenyl, and R 16 is an alkenyl group having 2 to 18 carbon atoms, such as vinyl, allyl, or hexenyl, and the subscripts x≧0, y≧0, and z>0, and the numbers (x+y)>0, and the subscripts x, y, and z have values ​​such that 0.9≦(x+y) / z and ≦1.3. Alternatively, the polyorganosilicate resin may comprise a unit of formula III): (R 15 3SiO 1 / 2 ) w (SiO 4 / 2 ) z [In the formula, each R 15 is as above, subscript z is as above, and subscript w>4.

[0062] The polyorganosilicate resin may contain an average of 0 to 30 mole percent alkenyl groups, alternatively 3 to 30 mole percent, alternatively 0.1 to 30 mole percent, alternatively 0.1 to 5 mole percent, or alternatively 3 to 10 mole percent alkenyl groups. The mole percent alkenyl groups in the resin is the ratio of the number of moles of alkenyl-containing siloxane units in the resin to the total number of moles of siloxane units in the resin multiplied by 100.

[0063] The Mn of the polyorganosilicate resin is typically greater than 1,500 Da, alternatively from 1,500 Da to 8,000 Da, alternatively from 2,000 to 7,500 Da. Mn can be measured by GPC in the method described below.

[0064] Methods for producing the resins are known in the art. For example, the resins can be prepared by treating a resin copolymer produced by the silica hydrosol capping process of Daudt et al. with at least an end-capping reagent, such as hexamethyldisilazane, or an alkenyl-containing end-capping agent. The method of Daudt et al. is disclosed in U.S. Pat. No. 2,676,182.

[0065] The method of Daudt et al. involves reacting a silica hydrosol under acidic conditions with a hydrolyzable triorganosilane such as trimethylchlorosilane, a siloxane such as hexamethyldisiloxane, or a mixture thereof, and recovering a copolymer having M and Q units. The resulting copolymer generally contains 2 to 5 weight percent hydroxyl groups.

[0066] Resins typically containing less than 2% silicon-bonded hydroxyl groups can be prepared by reacting the product of Daudt et al. with an endblocking agent, such as an alkenyl-containing endblocking agent and / or an endblocking agent free of aliphatic unsaturation, in an amount sufficient to provide 0 to 30 mole percent unsaturated organic groups in the final product. Examples of endblocking agents include, but are not limited to, silazanes, siloxanes, and silanes. Suitable endblocking agents are known in the art and are exemplified in U.S. Pat. Nos. 4,584,355, 4,591,622, and 4,585,836. The resins can be prepared using a single endblocking agent or a mixture of such agents.

[0067] Various suitable polyorganosilicate resins are commercially available from suppliers such as Dow Silicones Corporation (Midland, MI, USA), Momentive Performance Materials (Albany, NY, USA) and Bluestar Silicones USA Corp. (East Brunswick, NJ, USA). For example, DOWSIL® MQ-1600 solid resin, DOWSIL® MQ-1601 solid resin, and DOWSIL® 1250 surfactant, DOWSIL® 7466 resin, and DOWSIL® 7366 resin (all of which are commercially available from Dow Silicones Corporation (Midland, Michigan, USA)) are suitable for use herein. Such resins may be provided in an organic solvent.

[0068] (II) Peroxide The starting material (II) in the hybrid PSA composition is a radical curing catalyst containing an organic peroxide compound. Suitable organic peroxide compounds include dibenzoyl peroxide, 4-monochlorobenzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butylcumyl peroxide, tert-butyloxide 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,4-dichlorobenzoyl peroxide, di-tert-butylperoxy-diisopropylbenzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-di-tert-butylperoxyhexane-3,2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, or cumyl-tert-butylperoxide. The starting material (III) may be a single organic peroxide compound or a combination of two or more organic peroxide compounds. Alternatively, the starting material (II) may be benzoyl peroxide.

[0069] The amount of starting material (II) added to the hybrid PSA composition depends on the type and amount of catalyst selected, the selection of starting materials A) and B), and whether starting material A) has hydroxyl groups or aliphatic unsaturated groups (R 6 However, starting material (II) may be present in an amount of at least 2% by weight, based on the combined weight of starting materials (I), (II), and (III). Alternatively, Each R in the starting material (A) 6 When R is hydroxyl, the peroxide catalyst is present in an amount of 2% to 4% by weight. 6 When is an aliphatically unsaturated monovalent hydrocarbon group, the peroxide catalyst is present in an amount of at least 3 wt %, alternatively 3 wt % to 4 wt %.

[0070] (III) Solvent A solvent can optionally be used in the hybrid PSA compositions described herein. The solvent can facilitate the flow of the hybrid PSA composition and the introduction of certain starting materials, such as polyorganosilicate resins and / or peroxide compounds. The solvents used herein aid in the flow of the starting materials of the hybrid PSA composition but do not essentially react with the starting materials. The solvent can be selected based on the solubility and volatility of the starting materials in the hybrid PSA composition. Solubility refers to the solvent's ability to dissolve and / or disperse the starting materials of the hybrid PSA composition. "Volatility" refers to the vapor pressure of the solvent. If the solvent is too volatile (has too high a vapor pressure), bubbles may form in the hybrid PSA composition during the curing reaction, which may burst or otherwise weaken or negatively affect the properties of the reaction product. However, if the solvent is not sufficiently volatile (has too low a vapor pressure), the solvent may remain as a plasticizer in the reaction product of the hybrid PSA composition.

[0071] The solvent may include an organic solvent. The organic solvent may be an alcohol such as methanol, ethanol, isopropanol, butanol, or n-propanol; a ketone such as acetone, methyl ethyl ketone, or methyl isobutyl ketone; an aromatic hydrocarbon such as benzene, toluene, or xylene; an aliphatic hydrocarbon such as heptane, hexane, or octane; a glycol ether 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; a halogenated hydrocarbon such as dichloromethane, 1,1,1-trichloroethane, or methylene chloride; chloroform; dimethyl sulfoxide; dimethylformamide, acetonitrile; tetrahydrofuran, white spirit; mineral spirits, naphtha; n-methylpyrrolidone; or a combination thereof. Alternatively, the solvent may be selected from the group consisting of ethyl acetate, benzene, toluene, xylene, heptane, tetrahydrofuran, and combinations of two or more thereof.

[0072] Suitable solvents include polyorganosiloxanes with suitable vapor pressures, such as hexamethyldisiloxane, octamethyltrisiloxane, hexamethylcyclotrisiloxane, and other low molecular weight polyorganosiloxanes, such as 0.5-1.5 cSt DOWSIL™ 200 fluid and DOWSIL™ OS fluid, which are commercially available from Dow Silicones Corporation, Midland, Michigan, USA.

[0073] However, the amount of solvent will vary depending on various factors, such as the type of solvent selected and the amount and type of other starting materials selected. However, the amount of solvent may range from 0 to 70% by weight, alternatively from 2 to 50% by weight, or alternatively from 40 to 60% by weight, based on the weight of all starting materials in the hybrid PSA composition. The solvent can be added during preparation of the hybrid PSA composition, for example, to aid in the mixing and delivery of one or more starting materials. All or a portion of the solvent can optionally be removed after the hybrid PSA composition is prepared.

[0074] Method for producing hybrid PSA compositions The hybrid PSA composition can be prepared by a method that includes combining all of the starting materials by any convenient means, such as mixing at room temperature. The method may further include delivering one or more of the starting materials (e.g., the polyorganosilicate resin and / or the peroxide catalyst) in a solvent that can dissolve in the solvent when combined with one or more of the other starting materials in the hybrid PSA composition, after which all or substantially all of the solvent can be removed by conventional means, such as stripping and / or distillation, optionally under reduced pressure.

[0075] When preparing the hybrid PSA composition (IA), the starting material (IA), the grafted polyorganosiloxane, and the starting material (IB), the polyorganosilicate resin, can be combined to form the base simultaneously with combining (II) the peroxide and (III) the solvent, if any, by, for example, mixing all of the starting materials in any order. Alternatively, the base can be prepared by combining the starting materials (IA) and (IB) before adding the (II) peroxide.

[0076] In one embodiment, starting materials (IA) grafted polyorganosiloxane and starting materials (IB) polyorganosilicate resin can be combined by physical mixing at ambient temperature. Alternatively, one or both of starting materials (IA) and (IB) can be dissolved in solvent (III) prior to physical mixing.

[0077] In an alternative embodiment, starting materials (IA) and (IB) can be reacted to form the base before adding starting material (II) peroxide. For example, starting material (IA) can be R 6 When the hybrid pressure-sensitive adhesive base contains hydroxyl groups for 1) (IA) a functional polyorganosiloxane having poly(meth)acrylate groups, said functional polyorganosiloxane comprising the above unit formula and having R 6 are hydroxyl groups; and The polyorganosilicate resin (IB) described above, Optionally, the solvent (III) described above; and optionally (IC) a silyl phosphate, (ID) a condensation reaction catalyst, thereby forming a reaction mixture, thereby forming a reaction product of starting materials (IA) and (IB), and by-products; 2) removing all or a portion of the by-products during and / or after step 1); The method comprises: 3) (II) combining a peroxide catalyst (described above) and optionally adding additional (III) solvent to the reaction product of step 2), thereby forming a polyorganosiloxane hybrid pressure-sensitive adhesive composition.

[0078] Step 1) can be carried out by any convenient means, such as mixing. Step 1) can be carried out under inert conditions, for example, under nitrogen or other inert gas. Combining the starting materials can be carried out at ambient temperature. For example, a solvent can be optionally added to facilitate combining the starting materials. Starting material (IC) is a silyl phosphate that can be used in step 1), for example, to neutralize impurities. The amount of starting material (IC), if present, can be up to 0.02% by weight. Silyl phosphates and methods for preparing them are described, for example, in U.S. Pat. Nos. 4,177,200, 5,099,051, and 5,481,014, and the references cited therein.

[0079] The starting material (ID) condensation reaction catalyst used in step 1) may be a carboxylic acid. Some useful carboxylic acids include, but are not limited to, propanoic acid, 2-methylpropanoic acid, butanoic acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), 2-ethylhexanoic acid, heptanoic acid, hexanoic acid, octanoic acid (caprylic acid), oleic acid, linoleic acid, linolenic acid, cyclohexanecarboxylic acid, cyclohexylacetic acid, cyclohexenecarboxylic acid, benzoic acid, benzeneacetic acid, propanedioic acid (malonic acid), butanedioic acid (succinic acid), hexanedioic acid (adipic acid), 2-butenedioic acid (maleic acid), lauric acid, stearic acid, myristic acid, palmitic acid, isoanoic acid, or a combination of two or more thereof. In one embodiment, the acidic compound may be a mixture containing branched alkyl carboxylic acids. In one embodiment, the acidic compound is a mixture of predominantly tertiary aliphatic C10 carboxylic acids. This amount depends on various factors, including the type and amount of hydroxyl groups in starting materials (IA) and (IB), but the amount of starting material (ID) may be from 0.1% to 5% by weight, or alternatively from 0.1% to 1% by weight, based on the total weight of all starting materials.

[0080] Step 2) can be carried out by heating the resulting mixture, for example, to the reflux of the selected solvent. When the starting materials react, by-products are produced. The by-products may include water. All or a portion of the by-products can be removed during and / or after step 1). Without wishing to be bound by theory, it is believed that removal of the by-products can drive the reaction to completion. The by-products can be removed by any convenient means, such as stripping.

[0081] Step 3) can be carried out by combining (II) a peroxide catalyst and, optionally, (III) additional solvent with the reaction product of starting materials (IA) and (IB) from step 2) by any convenient means, such as mixing at ambient temperature.

[0082] adhesive articles The hybrid PSA composition prepared as described above can be used to form an adhesive article, such as a hybrid PSA (prepared by curing the hybrid PSA composition described above), on a substrate. Thus, the method may further include applying the hybrid PSA composition to a substrate.

[0083] The hybrid PSA composition can be applied to a substrate by any convenient means, for example, by a gravure coater, a comma coater, an offset coater, an offset gravure coater, a roller coater, a reverse roller coater, an air knife coater, or a curtain coater.

[0084] The substrate can be any material capable of withstanding the curing conditions (described below) used to cure the hybrid PSA composition and form a hybrid pressure-sensitive adhesive on the substrate. For example, any substrate capable of withstanding heat treatment at temperatures of 120°C or higher, or even 150°C or higher, is suitable. Examples of materials suitable for such substrates include plastic films such as polymethyl methacrylate (PMMA), polyimide (PI), polyether ether ketone (PEEK), polyethylene naphthalate (PEN), liquid crystal polyarylate, polyamideimide (PAI), polyether sulfide (PES), polyethylene terephthalate (PET), polyethylene (PE), or polypropylene (PP). Alternatively, the substrate can be a plastic such as those described above coated on a paper backing. Alternatively, the substrate can be a metal foil such as aluminum foil or copper foil. The thickness of the substrate is not critical; however, the thickness can be from 5 micrometers to 300 micrometers.

[0085] Alternatively, the substrate may be a fluorosilicone release liner, such as any one of the above substrates coated with a fluorosilicone release coating.

[0086] To improve bonding of the hybrid PSA to the surface of a substrate, the method for forming an adhesive article may optionally further comprise treating the surface of the substrate before applying the hybrid PSA composition. Treating the surface of the substrate can be done by any convenient means, such as applying a primer or subjecting the substrate to a corona discharge treatment, etching, or plasma treatment, followed by applying the hybrid PSA composition to the surface of the substrate.

[0087] Adhesive articles such as films or tapes can be prepared by applying the hybrid PSA composition described above onto the surface of the substrate described above. If a solvent is present, the method may optionally further comprise removing all or a portion of the solvent before and / or during curing. Solvent removal can be accomplished by any convenient means, such as heating the hybrid PSA composition at a temperature that will evaporate the solvent without completely curing it, for example, at a temperature of 70°C to 120°C, alternatively 50°C to 100°C, alternatively 70°C to 80°C, for a time sufficient to remove all or a portion of the solvent (e.g., 30 seconds to 1 hour, alternatively 1 minute to 5 minutes).

[0088] Curing of the hybrid PSA composition (and removal of solvent, if present) can be accomplished by heating at a temperature of 80°C to 210°C, alternatively 90°C to 205°C, alternatively 100°C to 205°C, alternatively 110°C to 200°C, for a time sufficient to cure the hybrid PSA composition (e.g., 30 seconds to 1 hour, alternatively 1 to 5 minutes). This forms a hybrid PSA on the surface of the substrate. Curing can be accomplished by placing the substrate in an oven. The amount of hybrid PSA composition applied to the surface of the substrate depends on the specific application, but this amount can be sufficient to achieve a hybrid PSA thickness of 5 micrometers to 100 micrometers, and for protective films, a thickness of 6 micrometers to 50 micrometers, alternatively 8 micrometers to 40 micrometers, alternatively 10 to 30 micrometers, after curing.

[0089] The methods described herein may optionally further comprise applying a removable release liner to the hybrid PSA on the side opposite the substrate, for example, to protect the hybrid PSA prior to use of the adhesive article. The release liner can be applied before, during, or after curing of the hybrid PSA composition, or after curing.

[0090] Alternatively, if the hybrid PSA is formed on a release liner, the method further comprises applying a substrate (as described above) to the hybrid PSA after it has cured. [Example]

[0091] These examples are intended to illustrate the invention and should not be construed as limiting the scope of the claims. The starting materials used in the examples are listed in Table 2 below.

[0092] [Table 2-1]

[0093] [Table 2-2]

[0094] This Reference Example A serves as a description of the process used to produce macromonomer Example MM-1 (100% BMA; nomenclature refers to weight percent and BMA = butyl methacrylate), which has 1.9 weight percent (3-mercaptopropyl)methyldimethoxysilane based on monomer. Ethyl acetate (EtOAc) was dried over molecular sieves, and the other components were used as supplied. A monomer mixture containing 75 g of EtOAc, 370 g of BMA, and 7 g of (3-mercaptopropyl)methyldimethoxysilane was prepared. 100 g of EtOAc was added to a 1-liter, four-neck glass reactor equipped with a condenser and an overhead mixer. The mixture was heated to 77°C and sparged with nitrogen for 30 minutes. Trigonox 125-C75 (tAPPiv, 1 g) in 10 g of EtOAc was added to the reactor and held for 5 minutes. The temperature was slowly increased to 85°C, then the monomer mixture was fed at 0.1 mL / min over 180 min, and the initiator solution (20 g EtOAc, 2 g Trigonox125-C75) was fed over 240 min (180 min + 60 min overfeed after the end of the monomer feed). The reaction was held at 85°C for 180 min after the end of the initiator feed, and then the resulting mixture was allowed to cool to room temperature. The resulting mixture was dried in a vacuum oven.

[0095] This Reference Example B serves as a description of the process used to produce macromonomer Example MM-2 (37 BMA / 63 MMA, nomenclature refers to weight percent and BMA = butyl methacrylate and MMA = methyl methacrylate), which has 8.2 weight percent (3-mercaptopropyl)methyldimethoxysilane based on monomer. The process was used to prepare another alkoxysilyl-functional (meth)acrylate macromonomer (Example MM-3) by varying the appropriate starting materials and their amounts, as shown in Table 3 below. A monomer mixture of toluene (5 g), MMA (252 g), BMA (148 g), and (3-mercaptopropyl)methyldimethoxysilane (36 g) was prepared. To a 1-liter, four-neck glass reactor equipped with a condenser and overhead mixer, toluene (80 g) was added. The solvent was heated to 85°C, then the monomer mixture (441 g) was fed over 1 hour, and the initiator solution (30 g toluene and 16.5 g Trigonox 25-C75 tBPPiv) was fed over 3 hours. At hour 2, a BA (butyl acrylate, 10 g) chase was added over 30 minutes. The reaction was held at 85°C for 80 minutes after the end of the initiator feed, then the mixture was allowed to cool to room temperature and collected. In MM-2, the reaction mixture was diluted with 160 g toluene and then collected; in MM-3, no additional dilution was required.

[0096] [Table 3] * BOM = Based on Monomer

[0097] [Table 4] a Molecular weight distribution determined by GPC using THF as eluent. b. Residual monomer concentration measured by HS-GC. A sample (approximately 20 mg) of the reaction mixture was added to a vial along with an internal standard (approximately 20 mg), and the vial was crimped. Headspace gas chromatography was performed by heating the vial and sampling the headspace to determine the ppm concentration of residual monomer. c. 29 Percent condensation of siloxane moieties determined by Si NMR. d.ND = Not Measured

[0098] In this Example C, grafted polysiloxane GP-1, a bis-hydroxyl-terminated polydimethylsiloxane with pendant polybutyl methacrylate groups was synthesized as follows. Prior to the start of the experiment, a 1-liter, four-necked round-bottom flask equipped with a stirrer and blade was pre-weighed and recorded. To this flask, 181.3 grams of OH-terminated PDMS1 and 18.17 grams of the macromonomer of Example MM-1 (having Mn = 8,000 g / mol and BMA = 100%) were added. To a round-bottom flask equipped with a Dean-Stark apparatus equipped with an overhead mechanical stirrer, thermocouple, and a water-cooled condenser attached to a nitrogen bubbler, 239.61 grams of toluene was charged. When the pot temperature reached 80-100°C under a nitrogen blanket, 0.47 mL of phosphazene catalyst 1 was added. Water, methanol, and toluene distillates were collected in the Dean-Stark apparatus while the reaction mixture continued to heat. After sufficient toluene was distilled to obtain a solution with a final concentration of 50% solids, heating was discontinued. Once a final concentration of 50% solids was reached, 0.20 mL of trioctylamine was added to the reaction flask under stirring to neutralize the reaction mixture, and the resulting mixture was allowed to cool to room temperature. After cooling to room temperature, the round-bottom flask equipped with a stir bar and blade was weighed and recorded. The NVC was then calculated based on the mass balance (the difference between the initial and final weights), assuming all of the polymer content remained in the flask.

[0099] In this Reference Example D, poly(meth)acrylate-grafted polyorganosiloxanes were prepared using the alkoxysilyl-functional (meth)acrylate macromonomers described above in Examples MM-1 to MM-3. Example D serves as a description of the process used to produce grafted polysiloxane GP-2. Prior to the start of the experiment, a 1-liter, four-necked, round-bottom flask equipped with a stir bar and blade was pre-weighed and recorded. To this flask were added 181.0 grams of OH-terminated PDMS1, 5.65 grams of Vi-terminated PDMS1, and 3.73 grams of Example MM-2 (having Mn = 2.3 kDa and BMA = 37%). To a round-bottom flask equipped with a Dean-Stark apparatus equipped with an overhead mechanical stirrer, thermocouple, and a water-cooled condenser attached to a nitrogen bubbler, 238 grams of toluene was charged. The heating mantle was plugged into a temperature controller to prevent the reaction mixture from heating above 120°C. When the pot temperature reached 80 °C, 0.47 mL of phosphazene catalyst 1 was added. The reaction mixture was continued to heat to 101 °C, and water, methanol, and toluene distillates were collected in a Dean-Stark apparatus. Typically, 45–100 g of distillate was removed to distill off enough toluene to achieve a final concentration of approximately 60% solids, after which heating was discontinued. Upon reaching a final concentration of 60% solids, 0.20 mL of trioctylamine was added to the reaction flask under stirring to neutralize the reaction mixture, and the resulting mixture was cooled to room temperature. After cooling to room temperature, the round-bottom flask, equipped with a stir bar and blade, was weighed and recorded. The NVC was then calculated based on the mass balance (the difference between the initial and final weights), assuming all of the polymer content remained in the flask. Additionally, the vinyl content of the solution was calculated.

[0100] Examples GP-3 through GP-6 were repeated using the procedure in Reference Example D above, except that the alkoxysilyl-functional (meth)acrylate macromonomer prepared in Example MM-2 was replaced with a different alkoxysilyl-functional (meth)acrylate macromonomer and the weight percent of the alkoxysilyl-functional (meth)acrylate macromonomer was varied. These examples are listed in Table 5.

[0101] [Table 5] a MW and PDI determined by GPC analysis * Ultra-high MW material may be present, but was filtered by GPC injection.

[0102] Preparation of reactive silicone pressure-sensitive adhesive compositions For the benchmark, a silicone PSA was prepared using a 500 milliliter, three-neck, round-bottom flask equipped with a stir bar and blade. 56.60 grams of OH-terminated PDMS 2, 90.66 grams of Resin 2, 34.02 grams of Resin 1, 67.97 grams of toluene, and 0.30 grams of the silyl phosphate solution were charged to a flask equipped with a Dean-Stark apparatus equipped with an overhead mechanical stirrer, thermocouple, and a water-cooled condenser attached to a nitrogen bubbler. A heating mantle was inserted into the temperature controller to prevent the reaction mixture from heating above 175°C. Stirring was initiated and continued until the material became a homogeneous mixture. 0.44 grams of benzoic acid was added at room temperature, and heating was initiated. Refluxing was observed at 120°C. Water and aromatic solvent (toluene, xylene) distillates were collected in the Dean-Stark apparatus. Heating was discontinued after 2 hours. The resulting PSA was cooled to approximately 50°C and poured off.

[0103] Preparation of reactive pressure-sensitive adhesive compositions In this Example E, hybrid PSA-1 was prepared using a 500 milliliter, three-neck, round-bottom flask equipped with a stir bar and blade. 112.91 g of bis-hydroxyl-terminated polydimethylsiloxane with pendant polybutyl methacrylate groups, synthesized as described above for GP-1 (NVC = 50.03%), 11.68 g of solvent (toluene), 90.66 g of Resin 2, 34.02 g of Resin 1, and 0.31 g of silyl phosphate solution were charged to a flask equipped with a Dean-Stark apparatus equipped with an overhead mechanical stirrer, thermocouple, and a water-cooled condenser attached to a nitrogen bubbler. A heating mantle was inserted into the temperature controller to prevent the reaction mixture from heating above 175°C. Stirring was initiated and continued until the material became a homogeneous mixture. 0.45 grams of benzoic acid was added at room temperature, and heating was initiated. Reflux was observed at 95°C. Water and aromatic solvent (toluene, xylene) distillate were collected in a Dean Stark apparatus. After 2 hours, heating was discontinued. The resulting PSA was cooled to about 50°C and poured off.

[0104] Preparation of Physically Mixed Polyorganosiloxane Hybrid Pressure-Sensitive Adhesive Compositions In this Reference Example F, hybrid PSAs were prepared using the poly(meth)acrylate-grafted polyorganosiloxanes of Examples GP-1 through GP-5 above. Example F is provided as a description of the process used to produce Hybrid PSA-2. The following starting materials were combined and mixed in a glass vial: 11.28 g of grafted polyorganosiloxane GP-1, 11.35 g of Resin 1, and 2.35 g of xylene. A 10% dibenzoyl peroxide solution (90% dibenzoyl peroxide dissolved in toluene) was prepared. 15.00 g of PSA-2, a dibenzoyl peroxide solution according to the desired peroxide level, and optionally, toluene according to the desired NVC were charged to a SpeedMixer™ cup and mixed in a FlackTek SpeedMixer™ at 3,000 RPM for 30 seconds.

[0105] Examples PSA-3 through PSA-7 were repeated using the procedure in Reference Example F above, except that the grafted polyorganosiloxane prepared in Example GP-1 was replaced with a different grafted polyorganosiloxane. These examples are listed in Tables 6 and 7.

[0106] [Table 6]

[0107] [Table 7]

[0108] Comparative Example PSA-8 - Cured with 1% Dibenzoyl Peroxide In this comparative example, PSA-8, GP-2, Resin 1, and xylene were added to a glass vial in the same proportions as PSA-3 and PSA-4 using the procedure of Reference Example F. Comparative Example PSA-8 differed in the addition of dibenzoyl peroxide to a desired level of 1%. Table 8 shows the same PSA compositions, differing only in dibenzoyl peroxide level. At least 2% dibenzoyl peroxide was required to achieve cure.

[0109] [Table 8]

[0110] Comparative Example PSA-9 - Physical Blend Hybrid PSA Using Vinyl-Functional Grafted Polyorganosiloxane In this Comparative Example PSA-9, a hybrid PSA was prepared using the procedure in Reference Example F above, except that the grafted polyorganosiloxane prepared in Example GP-1 was replaced with GP-6. Table 9 shows the use of the same macromonomer in various hybrid PSAs. Table 10 shows selected properties. Comparative PSA-9 was a physical mixture using a vinyl-functional grafted polysiloxane. It failed both the "wet" and "dry" peel tests. PSA-2 was a physical mixture using an OH-functional grafted polysiloxane. It passed the "dry" peel test but failed the "wet" peel test. PSA-1 was reacted with an OH-functional grafted polysiloxane. It passed the "wet" and "dry" peel tests.

[0111] [Table 9]

[0112] [Table 10]

[0113] Reference Example G - Preparation of film samples Films were prepared: A sheet of paper was placed on a vacuum plate under vacuum, and then a 2-mil thick sheet of polyester or a 2-mil thick sheet of polyester coated with a fluorosilicone release coating was placed on top of the paper. The desired composition, prepared as described above for Reference Example F, was poured onto the polyester or polyester coated with a fluorosilicone release coating, and a 4-mil coating bar was used to prepare a film. The films were placed in a Despatch™ oven. Each sheet was dried at 80°C for 2 minutes and then cured at 180°C for 2 minutes.

[0114] Reference Example: Details of H-GPC Experiment Molecular weight data were determined by analysis on a Waters 2695 model GPC. Poly(meth)acrylate-grafted polyorganosiloxane was dissolved in THF at a concentration of 5 mg solids / mL and filtered through a 0.45 μm PTFE syringe filter before injecting a 100 μL aliquot of the sample. The GPC was equipped with two Polymer Laboratories PLgel 5 μm Mixed-C columns (300 mm × 7.5 mm) preceded by a PLgel 5 μm guard column (50 mm × 7.5 mm) at a flow rate of 1.0 mL / min at 35 °C. Detection was performed using a Waters 2410 differential refractive index detector. Conventional calibration of 16 narrow polystyrene standards covering the range from 580 g / mol to 2,300,000 g / mol and fitted with a third-order polynomial curve.

[0115] Reference example I-NMR An Agilent 500 MHz DD2 (mi-MR-06) system equipped with a 16 mm silicon-free AutoX probe 29 Si NMR spectra were acquired. Samples were prepared in Si-free Teflon NMR tubes using CDCl3 + 0.02M Cr(acac)3. Standard parameters were applied, except that nt = 1024. The spectra were acquired on a Bruker Avance III HD NMR spectrometer equipped with a 5 mm TCI HC / Si cryoprobe (mi-MR-07). 1 H NMR spectra were acquired. Samples were prepared in 5 mm NMR tubes using CDCl3. Standard parameters were applied.

[0116] Reference Example J - Synthesis of HSPrMe2SiOMe A 3 M solution of CH3MgBr in diethyl ether (50 mL, 0.15 mol) was added dropwise to a solution of 3-mercaptopropyltrimethoxysilane (8.5 g, 0.043 mol) in 50 mL of THF, maintaining the temperature at 0-10 °C. The reaction mixture was stirred at 0 °C for 1 h and then treated dropwise with CH3OH (40 mL). The solid was filtered. The crude material was used directly in the next reaction. 5.4 g was recovered, giving a 75% yield of pure product. NMR was consistent with literature standards: Agina, EV, ACS Applied Materials & Interfaces, 2015, 22, 11755-11764.

[0117] Reference example K - Peel adhesion (PMMA) 1 inch x 8 1 / 2 strips were cut from the 2 mil polyester film prepared as described in Reference Example G and transferred to a clean PMMA panel by using an approximately 5 lb. roller. Peel adhesion (180 degrees) was tested according to PSTC-101 standard. A TMI peel and adhesion tester was used to pull 1 inch wide strips of the hybrid PSA at 12 inches / minute. Results were reported in grams / inch. Samples were passed if they showed adhesive failure / clean removal of the strip from the PMMA panel.

[0118] Reference example L-Adhesiveness Tack was tested according to ASTM D-2979. A PT-1000 probe tack tester was used to obtain tack measurements from hybrid PSA samples coated on 2 mil polyester film prepared as described in Reference Example G. The dwell time was set at 1.0 second. Results were reported in grams.

[0119] Reference Example M - "Wet" Peel Force A 2 mil thick sheet of polyester coated with a fluorosilicone release coating was used to sandwich a sample of the hybrid PSA composition prepared as described in Reference Example G between two 2 mil thick sheets of polyester to create a laminate (release liner / adhesive / 2 mil polyester film). Release was measured using a TMI Peel and Adhesion Tester by pulling the release liner side of the laminate from the polyester film side of a 1 inch wide strip of the laminate at 12 inches / minute.

[0120] Reference Example N - "Dry" Peel Force A 2 mil thick sheet of polyester was used to sandwich a sample of the hybrid PSA composition prepared as described in Reference Example G between 2 mil thick sheets of polyester coated with a fluorosilicone release coating to create a laminate (release liner / adhesive / 2 mil polyester film). Peel was measured using a TMI Peel and Adhesion Tester by pulling the release liner side of the laminate from the polyester film side of a 1 inch wide strip of the laminate at 12 inches / minute.

[0121] Definitions and Use of Terms The Summary and Abstract are incorporated herein by reference. Table 7 shows the abbreviations used herein.

[0122] [Table 11]

[0123] All amounts, ratios, and percentages are by weight unless otherwise indicated. The articles "a," "an," and "the" each refer to one or more, unless the context of the specification dictates otherwise. Disclosure of ranges includes the range itself and any subsumed within the range, as well as the endpoints. For example, disclosure of a range of 2.0 to 4.0 includes not only the range 2.0 to 4.0, but also 2.1, 2.3, 3.4, 3.5, and 4.0 individually, and any other number subsumed within the range. Further, disclosure of a range of 2.0 to 4.0 also includes subsets, such as 2.1 to 3.5, 2.3 to 3.4, 2.6 to 3.7, and 3.8 to 4.0, as well as any other subset subsumed within that range. Similarly, disclosure of a Markush group includes the group as a whole, as well as any individual elements and subgroups subsumed therein. For example, disclosure of the Markush group "a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group" includes its members, the individual alkyl, the subgroups alkyl and aryl, and any other individual members and subgroups contained therein.

[0124] "Alkyl" means an acyclic, branched or unbranched saturated monovalent hydrocarbon radical. Alkyl is exemplified by, but not limited to, methyl, ethyl, propyl (e.g., isopropyl and / or n-propyl), butyl (e.g., isobutyl, n-butyl, tert-butyl and / or sec-butyl), pentyl (e.g., isopentyl, neopentyl and / or tert-pentyl), hexyl, heptyl, octyl, nonyl, and decyl, as well as branched saturated monovalent hydrocarbon radicals of six or more carbon atoms.

[0125] "Alkenyl" means an acyclic, branched, or unbranched monovalent hydrocarbon group having a double bond between two carbon atoms. Alkenyl is exemplified by, but not limited to, vinyl, allyl, butenyl, pentenyl, and hexenyl (including branched and straight-chain species).

[0126] "Aryl" means a fully unsaturated cyclic hydrocarbon group. Aryl is exemplified by, but not limited to, cyclopentadienyl, phenyl, anthracenyl, and naphthyl. Monocyclic aryl groups can have 5 to 9 carbon atoms, alternatively 6 to 7 carbon atoms, or alternatively 5 to 6 carbon atoms. Polycyclic aryl groups can have 10 to 17 carbon atoms, alternatively 10 to 14 carbon atoms, or alternatively 12 to 14 carbon atoms.

[0127] "Aralkyl" means an alkyl group having a pendant and / or terminal aryl group, or an aryl group having a pendant alkyl group. Exemplary aralkyl groups include tolyl, xylyl, benzyl, phenylethyl, phenylpropyl, and phenylbutyl.

[0128] "Carbocycle" and "carbocyclic" each refer to a hydrocarbon ring. A carbocycle may be a monocyclic ring or a fused, bridged, or spiropolycyclic ring. A monocyclic carbocycle may have 3 to 9 carbon atoms, alternatively 4 to 7 carbon atoms, alternatively 5 to 6 carbon atoms. A polycyclic carbocycle may have 7 to 17 carbon atoms, alternatively 7 to 14 carbon atoms, alternatively 9 to 10 carbon atoms. A carbocycle may be saturated or partially unsaturated.

[0129] "Cycloalkyl" means a saturated carbocyclic ring. Monocyclic cycloalkyl groups are exemplified by cyclobutyl, cyclopentyl, and cyclohexyl.

[0130] "Halogenated hydrocarbon" refers to a hydrocarbon in which one or more hydrogen atoms bonded to a carbon atom have been replaced with a halogen atom. Halogenated hydrocarbon groups include haloalkyl groups, halogenated carbocyclic groups, and haloalkenyl groups. Haloalkyl groups include fluorinated alkyl groups such as trifluoromethyl (CF), fluoromethyl, trifluoroethyl, 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; and chlorinated alkyl groups such as chloromethyl and 3-chloropropyl. Halogenated carbocyclic groups include fluorinated cycloalkyl groups such as 2,2-difluorocyclopropyl, 2,3-difluorocyclobutyl, 3,4-difluorocyclohexyl, and 3,4-difluoro-5-methylcycloheptyl, and chlorinated cycloalkyl groups such as 2,2-dichlorocyclopropyl, 2,3-dichlorocyclopentyl, etc. Haloalkenyl groups include chloroallyl groups.

[0131] As used herein and in the appended claims, the term "(meth)acrylic acid" is intended to function as a generic term encompassing either or both acrylic acid and methacrylic acid.

[0132] As used herein and in the appended claims, the term "(meth)acrylate" is intended to function as a generic term encompassing either or both acrylate and methacrylate.

[0133] "M units" are units of the formula RSiO 1 / 2 where each R independently represents a monovalent atom or an organic group. A "D unit" refers to a siloxane unit having the formula RSiO 2 / 2where each R independently represents a monovalent atom or group. A "T unit" refers to a siloxane unit having the formula RSiO 3 / 2 where each R independently represents a monovalent atom or group. A "Q unit" refers to a siloxane unit having the formula SiO 4 / 2 means a siloxane unit having the formula:

Claims

1. 1. A polyorganosiloxane hybrid pressure-sensitive adhesive composition comprising: (I) a pressure-sensitive adhesive base comprising a physical mixture of starting materials (I-A) and (IB), a reaction product of starting materials (I-A) and (IB), or a combination of both said physical mixture and said reaction product, in an amount sufficient to provide from 15% to 40% by weight of starting material (I-A) and from 5% to 60% by weight of starting material (IB); The starting material (IA) is a functional polyorganosiloxane having poly(meth)acrylate groups, the functional polyorganosiloxane having the unit formula: [R ３ ｗ (R ５ -S-R") (OR ４ ) （２－ｗ） Si—O １／２ ] ｐ [R ３ ｖ (R ５ -S-R") (OR ４ ) （１－ｖ） Si—O ２／２ ] ｑ [(R ５ -S-R”)Si-O ３／２ ] ｋ (R ６ R ７ ２ SiO １／２ ) ｒ (R ７ ２ SiO ２／２ ) ｓ (R ６ R ７ SiO ２／２ ) ｔ (R ７ ３ SiO １／２ ) ｕ wherein each subscript w is independently 0, 1, or 2; each subscript v is independently 0 or 1; and each R ３ are independently selected monovalent hydrocarbon groups, and each R ４ are independently selected alkyl groups, and each R ５ are independently selected divalent hydrocarbon groups, each R″ is independently a (meth)acrylate polymer or copolymer, and each R ６ is selected from the group consisting of hydroxyl groups and aliphatically unsaturated monovalent hydrocarbon groups, and each R ７ are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation, with subscript p≧0, subscript q≧0, subscript k≧0, the numbers (p+q+k)≧1, subscript r≧0, subscript s≧0, subscript t≧0, subscript u≧0, the numbers (r+t)≧1, and the numbers (p+q+k+r+s+t+u) are sufficient to provide said polyorganosiloxane with a molecular weight of at least 50 kDa; The starting material (IB) is a polyorganosilicate resin having the unit formula (R １５ ２ R １６ SiO １／２ ) ｘ (R １５ ３ SiO １／２ ) ｙ (SiO ４／２ ) ｚ [In the formula, R １５ is an alkyl group, an aryl group, or an aralkyl group, and R １６ is an alkenyl group of 2 to 18 carbon atoms, and the subscripts x, y, and z are mole fractions, where subscript x≧0, subscript y≧0, subscript z>0, the numbers (x+y)>0, the numbers (x+y+z)≦1, and the subscripts x, y, and z have values ​​such that 0.9≦(x+y) / z≦1.3, wherein the polyorganosilicate resin further comprises a hydroxyl group content of up to 5 wt. %, based on the weight of the polyorganosilicate resin, and the polyorganosilicate resin has a number average molecular weight of >1,500 Da to 8,000 Da as measured by gel permeation chromatography; (II) a peroxide catalyst, which is a catalyst for each R in the starting material (IA) ６ is hydroxyl, the peroxide catalyst is present in an amount of 2% to 4% by weight, and each R ６ is the aliphatically unsaturated monovalent hydrocarbon group, wherein the peroxide catalyst is present in an amount of 3% to 4% by weight; and 0 to 70 wt. % of (III) a solvent, all percentages being by weight based on the total weight of all starting materials in the polyorganosiloxane hybrid pressure-sensitive adhesive composition.

2. In the starting material (IA), R ３ has 1 to 18 carbon atoms, and R ４ has 1 to 6 carbon atoms, and R ５ has 1 to 18 carbon atoms, and R ６ is hydroxyl or an alkenyl group of 2 to 18 carbon atoms, and R ７ has 1 to 18 carbon atoms, R″ has a DP of 1 to 1,000, the amount (p+r+u)=2, subscript k=0, the number (p+q) is 1 to 100, the number (r+t) is 1 to 100, and the number (p+q+r+s+t+u) is sufficient to provide the functional polyorganosiloxane with a molecular weight of 50 kDa to 1,000 kDa.

3. The subscript p is 1 or 2, and each R ３ is an alkyl group of 1 to 6 carbon atoms, and each R ４ is an alkyl group of 1 to 6 carbon atoms, and each R ５ is an alkylene group of 2 to 8 carbon atoms, R″ has a DP of 5 to 600, and each R ６ is hydroxyl or an alkenyl group selected from vinyl and hexenyl, and each R ７ The composition of claim 2, wherein is an alkyl group of 1 to 6 carbon atoms.

4. In starting material (IB), subscript x=0 and the polyorganosilicate resin has the unit formula: (R １５ ３ SiO １／２ ) ｗ (SiO ４／２ ) ｚ 2. The composition of claim 1, comprising: wherein subscript w>4.

5. 2. The composition of claim 1, wherein the peroxide catalyst is selected from the group consisting of dibenzoyl peroxide, 4-monochlorobenzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate, tert-butylcumyl peroxide, tert-butyloxide 2,5-dimethyl-2,5-di-tert-butylperoxyhexane, 2,4-dichlorobenzoyl peroxide, di-tertbutylperoxy-diisopropylbenzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-di-tert-butylperoxyhexane-3,2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, cumyl-tert-butyl peroxide, and combinations of two or more thereof.

6. 6. The composition of claim 5, wherein the peroxide catalyst comprises dibenzoyl peroxide.

7. The composition of claim 5 wherein the solvent is present and comprises an aromatic hydrocarbon.

8. 8. The composition of claim 7, wherein the solvent is selected from the group consisting of ethyl acetate, benzene, toluene, xylene, heptane, tetrahydrofuran, and combinations of two or more thereof.

9. 10. The composition of claim 1, wherein starting material (IA) is present in an amount of 17% to 25% by weight, starting material (IB) is present in an amount of 25% to 40% by weight, and starting material (III) is present in an amount of 40% to 60% by weight, all percentages being by weight based on the total weight of all starting materials in the composition.

10. In the starting material (IA), R per molecule ６ The composition according to any one of claims 1 to 9, wherein two or more of the following are hydroxyl groups.

11. In the starting material (IA), R per molecule ６ The composition according to any one of claims 1 to 9, wherein two or more of the following are aliphatically unsaturated monovalent hydrocarbon groups.

12. 11. A method for preparing the polyorganosiloxane hybrid pressure sensitive adhesive composition of claim 10, said method comprising: １） (IA) The functional polyorganosiloxane having a poly(meth)acrylate group, wherein the functional polyorganosiloxane has the unit formula: [R ３ ｗ (R ５ -S-R") (OR ４ ) （２－ｗ） Si—O １／２ ] ｐ [R ３ ｖ (R ５ -S-R") (OR ４ ) （１－ｖ） Si—O ２／２ ] ｑ [(R ５ -S-R”)Si-O ３／２ ] ｋ (R ６ R ７ ２ SiO １／２ ) ｒ (R ７ ２ SiO ２／２ ) ｓ (R ６ R ７ SiO ２／２ ) ｔ (R ７ ３ SiO １／２ ) ｕ wherein each subscript w is independently 0, 1, or 2; each subscript v is independently 0 or 1; and each R ３ are independently selected monovalent hydrocarbon groups, and each R ４ are independently selected alkyl groups, and each R ５ are independently selected divalent hydrocarbon groups, each R″ is independently a (meth)acrylate polymer or copolymer, and each R ６ is selected from the group consisting of hydroxyl groups and aliphatically unsaturated monovalent hydrocarbon groups, with the proviso that R ６ are hydroxyl groups, and each R ７ are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation, where subscript p≧0, subscript q≧0, subscript k≧0, the numbers (p+q+k)≧1, subscript r≧0, subscript s≧0, subscript t≧0, subscript u≧0, the numbers (r+t)≧1, and the numbers (p+q+k+r+s+t+u) are sufficient to provide said polyorganosiloxane with a molecular weight of at least 50 kDa; (IB) the polyorganosilicate resin; optionally (III) said solvent; and optionally (IC) a silyl phosphate; (I-D) a condensation reaction catalyst, thereby preparing a reaction mixture comprising a reaction product of the starting materials (I-A) and (I-B) and a by-product; 2) removing all or a portion of the by-products during and / or after step 1); and 3) (II) adding the peroxide catalyst and, optionally, further adding additional (III) solvent to the reaction product in step 2), thereby forming the polyorganosiloxane hybrid pressure-sensitive adhesive composition.

13. 13. A hybrid polyorganosiloxane pressure sensitive adhesive composition prepared by the method of claim 12.

14. 12. A method for preparing the polyorganosiloxane hybrid pressure sensitive adhesive composition of claim 11, said method comprising: １） (IA) The functional polyorganosiloxane having a poly(meth)acrylate group, wherein the functional polyorganosiloxane has the unit formula: [R ３ ｗ (R ５ -S-R") (OR ４ ) （２－ｗ） Si—O １／２ ] ｐ [R ３ ｖ (R ５ -S-R") (OR ４ ) （１－ｖ） Si—O ２／２ ] ｑ [(R ５ -S-R”)Si-O ３／２ ] ｋ (R ６ R ７ ２ SiO １／２ ) ｒ (R ７ ２ SiO ２／２ ) ｓ (R ６ R ７ SiO ２／２ ) ｔ (R ７ ３ SiO １／２ ) ｕ wherein each subscript w is independently 0, 1, or 2; each subscript v is independently 0 or 1; and each R ３ are independently selected monovalent hydrocarbon groups, and each R ４ are independently selected alkyl groups, and each R ５ are independently selected divalent hydrocarbon groups, each R″ is independently a (meth)acrylate polymer or copolymer, and each R ６ is selected from the group consisting of hydroxyl groups and aliphatically unsaturated monovalent hydrocarbon groups, with the proviso that R ６ are aliphatic unsaturated monovalent hydrocarbon groups, and each R ７ are independently selected monovalent hydrocarbon groups free of aliphatic unsaturation, where subscript p≧0, subscript q≧0, subscript k≧0, the numbers (p+q+k)≧1, subscript r≧0, subscript s≧0, subscript t≧0, subscript u≧0, the numbers (r+t)≧1, and the numbers (p+q+k+r+s+t+u) are sufficient to provide said polyorganosiloxane with a molecular weight of at least 50 kDa; (IB) the polyorganosilicate resin; (II) the peroxide catalyst; and optionally (III) said solvent, thereby forming said polyorganosiloxane hybrid pressure sensitive adhesive composition.

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