# US 7,408,012 B1 · Adhesive bonding systems having adherence to low energy surfaces > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,408,012 B1 - Document ID: US7408012B1 - Status: Granted - Kind: B1 - Application number: 11/107,830 - Filed: 2005-04-18 - Granted: 2008-08-05 - Earliest claimed: 2005-04-18 - Assignees: Loctite (R&D) Limited - Inventors: Brendan J. Kneafsey; Edward P. Scott - Web page: https://patentgrep.com/patent/US7408012B1 ## CPC - C08F 30/08: containing silicon - Y10T 428/2852: Adhesive compositions - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract This invention relates to (meth)acrylate-based polymerizable compositions and adhesive systems prepared therefrom, which include a alkylated borohydride or tetraalkyl borane metal or ammonium salt and a polymerizable siloxane. The inventive compositions and adhesive systems are particularly well suited for bonding applications which involve at least one low energy bonding surface, for example, the polyolefins, polyethylene, and polypropylene. ## Claims ### Claim 1 A polymerizable composition for bonding a low surface energy substrate to a similar or different substrate, comprising: a) at least one free-radically polymerizable monomer component, b) an effective amount of an initiator system for initiating polymerization of the free-radically polymerizable monomer, said initiator system comprising: alkylated borohydride or tetraalkyl borane metal or ammonium salts comprising formula VI below: wherein R10 is C1-C10 alkyl, R11 and R12, which may be the same or different, are selected from the group consisting of H, D, C1-C10 alkyl, C3-C10 cycloalkyl, phenyl, phenyl-substituted C1-C10 alkyl and phenyl-substituted C3-C10 cycloalkyl, provided that any two of R10-R12 may optionally be part of a carbocyclic ring, R13 is H, D or C1-C10 alkyl, and M+ is a metal ion or a quaternary ammonium ion comprising formula VII below wherein R14-R17, which may be the same or different, are selected from the group consisting of C1-C10 alkyl, C2-C10 alkenyl, C3-C10 cycloalkyl, aryl, C1-C10 alkylaryl, aryl C1-C10 alkyl and aryl C1-C10 cycloalkyl, provided that any two of R14-R17 may be part of an optionally unsaturated carbocyclic ring; and c) a polymerizable siloxane reactive with the free-radically polymerizable monomer component. ### Claim 2 (depends on 1) A composition according to claim 1, which is a two-part composition in which the free-radically polymerizable monomer component is provided in one part and the initiator system is provided in the other part. ### Claim 3 (depends on 1) A composition according to claim 1, wherein three of R10-R13 of the alkylated borohydride of formula VI are the same C1-C10 alkyl group and one of R1-R4 is phenyl or phenyl-substituted C1-C10 alkyl. ### Claim 4 (depends on 1) A composition according to claim 1, wherein three of R10-R13 of the alkylated borohydride of formula VI are the same C2-C4 alkyl group and one of R1-R4 is phenyl. ### Claim 5 (depends on 1) A composition according to claim 1, wherein each of R14-R17 of the quaternary ammonium ion of formula VII is the same C1-C5 alkyl group. ### Claim 6 (depends on 1) A composition according to claim 1, wherein the initiator system comprises: wherein R10-R12 are each the same C1-C6 alkyl group, R13 is phenyl; R14-R17 are each the same C1-C6 alkyl group. ### Claim 7 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is represented by (R3SiO1/2)w(R2SiO2/2)x(RSiO3/2)y(SiO4/2)z, wherein a portion of the total R content includes (meth)acrylate functionality. ### Claim 8 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is a composition made from (a) a silicon fluid formed as the reaction product of a first silane having at least one hydrolyzable functional group, and a second silane having a (meth)acrylic functional group and at least one hydrolyzable functional group; (b) a (meth)acrylate monomer; and (c) polymerization initiator. ### Claim 9 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is a member selected from the group consisting of ### Claim 10 (depends on 1) A composition according to claim 1 further comprising a cure indicator. ### Claim 11 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane comprises a silicone fluid formed as the reaction product of a first silane having at least one hydrolyzable functional group, and a second silane having a (meth)acrylic functional group and at least one hydrolyzable functional group. ### Claim 12 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is formed from (i) at least one silane within the formula R1mR2pSi(X)4−(m+p) A, wherein R1 is a (meth)acrylate functional group or a hydrolyzable group, and R2 is the same or different and is selected from the group consisting of monovalent ethylenically unsaturated radicals, hydrogen, C1-12 alkyl, C6-12 aryl, C7-18 alkylaryl, and a hydrolyzable group, X is a hydrolyzable group, m is an integer from 1 to 3, and m+p is an integer from 1 to 3; (ii) at least one silane within the formula R3qSi(X)4−q B, wherein R3 is the same as or different from R2 above and is selected from the group consisting of monovalent ethylenically unsaturated radicals, hydrogen, C1-12 alkyl, C6-12 aryl, and C7-18 alkylaryl, and q is an integer from 1 to 3, reacted with at least another silane within the formula of R4rR5sSi(X)4−(r+s) C, wherein R4 and R5 is the same or different and is selected from the group consisting of monovalent ethylenically unsaturated radicals, hydrogen, C1-12 alkyl, C6-12 aryl, C7-18 alkylaryl, r is an integer from 1 to 3, and r+s is an integer from 1 to 3, provided the silicone resin formed contains at least some hydrolyzable group, X; and combinations thereof. ### Claim 13 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is selected from compounds within formula V below: wherein R6, R7, R8 and R9 are the same or different and are selected from the group consisting of alkyl, alkenyl, aryl, and (meth)acryl, provided that at least one of R6, R7, R8 and R9 is (meth)acryl, having up to 10 carbon atoms (C1-10), or substituted versions thereof; R10 is alkyl having up to 10 carbon atoms; n is an integer between about 100 and 1,200; a is 1 or 2; b is 0, 1 or 2; and a+b is 1, 2 or 3. ### Claim 14 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is represented by the formula VI below: wherein R6 and R7 are the same or different and are selected from the group consisting of alkyl, alkenyl, aryl, and (meth)acryl, provided that at least one of R6 R7 is (meth)acryl, having up to 10 carbon atoms (C1-10), or substituted versions thereof, MA is (meth)acrylate and c is 0, 1 or 2. ### Claim 15 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is a structure represented by (R3SiO1/2)w(R2SiO2/2)x(RSiO3/2)y(SiO4/2)z, wherein w+x+y+z=1 and a portion of the total R content includes (meth)acrylate functionality. ### Claim 16 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is a member selected from the group consisting of acryloxy terminated ethyleneoxide-dimethylsiloxane-ethyleneoxide ABA block copolymer and and methacryloxypropyl terminated polydimethylsiloxane. ### Claim 17 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is present in the range from about 2% to about 50% by weight of the total composition. ### Claim 18 (depends on 1) A composition according to claim 1, wherein the polymerizable siloxane is present in the range from about 2% to about 30% by weight of the total composition. ### Claim 19 (depends on 1) A composite article comprising a first substrate and a second substrate bonded to the first substrate by an acrylic adhesive, wherein the acrylic adhesive comprises the polymerization product of a composition according to claim 1. ### Claim 20 (depends on 1) A cured adhesive composition comprising the polymerization product of a composition according to claim 1. ### Claim 21 (depends on 1) A bonded article comprising two substrates bonded by the polymerization product of a composition according to claim 1. ### Claim 22 (depends on 1) A two-part polymerizable adhesive composition according to claim 1, comprising: part A) an effective amount of an initiator system, a polymerizable siloxane, and at least one (meth)acrylate monomer, optionally with one or more of a toughener, filler and thickener, but without any compound that is reactive with the initiator system to free an alkylated borohydride or tetraalkyl borane metal or ammonium salt therefrom; and part B) at least one (meth)acrylate monomer together with a compound reactive with an initiator system to free an alkylated borohydride or tetraalkyl borane metal or ammonium salt therefrom and optionally with one or more of a toughener, filler and thickener. ### Claim 23 (depends on 1) A method for bonding together substrates, at least one of which is constructed of a low surface energy material, the steps of which comprise: applying a composition according to claim 1 to at least one of the substrates, bringing the substrates together with the composition, and allowing the composition to cure.