Adhesive bonding system having adherence to low energy surfaces
View Patent ↗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.
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 R 10 is C 1 -C 10 alkyl,
R 11 and R 12 , which may be the same or different, are selected from the group consisting of H, D, C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, phenyl, phenyl-substituted C 1 -C 10 alkyl and phenyl-substituted C 3 -C 10 cycloalkyl, provided that any two of R 10 -R 12 may optionally be part of a carbocyclic ring,
R 13 is H, D or C 1 -C 10 alkyl, and
M + is a metal ion or a quaternary ammonium ion comprising formula VII below
wherein R 14 -R 17 , which may be the same or different, are selected from the group consisting of C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 3 -C 10 cycloalkyl, aryl, C 1 -C 10 alkylaryl, aryl C 1 -C 10 alkyl and aryl C 1 - C 10 cycloalkyl, provided that any two of R 14 -R 17 may be part of an optionally unsaturated carbocyclic ring;
c) a polymerizable siloxane,
wherein the polymerizable siloxane is formed from
(i) at least one silane within the formula R 1 m R 2 p Si(X) 4-(m+p) A, wherein R 1 is a (meth)acrylate functional group, or a hydrolyzable group, and R 2 may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1-12 alkyl, C 6-12 aryl, C 7-18 alkylaryl, or 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 R 3 q Si(X) 4-q B, wherein R 3 may be the same as or different from R 2 above and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1-12 alkyl, C 6-12 aryl, and C 7-18 alkylaryl, and q is an integer from 1 to 3; or combinations thereof, reacted with at least another silane within the formula of R 4 r R 5 s Si(X) 4-(r+s) C, wherein R 4 and R 5 may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1-12 alkyl, C 6-12 aryl, C 7-18 alkylaryl, r is an integer from 1 to 3, and r+s is an integer from 1 to 3, provided the polymerizable siloxane formed contains at least one hydrolyzable group, X.
2. A 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 R 10 is C 1 -C 10 alkyl,
R 11 and R 12 , which may be the same or different, are selected from the group consisting of H, D, C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, phenyl, phenyl-substituted C 1 -C 10 alkyl and phenyl-substituted C 3 -C 10 cycloalkyl, provided that any two of R 10 -R 12 may optionally be part of a carbocyclic ring,
R 13 is H, D or C 1 -C 10 alkyl, and
M + is a metal ion or a quaternary ammonium ion comprising formula VII below
wherein R 14 -R 17 , which may be the same or different, are selected from the group consisting of C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 3 -C 10 cycloalkyl, aryl, C 1 -C 10 alkylaryl, aryl C 1 -C 10 alkyl and aryl C 1 -C 10 cycloalkyl, provided that any two of R 14 -R 17 may be part of an optionally unsaturated carbocyclic ring;
c) a polymerizable siloxane,
wherein the polymerizable siloxane is embraced by:
wherein R 18 , R 19 , R 20 and R 21 may be the same or different and are selected from the group consisting of hydrogen, hydroxyl, alkyl, alkoxy, alkenyl, alkenyloxy, aryl, and aryloxy; R 22 and R 23 may be the same or different and are selected from the group consisting of hydrogen, alkyl and aryl; and X is selected from alkylene, alkenylene, arylene, with or without interruption by a heteroatom.
3. 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 R 10 is C 1 -C 10 alkyl,
R 11 and R 12 , which may be the same or different, are selected from the group consisting of H, D, C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, phenyl, phenyl-substituted C 1 -C 10 alkyl and phenyl-substituted C 3 -C 10 cycloalkyl, provided that any two of R 10 -R 12 may optionally be part of a carbocyclic ring,
R 13 is H, D or C 1 -C 10 alkyl, and
M + is a metal ion or a quaternary ammonium ion comprising formula VII below
wherein R 14 -R 17 , which may be the same or different, are selected from the group consisting of C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 3 -C 10 cycloalkyl, aryl, C 1 -C 10 alkylaryl, aryl C 1 -C 10 alkyl and aryl C 1 -C 10 cycloalkyl, provided that any two of R 14 -R 17 may be part of an optionally unsaturated carbocyclic ring;
c) a polymerizable siloxane,
wherein the polymerizable siloxane is a diamino siloxane embraced by:
wherein R 26 and R 27 may be the same or different and are selected from the group consisting of alkylene, arylene, alkylene oxide, arylene oxide, alkylene esters, arlyene esters, alkylene amides and arylene amides; R 24 and R 25 may be the same or different and are selected from the group consisting of alkyl and aryl; R 22 and R 23 may be the same or different and are selected from the group consisting of hydrogen, alkyl and aryl and n is 1-1,200.
4. An adhesive bond formed between two substrates by the polymerization product of a composition, 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 R 10 is C 1 -C 10 alkyl,
R 11 and R 12 , which may be the same or different, are selected from the group consisting of H, D, C 1 -C 10 alkyl, C 3 -C 10 cycloalkyl, phenyl, phenyl-substituted C 1 -C 10 alkyl and phenyl-substituted C 3 -C 10 cycloalkyl, provided that any two of R 10 -R 12 may optionally be part of a carbocyclic ring,
R 13 is H, D or C 1 -C 10 alkyl, and
M + is a metal ion or a quaternary ammonium ion comprising formula VII below
wherein R 14 -R 17 , which may be the same or different, are selected from the group consisting of C 1 -C 10 alkyl, C 2 -C 10 alkenyl, C 3 -C 10 cycloalkyl, aryl, C 1 -C 10 alkylaryl, aryl C 1 -C 10 alkyl and aryl C 1 -C 10 cycloalkyl, provided that any two of R 14 -R 17 may be part of an optionally unsaturated carbocyclic ring, and
c) a polymerizable siloxane,
wherein the polymerizable siloxane is formed from
(i) at least one silane within the formula R 1 m R 2 p Si(X) 4-(m−p) A, wherein R 1 is a (meth)acrylate functional group, or a hydrolyzable group, and R 2 may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1-12 alkyl, C 6-12 aryl, C 7-18 alkylaryl, or 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 R 3 q Si(X) 4-q B, wherein R 3 may be the same as or different from R 2 above and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1-12 alkyl, C 6-12 aryl, and C 7-18 alkylaryl, and q is an integer from 1 to 3; or combinations thereof, reacted with at least another silane within the formula of R 4 r R 5 s Si(X) 4-(r+s) C, wherein R 4 and R 5 may be the same or different and may be selected from monovalent ethylenically unsaturated radicals, hydrogen, C 1-12 alkyl, C 6-12 aryl, C 7-18 alkylaryl, r is an integer from 1 to 3, and r+s is an integer from 1 to 3, provided the polymerizable siloxane formed contains at least some hydrolyzable group, X;
wherein the polymerizable siloxane is embraced by:
wherein R 18 , R 19 , R 20 and R 21 may be the same or different and are selected from the group consisting of hydrogen, hydroxyl, alkyl, alkoxy, alkenyl, alkenyloxy, aryl, and aryloxy; R 22 and R 23 may be the same or different and are selected from the group consisting of hydrogen, alkyl and aryl; and X is selected from alkylene, alkenylene, arylene, with or without interruption by a heteroatom, or
wherein the polymerizable siloxane is a diamino siloxane embraced by:
wherein R 26 and R 27 may be the same or different and are selected from the group consisting of alkylene, arylene, alkylene oxide, arylene oxide, alkylene esters, arlyene esters, alkylene amides and arylene amides; R 24 and R 25 may be the same or different and are selected from the group consisting of alkyl and aryl; R 22 and R 23 as may be the same or different and are selected from the group consisting of hydrogen, alkyl and aryl and n is 1-1,200.