# US 11,028,297 B2 · Dual cure adhesive composition and methods for its preparation and use

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- Number: US 11,028,297 B2
- Document ID: US11028297B2
- Status: Granted
- Kind: B2
- Application number: 16/621,756
- Filed: 2018-08-21
- Published: 2020-07-02
- Granted: 2021-06-08
- Earliest claimed: 2017-08-22
- Assignees: Dow Silicones Corporation
- Applicants: Dow Silicones Corporation
- Inventors: Gang Lu; Nick Shephard; Ryan Thomas; Matthew Olsen
- Web page: https://patentgrep.com/patent/US11028297B2

## CPC

- C09J 183/14: in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C09J183/10 takes precedence)
- C08G 77/08: characterised by the catalysts used
- C08G 77/16: to hydroxy groups
- C08G 77/18: to alkoxy or aryloxy groups
- C08G 77/48: in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms (C08G77/42 takes precedence)
- C09J 183/10: Block or graft copolymers containing polysiloxane sequences (obtained by polymerising a compound having a carbon-to-carbon double bond on to a polysiloxane C09J151/08, C09J153/00)
- C08G 77/442: containing vinyl polymer sequences
- C08K 5/14: Peroxides
- C08K 5/23: Azo-compounds
- C08K 5/57: Organo-tin compounds
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## Abstract

A dual cure (condensation and free radical reaction) adhesive composition is useful for electronics applications.

## Claims

### Claim 1

An adhesive composition comprising:
A) a poly(meth)acrylate clustered functional polyorganosiloxane comprising units of formulae:
(R2R1SiO1/2)aa(RR1SiO2/2)bb(R2SiO2/2)cc(RSiO3/2)dd(RSiO3/2)dd(SiO4/2)ee((Rff)O(3-ff)/2SiD1SiRffO(3-ff)/2)gg, where each D1 independently represents a divalent hydrocarbon group of 2 to 18 carbon atoms; each R independently represents a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, each R1 independently represents a methacryl-functional alkyl group or an acryl-functional alkyl group, subscript aa≥0, subscript bb≥0, a quantity (aa+bb)≥4, subscript cc>0, subscript dd≥0, subscript ee≥0, subscript ff is 0, 1, or 2, subscript gg≥2;
B) a poly-alkoxy endblocked resin-polymer blend comprising a reaction product of
i) a siloxane resin comprising units of formulae (R2′3SiO1/2) and (SiO4/2), where each R2′ is independently a monovalent hydrocarbon group, with the proviso that at least one R2′ per molecule has terminal aliphatic unsaturation, where the siloxane resin has a molar ratio of (R2′3SiO1/2) units to (SiO4/2) units ranging from 0.5:1 to 1.5:1,
ii) a polydiorganosiloxane comprising units of formulae (R2′3SiO1/2)ii and (R2SiO2/2)hh, where R2′ is as described above, subscript hh is 20 to 1000 and subscript ii has an average value of 2;
iii) an alkoxy-functional organohydrogensiloxane oligomer, wherein the alkoxy-functional organohydrogensiloxane oligomer comprises one or more of
formula (V)
where subscript a is 0 or a positive number, subscript c is 0 or 1, each R independently represents a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, each R3 is independently a monovalent hydrocarbon group of 1 to 8 carbon atoms, and D is a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that >90 mol % of D are linear divalent hydrocarbon groups;
formula (VIII)
where subscript c is 0 or 1, each R independently represents a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, each R3 is independently a monovalent hydrocarbon group of 1 to 8 carbon atoms, and D is a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that >90 mol % of D are linear divalent hydrocarbon groups;
formula (XI)
where subscript c is 0 or 1, each R independently represents a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, each R3 is independently a monovalent hydrocarbon group of 1 to 8 carbon atoms, and D is a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that >90 mol % of D are linear divalent hydrocarbon groups;
formula (XII)
where subscript c is 0 or 1, each R independently represents a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, each R3 is independently a monovalent hydrocarbon group of 1 to 8 carbon atoms, and D is a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that >90 mol % of D are linear divalent hydrocarbon groups; and
unit formula (R2SiO2/2)v(RHSiO2/2)t
where subscript c is 0 or 1, subscript v is 0 to 14, subscript t is 0 or more, subscript u is 1 or more, t+u is at least 3, each R independently represents a monovalent hydrocarbon group of 1 to 18 carbon atoms or a monovalent halogenated hydrocarbon group of 1 to 18 carbon atoms, each R3 is independently a monovalent hydrocarbon group of 1 to 8 carbon atoms, and D is a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that >90 mol % of D are linear divalent hydrocarbon groups; and
iv) a selective hydrosilylation reaction catalyst;
C) a condensation reaction catalyst; and
D) a free radical initiator.

### Claim 2 (depends on 1)

The composition of claim 1, further comprising one or more additional starting materials selected from the group consisting of E) a dual cure compound, F) an adhesion promoter, G) a corrosion inhibitor, H) a rheology modifier, I) a drying agent, J) a crosslinker, K) a filler, L) a spacer, M) an acid scavenger, N) a silanol functional polydiorganosiloxane, O) a fluorescent optical brightener, P) a chain transfer agent, Q) a (meth)acrylate monomer, R) a poly-alkoxy terminated polydiorganosiloxane, S) a colorant, and two or more of E), F), G), H), I), J), K), L), M), N), O), P), Q), R) and S).

### Claim 3 (depends on 1)

The adhesive composition of claim 1, where A) the poly(meth)acrylate clustered functional polyorganosiloxane has formula:
where subscript j is 0 to 2,000,000, and each subscript k is independently 1 to 12.

### Claim 4 (depends on 1)

The adhesive composition of claim 1, where A) the poly(meth)acrylate clustered functional polyorganosiloxane has formula:
where subscript j is 0 to 2,000,000, and each subscript k is independently 1 to 12.

### Claim 5 (depends on 1)

The adhesive composition of claim 1, where starting material B) i) has 3 to 30 mol % vinyl groups.

### Claim 6 (depends on 1)

The adhesive composition of claim 1, where starting material B)ii) is a polydiorganosiloxane selected from the group consisting of
i) dimethylvinylsiloxy-terminated polydimethylsiloxane,
ii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane),
iii) dimethylvinylsiloxy-terminated polymethylvinylsiloxane,
iv) trimethylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane),
v) trimethylsiloxy-terminated polymethylvinylsiloxane,
vi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylvinylsiloxane),
vii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylphenylsiloxane),
viii) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/diphenylsiloxane),
ix) phenyl,methyl,vinyl-siloxy-terminated polydimethylsiloxane,
x) dimethylhexenylsiloxy-terminated polydimethylsiloxane,
xi) dimethylhexenylsiloxy-terminated poly(dimethylsiloxane/methylhexenylsiloxane),
xii) dimethylhexenylsiloxy-terminated polymethylhexenylsiloxane,
xiii) trimethylsiloxy-terminated poly(dimethylsiloxane/methylhexenylsiloxane),
xiv) trimethylsiloxy-terminated polymethylhexenylsiloxane
xv) dimethylhexenyl-siloxy terminated poly(dimethylsiloxane/methylhexenylsiloxane),
xvi) dimethylvinylsiloxy-terminated poly(dimethylsiloxane/methylhexenylsiloxane)
xvii) a combination of two or more of i), ii), iii), iv), v) vi), vii), viii) ix), x), xi), xii), xiii), xiv), xv), and xvi).

### Claim 7 (depends on 1)

The adhesive composition of claim 1, where starting material B) iii) comprises an alkoxy-functional organohydrogensiloxane oligomer of formula (V):
where R and subscripts a and c are as described above, D is a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that >90 mol % of D are linear divalent hydrocarbon groups.

### Claim 8 (depends on 1)

The adhesive composition of claim 1, where starting material B) iii) comprises an alkoxy-functional organohydrogensiloxane oligomer of formula (VIII), where formula (VIII) is:
where R and subscript c are as described above, each D is independently a divalent hydrocarbon group of 2 to 18 carbon atoms, with the proviso that >90 mol % of D are linear divalent hydrocarbon groups.

### Claim 9 (depends on 1)

The adhesive composition of claim 1, where starting material B) iii) comprises an alkoxy-functional organohydrogensiloxane oligomer of formula (XI), formula (XII), or a combination thereof, where formula (XI) is
and formula (XII) is
where R and subscript c are as described above.

### Claim 10 (depends on 1)

The adhesive composition of claim 1, where starting material B) iv) comprises a cobalt complex of formula: [Co(R5)x(R6)y(R7)w]z, where a quantity (w+x+y)=4; subscript z is 1 to 6; each R5 is a ligand selected from carbon monoxide (CO), an isonitrile (CNR8), a cyanoalkyl (NCR8), NO+ (called a nitrosyl or nitrosonium) or cyano (CN−), where each R8 is independently an alkyl group of 1 to 18 carbon atoms; with the proviso that when R5 is positively charged, a negatively charged counteranion will be present, and when R5 is negatively charged, a positively charged counter cation is present; each R6 is independently a phosphine ligand exemplified by a diphenyl-bisphosphino alkane ligand, with the proviso that when subscript y>0, then subscript z is at least 2; and each R7 is an anionic ligand.

### Claim 11 (depends on 1)

The adhesive composition of claim 1, where starting material B)iv) comprises an iridium complex of formula: [Ir(R9)xx(R10)yy]zz, where subscript xx is 1 or 2, R9 is a 1,5-cyclooctadiene ligand or a 2,5-norbornadiene ligand, subscript yy is 0, 1 or 2, R10 is a ligand that can be activated off the complex at a temperature less than a boiling point of the organohydrogensiloxane oligomer, and subscript zz is 1 or 2.

### Claim 12 (depends on 1)

The adhesive composition of claim 1, where starting material B)iv) comprises a rhodium diphosphine chelate with a formula selected from (c1) and (c2), where
(c1) is [(R4(R112P)2)RhR12]2, where each R4 is independently a divalent hydrocarbon group, each R11 is independently a monovalent hydrocarbon group, and each R12 is a negatively charged ligand; and
(c2) is [(R4(R11P)2)Rh(R14)]R13, where R13 is an anion, and R14 is a donor ligand.

### Claim 13 (depends on 1)

The adhesive composition of claim 1, where starting material C) is selected from the group consisting of: an organotin compound and an organotitanium compound.

### Claim 14 (depends on 1)

The adhesive composition of claim 1, where starting material D) is selected from an azo compound or an organic peroxide compound.