# US 12,110,427 B2 · Polyorganosiloxane hybrid pressure sensitive adhesive and methods for the preparation and use thereof

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- Number: US 12,110,427 B2
- Document ID: US12110427B2
- Status: Granted
- Kind: B2
- Application number: 17/299,139
- Filed: 2020-03-13
- Published: 2022-03-10
- Granted: 2024-10-08
- Earliest claimed: 2019-03-14
- Assignees: Dow Silicones Corporation
- Applicants: Dow Silicones Corporation
- Inventors: Elizabeth Kelley; Timothy Mitchell; Jodi Mecca
- Web page: https://patentgrep.com/patent/US12110427B2

## CPC

- 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 77/08: characterised by the catalysts used
- C08G 77/12: containing silicon bound to hydrogen
- C08G 77/20: containing silicon bound to unsaturated aliphatic groups
- C08G 77/442: containing vinyl polymer sequences
- C08G 81/024: {Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G}
- C09J 7/38: Pressure-sensitive adhesives [PSA]
- C08G 77/70: {Siloxanes defined by use of the MDTQ nomenclature}
- C09J 2301/302: the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
- C09J 2301/414: presence of a copolymer
- C09J 2483/00: Presence of polysiloxane
- 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

## Abstract

A polydiorganosiloxane having both a silicon bonded aliphatically unsaturated group and a silicon bonded poly(meth)acrylate polymer or copolymer is useful in a polyorganosiloxane hybrid pressure sensitive adhesive composition that cures to form a polyorganosiloxane hybrid pressure sensitive adhesive. The polyorganosiloxane hybrid pressure sensitive adhesive composition can be wet-cast or dry-cast on a substrate and cured to form a polyorganosiloxane hybrid pressure sensitive adhesive article. An adhesive article including the polyorganosiloxane hybrid pressure sensitive adhesive is also disclosed.

## Claims

### Claim 1

A polyorganosiloxane hybrid pressure sensitive adhesive composition comprising:
(I) a polyorganosiloxane having both aliphatically unsaturated groups and poly(meth)acrylate groups, wherein the polyorganosiloxane comprises unit formula:
[R3w(R5—S—R″)(OR4)(2-w)Si—O1/2]p[R3v(R5—S—R″)(OR4)(1-v)Si—O2/2]q[(R5—S—R″)Si—O3/2]k(R6R72SiO1/2)r(R72SiO2/2)s(R6R7SiO2/2)t(R73SiO1/2)u,
where each subscript w is independently 0, 1, or 2, each subscript v is independently 0 or 1, each R3 is an independently selected monovalent hydrocarbon group; each R4 is an independently selected alkyl group; each R5 is an independently selected divalent hydrocarbon group, each R″ is independently a (meth)acrylate polymer or copolymer, each R6 is an independently selected aliphatically unsaturated monovalent hydrocarbon group, each R7 is an independently selected monovalent hydrocarbon group free of aliphatic unsaturation, subscript p≥0, subscript q≥0, subscript k≥0, a quantity (p+q+k)≥1, subscript r≥0, subscript s≥0, subscript t≥0, subscript u≥0, a quantity (r+t)≥1, and a quantity (p+q+k+r+s+t+u) is sufficient to provide a molecular weight of at least 50 kDa to the polyorganosiloxane;
(II) an organohydrogensilicon compound having, per molecule, at least 3 silicon bonded hydrogen atoms;
(III) a hydrosilylation reaction catalyst;
optionally (IV) a hydrosilylation reaction inhibitor;
(V) a polyorganosilicate resin; and
optionally (XX) a solvent.

### Claim 2 (depends on 1)

The composition of claim 1, where in (I) the polyorganosiloxane, R3 has 1 to 18 carbon atoms, R4 has 1 to 6 carbon atoms, R5 has 1 to 18 carbon atoms, R6 has 2 to 18 carbon atoms, and R7 has 1 to 18 carbon atoms, R″ has a has a DP of 1 to 1,000; subscript (p+r+u)=2, subscript k=0, a quantity (p+q) is 1 to 100, a quantity (r+t) is 1 to 100, a quantity (p+q+r+s+t+u) is sufficient to provide a molecular weight of 50 kDa to 1,000 kDa to the polyorganosiloxane.

### Claim 3 (depends on 2)

The composition of claim 2, where in (I) the polyorganosiloxane, subscript p is 1 or 2, each R3 is an alkyl group of 1 to 6 carbon atoms, each R4 is an alkyl group of 1 to 6 carbon atoms, each R5 is an alkylene group of 2 to 8 carbon atoms, R″ has a DP of 5 to 600, each R6 is an alkenyl group selected from vinyl, allyl and hexenyl, and each R7 is an alkyl group of 1 to 6 carbon atoms.

### Claim 4 (depends on 1)

The composition of claim 1, where (II) the organohydrogensilicon compound comprises a polyorganohydrogensiloxane of Formula II-1), Formula II-2), and a combination thereof, where
is R133SiO(R132SiO)aa(R13HSiO)bbSiR133 Formula I-1)
and
is R132HSiO(R132SiO)cc(R13HSiO)ddSiR132H, Formula II-2)
where subscript aa has an average value ranging from 0 to 2000, subscript bb has an average value ranging from 2 to 2000, subscript cc has an average value ranging from 0 to 2000, and subscript dd has an average value ranging from 0 to 2000; each R13 is independently a monovalent hydrocarbon group.

### Claim 5 (depends on 4)

The composition of claim 4, where the polyorganohydrogensiloxane is selected from the group consisting of:
a) dimethylhydrogensiloxy-terminated polydimethylsiloxane,
b) dimethylhydrogensiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane),
c) dimethylhydrogensiloxy-terminated polymethylhydrogensiloxane,
d) trimethylsiloxy-terminated poly(dimethylsiloxane/methylhydrogensiloxane),
e) trimethylsiloxy-terminated polymethylhydrogensiloxane, and
f) a combination thereof.

### Claim 6 (depends on 1)

The composition of claim 1, where the hydrosilylation reaction catalyst comprises 1,3-diethenyl-1,1,3,3-tetramethyldisiloxane complexes with platinum.

### Claim 7 (depends on 1)

The composition of claim 1, where (IV) the hydrosilylation reaction inhibitor is present and is selected from the group consisting of an acetylenic alcohol, a cycloalkenylsiloxane, an ene-yne compound, a triazole, a phosphine, a mercaptan, a hydrazine, an amines, a fumarate, a maleate, a nitrile, an ether, carbon monoxide, an alkene, an alcohol, a silylated acetylenic compound, and a combination thereof.

### Claim 8 (depends on 7)

The composition of claim 7, where the hydrosilylation reaction inhibitor comprises an acetylenic alcohol.

### Claim 9 (depends on 1)

The composition of claim 1, where (V) the polyorganosilicate resin comprises unit formula: (R152R16SiO1/2)x(R153SiO1/2)y(SiO4/2)z, where R15 is an alkyl group, an aryl group, or an aralkyl group, such as methyl and phenyl; and R16 is an alkenyl group of 2 to 18 carbon atoms, such as vinyl, allyl or hexenyl; subscript x≥0, subscript y≥0, subscript z>0, a quantity (x+y)>0, and subscripts x, y, and z have values such that 0.9≤(x+y)/z≤1.3.

### Claim 10 (depends on 9)

The composition of claim 9, where subscript x=0, and the polyorganosilicate resin comprises unit formula: (R153SiO1/2)w(SiO4/2)z, where subscript w>4.

### Claim 11 (depends on 1)

The composition of claim 1, where the solvent is present, and the solvent is an aromatic hydrocarbon.

### Claim 12 (depends on 1)

The composition of claim 1, where starting material (I) is present in an amount of 15 weight % to 40 weight %; starting material (II) is present in an amount sufficient to provide a molar ratio of SiH content of starting material (II) to aliphatically unsaturated group (R6) content of starting material (I) (the SiH:Vi ratio) of 1:1 to 40:1; starting material (III) is present in an amount sufficient to provide 1 ppm to 150 ppm of the platinum group metal; starting material (IV) is present in an amount sufficient to provide a weight ratio of starting material (III): starting material (IV) of up to 40:1; starting material (V) is present in an amount of 5 weight % to 60 weight %; and the solvent is present in an amount of 0 to 70 weight %, wherein all percentages are by weight based on combined weights of all starting materials.

### Claim 13 (depends on 12)

The composition of claim 12, where starting material (I) is present in an amount of 17% to 25%; starting material (II) is present in an amount sufficient to provide the SiH:Vi ratio 10:1 to 35:1; starting material (III) is present in an amount sufficient to provide 2 ppm to 50 ppm, of the platinum group metal; starting material (V) is present in an amount of 25% to 40%; and the solvent is present in an amount of 40% to 60%.

### Claim 14 (depends on 1)

A method for making an adhesive article substrate comprising:
optionally i) pre-treating a surface of a substrate,
ii) forming a film of the hybrid PSA composition of claim 1 on the surface of the substrate,
optionally iii) removing all or a portion of the solvent, and
iv) curing the hybrid PSA composition to form a hybrid PSA.

### Claim 15 (depends on 1)

The composition of claim 1, where in (I) the polyorganosiloxane, R″ comprises (meth)acrylate monomer units selected from the group consisting of acrylic acid, butyl acrylate, butyl methacrylate, 2-ethylhexylacrylate, 2-ethylhexylmethacrylate, isobutyl acrylate, isobutyl methacrylate, methyl methacrylate, methacrylic acid, benzyl methacrylate, phenyl methacrylate, and a combination thereof.

### Claim 16 (depends on 15)

The composition of claim 15, where the (meth)acrylate monomer units are selected from the group consisting of acrylic acid, butyl acrylate, butyl methacrylate, 2-ethylhexylacrylate, methyl methacrylate, and a combination thereof.

### Claim 17 (depends on 3)

The composition of claim 3, where in (I) the polyorganosiloxane, each R3 is methyl, each R4 is methyl or ethyl, each R5 is methyl, propyl, or undecyl, R″ has a DP of 5 to 600, each R6 is vinyl, and each R7 is methyl.