# US 10,370,499 B2 · Curable organosiloxane oligomer compositions

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- Number: US 10,370,499 B2
- Document ID: US10370499B2
- Status: Granted
- Kind: B2
- Application number: 15/108,827
- Filed: 2014-12-22
- Published: 2016-11-03
- Granted: 2019-08-06
- Earliest claimed: 2013-12-31
- Assignees: 3M Innovative Properties Company
- Applicants: 3M Innovative Properties Company
- Inventors: Kanta Kumar; James T. Wolter
- Web page: https://patentgrep.com/patent/US10370499B2

## CPC

- C08G 77/44: containing only polysiloxane sequences
- C08G 77/08: characterised by the catalysts used
- C08G 77/24: halogen-containing groups
- C08K 5/31: Guanidine; Derivatives thereof
- C08K 5/5399: Phosphorus bound to nitrogen
- C08L 83/00: Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L 83/08: containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C09D 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 C09D151/08, C09D153/00)
- C09J 7/401: {characterised by the release coating composition}
- C09J 2301/302: the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
- C09J 2483/005: in the release coating
- 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)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- 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)

## Abstract

A curable composition including (a) at least one organosiloxane compound, fluorinated organosiloxane compound, or combination thereof having reactive silane functionality including at least two hydroxysilyl moieties; (b) at least one organosiloxane oligomer, fluorinated organosiloxane oligomer, or combination thereof having reactive silane functionality including at least two hydrosilyl moieties; and (c) a catalyst composition including (1) at least one base selected from amidines, guanidines, phosphazenes, proazaphosphatranes, and combinations thereof, and (2) at least one Lewis acid. At least one of the components (a) and (b) has an average reactive silane functionality of at least three, and the composition is substantially free of organic solvent(s). An alkoxysilane compound may be optionally included in the curable composition. A process for coating the composition to prepare articles having the cross-linked composition on at least a portion of at least one major substrate surface is also disclosed.

## Claims

### Claim 1

A composition comprising the following components:
(a) at least one organosiloxane compound, fluorinated organosiloxane compound, or a combination thereof, comprising reactive silane functionality comprising at least two hydroxysilyl moieties;
(b) at least one organosiloxane oligomer, fluorinated organosiloxane oligomer, or a combination thereof, comprising reactive silane functionality comprising at least two hydrosilyl moieties; and
(c) a catalyst composition comprising (1) at least one base selected from amidines, guanidines, phosphazenes, proazaphosphatranes, and combinations thereof, and (2) at least one Lewis acid;
wherein at least one of said components (a) and (b) has an average reactive silane functionality of at least three, the composition is substantially free of an organic solvent, and the composition further comprises
(R″O)p—Si(R′)3-p[G-Si(R′)2]t—(W)s—[(R′)2SiO]q—[Si(R′)2-G]t—Si(R′)3-p—(OR″)p;
wherein:
G and W are oxy;
each R′ is independently selected from alkyl, alkylene, fluoroalkyl, aryl, fluoroaryl, cycloalkyl, fluorocycloalkyl, hetroalkyl, hetrofluoroalkyl, hetroaryl, hetrofluoroaryl, hetrocycloalkyl, hetrofluorocycloalkyl, oxyalkyl, oxyfluoroalkyl, oxyaryl, oxyfluoroaryl, oxycycloalkyl, oxyfluorocycloalkyl, oxyhetroalkyl, oxyhetrofluoroalkyl, oxyhetroaryl, oxyhetrofluoroaryl, oxyhetrocycloalkyl, and oxyhetrofluorocycloalkyl;
each R″ is independently selected from alkyl;
P is an integer selected from 1, 2 or 3;
each q is independently selected as an integer of 0-150, inclusive;
s is selected as an integer of 0-40, inclusive; and
each t is independently selected as an integer of 0 or 1.

### Claim 2 (depends on 1)

The composition of claim 1, wherein said components (a) and (b) each comprise an organosiloxane oligomer having a weight average molecular weight no greater than 5,000 Da, optionally wherein each organosiloxane oligomer is a dimethylsiloxane oligomer.

### Claim 3 (depends on 1)

The composition of claim 1, wherein said component (a) is hydroxyl-endblocked.

### Claim 4 (depends on 1)

The composition of claim 1, wherein said component (a) is represented by:
(HO)p—Si(R′)3-p—[G-Si(R′)2]t—O—[(R′)2SiO]q—[Si(R′)2-G]t—Si(R′)3-p—(OH)p
wherein each G is independently a divalent linking group;
each R′ is independently selected from alkyl, fluoroalkyl, aryl, fluoroaryl, cycloalkyl, fluorocycloalkyl, heteroalkyl, heterofluoroalkyl, heteroaryl, heterofluoroaryl, heterocycloalkyl, heterofluorocycloalkyl;
each p is independently an integer of 1, 2, or 3;
q is an integer of 0 to 150; and
each t is independently an integer of 0 or 1.

### Claim 5 (depends on 1)

The composition of claim 1, wherein said component (a) comprises a mixture of (1) at least one polyorganosiloxane, fluorinated polyorganosiloxane, or combination thereof having a weight average molecular weight in the range of 10,000 to 1,000,000 and (2) at least one organosiloxane oligomer, fluorinated organosiloxane oligomer, or combination thereof having a weight average molecular weight in the range of about 150 to about 5,000 Da.

### Claim 6 (depends on 1)

The composition of claim 1, wherein said component (b) is represented by the following general formula:
R′2R″SiO(R′2SiO)r(HR′SiO)sSiR″R′2
wherein each R′ is independently selected from H, alkyl, alkenyl, fluoroalkyl, aryl, fluoroaryl, cycloalkyl, fluorocycloalkyl, heteroalkyl, heterofluoroalkyl, heteroaryl, heterofluoroaryl, heterocycloalkyl, heterofluorocycloalkyl;
each R″ is independently H or R′;
r is an integer of 0 to 150, inclusive; and
s is an integer of 2 to 150, inclusive.

### Claim 7 (depends on 1)

The composition of claim 1, wherein the base of component (c) is selected from:
(1) amidine compounds that are represented by the following general formula:
(2) guanidine compounds that are represented by the following general formula:
(3) phosphazene compounds that are represented by the following general formula:
(4) proazaphosphatrane compounds that are represented by the following general formula:
and combinations thereof;]
wherein R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, monovalent organic groups, monovalent heteroorganic groups, and combinations thereof.

### Claim 8 (depends on 7)

The composition of claim 7, wherein the base is selected to include at least two amidine compounds, guanidine compounds, phosphazene compounds, or combinations thereof, and further wherein any two or more of R1, R2, R3, R4, R5, R6, and R7 of said at least two amidine, guanidine, and phosphazene compounds are bonded together to form at least one ring structure.

### Claim 9 (depends on 1)

The composition of claim 1, wherein said Lewis acid is selected from metal salts, trialkylborates, triarylborates, and combinations thereof.

### Claim 10 (depends on 1)

The composition of claim 1, further comprising at least one carboxylic acid, at least one carboxylic acid anhydride, or a combination thereof.

### Claim 11 (depends on 1)

The composition of claim 1, wherein said composition is substantially free of a tin catalyst.

### Claim 12 (depends on 1)

The composition of claim 1 wherein the catalyst composition (1) comprises at least one base selected from 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene (DBN), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), 2-tert-butyl-1,1,3,3-tetramethylguanidine, and combinations thereof.

### Claim 13 (depends on 1)

The composition of claim 1, wherein at least one of said component (a) or said component (b) is a fluorinated organosiloxane oligomer.

### Claim 14 (depends on 1)

The composition of claim 1, wherein said Lewis acid is a zinc(II) salt that is used in a 1:1 molar ratio with said base.

### Claim 15 (depends on 1)

A process comprising
(a) applying the composition according to claim 1 to at least a portion of a substrate; and
(b) at least partially curing said composition to form a cross-linked coating on the substrate.

### Claim 16 (depends on 15)

An article comprising the cross-linked coating prepared by the process of claim 15, wherein the at least a portion of the substrate is at least one major surface of the substrate, optionally wherein the cross-linked coating contacts the at least one major surface of the substrate.

### Claim 17 (depends on 16)

The article of claim 16, wherein said article further comprises a layer of a pressure-sensitive adhesive prepared by application of a photopolymerizable composition to said cross-linked coating, followed by irradiation of said photopolymerizable composition to effect photopolymerization thereof.