Room temperature curable siloxane-based gels

• US 10,294,333 B2
• Filed: 12/04/2013
• Issued: 05/21/2019
• Est. Priority Date: 12/12/2012
• Status: Active Grant

• Current Assignee: Solventum Intellectual Properties Company (Solventum Corp.)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Liu, Junkang J., Ishiwatari, Hironobu, Welke, Siegfried K., Kakinuma, Yoshiteru
• Primary Examiner(s): Ducheneaux, Frank D
• Application Number:
  US14/650,608
• Publication Number:
  US 20150376345A1
• Time in Patent Office: 1,994 Days
• Field of Search: None
• CPC Class Codes: A61L 24/046 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds A61L24/043 takes precedence
• CPC Class Codes: C08G 2220/00 Compositions for preparing gels other than hydrogels, aerogels and xerogels
• CPC Class Codes: C08G 77/16 to hydroxyl groups
• CPC Class Codes: C08G 77/44 containing only polysiloxane sequences
• CPC Class Codes: C08J 3/28 Treatment by wave energy or particle radiation
• CPC Class Codes: C08K 3/36 Silica
• CPC Class Codes: C08K 5/544 containing nitrogen
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: 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
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C09J 183/04 Polysiloxanes
• CPC Class Codes: 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
• CPC Class Codes: C09J 7/40 characterised by release liners
• CPC Class Codes: C09K 3/1018 Macromolecular compounds having one or more carbon-to-silicon linkages

Abstract

Siloxane-based gel compositions are prepared from room temperature condensation curable mixtures that include 0.5-45% by weight silicone resin with at least two hydroxyl groups, 99.5-55% by weight of at least one silanol-terminated siloxane fluid, and a co-curable compound with an amino group. The siloxane-based gel compositions can be used as adhesives or sealants in medical articles.

Claims

1. A gel composition comprising the reaction product of a condensation curable mixture comprising:

at least 0.5 to less than 45% by weight silicone resin comprising at least two hydroxyl groups;

at least 55 to less than 99.5% by weight of at least one silanol-terminated siloxane fluid; and

a co-curable compound comprising an amino group, wherein the condensation curable mixture is curable at room temperature and wherein the condensation curable mixture upon curing is a gel selected from a medical gel adhesive or a medical gel sealant, wherein the gel comprises a crosslinked matrix containing a liquid or fluid.

2. The gel composition of claim 1, wherein the co-curable compound comprising an amino group has the general structure:

R⁶_2-xR⁷_xN-G-Si(OR⁸)_yR⁹_3-y

wherein each R⁶ and R⁷ independently comprises a hydrogen atom or an alkyl, aryl, heteroalkyl, heteroaryl, or aralkyl group;

x is an integer of 0, 1, or 2;

G is a divalent linking group;

each R⁸ independently is an alkyl, aryl, heteroalkyl, heteroaryl, or aralkyl group;

each R⁹ independently is an alkyl, aryl, heteroalkyl, heteroaryl, or aralkyl group; and

y is an integer of 1, 2, or 3.

3. The gel composition of claim 2, wherein G is a divalent alkylene group having the general structure:

(—

CH₂-)_a

wherein a is an integer of 1 to 18.

4. The gel composition of claim 1, further comprising at least one non-reactive siloxane fluid.

5. The gel composition of claim 1, wherein the gel composition comprises a medical gel sealant.

6. The gel composition of claim 1, wherein the gel composition comprises a medical gel adhesive layer.

7. The gel composition of claim 1, wherein the gel composition comprises at least 0.5% by weight of extractable siloxane fluid.

8. An article comprising:

a substrate; and

a layer of adhesive gel disposed on at least a portion of at least one major surface of the substrate, the adhesive gel comprising the reaction product of a condensation curable mixture comprising;

at least 0.5 to less than 45% by weight silicone resin comprising at least two hydroxyl groups;

at least 55 to less than 99.5% by weight of at least one silanol-terminated siloxane fluid; and

a co-curable compound comprising an amino group, wherein the condensation curable mixture is curable at room temperature, and wherein the gel comprises a crosslinked matrix and a liquid or fluid.

9. The article of claim 8, wherein the co-curable compound comprising an amino group has the general structure:

R⁶_2-xR⁷_xN-G-Si(OR⁸)_yR⁹_3-y

wherein each R⁶ and R⁷ independently comprises a hydrogen atom or an alkyl, aryl, heteroalkyl, heteroaryl, or aralkyl group;

x is an integer of 0, 1, or 2;

G is a divalent linking group;

each R⁸ independently is an alkyl, aryl, heteroalkyl, heteroaryl, or aralkyl group;

each R⁹ independently is an alkyl, aryl, heteroalkyl, heteroaryl, or aralkyl group; and

y is an integer of 1, 2, or 3.

10. The article of claim 9, wherein G is a divalent alkylene group having the general structure:

(—

CH₂—

)_a

wherein a is an integer of 1 to 18.

11. The article of claim 8, wherein the adhesive gel further comprises at least one non-reactive siloxane fluid.

12. The article of claim 8, wherein the substrate comprises a release liner or a medical substrate.

13. The article of claim 8, wherein the reaction product of the condensation curable mixture has been exposed to ultra-violet radiation, gamma radiation, or an electron beam.

14. A method of preparing a medical article comprising:

providing a condensation curable gel precursor composition comprising;

at least 0.5 to less than 45% by weight silicone resin comprising at least two hydroxyl groups;

at least 55 to less than 99.5% by weight of at least one silanol-terminated siloxane fluid; and

a co-curable compound comprising an amino group, wherein the condensation curable gel precursor composition is curable at room temperature;

applying the condensation curable gel precursor composition to a substrate; and

permitting the condensation curable gel precursor composition to cure at room temperature to form a gel.

15. The method of claim 14, wherein providing the condensation curable gel precursor composition comprises mixing together of a 2 part mixture, the 2 part mixture comprising:

1) the at least 0.5 to less than 45% by weight silicone resin comprising at least two hydroxyl groups the;

at least 55 to less than 99.5% by weight of at least one silanol-terminated siloxane fluid; and

2) the co-curable compound comprising an amino group, wherein

     1) and

     2) are physically isolated from each other prior to mixing.

16. The method of claim 15, wherein the gel comprises a sealant.

17. The method of claim 14, wherein the gel comprises an adhesive.

18. The method of claim 17, wherein the substrate comprises a release liner or a medical substrate.

19. The method of claim 18, wherein the substrate comprises a release liner, and the method further comprises laminating the gel to a second substrate or to a surface.

20. The method of claim 14, wherein the co-curable compound comprising an amino group has the general structure:

R⁶_2-xR⁷_xN-G-Si(OR⁸)_yR⁹_3-y

wherein each R⁶ and R⁷ independently comprises a hydrogen atom or an alkyl, aryl, heteroalkyl, heteroaryl, or aralkyl group;

x is an integer of 0, 1, or 2;

G is a divalent linking group;

each R⁸ independently is an alkyl, aryl, heteroalkyl, heteroaryl, or aralkyl group;

each R⁹ independently is an alkyl, aryl, heteroalkyl, heteroaryl, or aralkyl group; and

y is an integer of 1, 2, or 3.

21. The method of claim 14, wherein the gel further comprises at least one non-reactive siloxane fluid.

22. The method of claim 14, further comprising exposing the condensation curable gel precursor composition to ultra-violet radiation, gamma radiation, or an electron beam.