Latently-curable organosilicone release coating composition

• US 4,504,645 A
• Filed: 09/23/1983
• Issued: 03/12/1985
• Est. Priority Date: 09/23/1983
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Melancon, Kurt C.
• Primary Examiner(s): Marquis, Melvyn I.
• Application Number:
  US06/535,040
• Time in Patent Office: 536 Days
• Field of Search: 528/15, 528/31, 528/32, 528/12, 525/478
• US Class Current: 528/15
• CPC Class Codes: C08G 77/12 containing silicon bound to hydrogen C08G77/045 takes precedence
• CPC Class Codes: C08G 77/20 containing silicon bound to unsaturated aliphatic groups C08G77/045 takes precedence
• CPC Class Codes: C08G 77/24 halogen-containing groups
• CPC Class Codes: C08G 77/70 Siloxanes defined by use of the MDTQ nomenclature
• CPC Class Codes: C08K 5/10 Esters; Ether-esters
• CPC Class Codes: C08K 5/20 Carboxylic acid amides
• CPC Class Codes: C08L 2666/34 Oxygen-containing compounds, including ammonium and metal salts
• 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

Abstract

A latently-curable, organosilicone composition comprises a metal catalyzed organosilicone composition capable of undergoing hydrosilation and, as hydrosilation inhibitor, an organic monohydrogen derivative of an unsaturated aliphatic 1,4-dicarboxylic acid, i.e., maleic acid or acetylene dicarboxylic acid. The organic monohydrogen derivatives of use in this invention effectively inhibit catalyzed hydrosilation reactions at low or room temperature while allowing efficient hydrosilation reaction rates to occur at elevated temperatures. These monhydrogen derivatives perform their inhibitive function effectively at low concentration. The latently curable composition may be coated on a substrate to provide a release surface for an adjacent adhesive layer.

Claims

1. A latently-curable organosilicone composition comprising the following components:

(a) an ethylenically-unsaturated polysiloxane,

(b) a polyhydrosiloxane,

(c) an amount of a platinum- or other metal-containing hydrosilation catalyst sufficient to facilitate the reaction of components (a) and (b), and

(d) an amount of an organic hydrosilation inhibitor sufficient to inhibit premature gelation of the mixture of components (a), (b), and (c) at low, ambient or room temperature but insufficient in amount to prevent hydrosilation of the mixture at an elevated temperature, said organic hydrosilation inhibitor having the structural formula ##STR8## wherein R² is ethynylene or cis-ethenylene;

R³ is a saturated or unsaturated organic group having 1 to 12 carbon atoms which is unsubstituted or substituted by 1 to 23 halogen atoms, and has up to 25 hydrogen atoms, and 0 to 5 non-peroxidic catenary oxygen atoms; and

X is --O-- or ##STR9## in which R⁴ is the same as defined for R³, and R³ and R⁴ together can form an alkylene group which with the N can form a 5- or 6-atom membered saturated azacyclic ring.

2. The composition according to claim 1 wherein R³ is selected from the group consisting of (1) acyclic saturated and unsaturated aliphatic groups having 1 to 12 carbon atoms, (2) alicyclic groups having 3 to 12 carbon atoms, (3) aryl groups having 6 to 12 carbon atoms, (4) alkaryl and aralkyl groups having 7 to 12 carbon atoms, (5) alkenylaryl and aralkenyl groups having 8 to 12 carbon atoms, and (6) alkoxyalkyl and poly(alkoxy)alkyl groups in which the alkyl groups have 2 to 4 carbon atoms.

3. The composition according to claim 1 wherein X is --O--.

4. The composition according to claim 1 wherein said organic hydrosilation inhibitor is selected from the group consisting of methyl hydrogen maleate, ethyl hydrogen acetylenedioate, allyl hydrogen maleate, butyl hydrogen maleate, 2-methoxyethyl hydrogen maleate, cyclohexyl hydrogen maleate, benzyl hydrogen maleate, octyl hydrogen maleate, isooctyl hydrogen maleate, 2-ethylhexyl hydrogen maleate, dodecyl hydrogen maleate, 2,2,2-trifluoroethyl hydrogen maleate, and N,N-bis(2-ethylhexyl)maleamic acid.

5. The composition according to claim 1 wherein component (a) has the empirical formula ##EQU3## wherein each R is bonded to a silicon atom and is selected from the group consisting of monovalent aliphatic or aromatic hydrocarbon radicals or halogenated derivatives thereof, cyanoalkyl radicals, and combinations thereof, R having 1 to 13 carbon atoms, R¹ is bonded to a silicon atom and is an ethylenically unsaturated aliphatic hydrocarbon monovalent radical having 2 to 6 carbon atoms, subscript a is a number from 0 to 3, subscript b is a number of from 0.005 to 2.0, and the sum of subscript a and subscript b is equal to a number from 0.8 to 3.

6. The composition according to claim 1 wherein component (b) has the empirical formula ##EQU4## wherein each R is bonded to a silicon atom and is independently selected from the group consisting of monovalent aliphatic or aromatic hydrocarbon radicals or halogenated derivatives thereof, cyanoalkyl radicals, and combinations thereof, R having 1 to 13 carbon atoms, subscript a is a number from 0 to 3, subscript b is a number from 0.005 to 2.0, and the sum of subscript a and subscript b is equal to a number from 0.8 to 3.

7. The composition according to claim 1 wherein component (c) is a platinum-containing catalyst.

8. The composition according to claim 5 wherein R has 1 to 4 carbon atoms.

9. The composition according to claim 5 wherein R is methyl.

10. The composition according to claim 5 wherein R¹ is vinyl or allyl.

11. The composition according to claim 5 wherein subscript a is a number from 0.5 to 2.

12. The composition according to claim 5 wherein said composition contains 0.1 to 99.9 weight percent of siloxane units of formula I, and 0.1 to 99.9 weight percent of siloxane units having the emperical formula ##EQU5## wherein each R is bonded to a silicon atom and is independently selected from the group consisting of monovalent aliphatic or aromatic hydrocarbon radicals or halogenated derivatives thereof, cyanoaljyl radicals, and combinations thereof, R having 1 to 13 carbon atoms, subscript a is a number from 0.to 3, subscript b is a number from 0.005 to 2.0, and the sum of subscript a and subscript b is equal to a number from 0.8 to 3.

13. The latently curable composition according to claim 5 wherein said composition contains from about 0.005 to 20 silicon-hydrogen linkages per silicon-bonded ethylenically-unsaturated unit.

14. The latently curable composition according to claim 5 wherein said composition contains in the range of 0.1 to 3.0 silicon-hydrogen linkages per silicon-bonded ethylenically-unsaturated unit.

15. The cured product of claim 1.

19. The composition according to claim 1 wherein said hydrosilation catalyst is a platinum-containing catalyst.

16. A kit for preparing a latently-curable organosilicone composition capable of undergoing hydrosilation and having component parts capable of being mixed when the composition is to be applied, said kit comprising the combination of

(1) a first package containing an ethylenically-unsaturated polysiloxane and an amount of a metal-containing hydrosilation catalyst sufficient to facilitate the hydrosilation reaction, and

(2) a second package containing a polyhydrosiloxane and as hydrosilation inhibitor an amount of an organic hydrosilation compound sufficient to inhibit prematrue gelation of the organosilicone composition at low ambient or room temperature but insufficient in amount to prevent hydrosilation at an elevated temperature, said compound having the structural formula ##STR10## wherein R² is ethynylene or cis-ethenylene;

R³ is a saturated or unsaturated organic group having 1 to 12 carbon atoms which is unsubstituted or substituted by 1 to 23 halogen atoms, and has up to 25 hydrogen atoms, and 0 to 5 non-peroxidic catenary oxygen atoms; and

X is --O-- or ##STR11## in which R⁴ is the same as defined for R³, and R³ and R⁴ together with the N can form a saturated azacyclic ring.

17. A latently-curable organosilicone composition comprising the following components:

(a) an ethylenically-unsaturated polysiloxane,

(b) a polyhydrosiloxane,

(c) an amount of a metal-containing catalyst sufficient to facilitate the reaction of components (a) and (b), and

(d) an amount of an organic hydrosilation inhibitor sufficient to inhibit premature gelation of the mixture of components (a), (b), and (c) at low, ambient or room temperature but insufficient in amount to prevent hydrosilation of the mixture at an elevated temperature, said organic hydrosilation inhibitor having the structural formula ##STR12## wherein R² is cis-ethenylene;

R³ is a saturated or unsaturated organic group having 1 to 12 carbon atoms which is unsubstituted or substituted by 1 to 23 halogen atoms, and has up to 25 hydrogen atoms, and 0 to 5 non-peroxidic catenary oxygen atoms; and

X is --O-- or ##STR13## in which R⁴ is the same as defined for R³, and R³ and R⁴ together can form an alkylene group which with the N can form a 5- or 6-atom membered saturated azacyclic ring.

18. The composition according to claim 17 wherein said hydrosilation inhibitor is 2-ethylhexyl hydrogen maleate.