Silicone acrylate hybride composition and method of making same

• US 8,124,689 B2
• Filed: 06/06/2007
• Issued: 02/28/2012
• Est. Priority Date: 06/06/2006
• Status: Active Grant

• Current Assignee: Dow Silicones Corporation (Dow, Inc.)
• Original Assignee: Dow, Inc.
• Inventors: Thomas, Xavier, Loubert, Gary, Mitchell, Timothy P.
• Primary Examiner(s): ZIMMER, MARC S
• Application Number:
  US12/303,362
• Publication Number:
  US 20090196911A1
• Time in Patent Office: 1,728 Days
• Field of Search: None
• US Class Current: 525/100
• CPC Class Codes: A61P 1/04 for ulcers, gastritis or reflux esophagitis, e.g. antacids, inhibitors of acid secretion, mucosal protectants
• CPC Class Codes: A61P 1/08 for nausea, cinetosis or vertigo; Antiemetics
• CPC Class Codes: A61P 11/00 Drugs for disorders of the respiratory system
• CPC Class Codes: A61P 17/00 Drugs for dermatological disorders
• CPC Class Codes: A61P 25/00 Drugs for disorders of the nervous system
• CPC Class Codes: A61P 25/02 for peripheral neuropathies
• CPC Class Codes: A61P 25/06 Antimigraine agents
• CPC Class Codes: A61P 25/08 Antiepileptics; Anticonvulsants
• CPC Class Codes: A61P 25/16 Anti-Parkinson drugs
• CPC Class Codes: A61P 25/18 Antipsychotics, i.e. neuroleptics; Drugs for mania or schizophrenia
• CPC Class Codes: A61P 25/24 Antidepressants
• CPC Class Codes: A61P 25/26 Psychostimulants, e.g. nicotine, cocaine
• CPC Class Codes: A61P 27/02 Ophthalmic agents
• CPC Class Codes: A61P 29/00 Non-central analgesic, antipyretic or antiinflammatory agents, e.g. antirheumatic agents; Non-steroidal antiinflammatory drugs [NSAID]
• CPC Class Codes: A61P 3/02 Nutrients, e.g. vitamins, minerals
• CPC Class Codes: A61P 3/04 Anorexiants; Antiobesity agents
• CPC Class Codes: A61P 3/10 for hyperglycaemia, e.g. antidiabetics
• CPC Class Codes: A61P 31/00 Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
• CPC Class Codes: A61P 31/10 Antimycotics
• CPC Class Codes: A61P 33/06 Antimalarials
• CPC Class Codes: A61P 37/08 : Antiallergic agents antiasthmatic agents A61P11/06; ophthalmic antiallergics A61P27/14
• CPC Class Codes: A61P 43/00 : Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00
• CPC Class Codes: A61P 5/00 : Drugs for disorders of the endocrine system
• CPC Class Codes: A61P 5/26 : Androgens
• CPC Class Codes: A61P 5/30 : Oestrogens
• CPC Class Codes: A61P 9/00 : Drugs for disorders of the cardiovascular system
• CPC Class Codes: C08F 265/04 : on to polymers of esters
• CPC Class Codes: C08F 283/12 : on to polysiloxanes
• CPC Class Codes: C08F 290/06 : Polymers provided for in subclass C08G
• CPC Class Codes: C08F 290/14 : Polymers provided for in subclass C08G
• CPC Class Codes: C08L 2666/02 : Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• CPC Class Codes: C08L 51/085 : on to polysiloxanes
• CPC Class Codes: C09J 151/003 : grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds C09J151/04, C09J151/06 take precedence
• CPC Class Codes: C09J 151/085 : on to polysiloxanes

Abstract

A silicone acrylate hybrid composition includes the reaction product of a silicon-containing pressure sensitive adhesive composition, an ethylenically unsaturated monomer, and an initiator. The silicon-containing pressure sensitive adhesive composition includes acrylate or methacrylate functionality. A method of making the hybrid composition includes polymerizing the ethylenically unsaturated monomer and the silicon-containing pressure sensitive adhesive composition in the presence of the initiator.

Claims

1. A silicone acrylate hybrid composition comprising the reaction product of:

A. a silicon-containing pressure sensitive adhesive composition comprising acrylate or methacrylate functionality and the condensation reaction product of;

a silicone resin,

a silicone polymer, and

a silicon-containing capping agent which provides said acrylate or methacrylate functionality, wherein said silicon-containing capping agent is of the general formula XYR′

₂SiZ wherein

X is a monovalent radical of the general formula AE- where E is —

O—

or —

NH— and

A is an acryl group or a methacryl group,

Y is a divalent alkylene radical having from 1 to 6 carbon atoms,

R′

is a methyl or a phenyl radical, and

Z is a monovalent hydrolyzable organic radical or a halogen;

wherein the silicone resin and silicone polymer are reacted to form a pressure sensitive adhesive, wherein the silicon-containing capping agent is introduced prior to, during, or after the silicone resin and silicone polymer are reacted, and wherein;

the silicon-containing capping agent reacts with the pressure sensitive adhesive after the silicone resin and silicone polymer have been condensation reacted to form the pressure sensitive adhesive;

or

the silicon-containing capping agent reacts in-situ with the silicone resin and silicone polymer;

B. an ethylenically unsaturated monomer; and

C. an initiator.

2. A hybrid composition as set forth in claim 1 wherein said ethylenically unsaturated monomer (B) is a compound selected from the group of aliphatic acrylates, aliphatic methacrylates, cycloaliphatic acrylates, cycloaliphatic methacrylates, and combinations thereof, each of said compounds having up to 20 carbon atoms in the alkyl radical.

3. A hybrid composition as set forth in claim 2 wherein said aliphatic acrylates are selected from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, iso-octyl acrylate, iso-nonyl acrylate, iso-pentyl acrylate, tridecyl acrylate, stearyl acrylate, lauryl acrylate, and combinations thereof, and said aliphatic methacrylates are selected from the group of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, iso-octyl methacrylate, iso-nonyl methacrylate, iso-pentyl methacrylate, tridecyl methacrylate, stearyl methacrylate, lauryl methacrylate, and combinations thereof.

4. A hybrid composition as set forth in claim 1 wherein said silicon-containing pressure sensitive adhesive composition (A) is present in said hybrid composition in an amount of from 5 to 95 parts by weight based on 100 parts by weight of said hybrid composition.

5. A hybrid composition as set forth in claim 1 wherein said ethylenically unsaturated monomer (B) is present in said hybrid composition in an amount of from 5 to 95 parts by weight based on 100 parts by weight of said hybrid composition.

6. A hybrid composition as set forth in claim 1 wherein said initiator (C) is present in said hybrid composition in an amount of from 0.005 to 3 parts by weight based on 100 parts by weight of said hybrid composition.

7. A hybrid composition as set forth in claim 1 wherein said silicon-containing capping agent is selected from the group of acrylate functional silanes, acrylate functional silazanes, acrylate functional disilazanes, acrylate functional disiloxanes, methacrylate functional silanes, methacrylate functional silazanes, methacrylate functional disilazanes, methacrylate functional disiloxanes, and combinations thereof.

8. A hybrid composition as set forth in claim 1 wherein said silicon-containing pressure sensitive adhesive composition comprises a concentration of silicon bonded hydroxyl groups and said silicon-containing capping agent is further defined as an endblocking agent that reacts with said concentration of silicon bonded hydroxyl groups to cap said silicon-containing pressure sensitive adhesive composition.

9. A hybrid composition as set forth in claim 1 wherein said monovalent hydrolyzable organic radical is of the general formula R″

O—

where R″

is an alkyl radical.

10. A hybrid composition as set forth in claim 1 wherein said endblocking agent is selected from the group of 3-methacryloxypropyldimethylchlorosilane, 3-methacryloxypropyldimethylmethoxysilane, 3-methacryloxypropyldimethylethoxysilane, (methacryloxymethyl)dimethylmethoxysilane, (methacryloxymethyl)dimethylethoxysilane, 3-methacryloxypropyldimethylsilazane, 3-acryloxypropyldimethylchlorosilane, 3-acryloxypropyldimethylmethoxysilane, 3-acryloxypropyldimethylsilazane, and combinations thereof.

11. A hybrid composition as set forth in claim 1 wherein

said silicone resin comprises a copolymer comprising triorganosiloxy units of the formula R³₃SiO_1/2 and tetrafunctional siloxy units of the formula SiO_4/2 in a ratio of about 0.6 to 0.9 triorganosiloxy units for each tetrafunctional siloxy unit, wherein each R³ independently denotes a monovalent hydrocarbon radical having from 1 to 6 carbon atoms;

and

said silicone polymer comprises at least one polydiorganosiloxane comprising AR³SiO units terminated with endblocking TR³ASiO1/2 units, wherein the polydiorganosiloxane has a viscosity of from about 100 centipoise to about 30,000,000 centipoise at 25°

C., each A radical is independently selected from R³ or halohydro-carbon radicals having from 1 to 6 carbon atoms, each T radical is independently selected from the group consisting of R³, OH, H or OR⁴, and each R⁴ is independently an alkyl radical having from 1 to 4 carbon atoms.

12. A hybrid composition as set forth in claim 11 wherein, prior to reacting of said silicon-containing capping agent, said silicone resin reacts in an amount of from 30 to 80 parts by weight and said silicone polymer reacts in an amount of from 20 to 70 parts by weight, both based on 100 parts by weight of said silicon-containing pressure sensitive adhesive composition.

13. A silicone acrylate hybrid composition comprising the reaction product of:

A. a silicon-containing pressure sensitive adhesive composition comprising acrylate or methacrylate functionality and the condensation reaction product of;

a silicone resin,

a silicone polymer, and

a silicon-containing capping agent which provides said acrylate or methacrylate functionality;

B. an ethylenically unsaturated monomer; and

C. an initiator;

blended with a non-hybrid pressure sensitive adhesive composition selected from the group of silicone pressure sensitive adhesive compositions, acrylic pressure sensitive adhesive compositions, polyurethane pressure sensitive adhesive compositions, natural rubber pressure sensitive adhesive compositions, synthetic rubber pressure sensitive adhesive compositions, and blends thereof.

14. A method of making a silicone acrylate hybrid composition comprising the steps of:

providing a silicon-containing pressure sensitive adhesive composition comprising acrylate or methacrylate functionality by condensation reacting a silicone resin, a silicone polymer, and a silicon-containing capping agent which provides the acrylate or methacrylate functionality, wherein said silicon-containing capping agent is of the general formula XYR′

₂SiZ wherein

X is a monovalent radical of the general formula AE- where E is —

O—

or —

NH— and

A is an acryl group or a methacryl group,

Y is a divalent alkylene radical having from 1 to 6 carbon atoms,

R′

is a methyl or a phenyl radical, and

Z is a monovalent hydrolyzable organic radical or a halogen;

wherein the silicone resin and silicone polymer are reacted to form a pressure sensitive adhesive, wherein the silicon-containing capping agent is introduced prior to, during, or after the silicone resin and silicone polymer are reacted, and wherein;

the silicon-containing capping agent reacts with the pressure sensitive adhesive after the silicone resin and silicone polymer have been condensation reacted to form the pressure sensitive adhesive;

or

the silicon-containing capping agent reacts in-situ with the silicone resin and silicone polymer; and

polymerizing an ethylenically unsaturated monomer and the silicon-containing pressure sensitive adhesive composition in the presence of an initiator.

16. A method of making a hybrid composition as set forth in claim 14 wherein the silicon-containing capping agent is reacted in situ with the silicone resin and the silicone polymer as the silicone resin and the silicone polymer are condensation reacting.

18. A method of making a hybrid composition as set forth in claim 14 further comprising the step of mixing the silicon-containing pressure sensitive adhesive composition, the ethylenically unsaturated monomer, and the initiator to form a pre-reaction mixture prior to said step of polymerizing.

15. A method of making a hybrid composition as set forth in 14 wherein the silicon-containing capping agent is reacted after the silicone resin and the silicone polymer have been condensation reacted.

17. A method of making a hybrid composition comprising the steps of:

providing a silicon-containing pressure sensitive adhesive composition comprising acrylate or methacrylate functionality by condensation reacting a silicone resin, a silicone polymer, and a silicon-containing capping agent which provides the acrylate or methacrylate functionality; and

polymerizing an ethylenically unsaturated monomer and the silicon-containing pressure sensitive adhesive composition in the presence of an initiator

at a temperature of from 50 to 100°

C.

19. A transdermal drug delivery system comprising:

I. an active agent for controlled transdermal delivery to a substrate; and

II. a silicone acrylate hybrid composition for maintaining contact with the substrate, said hybrid composition comprising the reaction product of;

A. a silicon-containing pressure sensitive adhesive composition comprising acrylate or methacrylate functionality and the condensation reaction product of;

a silicone resin,

a silicone polymer, and

a silicon-containing capping agent which provides said acrylate or methacrylate functionality;

B. an ethylenically unsaturated monomer; and

C. an initiator.

20. A system as set forth in claim 19 wherein said active agent is selected from the group of cardioactive medications, androgenic steroids, estrogens, hormones, external analgesics, progestational agents, drugs having an action on the central nervous system, nutritional agents, anti-inflammatory agents, antihistamines, respiratory agents, sympathomimetics, miotics, cholinergic agonists, antimuscarinic or muscarinic cholinergic blocking agents, mydriatics, psychicenergizers, anti-infectives, dermatological agents, humoral agents, antispasmodics, antidepressant drugs, anti-diabetic, anorectic drugs, anti-allergenics, tranquilizers, antipsychotics, decongestants, antipyretics, antimigrane agents, drugs for treating nausea and vomiting, anti-malarials, anti-ulcerative agents, peptides, drugs for Parkinson'"'"'s disease, drugs for spasticity, drugs for acute muscle spasms, anti-estrogen, anti-hormone agents, therapeutic agents, and combinations thereof.

21. A system as set forth in claim 19 wherein said active agent is disposed in said hybrid composition for the controlled transdermal delivery to the substrate.

22. A system as set forth in claim 19 wherein said active agent and said hybrid composition coexist in said system in discrete layers.

23. A system as set forth in claim 19 further comprising;

a backing layer for supporting said hybrid composition; and

/or

a release liner for protecting said hybrid composition and/or said active agent prior to the controlled transdermal delivery to a substrate.

24. A system as set forth in claim 19 selected from the group of patches, films, multi-layer dressings, reservoir systems, and combinations thereof.