ADHESIVE COMPOSITIONS WITH (METH)ACRYLIC-BASED BLOCK COPOLYMERS

• US 20190085222A1
• Filed: 03/14/2017
• Published: 03/21/2019
• Est. Priority Date: 03/18/2016
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Tse, Kiu-Yuen, Determan, Michael D.
• Granted Patent: US 10,640,690 B2
• Time in Patent Office: Days
• CPC Class Codes: A61K 9/7061 Polyacrylates
• CPC Class Codes: A61P 17/00 Drugs for dermatological disorders
• CPC Class Codes: A61P 17/02 for treating wounds, ulcers, burns, scars, keloids, or the like
• CPC Class Codes: C08L 2203/02 for biomedical use
• CPC Class Codes: C08L 2205/02 containing two or more polymers of the same C08L -group
• CPC Class Codes: C08L 2312/06 by radiation
• CPC Class Codes: C08L 53/00 Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• CPC Class Codes: C09J 133/08 Homopolymers or copolymers of acrylic acid esters
• CPC Class Codes: C09J 133/10 Homopolymers or copolymers of methacrylic acid esters
• CPC Class Codes: C09J 153/00 Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
• CPC Class Codes: C09J 2301/414 presence of a copolymer
• CPC Class Codes: C09J 2301/416 use of irradiation
• CPC Class Codes: C09J 2467/005 in the release coating

Abstract

Adhesive compositions are provided that contain a crosslink product resulting from exposure of a (meth)acrylic-based composition to electron beam radiation, gamma ray radiation, or both. More particularly, the (meth)acrylic-based composition includes a (meth)acrylic-based diblock copolymer and an optional (meth)acrylic-based triblock copolymer. These adhesive compositions are particularly well suited for application to biological surface such as skin.

Claims

1. An adhesive composition comprising a crosslinked polymeric product of a reaction mixture comprising:

a) a (meth)acrylic-based composition comprising

1) 0 to less than 10 weight percent of a (meth)acrylic-based triblock copolymer A-B-A based on a total weight of the (meth)acrylic-based composition, wherein

each A block is a polymerized product of a first monomer composition comprising an alkyl methacrylate;

the B block is a polymerized product of a second monomer composition comprising an alkyl acrylate;

the (meth)acrylic-based triblock copolymer A-B-A having 20 to 55 weight percent A blocks and 45 to 80 weight percent B block based on a total weight of the (meth)acrylic-based triblock copolymer A-B-A; and

2) greater than 90 to 100 weight percent of a (meth)acrylic-based diblock copolymer C-D based on the total weight of the (meth)acrylic-based composition, wherein

the C block is a polymerized product of a third monomer composition comprising an alkyl methacrylate;

the D block is a polymerized product of a fourth monomer composition comprising an alkyl acrylate; and

the (meth)acrylic-based diblock copolymer C-D having 5 to 30 weight percent C block and 70 to 95 weight percent D block based on a total weight of the (meth)acrylic-based diblock copolymer C-D; and

b) electron beam radiation and/or gamma ray radiation, wherein the adhesive composition is free of a chemical crosslinking agent.

2. The adhesive composition of claim 1, wherein each A block has a glass transition temperature equal to at least 50°

C. and wherein the B block has a glass transition temperature no greater than 20°

C. when measured using Dynamic Mechanical Analysis.

3. The adhesive composition of claim 1, further comprising an additive selected from a tackifier, plasticizer, filler, or a combination thereof.

4. The adhesive composition of claim 1, wherein the A blocks of the (meth)acrylic-based triblock copolymer A-B-A and the C block of the (meth)acrylic-based diblock copolymer C-D comprise the same alkyl methacrylate having a glass transition temperature as a homopolymer that is at least 50°

C. when measured using Dynamic Mechanical Analysis.

5. The adhesive composition of claim 1, wherein the B block of the (meth)acrylic-based triblock copolymer A-B-A and the D block of the (meth)acrylic-based diblock copolymer comprise the same alkyl acrylate having a glass transition temperature as a homopolymer that is no greater than 20°

C. when measured using Dynamic Mechanical Analysis.

6. The adhesive composition of claim 1, wherein the A blocks of the (meth)acrylic-based triblock copolymer A-B-A and the C block of the C-D (meth)acrylic-based diblock copolymer are poly(methyl methacrylate) and wherein the B block of the (meth)acrylic-based triblock copolymer A-B-A and the D block of the C-D (meth)acrylic-based diblock copolymer are each poly(n-butyl acrylate), poly(isooctyl acrylate), poly(2-octyl acrylate), poly(isobornyl acrylate), or poly(2-ethylhexyl acrylate).

7. The adhesive composition of claim 1, wherein the (meth)acrylic-based triblock copolymer A-B-A has a number average molecular weight (M_n) in a range of 25 to 150 kDaltons and wherein the (meth)acrylic-based diblock copolymer C-D has a number average molecular weight (M_n) in a range of 25 to 100 kDaltons.

8. The adhesive composition of claim 1, wherein the adhesive composition comprises 70 to 100 weight percent of the (meth)acrylic-based composition and 0 to 30 weight percent of an additive selected from a tackifier, plasticizer, filler, or combination thereof.

9. An adhesive article comprising:

a substrate; and

an adhesive composition layer having a first major surface attached to the substrate, wherein the adhesive composition layer comprises the adhesive composition of claim 1.

10. The adhesive article of claim 9, wherein the substrate is a backing layer.

11. The adhesive article of claim 9, further comprising a pharmaceutical agent.

12. The adhesive article of claim 9, further comprising an absorbent material positioned adjacent to but not covering an outer edge of a second major surface of the adhesive composition layer opposite the substrate.

13. The adhesive article of claim 9, wherein the adhesive article is adhered to skin.

14. A method of making an adhesive article, the method comprising:

a) providing an adhesive composition comprising a (meth)acrylic-based composition comprising

1) 0 to less than 10 weight percent of a (meth)acrylic-based triblock copolymer A-B-A based on a total weight of the (meth)acrylic-based composition, wherein

each A block is a polymerized product of a first monomer composition comprising an alkyl methacrylate;

the B block is a polymerized product of a second monomer composition comprising an alkyl acrylate;

the (meth)acrylic-based triblock copolymer A-B-A having 20 to 55 weight percent A blocks and 45 to 80 weight percent B block based on a total weight of the (meth)acrylic-based triblock copolymer A-B-A; and

2) greater than 90 to 100 weight percent of a (meth)acrylic-based diblock copolymer C-D based on the total weight of the (meth)acrylic-based composition, wherein

the C block is a polymerized product of a third monomer composition comprising an alkyl methacrylate;

the D block is a polymerized product of a fourth monomer composition comprising an alkyl acrylate; and

the (meth)acrylic-based diblock copolymer C-D having 5 to 30 weight percent C block and 70 to 95 weight percent D block based on a total weight of the (meth)acrylic-based diblock copolymer C-D,

wherein the adhesive composition is free of a chemical crosslinking agent;

b) forming an adhesive composition layer adjacent to a substrate; and

c) exposing the adhesive composition layer to electron beam radiation and/or gamma ray radiation to crosslink the adhesive composition layer composition.

15. The method of claim 14, wherein the electron beam radiation is in a range of 1 to 20 Mrads and/or the gamma ray radiation is in a range of 10 to 200 kilograys.