Energy curable pressure-sensitive adhesive compositions

• US 5,462,797 A
• Filed: 02/08/1994
• Issued: 10/31/1995
• Est. Priority Date: 09/05/1990
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Klun, Thomas P., DeVoe, Robert J., Zimmerman, Patrick G., Vesley, George F., Williams, Jerry W.
• Primary Examiner(s): Berman, Susan W.
• Application Number:
  US08/193,518
• Time in Patent Office: 630 Days
• Field of Search: 522/29, 522/96, 522/4, 522/18, 522/174, 522/24, 522/28, 522/182, 428/345, 428/355
• US Class Current: 428/345
• CPC Class Codes: C08F 283/006 on to polymers provided for in C08G18/00 C08F283/004 takes precedence
• CPC Class Codes: C08G 18/22 containing metal compounds
• CPC Class Codes: C08G 18/637 characterised by the in situ polymerisation of the compounds having carbon-to-carbon double bonds in a reaction mixture of saturated polymers and isocyanates
• CPC Class Codes: C08G 2170/40 Compositions for pressure-sensitive adhesives
• CPC Class Codes: C09J 175/04 Polyurethanes
• CPC Class Codes: Y10T 428/2809 including irradiated or wave energy treated component
• CPC Class Codes: Y10T 428/2852 Adhesive compositions

Abstract

The present invention provides a pressure-sensitive adhesive composition and a method for producing the same. The pressure-sensitive adhesive composition is produced by the combination of at least one free-radically photopolymerizable monomer and at least one set of polyurethane precursors, and a suitable photoinitiation system consisting of at least one salt of a cationic organometallic complex, an additional free-radical photo initiator and the application of sufficient energy to photopolymerize same by sequential exposure to visible electromagnetic radiation and then to ultraviolet electromagnetic radiation.

Claims

1. A pressure-sensitive adhesive composition comprising the polymerization reaction product of starting materials consisting essentially of:

(a) at least one free-radically polymerizable component selected from the group consisting of an acrylate, a methacrylate, and a vinyl ester;

(b) at least one polyurethane precursor component, said polyurethane precursor component comprising;

(i) a least one di- or polyisocyanate; and

(ii) at least one diol or polyol;

(c) at least one organometallic complex salt; and

(d) at least one free-radical photoinitiator selected from the group consisting of acetophenones, ketals, benzophenones, aryl gyloxylates, acylphosphine oxides and peroxides;

said reaction product being obtained by sequential exposure to visible electromagnetic radiation and then to ultraviolet electromagnetic radiation.

2. A composition according to claim 1, wherein said organometallic complex salt is of the structure

3. The composition according to claim 1 wherein said free-radically polymerizable component is an alkyl acrylate or alkyl methacrylate wherein said alkyl group contains from about 4 to about 14 carbon atoms.

4. The composition according to claim 1 wherein the ratio of the isocyanate groups to hydroxyl groups present in said polyurethane precursor component is in the range of from about 1:

2 to 2;

1.

5. The composition according to claim 1 wherein the ratio of the isocyanate groups to hydroxyl groups in said polyurethane precursor component is in the range of from about 1:

1.25 to 1.25;

1.

6. The composition according to claim 1 wherein said organometallic complex salt has the following structure

7. The composition according to claim 1 wherein the organometallic complex salt has the following structure:

space="preserve" listing-type="equation">[(L.sup.5)M].sup.+3 X.sub.f

wherein;

L⁵ represents pi-electron contributing ligands that can be the same or different selected from the group consisting of;

substituted and unsubstituted acyclic and cyclic unsaturated compounds and groups; and

substituted and unsubstituted carbocyclic aromatic and heterocyclic aromatic compounds, each capable of contributing two to twelve pi-electrons to the valence shell of M;

with the proviso that the total electronic charge contributed to M by L⁵ plus the ionic charge on M results in a residual net positive charge of e to the complex;

e is an integer having a value of 1 or 2, the residual electrical charge of the cation;

X is an anion selected from organic sulfonate anions and halogen-containing complex anions of a metal or metalloid; and

f is an integer selected from 1 or 2, the number of anions required to neutralize the positive charge e on the cation.

8. The composition according to claim 1 wherein said starting materials further comprise polar monomer copolymerizable with said at least one free-radically polymerizable component.

9. The composition according to claim 1 wherein said free-radically polymerizable component is partially polymerized to a syrup having a viscosity of from about 300 to 20,000 centipoise at room temperature.

10. The composition according to claim 1 wherein said polyisocyanate is an aliphatic polyisocyanate and said polyol is a hydroxy alkylated bisphenol.

11. The composition according to claim 1 comprising the polymerization reaction product of starting materials comprising:

(a) from about 60 to about 95 parts of said acrylate;

(b) from about 5 parts to about 40 parts of said at least one polyurethane precursor component comprising;

(1) an hydroxy alkylated bisphenol selected from the group consisting of;

hydroxyethylated bisphenol-A, and 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene; and

(2) at least one aliphatic polyisocyanate selected from the group consisting of;

hexamethylene diisocyanate, the isocyanurate and the biuret thereof, and 4,4'"'"'-methylenebis(cyclohexylisocyanate);

(c) from about 0.01 part to about 10 parts of said organometallic complex salt, and

(d) from about 0.01 to about 10 parts of said free-radical photoinitiator.

12. The composition according to claim 1 comprising the polymerization reaction product of starting materials comprising

(a) from about 70 parts to 80 parts of isooctyl acrylate;

(b) from about 20 parts to about 30 parts of at least one hydroxy alkylated bisphenol selected from the group consisting of;

hydroxyethylated bisphenol-A, and 9,9-bis[4-(2-hydroxy ethoxy)phenyl]fluroene; and

at least one aliphatic polyisocyanate selected from the group consisting of;

hexamethylene diisocyanate, the isocyanurate and the biuret thereof, and 4,4'"'"'-methylenebis(cyclohexylisocyanate),

(c) from about 0.01 part to about 10 parts of (eta⁵ -cyclopentadienyl)(eta⁶ -xylene)iron(+1)hexafluorophosphate,

(d) from about 0.01 to about 10 parts of 2,2-dimethoxy-2-phenylacetophenone; and

(e) from 0 to about 1 part 1,6-hexanediol diacrylate.

13. The composition according to claim 12 wherein said starting materials further comprise from about 2 to about 5 parts of a bifunctional monomer.

14. The composition according to claim 12 further comprising a polar monomer copolymerizable with said acrylate.

15. The composition according to claim 14 wherein said polar monomer copolymerizable with said acrylate is selected from strongly polar and moderately polar monomers.

16. The composition according to claim 1 wherein said starting materials further comprise at least one adjuvant selected from the group consisting of:

hydrophobic silica, glass microspheres, polymeric microspheres, and pigments.

18. A pressure-sensitive adhesive tape comprising at least one layer of the pressure-sensitive adhesive composition of claim 1 and a backing therefor.

17. A pressure-sensitive adhesive composition comprising the polymerization reaction product of starting materials consisting essentially of:

(a) at least one free-radically polymerizable component selected from the group consisting of an acrylate, a methacrylate, and a vinyl ester;

(b) at least one polyurethane precursor component, said polyurethane precursor component comprising;

(i) at least one di- or polyisocyanate; and

(ii) at least one diol or polyol;

(c) at least one organometallic complex salt; and

(d) at least one free-radical photoinitiator selected from the group consisting of acetophenones, ketals, benzophenones, aryl gyloxylates, acylphonsphine oxides and peroxides;

the ratio of the total weight of said free-radically polymerizable component to the total weight of said polyurethane precursor component being from about 70;

30 to about 90;

10;

said reaction product being obtained by sequential exposure to visible electromagnetic radiation and then to ultraviolet electromagnetic radiation.

19. A process for making a pressure-sensitive adhesive comprising the steps of:

(a) providing a composition comprising;

(i) at least one free-radically polymerizable component selected from the group consisting of an acrylate, a methacrylate and a vinyl ester;

(ii) at least one polyurethane precursor component, said polyurethane component comprising at least one di- or polyisocyanate and at least one diol or polyol;

(iii) at least one organometallic complex salt; and

(iv) at least one free-radical photoinitiator;

said composition being substantially free of an onium salt;

(b) exposing said composition to a sufficient amount of visible electromagnetic radiation to activate said organometallic complex salt; and

(c) thereafter exposing the photoreaction product obtained in step (b) to ultraviolet electromagnetic radiation to activate said free-radical photoinitiator;

wherein said process provides a pressure-sensitive adhesive.