Radiation-curable acrylate/silicone pressure-sensitive adhesive compositions

• US 5,514,730 A
• Filed: 07/25/1994
• Issued: 05/07/1996
• Est. Priority Date: 03/20/1991
• Status: Expired due to Term

• Current Assignee: 3M Company
• Original Assignee: 3M Company
• Inventors: Mazurek, Mieczyslaw H., Kinning, David J., Kantner, Steven S., Bogaert, Yvan A.
• Primary Examiner(s): Berman, Susan W.
• Application Number:
  US08/279,718
• Time in Patent Office: 652 Days
• Field of Search: 522/99, 522/79, 522/80, 522/84, 522/83, 525/477, 525/479, 525/925, 523/111, 528/25, 528/26, 528/28, 528/32, 521/154, 526/279, 526/931
• US Class Current: 522/99
• CPC Class Codes: C08F 290/068 Polysiloxanes
• 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: C09J 183/08 containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
• 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 4/06 Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• CPC Class Codes: Y10S 525/925 Polymer from at least one nonethylenic monomer having terminal ethylenic unsaturation other than polyurethanes, polyesters, polyepoxides, aminoplasts, and phenoplasts
• CPC Class Codes: Y10S 526/931 Pressure sensitive adhesive

Abstract

The present invention provides a radiation curable vinyl-silicone pressure-sensitive adhesive composition which combines the advantages of silicone and acrylate pressure-sensitive adhesives and which does not experience gross phase separation problems. The composition comprises at least about 20 weight percent of a certain telechelic silicone polymer, about 0.5 to about 80 weight percent of monofunctional free-radically polymerizable vinyl monomer copolymerizable with the silicone polymer, and a sufficient amount of a silicate MQ tackifying resin to impart a degree of adhesive tack to the cured composition at the use temperature, wherein the weight percentages of the silicone polymer and the monomer are based upon the total weight of the silicone polymer and monomer.

Claims

1. A pressure-sensitive adhesive formed from the free radical polymerization of a composition comprising:

(a) at least about 20 weight percent of polymer selected from the group consisting of polymers falling within the general formula ##STR20## and mixtures thereof, wherein;

X are monovalent moieties having ethylenic unsaturation which can be the same or different;

Y are divalent linking groups which can be the same or different and which serve to activate X toward free radical polymerization;

D are monovalent moieties which can be the same or different selected from the group consisting of hydrogen, an alkyl group of 1 to about 10 carbon atoms, and aryl;

R are divalent hydrocarbon groups which can be the same or different;

R¹ are monovalent moieties which can be the same or elected from the group consisting of alkyl and aryl;

R² are monovalent moieties which can be the same or different selected from the group consisting of alkyl and aryl;

R³ are monovalent moieties which can be the same or different selected from the group consisting of alkyl vinyl, and aryl;

R⁴ are monovalent moieties which can be the same or different selected from the group consisting of alkyl vinyl, and aryl; and

n is an integer of about 200 to about 1000;

(b) about 0.5 to about 80 weight percent of monofunctional free radically polymerizable vinyl monomer which is capable of copolymerizing with said polymer; and

(c) 80 to 200 parts per 100 parts by weight of element (a) of silicate MQ tackifying resin to impart a degree of adhesive tack to the cured composition at the use temperature;

wherein said weight percentages set forth in element (a) and element (b) are based upon the combined weights of said polymer of element (a) and said monomer of element (b).

2. The pressure-sensitive adhesive of claim 1 wherein said composition further comprises at least one of the additives selected from the group consisting of a filler, a nonpolar solvent, a multifunctional acrylate crosslinker, and a free radical initiator.

3. The pressure sensitive adhesive of claim 2, wherein said composition further comprises at least a nonpolar solvent and wherein said composition is cured in its swollen state.

4. The pressure-sensitive adhesive of claim 1 wherein said composition further comprises about 0.1 to about 5 weight percent of an initiator based upon the weight of said composition.

5. The pressure-sensitive adhesive of claim 4 wherein said initiator is a photoinitiator.

6. The pressure sensitive adhesive of claim 1 comprising the composition of claim 1 wherein X comprises ##STR21## R⁵ is selected from the group consisting of hydrogen and --COOH;

R⁶ is selected from the group consisting of hydrogen, methyl, and --CH₂ COOH;

n is an integer of about 200 to about 1000;

R is selected from the group consisting of alkylene of one to about 12 carbon atoms, alkyl arylene, and arylene;

R¹ and R² are independently selected from the group consisting of alkyl of one to about 12 carbon atoms, substituted alkyl of one to about 12 carbon atoms, aryl, and substituted aryl;

R³ and R⁴ are at least 50% methyl with the remainder selected from the group consisting of alkyl of about 2 to about 12 carbon atoms, substituted alkyl of about 2 to about 12 carbon atoms, vinyl, aryl, and substituted aryl; and

D is hydrogen.

7. The composition of claim 6 wherein n is an integer of about 200 to about 1000, R is alkylene of one to about 12 carbon atoms, and R¹, R² l , R³, R⁴ are methyl.

8. The pressure sensitive adhesive of claim 1 comprising the composition of claim 1 wherein

X comprises ##STR22## Y comprises ##STR23## D═

H;

R comprises --CH₂ CH₂ CH₂ --; and

R¹, R², R³, and R⁴ each comprise --CH₃.

9. The pressure-sensitive adhesive of claim 1 wherein

X comprises CH₂ ═

CH--;

Y comprises ##STR24## D═

H;

R comprises --CH₂ CH₂ CH₂ --; and

R¹, R², R³, and R⁴ each comprise --CH₃.

10. The pressure sensitive adhesive of claim 1 comprising the composition of claim 1 wherein

X comprises CH₂ ═

CH--;

Y comprises ##STR25## D═

H;

R comprises --CH₂ CH₂ CH₂ --; and

R¹, R², R³, and R⁴ each comprise --CH₃.

11. The pressure sensitive adhesive of claim 1 comprising the composition of claim 1 wherein

X comprises ##STR26## Y comprises ##STR27## D═

H, R comprises --CH₂ CH₂ CH₂ --; and

R¹, R², R³ and R⁴ each comprise --CH₃.

12. The pressure sensitive adhesive of claim 1 comprising the composition of claim 1 wherein

X comprises ##STR28## Y comprises ##STR29## D═

H, R comprises --CH₂ CH₂ CH₂ --; and

R¹, R², R³ and R⁴ each comprise --CH₃.

13. The pressure sensitive adhesive of claim 1 comprising the composition of claim 1 which further comprises about 2 to about 30 weight percent, based upon the total weight of said composition, of a compound of the formula ##STR30## wherein:

q is an integer selected from the group consisting of 0 and 1;

s is an integer selected from the group consisting of 1, 2 and 3;

r is an integer of about 35 to about 700;

R⁷ is a monovalent moieties which can be the same or different selected from the group consisting of alkyl, substituted alkyl, alkoxy, alkylamino, hydroxyl, aryl, and substituted aryl; and

X, Y, D, R, R², R³, and R⁴ are as defined in claim 1.

14. The pressure-sensitive adhesive of claim 1 wherein said free radically polymerizable vinyl monomer is selected from the group consisting of acrylic acid, methacrylic acid, esters of acrylic acid comprising about 4 to about 21 carbon atoms, esters of methyacrylic acid comprising from about 5 to about 21 carbon atoms, acrylamide, N,N-dimethyl acrylamide, styrene, vinyl toluene acrylonitrile, methacrylonitrile, N-vinyl pyrrolidone, N-vinyl caprolactam, vinylidene chloride, vinyl esters of carboxylic acids, and mixtures thereof.

15. The pressure-sensitive adhesive of claim 1 wherein said free radically polymerizable vinyl monomer is selected from the group consisting of acrylic acid, methacrylic acid, acrylonitrile, esters of acrylic acid comprising from about 4 to about 21 carbon atoms, N,N-dimethyl acrylamide, N-vinyl pyrrolidone, and mixtures thereof.

16. The pressure-sensitive adhesive of claim 1 wherein said free radically polymerizable vinyl monomer is selected from the group consisting of acrylic acid, methacrylic acid, butyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, 2-carboxyethyl acrylate, ethoxyethyl acrylate, perfluorooctyl acrylate, isooctyl acrylate, and mixtures thereof.

17. The pressure-sensitive adhesive of claim 1 wherein the composition further comprises about 0.05 to about 2 weight percent of a multifunctional acrylate monomer based upon the total weight of said composition.

18. The pressure sensitive adhesive of claim 1 comprising the composition of claim 1 which further comprises about 5 to about 100 parts by weight tackifier per 100 parts by weight free radically polymerizable vinyl monomer.

19. The pressure sensitive adhesive of claim 1 comprising the composition of claim 18 wherein said tackifier is selected from the group consisting of rosin acids, rosin esters, synthetic aromatic resins, synthetic aliphatic resins, terpene resins, and mixtures thereof.

20. The pressure sensitive adhesive of claim 1 comprising the composition of claim 1 which further comprises inert gas bubbles dispersed throughout.

21. The pressure sensitive adhesive of claim 1 comprising the composition of claim 1 which further comprises microbubbles selected from the group consisting of glass microbubbles, plastic microbubbles, and mixtures thereof.

22. The pressure-sensitive adhesive of claim 1 wherein the composition further comprises about 0.5 to about 15 weight percent of silica filler based upon the total weight of said composition.

23. The pressure-sensitive adhesive of claim 1 wherein said composition further comprises about 2 to about 30 weight percent, based upon the weight of the adhesive composition, of polymer of the formula ##STR31## wherein:

p is an integer of about 35 to about 199; and

X are monovalent moieties having ethylenic unsaturation which can be the same or different;

Y are divalent linking groups which can be the same or different and which serve to activate X toward free radical polymerization;

D are monovalent moieties which can be the same or different selected from the group consisting of hydrogen, an alkyl group of 1 to about 10 carbon atoms, and aryl;

R are divalent hydrocarbon groups which can be the same or different;

R¹ are monovalent moieties which can be the same or elected from the group consisting of alkyl and aryl;

R² are monovalent moieties which can be the same or different selected from the group consisting of alkyl and aryl;

R³ are monovalent moieties which can be the same or different selected from the group consisting of alkyl, vinyl, and aryl.