Curable (meth)acrylate compositions

• US 6,833,391 B1
• Filed: 05/27/2003
• Issued: 12/21/2004
• Est. Priority Date: 05/27/2003
• Status: Expired due to Fees

• Current Assignee: Sabic Innovative Plastics IP BV (Government of Saudi Arabia)
• Original Assignee: General Electric Company
• Inventors: Herrmann, Anne, Chisholm, Bret Ja
• Primary Examiner(s): Zalukaeva, Tatyana
• Application Number:
  US10/249,998
• Publication Number:
  US 20040249100A1
• Time in Patent Office: 574 Days
• Field of Search: 522/64, 522/26, 522/28, 522/182, 522/328, 526/328, 526/329.7, 526/293.2, 526/292.3, 428/64.1
• US Class Current: 522/28
• CPC Class Codes: C08F 222/1025 of aromatic dialcohols
• CPC Class Codes: G02B 1/04 made of organic materials, e.g. plastics G02B1/08 takes precedence
• CPC Class Codes: Y10T 428/21 Circular sheet or circular blank

Abstract

A curable composition includes a multifunctional (meth)acrylate; a substituted or unsubstituted arylether (meth)acrylate monomer; a brominated aromatic (meth)acrylate monomer; and a polymerization intiator. The compositions exhibit high refractive indices and, upon polymerization, the compositons provide films having excellent thermomechanical properties.

Claims

1. A curable composition, comprising:

a multifunctional (meth)acrylate according to the formula

 

wherein R¹ is hydrogen or methyl;

X¹ is O or S;

R² is C₁-C₆ alkylene disubstituted bisphenol-A or bisphenol-F, C₁-C₆ hydroxyalkylene disubstituted bisphenol-A or bisphenol-F, or their brominated forms; and

n is 2, 3, or 4;

a substituted or unsubstituted arylether (meth)acrylate monomer;

a brominated aromatic (meth)acrylate monomer according to the formula

 

wherein R⁵ is hydrogen or methyl;

X⁴ is O or S;

X⁵ is O or S;

m is 1, 2, or 3;

p is or 0 or 1; and

q is 4 or 5; and

a polymerization initiator.

2. The composition of claim 1, wherein the multifunctional (meth)acrylate is the reaction product of (meth)acrylic acid with a di-epoxide comprising bisphenol-A diglycidyl ether;

bisphenol-F diglycidyl ether;

tetrabromo bisphenol-A diglycidyl ether;

tetrabromo bisphenol-F diglycidyl ether;

1,3-bis-{4-[1-methyl-1-(4-oxiranylmethoxy-phenyl)-ethyl]-phenoxy}-propan-2-ol;

1,3-bis-{2,6-dibromo-4-[1-(3,5-dibromo-4-oxiranylmethoxy-phenoxyl)-1-methyl-ethyl]-phenoxy}-propan-2-ol;

or a combination comprising at least one of the foregoing di-epoxides.

3. The composition of claim 1, wherein the multifunctional (meth)acrylate comprises about 25 to about 75 weight percent based on the total weight of the composition.

4. The composition of claim 1, wherein the substituted or unsubstituted arylether (meth)acrylate monomer comprises

wherein R³ is hydrogen or methyl; X² is O or S;

X³ is O or S;

R₄ is substituted or unsubstituted C₁-C₆ alkyl or alkenyl;

Ar is substituted or unsubstituted C₆-C₁₂ aryl,including phenyl;

wherein the substitution on the R⁴ and Ar independently include fluorine, chlorine, bromine, iodine, C₁-C₆ alkyl, C₁-C₃ perhalogenated alkyl, hydroxy, C₁-C₆ ketone, C₁-C₆ ester, N,N—

(C₁-C₃) alkyl substituted amide, or a combination comprising at least one of the forgoing substituents.

5. The composition of claim 4, wherein the substituted or unsubstituted arylether (meth)acrylate monomer is phenoxyethyl (meth)acrylate, phenylthioethyl (meth)acrylate, or a combination comprising at least one of the foregoing substituted or unsubstituted arylether (meth)acrylate monomers.

6. The composition of claim 4, wherein the substituted or unsubstituted arylether (meth)acrylate monomer comprises about 15 to about 70 weight percent based on the total weight of the composition.

7. The composition of claim 4, further comprising an additional substituted or unsubstituted arylether (meth)acrylate monomer.

8. The composition of claim 1, wherein the brominated aromatic (meth)acrylate monomer is pentabromobenzyl (meth)acrylate, pentabromophenyl (meth)acrylate or a combination comprising at least one of the foregoing brominated aromatic (meth)acrylate monomers.

9. The composition of claim 1, wherein the brominated aromatic (meth)acrylate monomer comprises about 1 to about 20 weight percent based on the total weight of the composition.

10. The composition of claim 1, wherein the polymerization initiator is a phosphine oxide photoinitiator.

11. The composition of claim 1, wherein the multifunctional (meth)acrylate is the reaction product of (meth)acrylic acid with a di-epoxide comprising bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, tetrabromo bisphenol-A diglycidyl ether, tetrabromo bisphenol-F diglycidyl ether, 1,3-bis-{4-[1-methyl-1-(4oxiranylmethoxy-phenyl)-ethyl]-phenoxy}-propan-2-ol, 1,3-bis-{2,6-dibromo-4-[1-(3,5-dibromo-4-oxiranylmethoxy-phenyl)-1-methyl-ethyl]-phenoxy}-propan-2-ol, or a combination comprising at least one of the foregoing di-epoxides;

wherein the substituted or unsubstituted arylether (meth)acrylate monomer is phenylthioethyl (meth)acrylate, phenoxyethyl (meth)acrylate, or a combination comprising at least one of the foregoing substituted or unsubstituted arylether (meth)acrylate monomers;

wherein the brominated aromatic (meth)acrylate monomer is pentabromobenzyl (meth)acrylate; and

wherein the polymerization initiator is a phosphine oxide photoinitiator.

12. The composition of claim 1, comprising

about 45 to about 65 weight percent of the multifunctional (meth)acrylate;

about 30 to about 45 weight percent of the substituted or unsubstituted arylether (meth)acrylate monomer;

about 1 to about 10 weight percent of the brominated aromatic (meth)acrylate monomer; and

about 0.1 to about 5 weight percent of the phosphine oxide photoinitiator based on the total weight of the composition.

13. The composition of claim 12, cured by ultraviolet radiation.

14. An article formed from the cured composition of claim 13.

15. An optical film for backlit displays formed from the cured composition of claim 13.

16. A composition comprising, a multifunctional (meth)acrylate comprising the reaction product of (meth)acrylic acid with a di-epoxide comprising bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, tetrabromo bisphenol-A diglycidyl ether, tetrabromo bisphenol-F diglycidyl ether, 1,3-bis-{4-[1-methyl-1-(4-oxiranylmethoxy-phenyl)-ethyl]-phenoxy}-propan-2-ol, 1,3-bis-{2,6-dibromo-4-[1-(3,5-dibromo-4-oxiranylmethoxy-phenyl)-1-methyl-ethyl]-phenoxy}-propan-2-ol, or a combination comprising at least one of the foregoing di-epoxides;

phenylthioethyl (meth)acrylate;

pentabromobenzyl (meth)acrylate; and

a phosphine oxide photoinitiator.

17. A method of making a curable composition, comprising:

blending a multifunctional (meth)acrylate according to the formula

wherein R¹ is hydrogen or methyl;

X¹ is O or S;

R² is C₁-C₆ alkylene disubstituted bisphenol-A or b bisphenol-F, C₁-C₆ hydroxyalkylene disubstituted bisphenol-A or bisphenol-F, or their brominated forms; and

n is 2, 3, or 4,

a substituted or unsubstituted arylether (meth)acrylate monomer,

a brominated aromatic (meth)acrylate monomer according to the formula

 

wherein R⁵ is hydrogen or methyl;

X⁴ is O or S;

X⁵ is O or S;

m is 1, 2, or 3;

p is 0 or 1; and

q is 4 or 5, and

a polymerization initiator.

18. A curable composition, consisting of:

a multifunctional (meth)acrylate according to the formula

 

wherein R¹ is H or methyl;

X¹ is O or S;

R² is C₁-C₆ alkylene disubstituted bisphenol-A or bisphenol-F, C₁-C₆ hydroxyalkylene disubstituted-bisphenol-A or bisphenol-F, or their brominated forms; and

n is 2, 3, or 4;

a substituted or unsubstituted arylether (meth)acrylate monomer according to the formula

 

wherein R³ is hydrogen or methyl;

X² is O or S;

X³ is S;

R⁴ is substituted or unsubstituted C₁-C₆ alkyl or alkenyl;

Ar is substituted or unsubstituted C₆-C₁₂ aryl including phenyl;

wherein the substitution on the R⁴ and Ar is, independently, fluorine, chlorine, bromine, iodine, C₁-C₆ alkyl, C₁-C₃ perhalogenated alkyl, hydroxy, C₁-C₆ ketone, C₁-C₆ ester, N,N—

(C₁-C₃) alkyl substituted amide,or a combination comprising at least one of the forgoing substituents; and

a polymerization initiator.