Perfluoropolyether urethane additives having (meth)acryl groups and hard coats

• US 8,981,151 B2
• Filed: 04/08/2014
• Issued: 03/17/2015
• Est. Priority Date: 03/23/2005
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Klun, Thomas P., Jing, Naiyong, Pokorny, Richard J., Qiu, Zai-Ming, Pellerite, Mark J., Coggio, William D., Walker, Christopher B. Jr.
• Primary Examiner(s): Kumar, Shailendra
• Application Number:
  US14/247,379
• Publication Number:
  US 20140221689A1
• Time in Patent Office: 343 Days
• Field of Search: 564/209, 428/423.1, 528/44
• US Class Current: 564/209
• CPC Class Codes: C07C 235/08 having the nitrogen atom of at least one of the carboxamide groups bound to an acyclic carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
• CPC Class Codes: C08F 290/067 Polyurethanes; Polyureas
• CPC Class Codes: C08G 18/2885 containing halogen atoms
• CPC Class Codes: C08G 18/289 containing silicon
• CPC Class Codes: C08G 18/3802 having halogens
• CPC Class Codes: C08G 18/3825 containing amide groups C08G18/3821 takes precedence
• CPC Class Codes: C08G 18/50 having heteroatoms other than oxygen
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/673 containing two or more acrylate or alkylacrylate ester groups
• CPC Class Codes: C08G 18/7831 containing biuret groups
• CPC Class Codes: C08G 18/792 formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/8175 with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• CPC Class Codes: C09D 175/16 having terminal carbon-to-carbon unsaturated bonds
• CPC Class Codes: G02B 1/105 Protective coatings
• CPC Class Codes: G02B 1/14 Protective coatings, e.g. hard coatings
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

Fluorocarbon- and urethane-(meth)acryl-containing additives and hardcoats. The hardcoats are particularly useful as a surface layer on an optical device.

Claims

1. A fluorocarbon- and urethane-(meth)acryl-containing composition comprising a perfluoropolyether urethane having a perflurorpolyether moiety and a multi-meth(acryl) group having the chemical formula:

(R_i)_c—

(NHC(O)OQ(A)_p)_n,—

(NHC(O)XQ-R_f2(QXC(O)NH)_u)_r—

,—

(NHC(O)OQ(A)_tQ₁Q(A)_tOC(O)NH)_v—

wherein

R_i is a residue of a multi-isocyanate;

c is 1 to 50;

X is O, S or NR, where R is H or an alkyl group comprising 1 to 4 carbon atoms;

Q and Q₁ are each independently a connecting group of valency at least 2;

A is a (meth)acryl functional group having the formula (—

XC(O)C(R₂)═

CH₂), wherein R₂ is an alkyl group having 1 to 4 carbon atoms or H or F;

R_f2 is a multi-valent perfluoropolyether moiety having the formula Y((R_fc1O)_xC_d1F_2d1)_b,

wherein each R_fc1 is independently selected from;

—

CF(CF₃)CF₂—

, —

CF₂CF₂CF₂—

, and

(CH₂C(CH₃)(CH₂OCH₂CF₃)CH₂—

)_aa where aa is 2 or greater;

each x is independently an integer greater than or equal to 2, d1 is an integer from 0 to 6;

Y represents a polyvalent organic group or covalent bond having a valence of b, and b represents an integer greater than or equal to 2;

p is 2 to 6;

u is 1 to 3;

t is 1-6;

r is at least 1; and

n or v is at least 1.

2. The fluorocarbon- and urethane-(meth)acryl-containing composition of claim 1 wherein the perfluoropolyether urethane comprises

_n(_p(A)QO(O)CHN)—

R_i—

(NHC(O)XQ-R_f2(QXC(O)NH)_u)_r,

or

_v(HN(O)CO(A)_tQQ₁(A)_tQO(O)CHN)—

R_i—

(NHC(O)XQ-R_f2(QXC(O)NH)_u)_r.

4. The composition of claim 1 with the proviso that when X is O, Q is not methylene.

5. The composition of claim 1 wherein X is S or NR.

6. The composition of claim 1 wherein Q is an alkylene having at least two carbon atoms.

7. The composition of claim 1 wherein Q is a straight chain, branched chain, or cycle-containing connecting group.

8. The composition of claim 7 wherein Q is selected from the group consisting of a covalent bond;

an arylene;

an aralkylene; and

alkarylene.

9. The composition of claim 7 wherein Q comprises a heteroatom selected from O, N, and S.

10. The composition of claim 7 wherein Q comprises a heteroatom-containing functional group selected from carbonyl and sulfonyl.

11. The composition of claim 7 wherein Q is a straight chain alkylene group comprising heteroatoms selected from O, N, S;

a heteroatom-containing functional group selected from carbonyl and sulfonyl, and combinations thereof.

12. The composition of claim 7 wherein Q is branched chain or cycle-containing alkylene group.

13. The composition of claim 1 wherein Q is a nitrogen containing group.

14. The composition of claim 13 wherein Q contains an amide group.

15. The composition of claim 1 wherein the composition further comprises ethylene oxide repeat units.

16. The composition of claim 1 wherein n is 2.

3. A fluorocarbon- and urethane-(meth)acryl-containing composition comprising a perfluoropolyether urethane having a perflurorpolyether moiety and a multi-meth(acryl) group having the chemical formula:

(R_i)_c—

(NHC(O)XQR_f)_m,—

(NHC(O)OQ(A)_p)_n,R_f(Q)(XC(O)NH)_y)_z—

,

—

(NHC(O)OQ(A)_tQ₁(A)_tOC(O)NH)_v—

wherein

R_i is a residue of a multi-isocyanate;

c is 1 to 50;

X is O, S or NR, where R is H or an alkyl group comprising 1 to 4 carbon atoms;

R_f is a monovalent perfluoropolyether moiety comprising groups of the formula F(R_fcO)_xC_dF_2d,

wherein each R_fc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms, each x is an integer greater than or equal to 2, and d is an integer from 1 to 6;

Q and Q₁ are each independently a connecting group of valency at least 2;

A is a (meth)acryl functional group having the formula (—

XC(O)C(R₂)═

CH₂), wherein R₂ is an alkyl group having 1 to 4 carbon atoms or H or F;

p is 2 to 6;

y is independently 2 or greater;

t is 1-6;

m or z is at least 1;

n or v is at least 1; and

at least one of v or z is 1.