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

An optical display comprising:

• an optical substrate having a surface layer comprising the reaction product of a mixture comprising
• i) a hydrocarbon-based hardcoat composition;
• ii) at least one perfluoropolyether urethane having a perfluoropolyether moiety and at least one free-radically reactive group;
• iii) at least one fluorinated compound having at least one moiety selected from fluoropolyether, fluoroalkyl, and fluoroalkylene linked to at least one free-radically reactive group with a non-urethane linking group;
• and
• iv) optionally surface modified inorganic oxide particles.

A fluorocarbon- and urethane-(meth)acryl-containing composition comprising a perfluoropolyether urethane having a perfluoropolyether moiety and a multi-(meth)acry terminal group and having the formula:

• Ri—(NHC(O)XQRf)m,—(NHC(O)OQ(A)p)n;
• wherein
• Ri is the residue of a multi-isocyanate;
• X is O, S or NR, wherein R is H or an alkyl group having 1 to 4 carbon;
• Rf is a monovalent perfluoropolyether moiety comprising groups of the formula F(RfcO)xCdF2d—, wherein each Rfc is independently a fluorinated alkylene group having from 1 to 6 carbon atoms, each x is an integer greater than or equal to 2, and wherein d is an integer from 1 to 6;
• each Q is independently a connecting group having a valency of at least 2;
• A is a (meth)acryl functional group —XC(O)C(R2)═CH2 wherin R2 is an alkyl group of 1 to 4 carbon atoms or H or F;
• m is at least 1;
• n is at least 1;
• p is 2 to 6;
• m+n is 2 to 10;
• wherein each group having subscripts m and n is attached to the Ri unit.

A fluorocarbon- and urethane-acrylate-containing composition comprising a perfluoropolyether-substituted urethane(meth)acryl having the chemical formula:

• Rf-Q-(XC(O)NHQOC(O)C(R)═CH2)f wherein
• Rf is a monovalent perfluoropolyether moiety comprising groups of the formula F(RfcO)xCdF2d—, wherein each Rfc is independently a fluorinated alkylene group having 1 to 6 carbon atoms, each x is an integer greater than or equal to 2, and d is an integer from 1 to6;
• a is 2-15;
• each Q is independently a connecting group having a valency of at least 2;
• X is O or S;
• and
• wherein f is 1-5.

A fluorocarbon- and urethane-acrylate-containing composition comprising one or more perfluoropolyether urethanes with multi-(meth)acryl groups of the formula:

• Ri-(NHC(O)XQRf)m,—(NHC(O)OQ(A)p)n,—(NHC(O)XQG)o,—(NCO)q wherein
• Ri is a residue of a multi-isocyanate;
• X is O, S or NR, wherein R is H or an alkyl group having 1 to 4 carbon atoms;
• Rf is a monovalent perfluoropolyether moiety comprising groups of the formula:
• F(RfcO)xCdF2d—, wherein each Rfc is 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 is independently a connecting group of valency at least 2;
• G is selected from the group consisting of alkyl, aryl, alkaryl and aralkyl;
• where m is at least 1;
• where n is at least 1;
• where o is at least 1;
• where p is 2 to 6;
• and
• where q is 0 or greater.

A fluorocarbon- and urethane-acrylate-containing composition comprising one or more perfluoropolyether urethanes with multi-meth(acryl) groups having the chemical formula:

• (Ri)c—(NHC(O)XQRf)m,—(NHC(O)OQ(A)p)n,—(NHC(O)XQG)o, Rf(Q)(XC(O)NH)y)z—, —(NHC(O)XQD(QXC(O)NH)u)s—,-D1(QXC(O)NH)y)zz, —(NHC(O)OQ(A)tQ1Q(A)tOC(O)NH))v—,—(NCO)w;
• wherein
• Ri 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;
• Rf is a monovalent perfluoropolyether moiety comprising groups of the formula F(RfcO)xCdF2d, wherein each Rfc 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;
• G is selected from the group consisting of alkyl, aryl, alkaryl and aralkyl;
• D is selected from the group consisting of alkylene, arylene, alkarylene, fluoroalkylene, perfluoroalkylene, and aralkylene;
• optionally containing heteroatoms selected from O, N, and S;
• D1 is selected from the group consisting of alkyl, aryl, alkaryl, fluoroalkyl, perfluoroalkyl, and aralkyl, each group optionally containing heteroatoms selected from O, N, and S;
• m or z is at least 1;
• n or v is at least 1;
• o, s, v, and w are 0 or greater;
• and at least one of s, v, z, or zz is 1.

A fluorocarbon- and urethane-acrylate-containing compostion comprising one or more perfluoropolyether urethanes with multi-meth(acryl) groups having the chemical formula:

• (Ri)c—(NHC(O)XQRf)m,—(NHC(O)OQ(A)p)n,—(NHC(O)XQG)o,—(NHC(O)XQ-Rf2(QXC(O)NH)u)r,—(NHC(O)XQ-D(QXC(O)NH)u)s—,-D1(QXC(O)NH)y)zz, —(NHC(O)OQ(A)tQ1Q(A)tOC(O)NH))v—,—(NCO)w;
• wherein
• Ri 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;
• Rf is a monovalent perfluoropolyether moiety comprising groups of the formula F(RfcO)xCdF2d—, wherein each Rfc is independently a fluorinated alkylene group having 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;
• G is selected from the group consisting of alkyl, aryl, alkaryl and aralkyl;
• Rf2 is a multi-valent perfluoropolyether moiety having the formula Y((Rfc1O)xCd1F2d1)b, wherein each Rfc1 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;
• D is selected from the group consisting of alkylene, arylene, alkarylene, fluoroalkylene, perfluoroalkylene and aralkylene;
• optionally contains heteroatoms such as O, N, and S;
• D1 is selected from the group consisting of alkyl, aryl, alkaryl, fluoroalkyl, perfluoroalkyl, and aralkyl, each group containing heteroatoms selected from O, N, and S;
• where r is at least 1;
• where n or v is at least 1;
• and
• where m, o, s, v, and w are 0 or greater.

A protective film comprising:

• a light-tranmissive substrate having a a hardcoat surface layer comprising the reaction product of a mixture comprising
• i) a hydrocarbon-based hardcoat composition;
• ii) at least one additive comprising a perfluoropolyether urethane having a perfluoropolyether moiety and at least one free-radically reactive group;
• and
• iii) at least one fluorinated compound having at least one moiety selected from fluoropolyether, fluoroalkyl, and fluoroalkylene linked to at least one free-radically reactive group with a non-urethane linking group.

A protective film comprising:

• a light-tranmissive substrate having a surface layer comprising the reaction product of a mixture comprising
• i) at least one non-fluorinated crosslinking agent, and
• ii) at least one perfluoropolyether urethane having a perfluoropolyether moiety and at least one (meth)acryl terminal group;
• and
• a hardcoat layer comprising inorganic particles disposed between the substrate and the surface layer.

A polymerizable composition comprising:

• i) a hydrocarbon-based hardcoat composition;
• ii) at least one perfluoropolyether urethane having a perfluoropolyether moiety and at least one (meth)acryl terminal group;
• and
• iii) at least one fluorinated compound having at least one moiety selected from fluoropolyether, fluoroalkyl, and fluoroalkylene linked to at least one free-radically reactive group with a non-urethane linking group.