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

A fluorocarbon- and urethane-acrylate-containing additive 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 composed of groups comprising the formula:
• F(RfcO)xCdF2d—, wherein each Rfc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms, each x independently represents an integer greater than or equal to 2, and wherein d is an integer from 1 to 6;
• wherein a is 2-15;
• wherein Q is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene, a straight or branched chain or cycle-containing connecting group optionally containing heteroatoms such as O, N, and S and optionally a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof;
• wherein X is O or S;
• and
• wherein f is 1-5.

A fluorocarbon- and urethane-acrylate-containing additive 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 the residue of a multi-isocyanate;
• where X is O, S or NR, where R is H or lower alkyl of 1 to 4 carbon atoms;
• where Rf is a monovalent perfluoropolyether moiety composed of groups comprising the formula:
• F(RfcO)xCdF2d—, wherein each Rfc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms, each x independently represents an integer greater than or equal to 2, and wherein d is an integer from 1 to 6;
• where Q is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene, a straight or branched chain or cycle-containing connecting group optionally containing heteroatoms such as O, N, and S and optionally a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof;
• where G is selected from the group consisting of an alkyl, an aryl, an alkaryl and an aralkyl, wherein G optionally contains heteroatoms such as O, N, and S and optionally has heteroatom-containing functional groups such as carbonyl and sulfonyl and combinations of heteroatoms and heteroatom-containing functional groups;
• and G optionally contains pendant or terminal reactive groups selected from the group consisting of (meth)acryl groups, vinyl groups, allyl groups and —Si(OR3)3 groups, where R3 is a lower alkyl of 1 to 4 carbon atoms, wherein G also optionally has fluoroalkyl or perfluoroalkyl groups;
• where m is at least 1;
• where n is at least 1;
• where o is 0 or greater;
• where p is 2 to 6;
• where q is 0 or greater;
• wherein (m+n+o+q)=NNCO, where NNCO is the number of isocyanate groups originally appended to Ri;
• and
• wherein the quantity (m+n+o)/NNCO is greater than or equal to 0.67, and in which each unit referred to by the subscripts m, n, o, and q is attached to an Ri unit.

A fluorocarbon- and urethane-acrylate-containing additive 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)oRf(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 the residue of a multi-isocyanate;
• where c is 1 to 50;
• where X is O, S or NR, where R is H or lower alkyl;
• where Rf is a monovalent perfluoropolyether moiety composed of groups comprising the formula:
• F(RfcO)xCdF2d—, each Rfc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms and each x independently represents an integer greater than or equal to 2 and wherein d is an integer from 1 to 6;
• where Q is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene, a straight or branched chain or cycle-containing connecting group optionally containing heteroatoms such as O, N, and S and optionally a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof;
• wherein A is a (meth)acryl functional group having the chemical formula:
• (—XC(O)C(R2)═CH2), where R2 is a lower alkyl of 1 to 4 carbon atoms or H or F;
• where G is selected from the group consisting of an alkyl, an aryl, an alkaryl and an aralkyl, wherein G optionally contains heteroatoms such as O, N, and S and optionally has heteroatom-containing functional groups such as carbonyl and sulfonyl and combinations of heteroatoms and heteroatom-containing functional groups;
• and G optionally contains pendant or terminal reactive groups selected from the group consisting of (meth)acryl groups, vinyl groups, allyl groups and —Si(OR3)3 groups, where R3 is a lower alkyl of 1 to 4 carbon atoms;
• wherein G also optionally has fluoroalkyl or perfluoroalkyl groups;
• wherein D is selected from the group consisting of an alkylene, an arylene, an alkarylene, a fluoroalkylene, a perfluoroalkylene and an aralkylene and optionally contains heteroatoms such as O, N, and S;
• wherein D1 is selected from the group consisting of an alkyl, an aryl, an alkaryl, a fluoroalkyl, a perfluoroalkyl and an aralkyl group and optionally contains heteroatoms such as O, N, and S;
• where Q1 is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene, a straight or branched chain or cycle-containing connecting group optionally containing heteroatoms such as O, N, and S and optionally a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof;
• where m or z is at least 1;
• where n or v is at least 1;
• where o, s, v, and w are 0 or greater;
• where (m+n+o+[(u+1)s]+2v+w)=cNNCO, where NNCO is the number of isocyanate groups originally appended to Ri;
• the quantity (m+n+o+[(u+1)s]+2v)/(cNNCO) is greater than or equal to least 0.75, p is 2 to 6, t is 1 to 6, and u is independently 1 to 3, and in which each unit referred to by the subscripts m, n, o, s, v and w is attached to an Ri unit.

A hardcoat composition comprising:

• a hardcoat-compatible, monovalent perfluoropolyether moiety-containing urethane multi-(meth)acryl additive;
• a hydrocarbon hardcoat composition;
• and
• optionally a plurality of surface modified inorganic nanoparticles.

A fluorocarbon- and urethane-acrylate-containing additive 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 the residue of a multi-isocyanate;
• where c is 1 to 50;
• where X is O, S or NR, where R is H or lower alkyl;
• where Rf is a monovalent perfluoropolyether moiety composed of groups comprising the formula:
• F(RfcO)xCdF2d—, each Rfc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms and each x independently represents an integer greater than or equal to 2 and wherein d is an integer from 1 to 6;
• where Q is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene, a straight or branched chain or cycle-containing connecting group optionally containing heteroatoms such as O, N, and S and optionally a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof;
• wherein A is a (meth)acryl functional group having the chemical formula:
• (—XC(O)C(R2)═CH2), where R2 is a lower alkyl of 1 to 4 carbon atoms or H or F;
• where G is selected from the group consisting of an alkyl, an aryl, an alkaryl and an aralkyl, wherein G optionally contains heteroatoms such as O, N, and S and optionally has heteroatom-containing functional groups such as carbonyl and sulfonyl and combinations of heteroatoms and heteroatom-containing functional groups;
• and G optionally contains pendant or terminal reactive groups selected from the group consisting of (meth)acryl groups, vinyl groups, allyl groups and —Si(OR3)3 groups, where R3 is a lower alkyl of 1 to 4 carbon atoms;
• wherein G also optionally has fluoroalkyl or perfluoroalkyl groups;
• where Rf2 is a multi-valent perfluoropolyether moiety, Rf2 is composed of groups comprising 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 independently represents an integer greater than or equal to 2, and 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;
• wherein D is selected from the group consisting of an alkylene, an arylene, an alkarylene, a fluoroalkylene, a perfluoroalkylene and an aralkylene group and optionally contains heteroatoms such as O, N, and S;
• wherein D1 is selected from the group consisting of an alkyl, an aryl, an alkaryl, a fluoroalkyl, a perfluoroalkyl and an aralkyl group and optionally contains heteroatoms such as O, N, and S;
• where Q1 is independently a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene, a straight or branched chain or cycle-containing connecting group optionally containing heteroatoms such as O, N, and S and optionally a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof;
• where r is at least 1;
• where n or v is at least 1;
• where m, o, s, v, and w are 0 or greater;
• where (m+n+o+[(u+1)r]+[(u+1)s]+2v+w)=cNNCO, where NNCO is the number of isocyanate groups originally appended to Ri;
• the quantity (m+n+o+[(u+1)r]+[(u+1)s]+2v)/(cNNCO) is greater than or equal to least 0.75, p is 2 to 6, t is 1 to 6, and u is independently 1 to 3, and in which each unit referred to by the subscripts m, n, o, r, s, v and w is attached to an Ri unit.

A method for forming an optical display comprising:

• (a) forming an additive comprising a perfluoropolyether urethane having a monovalent perfluoropolyether moiety and a multi-(meth)acryl terminal group by first reacting a polyisocyanate with a hydroxyl functional acrylate and further reacting the resultant compound with a perfluoropolyether-containing alcohol or thiol having a monovalent perfluoropolyether moiety, said additive having no free isocyanate groups;
• (b) mixing said additive with a hydrocarbon-based hardcoat composition to form a hard coating composition;
• (c) applying said hard coating composition to an optical substrate;
• and
• (d) curing said hard coating composition to form a stain repellent optical hard coat on said optical substrate.

A method for forming an optical display comprising:

• (a) forming an additive comprising a perfluoropolyether urethane having a monovalent perfluoropolyether moiety and a multi-(meth)acryl terminal group by first reacting a polyisocyanate with a perfluoropolyether-containing alcohol, thiol or amine having a monovalent perfluoropolyether moiety and further reacting the resultant compound with hydroxyl functional multiacrylate, said additive having no free isocyanate groups;
• (b) mixing said additive with a hydrocarbon-based hardcoat composition to form a hard coating composition;
• (c) applying said hard coating composition to an optical substrate;
• and
• (d) curing said hard coating composition to form a stain repellent optical hard coat on said optical substrate.

A hard coating composition for optical displays comprising:

• a hydrocarbon-based hard coating composition;
• a compatibilizer selected from the group consisting of a free radically reactive fluoroalkyl group-containing compatibilizer, a free radically reactive fluoroalkylene group-containing compatibilizer, and a perfluoroalkyl substituted urethane mono or multi (meth)acrylate compatibilizer;
• and
• a perfluoropolyether-substituted urethane acrylate having the chemical formula:
• Rf-Q-(XC(O)NHQOC(O)C(R)═CH2)f:
• wherein Rf is a monovalent perfluoropolyether moiety composed of groups comprising the formula:
• F(RfcO)xCdF2d—, wherein each Rfc independently represents a fluorinated alkylene group having from 1 to 6 carbon atoms, each x independently represents an integer greater than or equal to 2, and wherein d is an integer from 1 to 6;
• wherein a is 2-15;
• wherein Q is a connecting group of valency at least 2 and is selected from the group consisting of a covalent bond, an alkylene, an arylene, an aralkylene, an alkarylene group, a straight or branched chain or cycle-containing connecting group optionally containing heteroatoms such as O, N, and S and optionally a heteroatom-containing functional group such as carbonyl or sulfonyl, and combinations thereof;
• wherein X is O or S;
• and
• wherein f is 1-5.