초록 ▼

Addition-fragmentation agents of the formula are disclosed having the following functional groups: 1) a labile addition-fragmentation group that can cleave and reform to relieve strain, 2) a free-radically polymerizable group, and 3) a surface-modifying functional group that associates with the surf

Addition-fragmentation agents of the formula are disclosed having the following functional groups: 1) a labile addition-fragmentation group that can cleave and reform to relieve strain, 2) a free-radically polymerizable group, and 3) a surface-modifying functional group that associates with the surface of a substrate.

대표청구항 ▼

1. An addition-fragmentation agent comprising: 1) a labile addition-fragmentation group, 2) a free-radically polymerizable group, and 3) a surface-modifying functional group that associates with the surface of a substrate, said addition-fragmentation agent of the formula: whereinR1, R2 and R3 are ea

1. An addition-fragmentation agent comprising: 1) a labile addition-fragmentation group, 2) a free-radically polymerizable group, and 3) a surface-modifying functional group that associates with the surface of a substrate, said addition-fragmentation agent of the formula: whereinR1, R2 and R3 are each independently Zm-Q-, Yp-Q′-, a (hetero)alkyl group or a (hetero)aryl group with the proviso that at least one of R1, R2 and R3 is Zm-Q-, and with the proviso that at least one of R1, R2 and R3 is Yp-Q′-Q is a covalent bond or a linking group, having a valence of m+1;Q′ is a covalent bond or a linking group, having a valence of p+1;Z is an ethylenically unsaturated polymerizable group (meth)acryloxy, (meth)acrylamido, and styrenic groups,Y is a functional group that bonds with a substrate on which the addition-fragmentation agent is disposed;m is 1 to 6;p is 1 or 2;each X1 is independently —O— or —NR4—, where R4 is H or C1-C4 alkyl, and n is 0 or 1. 2. The addition-fragmentation agent of claim 1 wherein at least one of R1, R2 and R3 contain both Zm-Q- and Yp-Q′-, where Q is a covalent bond or a linking group, having a valence of m+1;Q′ is a covalent bond or a linking group, having a valence of p+1;Z is an ethylenically unsaturated polymerizable group, and Y is an functional group that bonds with a substrate on which the addition-fragmentation agent is disposed. 3. The addition-fragmentation agent of claim 1 wherein Q is selected from from —O—, —S—, —NR4—, —SO2—, —PO2—, —CO—, —OCO—, —R6—, —NR4—CO—NR4—, NR4—CO—O—, NR4—CO—NR4—CO—O—R6—, —CO—NR4—R6—, —R6—CO—O—R6—, —O—R6—, —S—R6—, —NR4—R6—, —SO2—R6—, —PO2—R6—, —CO—R6—, —OCO—R6—, —NR4—CO—R6—, NR4—R6—CO—O—, and NR4—CO—NR4—, wherein each R4 is hydrogen, a C1 to C4 alkyl group, or aryl group, each R6 is an alkylene group having 1 to 6 carbon atoms, a 5- or 6-membered cycloalkylene group having 5 to 10 carbon atoms, or a divalent arylene group having 6 to 16 carbon atoms, with the proviso that Q-Z does not contain peroxidic linkages. 4. The addition-fragmentation agent of claim 1 where Q is an alkylene. 5. The addition-fragmentation agent of claim 1 where Q is a hydroxyl-substituted alkylene. 6. The addition-fragmentation agent of claim 1 where Q is an aryloxy-substituted alkylene. 7. The addition-fragmentation agent of claim 1 where Q is an alkoxy-substituted alkylene. 8. The addition-fragmentation agent of claim 1 wherein R1—X1— groups, and optionally R2—X1— and R3—X1— groups, are selected from H2C═C(CH3)C(O)—O—CH2—CH(OH)—CH2—O—, H2C═C(CH3)C(O)—O—CH2—CH(O—(O)C(CH3)═CH2)—CH2—O—, H2C═C(CH3)C(O)—O—CH(CH2OAr)—CH2—O—, H2C═C(CH3)C(O)—O—CH2CH2—N(H)—C(O)—O—CH(CH2OAr)—CH2—O—, H2C═C(H)C(O)—O—(CH2)4—O—CH2—CH(OH)—CH2—O—, H2C═C(CH3)C(O)—O—CH2—CH(O—(O)C—N(H)—CH2CH2—O—(O)C(CH3)C═CH2)—CH2—O—, CH3—(CH2)7—CH(O—(O)C—N(H)—CH2CH2—O—(O)C(CH3)C═CH2)—CH2—O—, H2C═C(H)C(O)—O—(CH2)4—O—CH2—CH(—O—(O)C(H)═CH2)—CH2—O— and H2C═C(H)C(O)—O—CH2—CH(OH)—CH2—O—, where Ar is an aryl group. 9. The addition-fragmentation agent of claim 1 wherein Y is a monophosphate, a phosphonate, a phosphonic acid, a hydroxamic acid, a carboxylic acid, and acetoacetate, an anhydride, an isonitrile group, a silyl, a disulfide, a thiol, an amino, a sulfinic acid, a sulfonic acid, a phosphine, a phenolic or a heterocyclic aromatic group. 10. The addition-fragmentation agent composition of claim 9 wherein Y is a silyl group of the formula: —SiR73, wherein each R7 group is independently selected from the group of alkoxy, acetoxy, and halide. 11. A polymerizable composition comprising the addition-fragmentation agent of claim 1, at least one free-radically polymerizable monomer, and an initiator. 12. The polymerizable composition of claim 11 comprising: a) 85 to 100 parts by weight of an (meth)acrylic acid ester;b) 0 to 15 parts by weight of an acid functional ethylenically unsaturated monomer;c) 0 to 10 parts by weight of a non-acid functional, ethylenically unsaturated polar monomer;d) 0 to 5 parts vinyl monomer; ande) 0 to 5 parts of a multifunctional (meth)acrylate;based on 100 parts by weight total monomer a) to e), andf) 0.1 to 10 parts by weight of the addition-fragmentation agent, based on 100 parts by weight of a) to e). 13. The polymerizable composition of claim 12 further comprising 0.01 to 5 parts of a multifunctional (meth)acrylate. 14. The polymerizable composition of claim 11 further comprising a surface-modified inorganic oxide of the formula: whereFiller is an inorganic oxide particle,R2 and R3 are each independently Zm-Q-, Yp-Q′-, a (hetero)alkyl group or a (hetero)aryl group;Q is a covalent bond or a linking group, having a valence of m+1;Q′ is a covalent bond or an or a linking group, having a valence of p+1;Z is an ethylenically unsaturated polymerizable group (meth)acryloxy, (meth)acrylamido, and styrenic groups,Y′ is the residue of the surface-modifying organic functional group that associates with a substrate on which the addition-fragmentation agent is disposed;m is 1 to 6;p is 1 or 2;X1 is independently —O— or —NR4—, where R4 is H or C1-C4 alkyl, andn is 0 or 1. 15. A hardcoat composition comprising one or more multifunctional (meth)acrylate monomers or (meth)acrylate oligomers, and the addition-fragmentation agent of claim 1.