Dental resin composition, method of manufacture, and method of use thereof
View Patent ↗A composition is disclosed comprising a polymerizable (meth)acrylate of the structure: wherein A is an anhydride; a is 0 or 1; n is 0, 1, 2, or 3; R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 6 alkyl)-O-(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene); x and y are each independently an integer of 1 to 10; z is an integer of 1 to 5; R 5 is hydrogen or methyl; M is wherein G and J are each independently O or NR 6 , wherein R 6 is hydrogen or C 1 -C 6 alkyl; m is 1, 2, 3, or 4; W is an organic group having the valency of z+1; and q is 0 or 1; and further wherein when a is 1, n+m+q is 1, 2, 3, or 4, and when a is 0, n+m+q is 1, 2, 3, 4, 5, or 6. The composition finds use as a dental resin.
1. A dental restorative composition comprising, based on total weight of the composition:
about 1 to about 99 weight percent of a polymerizable (meth)acrylate of the structure:
wherein
A is an anhydride;
a is 0 or 1;
n is 0, 1, 2, or 3;
R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 6 alkyl)-O—(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene);
x and y are each independently an integer of 1 to 10; z is an integer of 1 to 5;
R 5 is hydrogen or methyl;
wherein G and J are each independently O or NR 6 , wherein R 6 is hydrogen or C 1 -C 6 alkyl;
m is 1, 2, 3, or 4;
W is an organic group having the valency of z+1; and
q is 0 or 1;
wherein
is different from
and further wherein when a is 1, n+m+q is 1, 2, 3, or 4, and when a is 0, n+m+q is 1, 2, 3, 4, 5, or 6;
about 1 to about 90 weight percent of a filler system; and
a curing system; wherein the dental restorative composition does not require a separate dental bonding procedure and has a shear bonding strength to a dentin surface of at least 12.2 MPa after curing.
2. The composition of claim 1 , wherein R 1 , R 2 , R 3 , and R 4 are each independently hydrogen or C 1 -C 12 alkyl; and x and y are each independently an integer from 1 to 5.
3. The composition of claim 1 , wherein a is 0; R 1 , R 2 , R 3 , and R 4 are each independently hydrogen; x is 5; y is 2; and M is
wherein G is oxygen.
4. The composition of claim 3 , wherein n is 0, 1, or 2.
5. The composition of claim 1 , wherein the polymerizable (meth)acrylate has the structure:
wherein
R 6 and R 7 are each independently hydrogen, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 6 alkyl)-O—(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene);
z is an integer of 1 to 5.
6. The composition of claim 5 , wherein z is 1 to 3, R 1 , R 2 , R 3 , R 4 , R 6 , and R 7 are each independently hydrogen, hydroxy, or C 1 -C 12 alkyl, and x and y are each independently an integer from 1 to 6.
7. The composition of claim 1 , wherein the polymerizable (meth)acrylate is prepared by the reaction of an aromatic compound comprising anhydride functionality, carboxylic acid functionality, or a combination thereof; and a first hydroxy-containing (meth)acrylate monomer of the structure:
wherein
R 1 , R 2 , R 3 , and R 4 are each independently hydrogen, hydroxy, C 1 -C 12 alkyl, C 1 C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 6 alkyl)-O—(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene);
x and y are each independently an integer from 1 to 10;
R 5 is hydrogen or methyl; and
wherein G and J are each independently O or NR 6 , wherein R 6 is hydrogen or C 1 -C 6 alkyl.
8. The composition of claim 7 , wherein the aromatic compound is benzenetetracarboxylic acid; benzenetetracarboxylic acid dianhydride; 1,3-dihydro-1,3-dioxoisobenzofuran-4,5-dicarboxylic acid; pyromellitic dianhydride; benzene-1,2,4,5-tetracarboxylic acid; 1,3-dihydro-1,3-dioxoisobenzofuran-5,6-dicarboxylic acid; trimellitic anhydride; trimellitic acid; terephthalic acid; phthalic acid; phthalic anhydride; benzoic acid; or a combination comprising at least one of the foregoing aromatics.
9. The composition of claim 7 , wherein the reaction further comprises an additional hydroxy-containing (meth)acrylate of the structure:
wherein
W is an organic group having the valency of z+1;
z is an integer of 1 to 5; and
R 5 is hydrogen or methyl,
wherein the additional hydroxy-containing (meth)acrylate is different than the first hydroxy-containing (meth)acrylate.
10. The composition of claim 9 , wherein the additional hydroxy-containing (meth)acrylate has the structure:
wherein R 6 and R 7 are each independently hydrogen, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 6 alkyl)-O—(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene); z is an integer from 1 to 10; and R 5 is hydrogen or methyl.
11. The composition of claim 1 , further comprising an additional ethylenically unsaturated monomer and/or oligomer that is co-curable with the polymerizable (meth)acrylate.
12. A method of manufacturing a dental restorative composition, comprising:
mixing, based on total weight of the dental restorative composition,
about 1 to about 99 weight percent of a polymerizable (meth)acrylate of the structure:
wherein
A is an anhydride;
a is 0 or 1;
n is 0, 1, 2, or 3;
R 1 , R 2 , R 3 , R 4 each independently hydrogen, hydroxy, C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, (C 1 -C 6 alkyl)-O—(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene);
x and y are each independently an integer of 1 to 10;
z is an integer of 1 to 5;
R 5 is hydrogen or methyl;
wherein G and J are each independently O or NR 6 , wherein R 6 is hydrogen or C 1 -C 6 alkyl;
m is 1, 2, 3, or 4;
W is an organic group having the valency of z+1; and
q is 0 or 1;
wherein
is different from
and further wherein when a is 1, n+m+q is 1, 2, 3, or 4, and when a is 0, n+m+q is 1, 2, 3, 4, 5, or 6;
about 1 to about 90 weight percent of a filler system; and
a curing system; wherein
the dental restorative composition does not require a separate dental bonding procedure and has a shear bonding strength to a dentin surface of at least 12.2 MPa after curing.
13. A method of repairing a tooth, comprising preparing the tooth;
applying a dental restorative composition to a tooth, the dental restorative composition comprising, based on the total weight of the composition:
about 1 to about 99 weight percent of a polymerizable (meth)acrylate of the structure:
wherein
A is an anhydride:
a is 0 or 1;
n is 0, 1, 2, or 3;
R 1 , R 2 , R 3 , and R 4 are each independently hydrogen hydroxy, C 1 -C 12 alkyl, C 1 -C 12 perhaloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 perhaloalkoxy, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl (C 1 -C 6 alkyl)-O—(C 1 -C 6 alkylene), or hydroxy(C 1 -C 6 alkylene);
x and y are each independently an integer of 1 to 10; z is an integer of 1 to 5;
R 5 is hydrogen or methyl;
wherein G and J are each independently O or NR 6 , wherein R 6 is hydrogen or C 1 -C 6 alkyl;
m is 1, 2, 3, or 4;
w is an organic group having the valency of z+1; and
q is 0 or 1;
wherein
is different from
and further wherein a is 1,n+m+q is 1, 2, 3, or 4, and when a is 0, n+m+q is 1, 2, 3, 4, 5, or 6;
about 1 to about 90 weight percent of a filler system; a curing system; and curing the dental restorative composition; wherein the dental restorative composition does not require a separate dental bonding procedure and has a shear bonding strength to a dentin surface of at least 12.2 MPa after curing.