Dental compositions comprising addition-fragmentation agents

Patent metadata

Field	Value
Publication number	US-9414996-B2
Application number	US-201314437200-A
Country	US
Kind code	B2
Filing date	Oct 31, 2013
Priority date	Nov 12, 2012
Publication date	Aug 16, 2016
Grant date	Aug 16, 2016

Abstract

A curable dental composition comprising an addition-fragmentation agent and a curable dental resin is disclosed.

First claim

The invention claimed is:

1. A curable dental composition comprising:
a) at least one dental resin comprising at least two ethylenically unsaturated groups;
b) an addition-fragmentation agent comprising:
1) a labile addition-fragmentation group; and
2) at least two surface-binding functional groups; and
c) optionally an inorganic oxide filler,
wherein the addition-fragmentation agent is of the formula:

wherein
R 1 , R 2 and R 3 are each independently Y-Q′-, a (hetero)alkyl group or a (hetero)aryl group with the proviso that at least two of R′, R 2 and R 3 is Y p -Q′-
Q′ is a covalent bond or a linking group having a valence of p+1;
Y is a surface-binding organic functional group;
p is 1 or 2;
X 1 is independently —O— or —NR 4 —, where R 4 is H or C 1 -C 4 alkyl, and
n is 0 or 1
wherein
Y-Q′ is selected from a monophosphate, a phosphonate group, a phosphonic acid group, a hydroxamic acid group, a carboxylic acid group, and acetoacetate group, an anhydride group, an isonitrile group, a silyl group, a disulfide group, a thiol group, an amino group, a sulfinic acid group, a sulfonic acid group, a phosphine group, a phenolic group or a heterocyclic aromatic group.

2. The dental composition of claim 1 wherein Q′ is selected from —O—, —S—, —N(R 4 )—, —SO 2 —, —PO 2 —, —CO—, —OCO—, —R 6 —, —N(R 4 )—CO—N(R 4 )—, —N(R 4 )—CO—O—, —N(R 4 )—CO—N(R 4 )—CO—O—R 6 —, —CO—N(R 4 )—R 6 —, —R 6 —CO—O—R 6 —, —O—R 6 —, —S—R 6 —, —N(R 4 )—R 6 —, —SO 2 —R 6 —, —PO 2 —R 6 —, —CO—R 6 —, —OCO—R 6 —, —N(R 4 )—CO—R 6 —, —N(R 4 )—R 6 —CO—O—, and —N(R 4 )—CO—N(R 4 )—, wherein each R 4 is hydrogen, a C 1 to C 4 alkyl group, or aryl group, each R 6 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.

3. The dental composition of claim 1 wherein Q′ is an alkylene of the formula —C r H 2r —, where r is 1 to 10.

4. The dental composition of claim 1 wherein Q′ is a hydroxyl-substituted alkylene of the formula —CH 2 —CH(OH)—CH 2 —.

5. The dental composition of claim 1 wherein Q′ is an aryloxy-substituted alkylene, or an alkoxy-substituted alkylene.

6. The dental composition of claim 1 wherein the ethylenically unsaturated groups of the dental resin are (meth)acrylate groups.

7. The dental composition of claim 1 wherein the dental resin comprises an aromatic monomer having a refractive index of at least 1.50.

8. The dental composition of claim 1 wherein the dental resin is a low volume shrinkage resin.

9. The dental composition of claim 1 wherein the dental resin is an isocyanurate resin, a tricyclodecane resin, cyclic allylic sulfide resins; methylene dithiepane silane resins; and poly(meth)acryloyl-containing resins, or mixtures thereof.

10. The dental composition of claim 1 wherein the dental composition further comprises at least one other (meth)acrylate monomer is selected from the group consisting of ethoxylated bisphenol A dimethacrylate, 2-hydroxyethyl methacrylate, bisphenol A diglycidyl dimethacrylate, urethane dimethacrylate, triethlyene glycol dimethacrylate, glycerol dimethacrylate, ethylenegylcol dimethacrylate, neopentylglycol dimethacrylate (NPGDMA), polyethyleneglycol dimethacrylate, and mixtures thereof.

11. The dental composition of claim 1 wherein the inorganic oxide filler comprises nanoparticles.

12. The dental composition of claim 1 comprising a surface modified inorganic oxide filler.

13. A method of treating a tooth surface, the method comprising
a) providing a curable dental resin of claim 1 ;
b) placing the dental composition on a tooth surface in the mouth of a subject; and
c) hardening the hardenable dental composition.

14. The curable dental composition of claim 1 comprising a universal dental restorative comprising:
a) 15-30 wt % of a curable dental resin comprising at least two polymerizable, ethylenically unsaturated groups;
b) 70-85 wt % of an inorganic filler;
c) 0.1 to 10 parts by weight of the addition-fragmentation agent, relative to 100 parts by weight of a) and b),
said curable composition further comprising an initiator and;
<2% of stabilizers and pigments.

15. The curable dental composition of claim 1 comprising a flowable restorative composite comprising:
a) 25-50 wt % of a curable dental resin comprising at least two polymerizable, ethylenically unsaturated groups;
b) 50-75 wt % of an inorganic filler;
c) 0.1 to 10 parts by weight of the addition-fragmentation agent relative to 100 parts by weight of a) and b);
d) an initiator;
e) <2% stabilizers and pigments,
f) optionally 5-60 wt. % monomers having an acid-functional group; and
g) an initiator.

16. The curable dental composition of claim 1 comprising a resin-modified glass-ionomer adhesive comprising:
a) 10-25 wt. % of a partially (meth)acrylated poly(meth) acrylic acid;
b) 5-20% of a hydroxyalkyl (meth)acrylate;
c) 30-60% of fluoroaluminosilicate (FAS) acid reactive glass;
d) 0-20% non-acid reactive fillers;
e) 10-20% water;
f) 0.1 to 10 wt. % of the addition-fragmentation agent, relative to 100 parts by weight of a) and b); and
g) an initiator.

17. The curable dental composition of claim 1 further comprising a surface-modified inorganic filler of the formula:

where
Filler is an inorganic filler particle,
R 2 is Y p -Q′-, a (hetero)alkyl group or a (hetero)aryl group;
Q′ is a covalent bond or an organic (hetero)hydrocarbyl linking group having a valence of p+1;
Y′ is the residue of the surface-binding functional group Y;
p is 1 or 2;
X 1 is independently —O— or —NR 4 —, where R 4 is H or C 1 -C 4 alkyl, and
n is 0 or 1.

18. The curable dental composition of claim 17 wherein the Filler is silica.

19. The curable dental composition of claim 17 wherein the group Filler-Y′ p — is of the formula Silica-O—Si(R 7 ) 2 —
wherein each R 7 group is independently selected from the group of alkoxy, acetoxy, and halide.

Assignees

• 3M Innovative Properties Co

Inventors

• Joly Guy D
• Abuelyaman Ahmed S
• Fornof Ann R
• Craig Bradley D
• Krepski Larry R
• Moser William H
• Yurt Serkan
• Oxman Joel D
• Falsafi Afshin

Classifications

• A61K6/30

  Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives · CPC title

• A61K6/889

  Polycarboxylate cements; Glass ionomer cements · CPC title

• A61K6/887 Primary

  Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• A61K6/76 Primary

  comprising silicon-containing compounds · CPC title

• C09J133/14

  of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen · CPC title