Inorganic dental fillers including a silane treated surface

1. A surface-treated inorganic dental filler comprising:

an inorganic filler comprising particles having an average particle size of 5 nanometers to 20 microns, the particles having a surface modified with at least one silane represented by Formula I:

(R Si )—(CR 1 R 2 ) n —(NH—C(O)—O—CH 2 —CH 2 ) q —N(R 5 )—C(O)—NH—(CH 2 —CH 2 —O)—CR 3 R 4 —CH 2 -(A)   Formula I,

wherein:

each R Si is independently a silane-containing group of the formula —Si(Y p )(R 6 ) 3-p ;

Y is a hydrolysable group;

each R 1 , R 2 , and R 3 is independently selected from H, an alkyl group, an aryl group, an alkaryl group, and an aralkyl group;

each R 4 is independently selected from H, an alkyl group, an aryl group, an alkaryl group, an aralkyl group, and a group of the formula —(CH 2 ) m -(A);

each A is independently a (meth)acryl group of the formula X 1 —C(O)—C(R 7 )═CH 2 ;

X t is —O, —S, or —NR 7

R 5 is H, an alkyl group, a cycloalkyl group, an aryl group, an alkaryl group, an aralkyl group, a group of the formula (R Si )—(CR 1 R 2 ) n —(NH—C(O)—O—CH 2 —CH 2 ) q —, a group of the formula (R Si )—(CR 1 R 2 ) n —NH—C(O)—N(R′)—(CH 2 ) m —, a group of the formula —(CH 2 ) m -(A), a group of the formula —(CH 2 ) m —N(R′)—C(O)—NH—(CH 2 —CH 2 —O) t —CR 3 R 4 —CH 2 -(A), or a group of the formula —(CH 2 ) m —N(R 8 )—C(O)—NH—R 9 ;

R 6 is a monovalent alkyl or aryl group;

each R 7 is independently H or a C 1 -C 4 alkyl group;

R 8 is H or a group of the formula —(CH 2 ) m —NH—C(O)—NH—(CH 2 —CH 2 —O) t —CR 3 R 4 —CH 2 -(A), a group of the formula —(CH 2 ) m —NH—C(O)—NH—(CR 1 R 2 ) n —(R Si ), or a group of the formula —(CH 2 ) m —NH—C(O)—NH—R 9 ,

each R 9 is independently selected from an alkyl group, an aryl group, an alkaryl group, and an aralkyl group;

each m is independently an integer selected from 1 to 6;

each n is independently an integer selected from 1 to 6;

p is an integer selected from 1, 2, and 3

each q is independently 0 or 1; and

each t is independently 0 or 1,

with the proviso that at least one of R 1 , R 2 , R 3 , R 4 , and R 5 , as shown in Formula I, is not H.

2. The surface-treated inorganic dental filler of claim 1 , wherein the at least one silane is of the formula:

(R Si )—(CR 1 R 2 ) n —(NH—C(O)—O—CH 2 —CH 2 ) q —N(R 5 )—C(O)—NH—CR 3 R 4 —CH 2 -(A).

3. A surface-treated inorganic dental filler comprising:

an inorganic filler comprising particles having a surface modified with at least one silane represented by Formula II:

(R Si )—(CR 1 R 2 ) n —NH—C(O)—O—CR 3 R 4 -(L) q -CH 2 -(A)   Formula II,

wherein:

R Si is a silane-containing group of the formula —Si(Y p )(R 6 ) 3-p ;

Y is a hydrolysable group,

R 1 , R 2 , and R 3 are independently selected from H, an alkyl group, an aryl group, an alkaryl group, and an aralkyl group;

R 4 is H, an alkyl group, an aryl group, an alkaryl group, an aralkyl group, or —CH 2 —O—C(O)-Ph,

wherein the alkyl group, aryl group, alkaryl group, or aralkyl group may optionally be substituted with one or more of a catenary oxygen atom, —O—C(O)— groups, and —C(O)—O— groups;

L is a divalent alkylene group, a divalent arylene group, a divalent alkarylene group, a divalent aralkylene group, or

wherein the divalent alkylene group, divalent arylene group, divalent alkarylene group, or divalent aralkylene group may optionally be substituted with one or more of a catenary oxygen atom, —O—C(O)— groups, and —C(O)—O— groups; and

A is a (meth)acryl group of the formula X 1 —C(O)—C(R 7 )═CH 2 ;

X 1 is —O, —S, or —NR 7 ;

R 6 is a monovalent alkyl or aryl group;

each R 7 is independently H or a C 1 -C 4 alkyl group;

n is 1 to 6;

q is 0 or 1; and

p is 1, 2, or 3,

with the proviso that at least one of R 1 , R 2 , R 3 , and R 4 , as shown in Formula II, is not H.

4. The surface-treated inorganic dental filler of claim 1 , wherein each R 1 , R 2 , and R 3 is independently H or CH 3 .

5. The surface-treated inorganic dental filler of claim 1 , wherein R 4 is H, CH 3 , or a group of the formula —(CH 2 ) m -(A), wherein m is 1.

6. The surface-treated inorganic dental filler of claim 1 , the at least one silane is of the formula:

(R Si )—(CR 1 R 2 ) n —N(R 5 )—C(O)—NH—(CH 2 —CH 2 —O) t —CR 3 R 4 —CH 2 -(A).

7. The surface-treated inorganic dental filler of claim 1 , wherein A is —O—C(O)—CH═CH 2 or —O—C(O)—C(CH 3 )═CH 2 .

8. The surface-treated inorganic dental filler of claim 1 , wherein R Si is —Si(OCH 3 ) 3 or —Si(OCH 2 CH 3 ) 3 .

9. The surface-treated inorganic dental filler of claim 1 , wherein the inorganic filler is a non acid-reactive filler.

10. The surface-treated inorganic dental filler of claim 1 , wherein the inorganic filler comprises nano-particles, clusters of nano-particles, metal oxide particles, silica particles, zirconia particles, aluminosilicate glasses, doped aluminosilicate glasses, and a combination thereof.

11. The surface-treated inorganic dental filler of claim 1 , wherein the particles have at least 25% of the surface modified with the at least one silane.

12. A hardenable dental composition comprising:

a surface-treated inorganic filler of claim 1 ; and

at least one polymerizable resin.

13. The hardenable dental composition of claim 12 , further comprising an initiator system selected from the group consisting of photoinitiator systems, redox initiator systems, peroxide heat activated, and a combination thereof.

14. A method of preparing a surface-treated inorganic dental filler according to claim 1 , the method comprising contacting an inorganic filler with at least one silane of Formula I.

15. A method of preparing a surface-treated inorganic dental filler according to claim 3 , the method comprising contacting an inorganic filler with at least one silane of Formula II.

16. A hardened dental composition comprising a surface-treated inorganic filler according to claim 1 .

17. A method of preparing a hardenable dental composition, the method comprising:

contacting a surface-treated inorganic dental filler of claim 1 with a polymerizable resin under conditions effective to form the hardenable dental composition.

18. The surface-treated inorganic dental filler of claim 1 , at least one silane selected from:

wherein Me is —CH 3 , and Et is —CH 2 CH 3 .

19. A hardenable dental composition comprising:

a surface-treated inorganic dental filler of claim 18 ; and

at least one polymerizable resin.

20. A surface-treated inorganic dental filler comprising:

an inorganic filler comprising particles having a surface modified with at least one silane represented by Formula I:

(R Si )—(CR 1 R 2 ) n —(NH—C(O)—O—CH 2 —CH 2 ) q —N(R 5 )—C(O)—NH—(CH 2 —CH 2 —O)—CR 3 R 4 —CH 2 -(A)   Formula I,

wherein:

each R Si is independently a silane-containing group of the formula —Si(Y p )(R 6 ) 3-p ;

Y is a hydrolysable group;

each R 1 , R 2 , and R 3 is independently selected from H, an alkyl group, an aryl group, an alkaryl group, and an aralkyl group;

each R 4 is independently selected from H, an alkyl group, an aryl group, an alkaryl group, an aralkyl group, and a group of the formula —(CH 2 ) m -(A);

each A is independently a (meth)acryl group of the formula X 1 —C(O)—C(R 7 )═CH 2 ;

X t is —O, —S, or —NR 7

R 5 is H, an alkyl group, a cycloalkyl group, an aryl group, an alkaryl group, an aralkyl group, a group of the formula (R Si )—(CR 1 R 2 ) n —(NH—C(O)—O—CH 2 —CH 2 ) q —, a group of the formula (R Si )—(CR 1 R 2 ) n —NH—C(O)—N(R′)—(CH 2 ) m —, a group of the formula —(CH 2 ) m -(A), a group of the formula —(CH 2 ) m —N(R′)—C(O)—NH—(CH 2 —CH 2 —O) t —CR 3 R 4 —CH 2 -(A), or a group of the formula —(CH 2 ) m —N(R′)—C(O)—NH—R 9 ;

R 6 is a monovalent alkyl or aryl group;

each R 7 is independently H or a C 1 -C 4 alkyl group;

R 8 is H or a group of the formula —(CH 2 ) m —NH—C(O)—NH—(CH 2 —CH 2 —O) t —CR 3 R 4 —CH 2 -(A), a group of the formula —(CH 2 ) m —NH—C(O)—NH—(CR 1 R 2 )—(R Si ), or a group of the formula —(CH 2 ) m —NH—C(O)—NH—R 9 ,

each R 9 is independently selected from an alkyl group, an aryl group, an alkaryl group, and an aralkyl group;

each m is independently an integer selected from 1 to 6;

each n is independently an integer selected from 1 to 6;

p is an integer selected from 1, 2, and 3

each q is independently 0 or 1; and

each t is independently 0 or 1,

with the proviso that at least one of R 1 , R 2 , R 3 , R 4 , and R 5 , as shown in Formula I, is not H, and

with the proviso that the silane is not of the following formula: