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US4521550A - Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates - Google Patents
Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates Download PDF
US4521550A
US4521550A US06516956 US51695683A US4521550A US 4521550 A US4521550 A US 4521550A US 06516956 US06516956 US 06516956 US 51695683 A US51695683 A US 51695683A US 4521550 A US4521550 A US 4521550A
US06516956
AMERICAN DENTAL ASSOCIATION HEALTH FOUNDATION AN IL CORP
EXAMPLE 1b Synthesis of NTG (N-p-tolylglycine)
After the dentin surface was prepared by the foregoing treatments of Examples 1a, 1c, and 1e in a variety of sequences as indicated below, a mix of a composite resin (for example Adaptic® Dental Restorative, available from Johnson & Johnson, East Windsor, N.J.; Concise® from 3M Co., St. Paul, Minn.; or others from other companies) was made, applied to the opposing plunger part of a test assembly, slowly let down onto the dentin surface, and weighted with a pressure of about 1.0 MPa (150 psi) for 5 seconds to spread the composite on the dentin surface. The pressure during the resin application to the dentin was somewhat less than 1.0 MPa because the tapered part of the iris supported some of the load. The assembly was let stand in air for 15 minutes, then immersed in distilled water at room temperature until tested 1-10 days later. The testing method was essentially the same as that described in Bowen R. L., "Adhesive Bonding of Various Materials to Hard Tooth Tissues. I. Method of Determining Bond Strength," 44 J. Dent. Res. 690-695 (1965); with the following exceptions: holes were drilled and tapped, and stainless steel screws were inserted into the extracted teeth to augment retention in the gypsum embedments. The flat part of the diaphragm contacting the dentin was covered by a poly(tetrafluoroethylene) film called Chemflour Pressure-Sensitive Tape, available from Chemplast, Inc., Wayne, N.J., to assure no tensile load transmission by way of this part; the total assembly was immersed and stored in water; the immersion time was usually 2-5 days rather than one day, and two-way tables were not used so that more variables could be screened. As reported in Bowen, R. L., "Adhesive Bonding of Various Materials to Hard Tooth Tissues. II. Bonding to Dentin Promoted by a Surface-Active Comonomer," 44 J. Dent. Res. 895-903 (1965), there seemed to be no correlation between bond strength and immersion time within this time range. The tensile load was applied by an Instron Tensile Tester, Model TTCL, available from Instron Eng. Corp., Quincy, Mass., at a rate of about 500 psi/min to determine adhesive bond strengths. The average tensile bond strengths are given in Table 1 ranked in descending order of average strengths. Although there was good reproducibility for a given treatment of the same tooth (assembly), there was considerable variation between teeth (assemblies). When the strengths were over 6.9 MPa (70 kg/cm2 ; 1000 psi), there were many incidences of teeth being pulled loose from the gypsum embedment, composite coming loose from the plunger part of the assembly, and some cases of fractured dentin; some specimens were sacrificed for scanning electron micrograph study. The average coefficient of variation was 25%.
TABLE I__________________________________________________________________________Tensile Adhesive Strengths of a Composite Bonded to Treated DentinSurfaces                                  Standard                                         Adhesion                     Average Adhesion                                  Deviation +                                         Range                                              No. ofDentin Surface Treatments (psi)*                         (kg/cm.sup.2)                              (MPa)                                  (MPa)  (MPa)                                              Measurement__________________________________________________________________________Ferric oxalate, 6.8% + NTG--GMA, 10% + PMDM.sup.§                     2,180                         153  15.0                                  4.8     7.2-20.6                                              8Ferric oxalate, 6.8% + NPG, 10-11% + PMDM.sup.§                     1,910                         134  13.2                                  2.4     9.5-16.4                                              23Ferric oxalate, 6.8% + NTG--GMA + PMDM.sup.§                     1,900                         134  13.1                                  2.3    10.2-18.2                                              11Ferric oxalate, 6.8% + NPG--GMA + PMDM.sup.§                     1,830                         129  12.6                                  1.7    10.6-14.8                                              4Ferric oxalate, 6.8% + NTG--GMA + 4-META                     1,790                         125  12.3                                  2.4    10.8-14.5                                              6Ferric oxalate, 6.8% + NTG--GMA + PMDM∥                     1,780                         125  12.3                                  1.6    10.2-13.6                                              4Ferric oxalate, 6.8% + NPG--GMA + 4-META                     1,680                         118  11.6                                  3.7     5.5-16.5                                              9Ferric oxalate, 4% NTG--GMA +  PMDM.sup.§                     1,640                         115  11.3                                  1.3     9.8-12.6                                              5Ferric oxalate, 4% + NTG--PMDM∥                     1,610                         113  11.1                                  2.0     9.4-13.3                                              3Ferric oxalate, .sup. 6.8% + NPG--GMA.sup.  + 4-META.sup.                     1,310                         92   9.0 1.2    8.2-9.9                                              2Ferric oxalate, 2% + NTG--GMA + PMDM.sup.§                     1,260                         89   8.71                                  0.04   8.7-8.8                                              2Ferric oxalate, 6.8% + 4-META + NPG--GMA                     1,130                         80   7.8 1.8    5.4-8.9                                              4Water + NPG--GMA + 4-META 900 63   6.2 3.8    3.5-8.9                                              2Ferric oxalate, 6.8% + 4-META (no rinse)                     820 58   5.7 2.2    3.9-9.2                                              7Ferric oxalate, 6.8% + NPG--GMA (no rinse)                     780 55   5.4 1.7    3.7-8.2                                              6Water + NTG--GMA + PMDM.sup.§                     710 50   4.9 2.1    3.4-6.3                                              2Ferric oxalate, 6.8% + 4-META + 4-META                     560 39   3.89                                  0.38   3.6-4.1                                              2Ferric oxalate, sat.** + 4-META (no rinse)                     430 30   2.95                                  0.43   2.6-3.2                                              2Ferric oxalate, 6.8% + NPG--GMA + NPG--GMA.sup.++                     400 29   2.8 1.4    1.8- 3.8                                              2Ferric oxalate, 6.8% + 4-META (with rinse)                     390 28   2.7 1.4    1.7-3.7                                              2Water + 4-META (no rinse) 340 23   2.3 1.1    1.6-3.1                                              2Water + 4-META (with rinse)                     260 18   1.79                                  0.41   1.5-2.1                                              10Ferric oxalate, 6.8% + PMDM.sup.§ (no rinse)                     180 12   1.2 1.9    0.0-5.1                                              10Ferric oxalate, 6.8% (only)                     160 11   1.10                                  0.83   0.48-1.72                                              2Water + acetone (control) 8   0.6  0.06                                  0.09   0.00-0.20                                              5__________________________________________________________________________ *To convert pounds of force per square inch, psi, to megapascals, MPa, multiply by 0.0068948; to convert MPa to kilograms of force per square centimeter, kg/cm.sup.2, divide by 0.098044; to convert psi to kg/cm.sup.2, divide by 14.22. ##STR6## In the tests reported in this table, the NTG--GMA, PMDM, NPG--GMA, and 4META were applied as 5-6% solutions in acetone, and the NPG was applied as a 10-11% solution in acetone, unless otherwise indicated. .sup.§ The isomer having a melting point of about 163° C. The isomer with the melting point of about 153° C. .sup.∥ The ferric oxalate, the NPG--GMA, and the 4META solutions were each applied for only 30 seconds. **Saturated ferric oxalate solution; concentration estimated to be betwee 31 and 35%. .sup.++ Tensecond acetone rinse after each application.
In preliminary adhesion tests utilizing 6.8% aqueous ferric oxalate, 10% NTG-GMA in acetone, acetone, and then a crude solution of BTDA-HEMA in methanol (concentration not known), bond strengths averaged 1,960 psi (s.d.=510; n=5). In these tests, three samples were exposed to UV (an ultraviolet light source; Caulk® Nuva-Lite, 40 secs.) before the composites were applied, and two were not exposed to UV. The former averaged 2,140 psi bond strength and the latter (without UV) averaged 1,670 psi. Both are strong bonds; but the ultraviolet light apparently improved the bond strengths, probably by increasing the degree of polymerization of the BTDA-HEMA (which is a benzophenone dimethacrylate) in the presence of NTG-GMA and/or triethylamine (tertiary amines).
CH.sub.2 =--COO--CH(CH.sub.2).sub.j H).sub.q (CHOH).sub.m (CH.sub.2).sub.p OCO--C--CH.sub.2).sub.r H)
(b) contacting with the surface of the dentin or enamel a solution comprising N-phenylglycine in a solvent; and
(c) contacting the surface of the dentin or enamel with a first acetone solution comprising N-phenylglycine in acetone;
13. A method as in claim 12 wherein the concentration of the aqueous solution comprising ferric oxalate is about 6.8% of the hexahydrate.
19. An article of manufacture comprising in combination:
(b) a second closed compartment containing a composition comprising N-phenylglycine; and
20. An article of manufacture as in claim 19 wherein the first, second and third closed compartments are impervious to ultraviolet and visible light.
23. A structure comprising a composite material or resin bonded to a dentin or enamel surface which has been prepared by the method of claim 1.
27. A method for preparing the surface of dentin, enamel or industrial substrates for adhesion of composite materials or resins, which method comprises:
(a) contacting with the surface of the dentin, enamel or industrial substrate an aqueous solution comprising at least one acidic salt containing a polyvalent cation which is capable of changing valence by unit steps and which can bind to dentin, enamel, or industrial substrate surface sites, and at least one anion which forms a relatively water-insoluble precipitate or precipitates with cations of the substrate surface and which contains at least one carboxyl group;
q=0 to 12,
(2) --O)f (CH2)t H straight or branched aliphatic groups, with f=0 or 1, and with t=0 to 12;
(2) --O)f (CH2)t COOH, with t=0 to 12, and with f=0 or 1;
(3) --O)f (CH2)d O--H, with d=1 to 12, and with f=0 or 1;
(4) F, Cl, Br and I;
the number of R groups per molecule is 0 to 5, and these R groups may be in the para meta, or ortho positions relative to the nitrogen;
(d) contacting with the surface of the dentin, enamel, or industrial substrate a solution comprising at least one coupling agent of the formula: ##STR13## where: g=0 to 7;
CH.sub.2 =--COO(CH(CH.sub.2).sub.j H).sub.q (CHOH).sub.m (CH.sub.2).sub.p OCO--C--CH.sub.2).sub.r H)
X is a halide group; and the number of X groups per molecule is 0 to 8, and
US06516956 1983-01-10 1983-07-25 Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates Expired - Lifetime US4521550A (en)
US06457029 US4514527A (en) 1983-01-10 1983-01-10 Method for obtaining strong adhesive bonding of composites to dentin enamel and other substrates
US06516956 US4521550A (en) 1983-01-10 1983-07-25 Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates
DE19843490336 DE3490336T1 (en) 1983-07-25 1984-07-16
EP19840902974 EP0151612B1 (en) 1983-07-25 1984-07-16 Improving the adhesion of composites to dentin, enamel and other substrates
GB8506987A GB2159067B (en) 1983-07-25 1984-07-16 Improving the adhesion of composites to dentin, enamel and other substrates
PCT/US1984/001109 WO1985000514A1 (en) 1983-07-25 1984-07-16 Improving the adhesion of composites to dentin, enamel and other substrates
JP50297584A JPH0258244B2 (en) 1983-07-25 1984-07-16
DE19843490336 DE3490336C2 (en) 1983-07-25 1984-07-16 Treatment kit for preparing the surface of dentine, enamel or technical substrates for binding composite materials or resins, and method for the treatment of the surface of a technical substrate
CA 459512 CA1227383A (en) 1983-07-25 1984-07-24 Method for obtaining a strong adhesive bonding of composites to dentin, enamel and other substrates
US06457029 Continuation-In-Part US4514527A (en) 1983-01-10 1983-01-10 Method for obtaining strong adhesive bonding of composites to dentin enamel and other substrates
US06699079 Continuation-In-Part US4588756A (en) 1983-01-10 1985-02-07 Multi-step method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates
US4521550A true US4521550A (en) 1985-06-04
ID=24057769
US06516956 Expired - Lifetime US4521550A (en) 1983-01-10 1983-07-25 Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates
US (1) US4521550A (en)
EP (1) EP0151612B1 (en)
JP (1) JPH0258244B2 (en)
CA (1) CA1227383A (en)
DE (2) DE3490336C2 (en)
GB (1) GB2159067B (en)
WO (1) WO1985000514A1 (en)
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DE3490336T0 (en) grant
GB2159067B (en) 1987-03-04 grant
DE3490336T1 (en) 1985-09-19 grant
CA1227383A1 (en) grant
WO1985000514A1 (en) 1985-02-14 application
EP0151612B1 (en) 1989-01-25 grant
JPS60502055A (en) 1985-11-28 application
JPH0258244B2 (en) 1990-12-07 grant
GB8506987D0 (en) 1985-04-24 grant
EP0151612A1 (en) 1985-08-21 application
CA1227383A (en) 1987-09-29 grant
GB2159067A (en) 1985-11-27 application
DE3490336C2 (en) 1994-12-01 grant
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