Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
2002-01-11
2003-12-09
Szekely, Peter (Department: 1714)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C423S228000, C523S117000, C523S118000, C526S239000, C526S278000, C526S287000, C526S312000
Reexamination Certificate
active
06660785
ABSTRACT:
TECHNICAL FIELD
The invention relates to self-adhesive polymerizable monomers suitable for dental and medical applications.
BACKGROUND OF THE INVENTION
Conventional dental/medical compositions such as cements are either water-based ionic cements or resin based materials. The water-based cements have the advantage of a modest adhesion to hard tooth tissues and of a high fluoride ion release from inorganic filler material. They have the disadvantage of high water solubility, low abrasion resistance and an excessive opacity. The resin-based materials have the advantage of excellent mechanical properties, a suitable opacity and low water solubility. They have the disadvantage of a lack of adhesion, a very poor release of fluoride ions from an inorganic filler and a high shrinkage.
It has already been known to improve the adhesion of resin-based dental/medical composites by incorporation of phosphoric acid ester groups or carboxylic ester groups (U.S. Pat. Nos. 399,754, 2,709,690, 4,514,342, 4,806,381, DE-OS 3536077, DE-OS 2711234, EP 0058483, DE-OS 3150285, E. Masuhara et.al. Rep. Inst. Med. Dent.Eng. 1 (1967) 29-33, M. Takeyama et. al. J.Soc.Dent.Appar. 19 (1978) 179-185). However, the adhesion is still insufficient. Moreover compositions with such monomers have a high shrinkage during polymerization.
It is a problem of the invention to provide a self-adhesive polymerizabe monomer for dental compositions and a process for preparing said self-adhesive polymerizabe monomer, whereby the dental/medical composition which combine the favourable characteristics of water-based and resin-based conventional materials and have a high adhesion to hard dental tissue and lower shrinkage.
DESCRIPTION OF THE INVENTION
A self-adhesive polymerizable monomer that comprises at least two polymerizable moieties (i), at least one substituted or unsubstituted C
3
to C
20
alkylene or at least one substituted or unsubstituted C
5
to C
20
cycloalkylene (ii) that is connected with (i) by a linking unit, at least an acidic moiety selected from the group (iii)
or at least an ionic moiety selected from the group
which is connected with (ii) and wherein
the R
1
, R
2
, R
3
are the same or different substituted or unsubstituted residues of hydrogen or an alkylene having 2 to 20 carbon atoms, a cycloalkylene having 5 to 20 carbon atoms, an aryl or a heteroaryl having 4 to 12 carbon atoms,
X is a cationic counterion such as
and
Y is an anionic ion such as OH
−
, F
−
, Cl
−
, Br
−
, Tosyl
−
.
The polymerizable groups preferably are methacrylic or acrylic groups. The linking unit preferably is an ether or a thioether, an ester, a carbonate, a urethane moiety.
Preferably, the self-adhesive polymerizable monomer is characterized by the following formulas:
wherein
R
4
denotes a substituted or unsubstituted alkylene having 3 to 20 carbon atoms,
Z is an acidic moiety selected from the group
or an ionic moiety selected from the group
wherein
the R
1
, R
2
, R
3
are the same or different substituted or unsubstituted residues of Hydrogen or an alkylene having 2 to 20 carbon atoms, a cycloalkylene having 5 to 20 carbon atoms, an aryl or a heteroaryl having 4 to 12 carbon atoms,
X is a cation such as ammonium, sulfonium, sodium, potassium, strontium, calcium or magnesium salts
and
Y is an anion such as OH—, F—, Cl—, Br—, Tosyl—.
Most preferably the self-adhesive polymerizable monomer is characterized in the following formula:
The self-adhesive polymerizable monomer is used in a dental/medical composition comprising a filler, a polymerizable monomer, a polymerization initiator and a stabilizer.
The polymerizable monomer preferably is a mono- and polyfunctional (meth)acrylate, such as a reaction product of a polyepoxide with (meth)acrylic acid), a polyalkylenoxide di- and poly(meth)acrylate, an urethane di- and poly(meth) acrylate, preferably were used Bis-GMA diethylenglycol dimethacrylate, triethylenglycol dimethacrylate, 3,(4),8,(9)-dimethacryloyloxymethyltricyclodecane, dioxolan bismethacrylate, glycerol trimethacrylate, furfuryl methacrylate in a content of 5 to 80 wt-%.
The polymerization initiator is a thermal initiator, a redox-initiator or a photo initiator.
As filler is an inorganic filler and/or an organic filler.
The self-adhesive polymerizable monomer is usable in a self-adhesive dental/medical composition characterized by the combination of
A an adhesion to dentine of at least 5 MPa
B a fluoride release of at least 1 &mgr;g F
−
per week and per cm
2
of the exposed surface of the composition
C an opacity of at least C
0,7
=40% and
D a compressive strength of at least 200 MPa.
The self-adhesive polymerizable monomer is usable in a self-adhesive dental/medical cement comprising
25 to 50 wt-% of a self-adhesive polymerizable monomer,
0 to 25 wt-% of a polymerizable monomer,
50 to 75 wt-% of a filler and polymerization initiator and stabilizers.
The self-adhesive polymerizable monomer is usable in a self-adhesive dental/medical composite comprising
15 to 50 wt-% of a self-adhesive polymerizable monomer of claims 1 to 3,
0 to 35 wt-% of a polymerizable monomer,
50 to 85 wt-% of a filler and polymerization initiator and stabilizers.
The self-adhesive polymerizable monomer is usable in a self-adhesive dental/medical sealant comprising
45 to 90 wt-% of a self-adhesive polymerizable monomer of claims 1 to 3,
0 to 45 wt-% of a polymerizable monomer,
10 to 55 wt-% of a filler and polymerization initiator and stabilizers.
The self-adhesive polymerizable monomer is usable in a self-adhesive dental/medical primer comprising
15 to 80 wt-% of a self-adhesive polymerizable monomer of claims 1 to 3,
0 to 65 wt-% of a polymerizable monomer,
0 to 65 wt-% of a filler and polymerization initiator and stabilizers
20 to 85 wt-% of a diluent and polymerization initiator and stabilizers.
An adhesive dental composite containing radiopaque fillers provides a radio-opacity of at least 2 mm/mm Al, preferably at least 3 to 7 mm/mm Al, most preferably at least 7 mm/mmAl.
The self-adhesive dental/medical composites have a fluoride release of at least 1 &mgr;g/cm
2
, preferably at least 1-3 &mgr;g/cm
2
, most preferably at least 3-10 &mgr;g/cm
2
.
Furthermore the self-adhesive dental/medical composites show a opacity of at least 40%, preferably at least 20-40%, most preferably at least 5-20%.
REFERENCES:
patent: 399754 (1889-03-01), Keep
patent: 2709690 (1955-05-01), Narracott
patent: 4383052 (1983-05-01), Higo et al.
patent: 4514342 (1985-04-01), Billington et al.
patent: 4612384 (1986-09-01), Omura et al.
patent: 4657941 (1987-04-01), Blackwell et al.
patent: 4674980 (1987-06-01), Ibsen et al.
patent: 4806381 (1989-02-01), Engelbrecht et al.
patent: 5321053 (1994-06-01), Hino et al.
patent: 5705581 (1998-01-01), Fife et al.
patent: 5710194 (1998-01-01), Hammesfahr et al.
patent: 5730601 (1998-03-01), Bowman et al.
patent: 3150285 (1982-07-01), None
patent: 074708 (1983-03-01), None
patent: 088527 (1983-09-01), None
patent: 115410 (1984-08-01), None
patent: 058483 (1986-10-01), None
patent: 328772 (1989-08-01), None
patent: 554890 (1993-08-01), None
patent: 897709 (1999-02-01), None
patent: 98/46196 (1998-10-01), None
Klee Joachim E.
Walz Uwe
Bieber James B.
Dentsply DeTrey GmbH
Hura Douglas J.
Szekely Peter
LandOfFree
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