Polymerizable compositions based on epoxides

Details Polymerizable compositions based on epoxides Polymerizable compositions based on epoxides

1998-09-21

2001-06-12

Buttner, David J. (Department: 1712)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Compositions to be polymerized by wave energy wherein said...

C522S083000, C522S170000, C523S116000, C523S427000, C523S428000, C523S433000, C525S524000, C525S525000, C525S526000, C528S033000, C528S037000, C528S040000, C528S418000, C549S032000, C549S215000, C549S463000, C549S547000, C433S228100

Reexamination Certificate

active

06245828

ABSTRACT:

The invention relates to polymerizable compositions based on epoxides, new cycloaliphatic epoxides and their use.
Methacrylate and acrylate monomers have hitherto chiefly been used in polymerizable dental compositions. 2,2-Bis[4,1-phenylenoxy(2-hydroxy-3,1-propanediyl)-methacrylic acid ester]-propylidene (bis-GMA) [U.S. Pat. No. 3,066,112], described by Bowen, deserves particular attention. Mixtures of this methacrylate with triethylene glycol dimethacrylate are also used nowadays as the standard recipe for dental plastic direct filling materials. Methacryl derivatives of diformylated bis-(hydroxymethyl)tricyclo[5.2.1.0
2,6
]-decane have also proved suitable as monomers for dental composites [W. Gruber et al., DE-A-27 14 538; W. Schmitt et al., DE-C-28 16 823; J. Reiners et al., EP-A-0 261 520]. A great disadvantage of the known polymerizable dental compositions is the polymerization shrinkage which, for example when they are used as filling material, can cause secondary caries due to the formation of edge gaps. Furthermore, in acrylate-based dental compositions, the polymerization inhibition by oxygen leads to the formation of a so-called greasy layer which, for example in the case of fillings, is undesirable and even harmful. Finally, acrylate-based polymerizable dental compositions have a low adhesion to the tooth substance.
Although there is extensive experience with epoxides and cycloaliphatic epoxides U.S. Pat. No. 2,716,123, U.S. Pat. No. 2,750,395, U.S. Pat. No. 2,863,881, U.S. Pat. No. 3,187,018), such monomers and cationically polymerizable compositions formulated therefrom having the properties necessary for dental uses have not been commercially available at any point in time.
The preparation of bifunctional cycloaliphatic epoxides is already described in patents from the 1950s (U.S. Pat. No. 2,750,395, U.S. Pat. No. 900,506, U.S. Pat. No. 907,149, U.S. Pat. No. 2,745,847, U.S. Pat. No. 2,853,499, U.S. Pat. No. 3,187,018, U.S. Pat. No. 2,863,881, U.S. Pat. No. 2,853,498). Silicon-containing cycloaliphatic epoxides have been described by Crivello et al. in various publications (EP-A-0 449 027; J. Polym. Sci., Part A: Polym. Chem., 28 (1990) 479, ibid. 31 (1993) 2563; ibid. 31 (1993) 2729; ibid. 31 (1993) 3109; ibid. 31 (1993) 3121; ibid. 33 (1995) 2463). The known cycloaliphatic epoxides are essentially low molecular weight monomers which indeed have a somewhat reduced polymerization shrinkage [J. Adhes. Sci. Technol. 9 (10) 1995, 1343; DE-A-4 340 949], but because of their high density of functional groups, do not meet the requirements (processing, physical properties) for dental uses.
Only little is known of cationically curable epoxide compositions for dental uses: The patent U.S. Pat. No. 5,556,896 describes epoxide-containing compositions which must necessarily comprise spiroorthocarbonates as shrinkage-compensating monomers. The company Ciba described in 1958, in the patent AT-A-204 687, epoxide dental compositions based on bisphenol A which were cured by means of Lewis acid catalysts. The long curing time and the low mechanical strength and long-term stability were problematic in these formulations. The companies Minnesota Mining and Manufacturing Company and Wictorin et al. describe in patents (WO 96/13538 and WO 95/30402) cationically curable epoxy mixtures, preferably with 3,4-epoxycyclohexyl-methyl 3,4-epoxycyclohexanecarboxylate or bis(3,4-epoxycyclohexyl adipate). This type of epoxide is highly cytotoxic and in vitro tests showed for these monomers mutagenic properties, which are undesirable in dental use.
The object of the present invention is to provide polymerizable compositions which, by comparison with the known compositions, in addition to a high reactivity and the necessary mechanical properties, have a low volume shrinkage and have no mutagenic and only mild cytotoxic properties.
According to the invention, this object is achieved by polymerizable compositions comprising
(a) 3 to 80 wt. %, preferably 3 to 75 wt. %, and in particular 5 to 70 wt. % of an epoxide or a mixture of epoxides of the general formula:
 in which, for type A:
if n=2
Z denotes a cycloaliphatic or aromatic radical having 1 to 22, preferably 1 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR
2
and/or NR, or an aliphatic radical having 0 to 22, preferably 1 to 18 C atoms, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, NR or SiR
2
, wherein at least one C atom must be replaced by SiR
2
, and wherein R is an aliphatic radical having 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O and/or —O(C═O)—.
if n>2
Z denotes an aliphatic, cycloaliphatic or aromatic radical having 0 to 22, preferably 0 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR
2
and/or NR and wherein R is an aliphatic radical having 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O and/or —O(C═O)—,
and in which, for type B:
Z denotes an aliphatic, cycloaliphatic or aromatic radical having 0 to 22, preferably 0 to 18 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR
2
and/or NR and wherein R is an aliphatic radical having 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O and/or —O(C═O)—,
and in which, for type A and type B:
A denotes an aliphatic, cycloaliphatic or aromatic radical having 1 to 18, preferably 1 to 15 C atoms or a combination of these radicals, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR
2
and/or NR, wherein R is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═O and/or —O(C═O)—,
B
1
, B
2
, D and E independently of one another denote an H atom or an aliphatic radical having 1 to 9, preferably 1 to 7 C atoms, wherein one or more C atoms can be replaced by O, C═O, —O(C═O)—, SiR
2
and/or NR, wherein R is an aliphatic radical having 1 to 7 C atoms, in which one or more C atoms can be replaced by O, C═O and/or —O(C═O)—,
n denotes 2-7, preferably 2-5, in particular 2-4,
m denotes 1-10, preferably 1-7, in particular 1-5,
p denotes 1-5, preferably 1-4, in particular 1 or 2,
q denotes 1-5, preferably 1-4, in particular 1 or 2, and
x denotes CH
2
, S or O,
(b) 0 to 80, preferably 0 to 70 wt. % of an epoxide or a mixture of epoxides which differ from (a),
(c) 3 to 85, preferably 5 to 75 wt. % of fillers,
(d) 0.01 to 25, preferably 0.01 to 20 wt. % of initiators, retardants and/or accelerators,
(e) 0 to 25, preferably 0 to 20 wt. % of auxiliaries, the percentage data in each case being based on the total weight of the composition.
Preferred compositions according to the invention comprise, as component (a), one or more of the epoxides listed below:
i) 2,2-bis[4,1-phenylenoxy-3,1-propanediyl-3,4-epoxy-cyclohexylcarboxylic acid ester]propylidene
ii) 2,2-bis[4,1-phenylenoxy-3,1-propanediyl-oxy-methanediyl-3,4-epoxycyclohexyl]propylidene
iii) 2,2-bis[3,4-epoxycyclohexylmethanediyl(4,1-phenylenoxy-3,1-propylcarboxylic acid ester)]propylidene
iv) 2,2-bis[4,1-phenylenoxy-3,1-propanediyl-1,1,3,3-tetramethyldisiloxanyl-1,2-ethanediyl-3,4-epoxycyclohexyl]propylidene
v) 2,2-bis{4,1-phenylenoxy-3,1-propanediyl-3-oxatricyclo[3.2.1.0
2,4
]octyl-6-carboxy}propylidene
vi) 2,2-bis{4,1-phenylenoxy-3,1-propanediyl-3,8-dioxatricyclo[3.2.1.0
2,4
]octyl-6-carboxy}propylidene
vii) 2,2-bis{4,1-phenylenoxy-3,1-propanediyl-[3,5,7-tris(ethanediyl-3,4-epoxycyclohexyl)-1,3,5,7-tetramethylcyclotetrasiloxanyl]}propylidene
viii) bis[methanediyl-oxy-3,1-propanediyl-3,4-epoxycyclohexylcarboxylic acid ester]tricyclo[5.2.1.0
2,6
]decane
ix) bis[methanediyl-oxy-3,1-propanediyl-oxy-methanediyl-3

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