Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Compositions to be polymerized by wave energy wherein said...
Reexamination Certificate
2000-03-06
2002-06-11
Seidleck, James J. (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Compositions to be polymerized by wave energy wherein said...
C522S079000, C522S081000, C522S083000, C522S167000, C522S168000, C522S182000, C522S178000, C523S115000, C523S113000, C523S116000, C523S114000, C523S118000, C523S300000, C433S228100
Reexamination Certificate
active
06403671
ABSTRACT:
The invention relates to polymerizable, cross-linkable compositions, containing polyalkylbenzene derivatives and or derivatives of ring-shaped polycarboxylic acid and/or their anhydrides as well as their use in particular in dentistry. Such compositions adhere to different, but particularly to biological, substrates. Compounds of this type can be used or added for general purposes, but particularly in dentistry as components for polymerizable adhesion promoters, adhesion filling materials, adhesion cements, sealers and for similar mixtures.
Polymerizable mixtures based on monomer compounds provided with one or more unsaturated groups form the basis for a number of plastics, with mainly compounds with acrylate and methylacrylate groups being important in the dental and medical fields. Such mixtures are e.g. the basis for plastic filling and sealing materials. These polymerizable mixtures cannot generally however form a chemical compound with other materials, particularly biological substrates, unless these substrates themselves also contain sufficiently unpolymerized polymerizable groups.
A firmer connection can thus be achieved only via retention-rich surfaces, i.e. via a bond of a purely mechanical type, e.g. after etching the surface of biological or inorganic materials. By using adhesion promoters, i.e. substrates which on the one hand can chemically react with biological or inorganic material and on the other hand also bear a polymerizable group, this shortcoming can however be overcome.
A series of such adhesion promoters is already known, e.g. the organosilane-bearing vinyl or methylacryl groups. They are however limited in their adhesion effect on silicon dioxide, silicon dioxide-containing glasses as well as ceramics and metal oxides, or base metals forming these. They show no adhesion on biological substrates and particularly on tooth- or bone substrates, but have more of a separating effect. For substrates of this type a series of polymerizable adhesion promoters with other adhesion groups have been found. There are some which react with the collagen or collagen-like content of these substrates, such as e.g.
2-N-allyamino-4,6-dichloro-1,3,5-triazine (U.S. Pat. No. 4,203,220),
combinations of hydroxymethacrylester with dialdehydes (EP-A-0141324) or
epoxy methacrylates
Furthermore there are a number of polymerizable compounds which react with the apatite compounds of tooth- or bone substance. These adhesion-promoting compounds bear acid groups or reactive acid group derivatives. Examples of such polymerizable compounds are:
unsaturated organic esters of phosphoric- or phosphonic acids (DE-A-27 11 234, DE-A-31 50 285):
unsaturated organic esters of monofluorophosphoric acid (U.S. Pat. No. 3,997,504):
unsaturated organic esters of acids of phosphorus which contain chlorine or bromine directly bound to the phosphorus (EP-A-0 058 483);
unsaturated organic esters of phosphoric acid, which are present as cyclic pyrophosphates (anhydrides) (DE-A-30 48 410).
Polymerizable carboxylic acids and reactive carboxylic acid derivatives are also known which show adhesion to tooth substance, such as e.g.
4-methacryloyloxyethyltrimellitic acid and its anhydride (Takeyama, M. et al., J. Jap. Soc. f. Dent. App. a. Mat. 19, 179 (1978)) or
methacroyloxy-ethyl-o-phthalate (E. Mashuhara, K. Kojhima, N. Tarumi, N. Nakabayashi, H. Hotta, Rep. Inst. Med. Dent. Eng. 1, 29, (1967).
Reaction products of ethylenically unsaturated alcohols with 3 to 12 C atoms with cyclic anhydrides are also used as adhesion promoters (U.S. Pat. No. 4,659,751, Bowen).
Systems based on phosphoric acid are extremely hydrolysis-sensitive and those based on carboxylic acids have the disadvantage that a bond with the substrate can not be optimally carried out. Most adhesion molecules are in addition difficult to obtain by synthesis and can thus be used economically only with difficulty. There is therefore a great interest in obtaining easily accessible adhesion molecules which are hydrolysis-stable, bond more readily to the substrate than do the molecules in the prior art and can also be produced at favourable cost and economically.
The object of the invention is to make available polymerizable and cross-linkable compositions which show a high adhesion, in particular to biological substrates and quite particularly to hard tooth substance and dentine.
Surprisingly, compositions which contain molecules which have formed from the reaction of molecules of the general formula (1) or ring-shaped polycarboxylic acids and/or their anhydrides with a saturated ring system and at least four carboxyl groups as well as 0 or 1 heterocyclic ring atoms from the group N, O, S, with OH-functional (methyl)acrylates (general formula (3)), adheres to biological substrates, in particular to hard tooth substances such as enamel and dentine, to a greater degree than previously known. By combining these molecules in an adhesion-promoting composition a further increase in adhesion is unexpectedly observed.
The invention is explained in more detail in the following.
In the following, the term (meth)acrylates is understood to refer to methacrylate acid esters, acrylic acid esters, methylacrylamides, acrylamides as well as thiomethacrylic acid esters and thioacrylic acid esters.
The polymerizable cross-linkable compositions according to the invention have to contain adhesion-promoting substances alongside other components, such as for example fillers, monomers or solvents.
The composition according to the invention consists of:
(A) 1 to 99.99 wt.-%, preferably 5 to 70 wt.-%, of reaction products of OH-functional (meth)acrylates with
(i) the compounds of formula (1):
in which:
R1, R2, R3 and R4 are chosen independently from each other from the group
(a) hydrogen
(b) linear or branched hydrocarbon radicals with 1 to 20 C atoms, preferably methyl,
(c) linear or branched hetero aliphatics with 1 to 20 C atoms and heteroatoms chosen from the groups N, O, S, preferably O,
(d) halogens and pseudohalogens, preferably F, Cl, Br, CN, SCN, quite particularly preferably Cl, Br and
(e) the fragment of formula (2):
in which x can assume whole numerical values between 1 and 8,
and X is chosen from the group O, S,
preferably
with R5 or R6 corresponding to the above definition of R1 to R4,
on the condition that at least two random representatives of the group R1 to R4, R5, R6 correspond to the fragment of formula (2), the substitution pattern of the fragments of formula (2) being able to be ortho, meta or para (reaction product group A1) and the combination R1 to R4=H, X=
with R5=R6=fragment of formula (2) being preferred, and/or with
(ii) ring-shaped polycarboxylic acids with at least 4 ring carbon atoms and/or their anhydrides with a saturated ring system and at least four carboxyl groups as well as 0 or 1 hetero ring atoms from the group N, O, S (reaction product group A2) of the general formula (3),
where
a=0 to 6,
b=0 to 3,
c=0 or 1, and
X=0, NR1 or S,
R1 has the above meaning, except for (e) a fragment of formula (2), and
at least one carboxyl group and/or anhydride group of the above-named substance group is functionalized with unsaturated polymerizable groups,
(B) 0 to 98.99 wt.-%, preferably 5 to 70 wt.-%, of one or more polymerizable, unsaturated organic compounds with at least one CH
2
═C(R10)—COO-group, where R10 is ═H or methyl;
(C) 0.01 to 5 wt.-%, preferably 0.01 to 3 wt.-%, of initiators and optionally activators;
(D) 0 to 99 wt.-%, preferably 0 to 50 wt.-%, of customary solvents;
(E) 0 to 90 wt.-%, preferably 20 to 80 wt.-%, of customary fillers, pigments, thixotropy auxiliaries, plasticizers, diluting agents, rigidifying monomers, radical captors, stabilizers, other auxiliaries,
the given wt.-% referring in each case to the sum of all components (A) to (E).
Preferred compounds of formula (1) correspond to following formula (4)
in which x and y independently of each other can assume whole numerical values between 1 and 8 and R1, R2, R3 and R4 have the above-mentioned
Bissinger Peter
May Robert
Mikulla Markus
Birch & Stewart Kolasch & Birch, LLP
ESPE Dental AG
McClendon Sanza L.
Seidleck James J.
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