CA2026203A1 - Dental adhesive - Google Patents
Dental adhesiveInfo
- Publication number
- CA2026203A1 CA2026203A1 CA002026203A CA2026203A CA2026203A1 CA 2026203 A1 CA2026203 A1 CA 2026203A1 CA 002026203 A CA002026203 A CA 002026203A CA 2026203 A CA2026203 A CA 2026203A CA 2026203 A1 CA2026203 A1 CA 2026203A1
- Authority
- CA
- Canada
- Prior art keywords
- meth
- acid
- ester
- acryloyloxyethyl
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
Abstract
ABSTRACT
The adhesion of photopolymerizable dental filling materials to enamel and dentin is improved with adhesives containing (meth)acryloyloxyethyl-dihydrogen phosphate and/or di(meth)acryloyloxyethyl-hydrogen phosphate and acidic (meth)acryloyloxyethyl esters of carbonic acids. A
particular advantage in this regard is the very good adhesive strength to dentin direetly after hardening.
The adhesion of photopolymerizable dental filling materials to enamel and dentin is improved with adhesives containing (meth)acryloyloxyethyl-dihydrogen phosphate and/or di(meth)acryloyloxyethyl-hydrogen phosphate and acidic (meth)acryloyloxyethyl esters of carbonic acids. A
particular advantage in this regard is the very good adhesive strength to dentin direetly after hardening.
Description
2 ~ 3 "Dental Adhesive"
The invention relates to a dental adhesive that contains an acryloyloxyethyl dihydrogen phosphate and/or a diacryloyloxyethyl-hydrogen phosphate, a photopolymerization catalyst and an organic solvent.
When filling dental cavities with a polymerizable dental filling material with a plastic base, in order to improve adhesion between tooth enamel and the plastic, the tooth enamel is treated before the filling is applied with an acidic etching solution, such as a diluted phosphoric acid solution, and then if necessary, coated with a diluted sealing material, usually containing monomerous dimethacrylate, which is hardened chemically or by photopolymeri~ation. Because of their good physical characteristics, sealing materials which contain a finely graduated inorganic filler in addition to monomers have proven particularly successful. Their adhesion is based on a mechanical anchoring in the etched tooth enamel.
From a dental poiDt of view, however, etching of the dentin is not recommended. For this reason, adhesives are used to improve the adhesion between the dentin and plastic if anchoring through etching the enamel is not possible, for example, for cavities in the neck of a tooth. A large num~er of such dental adhesives ara known, as they, together with the use of compound fiIlings, are playing an increasingly larger role. An important problem in this regard appears to 2~2~2~
be the initial polymerization contraction of the compound, which leads to the formation of a crack between the filling and the solid tooth substance. This results in bacterial penetration, which damages the pulp and can cause secondary cavities.
Adhesive Restorative Dental Materials, 1961, pp 195-198, reports on the adhesion improving effect of dimethacryloyloxyethyl-hydrogen phosphate and some dihydrogen phosphates containing methacryloyloxy groups.
The German patent specification 27 1~ 234 mentions adhesives for teeth and dental materials which can contain dimethacryloyloxyethyl-hydrogen phosphate, for example, as phosphoric esters, together with other monomers if necessary, and amine/peroxide systems or UV sensitization materials as polymerization catalysts.
The European patent application 88 257 describes an adhesion improving material ("adhesion promotor") consisting of a solution of a dihydrogen phosphate exhibiting at least three methacryloyloxy groups in a volatile organic solvent, particularly an alkanol. An adhesive or sealing material ("intermediate bonding resin") can be used together with this material to increase the adhesion of the dental filling material to the tooth substance.
Other adhesives that improve the adhesion of photopolymerizable dental materials to dentin, which also contain methacryloyloxyethyl-hydrogen phosphates in addition ~&~
to a photopolymerization catalyst, are mentioned in the German patent specifications 34 14 163 and 34 14 165.
Carbonic acids and carbonic acid derivatives containing polymerizable groups, that display good adhesion to hard tooth substance, are also known, such as 4-methacryloyloxyethyl trimellitic acid and its anhydride, pyromellitic acid-dimethacryloyloxethyl ester, and esters of carboxynapthalene dicarbonic acid anhydrides exhibiting acryloyloxy- or methacryloyloxy groups in a remainder of alcohol (German patent specifications 35 10 962), as well as - ~meth)acryloyloxy~ alkane dicarbonic acids ~European patent application 206 810).
The German patent application 35 36 077 deals with oligomerous or prepolymerous connections with both polymerizable unsaturated groups and acid residues, their salts or active derivative residues, particularly with carboxylate, phosphate, phosphonate, sulfonate and borate residues and their reactive derivatives. These polymerizable mixtures containing connections can be used as adhesion inducing polymerizable layers betwe~en tooth substance and polymerizable plastic materials.
The agent described in the European patent application 282 280, which improves the adhesion of compound material to enamel and dentin, contains pol~meriæable connections with acid residues in the molecule, such as aromatic carbonic acids or phosphoric acids with acryloyloxy- or metacryloyloxy ~ ~ ~ s~
groups, such as 4-methacryloyloxyethoxy carbonyl pthalic acid or its anhydride.
The adhesive described in the European patent application 310 919, which improves adhesion between tooth substance and compound materials, contains a fluoralkyl ester of acrylic acid, fluoracrylic acid or methacrylic acid and/or its polymer or copolymert and in addition, if necessary, monomers which improve adhesion even more, with, for example, carbonic acid, phosphoric acid, mercaponic or sulphonic acid groups. It can be dried through chemical polymerization or photopolymerization.
The objective of the invention is to find an agent of the type described at the beginning, which improves the adhesion between hard tooth substance, particularly dentin, and photopolymerizable dental materials. The use of this agent should prevent, in particular, the formation of peripheral cracks and the secondary cavities caused by this, which results from the initial polymerization contraction.
The adhesive that meets this objective i5 characterized by the fact that it consists Oe 1 - 25 percent by weight of (meth)acryloyloxyethyl-dihydrogen phosphate and/or di(meth)acryloyloxyethyl-hydrogen phosphate, 3 - 40 percent by weight o~ at least one acidic carbonic acid ester of the group dicarbonic acid mono(meth)acryloyloxethyl ester, o-trimellitic acid mono(meth)acryloyloxyethyl ester and pyromellitic acid di(meth)acryloyloxyethyl ester, 0.05 - 5 - 2 ~ 3 percent by weight of the photopolymerization catalyst and a remainder of ethanol.
Preferably, the adhesive consists of 5-20 percent by weight of (meth)acryloyloxyethyl-dihydrogen phosphate and/or di(meth)acryloyloxyethyl-hydrogen phosphate, 5-30 percent by weiyht of at least one acidic carbonic acid ester of the group dicarbonic acid mono(meth)acryloyloxyethyl ester, o-trimellitic acid mono(meth)acryloyloxethyl ester and pyromellitic acid di(meth)acryloyloxethyl ester, 0.1-2 percent by weight of the photopolymeri~ation catalyst and a remainder of ethanol.
The monoacryloyloxyethyl esters and/or monomethacryloyloxethyl esters of alkane dicarbonic acids with 1-6 C atoms in a remainder of alkane, maleic acid, benzol dicarbonic acids and cyclohexanedicarbonic acids have proven to be good dicarbonic acid mono(meth)acryloyloxyethyl esters.
Adhesives containing a mixture of two of the unsaturated carbonic acid esters have proven to be particularly effective.
Ketones, such as those mentioned in the British patent specifications 1 408 265, have proven to be good phQtopolymerization catalysts. Camphoroquinone is preferred.
The adhesive in accordance with the invention improves the adhesion of photopolymerizable dental filling materials to both enamel and dentin. It can be used alone or with a 2 ~ ~
photopolymerizable sealing material. It is also possible, however, to apply the adhesive only in conjunction with the sealing material, if the latter is to be used to seal masticatory surfaces or exposed necks of teeth.
When the adhesive is used in accordance with the invention, high values for adhesion directly after hardening of the dental filling material (initial adhesion), and after 24 hours' suspension in warm water at 37C, are noticed, in particular. Surprisingly, the joint use of the unsaturated phosphate and the unsaturated acidic carbonic acid ester leads to values for adhesion that are twice as high as those when a phosphate or acidic ester is used alone. Peripheral cracks between the tooth substance and the filling material do not occur; the very good initial adbesion count0racts the formation of cracks caused by the contraction of the dental filling material during polymerization.
For a more detailed explanation, the following examples describe in more detail the composition of adhesives in accordance with the invention. The adhesion between dentin and plastic dental filling (compound dental filling) and between tooth enamel and plastic dental filling achieved with this adhesive using a photopolymerizable sealing material is determined.
~2~ 3 Example 1 5.0% dimethacryloyloxyethyl-hydrogen phosphate 15.0% maleic acid monoethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 2 5.0% dimethacryloyloxyethyl-hydrogen phosphate 15.0% pthalic acid monomethacryloyloxyethyl ester 79.9~ ethanol 0.1% camphoroquinone Example 3 5.0% dimethacryloyloxyethyl-hydrogen phosphate 15.0% succinic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 4 5.0% dimethacryloyloxyethyl-hydrogen phosphate 5.0% pthalic acid monomethacryloyloxyethyl ester 10.0~ maleic acid monoethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone ~&~Q~
Example 5 5.0% dimethacryloyloxyethyl-hydrogen phosphate 7.5% pthalic acid monomethacryloyloxyethyl ester 7.5% maleic acid monoethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 6 5.0% dimethacryloyloxyethyl-hydrogen phosphate -10.0% pthalic acid monomethacryloyloxyethyl ester 5.0% maleic acid monoethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 7 500% methacryloyloxyethyl-dihydrogen phosphate 15.0% maleic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 8 5.0% methacryloyloxyethyl-dihydrogen phosphate 15.0% succinic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone 2~&~3 Example 9 5.0% methacryloylDxyethyl-dihydrogen phosphate 15.0% succinic acid monomethacryloyloxy~khyl ester 79.9% ethanol 0.1% camphoroquinone Example 10 5.0% methacryloyloxyethyl-dihydrogen phosphate 5.0% pthalic acid monomethacryloyloxethyl ester 10.0% maleic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 11 5.0% methacryloyloxyPthyl-dihydrogen phosphate 5.0% pthalic acid monomethacryloyloxethyl ester 10.0% maleic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 12 5.0% methacryloyloxyethyl-dihydrogen phosphate 10.0% pthalic acid monomethacryloyloxethyl ester 5.0% maleic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone ~2~
Example 13 5.0% methacryloyloxyethyl-dihydrogen phosphate 15.0% pyromellitic acid dimethacryloyloxyethyl ester 79.9% ethanol O.1% camphoroquinone Example 14 5.0~ methacryloyloxyethyl-dihydrogen phosphate 15.0% o-trimellitic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 15 (comparison) 5.0% methacryloyloxyethyl-dihydrogen phosphate 94.9% ethanol 0.1% camphoroquinone Example 16 (comparison) 15.0% methacryloyloxyethyl-dihydrogen phosphate 84.9% ethanol 0.1% camphoroquinone Example 17 (comparison) 15.0% maleic acid monom~thacryloyloxyethyl ester 84.9% ethanol 0.1% camphoroquinone 2 ~ Q 3 Example 18 (comparison) 15.0% pthalic acid monomethacryloyloxethyl ester 84O9% ethanol 0.1% camphoroquinone Each of the adhesives described in the examples is spread on to the dentin surface of an extracted tooth, that has been sawed with a diamond saw, polished, cleaned (with a watery ethylene diaminotetraacetic acid solution, pH 8.5) and dried. After diluting the ethanol, Estiseal~ LC, a photopolymerizable sealing material made by Kulzer GmbH is applied and dried through 20 seconds' exposure to Translux~, a halogen light device made by Kulzer GmbH. Durafill, a photopolymerizable dental ~illing material (compound) made by Kulzer GmbH, is then applied and also dried through 20 seconds' e~posure to the halogen light device.
Th~ teeth treated in this manner undergo shearing tests to determine the adhesion of the plastic filling to the dentin. The values measured during this testing directly after hardening (maximum 30 sPconds) and after 24 hours' suspension in warm water at 37C are shown in Table 1. The respective adhesion values measured using two commercial adhesives, Scotchbond~ II and Gluma~, are also shown in the table, by way of comparison.
To determine the adhesion of the plastic filling to tooth enamel, the enamel surface of an extracted tooth, that has been sawed with a diamond saw, polished, cleaned twith a watery ethylene diaminotetraacetic acid solution, pH 8.5) and dried, is coated with one of the adhesives described in examples 1 and 5, either a) directly or b~ a~ter etching with a 35% phosphoric acid (Esticid0, made by Kulzer GmbH). After diluting the ethanol, Estiseal0 LC, a photopolymerizable sealing material made by Kulæer GmBH is applied and dried through 20 seconds' exposure to Translux0, a halogen light device made by Kulzer GmbH. Durafill, a photopolymerizable dental filling material (compound) made by Kulzer GmbH, is then applied and also dried through 20 seconds' exposure to the halogen light device.
The aclhesion values determined by shearing tests after 24 hours' suspension in warm water at 37C are given in Table II. The respective adhesion values measured using two commercial adhesives, Scotchbond0 II and Gluma0, and without using an adhesive, are also given in the table, by way of comparison.
~ 3 ~3.
Table I
Adhesion (N/mm2]
Example Dir~ctly after After 24 hours' hardening suspension in water, 37C
1 10.5 13.0 2 10.8 11.0 3 10.9 12.6 4 14.7 15.0 11.0 15.3 S 10.0 17.5 7 11.4 13.1 ~ 11.3 12.1 9 ~1.5 13.6 14.1 16.0 11 12.1 15.0 12 11.8 16.1 13 10.5 12.3 14 9.5 12.6 15 (comparison) 3.9 5.4 16 (comparison3 6.5 7.6 17 (comparison) 5.0 6.9 18 (comparison) S.2 7'.3 Scotchbond 2.4 7.1 Gluma 6.5 8.9 2 ~
Table II
Adhesion. (N/mm2]
Example After 24 hours' suspension in water, 37C
1 a~ 7 b) 15 a) 8 b) 15 : Scotchbond a) 3 ~ b) 11 - Gluma a) 2 b) 11 Without a) : adhesive b) 12 ~;
a) = not etched : b) = etched , :; : : :
' ~ ;
The invention relates to a dental adhesive that contains an acryloyloxyethyl dihydrogen phosphate and/or a diacryloyloxyethyl-hydrogen phosphate, a photopolymerization catalyst and an organic solvent.
When filling dental cavities with a polymerizable dental filling material with a plastic base, in order to improve adhesion between tooth enamel and the plastic, the tooth enamel is treated before the filling is applied with an acidic etching solution, such as a diluted phosphoric acid solution, and then if necessary, coated with a diluted sealing material, usually containing monomerous dimethacrylate, which is hardened chemically or by photopolymeri~ation. Because of their good physical characteristics, sealing materials which contain a finely graduated inorganic filler in addition to monomers have proven particularly successful. Their adhesion is based on a mechanical anchoring in the etched tooth enamel.
From a dental poiDt of view, however, etching of the dentin is not recommended. For this reason, adhesives are used to improve the adhesion between the dentin and plastic if anchoring through etching the enamel is not possible, for example, for cavities in the neck of a tooth. A large num~er of such dental adhesives ara known, as they, together with the use of compound fiIlings, are playing an increasingly larger role. An important problem in this regard appears to 2~2~2~
be the initial polymerization contraction of the compound, which leads to the formation of a crack between the filling and the solid tooth substance. This results in bacterial penetration, which damages the pulp and can cause secondary cavities.
Adhesive Restorative Dental Materials, 1961, pp 195-198, reports on the adhesion improving effect of dimethacryloyloxyethyl-hydrogen phosphate and some dihydrogen phosphates containing methacryloyloxy groups.
The German patent specification 27 1~ 234 mentions adhesives for teeth and dental materials which can contain dimethacryloyloxyethyl-hydrogen phosphate, for example, as phosphoric esters, together with other monomers if necessary, and amine/peroxide systems or UV sensitization materials as polymerization catalysts.
The European patent application 88 257 describes an adhesion improving material ("adhesion promotor") consisting of a solution of a dihydrogen phosphate exhibiting at least three methacryloyloxy groups in a volatile organic solvent, particularly an alkanol. An adhesive or sealing material ("intermediate bonding resin") can be used together with this material to increase the adhesion of the dental filling material to the tooth substance.
Other adhesives that improve the adhesion of photopolymerizable dental materials to dentin, which also contain methacryloyloxyethyl-hydrogen phosphates in addition ~&~
to a photopolymerization catalyst, are mentioned in the German patent specifications 34 14 163 and 34 14 165.
Carbonic acids and carbonic acid derivatives containing polymerizable groups, that display good adhesion to hard tooth substance, are also known, such as 4-methacryloyloxyethyl trimellitic acid and its anhydride, pyromellitic acid-dimethacryloyloxethyl ester, and esters of carboxynapthalene dicarbonic acid anhydrides exhibiting acryloyloxy- or methacryloyloxy groups in a remainder of alcohol (German patent specifications 35 10 962), as well as - ~meth)acryloyloxy~ alkane dicarbonic acids ~European patent application 206 810).
The German patent application 35 36 077 deals with oligomerous or prepolymerous connections with both polymerizable unsaturated groups and acid residues, their salts or active derivative residues, particularly with carboxylate, phosphate, phosphonate, sulfonate and borate residues and their reactive derivatives. These polymerizable mixtures containing connections can be used as adhesion inducing polymerizable layers betwe~en tooth substance and polymerizable plastic materials.
The agent described in the European patent application 282 280, which improves the adhesion of compound material to enamel and dentin, contains pol~meriæable connections with acid residues in the molecule, such as aromatic carbonic acids or phosphoric acids with acryloyloxy- or metacryloyloxy ~ ~ ~ s~
groups, such as 4-methacryloyloxyethoxy carbonyl pthalic acid or its anhydride.
The adhesive described in the European patent application 310 919, which improves adhesion between tooth substance and compound materials, contains a fluoralkyl ester of acrylic acid, fluoracrylic acid or methacrylic acid and/or its polymer or copolymert and in addition, if necessary, monomers which improve adhesion even more, with, for example, carbonic acid, phosphoric acid, mercaponic or sulphonic acid groups. It can be dried through chemical polymerization or photopolymerization.
The objective of the invention is to find an agent of the type described at the beginning, which improves the adhesion between hard tooth substance, particularly dentin, and photopolymerizable dental materials. The use of this agent should prevent, in particular, the formation of peripheral cracks and the secondary cavities caused by this, which results from the initial polymerization contraction.
The adhesive that meets this objective i5 characterized by the fact that it consists Oe 1 - 25 percent by weight of (meth)acryloyloxyethyl-dihydrogen phosphate and/or di(meth)acryloyloxyethyl-hydrogen phosphate, 3 - 40 percent by weight o~ at least one acidic carbonic acid ester of the group dicarbonic acid mono(meth)acryloyloxethyl ester, o-trimellitic acid mono(meth)acryloyloxyethyl ester and pyromellitic acid di(meth)acryloyloxyethyl ester, 0.05 - 5 - 2 ~ 3 percent by weight of the photopolymerization catalyst and a remainder of ethanol.
Preferably, the adhesive consists of 5-20 percent by weight of (meth)acryloyloxyethyl-dihydrogen phosphate and/or di(meth)acryloyloxyethyl-hydrogen phosphate, 5-30 percent by weiyht of at least one acidic carbonic acid ester of the group dicarbonic acid mono(meth)acryloyloxyethyl ester, o-trimellitic acid mono(meth)acryloyloxethyl ester and pyromellitic acid di(meth)acryloyloxethyl ester, 0.1-2 percent by weight of the photopolymeri~ation catalyst and a remainder of ethanol.
The monoacryloyloxyethyl esters and/or monomethacryloyloxethyl esters of alkane dicarbonic acids with 1-6 C atoms in a remainder of alkane, maleic acid, benzol dicarbonic acids and cyclohexanedicarbonic acids have proven to be good dicarbonic acid mono(meth)acryloyloxyethyl esters.
Adhesives containing a mixture of two of the unsaturated carbonic acid esters have proven to be particularly effective.
Ketones, such as those mentioned in the British patent specifications 1 408 265, have proven to be good phQtopolymerization catalysts. Camphoroquinone is preferred.
The adhesive in accordance with the invention improves the adhesion of photopolymerizable dental filling materials to both enamel and dentin. It can be used alone or with a 2 ~ ~
photopolymerizable sealing material. It is also possible, however, to apply the adhesive only in conjunction with the sealing material, if the latter is to be used to seal masticatory surfaces or exposed necks of teeth.
When the adhesive is used in accordance with the invention, high values for adhesion directly after hardening of the dental filling material (initial adhesion), and after 24 hours' suspension in warm water at 37C, are noticed, in particular. Surprisingly, the joint use of the unsaturated phosphate and the unsaturated acidic carbonic acid ester leads to values for adhesion that are twice as high as those when a phosphate or acidic ester is used alone. Peripheral cracks between the tooth substance and the filling material do not occur; the very good initial adbesion count0racts the formation of cracks caused by the contraction of the dental filling material during polymerization.
For a more detailed explanation, the following examples describe in more detail the composition of adhesives in accordance with the invention. The adhesion between dentin and plastic dental filling (compound dental filling) and between tooth enamel and plastic dental filling achieved with this adhesive using a photopolymerizable sealing material is determined.
~2~ 3 Example 1 5.0% dimethacryloyloxyethyl-hydrogen phosphate 15.0% maleic acid monoethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 2 5.0% dimethacryloyloxyethyl-hydrogen phosphate 15.0% pthalic acid monomethacryloyloxyethyl ester 79.9~ ethanol 0.1% camphoroquinone Example 3 5.0% dimethacryloyloxyethyl-hydrogen phosphate 15.0% succinic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 4 5.0% dimethacryloyloxyethyl-hydrogen phosphate 5.0% pthalic acid monomethacryloyloxyethyl ester 10.0~ maleic acid monoethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone ~&~Q~
Example 5 5.0% dimethacryloyloxyethyl-hydrogen phosphate 7.5% pthalic acid monomethacryloyloxyethyl ester 7.5% maleic acid monoethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 6 5.0% dimethacryloyloxyethyl-hydrogen phosphate -10.0% pthalic acid monomethacryloyloxyethyl ester 5.0% maleic acid monoethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 7 500% methacryloyloxyethyl-dihydrogen phosphate 15.0% maleic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 8 5.0% methacryloyloxyethyl-dihydrogen phosphate 15.0% succinic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone 2~&~3 Example 9 5.0% methacryloylDxyethyl-dihydrogen phosphate 15.0% succinic acid monomethacryloyloxy~khyl ester 79.9% ethanol 0.1% camphoroquinone Example 10 5.0% methacryloyloxyethyl-dihydrogen phosphate 5.0% pthalic acid monomethacryloyloxethyl ester 10.0% maleic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 11 5.0% methacryloyloxyPthyl-dihydrogen phosphate 5.0% pthalic acid monomethacryloyloxethyl ester 10.0% maleic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 12 5.0% methacryloyloxyethyl-dihydrogen phosphate 10.0% pthalic acid monomethacryloyloxethyl ester 5.0% maleic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone ~2~
Example 13 5.0% methacryloyloxyethyl-dihydrogen phosphate 15.0% pyromellitic acid dimethacryloyloxyethyl ester 79.9% ethanol O.1% camphoroquinone Example 14 5.0~ methacryloyloxyethyl-dihydrogen phosphate 15.0% o-trimellitic acid monomethacryloyloxyethyl ester 79.9% ethanol 0.1% camphoroquinone Example 15 (comparison) 5.0% methacryloyloxyethyl-dihydrogen phosphate 94.9% ethanol 0.1% camphoroquinone Example 16 (comparison) 15.0% methacryloyloxyethyl-dihydrogen phosphate 84.9% ethanol 0.1% camphoroquinone Example 17 (comparison) 15.0% maleic acid monom~thacryloyloxyethyl ester 84.9% ethanol 0.1% camphoroquinone 2 ~ Q 3 Example 18 (comparison) 15.0% pthalic acid monomethacryloyloxethyl ester 84O9% ethanol 0.1% camphoroquinone Each of the adhesives described in the examples is spread on to the dentin surface of an extracted tooth, that has been sawed with a diamond saw, polished, cleaned (with a watery ethylene diaminotetraacetic acid solution, pH 8.5) and dried. After diluting the ethanol, Estiseal~ LC, a photopolymerizable sealing material made by Kulzer GmbH is applied and dried through 20 seconds' exposure to Translux~, a halogen light device made by Kulzer GmbH. Durafill, a photopolymerizable dental ~illing material (compound) made by Kulzer GmbH, is then applied and also dried through 20 seconds' e~posure to the halogen light device.
Th~ teeth treated in this manner undergo shearing tests to determine the adhesion of the plastic filling to the dentin. The values measured during this testing directly after hardening (maximum 30 sPconds) and after 24 hours' suspension in warm water at 37C are shown in Table 1. The respective adhesion values measured using two commercial adhesives, Scotchbond~ II and Gluma~, are also shown in the table, by way of comparison.
To determine the adhesion of the plastic filling to tooth enamel, the enamel surface of an extracted tooth, that has been sawed with a diamond saw, polished, cleaned twith a watery ethylene diaminotetraacetic acid solution, pH 8.5) and dried, is coated with one of the adhesives described in examples 1 and 5, either a) directly or b~ a~ter etching with a 35% phosphoric acid (Esticid0, made by Kulzer GmbH). After diluting the ethanol, Estiseal0 LC, a photopolymerizable sealing material made by Kulæer GmBH is applied and dried through 20 seconds' exposure to Translux0, a halogen light device made by Kulzer GmbH. Durafill, a photopolymerizable dental filling material (compound) made by Kulzer GmbH, is then applied and also dried through 20 seconds' exposure to the halogen light device.
The aclhesion values determined by shearing tests after 24 hours' suspension in warm water at 37C are given in Table II. The respective adhesion values measured using two commercial adhesives, Scotchbond0 II and Gluma0, and without using an adhesive, are also given in the table, by way of comparison.
~ 3 ~3.
Table I
Adhesion (N/mm2]
Example Dir~ctly after After 24 hours' hardening suspension in water, 37C
1 10.5 13.0 2 10.8 11.0 3 10.9 12.6 4 14.7 15.0 11.0 15.3 S 10.0 17.5 7 11.4 13.1 ~ 11.3 12.1 9 ~1.5 13.6 14.1 16.0 11 12.1 15.0 12 11.8 16.1 13 10.5 12.3 14 9.5 12.6 15 (comparison) 3.9 5.4 16 (comparison3 6.5 7.6 17 (comparison) 5.0 6.9 18 (comparison) S.2 7'.3 Scotchbond 2.4 7.1 Gluma 6.5 8.9 2 ~
Table II
Adhesion. (N/mm2]
Example After 24 hours' suspension in water, 37C
1 a~ 7 b) 15 a) 8 b) 15 : Scotchbond a) 3 ~ b) 11 - Gluma a) 2 b) 11 Without a) : adhesive b) 12 ~;
a) = not etched : b) = etched , :; : : :
' ~ ;
Claims (9)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
lo Dental adhesive that contains an acryloyloxethyl-dihydrogen phosphate and/or diacryloyloxyethyl-hydrogen phosphate, a photopolymerization catalyst and an organic solvent, characterized by the fact that it consists of 1-25 percent by weight of (meth)acryloyloxyethyl-dihydrogen phosphate and/or di(meth)acryloyloxyethyl-hydrogen phosphate, 3-40 percent by weight of at least one acidic carbonic acid ester of the group dicarbonic acid mono(meth)acryloyloxyethylester, o-trimellitic acid mono(meth)acryloyloxyethyl ester and pyromellitic acid di(meth)acryloyloxyethyl ester, 0.05-5 percent by weight of a photopolymerization catalyst and a remainder of ethanol. - 2. Dental adhesive in accordance with Claim 1, characterized by the fact that it consists of 5-20 percent by weight of (meth)acryloyloxethyl-dihydrogen phosphate and/or di(meth)acryloyloxyethyl-hydrogen phosphate, 5-30 percent by welght of at least one acidic carbonic acid ester of the group dicarbonic acid mono(meth)acryloyloxyethyl ester, o-trimellitic acid mono(meth)acryloyloxethyl ester and pyromellitic acid di(meth)acryloyloxyethyl ester, 0.1-2 percent by weight of a photopolymerization catalyst and a remainder of ethanol.
- 3. Adhesive in accordance with Claim 1 or 2, characterized by the fact that the dicarbonic acids is an alkane dicarbonic acid with 1-6 C atoms in a remainder of alkane, maleic acid, a benzol dicarbonic acid or a cyclohexanedicarbonic acid.
- 4. Adhesive in accordance with one of the Claims 1 to 3, characterized by the fact that it contains (meth)acryloyloxyethyl-dihydrogen phosphate.
- 5. Adhesive in accordance with one of the Claims 1 to 3, characterized by the fact that it contains di(meth)acryloyloxyethyl-hydrogen phosphate.
- 6. Adhesive in accordance with one of the Claims 1 to 5, characterized by the fact that it contains two of the acidic carbonic acid esters.
- 7. Adhesive in accordance with one of the Claims 1 to 6, characterized by the fact that it contains the mono(meth)acryloyloxyethyl ester of succinic acid as an acidic carbonic acid ester.
- 8. Adhesive in accordance with one of the Claims 1 to 6, characterized by the fact that it contains maleic acid mono(meth)acryloyloxyethylestex and/or pthalic acid mono(meth)acryloyloxyethyl ester as an acidic carbonic acid ester.
- 9. Adhesive in accordance with one of the Claims 1 to 8, characterized by the fact that it contains camphoroquinone as photopolymerization catalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3934849 | 1989-10-19 | ||
| DEP3934849.0-42 | 1989-10-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2026203A1 true CA2026203A1 (en) | 1991-04-20 |
Family
ID=6391770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002026203A Abandoned CA2026203A1 (en) | 1989-10-19 | 1990-09-25 | Dental adhesive |
Country Status (10)
| Country | Link |
|---|---|
| US (1) | US5089051A (en) |
| EP (1) | EP0423430B1 (en) |
| JP (1) | JPH03133912A (en) |
| AT (1) | ATE88337T1 (en) |
| AU (1) | AU631689B2 (en) |
| BR (1) | BR9005248A (en) |
| CA (1) | CA2026203A1 (en) |
| DE (2) | DE59001245D1 (en) |
| FI (1) | FI905136A0 (en) |
| NO (1) | NO904517L (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932627A (en) | 1994-05-12 | 1999-08-03 | Dentsply Gmbh | Fluoride releasing dental primer composition and method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5177121A (en) * | 1981-02-13 | 1993-01-05 | Minnesota Mining And Manufacturing Company | Dentin and enamel adhesive |
| US5304585A (en) * | 1981-02-13 | 1994-04-19 | Minnesota Mining And Manufacturing | Dentin and enamel adhesive |
| US6093084A (en) * | 1988-08-01 | 2000-07-25 | Dentsply Research & Development Corp. | Device and method for dispensing polymerizable compositions |
| JP2634276B2 (en) * | 1990-02-15 | 1997-07-23 | 株式会社松風 | Primer composition |
| US5256447A (en) * | 1991-12-31 | 1993-10-26 | Minnesota Mining And Manufacturing Company | Adhesive composition and method |
| US5756559A (en) * | 1992-02-06 | 1998-05-26 | Dentsply Research & Development | Method and composition for adhering to tooth structure |
| US6191190B1 (en) | 1993-04-19 | 2001-02-20 | Dentsply Research & Development Corp. | Method and composition for adhering to tooth structure |
| US6391940B1 (en) | 1993-04-19 | 2002-05-21 | Dentsply Research & Development Corp. | Method and composition for adhering to metal dental structure |
| WO1996000559A1 (en) * | 1994-06-30 | 1996-01-11 | Minnesota Mining And Manufacturing Company | Method for bonding amalgam to dental surfaces |
| US5554030A (en) * | 1994-06-30 | 1996-09-10 | Minnesota Mining And Manufacturing Company | Method for bonding non-amalgam restorative materials to dental surfaces |
| US6313191B1 (en) | 1994-08-22 | 2001-11-06 | Dentsply Gmbh | Method and composition for priming and adhering to tooth structure |
| US5645429A (en) * | 1994-08-22 | 1997-07-08 | Dentsply Research & Development Corp. | Method for adhering to tooth structure |
| JP3487389B2 (en) * | 1994-11-21 | 2004-01-19 | 株式会社トクヤマ | Dental composition |
| DE69511822T2 (en) * | 1994-11-21 | 2000-05-25 | Tokuyama Corp | Dental mass and kit |
| US6500004B2 (en) | 2000-12-14 | 2002-12-31 | Ultradent Products, Inc. | Endodontic sealing compositions and methods for using such compositions |
| US5925690A (en) * | 1995-11-20 | 1999-07-20 | Tokuyama Corproation | Dental primer composition and kit |
| US5762502A (en) * | 1996-07-11 | 1998-06-09 | Bahn; Arthur N. | Process for adhering composites to human teeth |
| KR100392609B1 (en) * | 1996-12-26 | 2003-11-17 | 한솔제지주식회사 | Dental restorative composite resins with anti-carious activity |
| US6001897A (en) | 1997-01-13 | 1999-12-14 | American Dental Association Health Foundation | Polymerizable conditioners for adhesive bonding to dentin and enamel |
| US6071528A (en) * | 1997-02-19 | 2000-06-06 | Ultradent Products, Inc. | Adhesive antimicrobial and/or reparative dentin stimulating dental compositions and methods for forming and using such compositions |
| JP3520707B2 (en) * | 1997-03-03 | 2004-04-19 | 株式会社トクヤマ | Adhesive composition |
| US6353040B1 (en) | 1997-04-02 | 2002-03-05 | Dentsply Research & Development Corp. | Dental composite restorative material and method of restoring a tooth |
| US6262142B1 (en) | 1997-04-02 | 2001-07-17 | Dentsply Research & Development | Translucent wear resistant dental enamel material and method |
| US20040209975A1 (en) * | 1997-04-02 | 2004-10-21 | Subelka John C. | Dental composite restorative material and method of restoring a tooth |
| AU743626B2 (en) * | 1997-11-13 | 2002-01-31 | 3M Espe Ag | Metal-free dental filling system as a substitute for amalgam |
| US6407148B1 (en) | 1997-11-13 | 2002-06-18 | 3M Espe Ag | Metal-free dental filling system as a substitute for amalgam |
| US20050059753A1 (en) * | 1998-06-30 | 2005-03-17 | Junjie Sang | Method and composition for adhering to tooth structure |
| US6147137A (en) * | 1998-09-10 | 2000-11-14 | Jeneric/Pentron Incorporated | Dental primer and adhesive |
| DE19951063A1 (en) | 1999-10-22 | 2001-04-26 | Espe Dental Ag | Amalgam substitute, useful as dental filling material for restoration, contains component reducing hardening at interface between sealing system and filling material |
| JP4926348B2 (en) * | 2001-08-30 | 2012-05-09 | 株式会社ジーシー | Dental adhesive composition |
| CA2356579A1 (en) * | 2001-08-31 | 2003-02-28 | Micro Optics Design Corporation | Method, apparatus and adhesive composition for ophthalmic lens blocking |
| US20030199605A1 (en) * | 2002-04-23 | 2003-10-23 | Fischer Dan E. | Hydrophilic endodontic sealing compositions and methods for using such compositions |
| US20050173046A1 (en) * | 2002-08-26 | 2005-08-11 | Marc Savoie | Method, apparatus and adhesive composition for ophthalmic lens blocking |
| US6797767B2 (en) * | 2003-01-03 | 2004-09-28 | Pulpdent Corporation | Polymerizable composite material |
| JP4261288B2 (en) * | 2003-08-22 | 2009-04-30 | デンツプライ三金株式会社 | Dental adhesive composition |
| US20050255428A1 (en) * | 2004-05-14 | 2005-11-17 | Allan Coopersmith | Dental insert and method of tooth restoration |
| US7828550B2 (en) * | 2005-09-21 | 2010-11-09 | Ultradent Products, Inc. | Activating endodontic points and dental tools for initiating polymerization of dental compositions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1408265A (en) * | 1971-10-18 | 1975-10-01 | Ici Ltd | Photopolymerisable composition |
| GB1412754A (en) * | 1971-12-29 | 1975-11-05 | Ici Ltd | Photopolymerisable composition |
| GB1569021A (en) * | 1976-03-17 | 1980-06-11 | Kuraray Co | Adhesive cementing agents containing partial phosphonic orphosphonic acid esters |
| US4148988A (en) * | 1977-06-28 | 1979-04-10 | Mitsui Petrochemical Industries Ltd. | Curable composition |
| US4650847A (en) * | 1981-07-29 | 1987-03-17 | Kuraray Co., Ltd. | Adhesive composition |
| US4514342A (en) * | 1982-02-16 | 1985-04-30 | Dentsply Limited | Polyethylenically unsaturated monophosphates |
| US4521550A (en) * | 1983-01-10 | 1985-06-04 | American Dental Association Health Foundation | Method for obtaining strong adhesive bonding of composites to dentin, enamel and other substrates |
| JPS59140276A (en) * | 1983-01-31 | 1984-08-11 | Kuraray Co Ltd | Novel adhesive |
| JPS60202873A (en) * | 1984-03-27 | 1985-10-14 | G C Dental Ind Corp | Compound adhesive to dentin |
| DE3414165A1 (en) * | 1984-04-14 | 1985-10-17 | Kulzer & Co GmbH, 6393 Wehrheim | Photopolymerisable dental adhesive |
| DE3414163A1 (en) * | 1984-04-14 | 1985-10-17 | Kulzer & Co GmbH, 6393 Wehrheim | PHOTOPOLYMERIZABLE PHOSPHATE-CONTAINING DENTAL ADHESIVE LACQUER |
| DE3670076D1 (en) * | 1985-06-24 | 1990-05-10 | Tokuyama Soda Kk | ACRYLATE COMPOUND AND THE COMPOSITION CONTAINING IT. |
| DE3536077A1 (en) * | 1985-10-09 | 1987-04-09 | Muehlbauer Ernst Kg | POLYMERIZABLE ACID AND ACID DERIVATIVES COMPOUNDS, MIXTURES CONTAINING THE SAME AND THEIR USE |
| KR950003688B1 (en) * | 1986-10-30 | 1995-04-17 | 미쓰이세끼유 가가꾸 고오교오 가부시끼가이샤 | Curable coposition |
| JP2543516B2 (en) * | 1987-03-09 | 1996-10-16 | 三井石油化学工業株式会社 | Dental curable adhesive |
| JP2556854B2 (en) * | 1987-05-19 | 1996-11-27 | 宇部興産株式会社 | Light curable adhesive |
| DE3886868T2 (en) * | 1987-09-28 | 1994-04-28 | Daikin Ind Ltd | Adhesive composition for biomaterials. |
| US4863993A (en) * | 1987-12-09 | 1989-09-05 | Opi Products, Inc. | Surface priming composition for proteinaceous substrates; method of making and using same |
-
1990
- 1990-06-19 DE DE9090111505T patent/DE59001245D1/en not_active Expired - Fee Related
- 1990-06-19 AT AT90111505T patent/ATE88337T1/en not_active IP Right Cessation
- 1990-06-19 EP EP90111505A patent/EP0423430B1/en not_active Expired - Lifetime
- 1990-09-25 CA CA002026203A patent/CA2026203A1/en not_active Abandoned
- 1990-10-11 US US07/596,099 patent/US5089051A/en not_active Expired - Fee Related
- 1990-10-17 DE DE4032882A patent/DE4032882C2/en not_active Expired - Fee Related
- 1990-10-18 BR BR909005248A patent/BR9005248A/en not_active Application Discontinuation
- 1990-10-18 FI FI905136A patent/FI905136A0/en not_active Application Discontinuation
- 1990-10-18 JP JP2277946A patent/JPH03133912A/en active Pending
- 1990-10-18 NO NO90904517A patent/NO904517L/en unknown
- 1990-10-19 AU AU64809/90A patent/AU631689B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5932627A (en) | 1994-05-12 | 1999-08-03 | Dentsply Gmbh | Fluoride releasing dental primer composition and method |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0423430A2 (en) | 1991-04-24 |
| DE59001245D1 (en) | 1993-05-27 |
| EP0423430A3 (en) | 1991-07-24 |
| FI905136A0 (en) | 1990-10-18 |
| AU631689B2 (en) | 1992-12-03 |
| BR9005248A (en) | 1991-09-17 |
| NO904517D0 (en) | 1990-10-18 |
| JPH03133912A (en) | 1991-06-07 |
| ATE88337T1 (en) | 1993-05-15 |
| US5089051A (en) | 1992-02-18 |
| DE4032882C2 (en) | 1994-03-31 |
| NO904517L (en) | 1991-04-22 |
| AU6480990A (en) | 1991-04-26 |
| EP0423430B1 (en) | 1993-04-21 |
| DE4032882A1 (en) | 1991-04-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |