Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
  • C07F9/3826—Acyclic unsaturated acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
  • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
  • C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
  • C07F9/3821—Acyclic saturated acids which can have further substituents on alkyl substituted by B, Si, P or a metal

Definitions

• the invention relates to dental materials, in particular adhesion promoters or polymerizable cements such as, for example.
• adhesion promoters or polymerizable cements such as, for example.
• Compomers or glass ionomer cements with polymerizable acids as are known in principle from DE-A-3536076 and DE-A-3536077.
• Dental materials with polymerizable phosphoric acids as comonomers are known; they usually contain phosphoric acid and acrylates or methacrylates. From DE-A-19647140 it is known, for example, to esterify a hydroxyalkyl acrylate or methacrylate with phosphate.
• a disadvantage of these substances is the low stability to hydrolysis, since the ester bonds between phosphate and alkyl chain and between methacrylate and alkyl chain can easily be split hydrolytically. This reduces the storage stability of the dental material and leads to a reduced durability in the tooth under the conditions in the oral cavity.
• the dental materials contain phosphonic acids of the structure or salts of these acids given below:
• R alkyl group or alkylene group with at least 6 carbon atoms or aryl group
• R 7 H, methyl, ethyl, propyl, isopropyl or butyl, p is 1 or 2;
• R is H, alkyl or aryl, with R 8 is aryl or C n H 2n
• R 8 is C n H 2n -Si (R 5 ) 2 - [0-Si (R 5 ) 2 ] m -C n H 2n -
• R 5 is methyl, ethyl or phenyl
• R 8 is C n H 2n -COONH-C n H 2n where 4 ⁇ n ⁇ 12, and where R 8 has ether or other urethane groups can
• R 7 and p are as defined in a);
• R 10 selected from the group consisting of aryl groups, alkyl groups with at least 3 C atoms, or polyether groups with 1 to 10 polyether units, with R u selected identically or differently from the group consisting of alkyl groups and aryl groups, with X identical N, B or CH,
• R 7 COOR 9 , CONHR 9 , H or phenyl with R 9 selected from the group consisting of methyl, ethyl, propyl, isopropyl and butyl,
• the invention is based on the surprising finding that molecules with a relatively long-chain bridge between phosphonic acid group and reactive double bond, as defined in the claim, have high hydrolysis stability and, at the same time, improved adhesive properties.
• R 1 is hydrogen, an alkyl or aryl group.
• R x is preferably selected from the group consisting of hydrogen, methyl, ethyl and isopropyl.
• R 2 is an alkyl group with 4 to 18 carbon atoms, which can be unbranched or branched. It preferably contains 6 to 12 carbon atoms. Within the scope of the invention, R 2 can also be designed as an alkyl chain which is interrupted by ether groups or further urethane groups.
• the phosphonic acids have the following structure:
• R 3 or R 4 are aryl or alkyl groups.
• the alkyl groups can be unbranched or branched and preferably have 3 to 12 carbon atoms.
• the substituents R 5 are identical or different and represent methyl, ethyl or phenyl groups.
• M is 1 to 10.
• diphosphonates can preferably be used in the dental materials according to the invention:
• X is nitrogen, boron or a CH group
• R 6 is an unbranched or branched alkyl group with at least 3 C atoms, an aryl group or a polyether group with 1 to 10 polyether units
• the invention also relates to the use of a dental material according to the invention as an adhesion promoter, compomer or polymerizable cement.
• the dental material can consist exclusively of the phosphonic acids or their salts mentioned, it can contain one or more solvents and / or additional polymerizable monomers such as, in particular, acrylates or methacrylates.
• Suitable solvents for dental materials are familiar to the person skilled in the art; water, methanol, ethanol, isopropanol, acetone, ethyl methyl ketone, ethyl acetate and mixtures of the aforementioned substances are preferred.
• water-soluble methacrylates such as. B. Hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate is preferred.
• Other suitable (meth) acrylates are preferably (meth) acrylates which have at least two methacrylate groups, such as. B.
• Another acid in the form of a polymerizable carboxylic acid can also be added.
• Examples include maleic acid mono-2-methacryloyloxyethyl ester, phthalic acid mono-2-methacryloyloxyethyl ester and trimellitic acid mono-2-methacryloyloxyethyl ester.
• Dental materials according to the invention can in particular have the following ingredients:
• radical polymerization initiators - 0 to 2% by weight of radical polymerization initiators, - 0 to 80% by weight of fillers (depending on the intended application as an adhesion promoter, cement or compo mer)
• a proportion of 0-20% by weight of fillers is preferred for adhesion promoters; Cements and compomers are preferably solvent-free and the proportion of filler is preferably between 40 and 80% by weight.
• reaction mixture is diluted with 300 ml of water and 300 ml of 25% phosphoric acid are added with cooling. This mixture is extracted three times with 500 ml of dichloromethane, the organic phase is dried over MgSO 4 and the solvent is removed in vacuo. 42 g of a brown syrup are produced.
• the cooled batch is mixed in a solution from 1.16 ml of water and 10 ml of methanol and neutralized the sulfuric acid by adding a solution of 1.46 g of NaOH, 1.1 ml of water and 10 ml of methanol. In the end, however, the mixture must still maintain an acidic pH. The sodium sulfate is filtered off and the filtrate is completely concentrated in vacuo.
• composition of an adhesion promoter system consisting of a primer which contains one of the adhesive monomers according to the invention as an active substance, and a bond which is applied in a second step to a tooth substance previously provided with primer, is summarized below:
• Component 1 primer
• the individual substances of the primer are weighed into a glass vessel and mixed with stirring at room temperature until a homogeneous solution is obtained.
• the commercially available primer B from the Ecusit - Primer / Mono adhesion promoter system (Dental Material Deutschen mbH - Hamburg, Germany) is used as the bond.
• composition of an adhesion promoter system consisting of a component which contains, inter alia, one of the adhesion monomers according to the invention, is summarized in the table below.
• the individual substances of the adhesion promoter are weighed into a respective glass vessel and mixed with stirring at room temperature until a homogeneous solution is obtained.
• a shear bond test is carried out to measure the adhesion of composites to tooth hard substance using the adhesion promoters according to the invention.
• the primer from Example 4 is massaged into the ground dentin surface with a micro brush for 20 s.
• the same procedure is then followed with the bond from Example 4, the surface is blown and exposed for 20 s with a dental lamp (Translux EC, from Kulzer & Co GmbH, Wehrheim, Germany).
• a two-part Teflon mold with a 3.0 mm diameter cavity is placed on top, filled with a dental composite (Ecusit, Dental Material Weg mbH, Hamburg, Germany) and exposed for 40 s (Kulzer Translux EC).
• the adhesion promoter from Example 5 is massaged into the ground dentin surface with a micro brush for 20 s. The surface is then blown and exposed for 20 s with a dental lamp (Translux EC, Kulzer & Co GmbH, Wehrheim, Germany).
• the adhesion promoter from example 5 is massaged into the dentin surface again with a micro brush for 20 s, the surface is blown and exposed for 20 s with a dental lamp (Translux EC, from Kulzer & Co GmbH, Wehrheim, Germany).
• a two-part Teflon mold with a 3.0 mm diameter cavity is placed on it, with a dental composite (Ecusit, Dental Material Weg mbH, Hamburg, Germany) filled and exposed for 40 s (Kulzer Translux EC).
• Example 6 The bond from Example 6 is massaged into the ground dentin surface with a micro brush for 20 s, blown with compressed air and exposed for 20 s with a dental lamp (Translux EC, from Kulzer & Co GmbH, Wehrheim, Germany). A two-part Teflon mold with a 3.0 mm diameter cavity is placed on top, filled with a dental composite (Ecusit, Dental Material Weg mbH, Hamburg, Germany) and exposed for 40 s (Kulzer Translux EC).
• a dental lamp Translux EC

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Dental Preparations (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=8169179

Family Applications (1)

Country Status (5)

Cited By (10)

Families Citing this family (19)

Citations (3)

Family Cites Families (7)

• 2000
  • 2000-07-06 EP EP00114527A patent/EP1169996A1/de not_active Withdrawn
• 2001
  • 2001-07-03 EP EP01957913A patent/EP1296634B1/de not_active Expired - Lifetime
  • 2001-07-03 JP JP2002506680A patent/JP5128748B2/ja not_active Expired - Fee Related
  • 2001-07-03 US US10/332,344 patent/US6902608B2/en not_active Expired - Lifetime
  • 2001-07-03 WO PCT/EP2001/007602 patent/WO2002002057A1/de not_active Ceased
  • 2001-07-03 DE DE50107506T patent/DE50107506D1/de not_active Expired - Lifetime
• 2012
  • 2012-09-07 JP JP2012196901A patent/JP5681848B2/ja not_active Expired - Fee Related

Patent Citations (4)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events