Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/20—Protective coatings for natural or artificial teeth, e.g. sealings, dye coatings or varnish
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
  • C08F222/10—Esters
  • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
  • C08F222/106—Esters of polycondensation macromers

Definitions

• the present invention relates to dental materials comprising calix[n]arenes having low polymerization shrinkage and comparable mechanical properties.
• Calix[n]arenes are cyclic oligomers, known as 1 n -metacyclophanes (Scheme 1, formula 1), which are accessible by condensation of p-alkylphenols with formaldehyde (Scheme 1, formula 2) or of resorcinol with aldehydes (Scheme 1, formula 3), the phenolic OH groups being arranged in the endo (intraannular) or exo (extraannular) position.
• the particular bowl- or cup-like conformation of the calix[n]arenes has resulted in numerous applications in catalysis, chromatography, analysis or sensor technology (V. Böhmer, Angew. Chem., 107 (1995), 785-818).
• calix[n]arenes in combination with polymerizable formulations is known from the patent literature.
• U.S. Pat. No. 4,636,539, U.S. Pat. No. 4,718,966, U.S. Pat. No. 4,912,183, EP 235 935 and FR 2 795 077 describe the use of calix[n]arenes, not modified reactively, as accelerators for cyanoacrylate adhesives.
• U.S. Pat. No. 4,699,966 describes calix[n]arenes functionalized with acrylate or methacrylate groups and polymers thereof as sequestering agents for metal ions. Additional, more specific, polymerizable calix[n]arene and oxacalixarene derivatives with at least one phenolic side group are described in U.S. Pat. No. 5,216,185.
• JP 09-263560 describes calix[n]arene derivatives which are functionalized with (meth)acrylate, vinyl or propenyl groups and can be polymerized thermally or photochemically.
• JP 11-043524 describes similar systems which, however, are additionally modified with polyalkylene oxide groups.
• JP 2004-137395 claims a cellulose acrylate film comprising a polymerizable calix[n]arene derivative with the advantage of improved mechanical and optical properties.
• JP 2002-003563 and JP 09-263560 describe calix[n]arene derivatives comprising polymerizable groups (acrylate, methacrylate, vinyl, vinyl ether, and the like) and acid or anhydride groups. These find use as etching resists, adhesives, lacquers or coatings.
• GB 2 185 261 describes a radically polymerizable composition as adhesive filler comprising a calix[n]arene derivative.
• JP 02-124850 describes the preparation of calix[n]arene derivatives by heating p-tert-butylcalix[6]arenes with glycidyl methacrylate and tri(n-butyl)amine.
• U.S. Pat. No. 4,617,336 and CA 1 273 954 describe calixarenes with acrylate groups for the stabilizing of organic materials, in particular polymers.
• JP 2000-256362 describes polymerizable calix[n]arene derivatives which are functionalized with spiroorthoester groups. These compounds, which are distinguished by a polymerization without shrinkage in volume, are suitable, inter alia, for use as coating materials.
• JP 2000-264953 describes, finally, curable epoxy resins which acquire advantageous properties by addition of calix[n]arenes, such as a high crosslinking density, high resistance to heat and good mechanical properties.
• WO 2005/120229 describes substances which release terpenes and/or aromatic alcohols.
• the substances and compositions depicted can, inter alia, also comprise calix[n]arenes and are used, first and foremost, to prevent microorganisms from adhering to surfaces.
• compositions are described which prevent the development of microorganisms in jointing compounds.
• compositions comprising calix[n]arene for the cleaning of prostheses is described.
• U.S. Pat. No. 4,699,966 describes calix[n]arenes and polymers prepared therefrom, the calix[n]arenes being mixed with an initiator and polymerized using light.
• the use as filler-comprising dental material or as component in such materials is not described.
• EP 1 712 537 A1 describes a multitude of different calix[n]arenes in different compositions. These, though, comprise no filler and no additional radically polymerizable components.
• EP 432 990 A2 describes filler-free compositions for the masking and coating of metals. The materials are cured from a solution using actinic radiation. Filler-comprising dental materials with calix[n]arene are not disclosed.
• EP 196 895 B1 describes filler-free adhesive compositions which contain no filler.
• the polymers produced comprise calix[n]arene sequences.
• WO 2005/056741 A1 describes non-stick compositions. These are devoid of filler and have, as coating, even for prostheses and dental or oral care products, no direct reference to dental materials, which concern materials for the preservation or reconstruction of the masticatory apparatus. Filler-comprising compositions for dental use are not disclosed.
• WO 94/15907 A1 describes calix[n]arenes comprising cyano groups which are used devoid of filler and for which a slight shrinkage was observed. Filler-comprising dental materials are not disclosed.
• dental materials which, in comparison with the conventional materials based on normal methacrylates, are distinguished by a lower polymerization shrinkage and good mechanical properties and, in addition, allow additional advantageous properties, such as, e.g., self-adhesion, to be obtained.
• calix[n]arenes of the general formula (I): in which
• Y b 1 not present or O, ester, amide or urethane
• calix[n]arenes of the general formula (I) used according to the invention can be obtained, starting from suitably functionalized calix[n]arenes, by reaction with appropriate polymerizable compounds comprising acid groups.
• homogeneously substituted polymerizable calix[n]arenes can be prepared by modifying HO-functionalized calix[n]arenes with methacryloyl chloride:
• Nonhomogeneously substituted polymerizable calix[n]arenes can be analogously prepared by modifying HO-functionalized calix[n]arenes with mixtures of polymerizable acid chlorides, such as, e.g., methacryloyl and acryloyl chloride.
• polymerizable calix[n]arenes carrying additional acid groups can be synthesized by sequential reaction, e.g. polymerizable calix[n]arenes with dihydrogenphosphate groups by partial reaction with methylacryloyl chloride, followed by phosphorylation with phosphoryl chloride.
• Suitable functionalized calix[n]arenes for the synthesis of the polymerizable calix[n]arenes according to the invention corresponding to the general formula (I) are known from the literature; a survey thereof can be found in the review by V. Böhmer (Angew. Chem., 107 (1995), 785-818).
• differently substituted calixarenes can be synthesized stepwise by alternating hydroxymethylation and condensation steps and, finally, subsequent cyclization of the linear oligomers thus obtained.
• Suitable functionalized cyclic monomers for the synthesis of calix[n]arenes of the general formula (I) which can polymerize under radical conditions by ring opening are known from the literature.
• the synthesis of vinylcyclopropanes and of bicyclic cyclopropylacrylates is described by N. Moszner et al., Macromol. Rapid. Commun., 18 (1997), 775-780, or A. de Meijere et al., Eur. J. Org. Chem., 2004, 3669-3678.
• the synthesis of functionalized cyclic allyl sulphides has been published by R. A. Evans and E. Rizzardo in J. Polym. Sci., Part A. Polym. Chem., 39 (2001), 202-215; Macromolecules, 33 (2000), 6722-6731.
• the calix[n]arenes corresponding to the general formula (I) which can polymerize under radical conditions used according to the invention allow the preparation of dental materials which, in comparison with the conventional materials based on normal dimethacrylates, are distinguished by a lower polymerization shrinkage and good mechanical properties and, in addition, it is possible, e.g. by the use of calix[n]arenes corresponding to the general formula (I) which can polymerize under radical conditions and which comprise acid groups, to obtain additional properties, such as, e.g., self-adhesion.
• the materials according to the invention find use as self-adhesive dental materials, e.g. filling composites, cements and coating materials.
• the dental materials according to the invention can be used as adhesives.
• compositions according to the invention are focused on the use in the dental field, these materials have a broad range of uses, e.g. they can be used as protective and masking lacquers for optics, electronics and the motor vehicle industry.
• calix[n]arenes corresponding to the general formula (I) which can polymerize under radical conditions used according to the invention can be used in a mixture with conventional monomers which can polymerize under radical conditions, in particular with difunctional (meth)acrylate crosslinking agents.
• Suitable with regard to this are in particular crosslinking di- or polyfunctional acrylates or methacrylates, such as, e.g., bisphenol A di(meth)acrylate, Bis-GMA (an addition product of methacrylic acid and bisphenol A diglycidyl ether), UDMA (an addition product of 2-hydroxyethyl methacrylate and 2,2,4-trimethylhexamethylene diisocyanate), di-, tri- or tetraethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythrityl tetra(meth)acrylate, and 1,4-butanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate or 1,12-dodecanediol di(meth)acrylate.
• di- or polyfunctional acrylates or methacrylates such as, e.g., bisphenol A di(meth)acrylate,
• calix[n]arenes corresponding to the general formula (I) which can polymerize under radical conditions in a mixture with known monomers which can polymerize under radical conditions by ring opening with little shrinkage, such as, e.g., mono- or polyfunctional vinylcyclopropanes or bicyclic cyclopropaneacrylate derivatives (cf. DE 196 16 183 C2 or EP 03 022 855) or cyclic allyl sulphides (cf. U.S. Pat. No. 6,043,361 or U.S. Pat. No. 6,344,556), which, in addition, can also be used in combination with the di(meth)acrylate crosslinking agents listed above.
• mono- or polyfunctional vinylcyclopropanes or bicyclic cyclopropaneacrylate derivatives cf. DE 196 16 183 C2 or EP 03 022 855
• cyclic allyl sulphides cf. U.S. Pat. No. 6,043,361 or U.S. Pat. No
• Preferred monomers which can polymerize by ring opening are such vinylcyclopropanes as 1,1-di(ethoxycarbonyl)- or 1,1-di(methoxycarbonyl)-2-vinylcyclopropane or the esters of 1-ethoxycarbonyl- or 1-methoxycarbonyl-2-vinylcyclopropanecarboxylic acid with ethylene glycol, 1,1,1-trimethylolpropane, 1,4-cyclohexanediol or resorcinol.
• Preferred bicyclic cyclopropane derivatives are 2-(bicyclo[3.1.0]hex-1-yl)acrylic acid methyl or ethyl ester or the disubstitution products in the 3 position thereof, such as (3,3-bis(ethoxycarbonyl)bicyclo[3.1.0]hex-1-yl)acrylic acid methyl or ethyl ester.
• Preferred cyclic allyl sulphides are in particular the addition products of 2-(hydroxymethyl)-6-methylene-1,4-dithiepane or 7-hydroxy-3-methylene-1,5-dithiacyclooctane with 2,2,4-trimethylhexamethylene 1,6-diisocyanate or the asymmetric hexamethylene diisocyanate trimer Desmodur® VP LS 2294 from Bayer AG.
• calix[n]arenes corresponding to the general formula (I) which can polymerize under cationic conditions according to the invention in a mixture with known monomers which can polymerize under cationic conditions by ring opening with low shrinkage, such as, e.g., glycidyl ethers or cycloaliphatic epoxides, cyclic ketene acetals, spiroorthocarbonates, oxetanes or bicyclic orthoesters.
• Examples are: 2-methylene-1,4,6-trioxaspiro[2.2]nonane, 3,9-dimethylene-1,5,7,11-tetraoxaspiro[5.5]undecane, 2-methylene-1,3-dioxepane, 2-phenyl-4-methylene-1,3-dioxolane, bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexane dioxide, 3-ethyl-3-(hydroxymethyl)oxetane, 1,10-decanediylbis(oxymethylene)bis(3-ethyloxetane) or 3,3-(4-xylylenedioxy)bis(methyl-3-ethyloxetane) or additional epoxides mentioned in EP 0 879 257
• Silica polycondensates which can be obtained, for example, by hydrolytic condensation of silanes carrying groups which can polymerize under cationic conditions, preferably, e.g., epoxide, oxetane or spiroorthoester groups, are also suitable as matrix systems which can polymerize under cationic conditions.
• silica polycondensates are described, for example, in DE 41 33 494 C2 or U.S. Pat. No. 6,096,903.
• the dental materials according to the invention based on the calix[n]arenes corresponding to the general formula (I) which can polymerize under radical conditions can be polymerized using the known radical initiators (cf. Encyclopaedia of Polymer Science and Engineering, Vol. 13, Wiley-Intersci. Pub., New York, etc., 1988, 754ff.). Photoinitiators (cf. J. P. Fouassier and J. F. Rabek (Ed.), Radiation Curing in Polymer Science and Technology, Vol.
• UV or visible region such as, e.g.: benzoin ethers, dialkyl benzil ketals, dialkoxyacetophenones, acyl- or bisacylphosphine oxides, or ⁇ -diketones, such as 9,10-phenanthrenequinone, diacetyl, furil, anisil, 4,4′-dichlorobenzil and 4,4′-dialkoxybenzil and camphorquinone, are particularly suitable.
• azo compounds such as 2,2′-azobis(iso-butyronitrile) (AIBN) or azobis(4-cyanovaleric acid), or peroxides, such as dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroctoate, tert-butyl perbenzoate or di(tert-butyl)peroxide, can also be used.
• Benzopinacol and 2,2′-dialkylbenzopinacols are suitable as initiators for heat curing.
• Combinations with aromatic amines are also frequently preferred in order to accelerate the initiation using peroxides or ⁇ -diketones.
• Redox systems which have already proven to be worthwhile are: combinations of benzoyl peroxide or camphorquinone with amines, such as N,N-dimethyl-p-toluidene, N,N-di(hydroxyethyl-p-toluidene, ethyl p-(dimethylamino)benzoate or structurally related systems.
• redox systems consisting of peroxides and such reducing agents as, e.g., ascorbic acid, barbiturates or sulphinic acids are also suitable.
• the dental materials according to the invention based on the calix[n]arenes corresponding to the general formula (I) which can polymerize under cationic conditions can be cured with the known cationic photoinitiators, in particular with diaryliodonium or triarylsulphonium salts, if appropriate in the presence of suitable sensitizers, such as, e.g., camphorquinone.
• suitable sensitizers such as, e.g., camphorquinone.
• diaryliodonium salts which can be used in the visible region with camphorquinone or thioxanthones as sensitizer are the commercially accessible (4-octyloxyphenyl)phenyliodonium hexafluoroantimonate or (isopropylphenyl)(methylphenyl)iodonium tetrakis(pentafluorophenyl)borate.
• the dental materials according to the invention based on the polymerizable calix[n]arenes can comprise one or more fillers, preferably organic or inorganic particulate fillers.
• Preferred inorganic particulate fillers are amorphous spherical nanoparticulate fillers based on oxides, such as pyrogenic silica or precipitated silica, ZrO 2 and TiO 2 or mixed oxides of SiO 2 , ZrO 2 and/or TiO 2 with a mean particle size of 10 to 200 nm, minifillers, such as quartz, glass ceramic or glass powders with a mean particle size of 0.2 to 5 ⁇ m, and also fillers which are opaque to X-rays, such as ytterbium trifluoride or nanoparticulate tantalum(V) oxide or barium sulphate.
• fibrous fillers such as glass fibres, polyamide fibres or carbon fibres, can also be used.
• additives such as, e.g., stabilizers, UV absorbers, dyes or pigments, and also solvents, such as, e.g., water, ethanol, acetone or ethyl acetate, or lubricants, can, if required, be added to the dental materials according to the invention based on the polymerizable calix[n]arenes.
• the dental materials according to the invention are composed, depending on the intended purpose, preferably of the following components:
• Filling composites according to the invention preferably comprise:
• Coating materials according to the invention preferably comprise:
• Dental adhesives according to the invention preferably comprise:
• R 1 to R 6 random mixture of
• the clear brown solution obtained is precipitated from 500 ml of water, filtration is carried out and finally drying is carried out under high vacuum.
• the yield of product is 1.5 g.
• the MALDI-TOF analysis of the product gave a mixture of products of the 1-6-fold reaction of p-tert-butylcalix[6]arene with GMA.
• a composite fixing cement based on a methacrylate mixture (Material A, Comparison) and with incorporation of the calix[6]arene V-15 from Example 2 (Material B) was prepared in accordance with the Table 1 listed below using an “Exact” roller mill (Exakt Apparatebau, Norderstedt).
• Corresponding test specimens were prepared from the materials, which were exposed to a dental light source (Spectramat®, Ivoclar Vivadent AG) for 2 times 3 minutes and accordingly cured.
• the flexural strength and the flexural E-modulus were determined according to the ISO standard ISO-4049 (Dentistry—Polymer-based filling, restorative and luting materials).
• a filling composite based on a methacrylate mixture (Material C, Comparison) and with incorporation of the calix[6]arene V-15 from Example 2 (Material D) was prepared in accordance with the Table 3 listed below using an LPM 0.1 SP kneader (Linden, Marienheide). Test specimens were prepared and cured from the materials analogously to Example 3. The flexural strength, the flexural E-modulus and the polymerization shrinkage were determined according to the ISO standard ISO-4049.
• a filling composite based on a methacrylate mixture (Material E, Comparison) and with incorporation of the calix[6]arene V-9 from Example 1 (Material F) was prepared with the components in Table 5 using a VPL 1.5 kneader (Grieser, Lampertheim). Test specimens conforming to standard specifications were prepared and cured from the materials. The flexural strength, the flexural E-modulus and the polymerization shrinkage or the polymerization shrinking stress were determined according to the ISO standard ISO-4049.
• a filling composite based on a methacrylate mixture (Material E, Comparison) and with incorporation of the calix[4]arene V-10 from Example 3 (Material G) was prepared with the components in Table 6 using a VPL 1.5 kneader (Grieser, Lampertheim). Test specimens conforming to standard specifications were prepared and cured from the materials. The flexural strength, the flexural E-modulus and the polymerization shrinkage or the polymerization shrinking stress were determined according to the ISO standard ISO-4049.

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• 2007
  • 2007-07-30 DE DE102007035734A patent/DE102007035734A1/de not_active Ceased
  • 2007-08-08 AT AT07113977T patent/ATE499922T1/de active
  • 2007-08-08 EP EP07113977A patent/EP1970042B1/de not_active Not-in-force
  • 2007-08-08 DE DE502007006600T patent/DE502007006600D1/de active Active
  • 2007-08-29 US US11/897,228 patent/US20080058443A1/en not_active Abandoned
  • 2007-08-29 JP JP2007222584A patent/JP5383012B2/ja not_active Expired - Fee Related
• 2010
  • 2010-08-18 US US12/859,052 patent/US8466212B2/en not_active Expired - Fee Related

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