Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • 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
  • A61K6/893—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
  • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
  • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
  • C08G18/6245—Polymers having terminal groups containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

Definitions

• the present invention describes di- or higher-functional free-radically curable urethane prepolymers and their use in polymerizable compositions.
• the invention further describes the use of the polymerizable compositions in the dental field, for example as filling materials, core build-up materials, fastening cements, provisional crown and bridge materials, dental materials, model materials or for the production of inlays, onlays, veneers, crowns and bridges.
• Materials suitable for such applications preferably have high impact strength, high elasticity with high hardness and low tendency to swell. These properties are essentially determined by the monomers used.
• suitable monomers are primarily ethylenically unsaturated compounds, such as acrylic acid and / or methacrylic acid esters.
• urethane (meth) acrylates for example in the dental industry, 7,7,9-trimethyl-4,13-dioxo-3,14, -dioxa-5,12-diazahexadecan-1, 16-dioxy- Dimethacrylate (eg Plex 666-1, Röhm) is used, which has little elasticity due to its low molecular weight and only slightly improves the impact resistance.
• Urethane (meth) acrylates based on polyether show a significantly lower susceptibility to hydrolysis.
• these systems due to their hydrophilicity, these systems have an increased water absorption and thus an increased tendency to swell and lower strength, which is associated with easy discoloration. Such systems are therefore not suitable for aesthetically demanding applications.
• polyether urethane (meth) acrylates Another disadvantage of polyether urethane (meth) acrylates is their lack of oxidation resistance as a result of the oxidative polyether chain degradation.
• the polybutadiene-urethane (meth) acrylates show excellent elastic properties, but they are easily discolored by the double bonds present due to short-wave radiation, such as that contained in sunlight.
• urethane (meth) acrylates can also be produced from low molecular weight aliphatic and / or aromatic diols. However, these do not show as good elastic and impact modifying properties as the above-mentioned urethane (meth) acrylates, which contain soft segments on polyester, polyether, polybutadiene and / or polycarbonate units.
• the object of the present invention is to provide monomers from which compositions can be formulated which have improved impact strength, with high hardness and good elasticity.
• (D) 1 to 40% by weight, preferably 2 to 35% by weight, of a monofunctional compound which is reactive towards isocyanate groups and which additionally has one or more radical-curable groups.
• compositions which have been formulated with the monomers according to the invention show extremely little swelling.
• the monomers are toxicologically harmless and are therefore particularly suitable for use in the dental field.
• the ⁇ , ⁇ -terminated poly (meth) acrylate diols of component (A) are compounds which have two terminal hydroxyl groups.
• Component (B) is a radical-curable compound, for example based on (meth) acrylate, which according to DIN 53 240 OH numbers preferably has from 40 to 700 mg KOH / g and particularly preferably from 80 to 500 mg KOH / g ,
• Suitable representatives are, for example, polyhydroxy-containing polyester (meth) acrylate prepolymers, as described in US Pat. No. 4,206,205, DE-OS-40 40 290, DE-OS-33 16 592, DE-OS-37 04 098 and in "UV & EB Curing Formulations for Printing Inks Coatings and Paints ", ed. R. Holman and P. Oldring, published by SITA Technology, London (England) 1988, pp. 36f.
• Polyepoxy (meth) acrylate prepolymers which are accessible by reacting polyepoxides with (meth) acrylic acid, and / or polyurethane (meth) acrylate prepolymers containing polyhydroxy groups are used.
• Particularly preferred representatives are polyepoxy (meth) acrylate prepolymers containing polyhydroxy groups, such as 2,2-bis- [p- (2'-hydroxy-3'-methacryloyloxypropoxy) phenyl] propane (bis-GMA) or 2,2-bis- [ p- (2'-Hydroxy-3'-acryloyloxypropoxy) phenyl] propane (bis-GA) and polyhydroxy group-containing (meth) acrylate esters, such as glycerol mono (meth) acrylate, trimethylolpropane mono (meth) acrylate or pentaerythhtdi (meth) acrylate.
• bis-GMA 2,2-bis- [p- (2'-hydroxy-3'-methacryloyloxypropoxy) phenyl] propane
• bis-GA 2,2-bis- [ p- (2'-Hydroxy-3'-acryloyloxypropoxy) phenyl] propane
• Suitable polyisocyanates of component (C) are aliphatic, cycloaliphatic and / or aromatic in nature and have at least two free isocyanate groups.
• Diisocyanates X (NCO) 2 are preferably used, where X is an aliphatic hydrocarbon radical having 2 to 12 C atoms, a cycloaliphatic hydrocarbon radical having 5 to 18 C atoms aromatic hydrocarbon radical having 6 to 16 carbon atoms and / or an araliphatic hydrocarbon radical having 7 to 15 carbon atoms.
• diisocyanates examples include: 1,4-tetramethylene diisocyanate, 1,4-hexamethylene diisocyanate (HDI), 2,4,4-thmethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, meta- and para-tetramethylxylene diisocyanate, 1,4 -Phenylene diisocyanate, 2,6- and 2,4-toluene diisocyanate, 1, 5-naphthylene diisocyanate, 2,4 'and 4,4'--
• polyfunctional polyisocyanates known from polyurethane chemistry or to use modified polyisocyanates, for example those containing carbodiimide groups, allophanate groups, isocyanurate groups and / or biuret groups.
• modified polyisocyanates for example those containing carbodiimide groups, allophanate groups, isocyanurate groups and / or biuret groups.
• Particularly preferred isocyanates are isophorone diisocyanate and 2,4,4-trimethylhexamethylene diisocyanate.
• Compounds of component (D) have a functional group which is reactive toward isocyanates, for example a hydroxyl group or amino group, and moreover have one or more radical-curable groups.
• the radical-curable groups are preferably based on (meth) acrylate.
• the representatives of this component (D) can also be used as a mixture.
• Suitable representatives are, for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol di (meth) acrylate and / or
• Trimethylolpropane di (meth) acrylate. 2- are particularly preferred
• HEMA Hydroxyethyl methacrylate
• HOA 2-hydroxyethyl acrylate
• components (A) to (C), for example, are placed in a reactor or individually metered in and under anhydrous conditions, for example in a temperature range from -20 ° C to 160 ° C, preferably in a temperature range from 0 ° C to 130 ° C and particularly preferably in a temperature range from 20 ° C to 100 ° C to form an NCO containing prepolymers implemented.
• the equivalent ratio of isocyanate groups to compounds reactive towards isocyanate groups is 1.1: 1 to 8: 1, preferably 1.5: 1 to 4: 1.
• the isocyanate polyaddition reaction can take place in the presence of catalysts known from polyurethane chemistry, for example organo-tin compounds such as dibutyltin dilaurate or amine catalysts such as diazabicyclo [2.2.2] octane.
• organo-tin compounds such as dibutyltin dilaurate or amine catalysts such as diazabicyclo [2.2.2] octane.
• the synthesis can take place both in the melt and in a suitable solvent which can be added before or during the prepolymer preparation.
• suitable solvents are, for example, acetone, 2-butanone, tetrahydrofuran, dioxane, dimethylformamide, N-methyl-2-pyrrolidone (NMP), ethyl acetate, alkyl ethers of ethylene and propylene glycol and aromatic hydrocarbons.
• NMP N-methyl-2-pyrrolidone
• Component (D) is metered in completely or in portions to the NCO-containing prepolymers and, for example, in a temperature range from -20 ° C to 160 ° C, preferably in a temperature range from 0 ° C to 130 ° C and particularly preferably in a temperature range reacted from 20 C C to 100 ° C.
• the amount of component (D) to be used depends on the unreacted isocyanate groups of the prepolymer which are still present.
• the isocyanate content of the prepolymer is determined, for example, in accordance with DIN 53 185.
• the weight average molecular weight (M between 400 and 200,000 g / mol, preferably between 500 and 100,000 g / mol and particularly preferred) obtained from GPC measurements against polystyrene standards are between 600 and 50,000 g / mol.
• the molecular weights can also be outside these ranges, provided that the use of the polyurethane prepolymers according to the invention permits this.
• the urethane prepolymers according to the invention are suitable, for example, for producing curable compositions, such as dental compositions, or for coating, casting and gluing substrates.
• Curable formulations for example for use in the dental field, preferably contain the following components:
• compositions formulated with the urethane prepolymers according to the invention are notable for particularly good impact strength, good elasticity with high hardness and surprisingly low tendency to swell.
• Mono-, di- or higher-functional ethylenically unsaturated compounds preferably based on acrylate and / or methacrylate, are used as component (K2) used.
• component (K2) used can include both monomeric and higher molecular weight oligomeric or polymeric acrylates. Furthermore, they can be used in the formulations alone or in a mixture.
• Suitable monomers are, for example, the acrylic acid and methacrylic acid esters of mono-, di- or higher-functional alcohols. Examples include: methyl (meth) acrylate, isobutyl (meth) acrylate,
• Ethylene glycol di (meth) acrylate Ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate (TEGDMA), hexanediol di (meth) acrylate, dodecanediol di (meth) acrylate and trimethylolpropane tri (meth) acrylate.
• TEGDMA triethylene glycol di (meth) acrylate
• hexanediol di (meth) acrylate hexanediol di (meth) acrylate
• dodecanediol di (meth) acrylate trimethylolpropane tri (meth) acrylate.
• Bisphenol-A-di (meth) acrylate and the ethoxy- or propoxylated di (meth) acrylates derived therefrom can also be used advantageously.
• the monomers described in US Pat. No. 3,066,112 based on bisphenol A and glycidyl (meth) acrylate or their derivatives formed by addition of isocyanates are also suitable.
• diacryl and dimethacrylic acid esters of bis (hydroxymethyl) tricyclo [5.2.1.0 2 ' 6 ] decane mentioned in DE-C-28 16 823 and the diacryl and dimethacrylic acid esters of those with 1 to 3 ethylene oxide and / or propylene oxide units extended compounds of bis (hydroxymethyl) tricyclo [5.2.1.0 26 ] decane.
• Urethane (meth) acrylates such as 7,7,9-trimethyl-4,13-dioxo-5,12-diazahexadecane-1, 16-dioxy-dimethacrylate (UDMA), can also be part of component (K2).
• Fillers according to component (K3) can be inorganic fillers, for example quartz, ground glasses, non-water-soluble fluorides such as CaF 2 , silica gels and silica, in particular pyrogenic silica and their
• Fluoride-triggering fillers for example complex inorganic fluorides of the general formula A n MF m as described in DE-A-44 45 266, can also be used or added.
• A is a mono- or polyvalent cation
• M is a metal from the III, IV, V main or subgroup
• n is an integer from 1 to 3
• m is an integer from 4 to 6.
• Organic fillers can also be part of component (K3).
• component (K3) examples include customary pearl-shaped polymers and copolymers based on methyl methacrylate, which are available, for example, from Röhm under the name "Plexidon” or "Plex”.
• silanes for example
• the maximum average grain size of the inorganic fillers is preferably 15 ⁇ m, in particular 8 ⁇ m. Fillers with an average grain size of ⁇ 3 ⁇ m are very particularly preferably used.
• Initiators according to component (K4) are understood to mean initiator systems which bring about the radical polymerization of the monomers, for example photoinitiators and / or so-called redox initiator systems and / or thermal initiators.
• Suitable photoinitiators are, for example, ⁇ -diketones, such as camphorquinone, in conjunction with secondary and tertiary amines, or mono- and bisacylphosphine oxides, such as 2,4,6-thmethylbenzoyldiphenylphosphine oxide and bis- (2,6-dichlorobenzoyl) -4-n propylphenyl phosphine oxide.
• EP-A-0 073 413 EP-A-0 007 508, EP-A-0 047 902, EP-A-0 057 474 and EP A-0 184 095.
• Organic peroxide compounds together with so-called activators are suitable as redox initiator systems.
• Suitable organic peroxide compounds are, in particular, compounds such as lauroyl peroxide, benzoyl peroxide and p-chlorobenzoyl peroxide and p-methylbenzoyl peroxide.
• Suitable activators are, for example, tertiary aromatic amines, such as the N, N-bis (hydroxyalkyl) -3,5-xylidines known from US Pat. No. 3,541,068 and the N known from DE-A-26 58 530.
• N-bis (hydroxyalkyl) -3,5-di-t-butylaniline in particular N, N-bis ( ⁇ -oxybutyl) -3,5-di-t-butylaniline and N, N-bis (hydroxyalkyl) -3,4,5-trimethylaniline.
• Suitable activators are also the barbituric acids and barbituric acid derivatives described in DE-B-14 95 520 and the malonyl sulfamides described in EP-A-0 059 451.
• Preferred malonyl sulfamides are 2,6-dimethyl-4-isobutylmalonylsulfamide, 2,6-diisobutyl-4-propylmalonylsulfamide, 2,6-dibutyl-4-propylmalonylsulfamide, 2,6-dimethyl-4-ethylmalonylsulfamide and 2,6-dioctyl-4 -isobutylmalonylsulfamid.
• the polymerization is preferably carried out in the presence of heavy metal compounds and ionic halogen or pseudohalogen.
• Copper is particularly suitable as a heavy metal and chloride ion as a halide.
• the heavy metal is suitably used in the form of soluble organic compounds.
• the halide and pseudohalide ions are suitably used in the form of soluble salts, for example the soluble amine hydrochlorides and quaternary ammonium chloride compounds.
• the dental compositions according to the invention contain a redox initiator system composed of organic peroxide and activator, then peroxide and activator are preferably present in spatially separate parts of the dental composition according to the invention, which are homogeneously mixed with one another only immediately before use. If there are organic peroxide, copper compound, halide and malonylsulfamide and / or barbituric acid next to one another, it is particularly expedient that organic peroxide, malonylsulfamide and / or barbituric acid and the combination of copper compound / halide are present in three spatially separated components.
• the combination of copper compound / halide, polymerizable monomers and fillers can be kneaded into a paste and the other components in the manner described above each with a small amount of fillers or, in particular, thixotropic auxiliaries, such as silanized silica, and a plasticizer, for example phthalate knead two separate pastes.
• the polymerizable monomers can also be present together with organic peroxide and fillers.
• organic peroxide, copper compound, halide and malonyl sulfamide and / or barbituric acid can also be divided according to DE-A-199 28 238.
• soluble organic polymers can be used, for example, to increase the flexibility of the compositions.
• thixotropy aids can also be modified Layered silicates (bentonites) or organic modifiers, for example based on hydrogenated castor oils, are used.
• Layered silicates bentonites
• organic modifiers for example based on hydrogenated castor oils
• the components according to the invention can, for example, be distributed over two pastes as follows:
• Dental materials which contain the urethane prepolymers according to the invention can be used, for example, as filling materials, cements, provisional crown and bridge materials, veneering plastics, prosthesis materials, orthodontic materials, plastics for fissure sealing, modeling plastics or model plastics.
• the urethane prepolymers according to the invention and formulations produced therefrom are also suitable for the bonding and coating of substrates.
• the coating of wood, metal, glass or plastic may be mentioned as an example.
• the urethane prepolymers according to the invention and formulations produced therefrom are also suitable, for example, for the production of moldings.
• compositions containing the urethane prepolymers according to the invention are preferably formulated as two-component mixtures, these preferably being filled into a cartridge system and the compositions being applied, homogeneously mixed and cured via a static or dynamic mixing attachment.
• the invention is described in more detail below with reference to examples, which are not to be understood in any way as limiting the invention.
• the components listed in Table 1 and Table 2 are each 10g catalyst and 100g base paste kneaded. These are filled in 10: 1 cartridges from Mixpack, Rotnch. For use, they are pressed through a static mixing device by means of a dispenser and mixed in the process, so that curing takes place within a few minutes.
• test specimens produced with the non-inventive pastes 3 and 4 show, compared to the test specimens made from pastes according to the invention (bases 1 and 2), an increased swelling, a reduced modulus of elasticity and a greatly reduced impact strength.

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• Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oral & Maxillofacial Surgery (AREA)
• Life Sciences & Earth Sciences (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Epidemiology (AREA)
• Plastic & Reconstructive Surgery (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Dental Preparations (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Materials For Medical Uses (AREA)

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• 1999
  • 1999-12-17 DE DE19961342A patent/DE19961342B4/de not_active Expired - Fee Related
• 2000
  • 2000-12-15 US US10/149,607 patent/US7141616B2/en not_active Expired - Lifetime
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