NO754397L - - Google Patents
Info
- Publication number
- NO754397L NO754397L NO754397A NO754397A NO754397L NO 754397 L NO754397 L NO 754397L NO 754397 A NO754397 A NO 754397A NO 754397 A NO754397 A NO 754397A NO 754397 L NO754397 L NO 754397L
- Authority
- NO
- Norway
- Prior art keywords
- approx
- weight
- bis
- dimethylaniline
- hydroxyethyl
- Prior art date
Links
- 239000000463 material Substances 0.000 claims description 76
- 239000000203 mixture Substances 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 25
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 16
- 238000011049 filling Methods 0.000 claims description 16
- 239000012933 diacyl peroxide Substances 0.000 claims description 15
- DMTMWMUHQLDCKP-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-3,4-dimethylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1C DMTMWMUHQLDCKP-UHFFFAOYSA-N 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 14
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 claims description 11
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 7
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 7
- 239000011256 inorganic filler Substances 0.000 claims description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 7
- 150000002978 peroxides Chemical class 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- -1 methacryloxy group Chemical group 0.000 claims description 4
- SZSSMFVYZRQGIM-UHFFFAOYSA-N 2-(hydroxymethyl)-2-propylpropane-1,3-diol Chemical compound CCCC(CO)(CO)CO SZSSMFVYZRQGIM-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 3
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 description 22
- 239000011230 binding agent Substances 0.000 description 11
- 239000003381 stabilizer Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- DOLQYFPDPKPQSS-UHFFFAOYSA-N 3,4-dimethylaniline Chemical compound CC1=CC=C(N)C=C1C DOLQYFPDPKPQSS-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- JUVSRZCUMWZBFK-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-4-methylanilino]ethanol Chemical compound CC1=CC=C(N(CCO)CCO)C=C1 JUVSRZCUMWZBFK-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- JWQRYFYKHVZIDQ-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)-3,5-dimethylanilino]ethanol Chemical group CC1=CC(C)=CC(N(CCO)CCO)=C1 JWQRYFYKHVZIDQ-UHFFFAOYSA-N 0.000 description 4
- LDLCZOVUSADOIV-UHFFFAOYSA-N 2-bromoethanol Chemical compound OCCBr LDLCZOVUSADOIV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010348 incorporation Methods 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 230000002028 premature Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 208000002925 dental caries Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000006748 scratching Methods 0.000 description 2
- 230000002393 scratching effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011043 treated quartz Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- KIZCNUWGIVQQBK-UHFFFAOYSA-N (2-hydroxy-4-methylphenyl)-phenylmethanone Chemical compound OC1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 KIZCNUWGIVQQBK-UHFFFAOYSA-N 0.000 description 1
- IKICZOHPLZWTNX-UHFFFAOYSA-N 1-[n-(2-hydroxypropyl)-3,4-dimethylanilino]propan-2-ol Chemical compound CC(O)CN(CC(C)O)C1=CC=C(C)C(C)=C1 IKICZOHPLZWTNX-UHFFFAOYSA-N 0.000 description 1
- AFTBJQDQENGCPC-UHFFFAOYSA-N 2,5-ditert-butyl-4-methylphenol Chemical compound CC1=CC(C(C)(C)C)=C(O)C=C1C(C)(C)C AFTBJQDQENGCPC-UHFFFAOYSA-N 0.000 description 1
- JLZIIHMTTRXXIN-UHFFFAOYSA-N 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1C(O)=O JLZIIHMTTRXXIN-UHFFFAOYSA-N 0.000 description 1
- SIIHWPUTOQJUCK-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethyl-diphenylsilyl]ethyl 2-methylprop-2-enoate Chemical compound C(C(=C)C)(=O)OCC[Si](C1=CC=CC=C1)(C1=CC=CC=C1)CCOC(C(=C)C)=O SIIHWPUTOQJUCK-UHFFFAOYSA-N 0.000 description 1
- SXFHOXJWTISVLQ-UHFFFAOYSA-N 2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxycarbonyloxy]phenyl]propan-2-yl]phenoxy]carbonyloxyethyl 2-methylprop-2-enoate Chemical compound C1=CC(OC(=O)OCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)OCCOC(=O)C(C)=C)C=C1 SXFHOXJWTISVLQ-UHFFFAOYSA-N 0.000 description 1
- OAEQQQRHHSOVBJ-UHFFFAOYSA-N 4-[N-(4-hydroxybutyl)-3,4-dimethylanilino]butan-1-ol Chemical compound OCCCCN(C1=CC(=C(C=C1)C)C)CCCCO OAEQQQRHHSOVBJ-UHFFFAOYSA-N 0.000 description 1
- 241000283707 Capra Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- OLPICQSAMHSDPR-UHFFFAOYSA-N [3-[3-[2,3-bis(2-methylprop-2-enoyloxy)propoxy]phenoxy]-2-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC1=CC=CC(OCC(COC(=O)C(C)=C)OC(=O)C(C)=C)=C1 OLPICQSAMHSDPR-UHFFFAOYSA-N 0.000 description 1
- 210000003484 anatomy Anatomy 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000012259 ether extract Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical class CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
-
- 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
-
- 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
- C08F122/00—Homopolymers 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
- C08F122/10—Esters
- C08F122/1006—Esters of polyhydric alcohols or polyhydric phenols, e.g. ethylene glycol dimethacrylate
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Epidemiology (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dental Preparations (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerization Catalysts (AREA)
Description
Nye friradikal-katalyserte polymerisasjonsakselleratorerNew free radical-catalyzed polymerization accelerators
og materialer omfattende disse.and materials comprising these.
Foreliggende oppfinnelse vedrører nye friradikal-katalyserte polymerisasjonsakselleratorer og materialer omfattende disse, og mer spesielt slike akselleratorer og materialer som anvendes ved tannbehandling. The present invention relates to new free-radical-catalyzed polymerization accelerators and materials comprising these, and more particularly such accelerators and materials used in dentistry.
Polymeriserbare tannbehandlingsmaterialer er-velkj ente. De er f.eks. beskrevet i US-patent nr. 3-066.112, 3-539-533 og 3.835.090. Disse tannbehandlingsmaterialer omfatter generelt minst en flytende polymeriserbar akrylat- eller metakrylat-monomer, en diacylperoksyd-polymeriseringskatalysator eller -initiator, og en aminaksellerator for dannelse av friradikaler ved reaksjon med nevnte katalysator for polymerisering av monomeren. Materialet kan videre omfatte et uorganisk fyllstoff og stabilisator for å hindre en for tidlig polymerisering . Polymerizable dental treatment materials are well known. They are e.g. described in US Patent Nos. 3-066,112, 3-539-533 and 3,835,090. These dental treatment materials generally comprise at least one liquid polymerizable acrylate or methacrylate monomer, a diacyl peroxide polymerization catalyst or initiator, and an amine accelerator for the formation of free radicals by reaction with said catalyst for polymerization of the monomer. The material can further comprise an inorganic filler and stabilizer to prevent premature polymerization.
Disse tannbehandlingsmaterialer fremstilles generelt som to separate blandinger for lagring og salg før bruk, idet en blanding inneholder katalysatoren og ingen aktivator og den andre inneholder aktivator uten noen katalysator. Disse to blandinger kan begge være væsker, begge pastaer, en væske og en pasta, en væske og et faststoff eller lignende. De to blandingene kan hensiktsmessig være i væskeform (uten fyllstoff) eller pastaer (med fyllstoff); materialet ifølge oppfinnelsen er således eksemplifisert. I den foretrukne systemtype inneholder hver blanding eller sammensetning en flytende polymeriserbar monomer også betegnet som bindemidlet og et uorganisk fyllstoff (om ønsket) som hovedkomponenter. These dental treatment materials are generally prepared as two separate mixtures for storage and sale prior to use, one mixture containing the catalyst and no activator and the other containing the activator without any catalyst. These two mixtures can both be liquids, both pastes, a liquid and a paste, a liquid and a solid or the like. The two mixtures may conveniently be in liquid form (without filler) or pastes (with filler); the material according to the invention is thus exemplified. In the preferred type of system, each mixture or composition contains a liquid polymerizable monomer also referred to as the binder and an inorganic filler (if desired) as the main components.
Den første sammensetning (betegnet "katalysatorsammensetningen") inneholder i tillegg til en egnet mengde av en diacylperoksyd-polymeriseringskatalysator, typisk benzoylperoksyd. Den andre sammensetning (betegnet "aktivatorsammen- setningen" eller "universalsammensetningen") inneholder i tillegg en egnet mengde av en aminaksellerator for katalysatoren, typisk N,N-bis-(2-hydroksyetyl)-4-metylanilin i tidligere kjente aktivatorsammensetninger. Hver sammensetning inneholder vanligvis videre egnede mengder stabilisatorer for å hindre polymerisering av de'separate sammensetninger før blanding 'uten å ha noen skadelig innvirkning på de ønskede egenskaper slik som beskrevet nedenfor. The first composition (referred to as the "catalyst composition") additionally contains a suitable amount of a diacyl peroxide polymerization catalyst, typically benzoyl peroxide. The second composition (designated the "activator composition" or "universal composition") additionally contains a suitable amount of an amine accelerator for the catalyst, typically N,N-bis-(2-hydroxyethyl)-4-methylaniline in previously known activator compositions. Each composition usually further contains suitable amounts of stabilizers to prevent polymerization of the separate compositions prior to mixing without having any detrimental effect on the desired properties as described below.
Polymeriserbare tannbehandlingsmaterialer anvendes for en rekke forskjellige formål. De kan anvendes for direkte fylling av tenner som har vært utsatt for karies. De kan anvendes for å fylle sprekker i friske tenner for å hindre fremtidig karies. De kan videre benyttes som glaseringsforbin-deiser over sammensatte fyllinger for å gi en glatt, blank overflate. De er velkjente innen tannteknikken for å være overlegne tannbehandlingsmaterialer, spesielt for fortenner hvor det er viktig at en fylling tilsvarer tannfargen. Polymerizable dental treatment materials are used for a number of different purposes. They can be used for direct filling of teeth that have been exposed to caries. They can be used to fill cracks in healthy teeth to prevent future caries. They can also be used as glazing binders over composite fillings to give a smooth, glossy surface. They are well known in dental technology for being superior dental treatment materials, especially for front teeth where it is important that a filling matches the tooth colour.
Et polymeriserbart tannbehandlingsmateriale må være i besittelse av tre egenskaper for at det skal kunne være til nytte for tannlegen. For det første bør bindemiddeldelen for-bli fluid i et tidsrom som er tilstrekkelig langt til at tannlegen kan få anledning til å blande materialet og putte det på plass; denne tidsperiode kalles "geitiden". For det annet, når det først er anbragt på plass bør det hurtig herdes til en hard finish; denne tidsperiode kalles "gel til herde-tiden". For det tredje, bør herdematerialet herdne så nær som mulig til materi-alets eksponerte overflate; denne herding nær overflaten kalles "overflateherding". Et tannbehandlingsmateriale bør derfor sammensettes'slik at det har en tilstrekkelig lang geltid slik at tannlegen når å påføre det, slik at det har en så kort gel-til-herdetid som mulig i overensstemmelse med det ovenfor nevnte, og slik at overflateherdingen er så fullstendig som mulig. Et behandlingsmateriale har åpenbart liten verdi hvis det begynner å herdne i betydelig grad før tannlegen kan få det påført på det ønskede sted. En for lang geltid er også ugunstig. Gel-til-herdetiden bør være kort, slik at pasienten ikke behøver å avstå fra å spise eller vente i tannlegens kon-tor mens fyllingen herdner. Sluttelig, kvaliteten av overflateherdingen bestemmer hvor nær overflaten det til fast form polymeriserte bindemiddel strekker seg. Ved glaserings- og sprekkfyllings-anvendelser er graden av overflateherding meget viktig fordi bare et tynt lag av fyllingsmateriale befinner seg deri. A polymerizable dental treatment material must possess three properties in order for it to be of use to the dentist. Firstly, the binder part should remain fluid for a period of time that is sufficiently long for the dentist to have the opportunity to mix the material and put it in place; this period of time is called the "Goat Age". Secondly, once in place it should be quickly cured to a hard finish; this time period is called the "gel to harden time". Third, the curing material should cure as close as possible to the exposed surface of the material; this hardening near the surface is called "surface hardening". A dental treatment material should therefore be formulated so that it has a sufficiently long gel time so that the dentist has time to apply it, so that it has as short a gel-to-set time as possible in accordance with the above, and so that the surface hardening is as complete as possible. A treatment material is obviously of little value if it begins to harden to a significant extent before the dentist can apply it to the desired location. Too long a gel time is also unfavorable. The gel-to-harden time should be short, so that the patient does not have to refrain from eating or wait in the dentist's office while the filling hardens. Finally, the quality of the surface cure determines how close to the surface the solid polymerized binder extends. In glazing and crack filling applications, the degree of surface hardening is very important because only a thin layer of filling material is found there.
I tillegg til de ovenfor nevnte tre egenskaper må fyllingsmaterialet også ha termisk stabilitet. Således, mens materialet bør geldannes i løpet av relativt kort tid når først de to sammensetninger er blandet, bør de kunne lagres som to separate sammensetninger i et lengre tidsrom, fortrinnsvis i minst 6 måneder ved romtemperatur. For å oppnå denne stabilitet tilsettes ofte stabilisatorer til sammensetningene for å hindre for tidlig polymerisering. In addition to the three properties mentioned above, the filling material must also have thermal stability. Thus, while the material should gel within a relatively short time once the two compositions are mixed, they should be able to be stored as two separate compositions for a longer period of time, preferably for at least 6 months at room temperature. To achieve this stability, stabilizers are often added to the compositions to prevent premature polymerization.
Det vil vider.e sees at en aktiv aksellerator er ønskelig for visse typer behandlings- eller fyllingsmaterialer. Det er generelt godtatt innen teknikken at 120 sek. er en ønsket geltid for et ifylt materiale. Mens noen bindemiddelsystemer naturlig tenderer mot denne verdi ved bruk av tidligere kjente akselleratorer og mengder av stabilisatorer tilstrekkelig til å gi akseptabel termisk stabilitet, er andre mer langsomme eller trege under slike betingelser og gir således lengre geltider enn ønskelig. Enkelte av disse mer langsomme bindemiddelsystemer (slik som f.eks. de som omtales i ovennevnte US patent nr. 3.835.090) har imidlertid ønskede egenskaper slik som hardhet eller et brytningsindeks som tilsvarer det til fyllstoffet, hvilket ville gjøre dem til overlegne fyllingsmaterialer dersom deres lange geltid kunne forkortes under anvendelse av en aktiv aksellerator. It will also be seen that an active accelerator is desirable for certain types of treatment or filling materials. It is generally accepted in the art that 120 sec. is a desired gel time for a filled material. While some binder systems naturally tend towards this value using previously known accelerators and amounts of stabilizers sufficient to provide acceptable thermal stability, others are slower or sluggish under such conditions and thus give longer gel times than desired. However, some of these slower binder systems (such as, for example, those discussed in the above-mentioned US Patent No. 3,835,090) have desirable properties such as hardness or a refractive index equivalent to that of the filler, which would make them superior filler materials if their long gel times could be shortened using an active accelerator.
For materialer uten fyllstoff, slik som glaserings-og sprekktetnings-sammensetninger er det på den annen side generelt anerkjent at en kortere geltid, omkring 60 sek., er ønskelig. For å oppnå denne korte geltid, selv med mer aktive bindemiddelsystemer, er det nødvendig å ha en spesielt aktiv aksellerator. Sammensetningen inneholdende denne aktive aksellerator og en egnet mengde stabilisator, vil ha en slik kortere geltid og fremdeles ha den ønskede termiske stabilitet. For materials without filler, such as glazing and crack sealing compositions, on the other hand, it is generally recognized that a shorter gel time, around 60 sec., is desirable. To achieve this short gel time, even with more active binder systems, it is necessary to have a particularly active accelerator. The composition containing this active accelerator and a suitable amount of stabilizer will have such a shorter gel time and still have the desired thermal stability.
Bruken av en mer aktiv aksellerator i fyllingsmaterialer med eller uten fyllstoff forbedrer dessuten overflateherdingen til det resulterende polymeriserte bindemiddel. The use of a more active accelerator in filler materials with or without filler also improves the surface hardening of the resulting polymerized binder.
Komponentene i materialet bør velges slik at man optimaliserer de ønskede egenskaper som omtalt ovenfor, og hvilke påvirkes mest ved typen og mengden av aksellerator og katalysator. Bindemiddelsystemet kan velges ut fra styrke eller brytningsindeks, men valget derav har ikke en så alt overveiende effekt på de andre ønskede egenskaper til materialene som valget av aksellerator og katalysator har. The components in the material should be chosen in such a way as to optimize the desired properties as discussed above, and which are most affected by the type and amount of accelerator and catalyst. The binder system can be chosen on the basis of strength or refractive index, but the choice thereof does not have such an overwhelming effect on the other desired properties of the materials as the choice of accelerator and catalyst has.
Tidligere kjente katalysatorer er vanligvis diacyl-peroksyder som beskrevet i US-patent nr. 3-256.254 og US-patent nr. 3-580.955} idet det i sistnevnte patent beskrives metoder for fremstilling av disse katalysatorer samtidig som det gis en detaljert liste over disse. Previously known catalysts are usually diacyl peroxides as described in US patent no. 3-256,254 and US patent no. 3-580,955}, the latter patent describing methods for the production of these catalysts while also giving a detailed list of these .
Tidligere kjente akselleratorer er generelt substi-tuerte aniliner som beskrevet i det tidligere nevnte US-patent nr. 3-539-533 samt i US-patent nr. 3-5^1-068. Disse aniliner er vanligvis N,N-bis-(2-hydroksyetyl)-substituerte som beskrevet i sistnevnte US-patent, for tilveiebringelse av en forbedret fargestabilitet. Det sistnevnte patent beskriver tannfyllingsmaterialer hvor akselleratoren er N,N-bis-(2-hydroksyetyl)-3,5-dimetylanilin. Det antas at akselleratoren i dette patent er den mest relevante tidligere teknikk. Previously known accelerators are generally substituted anilines as described in the previously mentioned US Patent No. 3-539-533 and in US Patent No. 3-51-068. These anilines are usually N,N-bis-(2-hydroxyethyl)-substituted as described in the latter US patent, to provide an improved color stability. The latter patent describes dental filling materials where the accelerator is N,N-bis-(2-hydroxyethyl)-3,5-dimethylaniline. It is believed that the accelerator in this patent is the most relevant prior art.
Skjønt tidligere kjente polymeriserbare tannfyllingsmaterialer har vært gode, spesielt for bruk i de tilfeller hvor man har fyllinger med høyt fyllstoffinnhold, har de flere ulem-per . Although previously known polymerizable dental filling materials have been good, especially for use in cases where fillings with a high filler content are used, they have several disadvantages.
Por det første har tidligere kjente materialer har generelt hatt dårlig overflateherding, spesielt i ufylte systemer. Selv om denne ulempe ikke er ødeleggende for et materiale benyttet i fyllinger med høyt fyllstoffinnhold, er det ikke desto mindre et uønsket trekk. I en glaserings- eller sprekktetnings-sammensetning er imidlertid overflateherding av avgjørende betydning. Tidligere kjente glaseringsmaterialer har vært mangelfulle med hensyn til deres overflateherding og følgelig bare hatt begrenset suksess. Firstly, previously known materials have generally had poor surface curing, especially in unfilled systems. Although this disadvantage is not destructive for a material used in fillings with a high filler content, it is nevertheless an undesirable feature. In a glazing or crack sealing composition, however, surface hardening is of crucial importance. Previously known glazing materials have been deficient in their surface hardening and consequently have had only limited success.
For det annet har akselleratorer benyttet i tidligere kjente materialer vært mindre aktive enn ønskelig, og dette har resultert i lengre geltider for visse materialtyper inneholdende nevnte akselleratorer, enn foretrukket er. Secondly, accelerators used in previously known materials have been less active than desired, and this has resulted in longer gel times for certain material types containing said accelerators than is preferred.
Det er derfor et formål med foreliggende oppfinnelse å tilveiebringe et tannfyllingsmateriale som har god overflate herding. Et annet formål er å tilveiebringe en mer aktiv aksellerator for diacylperoksyd-polymeriseringskatalysatorer enn i den tidligere kjente teknikk. Disse og andre formål ved oppfinnelsen vil fremgå fra det nedenstående. It is therefore an object of the present invention to provide a dental filling material which has good surface hardening. Another object is to provide a more active accelerator for diacyl peroxide polymerization catalysts than in the prior art. These and other purposes of the invention will be apparent from the following.
Por å oppfylle disse formål tilveiebringer oppfinnelsen den nye aminaksellerator N,N-bis(2-hydroksyetyl)-3Ji+-dimetylanilin og polymeriserbare tannfyllingsmaterialer omfattende denne aksellerator. Akselleratoren ifølge oppfinnelsen er mer aktiv enn de tidligere kjente. I materialene ifølge oppfinnelsen gir denne nye aksellerator bedre overflateherding enn det som har vært tilfelle i den tidligere kjente teknikk. Porelig-gendeoppfinnelse tilveiebringer videre aminakselleratorene N,N-bis- ( 3-hydroksypropyl )'-3, 4-dimetylanilin og N,N-bis- ( 4-hydroksy-butyl)-3,4-dimetylanilin, hvilke også er mer aktive enn de tidligere kjente. Aminakselleratorene ifølge oppfinnelsen er derfor et stoff valgt fra gruppen bestående av N,N-bis-(2-hydroksyetyl)-3,4-dimetylanilin, N,N-bis-(2rhydroksypropyl)-3,4-dimetylanilin og N,N-bis-(2-hydroksybutyl)-3,4-dimetylanilin. In order to fulfill these purposes, the invention provides the new amine accelerator N,N-bis(2-hydroxyethyl)-3Ji+-dimethylaniline and polymerizable dental filling materials comprising this accelerator. The accelerator according to the invention is more active than the previously known ones. In the materials according to the invention, this new accelerator provides better surface hardening than has been the case in the previously known technique. The present invention further provides the amine accelerators N,N-bis-(3-hydroxypropyl)'-3,4-dimethylaniline and N,N-bis-(4-hydroxy-butyl)-3,4-dimethylaniline, which are also more active than those previously known. The amine accelerators according to the invention are therefore a substance selected from the group consisting of N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline, N,N-bis-(2-hydroxypropyl)-3,4-dimethylaniline and N,N- bis-(2-hydroxybutyl)-3,4-dimethylaniline.
Akselleratoren ifølge oppfinnelsen (formel I), kan fremstilles ved å omsette 3,4-dimetylanilin (II) med 2-brometanol (III) i alt vesentlig ifølge metoden til Tong et al, Journal of the American Chemical Society, 8_2, 1988 (1960). The accelerator according to the invention (formula I) can be prepared by reacting 3,4-dimethylaniline (II) with 2-bromoethanol (III) essentially according to the method of Tong et al, Journal of the American Chemical Society, 8_2, 1988 (1960 ).
Denne reaksjon kan illustreres som følger:This reaction can be illustrated as follows:
Inkorporering av akselleratoren ifølge oppfinnelsen Incorporation of the accelerator according to the invention
i stedet for f.eks. N,N-bis(2-hydroksyetyl)-4-metylanilin i det materiale som er angitt i eksemplet i nevnte US patent nr. 3-539-533, gir uventet og overraskende forbedring i forhold til de resultater som oppnås når den tidligere kjente aksellerator anvendes. Det er mer spesielt funnet at i sammensetningen i sistnevnte US-patent resulterer anvendelse av en ekvivalent mengde av akselleratoren ifølge oppfinnelsen som en erstatning for N,N-bis(2-hydroksyetyl)-4-metylanilin som benyttet deri, i en reduksjon av geltiden med ca. 60 %. Som en sammenligning instead of e.g. N,N-bis(2-hydroxyethyl)-4-methylaniline in the material indicated in the example in said US patent no. 3-539-533, gives an unexpected and surprising improvement in relation to the results obtained when the previously known accelerator is used. It is more particularly found that in the composition in the latter US patent the use of an equivalent amount of the accelerator according to the invention as a substitute for N,N-bis(2-hydroxyethyl)-4-methylaniline used therein results in a reduction of the gel time with approx. 60%. As a comparison
skal det nevnes at anvendelse av den tidligere kjente forbindelse N,N-bis-(2-hydroksyetyl)-3}5-dimetylanilin forårsaker en reduksjon i geltid med bare omkring 6 %, 1/10 så stor reduksjon som ved akselleratoren ifølge oppfinnelsen. Denne reduksjon i geltid for materialet omfattende en ekvivalent mengde av akselleratoren ifølge oppfinnelsen indikerer at akselleratoren er langt mer aktiv enn de tidligere kjente akselleratorer. it should be mentioned that the use of the previously known compound N,N-bis-(2-hydroxyethyl)-3}5-dimethylaniline causes a reduction in gel time by only about 6%, 1/10 as great a reduction as with the accelerator according to the invention. This reduction in gel time for the material comprising an equivalent amount of the accelerator according to the invention indicates that the accelerator is far more active than the previously known accelerators.
Inkorporering av akselleratoren ifølge oppfinnelsen i et langsomt eller tregt bindemiddelsystem med fyllstoff, slik som det som er beskrevet i nevnte US-patent nr. 3-835-090, viser akseptabel, geltid og god overflateherding ved følgende forsøk. For sammenligning gir bruk av den tidligere kjente forbindelse N,N-bis(2-hydroksyetyl)-4-metylanilin dårlig overflateherding Incorporation of the accelerator according to the invention in a slow or slow binder system with filler, such as that described in said US patent no. 3-835-090, shows acceptable gel time and good surface hardening in the following tests. By comparison, use of the previously known compound N,N-bis(2-hydroxyethyl)-4-methylaniline gives poor surface curing
og substitusjon av den tidligere kjente N,N-bis(2-hydroksyetyl)-3,5-dimetylanilin gir meget dårlig overflateherding. and substitution of the previously known N,N-bis(2-hydroxyethyl)-3,5-dimethylaniline gives very poor surface hardening.
For å teste overflateherding for en sammensetning med fyllstoff, fremstilles forsøksmaterialet (hensiktsmessig ved blanding av to sammensetninger som nevnt ovenfor) og anbringes på en glassplate eller en annen ikke-reaktiv overflate. Materialet gis anledning til å herdes og testes deretter ved skraping av dets overflate med en spiss trepinne. God overflateherding utvises av en tørr overflate som er motstandsdyktig mot skraping; bare et svakt lag av monomer er uherdet. Dårlig overflateherding indikeres av et betydelig lag av uherdet monomer; skraping oppnås lett og noe fyllstoff løsner. Meget dårlig overflateherding indikeres av et tykt lag monomer som lett tørkes av; fyllstoffet lar seg også lett skrape av. To test surface cure for a filler composition, the test material is prepared (conveniently by mixing two compositions as mentioned above) and placed on a glass plate or other non-reactive surface. The material is allowed to harden and is then tested by scratching its surface with a pointed wooden stick. Good surface hardening is demonstrated by a dry surface that is resistant to scratching; only a weak layer of monomer is uncured. Poor surface cure is indicated by a significant layer of uncured monomer; scraping is easily achieved and some filler loosens. Very poor surface curing is indicated by a thick layer of monomer that is easily wiped off; the filler can also be easily scraped off.
I ufylte systemer, slik som BIS-GMA:BADM-systemet beskrevet i ovennevnte US-patent nr. 3•539• 5335 (uten fyllstoff) gir inkorporering av ^akselleratoren ifølge oppfinnelsen en akseptabel geltid og god overflateherding ved følgende test. In unfilled systems, such as the BIS-GMA:BADM system described in the above-mentioned US Patent No. 3•539•5335 (without filler), incorporation of the accelerator according to the invention gives an acceptable gel time and good surface hardening in the following test.
For sammenligning resulterer bruken av de tidligere kjente forbindelser N,N-bis(2-hydroksyetyl)-4-metylanilin eller N,N-. bis-(2-hydroksyetyl)-3,5dimetylanilin i dårlig overflateherding. For comparison, the use of the previously known compounds N,N-bis(2-hydroxyethyl)-4-methylaniline or N,N-. bis-(2-hydroxyethyl)-3,5dimethylaniline in poor surface curing.
For å teste overflateherding for en ikke-fylt sammensetning, fremstilles forsøksmaterialet (hensiktsmessig ved sammenblanding av to sammensetninger som omtalt ovenfor) og et tynt lag av dette påføres på en glassplate for å herdes. Det herdede materiale tørkes deretter med et klede, og mengden som blir tilbake noteres. God overflateherding resulterer i omkring 90 % dekning, mens dårlig overflateherding resulterer i mindre enn 50 % dekning. Materialer omfattende forskjellige akselleratorer kan sammenlignes ved dette forsøk ved å anvende like mengder av hver sammensetning påført like store arealer. En sammenligning av et område dekket etter tørking viser den rela-tive grad av overflateherding for de to materialer To test surface cure for an unfilled composition, the test material is prepared (conveniently by mixing two compositions as discussed above) and a thin layer of this is applied to a glass plate to be cured. The hardened material is then wiped with a cloth and the amount remaining is noted. Good surface cure results in about 90% coverage, while poor surface cure results in less than 50% coverage. Materials comprising different accelerators can be compared in this experiment by using equal amounts of each composition applied to equal areas. A comparison of an area covered after drying shows the relative degree of surface hardening for the two materials
Tannfyllingsmaterialet ifølge oppfinnelsen omfatter minst en væskeformig polymeriserbar monomer valgt fra gruppen bestående av akrylat- og metakrylat-monomerer, en diacylperoksydkatalysator og aminakselleratoren ifølge oppfinnelsen, N,N-bis-(2-hydroksyetyl)-3,4-dimetylanilin, for dannelse av frie radikaler ved reaksjon med nevnte peroksydkatalysator for polymerisering av monomeren. Et fyllstoff og en stabilisator kan også inkorporeres i materialet om ønsket. Det er foretrukket at størstedelen av den væskeformige polymeriserbare monomer inneholder mer enn en akrylat- eller metakrylat-gruppe pr. molekyl. The dental filling material according to the invention comprises at least one liquid polymerisable monomer selected from the group consisting of acrylate and methacrylate monomers, a diacyl peroxide catalyst and the amine accelerator according to the invention, N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline, for the formation of free radicals by reaction with said peroxide catalyst for polymerization of the monomer. A filler and a stabilizer can also be incorporated into the material if desired. It is preferred that the majority of the liquid polymerizable monomer contains more than one acrylate or methacrylate group per molecule.
Den væskeformige polymeriserbare monomer kan f.eks. være: The liquid polymerizable monomer can e.g. be:
som er glycidyl-metakrylat-derivatet av bis-fenol-A, i det følgende betegnet BIS-GMA; trimetakrylat- og triakrylat-estere av alifatisk triol-glycerolforbindelser, trimetyloletan, trimetylolpropan og trimetylolbutan og lignende. Gruppen av materialer kan eksemplifiseres ved trimetylolpropan-trimetakrylat (TMPTMA), trimetylolpropantriakrylat (TMPTA) og lignende. which is the glycidyl methacrylate derivative of bis-phenol-A, hereinafter referred to as BIS-GMA; trimethacrylate and triacrylate esters of aliphatic triol-glycerol compounds, trimethylolethane, trimethylolpropane and trimethylolbutane and the like. The group of materials can be exemplified by trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA) and the like.
Andre akrylat- eller metakrylatmonomerer kan om ønsket, tilsettes til fyllingsmaterialene ifølge oppfinnelsen av forskjellige grunner: som fortynningsmidler, for å fremme et brytningsindeks i likhet med det til tannemaljen, for å øke hastigheten på polymeriseringsreaksjonen, og lignende. Eksempler på slike andre monomerer er: bis-fenol-A-dimetakrylat (BADM), trietylenglykol-dimetakrylat (TEGDM), 1,3-bis[2,3-di(metakryl-oksy)propoksy]-benzen (RGTMA), 1,3-bis-_(_3-metakryloksy-2-hydroksypropoksy)-benzen (RGDMA), 2,2-bis-[4-(2-metakryloksy-etoksy)-fenyl]-propan (SR-3^8), di-(2-metakryloksyetyl)difenyl- silan og metakrylatestere (CMDPO-25 metakrylat) hvori en metakryloksygruppe eller -grupper er festet til difenyloksyd-kjerner gjennom enkle metylenbindinger, idet monomerene representeres ved den generelle formel: hvor R i hvert tilfelle er minst en gruppe bestående av H og Other acrylate or methacrylate monomers can, if desired, be added to the filling materials according to the invention for various reasons: as diluents, to promote a refractive index similar to that of tooth enamel, to increase the speed of the polymerization reaction, and the like. Examples of such other monomers are: bis-phenol-A-dimethacrylate (BADM), triethylene glycol dimethacrylate (TEGDM), 1,3-bis[2,3-di(methacryl-oxy)propoxy]-benzene (RGTMA), 1 ,3-bis-_(_3-methacryloxy-2-hydroxypropoxy)-benzene (RGDMA), 2,2-bis-[4-(2-methacryloxy-ethoxy)-phenyl]-propane (SR-3^8), di-(2-methacryloxyethyl)diphenylsilane and methacrylate esters (CMDPO-25 methacrylate) in which a methacryloxy group or groups are attached to diphenyloxide nuclei through single methylene bonds, the monomers being represented by the general formula: where R in each case is at least one group consisting of H and
Diacylperoksydkatalysatoren kan være en hvilken som helst av de som er kjent i den tidligere teknikk, slik som f.eks. benzoylperoksyd, para-metylbenzoylperoksyd, 2,4-diklor-benzoylperoksyd og lignende. The diacyl peroxide catalyst may be any of those known in the prior art, such as e.g. benzoyl peroxide, para-methylbenzoyl peroxide, 2,4-dichloro-benzoyl peroxide and the like.
Stabilisatorer kan tilsettes til materialene, om ønsket, for å inhibere for tidlig polymerisering av materialet under lagring. Slike stabilisatorer er vanligvis fri-radikal-kjedereaksjon-terminatorer, slik som f.eks. en substituert fenol, slik som p-metoksyfenol, 2,5-di-t-butyl-4-metylfenol (kjent som BHT), en forbindelse med formelen: Stabilizers can be added to the materials, if desired, to inhibit premature polymerization of the material during storage. Such stabilizers are usually free radical chain reaction terminators, such as e.g. a substituted phenol, such as p-methoxyphenol, 2,5-di-t-butyl-4-methylphenol (known as BHT), a compound of the formula:
("Irganox 1010") og lignende; eller en stabilisator mot ultra-violett lys som kan bevirke misfarging av bindemidlet, slik som f.eks. 2-hydroksy-4-metylbenzofenon ("Cyasorb UV-9") eller lignende. ("Irganox 1010") and the like; or a stabilizer against ultra-violet light which can cause discolouration of the binder, such as e.g. 2-hydroxy-4-methylbenzophenone ("Cyasorb UV-9") or the like.
I tillegg til de ovenfor angitte bestanddeler kan materialet ifølge oppfinnelsen ytterligere omfatte et organisk fyllstoff slik som silisiumdioksyd, glasskuler, pulverisert glass, aluminiumoksyd, krystallinsk kvarts og lignende. Et slikt fyllstoff vil inkluderes dersom materialet ifølge oppfinnelsen eksempelvis skulle anvendes i sterkt fyllstoffholdige fyllinger, og ville bli behandlet med et egnet "keying"-middel som kjent In addition to the above-mentioned components, the material according to the invention can further comprise an organic filler such as silicon dioxide, glass beads, powdered glass, aluminum oxide, crystalline quartz and the like. Such a filler would be included if, for example, the material according to the invention were to be used in fillings containing a strong filler, and would be treated with a suitable "keying" agent as known
innen teknikken.in the field of technology.
Et foretrukket materiale ifølge oppfinnelsen omfatter fra ca. 35 - 90 vekt-% av en blanding av ca. 90 vekt-% ':BIS-GMA og ca. 10 vekt-% bis-fenol-A-dimetakrylat (BADM), fra ca. 65 - 10 vekt-% trietylenglykol-dimetakrylat (TEGDM), fra ca. 0,5- ca. 3,0 vekt-% av en diacylperoksydkatalysator og fra ca. 0,5 -2,0 vekt-% N,N-bis-(2-hydroksyetyl)-3,4-dimetylanilin. Et mer foretrukket materiale omfatter fra ca. 55 til ca. 75 vekt-% av ovennevnte BIS-GMA- og BADM-blanding, fra ca. 45 - ca. 25 vekt-% TEGDM, fra ca. 1 - ca. 2,5 vekt-% av en diacylperoksydkatalysator, og fra ca. 1 - ca. 1,5 vekt-% N,N-bis(2-hydroksyetyl)-3,4-dimetylanilin. Det mest foretrukne materiale ifølge oppfinnelsen omfatter fra ca. 65 - 70 vekt-56 av nevnte BIS-GMA- og BADM-blanding, fra ca. 27 til ca. 32 vekt-% TEGDM, ca. 1 vekt-% benzoylperoksyd og ca. 1,2 vekt-% N,N-bis-(2-hydroksyetyl)-3,4-dimetylanilin. A preferred material according to the invention comprises from approx. 35 - 90% by weight of a mixture of approx. 90% by weight ':BIS-GMA and approx. 10% by weight bis-phenol-A-dimethacrylate (BADM), from approx. 65 - 10% by weight triethylene glycol dimethacrylate (TEGDM), from approx. 0.5- approx. 3.0% by weight of a diacyl peroxide catalyst and from approx. 0.5-2.0% by weight N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline. A more preferred material comprises from approx. 55 to approx. 75% by weight of the above BIS-GMA and BADM mixture, from approx. 45 - approx. 25% by weight TEGDM, from approx. 1 - approx. 2.5% by weight of a diacyl peroxide catalyst, and from approx. 1 - approx. 1.5% by weight of N,N-bis(2-hydroxyethyl)-3,4-dimethylaniline. The most preferred material according to the invention comprises from approx. 65 - 70 weight-56 of said BIS-GMA and BADM mixture, from approx. 27 to approx. 32% by weight TEGDM, approx. 1% by weight benzoyl peroxide and approx. 1.2% by weight of N,N-bis-(2-hydroxyethyl)-3,4-dimethylaniline.
Et annet foretrukket materiale ifølge oppfinnelsen omfatter fra ca. 40 til ca. 80 vekt-% CMDPO-25-metakrylat, fra ca. 60 - ca. 20 vekt-% trimetylolpropan-trimetakrylat TMPTMA), fra ca. 0,5 - ca. 3,0 vekt-% N,N-bis-(2-hydroksyetyl)~3,4-dimetylanilin og fra ca. 0,5 - ca. 3,0 vekt-% av en diacylperoksydkatalysator. Et mer foretrukket materiale av denne annen type omfatter fra ca. 55 - ca. 65 vekt-% CMDPO-25-metakrylat, Another preferred material according to the invention comprises from approx. 40 to approx. 80% by weight CMDPO-25 methacrylate, from approx. 60 - approx. 20% by weight trimethylolpropane trimethacrylate TMPTMA), from approx. 0.5 - approx. 3.0% by weight of N,N-bis-(2-hydroxyethyl)~3,4-dimethylaniline and from approx. 0.5 - approx. 3.0% by weight of a diacyl peroxide catalyst. A more preferred material of this second type comprises from approx. 55 - approx. 65% by weight CMDPO-25 methacrylate,
fra ca. 42 - ca. 32 vekt-% trimetylolpropan-trimetakrylat (TMPTMA), ca. 1,2 vekt-% N,N-bis-(2-hydroksyetyl)~3,4-dimetylanilin og ca. 1,5 vekt-% benzoylperoksyd. Denne andre type av foretrukket materiale kan blandes med uorganisk fyllstoff, (f.eks. silanbehandlet kvarts), fortrinnsvis fra ca. fire til ca. fem ganger dets vekt av uorganisk fyllstoff. from approx. 42 - approx. 32% by weight trimethylolpropane trimethacrylate (TMPTMA), approx. 1.2% by weight of N,N-bis-(2-hydroxyethyl)~3,4-dimethylaniline and approx. 1.5% by weight benzoyl peroxide. This second type of preferred material can be mixed with inorganic filler, (e.g. silane-treated quartz), preferably from approx. four to approx. five times its weight of inorganic filler.
Materialet ifølge oppfinnelsen anvendes fortrinnsvis som to sammensetninger som nevnt ovenfor, hvorav en inneholder akselleratoren og er fri for peroksyder (akselleratorsammenset-ningen) og hvorav en inneholder peroksydkatalysatoren fri for akselleratoren (katalysatorsammensetningen). Disse sammensetninger, som også kan inneholde fyllstoff, blandes deretter for å initiere polymeriseringsreaksjonen. Den akselleratorholdige sammensetning ansees også for å være en del av foreliggende oppfinnelse. The material according to the invention is preferably used as two compositions as mentioned above, one of which contains the accelerator and is free of peroxides (the accelerator composition) and one of which contains the peroxide catalyst free of the accelerator (the catalyst composition). These compositions, which may also contain fillers, are then mixed to initiate the polymerization reaction. The accelerator-containing composition is also considered to be part of the present invention.
Mens akselleratoren ifølge oppfinnelsen er eksempli fisert ovenfor slik den benyttes i to foretrukne formuleringer, skal det forstås at et fyllingsmateriale omfattende en hvilken som helst væskeformig polymeriserbar akrylat- eller metakrylat-monomer og en hvilken som helst diacylperoksydkatalysator med N,N-bis-(2-hydroksyetyl)-3,4-dimetylanilin, omfattes av foreliggende oppfinnelse. Materialet ifølge oppfinnelsen kan anvendes uten fyllstoff som en glaserings- eller sprekktetnings-sammensetning eller med fyllstoff for bruk ved direkte fylling av hull i tenner. While the accelerator of the invention is exemplified above as used in two preferred formulations, it is to be understood that a filler material comprising any liquid polymerizable acrylate or methacrylate monomer and any diacyl peroxide catalyst with N,N-bis-(2 -hydroxyethyl)-3,4-dimethylaniline, is covered by the present invention. The material according to the invention can be used without filler as a glazing or crack sealing composition or with filler for use when directly filling holes in teeth.
En- foretrukken bruk av behandlingsmaterialet ifølge oppfinnelsen er som en glaseringsforbindelse over sammensatte fyllinger for å gi en varig, glatt, blank overflate. A preferred use of the treatment material according to the invention is as a glazing compound over composite fillings to provide a lasting, smooth, glossy surface.
Utførelsen av foreliggende oppfinnelse illustreres i følgende eksempler, hvori alle delangivelser er ved vekt dersom ikke annet er angitt. The embodiment of the present invention is illustrated in the following examples, in which all partial indications are by weight unless otherwise stated.
Eksempel IExample I
N, N- bis-( 2- hydroksyetyl)- 3j 4- dimetylanilin.N,N-bis-(2-hydroxyethyl)-3j 4-dimethylaniline.
En blanding av 242 deler 3 >4-dimetylanilin, 500 deler 2-brometanol, 1400 deler 95 % etanol og 210 deler natriumkarbo-nat, oppvarmes under tilbakeløp og ved oppvarming i 24 timer, hvoretter 600 deler avionisert vann tilsettes og det hele til-bakeløpskokes i ytterligere 1 time. Etter destillasjon av opp-løsningen for å fjerne etanol, tilsettes ytterligere 300 deler avionisert vann og oppløsningens pH-verdi innstilles til ca. 8,5 ved tilsetning av vandig natriumhydroksyd. Denne basiske oppløs-ning ekstraheres deretter en gang med 450 deler dietyleter og to ganger med 150 deler dietyleter. De kombinerte eterekstrakter vaskes to ganger med 300 deler saltoppløsning og tørkes over magnesiumsulfat. Den resulterende eteroppløsning destilleres i vakuum for å fjerne først eteren og deretter det uomsatte utgangsmateriale. Fraksjonen som koker ved 157^l65°C (0,1 mm) isoleres, og dette gir N,N-bis-(2-hydroksyetyl)-354-dimetylanilin, sm.p. 54-57°C. A mixture of 242 parts of 3>4-dimethylaniline, 500 parts of 2-bromoethanol, 1400 parts of 95% ethanol and 210 parts of sodium carbonate is heated under reflux and by heating for 24 hours, after which 600 parts of deionized water are added and the whole simmer for a further 1 hour. After distillation of the solution to remove ethanol, a further 300 parts of deionized water are added and the pH value of the solution is adjusted to approx. 8.5 by adding aqueous sodium hydroxide. This basic solution is then extracted once with 450 parts of diethyl ether and twice with 150 parts of diethyl ether. The combined ether extracts are washed twice with 300 parts of saline and dried over magnesium sulfate. The resulting ether solution is distilled in vacuo to remove first the ether and then the unreacted starting material. The fraction boiling at 157^165°C (0.1 mm) is isolated, and this gives N,N-bis-(2-hydroxyethyl)-354-dimethylaniline, m.p. 54-57°C.
Eksempel II-Example II-
To sammensetninger fremstilles ved å blande følgende bestanddeler: Two compositions are prepared by mixing the following ingredients:
Like vektmengder av sammensetning A og sammensetning B sammenblandes og påføres på en glattplate. Det herdede materiale utviser god overflateherding ved de ovenfor beskrevne forsøk for overflateherding. Equal amounts by weight of composition A and composition B are mixed together and applied to a smooth plate. The hardened material shows good surface hardening in the surface hardening tests described above.
Eksempel IIIExample III
Ved å følge metoden i eksempel II, men ved å benytte en ekvivalent mengde av N,N-bis-(2-hydroksyetyl)-3,5-dimetylanilin i stedet for N,N-bis- ( 2-hydroksyetyl)-3,4-dimetylanilin fremstilles to tilsvarende sammensetninger. Materialet, frem-stilt ved blanding av disse sammensetninger viser dårlig overflateherding undersøkt ved den ovenfor beskrevne overflate-herdingstest. Following the method of Example II, but using an equivalent amount of N,N-bis-(2-hydroxyethyl)-3,5-dimethylaniline instead of N,N-bis-(2-hydroxyethyl)-3, 4-Dimethylaniline produces two corresponding compositions. The material, produced by mixing these compositions, shows poor surface hardening examined by the surface hardening test described above.
Eksempel IVExample IV
To sammensetninger fremstilles ved å blande følgende bestanddeler: Two compositions are prepared by mixing the following ingredients:
Kvartsen behandles med silan- før dens tilsetning til de andre bestanddeler slik som angitt i ovennevnte US patent nr. 3.066.112. Like vektmengder av disse to sammensetninger blandes og innføres i en cavitet for derved å gi et sterkt fylt fyllingsmateriale med god overflateherding. The quartz is treated with silane prior to its addition to the other components as stated in the above-mentioned US patent no. 3,066,112. Equal amounts of these two compositions by weight are mixed and introduced into a cavity to thereby provide a strongly filled filling material with good surface hardening.
Eksempel VExample V
To sammensetninger fremstilles og undersøkes som i eksempel II under anvendelse av følgende bestanddeler: Two compositions are prepared and tested as in Example II using the following ingredients:
Den resulterende glaseringsformulering gir utmerket overflateherding og, når den påføres på en tann som har en fylling med høyt fyllstoffinnhold, blir ikke dens anatomi skjult. Eksempel VI I The resulting glaze formulation provides excellent surface hardening and, when applied to a tooth that has a high-filler content restoration, its anatomy is not obscured. Example VI I
Følgende sammensetninger fremstilles under anvendelse av identiske stabilisatornivåer og ekvimolare mengder av forskjellige aminakseleratorer. Geltidene måles for blandingen av hver akseleratorsammensetning med en like stor vekttmengde av en felles katalysatorsammensetning. The following compositions are prepared using identical stabilizer levels and equimolar amounts of different amine accelerators. The gel times are measured for the mixture of each accelerator composition with an equal amount by weight of a common catalyst composition.
En betydelig kortere geltid for materialet inneholdende akselleratoren ifølge oppfinnelsen demonstrerer dets større aktivitet sammenlignet med tidligere kjente akselleratorer . A significantly shorter gel time for the material containing the accelerator according to the invention demonstrates its greater activity compared to previously known accelerators.
Eksempel VIIExample VII
To sammensetninger fremstilles og sammenlignes som i eksempel VI, men under anvendelse av et BIS-GMA og BADM-monomer-system. Bestanddelene er følgende: Two compositions are prepared and compared as in Example VI, but using a BIS-GMA and BADM monomer system. The components are the following:
Den benzoylperoksydbehandlede kvarts fremstilles ved å oppløse peroksydet i et egnet oppløsningsmiddel (f.eks. aceton, metylenklorid eller lignende) og oppløsningsmidlet gis anledning til å fordampe fra en blanding av oppløsningen og kvartsen. The benzoyl peroxide-treated quartz is prepared by dissolving the peroxide in a suitable solvent (eg acetone, methylene chloride or the like) and the solvent is allowed to evaporate from a mixture of the solution and the quartz.
Den betydelig kortere geltid for materialet inneholdende akselleratoren ifølge oppfinnelsen demonstrerer dets større aktivitet sammenlignet med tidligere kjente akselleratorer . The significantly shorter gel time for the material containing the accelerator according to the invention demonstrates its greater activity compared to previously known accelerators.
Eksempel VIIIExample VIII
Følgende sammensetninger fremstilles under anvendelse av varierende stabilisatornivåer, men ekvimolare aksellerator-nivåer for dannelse av sammensetninger omfattende forskjellige akselleratorer, men med samme geltid, slik at akselleratorens identitet er det eneste variable som påvirker overflateherdingen. Overflateherdingen til hvert av de herdede materialer testes ved bruk av det ovenfor beskrevne forsøk for overflateherding, og resultatene som oppnås er gitt nedenfor. The following compositions are prepared using varying stabilizer levels but equimolar accelerator levels to form compositions comprising different accelerators but with the same gel time, so that the identity of the accelerator is the only variable affecting surface cure. The surface cure of each of the cured materials is tested using the surface cure test described above, and the results obtained are given below.
Claims (12)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US53807675A | 1975-01-02 | 1975-01-02 |
Publications (1)
Publication Number | Publication Date |
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NO754397L true NO754397L (en) | 1976-07-05 |
Family
ID=24145378
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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NO754397A NO754397L (en) | 1975-01-02 | 1975-12-29 |
Country Status (18)
Country | Link |
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JP (1) | JPS5192884A (en) |
AR (1) | AR213618A1 (en) |
AT (1) | AT342209B (en) |
AU (1) | AU8798975A (en) |
BE (1) | BE837206A (en) |
BR (1) | BR7600008A (en) |
DE (1) | DE2559213A1 (en) |
DK (1) | DK595275A (en) |
ES (1) | ES444016A1 (en) |
FI (1) | FI753720A (en) |
FR (1) | FR2401180A1 (en) |
GB (1) | GB1497900A (en) |
IL (1) | IL48775A0 (en) |
IT (1) | IT1052673B (en) |
NL (1) | NL7515259A (en) |
NO (1) | NO754397L (en) |
SE (1) | SE7514774L (en) |
ZA (1) | ZA7610B (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA1112397A (en) * | 1975-12-15 | 1981-11-10 | Russell N. Kemper | Peroxide-catalyzed composition useful for sealing pits and fissures in teeth |
DE2728764A1 (en) * | 1977-06-25 | 1979-01-18 | Bayer Ag | FORMULATED DENTAL FILLING MATERIALS |
AT386441B (en) * | 1984-07-16 | 1988-08-25 | Kunex Tuerenwerk | SOUND-INSULATING, AREA COMPONENT |
-
1975
- 1975-12-29 NO NO754397A patent/NO754397L/no unknown
- 1975-12-30 DK DK595275A patent/DK595275A/en not_active Application Discontinuation
- 1975-12-30 AR AR261795A patent/AR213618A1/en active
- 1975-12-30 BE BE163222A patent/BE837206A/en unknown
- 1975-12-30 SE SE7514774A patent/SE7514774L/en not_active Application Discontinuation
- 1975-12-30 DE DE19752559213 patent/DE2559213A1/en active Pending
- 1975-12-31 NL NL7515259A patent/NL7515259A/en not_active Application Discontinuation
- 1975-12-31 GB GB53318/75A patent/GB1497900A/en not_active Expired
- 1975-12-31 FR FR7540279A patent/FR2401180A1/en not_active Withdrawn
- 1975-12-31 FI FI753720A patent/FI753720A/fi not_active Application Discontinuation
- 1975-12-31 AU AU87989/75A patent/AU8798975A/en not_active Expired
- 1975-12-31 ES ES444016A patent/ES444016A1/en not_active Expired
- 1975-12-31 IT IT52932/75A patent/IT1052673B/en active
-
1976
- 1976-01-01 IL IL48775A patent/IL48775A0/en unknown
- 1976-01-02 ZA ZA760010A patent/ZA7610B/en unknown
- 1976-01-02 BR BR7600008A patent/BR7600008A/en unknown
- 1976-01-02 AT AT2176A patent/AT342209B/en not_active IP Right Cessation
- 1976-01-05 JP JP51000018A patent/JPS5192884A/ja active Pending
Also Published As
Publication number | Publication date |
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FI753720A (en) | 1976-07-03 |
AU8798975A (en) | 1977-07-07 |
DK595275A (en) | 1976-07-03 |
FR2401180A1 (en) | 1979-03-23 |
AT342209B (en) | 1978-03-28 |
SE7514774L (en) | 1976-07-05 |
ZA7610B (en) | 1977-08-31 |
IL48775A0 (en) | 1976-03-31 |
DE2559213A1 (en) | 1976-07-08 |
GB1497900A (en) | 1978-01-12 |
BE837206A (en) | 1976-06-30 |
ES444016A1 (en) | 1977-08-16 |
BR7600008A (en) | 1976-08-03 |
ATA2176A (en) | 1977-07-15 |
AR213618A1 (en) | 1979-02-28 |
NL7515259A (en) | 1976-07-06 |
IT1052673B (en) | 1981-07-20 |
JPS5192884A (en) | 1976-08-14 |
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