DK157727B - POLYMERIZABLE DENTAL MATERIALS WITH ACCELERATED CURRENCY SPEED - Google Patents
POLYMERIZABLE DENTAL MATERIALS WITH ACCELERATED CURRENCY SPEED Download PDFInfo
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- 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
- C08F4/40—Redox systems
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- 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
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- Oral & Maxillofacial Surgery (AREA)
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Description
iin
DK 157727 BDK 157727 B
Opfindelsen angår et polymeriserbart tandreparationsmateriale, der er i stand til at hærde hurtigt under dannelse af et produkt i form af et polymerisat med et forholdsvis højt indhold af uopløselig komponent.The invention relates to a polymerizable tooth repair material which is capable of curing rapidly to form a product in the form of a polymerizate having a relatively high insoluble component content.
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Polymeriserbare midler til tænder, der er baseret på anvendelsen af methacrylatmonomerer, f.eks. reaktionsproduktet af bis-glycidyletheren af bisphenol A og methacry1 syre (i det følgende angivet som BIS-GMA), anvendes almindeligvis som fyldninger 10 og midler til plombering og fyldning af huller, revner og lignende, og er særdeles velegnede til en lang række tandrestaurerings- og tandreparationsbehandlinger. Sådanne midler indeholder typisk én eller flere methacrylatmonomerer og mindst én komponent af et fri radikaldannende (redox) polymerisations-15 system for nævnte monomer eller nævnte monomerer. Det således fremstillede monomermateriale indeholder sædvanligvis peroxid-typekatalysatoren (oxidationsmiddel), som senere kommer i kontakt med det reducerende middel (reduktionsmiddel) kort før anvendelsen til tandbehandling. Ved kontakt af oxidationsmid-20 let med de reducerende midler - som hensigtsmæssigt sædvanligvis foreligger i pastaform - sker der polymerisation, som fører til dannelsen af et polymerisat med de fysiske egenskaber, som er nødvendig til at opretholde god strukturintegritet i mundhulen, f.eks. høj trykstyrke, høj grad af uopløselighed, 25 etc. Sidstnævnte betingelse er særdeles ønskelig for at formindske udludningen af vigtige bestanddele og den dermed følgende forringelse af polymerisatet.Polymerisable agents for teeth based on the use of methacrylate monomers, e.g. the reaction product of the bis-glycidyl ether of bisphenol A and methacrylic acid (hereinafter referred to as BIS-GMA), is commonly used as fillings 10 and fillers and fillers, cracks and the like, and is particularly suitable for a wide variety of dental restorations. and dental repair treatments. Such agents typically contain one or more methacrylate monomers and at least one component of a free radical-forming (redox) polymerization system for said monomer (s). The monomer material thus prepared usually contains the peroxide type catalyst (oxidizing agent) which later comes into contact with the reducing agent (reducing agent) shortly before use for dental treatment. Upon contact of the oxidizing agent with the reducing agents - which is suitably usually in paste form - polymerization occurs which leads to the formation of a polymer with the physical properties necessary to maintain good structural integrity of the oral cavity, e.g. high compressive strength, high degree of insolubility, etc. The latter condition is highly desirable in order to reduce the leaching of important constituents and the consequent deterioration of the polymer.
Hurtig og fuldstændig hærdning er således særdeles ønskelig. I 3 0 en vi s udstrækn i ng vokser hærdningshastigheden med forøget katalysatorkoncentration. Korrelativ forøgelse i hærdningsgraden opnås imidlertid ikke nødvendigvis. I virkeligheden forholder det sig ofte således, at store katalysatorkoncentrationer svækker hærdn ingsgraden og således giver en forholdsvis større 35 procentdel af uopløselige og udludelige komponenter i det færdige polymerisat. Store mængder af peroxidkatalysator forøger desuden muligheden for forpolymeri sat ion af methacry1atmono-mer, dvs. før kontakt med reduktionsmiddel, således at derThus, rapid and complete curing is highly desirable. In 30 days, the cure rate increases with increased catalyst concentration. However, correlative increase in the cure rate is not necessarily achieved. In fact, it is often the case that large catalyst concentrations weaken the cure rate and thus provide a comparatively greater 35 percent of insoluble and non-soluble components of the finished polymer. Large amounts of peroxide catalyst also increase the possibility of prepolymerization of methacrylate monomers, i.e. before contact with reducing agent so that there
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2 ofte kræves anvendelse af hjælpestoffer, ofte i usædvanligt store mængder med en stabiliserende eller polymerisationshæmmende virkning. Sådanne retarderende virkninger viser sig imidlertid nødvendigvis i nogen udstrækning under monomeroxi-5 dationsmiddel-reduktionsmiddel-kontakten og undertrykker derved hærdningshastigheden og uundgåeligt hæra'ni ngsgraden .2, the use of excipients is often required, often in unusually large quantities with a stabilizing or polymerization inhibitory effect. However, such retarding effects necessarily appear to some extent during the monomer oxidant-reducing agent contact, thereby suppressing the cure rate and inevitably the degree of cure.
Formålet med opfindelsen er at tilvejebringe polymeriserbare midler til tænder uden eller i ringere grad med de foregående 10 og beslægtede ulemper, nærmere bestemt midler, som er i stand til hurtigt at hærde til dannelse af et polymerisat med et forholdsvis højt indhold af uopløselig komponent, som har god strukturstabilitet under de betingelser, som eksisterer i den menneskelige mundhule, hvori ethvert krav til anvendelsen af 15 højere katalysatorkoncentrationer til opnåelse af effektiv hærdningshastighed og -grad undgås, som har de før beskrevne gunstige egenskaber, selv om der ikke indgår fyldstof og/eller koblingskomponenter og lignende, og hvori stabiliteten af·monomer i nærværelse af peroxidkatalysator er forbedret effek-20 tivt.The object of the invention is to provide polymerizable agents for teeth without or to a lesser extent with the foregoing and related disadvantages, in particular, which are capable of rapidly curing to form a polymerisate having a relatively high insoluble component content which have good structural stability under the conditions existing in the human oral cavity, avoiding any requirement for the use of 15 higher catalyst concentrations to achieve effective cure rate and degree, having the previously described beneficial properties, even if no filler and / or coupling components and the like, and wherein the stability of monomer in the presence of peroxide catalyst is effectively improved.
Yderligere udførelsesformer og fordele ved den foreliggende opfindelse vil fremgå af den efterfølgende beskrivelse.Further embodiments and advantages of the present invention will become apparent from the following description.
25 Formålet opnås i overensstemmelse med opfindelsen, som angår et polymeriserbart tandreparationsmateriale omfattende mindst én methacry1atmonomer med 2-4 polymeriserbare dobbeltbindinger, fra ca. 0 til 400%, beregnet på monomeren, uorganisk partikelformet fyldstof, fra ca. 0 til 5%, beregnet på monomeren, 30 si 1ankoblingsmiddel, en effektiv katalysator-aktiverende mængde accelerator omfattende cupriion og fra ca. 0,5 til 5,0%, beregnet på monomeren, af en forbindelse valgt blandt (a) fri radikalfrigivende polymerisationskatalysator omfat tende en organisk peroxyforbindelse, (b) reduktionsmiddel for 35 peroxyforbindelsen og (c) blandinger af (a) og (b), hvori kon centrationen af (b) ikke overstiger ca. 40% af den samlede mængde af (a) og (b), hvilket materiale er ejendommeligt ved, at cupriionen er dispergeret i monomeren, og at den er valgt 3The object is achieved in accordance with the invention, which relates to a polymerizable tooth repair material comprising at least one methacrylate monomer with 2-4 polymerizable double bonds, from about 0 to 400%, based on the monomeric, inorganic particulate filler, from ca. 0 to 5%, based on the monomer, 30 s 1 coupling agent, an effective catalyst-activating amount of accelerator comprising cuprion and from about 0.5 to 5.0%, based on the monomer, of a compound selected from (a) free radical release polymerization catalyst comprising an organic peroxy compound, (b) reducing agent for the peroxy compound, and (c) mixtures of (a) and (b) in which the concentration of (b) does not exceed approx. 40% of the total amount of (a) and (b), which is peculiar in that the cupriion is dispersed in the monomer and selected
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blandt cupri acetat, cupri acetylacetonat, cuprichlorid og blandinger deraf.among cupri acetate, cupri acetylacetonate, cuprichloride and mixtures thereof.
Cuproioner kan eventuelt indgå foruden cupri ionerne, selv om 5 cupri forbi ndel ser har vist sig generelt at være mere effektive med hensyn til opnåelse af både høj hærdningsgrad og -hastighed. Det foretrækkes derfor specielt heri, at cupriion Cu++ udgør mindst ca. 50% af den samlede mængde anvendt kobberion. Som det vil blive påvist i det følgende, giver imidlertid an-10 vendeisen af cuprosalte alene en signifikant forbedring i sammenligning med prøveforsøg, som helt udelader kobberionen. Hvadenten dette skyldes nærværelsen af cupriioner, som uvægerligt findes i cuprosalte, eller cuproionen eller en kombination heraf, har man ikke noget klart indtryk af.Cup ions may optionally be included in addition to the cupri ions, although 5 cupri pastes have generally been found to be more effective in achieving both high cure rate and rate. Therefore, it is particularly preferred herein that cupriion Cu ++ constitute at least approx. 50% of the total amount of copper ion used. However, as will be demonstrated in the following, the use of cuprous salts alone provides a significant improvement over test trials which completely omit the copper ion. Whether this is due to the presence of cup rions, which are invariably found in cuprous salts, or the cup rions or a combination thereof, has no clear impression of.
15 Mængden af indgående kobberion i monomermaterialet er særdeles ringe, idet den sædvanligvis varierer fra ca. 5 til 100 ppm, fortrinsvis 8-50 ppm, beregnet på den samlede mængde monomer. Sagt på en anden måde er mængden af kobberion mindst den mæng-20 de, som er nødvendig til at give effektiv katalysatoraktiverende eller -accelererende virkning. Udtrykket "samlet mængde monomer" anvendes heri som betegnelse for den samlede mængde monomer, som indgår på det tidspunkt, hvor polymerisationen ' faktisk finder sted. Ifølge en foretrukket udførelsesform 25 indgår peroxykata1ysator, monomer og fyldstof, hvis det anvendes, i et første pastamateriale, der benævnes soro "oxidationsmiddel "-pastaen, og reduktionsmidlet for nævnte peroxykataly-sator indgår i en anden "reduktionsmiddel"-pasta, som fortrinsvis indeholder de samme komponenter som den første pasta, 30 bortset fra peroxykatalysatoren. Pastaerne blandes kort tid før dental anvendelse, hvorved polymerisation initieres. Kobberionen kan sættes til begge eller én af pastasammensætningerne, men det foretrækkes specielt, at det indgår i oxidationsmidlet. I hvert tilfælde refererer kobberionkoncentratio-35 nen i denne udførelsesform til den samlede mængde monomer, som indgår i både oxidationsmiddel- og reduktionsmiddelpastaen. På basis af katalysatoren varierer koncentrationen af kobber i on fra ca. 0,02 til 0,4% af peroxyforbinde1 sen. Det foretrækkes 4The amount of copper ion contained in the monomer material is extremely low, usually varying from approx. 5 to 100 ppm, preferably 8-50 ppm, based on the total amount of monomer. Stated another way, the amount of copper ion is at least the amount needed to provide effective catalyst activating or accelerating action. The term "total amount of monomer" is used herein to denote the total amount of monomer included at the time of polymerization actually taking place. According to a preferred embodiment 25, the peroxy catalyst, monomer and filler, if used, are included in a first paste material called the soro oxidant paste, and the reducing agent for said peroxy catalyst is included in a second "reducing agent" paste which preferably contains the same components as the first paste, except for the peroxy catalyst. The pastes are blended shortly before dental use, thereby initiating polymerization. The copper ion can be added to both or one of the paste compositions, but it is particularly preferred that it be included in the oxidizing agent. In each case, the copper ion concentration in this embodiment refers to the total amount of monomer contained in both the oxidizing agent and the reducing agent paste. On the basis of the catalyst, the concentration of copper in on varies from approx. 0.02 to 0.4% of the peroxy compound. It is preferred 4
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almindeligvis at sætte kobberforbindelsen til det flydende monomersystem (uden fyldstof), som er beregnet til oxidationsmiddelpastaen .generally, to put the copper compound into the liquid monomer system (without filler) intended for the oxidizing agent paste.
5 Kobberforbindelsen kan sættes til blandingen ved, at den fordeles i den normalt flydende monomerkomponent.The copper compound can be added to the mixture by distributing it in the normally liquid monomer component.
Den nødvendige dispergering kan opnås ved at sætte kobberforbindelsen til monomeren som en opløsning i et opløsningsmid-10 del, fortrinsvis et polært organisk opløsningsmiddel med lavt kogepunkt, såsom ether eller lavere alkanol, f.eks. methanol.The necessary dispersion can be obtained by adding the copper compound to the monomer as a solution in a solvent, preferably a low boiling point polar organic solvent such as ether or lower alkanol, e.g. methanol.
Da opløsningsmidlet kun er en bærer for kobberforbindelsen, er det særligt hensigtsmæssigt, at det er meget flygtigt, således at almindeligvis størstedelen eller hele mængden af opløs-15 ningsmidlet fjernes ved de efterfølgende behandlinger, f.eks. blanding, etc. Den anvendte opløsningsmiddelmængde er temmelig ringe. Til at give 80 ppm Cu++, og under anvendelse kun af en 1% opløsning i methanol, vil voluminet af opløsningsmiddel således kun blive 12,5% af monomervolumi net og 2,5% af en egnet 20 pasta på vægtbasis.Since the solvent is only a carrier for the copper compound, it is particularly desirable that it is very volatile, so that generally the majority or all of the solvent is removed by the subsequent treatments, e.g. mixture, etc. The amount of solvent used is rather low. Thus, to give 80 ppm Cu ++ and using only a 1% solution in methanol, the volume of solvent will be only 12.5% of monomer volume and 2.5% of a suitable 20 weight by weight paste.
Alternativt kan kobberforbindelsen optages på fy 1dstofkomponenten, f.eks. silica, hvis et sådant materiale anvendes, til blanding med monomerkomponenten eller monomerkomponenterne.Alternatively, the copper compound may be included on the liquid component, e.g. silica, if such material is used, for admixture with the monomer component (s).
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Foruden kobberforbinde1 sen er de foretrukne blandinger heri som følger: Vægtdele 30 Monomer(er) 100In addition to the copper compound, the preferred mixtures herein are as follows: Part by weight 30 Monomer (s) 100
Uorganisk partikel formet fyldstof 0-400Inorganic particulate filler 0-400
Silankoblingsmiddel 0,5-5,0Silane coupling agent 0.5-5.0
Peroxykatalysator 0,5-5,0Peroxycatalyst 0.5-5.0
Reduktionsmiddel 0,3-2,0Reducing agent 0.3-2.0
Methacrylatmonomeren vælges blandt stoffer, som har mindst to 35 og fortrinsvis 2-4 polymeriserbare dobbeltbindinger per molekyle, således at det hærdede sammensatte materiale er tværbundet og mere velegnet til anvendelse i mundhulen. De mest foretrukne monomerer er de, som har to polymeriserbare dobbeltbin-The methacrylate monomer is selected from substances having at least two 35 and preferably 2-4 polymerizable double bonds per molecule such that the cured composite is crosslinked and more suitable for use in the oral cavity. The most preferred monomers are those which have two polymerizable double bonds.
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5 dinger per molekyle. Ønskelige egenskaber for sådanne monomerer omfatter ringe volumenformindskelse ved polymer i sat i on, ringe varmeudvikling under polymerisation, ringe vandoptagelse og evnen til at hærde hurtigt og fuldstændigt i munden. Det er 5 også ønskeligt, at monomererne har lav flygtighed og ikke virker irriterende på tandkødet.5 things per molecule. Desirable properties for such monomers include poor volume reduction by polymer added, poor heat generation during polymerization, poor water uptake and the ability to cure rapidly and completely in the mouth. It is also desirable that the monomers have low volatility and do not irritate the gums.
Methacry1atmonomererne, som er særligt velegnede i forbindelse med denne opfindelse, er dem, der kan illustreres ved hjælp af 10 følgende almene formler: [(M-A-O)n - Ar]2~B (M - A - 0C0)2ArThe methacrylate monomers particularly useful in this invention are those which can be illustrated by the following general formulas: [(M-A-O) n - Ar] 2 ~ B (M - A - OCO) 2Ar
I III II
(M - A)n CRp M2R' (M - A - OCO - NH) 2R3(M - A) n CRp M2R '(M - A - OCO - NH) 2R3
15 111 IV V15 111 IV V
CH2 - MCH2 - M
CH - M'CH - M '
Ch'2 - M VICh'2 - M VI
20 hvori M er methacry!oyloxy, dvs. CH2 = C(CH3)C00-, M' er methacryloyloxy eller hydroxyl, A er alkylen med 1-3 car-bonatomer, såsom methylen, propylen, isopropylen, hydroxy-alkylen med 1-3 carbonatomer, såsom hydroxymethylen, 2-hy- 25 droxypropylen eller acetoxyalkylen med 3-5 carbonatomer i alkylengruppen, såsom 2-acetoxypropy1 en, 3-acetoxyamylen etc., n er 1-4, fortrinsvis 1-2, m er 2 eller 3, og p er 1 eller 2 med den forudsætning, at summen af m og p er 4, R er hydrogen, methyl, ethyl eller -A-M, hvori A og M 30 har de tidligere beskrevne betydninger, Ar er phenylen, f.eks. o-phenylen, m-phenylen eller p-phenylen, alkylsub-stitueret phenylen, f.eks. tolylen eller 5-t-butyl-m-phe=· nylen eller cykloalifatisk med 6-10 carbonatomer, såsom l,3^cyklohexylen, B er 3S χ ^ /C\ 5Wherein M is methacryloxy, ie. CH2 = C (CH3) C00-, M 'is methacryloyloxy or hydroxyl, A is alkylene having 1-3 carbon atoms such as methylene, propylene, isopropylene, hydroxyalkylene having 1-3 carbon atoms such as hydroxymethylene, 2-hydroxyl. Dioxypropylene or acetoxyalkylene having 3-5 carbon atoms in the alkylene group such as 2-acetoxypropylene, 3-acetoxyamylene, etc., n is 1-4, preferably 1-2, m is 2 or 3, and p is 1 or 2 provided that wherein the sum of m and p is 4, R is hydrogen, methyl, ethyl or -AM wherein A and M 30 have the meanings previously described; Ar is phenylene, e.g. o-phenylene, m-phenylene or p-phenylene, alkyl-substituted phenylene, e.g. tolylene or 5-t-butyl-m-phe = nylene or cycloaliphatic having 6-10 carbon atoms, such as 1,3 cyclohexylene, B is 3S χ
RR
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4 r hvori R og R uafhængigt er hydrogen, alkyl, f.eks. C-^-C^, eller substitueret alkyl, og R' er alkylen med 2-12 carbon- 2 2 2 atomer, såsom ethylen, dodecylen etc., eller -R (0-R ) OR , 2 * hvori R er alkylen med 2 eller 3 carbonatomer, såsom 3 ethylen, propylen eller isopropylen, og x er 0-5, og R er 5 phenylen, tolylen, methylen-bis-phenylen eller alkylen med 2-12 carbonatomer.Wherein R and R are independently hydrogen, alkyl, e.g. Or substituted alkyl, and R 'is alkylene having 2-12 carbon atoms such as ethylene, dodecylene, etc., or -R (O-R) OR, 2 * wherein R is alkylene with 2 or 3 carbon atoms, such as 3 ethylene, propylene or isopropylene, and x is 0-5 and R is phenylene, tolylene, methylene bis-phenylene or alkylene with 2-12 carbon atoms.
Monomerer med de ovennævnte formler er velkendte og almindeligvis i handelen tilgængelige materialer. Alternativt tillo vejebringes de let ved anvendelse af almindelige syntese-veje, f.eks. ved omsætning af en phenolisk forbindelse, såsom diphenolisk syre, phloroglucinol eller bisphenol A med glycidylmethacrylat i nærværelse af forskellige tertiære aminer eller ved omsætning af methacrylsyre med et epoxid indeholdende en forbindelse, såsom diglycidyletheren af en bisphenol. Nogle af disse monomerer fremstilles også ved omsætning af passende alkoholer med methacrylsyre, methacrylylchlorid eller methacrylsyreanhydrid.Monomers of the above formulas are well-known and commonly available commercially available materials. Alternatively, they are readily facilitated by using ordinary synthetic routes, e.g. by reacting a phenolic compound such as diphenolic acid, phloroglucinol or bisphenol A with glycidyl methacrylate in the presence of various tertiary amines or by reacting methacrylic acid with an epoxide containing a compound such as the diglycidyl ether of a bisphenol. Some of these monomers are also prepared by reacting appropriate alcohols with methacrylic acid, methacrylyl chloride or methacrylic anhydride.
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Eksempler pa monomerer med disse formler omfatter: CH2=C (CH3) COOCH2CH2-OCO—j-gj— C00CH2CH20C0C (CH3) =€H2, 25 ch2=c (ch3) æ2oa)j^ (ch3 ) = ch2Examples of monomers of these formulas include: CH2 = C (CH3) COOCH2CH2-OCO-j-gj- C00CH2CH20CO (CO3) = € H2, ch2 = c (ch3) (2O) j2 (ch3) = ch2
HO CH3 CH3 OHHO CH3 CH3 OH
30 C{CH2OCOC(CH3) = ch2j4, CH3CH2C i CH2-0-C-C=CH2)3, o ch3 35 CH2= C(CH3)COO(CH2)4OCOC(CH3)=CH2, CH2= C(CH3)COOCH2CH2OCH2CH2OCH2CH2OCOC(CH2)=CH2,C {CH2OCOC (CH3) = ch2j4, CH3CH2C in CH2-0-CC = CH2) 3, o ch3 CH2 = C (CH3) COO (CH2) 4OCOC (CH3) = CH2, CH2 = C (CH3) COOCH2CH2OCH2CH2OCH2CH2OCOC ( CH2) = CH 2,
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ch2=c (ch3) cooch2ch (oh) ch2-o-0-o^h2^h (OH) ch2ococ (ch3) =CHch2 = c (ch3) cooch2ch (oh) ch2-o-0-o ^ h2 ^ h (OH) ch2ococ (ch3) = CH
5 ch2= c (ch3) c (ch3) 2—^0^— o-c°c (ch3) =ch2 ' CH2=C (CH3) COO-CH2CH (OH) CH2-0-U) /—(o V" °CH2CH (OH) CH2OCOC (CH3) =ch 10 I 9 OCH2CH (OH) OCOC (CH31=CH2 ch3 CH2= C (Οί3) 00><Ή2(Ώ2ΟΟΟΝΗ-γ^Ν 15 \^smcoocH2cH2ococ (ay =CH25 ch 2 = c (ch 3) c (ch 3) 2 - 0 O - ° c (ch 3) = ch 2 'CH 2 = C (CH 3) COO-CH 2 CH (OH) CH 2 -O-U) / - (o V " ° CH2CH (OH) CH2OCOC (CH3) = ch 10 I 9 OCH2CH (OH) OCOC (CH31 = CH2 ch3 CH2 = C (Οί3) 00> <Ή2 (Ώ2ΟΟΟΝΗ-γ ^ Ν 15 \ ^ smcoocH2cH2ococ (ay = CH2
CHCH
CH2=C (CH3) GOO-CH2CH--OCCNH-CH2CH2C -C-C -CH2-NHCOOCH-CH2'-OCO-C (CH3) =CH2 ' * H ' i,„CH2 = C (CH3) GOO-CH2CH - OCCNH-CH2CH2C -C-C -CH2-NHCOOCH-CH2'-OCO-C (CH3) = CH2 '* H' i, "
CH CH CHCH CH CH
20 Monomerer med formlerne I, II, III og IV foretrækkes ved ud øvelsen af den foreliggende opfindelse. Af disse monomerer foretrækkes specielt I, II og IH, idet monomererne IV oftere anvendes i blanding med én eller flere af monomererne I, II og III.Monomers of formulas I, II, III and IV are preferred in the practice of the present invention. Of these monomers, I, II and IH are particularly preferred, with monomers IV being more frequently used in admixture with one or more of monomers I, II and III.
2525
Andre nyttige methacrylatmonomerer, som er velegnede til anvendelse ved udøvelsen af den foreliggende opfindelse, omfatter dan, som har de følgende formler, hvori M og Ar har de tidligere definerede betydninger.Other useful methacrylate monomers suitable for use in the practice of the present invention include dan which has the following formulas wherein M and Ar have the meanings previously defined.
30 4 4 (MR OAr)2C(CH3)2, hvori R er isopropylen, r c 5 (MR OAr)2 og (MR 0)2Ar, hvori R er 2-hydroxypropylen, MA R^M, hvori R^ er hydroxycyklopentyl eller hydroxycyklo= 8 8 35 hexyl, og A er 2-hydroxyethylén, og M2R/ hvori R er:4 4 (MR OAr) 2C (CH 3) 2 wherein R is isopropylene, rc 5 (MR OAr) 2 and (MR 0) 2Ar wherein R is 2-hydroxypropylene, MA R 1 M, wherein R 1 is hydroxycyclopentyl or hydroxycyclo = 8.8 hexyl and A is 2-hydroxyethylene and M 2 R / wherein R is:
„ DK 157727B"DK 157727B
OISLAND
(Λ) ΟΪΌ-· prr '-' CH3 5 (Βί /“λ (C) 10 0 “^0^— CI^- eller(Λ) ΟΪΌ- · prr '-' CH3 5 (Βί / “λ (C) 10 0“ ^ 0 ^ - CI ^ - or
(ϋ) .—V(ϋ). — V
^H2-\0)-CH2- 15^ H2- \ O) -CH2- 15
Fremstillingsdetaljer for mange af disse monomerer er angivet i US patentskrifterne nr. 3.066.112, 3.721.644, 3.730.947, 3.770.881 og 3.774.305. En tertiær eutektisk monomerblanding, der ligeledes er velegnet til anvendelse 20 i forbindelse med den foreliggende opfindelse,er beskrevet i US patentskrift nr. 3.539.526. Alle de førnævnte patentskrifter er som helhed at anse for inkorporeret i den foreliggende tekst.Preparation details for many of these monomers are set forth in U.S. Patent Nos. 3,066,112, 3,721,644, 3,730,947, 3,770,881 and 3,774,305. A tertiary eutectic monomer mixture which is also suitable for use in the present invention is described in U.S. Patent No. 3,539,526. All of the aforementioned patents as a whole are to be considered as incorporated in the present text.
25 Det må forstås, at blanding af to eller flere passende methacrylatmonomerer falder inden for den foreliggende opfindelses omfang. Afhængig af valget af monomerer er det i virkeligheden ofte særdeles fordelagtigt med blandinger til optimering af egenskaberne af det resulterende middel 30 til tænder. Det foretrækkes således, at monomeren eller monomerblandingen har en viskositet fra ca. 100 til ca.It is to be understood that mixing two or more suitable methacrylate monomers falls within the scope of the present invention. In fact, depending on the choice of monomers, it is often very advantageous for mixtures to optimize the properties of the resulting agent 30 for teeth. Thus, it is preferred that the monomer or monomer mixture has a viscosity of approx. 100 to approx.
10.000 centipoise bestemt ved anvendelse af et Brookfield-viskosimeter ved 20 omdrejninger pr. minut ved stuetemperatur.10,000 centipoise determined using a Brookfield viscometer at 20 rpm. minute at room temperature.
Det uorganiske partikelformede fyldstof, der anvendes i midlerne ifølge opfindelsen,omfatter smeltet silica, kvarts, 35The inorganic particulate filler used in the compositions of the invention comprises molten silica, quartz,
j DK 157727 Bj DK 157727 B
krystallinsk silica., amorft silica, sodaglasperler, glasstænger, keramiske oxidér, partikelformet silicatglas, røntgenstråleuigennemtrængelige glasser,(barium- og stro.ntiumglas) og syntetiske mineraler, såsom β-eucryptik 5 (LiAlSiC>4) , idet sidstnævnte har en negativ varmeudvidelses-koefficient. Det er også muligt at anvende findelte materialer og pulverformet hydroxylapatit, selv om materialer, der reagerer med silankoblingsmidler,foretrækkes. Anvendeligt som fyldstof er desuden kolloide eller submikron silicaer ^ overtrukket med en polymer. Små pigmentmængder, som gør det muligt, at midlet kan tilpasses forskellige tandfarver, kan indgå. Egnede pigmenter omfatter jernoxidsort, kadmiumgule og oranger, fluorescerende zinkoxider, titaniumdioxid etc.. Fyldstofpartiklerne vil almindeligvis være under ca.crystalline silica., amorphous silica, soda beads, glass bars, ceramic oxides, particulate silicate glass, X-ray impermeable glasses, (barium and straw glass) and synthetic minerals such as β-eucryptics 5 (LiAlSiC> 4), the latter having a negative coefficient. It is also possible to use finely divided materials and powdered hydroxylapatite, although materials that react with silane coupling agents are preferred. In addition, as a filler, colloidal or submicron silicas are coated with a polymer. Small amounts of pigment which allow the agent to be adapted to different tooth colors can be included. Suitable pigments include iron oxide black, cadmium yellow and oranges, fluorescent zinc oxides, titanium dioxide, etc. The filler particles will generally be less than approx.
15 50 mikron i diameter og fortrinsvis under 30 mikron. Det skal bemærkes, at fyldstoffet er en valgfri bestanddel, idet produkter uden fyldstof anvendes, hvor midler til tænderne er beregnet til anvendelse som belægning, tandsideklæbestof til amalgamplomber eller klæbestof.About 50 microns in diameter and preferably below 30 microns. It should be noted that the filler is an optional component, with products without filler being used where the teeth for the teeth are intended for use as a coating, toothpaste adhesive for amalgam seals or adhesive.
2020
Silankoblingsmidlerne er stoffer, som indeholder mindst én polymeriserbar dobbeltbinding til reaktion med methacrylat- monomererne. Eksempler på egnede koblingsmidler er vinyl= trichlorsilan, tris(acetoxy)vinylsilan, 1-N(vinylbenzyl= 25 aminoethyl)aminopropyltrimethoxysilan-3 eller 3-methacryl= oxypropyltrimethoxysilan. Det sidstnævnte stof foretrækkes til anvendelse med methacrylatmonome rer på grund af den ensartede reaktivitet af dobbeltbindingerne.The silane coupling agents are substances which contain at least one polymerizable double bond for reaction with the methacrylate monomers. Examples of suitable coupling agents are vinyl = trichlorosilane, tris (acetoxy) vinylsilane, 1-N (vinylbenzyl = aminoethyl) aminopropyltrimethoxysilane-3 or 3-methacrylic = oxypropyltrimethoxysilane. The latter substance is preferred for use with methacrylate monomers because of the uniform reactivity of the double bonds.
3030
Peroxykatalysatorer, som er velegnede heri og er i stand til at initiere polymerisation af methacrylatmonomeren (eller -monomererne), er velkendte i teknikken til sådan anvendelse og omfatter uden derfor at være begrænset hertil konventionelle peroxy- såvel som hydroperoxyforbindelser, såsom cumen= 3 5 hydrogenperoxid, p-methanhydrogenperoxid, dnsopropylbenzen-hydrogenperoxid og t-butylhydrogenperoxider. Hydrogenperoxider erPeroxy catalysts suitable herein and capable of initiating polymerization of the methacrylate monomer (s) are well known in the art for such use and include, without limitation, conventional peroxy as well as hydroperoxy compounds such as cumene = hydrogen peroxide. , p-methane hydrogen peroxide, dnsopropylbenzene hydrogen peroxide and t-butyl hydrogen peroxides. Hydrogen peroxides are
10 DK 157727 BDK 157727 B
de foretrukne former af organisk peroxypolymerisationska-talysator, idet cumenhydrogenperoxid (CHP) særligt foretrækkes. Om ønsket kan peroxidstabilisatorer, såsom ascorbinsyre, maleinsyre og lignende, indgå i små mængder.the preferred forms of organic peroxypolymerization catalyst, with cumene hydrogen peroxide (CHP) being particularly preferred. If desired, peroxide stabilizers such as ascorbic acid, maleic acid and the like may be present in small amounts.
5 Reducerende midler, som er nyttige heri, omfatter alminde ligvis ethvert stof, som er i stand til at reagere med peroxyforbindeIsen til dannelse af polymerisationsinitierende, fri radikalformer, således som det er kendt i teknikken. Særligt velegnet heri er et substitueret thiourinstof med I g formlenReducing agents useful herein generally include any substance capable of reacting with the peroxy compound to form polymerization-initiating free radical forms, as is known in the art. Particularly suitable herein is a substituted thiourea of 1 g of formula
Y SY S
X-----n-------C-----ZX n ----- ----- ------- C Z
hvori X er H eller Y, og Y er alkyl med 1-8 carbonatomer, 15 såsom methyl, butyl, octyl, cykloalkyl med 5-6 carbonatomer, såsom cyklopentyl, cyklohexyl, chlor, hydroxy eller mercap= to, der er substitueret med alkyl med 1-8 carbonatomer, såsom chlorethyl, mercaptoethyl, hydroxymethyl og chloroctyl, alkenyl med 3-4 carbonatomer, såsom allyl eller methallyl, 20 aryl med 6-8 carbonatomer, såsom phenyl eller xylyl, og chlor-, hydroxy-, methoxy- eller sulfonylsubstitueret phe= nyl, såsom chlorphenyl, phenylsulfonyl, hydroxyphenyl og methoxyphenyl, acyl med 2-8 carbonatomer, såsom acetyl, butyryl, octanoyl, chlor- eller methoxysubstitueret acyl, 25 såsom chloracetyl, chlorbenzoyl, chlortoluoyl og methoxy= benzoyl, aralkyl med 7-8 carbonatomer, såsom benzyl, el.ler chlor- eller methylsubstitueret aralkyl, såsom methoxybenzyl, og Z er Νϊ^, NHX eller Eksempler på forbindelser, som er velegnede til brug ved udøvelsen af denne opfindelse er 30 methylthiourinstof, isopropylthiourinstof, butylthiourinstof, octylthiourinstof, benzylthiourinstof, acetylthiourinstof, benzoylthiourinstof, octanoylthiourinstof, cyklohexylthio= urinstof, allylthiourinstof, 1,1,3-triphenylthiourinstof, 1,1,3-trimethylthiourinstof, 2,4-xylylthiourinstof, p-35 tolylsulfonylthiourinstof, l-octyl^3-phenylthiourinstof, o-methoxyphenylthiourinstof, m-hydroxyphenylthiourinstof, 1,1-diallylthiourinstof, 1,3-diallylthiourinstof, 2-methal-lylthiourinstof, o-methoxybenzylthiourinstof, l-(hydroxy=wherein X is H or Y and Y is alkyl of 1-8 carbon atoms, such as methyl, butyl, octyl, cycloalkyl of 5-6 carbon atoms, such as cyclopentyl, cyclohexyl, chloro, hydroxy or mercap = 2 substituted by alkyl with 1-8 carbon atoms such as chloroethyl, mercaptoethyl, hydroxymethyl and chloroctyl, alkenyl of 3-4 carbon atoms such as allyl or methallyl, aryl of 6-8 carbon atoms such as phenyl or xylyl, and chloro, hydroxy, methoxy or sulfonyl-substituted phenyl such as chlorophenyl, phenylsulfonyl, hydroxyphenyl and methoxyphenyl, acyl of 2-8 carbon atoms such as acetyl, butyryl, octanoyl, chloro or methoxy substituted acyl such as chloroacetyl, chlorobenzoyl, chloro toluyl and methoxyphenyl 8 carbon atoms such as benzyl, or chloro or methyl substituted aralkyl such as methoxybenzyl and Z are Νϊ, NHX or Examples of compounds suitable for use in the practice of this invention are 30 methylthiourea, isopropylthiourea or, butylthiourea, octylthiourea, benzylthiourea, acetylthiourea, benzoylthiourea, octanoylthiourea, cyclohexylthio = urea, allylthiourea, 1,1,3-triphenylthiourea, 1,1,3-trimethylthiourea, 1,1,3-trimethylthiourea ^ 3-phenylthiourea, o-methoxyphenylthiourea, m-hydroxyphenylthiourea, 1,1-diallylthiourea, 1,3-diallylthiourea, 2-methyl-thiourea, o-methoxybenzylthiourea, 1- (hydroxy =
DK 157727BDK 157727B
methyl)-3-methylthiourinstof, 1,1-dibutylthiourinstof, 1,3- dibutylthiourinstof, 1-(p-chlorphenyl)-3-methylthiourinstof, l-butyl-3-butyrylthiourinstof, l-acetyl-3-phenylthiourin- stof, l-methyl-3-(p-vinylphenyl)thiourinstof, l-methyl-3-0- tolylthiourinstof, l-methyl-3-pentylthiourinstof, 3-methyl-5 3-pentylthiourinstof, 3-methyl-l,l-diphenylthiourinstof og l-acetyl-3-(2-mercaptoethyl)thiourinstof, Selv om ethvert af de ovennævnte thiourinstoffer kan anvendes i forbindelse med den foreliggende opfindelse, foretrækkes de monosubstituerede thiourinstoffer, dvs. de med de førnævnte formler, 10 hvori X er H, og Z er NH^. Phenylthiourinstof, acetylthio= urinstof og ally1thiourinstof foretrækkes specielt. Midlet indeholder fortrinsvis ca. 0,5-ca. 1 vægt% reduktionsmiddel.methyl) -3-methylthiourea, 1,1-dibutylthiourea, 1,3-dibutylthiourea, 1- (p-chlorophenyl) -3-methylthiourea, 1-butyl-3-butyrylthiourea, 1-acetyl-3-phenylthiourea, 1 -methyl-3- (p-vinylphenyl) thiourea, 1-methyl-3-O-tolylthiourea, 1-methyl-3-pentylthiourea, 3-methyl-3-pentylthiourea, 3-methyl-1,1-diphenylthiourea and l -acetyl-3- (2-mercaptoethyl) thiourea Although any of the above thioureas may be used in connection with the present invention, the monosubstituted thioureas, i.e. those of the aforementioned formulas, wherein X is H and Z is NH 2. Phenylthiourea, acetylthiourea and allythiourea are particularly preferred. Preferably, the agent contains approx. 0.5-ca. 1% by weight of reducing agent.
De følgende eksempler belyser den foreliggende opfindelse.The following examples illustrate the present invention.
1515
Eksemplerne 1-14.Examples 1-14.
Der fremstilles røntgenstråleuigennemtrængelige reduktions- 20 middelpastaer af følgende sammensætninger: 25 30 35X-ray impermeable reducing agent pastes are prepared from the following compositions: 25 30 35
DK 157727BDK 157727B
12 S ammens ætn ing i vægt%.12 S ammation in weight%.
Bestanddel A B C D E F G HIngredient A B C D E F G H
•WoL 10,27 10,24 10,27 10,27 10,27 10,27 10,27 10,27 2HMDm 10,27 10,24 10,27 10,27 10,27 10,27 10,27 10,27 5 3A-174 1,03 1,02 1,03 1,03 1,03 1,03 1,03 1,03 Aætylthiourinstof 0,43 0,43 0,43 0,43 0,43 0,43 0,43 0,43• WoL 10,27 10,24 10,27 10,27 10,27 10,27 10,27 10,27 2HMDm 10,27 10,24 10,27 10,27 10,27 10,27 10,27 10, 27 5 3A-174 1.03 1.02 1.03 1.03 1.03 1.03 1.03 1.03 Ethylthiourea 0.43 0.43 0.43 0.43 0.43 0.43 0, 43 0.43
Ascorbinsyre - 0,07 - - - *Ca* - - 0,00022 0,00044 /)011 ,0022 ,0033 ,0044 5lmsil A-10 41,86 41,86 41,86 41,86 41,86 41,86 41,86 41,86 10 6Coimng 7724 36,14 36,14 36,14 36,14 36,14 36,14 36,14 36,14 I alt 100 100 100 100 100 100 100 100 1 - Bis (GMA) 2 - 1,6-hexandioldimethacrylat 3 - z-methacryloxypropyltrimethoxysilan 4 15 - i form af cupriacetat tilsat fra methanolopløsning til monomerblanding 5 - amorft silica (Illinois Minerals} 6 - bariumglas (Corning).Ascorbic Acid - 0.07 - - - * Ca * - - 0.00022 0.00044 /) 011, 0022, 0033, 0044 5lmsil A-10 41.86 41.86 41.86 41.86 41.86 41.86 41.86 41.86 10 6Coimng 7724 36.14 36.14 36.14 36.14 36.14 36.14 36.14 36.14 Total 100 100 100 100 100 100 100 100 1 - Bis (GMA) 2 - 1,6-hexanediol dimethacrylate 3- z -methacryloxypropyltrimethoxysilane 4 - in the form of cupriacetate added from methanol solution to monomer mixture 5- amorphous silica (Illinois Minerals} 6 - barium glass (Corning).
Der fremstilles røntgenstråleuigennemtrængelige oxidations-20 middelpastaer af følgende sammensætninger: 13X-ray impermeable oxidizing agent pastes are prepared from the following compositions: 13
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Sammensætning i vægt%.Composition in weight%.
Bestanddel I. J.Component I. J.
Nupol '9,94 9,78 HMDMA 9,94 9,78 5 A - 174 0,99 0,98Nupol '9.94 9.78 HMDMA 9.94 9.78 5 A - 174 0.99 0.98
Maleinsyremaleic acid
Ascorbinsyre 0,07 -Ascorbic Acid 0.07 -
Cumenhydrogenperoxid (80%) 1,05 1,05Cumene hydrogen peroxide (80%) 1.05 1.05
Imsil A-10 41,93 41,79 10 Corning 7724 36,06 36,22 I alt 100 100Imsil A-10 41.93 41.79 10 Corning 7724 36.06 36.22 Total 100 100
Lige vægtdele af oxidationsmiddelpasta og reduktionsmiddelpasta blandes som angivet i de efterfølgende eksempler. Hærdningstider er angivet i minutter og omfatter den tid, 15 som er nødvendig til blanding, ca. 30 sekunder. Hærdningsreaktionens ophør bestemmes ved, at materialet ikke længere kan deformeres med en spatel. Det kan også ske ved at måle procenten af polymerisat, der er uopløseligt i methanol, efter endt hærdningsreaktion. Prøver af den polymerdannende 20 masse udtages med mellemrum under hærdningsreaktionen. Hærdningsreaktionens ophør angives ved hjælp af det punkt, hvor det procentiske indhold af uopløseligt stof forbliver i alt væsentligt konstant. Resultaterne er sammenfattet som følger: 14Equal parts by weight of oxidizing agent and reducing agent paste are mixed as indicated in the following examples. Curing times are given in minutes and include the time required for mixing, approx. 30 seconds. The cessation of the curing reaction is determined by the fact that the material can no longer be deformed with a spatula. It can also be done by measuring the percentage of polymer soluble insoluble in methanol after curing reaction. Samples of the polymer-forming mass are sampled at intervals during the curing reaction. The cessation of the curing reaction is indicated by the point at which the percent soluble content remains substantially constant. The results are summarized as follows:
DK 1S7727BDK 1S7727B
Eksempel Oxidations- Reduk- ppm Cu Hærdning Temperatur nr. middel- tions- i reduktions- minutter o pasta middel- middelpasta . . .....pasta.....Example Oxidation Reduction ppm Cu Curing Temperature No. average- in reduction minutes o paste medium paste. . .....pasta.....
51 J C 2,2 3,5-4,3 21 2 " D 4,4 2,8-3,2 23 3 " E 11,0 1,8-2,2 23 4 " F 22,0 1,7-2,2 20,5 5 " G 33,0 1,5-1,8 21,5 10 6 " H 44,0 1,3-1,8 23 7 " A intet 4,0-5,0 27 8 1 C 2,2 3,3-3,8 21 9 " X> 4,4 2,7-3,5 22,5 10 " E 11,0 1,8-2,2 23 15 11 " F 22,0 1,7-2,0 20,5 12 " G 33,0 1,3-1,7 21 13 " H 44,0 1,25-1,6 23 14 " A intet 3,3-4,0 21 20 X hvert af forsøgene sker hærdningen i luft, dvs. i et ++ åbent kar. Forøget koncentration af Cu giver en hurtigere hærdning.51 JC 2.2 3.5-4.3 21 2 "D 4.4 2.8-3.2 23 3" E 11.0 1.8-2.2 23 4 "F 22.0 1.7 -2.2 20.5 5 "G 33.0 1.5-1.8 21.5 10 6" H 44.0 1.3-1.8 23 7 "A nothing 4.0-5.0 27 8 1 C 2.2 3.3-3.8 21 9 "X> 4.4 2.7-3.5 22.5 10" E 11.0 1.8-2.2 23 15 11 "F 22 , 0 1.7-2.0 20.5 12 "G 33.0 1.3-1.7 21 13" H 44.0 1.25-1.6 23 14 "A nothing 3.3-4, 0 21 20 X each of the tests cures in air, ie. in a ++ open vessel. Increased concentration of Cu results in faster curing.
I sammenligning med eksemplerne 7 og 14, som udelader kobberacceleratoren, viser de anførte data en forbedring i 25 hærdningshastigheden for den foreliggende opfindelse.Compared with Examples 7 and 14 which omit the copper accelerator, the data presented shows an improvement in the cure rate of the present invention.
Lignende kombinationer (1:1) af reduktionsmiddelpasta B med X og J giver tilsvarende resultater.Similar combinations (1: 1) of reducing agent paste B with X and J give similar results.
Eksemplerne 15-17.Examples 15-17.
Fremgangsmåden fra de foregående eksempler gentages, men der 30 anvendes en Nupol: HMDMA (71:29) monomerblanding efter vægt i hvert af oxidationsmiddel- og reduktionsmiddelprodukterne.The procedure of the preceding examples is repeated, but a Nupol: HMDMA (71:29) monomer mixture by weight is used in each of the oxidant and reducing agent products.
Fyldstof udelades helt i hvert af eksemplerne. Kobberioner leveres af følgende forbindelser:Filler is completely omitted in each of the examples. Copper ions are provided by the following compounds:
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1515
Eksempel hr. Accelerator 15 cupriacetat 16 cuprichlorid 5 17 cupriacetonylacetonat (intet opløsningsmiddel) X hvert tilfælde opnås forbedret hærdningshastighed i sammenligning med identiske kontrolforsøg, hvor der ikke indgår nogen kobberforbindelse.Example Mr Accelerator 15 cupriacetate 16 cuprichloride 5 17 cupriacetonylacetonate (no solvent) X each case, improved cure rate is achieved compared to identical control experiments where no copper compound is included.
Eksemplerne 18-20.Examples 18-20.
10 Fremgangsmåden fra eksemplerne 15-17 gentages, men under anvendelse af følgende stoffer som acceleratorer:The procedure of Examples 15-17 is repeated, but using the following substances as accelerators:
Eksempel nr'.' Accelerator (Vægtforhold) 18 cupriacetat/cuprichlorid (50:50) 19 cupriacetat/cuprochlorid (50:50) 15 20 cuprichlorid/cuprochlorid (50:50).Example No. ' Accelerator (Weight ratio) 18 cupriacetate / cuprichloride (50:50) 19 cupriacetate / cuprochloride (50:50) 15 20 cuprichloride / cuprochloride (50:50).
Resultaterne svarer til resultaterne i de foregående eksempler.The results are similar to the results in the previous examples.
Eksemplerne 21-34.Examples 21-34.
Hvert af eksemplerne 1-14 gentages, bortset fra, at cupri= 20 acetatet optages på fyldstoffet og derpå sættes til mono= mermaterialet. Lignende forbedring opnås i hærdningshastighed i sammenligning med kontrolforsøg, hvor kobberforbindelsen udelades.Each of Examples 1-14 is repeated except that the cupri = 20 acetate is taken up on the filler and then added to the monomer material. Similar improvement is achieved in cure rate compared to control experiments where the copper compound is omitted.
Eksemplerne' 35-37.Examples' 35-37.
25 Der fremstilles følgende reduktionsmiddelholdige og oxida-tionsmiddelholdige materialer:The following reducing agent-containing and oxidizing agent-containing materials are prepared:
DK 157727 BDK 157727 B
1616
Beduk ti onsmi dde 1-.Mark to Wed 1-4.
Sammensætning i' vægtsComposition in 'weight
Bestanddel K L MIngredient K L M
NUPOL 9,9 9,9 9,9 5 HMDMA 9,9 9,9 9,9NUPOL 9.9 9.9 9.9 5 HMDMA 9.9 9.9 9.9
Acetylthiourinstof 0,45 0,45 0,45Acetylthiourea 0.45 0.45 0.45
Cu++ 0,0002 0,0005 0,0010Cu ++ 0.0002 0.0005 0.0010
Corning 7724a 36,25 36,25 . 36,25 XMS1L A-10a 42,25 42,25 42,25 10 Kolloidt silica 1,/30 1,30 1,30 a. Silaniseret.Corning 7724a 36.25 36.25. 36.25 XMS1L A-10a 42.25 42.25 42.25 10 Colloidal Silica 1, / 30 1.30 1.30 a. Silanized.
Oxi dat jonsmiddels afflmensætning - NOxi dat ioning agent affliction - N
Bestanddel Sammens ætn ing i vægt% NUPOL 9,325 15 HMDMA 9,325 CHP (80S) 1,05Ingredient Composition weight% NUPOL 9,325 HMDMA 9,325 CHP (80S) 1.05
Corning 7724a 36,25 IMSIL A-10a 46,25Corning 7724a 36.25 IMSIL A-10a 46.25
Kolloidt silica 1,80 20 a. Silaniseret.Colloidal Silica 1.80 20 a. Silanized.
Oxidationsmiddelpastaen blandes på en ren glasplade med hvert af de tre reduktionsmiddelpastaer i et 1:1 forhold. Hærdningstider for hver af de tre blandinger bestemmes som den tid, der hengår, før det blandede materiale er modstands-25 dygtig over for dimensionsændring ved hjælp af en plastspatel. Resultaterne er sammenfattet som følger:The oxidant paste is mixed on a clean glass plate with each of the three reducing agent pastes in a 1: 1 ratio. Curing times for each of the three blends are determined as the time remaining before the blended material is resistant to dimensional change by a plastic spatula. The results are summarized as follows:
Claims (11)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US14519980A | 1980-04-29 | 1980-04-29 | |
| US14519980 | 1980-04-29 |
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| DK189781A DK189781A (en) | 1981-10-30 |
| DK157727B true DK157727B (en) | 1990-02-12 |
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| DK189781A DK157727B (en) | 1980-04-29 | 1981-04-29 | POLYMERIZABLE DENTAL MATERIALS WITH ACCELERATED CURRENCY SPEED |
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| Country | Link |
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| JP (1) | JPS56169609A (en) |
| AT (1) | AT376125B (en) |
| AU (1) | AU554532B2 (en) |
| BE (1) | BE888599A (en) |
| BR (1) | BR8102607A (en) |
| CA (1) | CA1223696A (en) |
| CH (1) | CH649465A5 (en) |
| DE (1) | DE3116132A1 (en) |
| DK (1) | DK157727B (en) |
| ES (1) | ES8206560A1 (en) |
| FR (1) | FR2481114A1 (en) |
| GB (2) | GB2075035B (en) |
| IE (1) | IE51152B1 (en) |
| MX (1) | MX156002A (en) |
| NL (1) | NL8102128A (en) |
| NO (1) | NO158991C (en) |
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| PH (1) | PH17044A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3928987A1 (en) * | 1989-09-01 | 1991-03-28 | Siegfried Reiss | METHOD AND SHAPE FORM FOR PRODUCING SHAPINGS FOR THE DENTAL AREA |
| DE4339399A1 (en) * | 1993-11-18 | 1995-05-24 | Thera Ges Fuer Patente | Dental inserts prodn. for use with composite filling materials. |
| US20070100019A1 (en) * | 2005-08-02 | 2007-05-03 | Fuming Sun | Catalyst system for dental compositions |
| DE102005039590B4 (en) * | 2005-08-19 | 2008-05-21 | Heraeus Kulzer Gmbh | Polymerizable dental composition with a 2-component initiator system |
| EP1849449A1 (en) * | 2006-04-26 | 2007-10-31 | 3M Innovative Properties Company | Filler containing composition and process for production and use thereof |
| WO2008134024A2 (en) * | 2007-04-25 | 2008-11-06 | Dentsply International Inc. | Self-adhesive dental cement |
| JP2009292761A (en) * | 2008-06-04 | 2009-12-17 | Kuraray Medical Inc | Curable composition for dental use |
| JP5388482B2 (en) * | 2008-06-04 | 2014-01-15 | クラレノリタケデンタル株式会社 | Dental curable composition |
| CN102702405B (en) * | 2012-07-05 | 2014-04-09 | 东营市诺尔化工有限责任公司 | Method for preparing ultralow-residue water absorbing resins |
| JP6112887B2 (en) * | 2013-02-05 | 2017-04-12 | 株式会社トクヤマデンタル | Dental curable composition |
| JP6086797B2 (en) * | 2013-04-25 | 2017-03-01 | クラレノリタケデンタル株式会社 | Dental polymerizable composition |
| JP6857600B2 (en) | 2014-07-10 | 2021-04-14 | スリーエム イノベイティブ プロパティズ カンパニー | Two-component self-adhesive dental composition, its manufacturing method, and its use |
| AU2016218284A1 (en) | 2015-02-09 | 2017-07-27 | Zest Ip Holdings, Llc | Dental compositions and methods of use |
| AU2018394851B2 (en) * | 2017-12-26 | 2021-03-11 | Tokuyama Dental Corporation | Chemical polymerization initiator, adhesive composition, adhesive composition kit, dental material, dental material kit, and method of storing adhesive composition |
| EP3808324A1 (en) * | 2019-09-26 | 2021-04-21 | Shofu Inc. | Curable composition containing transition metal adsorbent |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB714868A (en) * | 1951-12-24 | 1954-09-01 | Dental Fillings Ltd | Improvements in or relating to polymerisation products |
| GB1177879A (en) * | 1967-09-04 | 1970-01-14 | Sumitomo Chemical Co | Catalyst System and process for the Polymerisation of Vinyl Compounds |
| JPS4842467B1 (en) * | 1970-12-04 | 1973-12-12 | ||
| JPS5223509B2 (en) * | 1973-04-26 | 1977-06-24 | ||
| JPS587646B2 (en) * | 1974-05-31 | 1983-02-10 | 東亞合成株式会社 | Niekiseikoukaseisoseibutsu |
| JPS516224A (en) * | 1974-07-05 | 1976-01-19 | Johnson & Johnson | |
| US3991008A (en) * | 1974-08-12 | 1976-11-09 | The Kendall Company | Dental compositions having improved color stability |
| JPS51131197A (en) * | 1975-05-08 | 1976-11-15 | Sankin Ind Co | Uniiliquid type dental cement |
-
1981
- 1981-04-16 NZ NZ196864A patent/NZ196864A/en unknown
- 1981-04-16 ZA ZA00812567A patent/ZA812567B/en unknown
- 1981-04-23 DE DE19813116132 patent/DE3116132A1/en not_active Withdrawn
- 1981-04-27 AT AT0187781A patent/AT376125B/en not_active IP Right Cessation
- 1981-04-27 SE SE8102634A patent/SE450547B/en not_active IP Right Cessation
- 1981-04-28 AU AU69911/81A patent/AU554532B2/en not_active Ceased
- 1981-04-28 FR FR8108413A patent/FR2481114A1/en active Granted
- 1981-04-28 ES ES501695A patent/ES8206560A1/en not_active Expired
- 1981-04-28 BE BE0/204628A patent/BE888599A/en not_active IP Right Cessation
- 1981-04-28 BR BR8102607A patent/BR8102607A/en unknown
- 1981-04-28 PH PH25567A patent/PH17044A/en unknown
- 1981-04-28 NO NO811448A patent/NO158991C/en unknown
- 1981-04-28 CA CA000376461A patent/CA1223696A/en not_active Expired
- 1981-04-28 CH CH2760/81A patent/CH649465A5/en not_active IP Right Cessation
- 1981-04-29 MX MX187116A patent/MX156002A/en unknown
- 1981-04-29 IE IE958/81A patent/IE51152B1/en unknown
- 1981-04-29 NL NL8102128A patent/NL8102128A/en not_active Application Discontinuation
- 1981-04-29 DK DK189781A patent/DK157727B/en not_active Application Discontinuation
- 1981-04-29 GB GB8113265A patent/GB2075035B/en not_active Expired
- 1981-04-30 JP JP6615881A patent/JPS56169609A/en active Pending
-
1983
- 1983-08-11 GB GB838321611A patent/GB8321611D0/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| BR8102607A (en) | 1982-01-19 |
| AU6991181A (en) | 1981-11-05 |
| GB2075035B (en) | 1984-07-25 |
| ATA187781A (en) | 1984-03-15 |
| FR2481114A1 (en) | 1981-10-30 |
| DK189781A (en) | 1981-10-30 |
| PH17044A (en) | 1984-05-17 |
| IE810958L (en) | 1981-10-29 |
| NZ196864A (en) | 1984-04-27 |
| NO158991C (en) | 1988-11-23 |
| ES501695A0 (en) | 1982-08-16 |
| CH649465A5 (en) | 1985-05-31 |
| NO811448L (en) | 1981-10-30 |
| GB8321611D0 (en) | 1983-09-14 |
| MX156002A (en) | 1988-06-14 |
| CA1223696A (en) | 1987-06-30 |
| JPS56169609A (en) | 1981-12-26 |
| SE8102634L (en) | 1981-10-30 |
| NL8102128A (en) | 1981-11-16 |
| ZA812567B (en) | 1982-11-24 |
| AT376125B (en) | 1984-10-10 |
| NO158991B (en) | 1988-08-15 |
| FR2481114B1 (en) | 1984-11-30 |
| ES8206560A1 (en) | 1982-08-16 |
| AU554532B2 (en) | 1986-08-28 |
| GB2075035A (en) | 1981-11-11 |
| SE450547B (en) | 1987-07-06 |
| IE51152B1 (en) | 1986-10-15 |
| BE888599A (en) | 1981-08-17 |
| DE3116132A1 (en) | 1982-02-04 |
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Legal Events
| Date | Code | Title | Description |
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| PHB | Application deemed withdrawn due to non-payment or other reasons |