NO130343B - - Google Patents
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- NO130343B NO130343B NO04124/70A NO412470A NO130343B NO 130343 B NO130343 B NO 130343B NO 04124/70 A NO04124/70 A NO 04124/70A NO 412470 A NO412470 A NO 412470A NO 130343 B NO130343 B NO 130343B
- Authority
- NO
- Norway
- Prior art keywords
- parts
- binder
- bis
- materials
- dental
- Prior art date
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- 239000000463 material Substances 0.000 claims description 29
- 238000011049 filling Methods 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229920000193 polymethacrylate Polymers 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 239000011953 free-radical catalyst Substances 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- -1 hydroxyalkyl ethers Chemical class 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 208000002925 dental caries Diseases 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 4
- 229960000969 phenyl salicylate Drugs 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 229940106691 bisphenol a Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 210000000214 mouth Anatomy 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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 2
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- 239000005548 dental material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000015927 pasta Nutrition 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 2
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- RNAMYOYQYRYFQY-UHFFFAOYSA-N 2-(4,4-difluoropiperidin-1-yl)-6-methoxy-n-(1-propan-2-ylpiperidin-4-yl)-7-(3-pyrrolidin-1-ylpropoxy)quinazolin-4-amine Chemical compound N1=C(N2CCC(F)(F)CC2)N=C2C=C(OCCCN3CCCC3)C(OC)=CC2=C1NC1CCN(C(C)C)CC1 RNAMYOYQYRYFQY-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- IMDPTYFNMLYSLH-UHFFFAOYSA-N 3-silylpropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCC[SiH3] IMDPTYFNMLYSLH-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- SIJLYRDVTMMSIP-UHFFFAOYSA-N 4-Bromo-1-butanol Chemical compound OCCCCBr SIJLYRDVTMMSIP-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical group OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 210000004283 incisor Anatomy 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- YGSDEFSMJLZEOE-UHFFFAOYSA-M salicylate Chemical compound OC1=CC=CC=C1C([O-])=O YGSDEFSMJLZEOE-UHFFFAOYSA-M 0.000 description 1
- 229960001860 salicylate Drugs 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
Classifications
-
- 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
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
Description
Den foreliggende oppfinnelse går ut på forbedrede, formbare tannfyllingsmaterialer omfattende akrylat- eller metakrylatestre av hydroksyalkyletre, d.v.s. hemietre med di- eller tri-primære di-oler eller trioler av difenoler. Med tannfyllingsmaterialer menes i denne forbindelse .ikke bare materialer som anvendes til fylling i tannkaviteter, men også materialer som anvendes til andre tannres-taureringsarbeider. I disse materialer blir polymerisasjonen startet av katalysatorer som frembringer frie radikaler. Etter at polymeriseringen er startet, blir materialet anbragt i tannhulrom for å skaffe polymeriserte materialer som under forholdene i munnhulen har utmerket motstand mot fuktighet og er sterke og varige. The present invention concerns improved, moldable dental filling materials comprising acrylate or methacrylate esters of hydroxyalkyl ethers, i.e. hemietrees with di- or tri-primary di-ols or triols of diphenols. In this context, dental filling materials mean not only materials used for filling dental cavities, but also materials used for other dental restoration work. In these materials, the polymerization is initiated by catalysts that produce free radicals. After the polymerization has started, the material is placed in dental cavities to obtain polymerized materials that, under the conditions in the oral cavity, have excellent resistance to moisture and are strong and durable.
Dei; er funnet at de polykarbinoler som er hemietre av visse difenoler, er motstandsdyktige mot hydrolytisk forringelse og har ut-merkede egenskaper for dentalformål, idet de har en meget god styrke og en lav fblsomhet for fuktighet, samtidig som de i forbindelse med egnede uorganiske fyllstoffer gir fyllinger hvis farge svarer til den vanlige tannfarge, og som er egnet for såvel fortenner som tenner lenger inne i munnen. Fyllingene oppviser relativt liten krymping ved polymeriseringen og har fordelaktige varmeutvidelsesegenskaper over et område som omfatter alle vanlige forhold i munnen fra ca. They; it has been found that the polycarbinols which are hemi-trees of certain diphenols are resistant to hydrolytic deterioration and have excellent properties for dental purposes, in that they have very good strength and a low permeability to moisture, while in connection with suitable inorganic fillers they give fillings whose color corresponds to the usual tooth colour, and which are suitable for both incisors and teeth further inside the mouth. The fillings show relatively little shrinkage during polymerization and have advantageous thermal expansion properties over a range that includes all normal conditions in the mouth from approx.
0° C til ca. 60° C. 0° C to approx. 60°C.
Det er funnet at spesielt verdifulle monomerer for tildannelse av tannfyllingsmaterialer er polymetakrylatene av diol- og triol-hemietrene av difenoler. Disse metakrylater er frie for aktive hydrogenatomer og kan dannes ved forestring av hydroksyalkyletre av difenoler med primært hydroksyl i endestillingen. Det skal bemerkes at "poly" i denne sammenheng ikke henviser til noen polymer, men til nær-været av to eller tre metakrylat-rester i en monomer. Fagfolk vil være klar over at den grunnleggende difenol-forbindelse ved hver fenol-OH-gruppe er foretret med" en OH-gruppe av et diol eller triol som danner et bishemieter. Et separat molekyl av diol eller triol er nbdvendig for hver fenol-OH-gruppe. Gjenværende OH-grupper, f.eks. It has been found that particularly valuable monomers for the preparation of dental filling materials are the polymethacrylates of the diol and triol hemiethers of diphenols. These methacrylates are free of active hydrogen atoms and can be formed by esterification of hydroxyalkyl ethers of diphenols with primary hydroxyl in the end position. It should be noted that "poly" in this context does not refer to any polymer, but to the presence of two or three methacrylate residues in a monomer. Those skilled in the art will appreciate that the basic diphenol compound at each phenolic OH group is etherified with an OH group of a diol or triol forming a bisemiether. A separate molecule of diol or triol is required for each phenolic OH -group Remaining OH groups, e.g.
i diolene, blir deretter forestret med akryl- eller metakrylsyre for å gi de nyttige bindemidler for tannfyllingsmaterialer som skaffes ifblge den foreliggende oppfinnelse, og som er frie for aktive hydrogenatomer. De difenoler som anvendes, d.v.s. de hydroksyaromatiske forbindelser,. har minst to aromatiske kjerner som er forbundet di-rekte eller via en innskutt gruppe som er -0-, -CH2-, CHCH-Jp, in the diols, are then esterified with acrylic or methacrylic acid to give the useful binders for dental filling materials obtained according to the present invention, which are free of active hydrogen atoms. The diphenols used, i.e. the hydroxyaromatic compounds,. has at least two aromatic nuclei which are connected directly or via an intercalated group which is -0-, -CH2-, CHCH-Jp,
For at polymerisasjonen av disse polymetakrylater skal kunne finne sted hurtig etter igangsettelsen, anvendes der vanligvis en akselerator. Det vil være klart for fagfolk at mengdene reguleres slik at den innle-dende herding utsettes noen minutter etter blanding^ vanligvis 3-5 minutter for tannfyllingsmaterialer. Dette gir tid til blanding, fylling i et tannhulrom og komprimering for herdingen eller stivningen er kommet så langt at materialet ikke kan bearbeides. Vanligvis blir 0,05 - 5 vektprosent akselerator opplost i bindemiddelet. En foretrukket andel er 0,2 - 0,5 vektprosent for aromatiske tertiære aminer som dimetyl-p-toluidin. N,N-bis(hydroksy-lavere-alkyl)-aromatiske aminer anvendes i mengder på 0,2 - 3$. I disse inneholder det lavere alkyl vanligvis 2-6 karbonatomer. Det er' bnskelig at monomerene er frie for eventuelle peroksydforbindelser som kan foreligge som urenheter i materialet. En behandling med reduksjonsmiddel for bruk er -således onskel.ig. Hvis denne forsiktighetsregel ikke tas, kan lagringstiden bli meget kort. In order for the polymerization of these polymethacrylates to take place quickly after initiation, an accelerator is usually used. It will be clear to those skilled in the art that the quantities are regulated so that the initial curing is delayed a few minutes after mixing, usually 3-5 minutes for dental filling materials. This allows time for mixing, filling in a tooth cavity and compaction before the hardening or hardening has progressed so far that the material cannot be processed. Usually 0.05 - 5% by weight of accelerator is dissolved in the binder. A preferred proportion is 0.2 - 0.5% by weight for aromatic tertiary amines such as dimethyl-p-toluidine. N,N-bis(hydroxy-lower alkyl)-aromatic amines are used in amounts of 0.2 - 3%. In these, the lower alkyl usually contains 2-6 carbon atoms. It is desirable that the monomers are free of any peroxide compounds that may be present as impurities in the material. A treatment with a reducing agent for use is -thus onskel.ig. If this precaution is not taken, the storage time can be very short.
Fremgangsmåter til proving av dentalmaterialer er angitt i Procedures for testing dental materials are specified in
"Guide to Dental Materials", American Dental Association, 2. og 3. utgave, og i et forslag om "Tentative Specification for Composite Resin Filling Materials", september 1967- "Guide to Dental Materials", American Dental Association, 2nd and 3rd editions, and in a proposal for a "Tentative Specification for Composite Resin Filling Materials", September 1967-
De fyllstoffer som anvendes i materialet ifolge oppfinnelsen, The fillers used in the material according to the invention,
kan inneholde små mengder av pigmenter med!henblikk på enten synlig farge eller fluoriserende virkning, små glasskuler eller -partikler, krystallinske'materialer som f.eks. litiumaluminiumsilikater, hydrok-syapatitt, siliciumoksyd eller siliciumholdige materialer, aluminium-oksyd eller materialer som inneholder aluminium eller alun eller glass-materialer som f.eks. borosilikatglass. Partiklene bor stort sett være mindre enn 50 mikrometer og fortrinnsvis mindre enn 30 mikrometer. may contain small amounts of pigments with regard to either visible color or fluorescent effect, small glass balls or particles, crystalline materials such as e.g. lithium aluminum silicates, hydroxyapatite, silicon oxide or silicon-containing materials, aluminum oxide or materials containing aluminum or alum or glass materials such as e.g. borosilicate glass. The particles should generally be smaller than 50 micrometers and preferably smaller than 30 micrometers.
Et i handelen tilgjengelig litiumaluminiumsilikat anvendes i visse eksempler for å skaffe et generelt verdifullt fyllstoff som tjener som et eksempel. Partiklene opptrer i storrelser fra under 1 mikrometer og opp til 44 mikrometer med et gjennomsnitt på ca. 2 til 15 mikrometer,.eller er i visse tilfelle opp til ca. 85 til 90 mikrometer. Andre fyllstoffer kan anvendes i hoe andre andeler og kan ha egenskaper som er noe forskjellige fra de angitte noyaktige tall. Valget av fyllstoff er ikke av kritisk betydning i den foreliggende oppfinnelse. A commercially available lithium aluminum silicate is used in certain examples to provide a generally valuable filler that serves as an example. The particles appear in sizes from less than 1 micrometer and up to 44 micrometers with an average of approx. 2 to 15 micrometres, or is in certain cases up to approx. 85 to 90 micrometers. Other fillers can be used in different proportions and may have properties that are somewhat different from the exact figures given. The choice of filler is not of critical importance in the present invention.
Det foretrekkes at fyllstoffene behandles for å forbedre binde-middelets adhesjon, idet der f.eks. anvendes en vanlig vinylsilanbe-handling eller en annen lignende forbehandling. It is preferred that the fillers are treated to improve the adhesion of the binder, as there e.g. a normal vinyl silane treatment or another similar pre-treatment is used.
Det er funnet at den mest tilfredsstillende konsistens med hensyn til bearbeidbarheten av tannfyllingsmaterialer oppnås når fyllstoffer med partikkelstorrelser hvis gjennomsnitt ligger fra 2 til 15 mikrometer, blandes i en molle med organisk bindemiddel som inneholder 0,5 til 2 molprosent tertiær aminakselerator (inneholdende eventuelt onskelig fortynningsmiddel) i andeler på 60 til 85 vektprosent fyllstoff og 40 til 14 vektprosent bindemiddel. Det fore-trukne område er 65 - 80$ fyllstoff avhengig av dettes egenvekt. I begge tilfeller blir de lavere prosentandeler anvendt sammen med mere seigtflytende bindemidler. De noyaktige andeler kan endres i avhen-gighet av individuelle onsker, temperaturkrav etc. It has been found that the most satisfactory consistency with respect to the workability of dental filling materials is obtained when fillers with particle sizes averaging from 2 to 15 micrometers are mixed in an organic binder molle containing 0.5 to 2 mole percent tertiary amine accelerator (containing any desired diluent ) in proportions of 60 to 85 weight percent filler and 40 to 14 weight percent binder. The preferred range is 65 - 80$ filler depending on its specific gravity. In both cases, the lower percentages are used together with more viscous binders. The exact proportions can be changed depending on individual wishes, temperature requirements etc.
Ifolge oppfinnelsen er der således skaffet et tannfyllingsmateriale som består av to komponenter som skal blandes umiddelbart for plomberingen, og etterat det. er herdet og utsatt for fuktighet, har en fuktighetsabsorbsjon på mindre enn 2$, samtidig som de to komponent er i stabile kombinasjoner inneholder et uorganisk partikkelformet fyllstoff, et flytende polymeriserbart polymetakrylat- eller polyakrylat-bindemiddel, eri akselerator for fri-radikal-polymerisering og en fri-radikal-katalysator, idet bindemiddelet er hovedsakelig fritt for aktive hydrogenatomer og peroksyder, karakterisert ved at bindemiddelet har formelen According to the invention, a dental filling material has thus been obtained which consists of two components which are to be mixed immediately before the filling, and afterwards. is cured and exposed to moisture, has a moisture absorption of less than 2$, while the two components are in stable combinations containing an inorganic particulate filler, a liquid polymerizable polymethacrylate or polyacrylate binder, eri accelerator for free-radical polymerization and a free-radical catalyst, in that the binder is mainly free of active hydrogen atoms and peroxides, characterized in that the binder has the formula
MO-D-OXO-D-OM, MO-D-OXO-D-OM,
hvor M er metakrylat eller akrylat-, D er alkylen med 2-6 karbonatomer og X er where M is methacrylate or acrylate-, D is the alkylene with 2-6 carbon atoms and X is
hvor y betyr en binding, , where y means a bond, ,
Blandingen av bindemiddelet og fyllstoffet kan utfores etter The mixing of the binder and the filler can be carried out after
en hvilken som helst egnet fremgangsmåte og fortrinnsvis med sa liten inneslutning av luftbobler som mulig. Blanding eller knaing ved generelt tilgjengelige prosesser gir en tilstrekkelig blanding. Blanding i kulemSller kan være mindre bnskelig hvis der er innlemmet et kuleformet fyllmateriale. For egnet forsendelse til tannleger foretrekkes der to-komponentsystemer. Disse kan være to pastaer, en pasta og en væske eller en væske og et fast stoff. Katalysatoren blir da innlemmet i den ene komponent og akseleratoren i den andre. Det er bnskelig å unngå innlemmelse av luft under innblandingen av katalysator med en spatel for det polymeriserende materiale anbringes i dentalhulrom. Det er bnskelig at viskositeten ikke ligger over ca. 10 000 cP. Skjbnt en lav konsentrasjon av metakrylatgrupper (milli-ekvivalenter pr. gram ester) reduserer trykkstyrken noe, medfbrer den fordeler med hensyn til reduksjon av krympningen ved polymeriseringen. Det foretrekkes derfor vanligvis at polyetermetakrylatestrene ikke har særlig lav molekylvekt, d.v.s. der foretrekkes en molekylvekt på 400 eller mer sammenlignet med 100 for metylmetakrylat. any suitable method and preferably with as little entrapment of air bubbles as possible. Mixing or kneading by generally available processes gives an adequate mixture. Mixing in spherical fillers may be less desirable if a spherical filler material is incorporated. For suitable shipment to dentists, two-component systems are preferred. These can be two pastes, a paste and a liquid or a liquid and a solid. The catalyst is then incorporated into one component and the accelerator into the other. It is desirable to avoid the incorporation of air during the mixing of catalyst with a spatula before the polymerizing material is placed in dental cavities. It is desirable that the viscosity does not exceed approx. 10,000 cP. Although a low concentration of methacrylate groups (milli-equivalents per gram of ester) reduces the compressive strength somewhat, it brings advantages with respect to reduction of shrinkage during polymerization. It is therefore usually preferred that the polyether methacrylate esters do not have a particularly low molecular weight, i.e. there, a molecular weight of 400 or more is preferred compared to 100 for methyl methacrylate.
I formelen for bindemiddelet er X således kjernen av et difenol med minst 2 aromatiske ringer og fra 12 til 24 karbonatomer. Eksempler på slike difenoler er 2,2-bis(4-hydroksyfenyl)propari (bisfenol A), 2,2-bis(4-hydroksyfenyl)butan (bisfenol B), bis(4-hydroksyfenyl)metan (bisfenol F), bifenol HOCgH^CgH^OH, l,l-bis(p-hydroksyfenyl)cyklo-heksan (HOCgH^JgCg^, 2, 2-bis (4-hydroksyf enyl)-heksafluorpropan (H<OC>gH4)2C(CF3)2 og l,l-bis(4-hydroksyfenyl)etan (HOCgH^)^CHCH^. Eventuelle tilstedeværende substituenter inneholder ikke aktive hydrogenatomer. In the formula for the binder, X is thus the nucleus of a diphenol with at least 2 aromatic rings and from 12 to 24 carbon atoms. Examples of such diphenols are 2,2-bis(4-hydroxyphenyl)propari (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), bis(4-hydroxyphenyl)methane (bisphenol F), biphenol HOCgH^CgH^OH, l,l-bis(p-hydroxyphenyl)cyclohexane (HOCgH^JgCg^, 2, 2-bis (4-hydroxyphenyl)-hexafluoropropane (H<OC>gH4)2C(CF3)2 and 1,1-bis(4-hydroxyphenyl)ethane (HOCgH^)^CHCH^ Any substituents present do not contain active hydrogen atoms.
Det vil forstås at fremstillingsmetodene, som ikke utgjor noen del av den foreliggende oppfinnelse, må skaffe materialer med den egnede struktur, men at der samtidig kan dannes også andre materialer som kan bidra til anvendeligheten av materialene. It will be understood that the production methods, which form no part of the present invention, must provide materials with the appropriate structure, but that at the same time other materials can also be formed which can contribute to the applicability of the materials.
Det kan være onskelig å anvende to eller endog flere forskjellige glykoler eller å kombinere estre av to eller flere forskjellige glykoler. Dette bidrar til å redusere krystalliniteten. I slike tilfelle vil alle D-ene i et molekyl ikke være de samme. It may be desirable to use two or even more different glycols or to combine esters of two or more different glycols. This helps to reduce the crystallinity. In such cases, all the Ds in a molecule will not be the same.
Viskositeten av estrene kan okes ved anvendelse av fra noen få prosent og opp til 50 molprosent eller mer av et triprimært triol med lav molekylvekt, f.eks. trimetylolpropan og forestring av alle hydrok-sylgrupper om nodvendig ved å tvinge igjennom reaksjonen. Struktur-formler for blandede polyestre innbefattende slike triolkjerner er meget vanskelig å demonstrere, men hvis T betegner kjernen av et tri-' primært triol, kan strukturen i visse tilfelle være The viscosity of the esters can be increased by using from a few percent and up to 50 mole percent or more of a low molecular weight triprimary triol, e.g. trimethylolpropane and esterification of all hydroxyl groups if necessary by forcing the reaction through. Structural formulas for mixed polyesters including such triol nuclei are very difficult to demonstrate, but if T denotes the nucleus of a tri-' primary triol, the structure may in certain cases be
^M(0-D-0-)n X-0-DO-J^T, hvor X, D, M og n har den samme betydning som ovenfor. Mange forskjellige variasjoner er mulige avhengig av rekke-følgen av reaksjonene. ^M(0-D-0-)n X-0-DO-J^T, where X, D, M and n have the same meaning as above. Many different variations are possible depending on the order of the reactions.
En alminnelig fremgangsmåte til etter tur å fremstille glykol-hemietre av bisfenoler fulgt av forestring med metakrylatsyre er å kondensere med et alkylenoksyd og deretter forestre under anvendelse av syrekatalysatorer. Fremgangsmåten behover ikke å beskrives i de-talj, idet den er kjent i faget og har vært utfort industrielt. Et eksempel vil bli nevnt nedenfor i forbindelse med bismetakrylatet av 2,2-bis(4-hydroksyetoksyfenyl)propan, som også har vært tilgjengelig i handelen. A common method to in turn prepare glycol hemiethers from bisphenols followed by esterification with methacrylate acid is to condense with an alkylene oxide and then esterify using acid catalysts. The method does not need to be described in detail, as it is known in the art and has been carried out industrially. An example will be mentioned below in connection with the bismethacrylate of 2,2-bis(4-hydroxyethoxyphenyl)propane, which has also been commercially available.
Generelt blir alkylenoksydet, f.eks. etylenoksyd, kondensert med bisfenolet, f.eks. 2,2-bis(4-hydroksyfenyl)propan (bisfenol A), passende i nærvær av trietylamin ved ca. 150°C. I dette belysende eksempel blir hemieteren isolert fra metanol som et krystallinsk fast stoff som smelter ved 110 - 112°C. Alternative fremgangsmåter til fremstilling av hemietre omfatter omsetning av natrium- eller kalium-salter av bisfenol og et hydroksyalkylbromid eller -klorid, f.eks. 4-brombutanol, 2-kloretanol eller lignende. In general, the alkylene oxide, e.g. ethylene oxide, condensed with the bisphenol, e.g. 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), suitably in the presence of triethylamine at ca. 150°C. In this illustrative example, the hemiether is isolated from methanol as a crystalline solid melting at 110 - 112°C. Alternative methods for the production of hemietree include reaction of sodium or potassium salts of bisphenol and a hydroxyalkyl bromide or chloride, e.g. 4-bromobutanol, 2-chloroethanol or the like.
Hemieteren blir forestret. En rå reaksjonsblanding kan passende anvendes uten isolering ved tilsetning av en polymerisasjonshemmer, f.eks. cuproklorid, og p-toluensulfonsyre som katalysator sammen med den passende mengde metakrylsyre. Andre metoder til forestring omfatter omsetning med metakrylylklorid eller transforestring med metylmetakrylat. The hemiether is esterified. A crude reaction mixture can conveniently be used without isolation by adding a polymerization inhibitor, e.g. cuprochloride, and p-toluenesulfonic acid as catalyst together with the appropriate amount of methacrylic acid. Other methods of esterification include reaction with methacrylyl chloride or transesterification with methyl methacrylate.
De ovennevnte fremgangsmåter anvendes med etylenoksyd, 1,2-propy-lenoksyd og 1,2-butylenoksyd og med 2,2-bis(4-hydroksyfenyl)propan, 2,2-bis(4-hydroksyfenyl)butan, bis(4-hydroksyfenyl)metan, 2,2-bis(4-hydroksyfenyl)heksafluorpropan og bifenol for å gi de forskjellige hemietre og metakrylatene av disse. The above-mentioned methods are used with ethylene oxide, 1,2-propylene oxide and 1,2-butylene oxide and with 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, bis(4- hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane and biphenol to give the various hemitrees and their methacrylates.
Fordi den er lett tilgjengelig, foretrekkes for tiden folgende Because it is readily available, the following is currently preferred
forbindelse: connection:
Eksempel 1 Example 1
4, 4*- Di( 2- hydroksyetoksy) bisfenol A. En trehalset 1 liters kolbe med rund bunn og utstyrt med en rorepinne, termometer, gass-innlopstilkobling og torris-fingerkondensator fylles med 342,0 deler (1,50 mol) bisfenol A. Systemet spyles med nitrogen og 2,5 volumdeler trietylamin fores' inn. Reaksjordblandingen oppvarmes til 155°C, Ti-.ror fyllingen foreligger i smeltet form. Etylenoksyd (145 deler, 3,3 mol) blir deretter kontinuerlig innfort som en gass gjennom en stromnings-måler med en hastighet av ca. 600 ml pr. minutt. Denne tilsetnings-hastighet er tilstrekkelig til å holde reaksjonstemperaturen på 155°C til 160°G i nesten hele tilsetningsperioden uten anvendelse av ytter-ligere varme og uten noe vesentlig tilbakelop av etylenoksyd. Tilset-ningen krever to timer. Blandingen tillates å kjolne til 110°C, hvor-etter gjenværende etylenoksyd spyles ut med nitrogen og 0,50 deler (0,013 mol) natriumborhydroksyd fores inn. Etter omroring i 15 minuttei er temperaturen av den nesten fargelose opplosning 80°C. Metanol (950 volumdeler) tilsettes og oppløsningen avkjoles og tillates å krystallisere. Etter filtrering og torking fås der 349 deler av et hvitt krystallinsk produkt med et smeltepunkt på 108°G til 111°G. 4, 4*- Di(2- hydroxyethoxy) bisphenol A. A three-necked 1 liter round-bottomed flask equipped with a stir bar, thermometer, gas inlet connection and torri-ice finger condenser is charged with 342.0 parts (1.50 mol) of bisphenol A. The system is flushed with nitrogen and 2.5 parts by volume of triethylamine are introduced. The reaction soil mixture is heated to 155°C, the Ti-.ror filling is available in molten form. Ethylene oxide (145 parts, 3.3 moles) is then continuously fed as a gas through a flow meter at a rate of approx. 600 ml per minute. This addition rate is sufficient to maintain the reaction temperature at 155°C to 160°G for almost the entire addition period without the use of additional heat and without any significant reflux of ethylene oxide. The addition requires two hours. The mixture is allowed to cool to 110°C, after which the remaining ethylene oxide is flushed out with nitrogen and 0.50 parts (0.013 mol) of sodium borohydride are introduced. After stirring for 15 minutes, the temperature of the almost colorless solution is 80°C. Methanol (950 parts by volume) is added and the solution is cooled and allowed to crystallize. After filtration and drying, 349 parts of a white crystalline product with a melting point of 108°G to 111°G are obtained.
4, 4'- Di( 2- m. etakryloksyetoksy) bisfenol A. En trehalset 500 milliliters kolbe med rund bunn og utstyrt med magnetisk rorer, termometer, Barrett-felle og -kondensator og luftinnlop fylles med 158,2 deler (0,500 mol) 4,4'-Di-(2-hydroksyetoksy)bisfenol A, 94,6 deler 4, 4'- Di(2-m.ethacryloxyethoxy) bisphenol A. A three-necked 500-milliliter round-bottom flask equipped with a magnetic stirrer, thermometer, Barrett trap and condenser, and air inlet is filled with 158.2 parts (0.500 mol) 4,4'-Di-(2-hydroxyethoxy)bisphenol A, 94.6 parts
(1,10 mol) metakrylsyre, 0,25 deler 0,1$'s cuproklorid, 7,6 deler 3$'s p-toluensulfonsyre og 50 volumdeler toluen. En langsom luftstrom fores inn i systemet mens blandingen koker med raskt tilbakelop og vann fjernes. Etter 2 timer har der samlet seg 1,1 mol med vann og blandingen avkjoles til værelsetemperatur. Produktet fortynnes med 250 volumdeler toluen, vaskes fire ganger med 100 volumdeler konsentrert ammoniumhydroksyd og tre ganger med tilsvarende porsjoner av mettet natriumklorid. Toluenet fjernes ved 60°C med en luftstrom, og der blir tilbake 206,7 deler lysegult, harpikslignende etoksylert bisfenol-A-bismetakrylat med et hydroksylinnhold på 0,215 meq/g, en CC , -umet-tethet på 4,04 meq/g og en Brookfield-viskositet på 2000 cP. (1.10 moles) of methacrylic acid, 0.25 parts of 0.1$'s cuprochloride, 7.6 parts of 3$'s p-toluenesulfonic acid and 50 parts by volume of toluene. A slow stream of air is fed into the system while the mixture boils with rapid reflux and water is removed. After 2 hours, 1.1 mol of water have accumulated and the mixture is cooled to room temperature. The product is diluted with 250 parts by volume of toluene, washed four times with 100 parts by volume of concentrated ammonium hydroxide and three times with corresponding portions of saturated sodium chloride. The toluene is removed at 60°C with a stream of air, and there remains 206.7 parts of pale yellow, resin-like ethoxylated bisphenol-A bismethacrylate with a hydroxyl content of 0.215 meq/g, a CC , -unsaturation of 4.04 meq/g and a Brookfield viscosity of 2000 cP.
Eksempel 2 Example 2
Et stabilt 2-komponents tannfyllingsmateriale ifolge oppfinnelsen fremstilles fra det ovennevnte etoksylerte bisfenol-A-bismetakrylat med tilsetning av 0,75 vektprosent N,N-bis(2-hydroksyetyl)-3,5-xylidin og 1,0$ av adduktet av glycidyl-metakrylat og fenylsalicylat■(frem-stilt som beskrevet i eksempel 3 nedenfor). Denne honnihglignende væske blandes i en andel av 28 vektprosent med 72 vektprosent av et pulverformet litiumaluminiumsilikat (kalsinert petalitt) som er be-handlet med vinylsilan og har absorbert ca. 0,5$ av sin egen vekt av benzoylperoksyd. Blandingen stopes til prøvestykker for anvendelse i prover i overensstemmelse med American Dental Association. Vannab-sorbsjonen etter 500 timer er bare G>3 vektprosent. Polymerisasjons-krympningen er 0,9$ sammenlignet med ca. 7$ for metylmetakrylatsystem-er. Trykkstyrken er 24 800 N/cm og strekkstyrken ved diametrale prover 4 100 N/cm . A stable 2-component dental filling material according to the invention is produced from the above-mentioned ethoxylated bisphenol-A-bismethacrylate with the addition of 0.75% by weight of N,N-bis(2-hydroxyethyl)-3,5-xylidine and 1.0$ of the adduct of glycidyl -methacrylate and phenyl salicylate (prepared as described in example 3 below). This honey-like liquid is mixed in a proportion of 28% by weight with 72% by weight of a powdered lithium aluminum silicate (calcined petalite) which has been treated with vinyl silane and has absorbed approx. 0.5$ of its own weight of benzoyl peroxide. The mixture is poured into specimens for use in specimens in accordance with the American Dental Association. The water absorption after 500 hours is only G>3 weight percent. The polymerization shrinkage is 0.9$ compared to approx. 7$ for methyl methacrylate systems. The compressive strength is 24,800 N/cm and the tensile strength in diametrical samples 4,100 N/cm.
Eksempel 3 Example 3
Der fremstilles tannfyllingsmaterialer under anvendelse av pig-menterte siliciumholdige materialer som inert uorganisk fyllstoff.• Dental filling materials are produced there using pigmented silicon-containing materials as inert inorganic filler.•
Et eksempel er findelt (partikkelstorrelse fortrinnsvis under 50 mikrometer) pulverformet borosilikat-glass som blandes grundig med ca. 0,1$ fluoriserende pigment, ca. 0,01$ rå sienna og noen få tusendedels prosent meget findelte sorte og gule pigmenter. Denne kombinasjon er funnet å ligne vanlig tannfarge i mange tilfelle og kan farges ytter-ligere om nodvendig. Det er onskelig å behandle fyllstoffet for å bed-re dets fukting med harpikser. Silanbehandling f.eks. med metakrylyl-oksypropylsilan er egnet. An example is finely divided (particle size preferably below 50 micrometres) powdered borosilicate glass which is thoroughly mixed with approx. 0.1$ fluorescent pigment, approx. 0.01$ raw sienna and a few thousandths of a percent of very finely divided black and yellow pigments. This combination has been found to resemble ordinary tooth color in many cases and can be colored more strongly if necessary. It is desirable to treat the filler to improve its wetting with resins. Silane treatment e.g. with methacrylyloxypropylsilane is suitable.
En måte som materialet kan distribueres på, er som et to-komponents system av flytende og faste komponenter som kan forenes, enten fra separate beholdere eller ved at en tetning som skiller på forhånd fastlagte mengder, brytes. Den torre bestanddel utgjores av 69,65 deler av det ovennevnte uorganiske fyllstoff (inneholdende pigmenter) One way in which the material can be distributed is as a two-component system of liquid and solid components that can be combined, either from separate containers or by breaking a seal separating predetermined quantities. The dry component is made up of 69.65 parts of the above-mentioned inorganic filler (containing pigments)
som blandes grundig med 0,35 deler benzoylperoksyd. Den resulterende blanding er et tort pulver. Den flytende komponent fremstilles fra 29,50 deler av bismetakrylatet av 2,2-bis(p-hydroksyetoksyfenyl)propan: which is mixed thoroughly with 0.35 parts of benzoyl peroxide. The resulting mixture is a dry powder. The liquid component is prepared from 29.50 parts of the bismethacrylate of 2,2-bis(p-hydroxyethoxyphenyl)propane:
inneholdende ca. 0,01% metylhydroksykinon som inhibitor. containing approx. 0.01% methylhydroxyquinone as an inhibitor.
Et addukt fremstilles fra fenylsalicylat (318 deler, 1,5 mol) med glycidyl-metakrylat (113 deler, 0,83 mol) og ca. 4,3 deler dimetyl-p-toluidin ved oppvarmning til 60°C i ca. 6 dager fulgt av fjerning av ikke omsatt salicylat, forst ved krystallisering og deretter ved milde alkaliske vaskeprosesser. An adduct is prepared from phenyl salicylate (318 parts, 1.5 mol) with glycidyl methacrylate (113 parts, 0.83 mol) and approx. 4.3 parts of dimethyl-p-toluidine by heating to 60°C for approx. 6 days followed by removal of unreacted salicylate, first by crystallization and then by mild alkaline washing processes.
Bis-metakrylatharpiksen blandes grundig med 0,29 deler av det ovennevnte fenyl-salicylat-addukt med glycidyl-metakrylat og 0,21 deler N,N-bis(2-hydroksyetyl)-3,5-xylidin. Passende mengder (tilsammen ca. 0,5 til 2,0 gram) av disse komponenter i de angitte mengdeforhold (70: 30) anbringes i forskjellige deler av en pakning med en membran som kan bringes til å briste. Blandingen utfores ved å bryte membranen og kna det faste stoff og væsken sammen. Dette kan utfores raskt og pastaen - anvendes til å fylle på forhånd preparerte hulrom i tenner. Pastaen stivner raskt til en god fylling. The bis-methacrylate resin is thoroughly mixed with 0.29 parts of the above phenyl salicylate adduct with glycidyl methacrylate and 0.21 parts of N,N-bis(2-hydroxyethyl)-3,5-xylidine. Appropriate quantities (in total approx. 0.5 to 2.0 grams) of these components in the specified proportions (70:30) are placed in different parts of a pack with a membrane that can be caused to burst. Mixing is done by breaking the membrane and kneading the solid and liquid together. This can be done quickly and the paste - used to fill previously prepared cavities in teeth. The pasta hardens quickly into a good filling.
En alternativ fremgangsmåte er å fremstille to pastaer som blandes mekanisk eller ved hjelp av en spatel i like mengder. Pastaene kan fremstilles slik at de har en viskositet i området fra 100 til 8000 cP og fortrinnsvis 1000 til 4000 cP. An alternative method is to prepare two pastes that are mixed mechanically or with the help of a spatula in equal amounts. The pastes can be prepared so that they have a viscosity in the range from 100 to 8000 cP and preferably 1000 to 4000 cP.
Der fremstilles en pasta inneholdende 72 deler av det ovennevnte siliciumholdige fyllstoff med 27,27 deler av den.-ovennevnte harpiks, 0,28 deler av adduktet av fenylsalicylat og glycidyl-metakrylat og 0,45 deler av N,N-bis(hydroksyetyl)-p-toluidin. Den annen pasta inneholder 25,58 deler harpiks, 74 deler siliciumholdig fyllstoff, 0,42 deler benzoylperoksyd og spor (500 deler pr. million, 0,05$) av i handelen tilgjengelig butylert hydroksytoluen som inhibitor. Like porsjoner av de to pastaer pakkes f.eks. i tuber, og små mengder klemmes ut og blandes etter behov. Den resulterende sammensetning er effektiv til fylling av hulrom. There is prepared a paste containing 72 parts of the above-mentioned siliceous filler with 27.27 parts of the above-mentioned resin, 0.28 parts of the adduct of phenyl salicylate and glycidyl methacrylate and 0.45 parts of N,N-bis(hydroxyethyl) -p-toluidine. The second paste contains 25.58 parts resin, 74 parts siliceous filler, 0.42 parts benzoyl peroxide and traces (500 parts per million, $0.05) of commercially available butylated hydroxytoluene as an inhibitor. Equal portions of the two pastas are packed, e.g. in tubes, and small amounts are squeezed out and mixed as needed. The resulting composition is effective for filling cavities.
Claims (2)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US87360069A | 1969-11-03 | 1969-11-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
NO130343B true NO130343B (en) | 1974-08-19 |
Family
ID=25361962
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
NO04124/70A NO130343B (en) | 1969-11-03 | 1970-10-29 |
Country Status (12)
Country | Link |
---|---|
JP (1) | JPS4933877B1 (en) |
AU (1) | AU2177070A (en) |
BE (1) | BE758384R (en) |
CA (1) | CA955000A (en) |
DE (1) | DE2053901A1 (en) |
DK (1) | DK130626B (en) |
FR (1) | FR2080875B2 (en) |
GB (1) | GB1328854A (en) |
IT (1) | IT954101B (en) |
NL (1) | NL7015556A (en) |
NO (1) | NO130343B (en) |
SE (1) | SE7014310L (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS50157284U (en) * | 1974-06-13 | 1975-12-26 | ||
DE3248602A1 (en) * | 1982-12-30 | 1984-07-12 | Röhm GmbH, 6100 Darmstadt | ACRYLIC RESINS WITH LOW WATER ABSORPTION |
EP0312120B1 (en) * | 1982-12-30 | 1992-03-04 | Röhm Gmbh | Process for preparing moulding materials of acrylic resins with slight water absorption |
DE3248601A1 (en) * | 1982-12-30 | 1984-07-12 | Röhm GmbH, 6100 Darmstadt | POLYMERISATE WITH LOW WATER ABSORPTION |
-
1970
- 1970-10-23 DK DK540870AA patent/DK130626B/en unknown
- 1970-10-23 NL NL7015556A patent/NL7015556A/xx unknown
- 1970-10-23 DE DE19702053901 patent/DE2053901A1/en active Pending
- 1970-10-23 SE SE7014310A patent/SE7014310L/sv unknown
- 1970-10-29 NO NO04124/70A patent/NO130343B/no unknown
- 1970-11-02 FR FR7039445A patent/FR2080875B2/fr not_active Expired
- 1970-11-02 JP JP45096797A patent/JPS4933877B1/ja active Pending
- 1970-11-02 AU AU21770/70A patent/AU2177070A/en not_active Expired
- 1970-11-02 CA CA097,186A patent/CA955000A/en not_active Expired
- 1970-11-02 GB GB5207170A patent/GB1328854A/en not_active Expired
- 1970-11-02 IT IT54433/70A patent/IT954101B/en active
- 1970-11-03 BE BE758384D patent/BE758384R/en active
Also Published As
Publication number | Publication date |
---|---|
SE7014310L (en) | 1971-05-04 |
NL7015556A (en) | 1971-05-05 |
CA955000A (en) | 1974-09-17 |
DK130626B (en) | 1975-03-17 |
BE758384R (en) | 1971-05-03 |
JPS4933877B1 (en) | 1974-09-10 |
DE2053901A1 (en) | 1971-05-13 |
FR2080875A2 (en) | 1971-11-26 |
IT954101B (en) | 1973-08-30 |
DK130626C (en) | 1975-08-18 |
GB1328854A (en) | 1973-09-05 |
FR2080875B2 (en) | 1973-10-19 |
AU2177070A (en) | 1972-05-04 |
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