JPH0555559B2 - - Google Patents
Info
- Publication number
- JPH0555559B2 JPH0555559B2 JP62335727A JP33572787A JPH0555559B2 JP H0555559 B2 JPH0555559 B2 JP H0555559B2 JP 62335727 A JP62335727 A JP 62335727A JP 33572787 A JP33572787 A JP 33572787A JP H0555559 B2 JPH0555559 B2 JP H0555559B2
- Authority
- JP
- Japan
- Prior art keywords
- acrylate
- meth
- adhesive
- glycol
- radically polymerizable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 claims description 36
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 25
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 17
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 9
- 239000003479 dental cement Substances 0.000 claims description 9
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 3
- 239000003701 inert diluent Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 description 31
- 239000000853 adhesive Substances 0.000 description 28
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 27
- 239000000463 material Substances 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 13
- 210000004268 dentin Anatomy 0.000 description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000003505 polymerization initiator Substances 0.000 description 7
- -1 polyol compound Chemical group 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 210000003298 dental enamel Anatomy 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- 239000000805 composite resin Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WGKYSFRFMQHMOF-UHFFFAOYSA-N 3-bromo-5-methylpyridine-2-carbonitrile Chemical compound CC1=CN=C(C#N)C(Br)=C1 WGKYSFRFMQHMOF-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052586 apatite Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 210000000214 mouth Anatomy 0.000 description 2
- 229920000847 nonoxynol Polymers 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- BEVWMRQFVUOPJT-UHFFFAOYSA-N 2,4-dimethyl-1,3-thiazole-5-carboxamide Chemical compound CC1=NC(C)=C(C(N)=O)S1 BEVWMRQFVUOPJT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFSAUHSCHWRZKM-UHFFFAOYSA-N Padimate A Chemical compound CC(C)CCOC(=O)C1=CC=C(N(C)C)C=C1 OFSAUHSCHWRZKM-UHFFFAOYSA-N 0.000 description 1
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 229930006711 bornane-2,3-dione Natural products 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- UJKWLAZYSLJTKA-UHFFFAOYSA-N edma Chemical compound O1CCOC2=CC(CC(C)NC)=CC=C21 UJKWLAZYSLJTKA-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- MKVYSRNJLWTVIK-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O.CC(=C)C(O)=O MKVYSRNJLWTVIK-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- IIRDTKBZINWQAW-UHFFFAOYSA-N hexaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCO IIRDTKBZINWQAW-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GLZWNFNQMJAZGY-UHFFFAOYSA-N octaethylene glycol Chemical compound OCCOCCOCCOCCOCCOCCOCCOCCO GLZWNFNQMJAZGY-UHFFFAOYSA-N 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Description
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[Industrial Application Field] The present invention is a dental treatment with excellent adhesive properties used for bonding between living tooth tissue and materials for repairing the tissue (metal materials, organic polymer materials, ceramic materials, etc.). The present invention relates to an adhesive composition for [Prior Art] Traditionally, in the field of dental materials, various metal materials (for example, gold, silver, platinum,
alloys, amalgams, etc.), organic polymer materials (e.g.
polymethyl methacrylate, polycarbonate,
polymethyl methacrylate, polycarbonate,
polyfunctional vinyl cured products, composite resins, etc.),
Ceramic materials (eg, porcelain, implant materials, etc.) are used. However, these materials do not inherently adhere to living tooth tissue. Therefore, for the purpose of adhesion between the restorative material and the living tooth tissue, we aim to improve the interaction with the main inorganic components such as apatite (calcium phosphate) or the main organic components such as collagen (protein) that form the dental tissue. Dental adhesive compositions have been proposed in which the adhesive component is a compound having various polar groups (phosphoric acid group, hydroxyl group, acid anhydride group, etc.). [Problems to be Solved by the Invention] However, although the above-mentioned conventional technology has a certain degree of adhesion to enamel in living tooth tissue, it has no adhesion performance to dentin at all. This is due to physical and chemical structural factors of living dentin. In other words, dentin has a structure in which countless dentinal tubules run and are filled with fluid, and the ratio of proteins such as collagen is considerably higher than that of enamel, making it difficult to bond. It can be said that the environment is extremely harsh. Therefore, in the adhesives according to the prior art described above, apatite, which is the main inorganic component, is pretreated with an etching agent such as phosphoric acid in order to achieve a certain degree of adhesiveness to living dentin through the so-called anchor effect. However, since the adhesive strength is still insufficient, over a long period of time, gaps may form between the restorative material and the dentin, and in some cases, the restorative material may even fall off. However, it cannot be said that sufficiently high adhesiveness is obtained. The purpose of the present invention is to have a strong adhesive force to enamel in the living tooth tissue, and to avoid the troublesome etching agent such as phosphoric acid, which is essential in conventional methods, in bonding dentin and restorative materials. The object of the present invention is to provide a novel dental adhesive composition that does not require pretreatment, has a practically sufficient adhesive strength, and is photopolymerizable. [Means for Solving the Problems] That is, the dental adhesive composition of the present invention comprises (a) an isocyanate group-containing urethane prepolymer represented by the following structural formulas (1), (2) and (3). (b) one or more radically polymerizable unsaturated monomers; (b) one or more radically polymerizable unsaturated monomers;
and (c) a dental adhesive composition containing a photopolymerization initiator as a main component. (In the formula, m is an integer of 1 to 100, n is an integer of 1 to 100, and n/(m+n) is 0.40 to 0.80, and the propylene oxide units and ethylene oxide units may be bonded randomly. ) [Function] The isocyanate group-containing urethane prepolymer which is the component (a) of the present invention has 2 isocyanate groups (-NCO) in the molecule relative to the polyol compound.
It is obtained by reacting a compound having more than one isocyanate, that is, a polyisocyanate, so that some of the isocyanate groups remain. As the polyol compound, a polyether polyol containing ethylene oxide units and propylene oxide units in a specific composition ratio is used. This polyether polyol can be obtained by a known method. The polyether polyol can be prepared by a known method.
ethylene glycol, propylene glycol,
Adding an alkali catalyst such as caustic potash or caustic soda to an active hydrogen compound such as 1,6-hexanediol,
It can be obtained by addition polymerizing alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, etc. to this. The polyol compound preferably has a hydroxyl group at its terminal in order to obtain excellent adhesive properties. Specifically, such an isocyanate group-containing urethane prepolymer is
In the presence of a known catalyst such as a tertiary amine or dibutyltin laurate, an organic diisocyanate such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, etc. is added in an amount such that the NCO group is present in excess. It is obtained by reacting at a NCO/OH equivalent ratio. Among these urethane prepolymers, propylene glycol is used as the active hydrogen compound,
Urethane prepolymers represented by the structural formulas (1), (2), and (3) obtained by using diols obtained by addition polymerizing ethylene oxide and propylene oxide thereto are preferably used. In particular, urethane prepolymers having at least two free isocyanate groups in one molecule obtained by using tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate or hexamethylene diisocyanate as the terminal isocyanate agent are particularly high. This is preferable because adhesive strength can be obtained. Further, the urethane prepolymer preferably has free isocyanate groups at both ends. The molecular weight of these urethane prepolymers is preferably 400 to 50,000, especially in order to obtain good solubility and excellent adhesion to radically polymerizable unsaturated monomers.
Particularly preferred is 400 to 20,000. In addition, in the isocyanate group-containing urethane prepolymers represented by formulas (1) to (3), the ratio of ethylene oxide units to the total amount of propylene oxide units and ethylene oxide units constituting the main chain of the prepolymer is 40 to 80. It is a prepolymer made hydrophilic or water-soluble by setting the mole %, that is, n/(m+n), to 0.40 to 0.80. Isocyanate group-containing urethane prepolymers contain isocyanate groups present in the molecule, organic components (particularly collagen containing many active hydrogen groups in the molecule), which are the main components of dentin in living tooth tissue, and water (body fluids). ) to develop adhesion with the restorative material, and in particular, urethane prepolymers containing two or more free isocyanate groups in one molecule are effective in achieving excellent adhesion. , is preferably used. The isocyanate group-containing urethane prepolymer can be used alone, but in order to improve workability when using the composition, it may be used with a diluent that is inert with respect to isocyanate groups, such as acetone, methyl ethyl ketone, ethyl acetate, toluene, Xylene, trichloroethane, etc. may also be added. The dental adhesive composition of the present invention basically comprises (a)
Although it is possible to obtain conventional adhesive strength using only the components, for example, when adhesive work is intended for use in the oral cavity, there are often time constraints on curing the adhesive layer. However, the radically polymerizable unsaturated monomer, component (b) of the present invention, is a necessary component for quickly solidifying the adhesive layer by light irradiation in the presence of the photopolymerization initiator, component (c). Any radically polymerizable unsaturated monomer that does not interfere with the adhesive performance of component (a) can be used, and monofunctional or polyfunctional monomers may be used. Specific examples of monofunctional unsaturated monomers include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-
Hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, benzyl (meth)acrylate, vinyl acetate, styrene, acrylonitrile, glycidyl methacrylate, among others, methyl acrylate, methyl methacrylate, 2-hydroxyl methacrylate and vinyl acetate. is preferably used. In addition, as an example of a bifunctional unsaturated monomer, the following general formula (4) (In the formula, R 1 is a hydrogen atom or a methyl group, p is 1
~20 integer. ) Polyethylene glycol di(meth)acrylate etc. can be used, and specific examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene. Glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate acrylate, decaethylene glycol di(meth)acrylate, polyethylene glycol(meth)diacrylate with p=14,
Examples include polyethylene glycol di(meth)acrylate with p of 17, polyethylene glycol di(meth)acrylate with p of 19, etc.
Among them, ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, and polyethylene glycol di(meth)acrylate with p=14 are preferably used. Also, the following general formula (5) (In the formula, R 1 is a hydrogen atom or a methyl group, R 2 is an alkylene group having 1 to 8 carbon atoms or
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According to the dental adhesive composition of the present invention, there is no need for complicated pretreatment with an etching agent such as phosphoric acid, which was essential in the conventional technology, when bonding living tooth tissue, especially dentin, and a restorative material. Adhesion strength sufficient for practical use can be obtained. Furthermore, since it has photopolymerizability, it can be solidified in a short time by light irradiation before its original adhesive strength is exerted, and it is also easy to handle in the oral cavity. [Examples of the Invention] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. [Restoration material-A (visible light curing composite resin)
Manufacturing of]
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ãåŸãã[Table] A mixture (paste) consisting of a multifunctional monomer, an inorganic fuel, and a visible light polymerization initiator shown in the above formulation, that is, a visible light curing composite resin, was produced in a dark room, and Restorative Material-A was prepared. Obtained. [Manufacture of restorative material-B (visible light-curable dental crown resin)] 2,2-bis[4-(3-methacryloxy-2)
-Hydroxypropoxy)phenyl}propane (hereinafter abbreviated as Bis-GMA)...40g 3G...60g Camphorquinone...0.7g Isoamyl 4-(N,N-dimethylamino)benzoate...2.8g The above combination formula A mixture consisting of a polyfunctional monomer shown by the formula and a visible light polymerization initiator, that is, a visible light curing resin for dental crowns was produced in a dark room to obtain a restorative material-B. [Adhesion evaluation procedure and adhesive strength measurement method] (1) Cut the fresh morning tooth immediately after tooth extraction with a precision cutter (Isometric, manufactured by BÃŒhler) to expose the dentin and enamel planes; Polish thoroughly under running water using No. 1000 waterproof abrasive paper. In some cases, the enamel plane is etched by a conventional method using a phosphoric acid etching agent (manufactured by Shishi Dental Industry Co., Ltd.). (2) Apply the dental adhesive composition to the dentin or enamel plane, and if volatile components such as solvents are present, let the volatile components evaporate and scatter with an air flow for about 10 seconds. (3) After installing a cylindrical silicone ring (one side can be opened) with an inner diameter of about 5 mm, a height of about 5 mm, and a wall thickness of about 3 mm on the flat surface coated with the dental adhesive composition, the liquid inside this silicon ring is The height of the repair material is approximately 3
Fill it to 1 mm. (4) Attach a visible light irradiator (GC light,
Co., Ltd.) and irradiate it with visible light for 60 seconds to harden the restoration material and adhesive. (5) After about 10 minutes, remove the silicone ring and obtain an adhesive test piece with the repair material adhered to the surface of the sample to be adhered. (6) After storing the entire adhesive test piece in water at 37°C for a predetermined period, a spacer for adhesion testing (an acrylic rod with the same diameter as the restoration material) was placed on top of the restoration material. First,
(manufactured by Dentistry Kogyo Co., Ltd.), set it in a specified test holder, and conducted a tensile test.
Adhesive strength was measured. The measurement conditions are shown below. Tensile tester: Toyo Baldwin Tensilon Crosshead speed (tensile speed): 0.5mm/
min Chart speed: 10mm/min Full scale: 5KgW or 20KgW [Synthesis of isocyanate group-containing urethane prepolymer] By ring-opening copolymerization of propylene oxide and ethylene oxide using a known method using propylene glycol as an active hydrogen compound. Various polyether glycols listed in Table 1 were produced having different molar ratios of ethylene oxide units (hereinafter abbreviated as EO) and propylene oxide units (hereinafter abbreviated as PO) and average molecular weights. Next, tolylene diisocyanate (2,4/2,6 isomer ratio: 80/
20, hereinafter abbreviated as TDI), 4,4-diphenylmethane diisocyanate (hereinafter abbreviated as MDI) and hexamethylene diisocyanate (hereinafter abbreviated as MDI).
(abbreviated as HDI) and polyether glycol isocyanating agent at a molar ratio of 1:2 and reacted to obtain various urethane prepolymers containing isocyanate groups at both terminals and having the abbreviations shown in Table 1.
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[Table] [Preparation of mixtures of radically polymerizable unsaturated monomers and visible light polymerization initiators] Mixtures of various radically polymerizable unsaturated monomers and visible light polymerization initiators were prepared in a dark room using a general-purpose mixer. Tables 2 to 4 show the compositions and abbreviations of these mixtures. In addition, the abbreviation EDMA shown in the column of radically polymerizable unsaturated monomer species in the table indicates urethane dimethacrylate having the following structural formula.
ãè¡šããtableã
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ãè¡šã
å®æœäŸ ïŒã64
ãã¬ããªããŒã®åæã§è£œé ããåçš®ã®äž¡æ«ç«¯
ã€ãœã·ã¢ããŒãåºå«æãŠã¬ã¿ã³ãã¬ãããŒãšã©ãž
ã«ã«éåæ§äžé£œåã¢ãããŒã»å¯èŠå
éåéå§å€æ··
åç©ã®LCâ15ãšãããããåééã¥ã€æ··åãæ¥
çå€çµæç©ãåŸãã
ãããã®æ¥çå€çµæç©ã«ã€ããŠãåèšããæ¥ç
æ§è©äŸ¡æé ããã³æ¥ç匷床枬å®æ¹æ³ã«æ²¿ã€ãŠãšã
ãã³ã°åŠçãããªãçæ¯ã®è±¡ç質é¢ã«å¯Ÿãã修埩
æâã®æ¥çæ§ãè©äŸ¡ããçµæã第ïŒè¡šã«ç€ºã
ãã
åæ§ã«ãåçš®ã®ã€ãœã·ã¢ããŒãåºå«æãŠã¬ã¿ã³
ãã¬ããªããŒãšLCâ16ãLCâ22ãŸãã¯LCâ23
ãšãçšããæ¥çå€çµæç©ã«ã€ããŠã®è©äŸ¡çµæã第
ïŒè¡šã第ïŒè¡šã«ç€ºããã[Table] Examples 1 to 64 The same weight of various urethane prepomer containing isocyanate groups at both terminals and LC-15, a mixture of radically polymerizable unsaturated monomer and visible light polymerization initiator, prepared by prepolymer synthesis The mixture was mixed to obtain an adhesive composition. Regarding these adhesive compositions, the adhesion of Restorative Material-A to the dentin surface of bovine teeth that was not subjected to etching treatment was evaluated according to the above-described adhesion evaluation procedure and adhesive strength measurement method, and the results are shown in Table 5. Indicated. Similarly, various isocyanate group-containing urethane prepolymers and LC-16, LC-22 or LC-23
Tables 5 to 8 show the evaluation results for adhesive compositions using the following.
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šããtableã
ãè¡šã
å®æœäŸ 65ã97
ãã¬ããªããŒã®åæã§è£œé ããã€ãœã·ã¢ããŒ
ãåºå«æãŠã¬ã¿ã³ãã¬ããªããŒTPTâ11ãšãå
çš®ã®ã©ãžã«ã«éåæ§äžé£œåã¢ãããŒã»å¯èŠå
éå
éå§å€æ··åç©ãšãããããåééã¥ã€æ··åãæ¥ç
å€çµæç©ãåŸãã
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æé ã§ä¿®åŸ©æâã®æ¥çæ§ãè©äŸ¡ããçµæã第ïŒ
è¡šã第10è¡šã«ç€ºããã[Table] Examples 65 to 97 The isocyanate group-containing urethane prepolymer TPT-11 produced by prepolymer synthesis and a mixture of various radically polymerizable unsaturated monomers and visible light polymerization initiators were mixed in equal weights and bonded. A drug composition was obtained. The adhesion of these adhesive compositions to Restorative Material-A was evaluated in the same manner as in Example 1, and the results were
It is shown in Tables to Table 10.
ãè¡šããtableã
ãè¡šã
å®æœäŸ 98ã109
äž¡æ«ç«¯ã€ãœã·ã¢ããŒãåºå«æãŠã¬ã¿ã³ãã¬ããª
ããŒãšã©ãžã«ã«éåæ§äžé£œåã¢ãããŒã»å¯èŠå
é
åéå§å€æ··åç©ãšã®é
åééæ¯ãå€åãããããš
ãé€ããå®æœäŸïŒã17ã33ãŸãã¯49ãšå
šãåæ§ã«
ããŠæ¥çå€çµæç©ãåŸããã®æ¥çæ§ãè©äŸ¡ããã
çµæã第11è¡šã«ç€ºããã[Table] Examples 98 to 109 Examples 1, 17, 33 or An adhesive composition was obtained in exactly the same manner as No. 49, and its adhesiveness was evaluated.
The results are shown in Table 11.
ãè¡šã
å®æœäŸ 110ã117
å®æœäŸïŒããã³36ã§åŸãæ¥çå€çµæç©ãçšãã
äžèšçš®ä¿®åŸ©æã«å¯Ÿããæ¥çæ§ãå®æœäŸïŒãšåæ§ã«
ããŠè©äŸ¡ãããçµæã第12è¡šã«ç€ºããã[Table] Examples 110 to 117 Using the adhesive compositions obtained in Examples 4 and 36,
Adhesion to the following types of repair materials was evaluated in the same manner as in Example 1. The results are shown in Table 12.
ãè¡šããtableã
ãè¡šã
æ¯èŒäŸ ïŒã14
äž¡æ«ç«¯ã€ãœã·ã¢ããŒãåºå«æãŠã¬ã¿ã³ãã¬ããª
ããŒã®ä»£ããã«ããã¬ããªããŒã®åæã§è£œé ã
ãåçš®ã®ããªãšãŒãã«ã°ãªã³ãŒã«ã䜿çšããããš
ãé€ããå®æœäŸïŒãšå
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ãåŸããã®æ¥çæ§ãè©äŸ¡ãããçµæã第13è¡šã«ç€º
ããã[Table] Comparative Examples 1 to 14 Adhesive compositions were prepared in exactly the same manner as in Example 1, except that various polyether glycols produced by prepolymer synthesis were used instead of the urethane prepolymer containing isocyanate groups at both terminals. The product was obtained and its adhesiveness was evaluated. The results are shown in Table 13.
ãè¡šã
æ¯èŒäŸ 15ã20
äž¡æ«ç«¯ã€ãœã·ã¢ããŒãåºå«æãŠã¬ã¿ã³ãã¬ããª
ããŒã®ä»£ããã«ããã¬ããªããŒã®åæã§è£œé ã
ãåçš®ã®ããªãšã¹ãã«ã°ãªã³ãŒã«ã䜿çšããããš
ãé€ããå®æœäŸïŒãšå
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ãåŸããã®æ¥çæ§ãè©äŸ¡ãããçµæã第14è¡šã«ç€º
ããã[Table] Comparative Examples 15 to 20 Adhesive compositions were prepared in exactly the same manner as in Example 1, except that various polyester glycols produced by prepolymer synthesis were used instead of the urethane prepolymer containing isocyanate groups at both ends. was obtained and its adhesion was evaluated. The results are shown in Table 14.
ãè¡šã
æ¯èŒäŸ21ã23
äž¡æ«ç«¯ã€ãœã·ã¢ããŒãåºå«æãŠã¬ã¿ã³ãã¬ããª
ããŒã®ä»£ããã«ããã¬ããªããŒã®åæã§è£œé ã
åçš®ã®äž¡æ«ç«¯ã©ãžã«ã«éåæ§ããã«åºå«åªãŠã¬ã¿
ã³ãã¬ããªããŒã䜿çšããããšãé€ããå®æœäŸ
125ãšå
šãåæ§ã«ããŠæ¥çå€çµæç©ãåŸããã®æ¥
çæ§ãè©äŸ¡ãããçµæã第15è¡šã«ç€ºããã[Table] Comparative Examples 21 to 23 Examples except that instead of the urethane prepolymer containing isocyanate groups at both ends, various urethane prepolymers containing radically polymerizable vinyl groups at both ends, which were produced by prepolymer synthesis, were used.
An adhesive composition was obtained in exactly the same manner as No. 125, and its adhesiveness was evaluated. The results are shown in Table 15.
ãè¡šã
æ¯èŒäŸ 24ã29
ïŒå®èœã€ãœã·ã¢ããŒãåºå«æãŠã¬ã¿ã³ãã¬ããª
ããŒã®ä»£ããã«ããã¬ããªããŒã®åæã§è£œé ã
åçš®ã®ïŒå®èœã©ãžã«ã«éåæ§ããã«åºå«æãŠã¬ã¿
ã³ãã¬ããªããŒã䜿çšããããšãé€ããå®æœäŸïŒ
ãšå
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ãè©äŸ¡ãããçµæã第16è¡šã«ç€ºããã[Table] Comparative Examples 24 to 29 Example 1, except that instead of the trifunctional isocyanate group-containing urethane prepolymer, various trifunctional radically polymerizable vinyl group-containing urethane prepolymers produced by prepolymer synthesis were used.
An adhesive composition was obtained in exactly the same manner as above, and its adhesiveness was evaluated. The results are shown in Table 16.
ãè¡šã
æ¯èŒäŸ 30ã37
åçš®ã®ã©ãžã«ã«éåæ§äžé£œåã¢ãããŒã»å¯èŠå
éåéå§å€æ··åç©ã ããé
åããæ¥çå€çµæç©ã
åŸãå®æœäŸïŒãšå
šãåæ§ã«ããŠãã®æ¥çæ§ãè©äŸ¡
ãããçµæã第17è¡šã«ç€ºããã[Table] Comparative Examples 30 to 37 Adhesive compositions containing only mixtures of various radically polymerizable unsaturated monomers and visible light polymerization initiators were obtained, and their adhesive properties were evaluated in exactly the same manner as in Example 1. The results are shown in Table 17.
Claims (1)
ã·ã¢ããŒãåºå«æãŠã¬ã¿ã³ãã¬ããªããŒã®äžçš®
以äžãŸãã¯è©²ãŠã¬ã¿ã³ãã¬ããªããŒã«äžæŽ»æ§åž
éå€ãçµåããçµæç©ã (b) ã©ãžã«ã«éåæ§äžé£œåã¢ãããŒã®äžçš®ä»¥äžã
ããã³ (c) å éåéå§å€ ãäž»æåãšããŠå«æããæ¯ç§çšæ¥çå€çµæç©ã ïŒåŒäžãïœã¯ïŒã100ã®æŽæ°ãïœã¯ïŒã100ã®æŽ
æ°ãïœïŒïŒïœïŒïœïŒã¯0.40ã0.80ã§ãããããã
ã¬ã³ãªããµã€ããŠããããšãšãã¬ã³ãªããµã€ããŠ
ãããã¯ãã©ã³ãã ã«çµåããŠããŠããããïŒ[Scope of Claims] 1 (a) One or more isocyanate group-containing urethane prepolymers represented by the following structural formulas (1), (2), and (3), or a composition in which an inert diluent is bonded to the urethane prepolymers. (b) one or more radically polymerizable unsaturated monomers;
and (c) a dental adhesive composition containing a photopolymerization initiator as a main component. (In the formula, m is an integer of 1 to 100, n is an integer of 1 to 100, and n/(m+n) is 0.40 to 0.80, and the propylene oxide units and ethylene oxide units may be bonded randomly. )
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62335727A JPH01113478A (en) | 1987-07-31 | 1987-12-28 | Dental adhesive composition |
AU18145/88A AU608857B2 (en) | 1987-07-31 | 1988-06-20 | Dental adhesive composition |
US07/221,549 US4968725A (en) | 1987-07-31 | 1988-07-20 | Dental adhesive composition |
DE8888112155T DE3874835T2 (en) | 1987-07-31 | 1988-07-27 | DENTAL ADHESIVE COMPOSITION. |
EP88112155A EP0301516B1 (en) | 1987-07-31 | 1988-07-27 | Dental adhesive composition |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP19031487 | 1987-07-31 | ||
JP62-190314 | 1987-07-31 | ||
JP62335727A JPH01113478A (en) | 1987-07-31 | 1987-12-28 | Dental adhesive composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH01113478A JPH01113478A (en) | 1989-05-02 |
JPH0555559B2 true JPH0555559B2 (en) | 1993-08-17 |
Family
ID=16256110
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62335727A Granted JPH01113478A (en) | 1987-07-31 | 1987-12-28 | Dental adhesive composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH01113478A (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8044234B2 (en) * | 2005-05-05 | 2011-10-25 | Tyco Healthcare Group Lp | Bioabsorbable surgical composition |
CA2618065C (en) * | 2005-08-10 | 2014-06-10 | Dentsply International Inc. | Methods for preparing chair-side dental crowns |
JP7286912B2 (en) * | 2016-12-15 | 2023-06-06 | æ±ãœãŒæ ªåŒäŒç€Ÿ | Allophanate group-containing polyisocyanate prepolymer |
-
1987
- 1987-12-28 JP JP62335727A patent/JPH01113478A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPH01113478A (en) | 1989-05-02 |
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