CN1112413A - 牙科填充组合物及方法 - Google Patents
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Abstract
一种牙根槽密封用牙科填充组合物,它包括液态
可聚合的有机单体和填料。可聚合的有机单体包括
一种双环氧化合物和单伯胺和/或二仲二胺单体。
填料占组合物重量的40—85%,并提供至少
3mm/mmAl的辐射不透明度。一种密封牙槽的方
法,包括在牙齿中形成一牙槽,用这种牙根槽密封用
牙科填充组合物密封该槽。
Description
本发明涉及牙科填充组合物。根据本发明的牙科填充组合物适合与填料一起形成环氧化物-胺加成聚合物。该牙科填充组合物包括填料和双环氧化合物,单伯胺和/或二仲二胺。本发明的牙科填充组合物聚合形成适合于密封牙根槽的热塑性线形高聚物。填料占牙科填充组合物重量的40-85%。牙科填充材料是通过聚合作用而形成的,并且它的辐射不透明度大于3mm/mmAl。其临床操作时间不足大约2小时,而凝结时间约0.5小时至约40小时。
Blahman等人在USSR311637和311638中公开了牙科填充材料。Feichtinger等人在美国专利3317469中公开了缩水甘油基聚醚与二氨甲基三环癸烷的反应产物。Lee在美国专利3327016中公开了用1,4-二(氨甲基)环己烷固化的环氧化物组合物。Toepel等人在美国专利3673558中公开了加聚产物及它们的制造方法。Rogier在美国专利4229376中公开了条环聚胺。Rogier在美国专利4296004中公开了多环聚胺。Horhold等人在美国专利4308085中公开了用于制备高分子热塑性环氧化物-胺-聚合加合物的方法。
Fujisawa等人在美国专利4931096中公开了用于填充牙根槽的密封剂。Chang等人在美国专利4950697中公开了热塑性和可注射的牙髓病填充组合物。美国专利5236362中描述了一种牙根槽填充和粘合组合物。用于环氧化物-胺聚合作用的多官能团的脂肪族或芳香胺如六亚甲基二胺,二亚乙基三胺,三亚乙基四胺,亚甲基双苯胺或间-亚苯基二胺,以及叔胺引发剂如2,4,6-三(二甲氨基乙基)苯酚或三乙醇胺可以产生不溶的交联网状聚合物。交联网状聚合物在聚合过程中容易产生很大收缩,这将导致边缘裂缝和缺口的形成。
现有技术中用作牙根槽的牙科填充材料具有相对较长的凝结时间、较高的粘度并且易褪色。有时使用多聚甲醛,参见前苏联专利1510131和化学文摘115(1991)78952Z。其它的产品包含低分子量的有机物如CHI3,参见日本专利9127308A2,和化学文摘115(1991)78973g。用咪唑啉或BF3硬化的脂肪族或脂环族环氧化物也被用作牙科填充材料,参见前苏联专利549150、545353、52106和349396,但这些物质具有诱变性质。其它的牙科填充材料包含环氧化物、二亚乙基二胺和填料如陶瓷粉、二氧化硅和沸石,参见前苏联专利311638和311637。这些填料不能形成基本不透明性。单独使用一种凝结脂肪胺是不好的,因为它不能抵抗由于收缩和温度的变化引起的张力。脂肪胺在环氧化物-胺加成聚合过程中会产生副反应(羟基的醚化)。因此一部分胺基没有反应。
使用双酚二缩水甘油醚和N,N′-二苯甲基二胺已经合成了高
分子量的线形环氧化物-胺加成聚合物(Mn10000至20000g/mol),参见DD141667,US4308085,GB2045269,CS227363;也可使用单伯胺,参见DD154945,DD214381,DD261365。制得的加成聚合物也用作光学和静电复印的粘合剂。
本发明的一个目的是提供一种辐射不透明度至少为3mm/mmAl的牙科填充材料。
本发明的另一个目的是提供一种辐射不透明度至少为3mm/mmAl并且粘度小于20000厘泊的牙根填充组合物。
用于密封牙根槽的牙科填充组合物包括液态的可聚合的有机单体和填料。可聚合的有机单体包括双环氧化合物和单伯胺和/或二仲二胺。填料占组合物重量的40-85%,并提供至少3mm/mmAl的辐射不透明度。一种密封牙槽的方法,包括在牙上形成一槽,用这种牙根槽密封用牙科填充组合物密封该槽。
根据本发明的牙科填充材料包括液体可聚合的有机单体和填料,它适合用于密封例如通过牙根槽操作形成的牙根槽。可聚合的有机单体有双环氧化合物、单伯胺和/或二仲二胺。与双环氧化合物形成交联聚合物的未取代的脂肪族单伯胺,不是优选的用于本发明牙科填充材料中的可聚合的有机单体。根据本发明,作为无机和/或有机填料颗粒的填料在牙科填充材料中含量优选为40-85%(重量)。
一种本发明的牙科填充材料聚合后形成具有一个或多个下面通式Ⅰ,Ⅱ和Ⅲ的环氧化物-胺加成聚合物:
其中R是从双环氧化合物形成的部分;
R1具有2至12个碳原子的取代的烷基,环烷基、取代的环烷基,具有6至20个碳原子的芳基,取代的芳基,芳烷基或取代的芳烷基。
R2是双官能团的烷基,具有2至12个碳原子的取代的烷基,环烷基,取代的环烷基,具有6至20个碳原子的芳基,芳烷基,取代的芳基,取代的芳烷基,而n,m,x和y各自独立地为1至1000的整数,当取代时,R1和R2各自独立地被1个或多个烷氧基、卤素、硝酸根、酰基或羧烷基部分取代。
可用于本发明牙科填充组合物的双环氧化合物包括双酚A二
缩水甘油醚(2,2-双〔4-(2,3-环氧丙氧基)苯基〕丙烷),双酚F二缩水甘油醚(是一种双〔4-(2,3-环氧丙氧基)苯基〕甲烷和2,4-同系物的异构混合物(CIBA-Geigy)),丁二醇二缩水甘油醚,N,N-二缩水甘油基苯胺,和△3-四氢化邻苯二甲酸二缩水甘油酯(有时称双(2,3-环氧丙氧基)环已基-3-烯二羧酸酯)。可用于本发明的单胺有苯胺,对-氟苯胺,苯甲胺,1-氨基金刚烷,α-苯乙胺,二甲基(氨甲基)氧化膦和乙醇胺。可用于本发明的二胺有N,N′-二苄基亚乙基二胺,N,N-二苄基-3,6-二氧杂辛二胺-1,8,N,N′-二苄基-5-氧杂壬二胺-1,9,N,N′-二苄基-(2,2,4)/(2,4,4)三甲基六亚甲基二胺。
可用于本发明的填料有包含无机化合物的无机填料如La2O3,ZrO2,BiPO4,CaWO4,BaWO4、SrF2和Bi2O3;有机填料如聚合物颗粒;以及有机和无机填料的混合物。
本发明的牙科填充材料克服了现有技术的填充材料的一些问题,例如褪色和释放甲醛。本发明的牙科填充材料具有下面的优点:低的粘度,相对较短的凝结时间,在有机溶剂中相对高的溶解度,热塑性性能,和高的辐射不透明度(RO)即大于3mm/mmAl。当使用填料La2O3,BiPO4,CaWO4和BaWO4时,可获得较高的辐射不透明度,例如大于7mm/mmAl。
例如含有双酚A二缩水甘油醚,N,N′-二苄基亚乙基二胺和CaWO4的牙科填充组合物的粘度(Brookfield)(η)为2100厘泊,凝
结时间为3小时,辐射不透明度(RO)为9.2mm/mmAl。
本发明提供由双组分糊状体系制得的牙科填充材料,优选使用lentulo或空心探针将这双组分糊状体系引入到牙根,因为它们的粘底很低。本发明的牙科填充材料形成时产生的收缩小。这就防止了高收缩材料的收缩缝及随后的边缘裂缝。本发明的牙科填充材料具有低的吸水性和与牙质良好的粘合性。由它形成的复合材料很容易通过加热,钻孔或溶于有机溶剂而除去,因此适合用作暂时的填充材料。
本发明的组合物优选具有低于20000厘泊的粘度,并优选通过管道直径1mm的探针进入牙根。用于本发明组合物中的可聚合的环氧化物单体优选为双酚A二缩水甘油醚,双酚F二缩水甘油醚,丁二醇二缩水甘油醚或△3-四氢化邻苯二甲酸二缩水甘油酯。
实施例1-4中列出的凝结时间是根据ISO6876的方法来测定的(1986-12-01:牙科用牙根槽密封材料)。
实施例1
将3.404g(10.00mmol)双酚A二缩水甘油醚(也称为2,2-双〔4-(2,3-环氧丙氧基)苯基〕丙烷),2.404g(10.00mmol)N,N′-二苄基亚乙基二胺和18.000g CaWO4均匀混合,得到牙科填充材料。这种牙科填充材料的粘度(Brookfield)(η)为3200厘泊,凝结时间为24小时(37℃下),辐射不透明为9.5mm/mmAl。聚合后得到的牙科填充产物可溶于有机溶剂,如CHCl3或CHCl3/乙醇混
合物。
实施例2
实用的热凝结牙科填充组合物制成A和B的双组分糊状体系。
A是将142.570g(374.36mmol)数均分子量(Mn)约380g/mol的双酚A二缩水甘油醚(也称为2,2-双〔4-(2,3-环氧丙氧基)苯基〕丙烷),11.680g(37.44mmol)双酚F二缩水甘油醚(它是双〔4-(2,3-环氧丙氧基)苯基〕甲烷和双〔2-(2,3-环氧丙氧基)苯基〕甲烷的异构化混合物,由CIBA-Geigy出售),和241.463g CaWO4,60.366g ZrO2,0.637g Fe2O3和4.277g Aerosil 200(Degussa出售)均匀混合得到。
糊B是将22.064g(205.90mmol)苯甲胺,70.112g(205.90mmol)N,N′-二苄基-5-氧杂壬二胺-1,9,392.068g CaWO4,98.017g ZrO2和25.663g Aerosil(由Degussa出售)均匀混合而制得。A与B的混合体积比为1∶1。得到填充材料的凝结时间为7小时(37℃下),而操作时间为2∶23小时(于23℃)。该组合物的特性数值如下:辐射不透明度(RO)为11.6mm/mm Al,流45mm(flow 45mm),膜厚10μm,溶解度0.23%(全部根据ISO 6876测试),并且体积收缩率为1.63%。
实施例3
实用的热凝结牙科填充组合物制成A和B的双组分糊状体系。
A是将128.313g(337.67mmol)数均分子量(Mn)约380g/mol
的双酚A二缩水甘油醚(也称为2,2-双〔4-(2,3-环氧丙氧基)苯基〕丙烷),10.535g(33.77mmol)双酚F二缩水甘油醚(它是双〔4-(2,3-环氧丙氧基)苯基〕甲烷和双〔2-(2,3-环氧丙氧基)苯基〕甲烷的异构混合物,由CIBA-Geigy出售)和294.551g CaWO4、73.638g ZrO2和0.637g Fe2O3以及1.426g Aerosil200均匀混合而得到。
糊B是将28.140g(185.72mmol)1-氨基金刚烷,63.241g(185.72mmol)N,N′-二苄基-5-氧杂壬二胺-1,9,8.554g Aerosil 200,365.519g CaWO4,91.380g ZrO2和11.364g OL-31(由Bayer出售的硅油)均匀混合而制得。A与B的混合体积比为1∶1。凝结时间为8小时(37℃下),而操作时间为16小时(23℃下)。该组合物的特性值如下:辐射不透明度为10.1mm/mm Al,流35mm,膜厚15μm,溶解度0.27%(全部根据ISO 6876而测定),而体积收缩率为1.13%。
实施例4
将2.000g(5.88mmol)双酚A二缩水甘油醚,1.413g(5.88mmol)N,N′-二苄基亚乙基二胺和8.000g La2O3均匀混合得到实用的热凝固牙科填充材料。它的凝结时间为6小时(37℃下),而辐射不透明度为6.3mm/mm Al。
应该理解,虽然本发明是根据特定实施方案而详细描述的,但不应认为它仅局限于这类实施方案,而可以在不背离本发明精神和权
利要求书限定的范围前提下以其它方式使用。
Claims (24)
1、一种牙根密封用牙科填充组合物,包括:液态可聚合的有机单体和填料,所说可聚合的有机单体包括可聚合的环氧化物部分和胺部分,所说环氧化物单体是一种双环氧化合物,所说的含胺单体为单伯胺和/或二仲二胺,所说填料占上述组合物的40-85%(重量),并且提供至少3mm/mmAl的辐射不透明度。
2、一种权利要求1的组合物,其中所说的单体聚合后形成可密封牙根槽的热塑性线形聚合物。
3、一种权利要求1的组合物,其中所说的可聚合的环氧化物单体是双酚A二缩水甘油醚,双酚F二缩水甘油醚,丁二醇二缩水甘油醚或△3-四氢化邻苯二甲酸二缩水甘油酯。
4、一种权利要求1的组合物,其中所说的单胺是苯甲胺,金刚烷胺,α-苯乙胺,或乙醇胺;所说的二胺是N,N-二苄基亚乙基二胺,N,N′-二苄基-3,6-二氧杂辛二胺-1,8,N,N′-二苄基-5-氧杂壬二胺-1,9,N,N′-二苄基-(2,2,4)/(2,4,4)-三甲基六亚甲基二胺。
5、一种权利要求1的组合物,其中所说的填料是La2O3、ZrO2、BiPO4、BaWO4,SrF2,Bi2O3和/或聚合物颗粒。
6、一种权利要求1的组合物,其中所说的组合物由双组分形成,该双组分适合混合一起后开始聚合。
7、一种权利要求1的组合物,其中所述的双环氧化合物,单胺和/或二胺适合于形成可溶于CHCl3和/或C2H5OH的复合物。
8、一种权利要求1的组合物,其中所说的填料提供至少3mm/mmAl的辐射不透明度。
9、一种权利要求1的组合物,其中所说的填料提供至少5mm/mmAl的辐射不透明度。
10、一种权利要求1的组合物,其中所说的组合物适合于在37℃下,于0.5-40小时内凝结。
11、一种权利要求1的组合物,其中所说的组合物适合于在0.5-3小时内凝结。
12、一种权利要求1的组合物,其中所说的组合物具有低于5000厘泊的粘度。
14、一种密封牙槽的方法,包括在牙齿上形成一槽,用牙根槽密封用牙科组合物密封上述的槽,该组合物包括:液态可聚合的有机单体和填料,所说可聚合的有机单体包括环氧化物单体和胺单体,所说环氧化物单体为双环氧化合物,所说的胺单体为单伯胺和/或二仲二胺,所说填料占上述组合物的40-85%(重量)并提供至少3mm/mmAl的辐射不透明度。
15、一种权利要求14的方法,其中所说的可聚合物的环氧化物单体是双酚A二缩水甘油醚,双酚F二缩水甘油醚,丁二醇二缩水甘油醚或△3-四氢化邻苯二甲酸二缩水甘油酯。
16、一种权利要求14的方法,其中所说的单胺是苯甲胺,金刚烷胺、α-苯乙胺或乙醇胺,所说的二胺是N,N′-二苄基亚乙基二胺,N,N′-二苄基-3,6-二氧杂辛二胺-1,8,N,N′-二苄基-5-氧杂壬二胺-1,9,N,N′-二苄基-(2,2,4)/(2,4,4)-三甲基六亚甲基二胺。
17、一种权利要求14的方法,其中所说的填料是La2O3,ZrO2,BiPO4,BaWO4,SrF2,Bi2O3和/或聚合物颗粒。
18、一种权利要求14的方法,其中所说的组合物由双组分形成,该双组分适合混合一起后开始聚合。
19、一种权利要求14的方法,其中所说的填料提供至少3mm/mmAl的辐射不透明度。
20、一种权利要求14的方法,其中所说的组合物适合于在0.5-3小时内凝结。
21、一种权利要求14的方法,其中所说的组合物具有低于20000厘泊的粘度,并且通过槽直径1mm的探针进入到牙根。
22、一种权利要求21的方法,其中所说的组合物聚合时体积收缩率低于3%,并且具有与牙质的基本粘合性。
23、一种权利要求14的方法,其中所说的组合物的粘度低于5000厘泊。
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US08/217,998 US5624976A (en) | 1994-03-25 | 1994-03-25 | Dental filling composition and method |
US217,998 | 1994-03-25 |
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US (1) | US5624976A (zh) |
EP (1) | EP0673637B1 (zh) |
JP (1) | JPH083014A (zh) |
KR (1) | KR950031013A (zh) |
CN (1) | CN1112413A (zh) |
AT (1) | ATE194766T1 (zh) |
AU (1) | AU699521B2 (zh) |
CA (1) | CA2144584C (zh) |
DE (1) | DE69518030T2 (zh) |
ES (1) | ES2149288T3 (zh) |
FI (1) | FI951408A (zh) |
ZA (1) | ZA952422B (zh) |
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- 1995-03-14 AU AU14838/95A patent/AU699521B2/en not_active Expired
- 1995-03-24 DE DE69518030T patent/DE69518030T2/de not_active Expired - Lifetime
- 1995-03-24 KR KR1019950006385A patent/KR950031013A/ko not_active Application Discontinuation
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- 1995-03-24 ES ES95104386T patent/ES2149288T3/es not_active Expired - Lifetime
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CN106659642A (zh) * | 2014-07-02 | 2017-05-10 | 登特斯普伊德特雷有限公司 | 牙科组合物 |
CN106659642B (zh) * | 2014-07-02 | 2019-09-17 | 登特斯普伊德特雷有限公司 | 牙科组合物 |
CN112867747A (zh) * | 2018-10-01 | 2021-05-28 | Sika技术股份公司 | 用于环氧树脂的固化剂 |
CN112867747B (zh) * | 2018-10-01 | 2024-03-01 | Sika技术股份公司 | 用于环氧树脂的固化剂 |
CN114007571A (zh) * | 2019-04-11 | 2022-02-01 | 登士柏德特里有限公司 | 牙科组合物 |
Also Published As
Publication number | Publication date |
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CA2144584A1 (en) | 1995-09-26 |
ES2149288T3 (es) | 2000-11-01 |
EP0673637B1 (en) | 2000-07-19 |
DE69518030T2 (de) | 2000-12-21 |
CA2144584C (en) | 2002-08-27 |
EP0673637A1 (en) | 1995-09-27 |
DE69518030D1 (de) | 2000-08-24 |
US5624976A (en) | 1997-04-29 |
AU1483895A (en) | 1995-10-05 |
ZA952422B (en) | 1996-01-11 |
KR950031013A (ko) | 1995-12-18 |
JPH083014A (ja) | 1996-01-09 |
AU699521B2 (en) | 1998-12-03 |
FI951408A (fi) | 1995-09-26 |
ATE194766T1 (de) | 2000-08-15 |
FI951408A0 (fi) | 1995-03-24 |
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