CN103491929B - 牙科粘结剂组合物 - Google Patents

牙科粘结剂组合物 Download PDF

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CN103491929B
CN103491929B CN201280007667.3A CN201280007667A CN103491929B CN 103491929 B CN103491929 B CN 103491929B CN 201280007667 A CN201280007667 A CN 201280007667A CN 103491929 B CN103491929 B CN 103491929B
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B·德朗贝尔
D·布朗卡尔
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    • A61K6/884Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
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Abstract

本发明涉及具有多于50%重量的波特兰粘结剂的牙科粘结剂组合物,其特征在于该组合物还包含选自带有磺酸盐官能团的苯乙烯类聚合物、乙烯基类聚合物和丙烯酸类聚合物的聚合物。

Description

牙科粘结剂组合物
技术领域
本发明涉及牙科粘结剂(cimentdentaire)组合物,包含占大部分的波特兰(Portland)粘结剂。这种牙科粘结剂组合物用于充填例如由于钻削而在牙齿中形成的空腔,尤其是牙根管系统中和深度龋齿中的空腔。牙医越来越倾向于使用这类基于波特兰粘结剂的牙科粘结剂组合物,因为其具有良好的生物相容性且能够保证良好的密封性,因而形成了对抗由微生物产生的感染的屏障。
背景技术
在现有技术中,已经知晓文献US-5415547、US-5769638、EP-1531779和WO2010/034938。在这后一文献中,牙科粘结剂组合物包含64%的波特兰粘结剂(或波特兰熟料)、3%的天然石膏、15%的作为粘合剂的碳酸钙和18%的作为阻光剂的氯化钡。这种牙科粘结剂组合物被认为比现有技术的粘结剂组合物具有优势,尤其是涉及较短的凝固时间并且更容易搅拌和操作。在此文献中还提及这种牙科粘结剂组合物符合通常所要求的性能,即密封封闭所有空腔,尤其是牙根管系统中和深度龋齿中的空腔,具有生物相容性,刺激根尖周组织再生,硬化不受水分影响,具有体积稳定性,既不被腐蚀也无电化学活性,不会对牙齿及邻近组织染色,临床操作容易并且具有与牙本质不同的放射学不透明性。这些性能中的一些由波特兰粘结剂提供,其它性能由氯化钡提供,如放射学不透明性。碳酸钙由于其粘合性能而确保了操作容易性。文献WO2010/034938没有给出关于比现有技术要短的凝固时间的任何数字指示。
对于从业医生即牙科医生或口腔科医生来说,凝固时间以及搅拌和操作(manipulation)的容易性是特别重要的参数。凝固时间必须是合理的,即远小于1小时。不过它也不能太短,即不能小于5分钟,以便留给牙医足够的时间来准备糊料(组合物+水)并且按照规定充填空腔。该凝固时间以及该搅拌和操作是在符合欧洲标准的常规塑性条件下可测量的参数。该搅拌和操作是牙医在操作加水的粘结剂时可感知的参数。糊料(组合物+水)既不能太糊状也不能太粒状,以便能够按照规定实现充填。
发明内容
本发明的目标在于定义新的牙科粘结剂组合物,其当然满足上述现有技术的要求并且对于给定塑性来说还能够进一步减少凝固时间,而不会损害操作和搅拌。
此目的根据本发明通过具有多于50%重量的波特兰粘结剂的牙科粘结剂组合物而实现,其特征在于该组合物还包含带有磺酸盐官能团的聚合物。该聚合物选自带有磺酸盐官能团的苯乙烯类聚合物、乙烯基类聚合物和丙烯酸类聚合物。该聚合物可以以0.1-25%重量存在。优选地,该聚合物是聚苯乙烯磺酸钠。这种聚合物除了可以显著减少凝固时间外还提供与以下事实有关的优点:它具有抗菌、抑菌和/或抗生性能。它因此执行双重功能,即减少凝固时间的功能和抗菌的功能。与这两个性能有关的良好结果利用分子量为大约70000克/摩尔-500000克/摩尔的聚苯乙烯磺酸钠而获得。最佳结果利用70000克/摩尔的该短聚合物而获得。
除了波特兰粘结剂和具有磺酸盐官能团的聚合物之外,该组合物还可包含石膏、阻光剂如ZrO2或BaSO4,和/或粘合剂如甲酸盐、抗坏血酸盐和/或葡糖酸盐,例如钙的甲酸盐、抗坏血酸盐和/或葡糖酸盐。抗坏血酸钙是已知的并且用于治疗维生素C缺乏症。葡糖酸钙是已知的并且用于治疗低钙血症。
本发明牙科粘结剂组合物的一般配方可包含:
-60%至95%重量的波特兰粘结剂,
-0.1%至25%重量的聚苯乙烯磺酸钠,
-0.1%至5%的石膏,
-0.1%至25%的BaSO4
-0.1%至25%的甲酸钙。
本发明牙科粘结剂组合物的优选配方可以包含:
-70%至80%重量的波特兰粘结剂,
-1%至15%重量的聚苯乙烯磺酸钠,
-2%至5%的石膏,
-10%至25%的BaSO4
-1%至15%的甲酸钙。
显然,作为聚苯乙烯磺酸钠的替代,在本发明范围内可以使用聚乙烯基磺酸盐或聚丙烯酸类磺酸盐,例如钠或其它相容元素的盐。
本发明的本质在于使用特殊的聚合物,其带有磺酸盐官能团以实现有利的双重功能,即减少凝固时间并且中和或破坏细菌或微生物。
具体实施方式
下面将通过若干牙科粘结剂组合物的实施例来对本发明进行阐述,其中的一些实施例基于本发明。以下给出的数值以%重量表示。凝固时间(tempsdeprise)使用标准NFENISO6876:2003来确定。
实施例1
制备不在本发明范围内的牙科粘结剂组合物,包含75.5%的波特兰粘结剂、3.5%的石膏和21%的ZrO2。塑性,即水/组合物之比被固定在0.37,这对应于依照现行欧洲标准的常规塑性。测量凝固时间为48分钟。该组合物不含本发明所推荐的带有磺酸盐官能团的聚合物。
实施例2
制备本发明牙科粘结剂组合物,包含71%的波特兰粘结剂、3.2%的石膏和19.8%的ZrO2、3%的抗坏血酸钙和3%的分子量为500000克/摩尔的聚苯乙烯磺酸钠。该组合物与水以水/组合物之比为0.37进行混合,这对应于依照现行欧洲标准的常规塑性。测量凝固时间为29分钟。
实施例3
制备本发明牙科粘结剂组合物,包含71%的波特兰粘结剂、3.2%的石膏和19.8%的ZrO2、3%的葡糖酸钙和3%的分子量为70000克/摩尔的聚苯乙烯磺酸钠。该组合物与水以水/组合物之比为0.37进行混合,这对应于依照现行欧洲标准的常规塑性。测量凝固时间为25分钟。
实施例4
制备本发明牙科粘结剂组合物,包含71%的波特兰粘结剂、3.2%的石膏和19.8%的ZrO2、3%的抗坏血酸钙和3%的分子量为70000克/摩尔的聚苯乙烯磺酸钠。该组合物与水以水/组合物之比为0.37进行混合,这对应于依照现行欧洲标准的常规塑性。测量凝固时间为14分钟。
实施例5
制备本发明牙科粘结剂组合物,包含76.8%的波特兰粘结剂、3.2%的石膏和10%的BaSO4、10%的甲酸钙,无聚合物。该组合物以水/组合物之比为0.37进行混合,这对应于依照现行欧洲标准的常规塑性。测量凝固时间为27分钟。
实施例6
制备本发明牙科粘结剂组合物,包含86.8%的波特兰粘结剂、3.2%的石膏和10%的BaSO4,无聚合物且无粘合剂。该组合物与水以水/组合物之比为0.35进行混合,这对应于依照现行欧洲标准的常规塑性。测量凝固时间为41分钟。
实施例7
制备本发明牙科粘结剂组合物,包含74.8%的波特兰粘结剂、3.2%的石膏和10%的BaSO4、10%的甲酸钙和2%的分子量为70000克/摩尔的聚苯乙烯磺酸钠。该组合物与水以水/组合物之比为0.325进行混合,这对应于依照现行欧洲标准的常规塑性。测量凝固时间为16分钟。
因而可以看出,实施例2、3和4的本发明牙科粘结剂组合物所具有的凝固时间远小于不在本发明范围之内的实施例1的牙科粘结剂组合物的凝固时间。实施例4在凝固时间方面提供了最佳结果,即14分钟,这个时间对于牙医来说既不过长也不过短。
实施例5、6和7显示出,聚苯乙烯磺酸钠与粘合剂(甲酸钙)一样对凝固时间具有积极作用。凝固时间从既无聚合物也无粘合剂的41分钟,到具有粘合剂但无聚合物的27分钟,以及再到既有粘合剂又有聚合物的16分钟。通过将组分的粒度降低到大约10微米或更小可以减少凝固时间,一直到大约10分钟。聚合物的粒度可任选地较大,因为将聚合物研磨成非常细的颗粒会影响聚合物的链。在这种粒度下,获得的抗压强度为按照标准NFENISO9917-1:2008的大约90+/-10兆帕。
在不超出本发明范围的情况下,波特兰粘结剂的比例可以是60%-95%重量,优选70%-80%重量,聚苯乙烯磺酸钠的比例可以是0.1%-25%重量,优选1%-5%重量,石膏的比例可以是0.1%-5%重量,优选1%-5%重量,ZrO2的比例可以是0.1%-25%重量,优选5%-15%重量,抗坏血酸钙和/或葡糖酸钙的比例可以是0.1%-25%重量,优选0.1%-15%重量。抗坏血酸盐和葡糖酸盐可以混合或者分开使用。作为ZrO2和/或BaSO4的替代,可以使用其它的阻光剂,只要它是相容的并且无毒即可。可以设想在某些配方中省去石膏。还可以在某些配方中省去抗坏血酸盐和/或葡糖酸盐。可以用其它粘合剂来代替抗坏血酸盐和/或葡糖酸盐,只要其是相容的并且无毒即可,例如甲酸钙。聚苯乙烯磺酸钠可被其它带有磺酸盐官能团的聚合物代替。
优选的组合物包含74.8%重量的波特兰粘结剂、3.2%重量的石膏、10%重量的甲酸钙、10%重量的BaSO4和2%重量的分子量为70000克/摩尔的聚苯乙烯磺酸钠。除聚合物之外的成分的粒度为10微米或更小。
通过本发明得到同时具有短凝固时间和抗菌性能的牙科粘结剂组合物。

Claims (9)

1.牙科粘结剂组合物,该组合物具有多于50%重量的波特兰粘结剂并且包含选自带有磺酸盐官能团的苯乙烯类聚合物、乙烯基类聚合物和丙烯酸类聚合物的聚合物,其特征在于该聚合物为聚苯乙烯磺酸钠,
其中该组合物包含0.1%-25%重量的聚苯乙烯磺酸钠并且该聚苯乙烯磺酸钠具有70000克/摩尔-500000克/摩尔的分子量。
2.权利要求1的组合物,包含石膏。
3.权利要求1的组合物,包含阻光剂。
4.权利要求1的组合物,包含粘合剂。
5.权利要求4的组合物,其中该粘合剂选自甲酸钙、抗坏血酸盐或葡糖酸盐。
6.权利要求1的组合物,其中任选地除聚合物之外的该组合物的不同成分的粒度为小于10微米。
7.权利要求1的组合物,具有大约10分钟的凝固时间以及90兆帕的抗压强度。
8.权利要求1的组合物,包含:
-60%至95%重量的波特兰粘结剂,
-0.1%至25%重量的聚苯乙烯磺酸钠,
-0.1%至5%的石膏,
-0.1%至25%的BaSO4
-0.1%至25%的甲酸钙。
9.权利要求1的组合物,包含:
-70%至85%重量的波特兰粘结剂,
-0.1%至5%重量的聚苯乙烯磺酸钠,
-1%至5%的石膏,
-5%至15%的BaSO4
-0.1%至15%的甲酸钙。
CN201280007667.3A 2011-02-03 2012-02-03 牙科粘结剂组合物 Expired - Fee Related CN103491929B (zh)

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FR1150866A FR2971147B1 (fr) 2011-02-03 2011-02-03 Composition de ciment dentaire.
FR1150866 2011-02-03
PCT/FR2012/050238 WO2012104563A2 (fr) 2011-02-03 2012-02-03 Composition de ciment dentaire.

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US20130310481A1 (en) 2013-11-21
US9155686B2 (en) 2015-10-13
EP2670374A2 (fr) 2013-12-11
WO2012104563A2 (fr) 2012-08-09
FR2971147A1 (fr) 2012-08-10
CN103491929A (zh) 2014-01-01
RU2013140562A (ru) 2015-03-10
FR2971147B1 (fr) 2013-08-16

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