CN102862985B - 一种可水解磷硅酸钾钙活性材料的制备及其应用 - Google Patents
一种可水解磷硅酸钾钙活性材料的制备及其应用 Download PDFInfo
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- 235000019353 potassium silicate Nutrition 0.000 title claims abstract description 73
- 229910052913 potassium silicate Inorganic materials 0.000 title claims abstract description 73
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- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 12
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Abstract
本发明公开了一种可水解磷硅酸钾钙活性材料的制备及其应用,以二氧化硅石英粉、磷酸二氢钾、氧化钙为主要原料,碳酸钾做助剂按质量百分比:二氧化硅44±6%,磷酸二氢钾17±3%,碳酸钾10±3%,氧化钙28±4%混合后放入高温熔炉中加热到1450-1550℃进行高温液相化学反应合成磷硅酸钾钙;将合成磷硅酸钾钙冷却到常温;再使用气流磨将磷硅酸钾钙粉碎到1~500μm的颗粒大小;本发明旨在提供一种用于控制牙齿过敏、抑制牙菌斑、坚固牙釉质的可水解磷硅酸钾钙活性材料的制备及其应用。
Description
技术领域
本发明涉及一种用于口腔护理的新型活性材料,尤其是指可使用于口腔护理用品,可协助控制牙齿过敏、抑制牙菌斑、坚固牙釉质的一种可水解磷硅酸钾钙活性材料的制备及其应用。
背景技术
近年来,随着经济发展和人民生活水平提高,人们对口腔卫生和健康要求越来越高。传统的口腔清洁护理用品(如牙膏、漱口水等)已不能满足消费者对口腔保健的需求。因此新的功效性口腔清洁护理用品的研究进展很快,往往通过添加有效成份(如中药、硝酸钾、氟化钠等)来改善口腔问题,包括防龋、抑制牙菌斑、抗牙本质敏感、减轻牙龈相关问题、除渍增白、抗牙结石、减轻口臭等效果,而往往这些护理用品的效果并不显著,达不到预期的效果,还是会有一些牙菌不能消除或牙龈问题还是存在的现象,因此,解决这些问题具有重要的研究和应用推广价值。
发明内容
本发明的目的是提供一种用于口腔的可水解磷硅酸钾钙活性材料的制备方法。通过本发明的活性此类可协助控制牙齿过敏、抑制牙菌斑、坚固牙釉质,以弥补传统口腔用品的功效性不足的缺点。
本发明的目的通过下述技术方案实现:一种可水解磷硅酸钾钙活性材料的制备及其应用的制备的方法,其中:以二氧化硅石英粉、磷酸二氢钾、氧化钙为主要原料,碳酸钾做助剂按质量百分比:
二氧化硅44±6%
磷酸二氢钾17±3%
碳酸钾10±3%
氧化钙28±4%
混合后放入高温熔炉中加热到1450-1550℃进行高温液相化学反应合成磷硅酸钾钙,化学反应式为:SiO2+KH2PO4+K2CO3+CaO=KCaPSiO6+CO2↑+K2O↑+H2O↑;将合成磷硅酸钾钙冷却到常温;再使用气流磨将磷硅酸钾钙粉碎到1~500μm的颗粒大小。
此方法合成的磷硅酸钾钙中个元素质量百分含量为:硅含量24±4%,磷含量为:4±2%,钾含量为:8±2%,钙含量为:21±4%,氧含量为:42±6%。
上述的一种可水解磷硅酸钾钙活性材料的制备及其应用:活性材料在口腔中的应用形式之一为护牙剂。主要成分的质量百分比为:2.5~7.5%磷硅酸钾钙,19.0~25%聚乙二醇400,8.2~10.5%增稠氧化硅,50~60%甘油,0.8~1.0%钛白粉,0.6~0.8%香精,0.3~0.8%十二脂硫酸钠,0.4~0.8%卡波姆,0.2~0.4%AK糖。
上述的一种可水解磷硅酸钾钙活性材料的制备及其应用:磷硅酸钾钙用作护牙剂,采用1~30μm的磷硅酸钾钙为活性成分添加甘油等辅料制备而成,按护牙剂配方要求以质量百分比计,制备方法为:将0.6~0.8%的香精,0.3~0.8%的十二脂硫酸钠,0.4~0.8%的卡波姆,0.2~0.4%的AK糖在预混锅里加少量纯净水溶解至均匀,再加入19.0~25%的聚乙二醇400,8.2~10.5%的增稠氧化硅,50~60%的甘油,0.8~1.0%的钛白粉,2.5~7.5%的磷硅酸钾钙,均质搅拌、研磨和捏合使膏料充分混合均匀,然后抽真空60~120min直至真空度达-0.096mpa为止,最后打入储存锅中陈化120~240min。即制得用于口腔保健的磷硅酸钾钙护牙剂。
上述的一种可水解磷硅酸钾钙活性材料的制备及其应用:磷硅酸钾钙为可水解的不定型活性材料,化学式为KCaPSiO6。
一种可水解磷硅酸钾钙活性材料的制备方法,包括如下步骤:
(1)高温液相合成
根据磷硅酸钾钙的成分要求,以二氧化硅石英粉、磷酸二氢钾粉体、氧化钙粉体为主要原料,碳酸钾粉体做助剂按质量比例(二氧化硅44±6%,磷酸二氢钾17±3%,碳酸钾10±3%,氧化钙28±4%)充分混合后在高温熔炉中加热到1450℃—1550℃进行高温液相化学反应3-5小时合成磷硅酸钾钙。反应过程为:SiO2+K3PO4+K2CO3+CaO=KCaPSiO6+CO2↑+2K2O↑。
(2)常温固相粉碎
将合成磷硅酸钾钙冷却到常温。再使用气流磨将磷硅酸钾钙粉碎到1~500μm的颗粒大小。此方法合成的磷硅酸钾钙中各元素的质量百分含量为:硅含量为24±5%,磷含量为:10±3%,钾含量为:5±2%,钙含量为:30±5%。
选取1~30μm的磷硅酸钾钙为活性成分添加甘油等辅料制备护牙剂,按护牙剂配方要求以质量百分比计,将0.6~0.8%的香精,0.3~0.8%的十二脂硫酸钠,0.4~0.8%的卡波姆,0.2~0.4%的AK糖在预混锅里加少量纯净水溶解至均匀,再加入19.0~25%的聚乙二醇400,8.2~10.5%的增稠氧化硅,50~60%的甘油,0.8~1.0%的钛白粉,2.5~7.5%的磷硅酸钾钙,均质搅拌、研磨和捏合使膏料充分混合均匀,然后抽真空60~120min直至真空度达-0.096mpa为止。随后打入储存锅中陈化120~240min。即制得用于口腔保健的磷硅酸钾钙护牙剂。
可水解磷硅酸钾钙活性材料是一种具有特殊化学组成和无定型结构的活性材料。当这种材料与液体接触时,能够在材料表面迅速发生一系列水解反应,如材料表面钾离子、钙离子可迅速与水中的H+或H3O+发生离子交换,同时水解出磷酸根,硅羟基离子,直至液体中的各种离子(K、Si、Ca、P)趋于饱和。其水解过程为:KCaPSiO6+H2O→K++Ca2++PO43-+Si·OH-+H+。研究表明在口腔护理用品种这些离子对控制牙齿过敏、牙龈出血、消除牙菌斑、坚固牙釉质具有显著作用。其中钙成分可有效补充牙齿中的钙流失,磷酸根离子能与牙齿中钙紧密结合,从而增强牙釉质的抗酸能力,增加牙齿的保护层,达到抗过敏的功效。液体中硅羟基的出现显著提高牙表面pH值,高pH值能显著抑制牙菌斑中酸性菌的活性和代谢。
具体实施方式
下面结合实施例对本发明作下一步详细的描述,但本发明的实施方式不限于这几种。
实施例1
根据磷硅酸钾钙颗粒的化学组分要求,称量所需要的二氧化硅4400g、磷酸二氢钾1700g、碳酸钾1000g和氧化钙2800g,混合放入高温熔炉中加热至1500℃,液相下保温180min到化学合成反应完全。将合成好的磷硅酸钾钙取出冷却至室温,破碎后用气流磨粉碎至1~30μm。此方法合成的磷硅酸钾钙中硅质量百分含量为:24%,磷含量为:10%,钾含量为:5%,钙含量为:30%。
按护牙剂配方要求以质量百分比计将0.7%的香精,0.8%的十二脂硫酸钠,0.5%的卡波姆,0.3%的AK糖加入预混锅里中,添加8.8%的纯净水使各成分溶解至均匀,再加入22%的聚乙二醇400,9%的增稠氧化硅,50%的甘油,0.9%的钛白粉,7%的磷硅酸钾钙,均质搅拌、研磨和捏合使膏料充分混合均匀,然后抽真空60min直至真空度达-0.096mpa。随后打入储存锅中陈化120min。即制得含磷硅酸钾钙的口腔护牙剂。
实施例2
取按实施例1法制备的磷硅酸钾钙粉体(1~30μm)少许,180℃下干燥至恒重,精密测定7.000g,放入装有100ml去离子水的密封聚乙烯瓶中,37℃下静态放置水解6h。采用诱导耦合等离子发射光谱法测定Si、Ca、K、P的浓度如表所示。对照标准曲线可知,磷硅酸钾钙在去离子水可以迅速水解,反应6h可测得去离子水中Si浓度为0.18μg/L,Ca浓度为0.07μg/L,K浓度为0.05μg/L,P浓度为0.13μg/L。
离子 | Si | Ca | K | P |
离子浓度(μm·mL-1) | 17 | 106 | 61 | 26 |
实施例3
取7g按实施例1制备的磷硅酸钾钙粉末270℃的烘箱中干热灭菌120min,冷却后在无菌烧杯中,各加入100ml超纯水(即浸提比例为0.07g/ml),用封口薄膜封住烧杯口,37℃浸提24h。取出浸提液,按照DMEM培养基(干粉)说明书的配制比例,仅用浸提液溶解培养基来配制细胞培养液,调节pH值为7.4,用孔径为0.4μm的滤膜过滤后,加入10%新生牛血清、100U/ml青霉素、100mg/ml链霉素,4℃储存备用。细胞形态学观察将生长状态良好的L-929小鼠成纤维细胞按3×104/ml的密度接种于6孔板。试验分为3组,阴性对照组,磷硅酸钾钙组和阳性对照组,每组3个平行样。阳性对照选用6.4g/L的苯酚溶液;阴性对照用DMEM培养基。细胞按3×104/ml的密度接种于96孔培养板中,每孔体积100μl,细胞分组及处理同上。细胞培养24h,用WST-1法分析细胞活性,用酶标仪在490nm波长下测定吸光度[D(490)]值,按下式计算细胞相对增殖度(relativegrowthrate,RGR)。RGR(%)=供试品组细胞D(490)值/阴性对照组细胞D(490)值×100%;按照RGR值将样品的毒性反应分级如下:0级为RGR≥100%;1级为75%~99%;2级为50%~74%;3级为25%~49%;4级为1%~24%;5级为<1%。
本实施例采用体外细胞培养法对磷硅酸钾钙的生物安全性进行研究。体外细胞培养法选用L-929鼠成纤维细胞,用MTT试验法对材料的细胞毒性进行评价。MTT实验结果见下表,可以看出磷硅酸钾钙的细胞毒性为0级符合生物医用材料的要求。
试验组(n=3) | 阴性对照 | 磷硅酸钾钙 | 阳性对照 |
细胞相对增值率RGR(%) | 96±7 | 102±14 | 8±6 |
实施例4
对人工龋质釉矿化的体外试验研究。
取新鲜拔除牛切牙经清洗筛选后将牙冠切割成5×5×2mm大小的釉质块,磨平抛光去处表层大概150μm。选择硬度值范围为298.30-313.80KHN釉质快75个,超声清洗自然干燥后,釉质块表面开窗4mm×4mm大小,其余部位涂布两层抗酸指甲油。将选好的标本放入脱矿液中脱矿72h以形成人工龋,选择硬质值范围为166.8-176.50KHN釉质快用于再矿化试验。
将釉质块随机分为三组,去离子水阴性对照组,磷硅酸钾钙护牙剂(按实施例1方法制备)试验组、NaF阳性对照组。矿化液为磷硅酸钾钙浓度每100ml去离子水含粉体3g(37℃静置24h),NaF组为1000ppm,pH值用NaOH调至7.0。然后各组分别进行循环试验,每天循环包括2h脱矿,其余时间分别浸泡在去离子水、磷硅酸钾钙护牙剂和NaF溶液中,100转/分,37℃,共循环12天。用显微硬度仪测量硬度值。用表面显微硬度恢复百分比(%SMHR)对硬度值进行衡量计算,其公式如下:%SMHR=(循环后的硬度值-脱矿后的硬度值)×100/(基线硬度值-脱矿后的硬度值)。
试验组 | 阴性对照 | 磷硅酸钾钙护牙剂 | 阳性对照 |
表面显微硬度恢复百分比(%SMHR) | 8.2±0.7 | 50.0±2.6 | 40.9±1.9 |
显微硬度值(见上表)显示磷硅酸钾钙护牙剂具有使早期釉质龋在矿化的作用。
实施例5
磷硅酸钾钙护牙剂对牙面菌斑pH值的影响
选取10名无牙周疾病的身体健康的受试者,分两组测定其使用磷硅酸钾钙护牙剂(按实施例1方法制备)和去离子水漱口5min后,不同时间点上的上颌第一中切牙近中邻面接触点下方的菌斑的pH值。采用微型电极接触法,原位测试菌斑pH的动态变化。测试时需用去除牙面多余的唾液后将微型pH指示电极轻轻插入牙面部位的菌斑内,但pH计显示稳定的读数时记录pH值。不同时间记录的pH值(见下表)显示磷硅酸钾钙护牙剂能明显提高牙面菌斑内的pH值。
时间(min) | 0 | 5 | 10 | 30 | 60 | 120 |
去离子水 | 6.84±0.06 | 6.80±0.12 | 6.79±0.12 | 6.84±0.05 | 6.89±0.10 | 6.93±0.10 |
磷硅酸钾钙护牙剂 | 6.85±0.11 | 7.84±0.12 | 8.64±0.16 | 8.36±0.16 | 8.05±0.12 | 7.59±0.13 |
实施例6
磷硅酸钾钙护牙剂对牙面菌斑内钙磷浓度的影响
选取10名无牙周疾病的身体健康的受试者,分两组测定其使用磷硅酸钾钙护牙剂(按实施例1方法制备)和去离子水漱口5min后,让受试者做吞咽动作,冲洗牙面,棉卷隔湿,用无菌齿科探针收集受试者龈上菌斑并迅速置于1.5ml离心管中冰浴保存。沉重计算菌斑湿重。分别加入高氯酸震荡消化和氢氧化钠溶液中和,取上清液保存,用分光光度计测钙磷含量。下表可见当使用磷硅酸钾钙护牙剂的受试者,牙菌斑内钙磷浓度要明显高于使用去离子水的钙磷浓度。
分组 | n | Ca(mg/g) | P(mg/g) |
去离子水 | 5 | 2.77±0.16 | 1.70±0.10 |
磷硅酸钾钙护牙剂 | 5 | 4.25±0.47 | 1.94±0.12 |
本发明一种可水解磷硅酸钾钙活性材料的制备及其应用可用于口腔清洁护理用品用作为功能性物质用于控制牙齿过敏、抑制牙菌斑、坚固牙釉质。
综上所述,本发明已如说明书内容,制成实际样品且经多次使用测试,从使用测试的效果看,可证明本发明能达到其所预期之目的,实用性价值乃无庸置疑。以上所举实施例仅用来方便举例说明本发明,并非对本发明作任何形式上的限制,任何所属技术领域中具有通常知识者,若在不脱离本发明所提技术特征的范围内,利用本发明所揭示技术内容所作出局部更动或修饰的等效实施例,并且未脱离本发明的技术特征内容,均仍属于本发明技术特征的范围内。
Claims (4)
1.一种可水解磷硅酸钾钙活性材料的制备方法,其特征在于,以二氧化硅石英粉、磷酸二氢钾、氧化钙为主要原料,碳酸钾做助剂按质量百分比:
二氧化硅44±6%
磷酸二氢钾17±3%
碳酸钾10±3%
氧化钙28±4%
混合后放入高温熔炉中加热到1450-1550℃进行高温液相化学反应合成磷硅酸钾钙,化学反应式为:SiO2+KH2PO4+K2CO3+CaO=KCaPSiO6+CO2↑+K2O↑+H2O↑;将合成磷硅酸钾钙冷却到常温;再使用气流磨将磷硅酸钾钙粉碎到1~500μm的颗粒大小,此方法合成的磷硅酸钾钙中各元素质量百分含量为:硅含量24±4%,磷含量为:4±2%,钾含量为:8±2%,钙含量为:21±4%,氧含量为:42±6%。
2.一种可水解磷硅酸钾钙活性材料的应用,其特征在于:该应用为护牙剂,护牙剂的主要成分的质量百分比为:
2.5~7.5%磷硅酸钾钙活性材料,19.0~25%聚乙二醇400,8.2~10.5%增稠氧化硅,50~60%甘油,0.8~1.0%钛白粉,0.6~0.8%香精,0.3~0.8%十二脂硫酸钠,0.4~0.8%卡波姆,0.2~0.4%AK糖,磷硅酸钾钙活性材料由权利要求1所述的一种可水解磷硅酸钾钙活性材料的制备方法所制得。
3.根据权利2所述一种可水解磷硅酸钾钙活性材料的应用,其特征在于,所述的护牙剂采用1~30μm的可水解磷硅酸钾钙活性材料。
4.根据权利2所述一种可水解磷硅酸钾钙活性材料的应用,其特征在于,所述的护牙剂的制备方法为:将0.6~0.8%的香精,0.3~0.8%的十二脂硫酸钠,0.4~0.8%的卡波姆,0.2~0.4%的AK糖在预混锅里加少量纯净水溶解至均匀,再加入19.0~25%的聚乙二醇400,8.2~10.5%的增稠氧化硅,50~60%的甘油,0.8~1.0%的钛白粉,2.5~7.5%的可水解磷硅酸钾钙活性材料,均质搅拌、研磨和捏合使膏料充分混合均匀,然后抽真空60~120min直至真空度达-0.096mpa为止,最后打入储存锅中陈化120~240min,即制得用于口腔保健的磷硅酸钾钙护牙剂。
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Effective date of registration: 20160621 Address after: 511400, 4-18, Luopu street, Guangzhou, Olympic Garden, Guangzhou, Guangdong, Panyu District Patentee after: Guangzhou promise Medical Technology Co., Ltd. Address before: Large apartment Meilan District Haidian three road 570208 Hainan city of Haikou Province in the 16 building 402 room Patentee before: Xu Yangbo |