CN1101348C - 含有氧化锆和氧化锂的具有高化学稳定性和低粘度的硼硅酸盐玻璃 - Google Patents
含有氧化锆和氧化锂的具有高化学稳定性和低粘度的硼硅酸盐玻璃 Download PDFInfo
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Abstract
本发明涉及一种硼硅酸盐玻璃，它具有高化学稳定性和低粘度，含有氧化锆和氧化锂，该玻璃具有一级抗水解性-根据DIN ISO 719、一级耐酸性-根据DIN 121 16、一级抗苛性碱性-根据DIN ISO 659，低的工作点VA为1180-1230℃并且线性热膨胀系数α20/300＝4.9×10-6K-1，具有下列组成(重量百分比，基于氧化物)：SiO2 73.0-75.0，B2O37.0-10.0，Al2O3 5.0-7.0，ZrO2 1.0-3.0，Li2O 0.5-1.5，Na2O 0-10.0，K2O 0-10.0，MgO 0-3.0，CaO 0-3.0，BaO 0-3.0，SrO 0-3.0，ZnO0-3.0，其SiO2/B2O3大于或等于7.5，∑SiO2+Al2O3+ZrO2 80.0-83.0，∑MgO+CaO+BaO+SrO+ZnO小于或等于3.0以及氟化物0-3。该玻璃特别适用于用作通用的主要医药包装材料，如安瓿玻璃。
Description
本发明涉及含有氧化锆和氧化锂的硼硅酸盐玻璃，该玻璃具有一级抗水解性、耐酸性和耐苛性碱性并且具有低粘度，特别是在处理范围内。
作为主要包装材料，例如作为安瓿玻璃，医药工业要求玻璃具有极高的化学稳定性。迄今为至，已知的工业医药安瓿玻璃具有一级(H)的抗水解性(根据DIN ISO 719)、一级(S)的耐酸性(根据DIN 12116)和二级(L)的耐苛性碱性(根据DIN ISO 695)。现有技术的代表是透明玻璃FiolaxTM，编号为8412(SiO2 74.7，B2O3 10.0，Al2O3 5.0，Na2O6.5，CaO 1.5，BaO 2.0，氟化合物0.3，百分重量)以及JENA仪器玻璃Ggl490/5(SiO2 73.2，B2O3 11.0，Al2O3 5.3，Na2O 7.0，K2O 0.2，CaO 0.8，BaO 2.5，百分重量)，它们具有100mg/dm2的失重(根据DIN ISO 695)。一级耐苛性碱性，即失重小于75mg/dm2至今通过工业医药安瓿玻璃还不能达到。
但是，医药工业的一个重要要求是提供具有明显改进的抗苛性碱性的主要包装材料，从而可以包装新近开发出的对容器具有强碱性作用的注射液。实际经验表明要想保证在生产工艺中的抗苛性碱性，就要求在实验室中开发出失重小于65-70mg/dm2，即在一级苛性碱范围内的玻璃。
当然，达到这个要求必需不能损害其它重要的玻璃和玻璃生产性能。举例来说，必需保持H＝1和S＝1。此外，对于透明工业玻璃FiolaxTM，编号8412和Ggl 490/5来说，线性热膨胀系数α20/300大约为4.9×10-6K-1，并且出于质量和成本原因，其粘度在整个熔化、处理和冷却范围内不能太高。
评价玻璃的可操作性的一个基本参数是工作点(VA)，在该点下玻璃的粘度为104dPas。对于医药安瓿玻璃来说，该VA值应该不超过1220-1230℃，以防止发生玻璃成分，主要是碱金属氧化物和硼酸的不利的蒸发现象以及在玻璃管生产中以及在随后的将玻璃管转变成安瓿瓶的过程中节约能量。在玻璃的热形成过程中发生的蒸发将使安瓿瓶变得不适用。
在冷却区中的玻璃粘度的特征在于玻璃的转变温度Tg，该温度对应的粘度大约为1013dPas。为了在冷却区中节能，同样它不能太高。
在专利说明书中DE3722130 C2和DD301821 A7中所说的医药容器玻璃不满足这些高要求。
具有在DE3722130 C2中所说的组成的玻璃不属于一级苛性碱中。描述了灯玻璃和防火玻璃的专利说明书DE4230607 C1所要求的范围仅仅指出了一种具有一级抗苛性碱性的特定组合物。虽然通过具有在DD301821 A7中所说的组合物的某些玻璃可以达到L＝1，但是很显然首先是仅仅达到一级苛性碱性，其次在抗苛性碱性试验中的失重当将具有一定组成的熔体重复多次时呈现出发散数值，因此L＝1不是总能达到。这就需要进行改进以获得可靠的抗苛性碱性。
本发明的目的在于开发出具有高化学稳定性和低粘度的硼硅酸盐玻璃，特别是具有一级抗水解性(根据DIN ISO 719)、一级耐酸性(根据DIN 12116)，特别是一级抗苛性碱性(根据DIN ISO 659)，其失重＜65-70mg/dm2，工作点＜1220-1230℃并且线性热膨胀系数α20/300＝4.8-5.0×10-6K-1。
根据本发明，该目的是通过权利要求1所说的玻璃而实现的，该玻璃含有一定量的氧化锆和氧化锂。
具有H＝1、S＝1、L＝1(失重小于65-70mg/dm2)、VA值小于1230℃和α20/300＝4.8-5.0×10-6K-1的玻璃可以在下列组合物范围内制造(重量百分比，基于氧化物)，SiO2 73.0-75.0(优选地为73.5-75.0)，B2O3 7.0-10.0(优选地为8.0-10.0)，Al2O3 5.0-7.0(优选地为5.0-6.0)，ZrO2 1.0-3.0(优选地为1.0-2.5)，Li2O 0.5-1.5，Na2O 0-10.0，K2O 0-10.0，MgO 0-3.0，CaO 0-3.0，BaO 0-3.0，SrO 0-3.0，ZnO 0-3.0和氟化物0-3.0，玻璃形成体SiO2和B2O3之间的比值为大于或等于7.5，SiO2+Al2O3+ZrO2的和为80.0-83.0％重量并且二价添加物的和(MgO+CaO+BaO+SrO+ZnO)小于或等于3.0％重量。碱金属氧化物的和(Li2O+Na2O+K2O)优选地限制为7.0-10.0％重量。
下列组合物范围(重量百分比，基于氧化物)是特别优选的：SiO273.5-75.0，B2O3 8.0-10.0，Al2O3 5.0-6.0，ZrO2 1.0-2.5，Li2O 0.5-1.5，Na2O 0.5-5.0，K2O 0.5-5.0，CaO 0.5-2.0，SiO2/B2O3大于或等于7.5，∑SiO2+Al2O3+ZrO2 81.0-83.0，而∑ Li2O+Na2O+K2O 7.0-9.5。
这些玻璃还具有一些对于无缺陷和廉价批量生产是必需的优点。例如，它们满足涉及熔化行为的所需条件、结晶和分层稳定性、导电性、作为耐火材料的腐蚀性能、澄清性能、蒸发性能等。
从普通容器玻璃组合物开始(重量百分比，基于氧化物)，SiO275，B2O3 11，Al2O3 5，∑ Na2O3+K2O 7，∑ BaO+CaO 2，导致该新组合物的优化过程如下：
为了达到失重小于65-70mg/dm2的一级抗苛性碱性同时获得相当的低的工作点，VA＜1220-1230℃，必须向上述硼硅酸盐玻璃中加入1-3％重量的氧化锆和0.5-1.5％重量的氧化锂(在DE3722130C2中完全不存在)。此外，玻璃形成体二氧化硅和三氧化二硼的比必须大于或等于7.5。该新型组合物在该比值或相当低的氧化硼含量(7.0-10.0％重量)方面不同于DE3722130C2和DD301821A7。
通过改变其它的成分(氧化铝、碱金属氧化物、碱土金属氧化物或氧化锌)，可以将该组合物优化，而且其它的重要玻璃或玻璃生产性能可以能得到改进或相匹配。
由于一般的硼硅酸盐玻璃SiO2-B2O3-Al2O3-M2O-MO-AC(＝其它的组分)已经有一段时间为人们所已知了，并且在多种情况下进行了科学的研究以及实际用于多种用途，因此，所发现的溶液是极其出乎人们意外的。
另外，基于线性模式的优化计算对于确定具有高抗苛性碱性的组合物范围是不适用的，这是因为玻璃的抗苛性碱性不会随着SiO2/B2O3比值的增加而线性增加，因此这种技术不能确定失重的范围。
加入二氧化锆和少量的氧化硼可以改进抗水、酸和苛性碱性。但是氧化锆的加入受到其在玻璃中的低溶解性和玻璃粘度增加的限制。氧化硼含量的降低也会引起粘度的增加，但是这可以通过加入碱金属氧化物，特别是氧化锂而得到补偿。
当选择碱金属氧化物时，应该考虑多种因素：玻璃熔体中的氧化锂的含量过大将会对熔化端的耐火材料产生难以接受的强烈攻击，因此0.5-1.5％重量的氧化锂是最佳的。正象氧化锂与氧化钠相比在所说的硼硅酸盐玻璃熔体中的蒸发要小那样，氧化钠的蒸汽压力比氧化钾的要小。这就告诉我们要单单使用或主要使用氧化钠(在所给定的最大氧化锂含量下)。氧化钠原料的低成本也是一个优势。
在该新型玻璃的特殊应用中，例如制造光电倍增管中，完全不用氧化钾是不利的。这是因为氧化钾原料可含极少量的放射性杂质，这些杂质在某些条件下会使光电倍增管的噪音量增加。
与其相反，在低氧化钙和没有氧化钙的合成变化形式中，必须采用相当大量的氧化钾，以产生所需的α20/300值。
对于没有氧化钙的合成来说，下列组合物范围是有利的(％重量，基于氧化物)：SiO2 73.5-75.0，B2O3 8.0-10.0，Al2O3 5.0-6.0，ZrO2 1.0-2.5，Li2O 0.5-1.5，Na2O 0-3.0，K2O 4.0-7.0，SiO2/B2O3大于或等于7.5，∑SiO2+Al2O3+ZrO2 81.0-83.0，∑ Li2O+Na2O+K2O 7.0-10.0。
已经知道在通过将玻璃在高成型温度下再加热而将玻璃管转变成安瓿瓶的过程中较高的氧化钠含量将会导致玻璃表面风化得特别快。但是这点可以通过加入氧化锆和氧化锂并且还可以通过仅仅使用氧化钾或同时使用氧化钾和氧化钠以及加入少量的氧化锌而使VA值降低来消除。
由于在工业硼硅酸盐玻璃中的蒸发产物，通常是偏硼酸盐与所用的碱金属氧化物(M2O)的类型无关，在高温下具有下列硼酸模数：￥＝B2O3/(B2O3+M2O)(摩尔％)为0.53-0.58，该数值非常接近于玻璃组合物的硼酸模数，这使得蒸发很容易，因此必须通过其它手段，即通过大量增加粘度而降低熔化过程中的蒸发。
这一点可以通过相当高的氧化硅(73.0-75.0％重量)和氧化铝(5.0-7.0％重量)含量而实现。
这种水平的氧化铝含量表示该新型玻璃组合物进一步区别于DD301821A7的组合物。DE4230607C1的玻璃组合物也含有相当少量的氧化铝，1.5-4.0％重量。
如果氧化硅和氧化铝的比例增加甚至超过了所要求的范围，其粘度和VA值将增加太多，这将不利于澄清。高氧化铝含量还会使耐酸性得到显著地降低。
考虑到这种高质量通用的药物安瓿玻璃的组分的全部优点和不利影响，已经证明下列玻璃组合物是特别有利的(％重量，基于氧化物)：SiO2 74.9-74.5，B2O3 8.5-9.5(特别优选的是9.0-9.5)，Al2O3 5.3-6.0(特别优选的是5.3-5.8)，ZrO2 1.6-2.0，Li2O 0.7-1.3(特别优选的是0.9-1.1)，Na2O3.0-5.0.K2O 2.0-5.0(特别优选的是2.0-4.0)，CaO 0.5-1.6(特别优选的是0.8-1.2)，∑ SiO2+Al2O3+ZrO2 81.3-82.0，而∑ Li2O+Na2O+K2O 7.0-9.5(特别优选的是7.0-9.0)。
因此，在α值约为4.9×10-6K-1时，可以达到特别好的H＝1、S＝1和L＝1(失重＜65mg/dm2)的化学稳定性并且VA值低到小于或等于1200℃。
由于氧化钙对耐酸性具有稳定作用，因此，如果可以的话，可以向玻璃中加入少量氧化钙。类似地，少量氧化钡有助于进一步降低粘度并降低熔点。另一方面，该玻璃还必须含有很少量的氧化钙和氧化钡，或几乎没有，这是因为已经知道这些成分会以不合适的形式与某些特定的射入溶液起反应。
如果有代表性的医药和工业应用领域在化学稳定性方面没有很高的要求，那通过加入二价成分SrO、MgO和ZnO并改变CaO和BaO含量而进一步改变玻璃性能。
但是，它们的总含量必须保持在最高3.0％重量，该新型组合物通过该值而区别于DE4230607 C1中所述的组合物，(∑MgO+CaO+BaO+ZnO+SrO+ZrO2＝6-10＝∑ MgO+CaO+BaO+ZnO+SrO＝3-9.5，如果ZrO2＝0.5-3)。
此外，可以向该新型玻璃组合物中加入少量氟化物以加速熔化或降低粘度，或已知的澄清剂，如氯化物和Sb2O3。
操作实施例：
表1表示与本发明有关的新型玻璃组合物及其基本性能。
可以看出，如果获得所定义的热膨胀系数α20/300＝4.9×10-6K-1时，抗苛性碱性L(用低失重值58-65mg/dm2表示)非常稳定地在一级中，工作点较低，VA值为1180-1220℃。表1新型玻璃的例子以重量百分比计的玻璃组合物玻璃编号 1 2 3 4 5SiO2 74.3 74.2 74.3 74.3 74.3B2O3 9.3 8.8 9.3 9.3 9.3Al2O3 5.5 5.8 5.5 5.5 5.5ZrO2 1.8 1.8 1.8 1.8 1.8Li2O 1.0 1.0 1.0 1.0 1.0Na2O 4.0 3.0 3.5 3.0 2.0K2O 3.0 4.0 3.8 4.6 6.1CaO 1.1 1.4 0.8 0.5 -SiO2/B2O3 8.0 8.4 8.0 8.0 8.0∑ SiO2+Al2O3+ZrO2 81.6 81.8 81.6 81.6 81.6∑ Li2O+Na2O+K2O 8.0 8.0 8.3 8.6 9.1基本玻璃性能 1 2 3 4 5α20/300(10-6K-1) 4.9 4.9 4.9 4.9 4.9L(mg/dm2) 62 58 63 64 65VA(℃) 1180 1200 1190 1200 1220
下列数据是针对实施例1给出，以证明进一步的有利性能：密度ρ：2.36g/cm3玻璃转变温度Tg：540℃退火点A.P.：550℃软化点Ew：785℃结晶和分层稳定性：适用于当批量生产产品时无缺陷地生产玻璃。
Tg和A.P.证实该玻璃即使在冷却区中也具有相当低的和良好的粘度，因此可以廉价地冷却。
以常规方式，在用煤气加热的实验炉中、在1620℃中、在0.5升坩埚中、在约4小时内制备玻璃，然后浇铸在金属模中成块并冷却。所用的原料为砂子，H3BO3，Al(OH)3，碱金属和碱土金属碳酸盐和硝酸盐，二氧化锆和ZnO。该玻璃具有良好的熔化性能。所用的原料还可以是常用于工业玻璃的。
该新型玻璃主要适用于用作通用的主要医药包装材料，如安瓿玻璃。它还可以作为仪器玻璃而用于实验或其它技术领域。
Claims (8)
1.硼硅酸盐玻璃，它具有高化学稳定性和低粘度，含有氧化锆和氧化锂，其特征在于为下列组合物(重量百分比，基于氧化物)：SiO2 73.0-75.0B2O3 7.0-10.0Al2O3 5.0-7.0ZrO2 1.0-3.0Li2O 0.5-1.5Na2O 0-10.0K2O 0-10.0MgO 0-3.0CaO 0-3.0BaO 0-3.0SrO 0-3.0ZnO 0-3.0氟化物 0-3.0SiO2/B2O3 大于或等于7.5∑ SiO2+Al2O3+ZrO2 80.0-83.0∑ MgO+CaO+BaO+SrO+ZnO 小于或等于3.0。
2.根据权利要求1的含有氧化锆和氧化锂的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 73.5-75.0B2O3 8.0-10.0Al2O3 5.0-6.0ZrO2 1.0-2.5Li2O 0.5-1.5Na2O 0-10.0K2O 0-10.0MgO 0-3.0CaO 0-3.0BaO 0-3.0SrO 0-3.0ZnO 0-3.0SiO2/B2O3 大于或等于7.5∑ SiO2+Al2O3+ZrO2 80.0-83.0∑ Li2O+Na2O+K2O 7.0-10.0∑ MgO+CaO+BaO+SrO+ZnO 小于或等于3.0。
3.根据权利要求1或2的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 73.5-75.0B2O3 8.0-10.0Al2O3 5.0-6.0ZrO2 1.0-2.5Li2O 0.5-1.5Na2O 0.5-5.0K2O 0.5-5.0CaO 0.5-2.0SiO2/B2O3 大于或等于7.5∑ SiO2+Al2O3+ZrO2 81.0-83.0∑ Li2O+Na2O+K2O 7.0-9.5。
4.根据权利要求1或2的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 73.5-75.0B2O3 8.0-10.0Al2O3 5.0-6.0ZrO2 1.0-2.5Li2O 0.5-1.5Na2O 0-3.0K2O 4.0-7.0SiO2/B2O3 大于或等于7.5∑ SiO2+Al2O3+ZrO2 81.0-83.0∑ Li2O+Na2O+K2O 7.0-10.0。
5.根据权利要求1-3至少一个的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 74.0-74.5B2O3 8.5-9.5Al2O3 5.3-6.0ZrO2 1.6-2.0Li2O 0.7-1.3Na2O 3.0-5.0K2O 2.0-5.0CaO 0.5-1.6∑ SiO2+Al2O3+ZrO2 81.3-82.0∑ Li2O+Na2O+K2O 7.0-9.5。
6.根据权利要求5的硼硅酸盐玻璃，其特征在于下列组合物(重量百分比，基于氧化物)：SiO2 74.0-74.5B2O3 9.0-9.5Al2O3 5.3-5.8ZrO2 1.6-2.0Li2O 0.9-1.1Na2O 3.0-5.0K2O 2.0-4.0CaO 0.8-1.2∑ SiO2+Al2O3+ZrO2 81.3-82.0∑ Li2O+Na2O+K2O 7.0-9.0。
7.根据前面权利要求中至少一个的硼硅酸盐玻璃的用途，该玻璃具有一级抗水解性一根据DIN ISO 719、一级耐酸性一根据DIN 12116、一级抗苛性碱性一根据DIN ISO 659，其失重＜70mg/dm2，最大工作点VA＜1230℃并且线性热膨胀系数α20/300＝4.8-5.0×10-6K-1，它被用作主要医药包装材料，作为仪器玻璃用于实验室或其它技术领域。
8.根据权利要求7的用途，其中所述主要医药包装材料是安瓿玻璃。
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| DE19536708.1 | 1995-09-30 | ||
| DE19536708A DE19536708C1 (de) | 1995-09-30 | 1995-09-30 | Zirkon- und lithiumoxidhaltiges Borosilicatglas hoher chemischer Beständigkeit und geringer Viskosität und dessen Verwendung |
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- 1996-09-21 DE DE59602322T patent/DE59602322D1/de not_active Expired - Lifetime
- 1996-09-21 EP EP96115187A patent/EP0765847B1/de not_active Expired - Lifetime
- 1996-09-21 ES ES96115187T patent/ES2135828T3/es not_active Expired - Lifetime
- 1996-09-26 BR BR9603894A patent/BR9603894A/pt not_active IP Right Cessation
- 1996-09-27 UA UA96093738A patent/UA55368C2/uk unknown
- 1996-09-27 HU HU9602656A patent/HU214878B/hu not_active IP Right Cessation
- 1996-09-27 RU RU96119747A patent/RU2127709C1/ru not_active IP Right Cessation
- 1996-09-30 US US08/722,668 patent/US5736476A/en not_active Expired - Lifetime
- 1996-09-30 AR ARP960104553A patent/AR003754A1/es unknown
- 1996-09-30 CN CN96113360A patent/CN1101348C/zh not_active Expired - Lifetime
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| US5219801A (en) * | 1991-03-22 | 1993-06-15 | Pilkington Plc | Borosilicate glass composition |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2135828T3 (es) | 1999-11-01 |
| US5736476A (en) | 1998-04-07 |
| HUP9602656A2 (en) | 1997-04-28 |
| HU214878B (hu) | 1998-07-28 |
| DE59602322D1 (de) | 1999-08-05 |
| JPH09118541A (ja) | 1997-05-06 |
| HU9602656D0 (en) | 1996-11-28 |
| UA55368C2 (uk) | 2003-04-15 |
| AR003754A1 (es) | 1998-09-09 |
| DE19536708C1 (de) | 1996-10-31 |
| BR9603894A (pt) | 1998-06-02 |
| CN1155524A (zh) | 1997-07-30 |
| JP4215176B2 (ja) | 2009-01-28 |
| HUP9602656A3 (en) | 1998-04-28 |
| EP0765847A1 (de) | 1997-04-02 |
| RU2127709C1 (ru) | 1999-03-20 |
| EP0765847B1 (de) | 1999-06-30 |
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