CN1039405C - 高折射光致变色玻璃 - Google Patents

高折射光致变色玻璃 Download PDF

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CN1039405C
CN1039405C CN95100972A CN95100972A CN1039405C CN 1039405 C CN1039405 C CN 1039405C CN 95100972 A CN95100972 A CN 95100972A CN 95100972 A CN95100972 A CN 95100972A CN 1039405 C CN1039405 C CN 1039405C
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R·卡斯纳
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Schott AG
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    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00Compositions for glass with special properties
    • C03C4/04Compositions for glass with special properties for photosensitive glass
    • C03C4/06Compositions for glass with special properties for photosensitive glass for phototropic or photochromic glass
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/062Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/068Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths

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Abstract

本文描述了一种高折射光致变色玻璃,其折射率为1.69-1.7,色散本领倒数至少为35,密度最大为3.5g/cm3以及组成为(用氧化物重量百分比表示):SiO215-33;B2O312-22;∑SiO2+B2O3;30-50;Li2O 0.5-5.0;Na2O 0-3;K2O 0-12;∑碱金属氧化物4-12;BaO 0-23;SrO 0-23;∑SrO+BaO 0-23;ZrO25-14;Nb2O515-24;Ta2O52-11。另外,玻璃还具有作为光致变色载体0.10-0.35Ag2O;0.15-0.65Cl-;0.15-0.45Br-和0.005-0.030CuO。假如希望在曝光状态下变成棕色,可按已知的方法向玻璃中添加1-3ppm金或一种或多种铂系金属,尤其是钯。如果希望有基色,为了着色,玻璃可含至多2%(重量)的着色氧化物。

Description

高折射光致变色玻璃
本发明涉及密度比较低的高折射光致变色玻璃,这种玻璃可用作眼镜镜片,它含有作为光致变色载体的卤化银和氧化铜淀积物。
近期的眼镜使用加强镜片,这种镜片的折射率高,密度低,优点是透镜厚度薄,重量轻,尤其在实际使用时使人感觉到校正视觉误差的精度高。这种镜片(参见如US4084 978)几乎仅涉及无色或离子染色型。因为最近几年来光致变色性镜片作为调整眼镜镜片越来越重要,在该领域也需求高折射光致变色性镜片。
EP0063790-A首次成功地结合了光致变色性镜片要求的光致变色性,高折射率和低密度。但是,这种镜片的缺点是为了具有足够的光致变色性动力学,即在日光照射时很快地加深色度且没有照射时变亮,必须包含比较多的卤化物成分。然而,由于玻璃混合物熔化时卤化物较多和改变的蒸发,而使得很难保持光致变色特性恒定。
DE3825210-C2第一次描述了密度低和卤素含量低的高折射光致变色玻璃。这种玻璃的折射率nd约为1.60至1.61,色散本领倒数(Abbe coefficient)约为41.5至43,密度小于3g/cm3
本发明的目的是提供一种光致变色玻璃,该玻璃的折射率明显高于1.61,密度尽可能的低且色散本领倒数高。
本发明的目的是通过权利要求1描述的玻璃实现的。该玻璃包含(按氧化物重量%计)15-33 SiO2;15-22 B2O3;∑SiO2+B2O3 30-50;Li2O 0.5-5;Na2O 0-3;K2O 0-11;∑碱金属氧化物4-12;BaO 0-23 SrO0-23;∑BaO+SrO 0-23;ZrO2 5-14;Nb2O5 15-24;Ta2O5 2-11以及向这种玻璃粉组成中添加作为光致变色性的载体Ag2O 0.1-0.35;Cl-0.15-0.65;Br-0.15-0.45;CuO 0.005-0.030。
这种玻璃粉即不包含铅又不包含镉和锌,除了不可避免的原料杂质之外,没有Al2O3、CaO、MgO和La2O3存在。Al2O3常常是其它光致变色玻璃的一个重要组分,但在该玻璃体系中是不利的因素。首先,它降低耐酸侵蚀的化学稳定性,其次,增加了退火时不希望的相分离倾向。此外,该玻璃除了不可避免的原料杂质外也不含TiO2,TiO2也是高折射镜片的一个典型的组分,但在该玻璃组分中,它不利地影响相分离和结晶趋势。
该玻璃中的SiO2重量组成为15-33%(重量)。若用量少于15%(重量),会明显地降低玻璃的化学稳定性。用量超过33%(重量),则不能获得要求的至少1.690的折射率。
SiO2的含量优选为20-29%(重量),更优选为21-27%(重量)。B2O3的含量应为12-22%(重量),若用量少于12%(重量),对玻璃的稳定性和可熔化性产生不利的影响,若用量超出22%(重量),可对玻璃的化学特性和水解特性有不利的影响。B2O3的含量优选为14-18%(重量)。组分SiO2+B2O3的总量应为30-50%(重量),在该范围内的玻璃具有良好的可熔化性和化学稳定性。当这些组分的总量为35-47%(重量)时是优选的,更优选为38-47%(重量)。
碱金属氧化物有助于玻璃易于熔化。要求氧化锂的用量为0.5-5,优选为0.5-4,更优选为0.5-2。氧化钠的含量不是必不可少的,但在玻璃中,其用量可达3%(重量)。氧化钾的用量为0-11%(重量),优选为0-8%(重量),当玻璃的氧化钾含量为1-6%(重量)时是最优选的。但是碱金属氧化物的总量应为4-12%(重量)。碱金属氧化物的含量低于4%时,将增加玻璃熔化的难度,高于12%重量)会带来耐化学性,过分的相分离和光致变色性的不利影响的问题。事实表明,碱金属氧化物的含量一般为6.5-10%(重量)时可获得有利的结果。
在该玻璃中可以有碱土金属氧化物钡和锶存在,其量各为0-23%(重量),但这些氧化物的总量不能超出23%(重量),否则降低耐酸性,对光致变色性的动力学有不利的影响。优选的是只有碱土金属氧化物的氧化锶存在,而且用量优选地为17-23%(重量)。
氧化锆、氧化铌和氧化钽主要起提高折射率的作用。ZrO2成分增加玻璃的化学稳定性。Nb2O5和Ta2O5使最终玻璃具有很好的稳定性,而对光致变色性不产生不利的影响。玻璃中ZrO2的用量为5-14%(重量),优选地为5-8%(重量)。玻璃中Nb2O5的用量为15-24%(重量),优选为18-20%(重量)。玻璃中Ta2O5的用量为2-11%(重量),优选地(按Ta2O5的最大值计)为2-8%(重量)。
这些玻璃粉还可按已知的方法含有作为光致变色性的载体:0.1-0.35%(重量)Ag2O;0.15-0.65%(重量)Cl-;0.15-0.45%(重量)Br-和0.005-0.030%(重量)CuO。
一种特别好的玻璃粉组合物有(按氧化物重量%计)如下的组成:SiO2 20-29;B2O3 14-18;∑SiO2+B2O3 38-47;Li2O 0.5-4;Na2O 0-3;K2O 1-6;R2O 4-12;SrO 17-23;ZrO2 5-8;Nb2O5 18-22;Ta2O5 5-10.5。
这种玻璃粉组合物含有附加的已经述及的必需量的Ag2O,Cl-、Br-和CuO作为光致变色性的载体。
描述的光致变色玻璃在日光的影响下变色。变成灰色到蓝灰色。如果希望在被曝光的状态下变成棕色,那么玻璃中按已知的方法还需添加1-3ppm的金或一种或多种铂系金属,尤其是钯。
此外,也还具有的优点是如通过添加至多2%(重量)的着色氧化物使玻璃着色。尤其适用的是如至多1%(重量)Er2O3,至多1%(重量)Nd2O3,至多0.1%(重量)CoO,至多0.3%(重量)NiO或至多0.1%(重量)Cr2O3的一种或多种氧化物。
本发明的玻璃具有的高折射率ne为1.69-1.70或以上,色散本领倒数为35-39或以上,密度为不高于3.5g/cm3
本发明的玻璃具的突出的光致变色性特性,满足了眼镜镜片的需要,如具有减少反射层的可涂层性以及足够的抵抗化学洗涤剂和眼镜在常规使用中所能碰到的其它物质的能力。
实施例
将各种玻璃在1300℃的铂坩埚内熔化,然后倒入一个钢模中,在一个箱式炉内以每小时约80℃冷却。将经冷却的浇铸块切割成试样,试样在600-650℃加热约0.5小时。接着将试样抛光制成2mm厚的薄片,测定试样的光致变色性动力学。测试结果、玻璃的组成和其物理特性都示于表中。
表中示出了546nm时的折射率ne,相应的阿贝常数(Abbekonstante)υe,20℃时的密度d(g/cm3),未经曝光玻璃的原始透射能力to(用%表示),23℃时的饱和透射能力ts(用%表示)和透射能力tr,该数据是在饱和状态下变亮30分钟后得到的(一般,ne和nd之间的关系为ne-0.003≈nd)。
实施例      1      2     3      4      5      6      7      8      9     10
SiO2     25.7     30.7    28.7     31.5     20.5     20.5     34.8     24.8     15.0     25.5
B2O3     14.0     12.0    14.0     12.3     17.3     17.3     13.0     13.0     21.3     13.0
Li2O     1.7     1.7    1.7     1.7     1.7     1.7     1.7     1.7     1.7     1.0
Na2O     1.8     1.8     2.0     1.5     2.0
K2O     5.3     5.3    7.0     7.2     6.1     6.1     6.1     4.1     6.1     4.1
SrO     5.6     12.1     22.1     22.1     22.1     22.1
BaO     8.0     8.0    8.0     22.1     10.0
ZrO3     14.0     8.0    8.0     8.2     5.2     5.2     5.2     5.2     5.2     7.7
Nb2O5     18.9     21.8    21.8     22.1     19.5     19.5     19.5     19.5     19.5     18.0
Ta2O5     10.1     10.1    10.1     10.2     5.6     5.6     5.6     5.6     5.6     5.6
Ag2O     0.17     0.17    0.17     0.175     0.171     0.171     0.25     0.25     0.21     0.16
Cl-     0.30     0.30    0.30     0.31     0.39     0.39     0.64     0.64     0.50     0.40
Br-     0.26     0.26    0.26     0.27     0.34     0.34     0.32     0.32     0.32     0.28
CuO     0.012     0.012    0.012     0.012     0.015     0.015     0.027     0.027     0.020     0.017
ne     1.70166     1.69822    1.69481     1.69020     1.71070     1.70842     1.70472     1.70388     1.70110     1.70125
vf     35.3     35.1    35.2     35.2     37.2     38.0     39.1     39.0     39.1     39.2
d     3.34     3.30    3.40     3.19     3.44     3.47     3.47     3.45     3.40     3.46
%τO     87.0     88.0    85.0     87.5     83.9     86.8     86.2     85.0     83.2     83.7
%τS     19.2     26.7    29.8     26.8     35.0     40.4     21.6     17. 5     32.3     16.7
%τR     76.9     66.8    75.1     80.3     79.2     76.7     74.3     73.8     78.9     75.4
实施例     11     12     13     14     15     16     17
SiO2     25.5     26.0     26.0     25.0     24.0     24.0     24.0
B2O3     15.0     15.0     17.0     17.0     17.0     17.0     17.0
Li2O     1.0     0.5     0.5     0.5     2.5     3.5     3.5
Na2O     2.0     1.5     1.5     1.0     1.5     1.5     1.5
K2O     4.1     4.1     4.1     4.1     2.1     2.1     2.1
SrO     20.1     20.1     20.1     20.1     20.1     19.1     7.7
BaO     19.1
ZrO3     7.7     7.7     7.7     7.7     7.7     7.7     7.7
Nb2O5     18.0     18.5     18.5     18.5     18.5     18.5     18.5
Ta2O5     5.6     5.6     5.6     5.6     5.6     5.6     5.6
Ag2O     0.18     0.18     0.18     0.16     0.18     0.18     0.18
Cl-     0.40     0.40     0.40     0.35     0.40     0.40     0.40
Br-     0.25     0.25     0.25     0.25     0.32     0.32     0.32
CuO     0.020     0.020     0.020     0.020     0.027     0.027     0.027
ne     1.69431     1.69379     1.69122     1.69418     1.70355     1.70335     1.69800
vf     39.3     38.8     38.8     38.4     39.3     39.4     38.8
d     3.39     3.38     3.35     3.37     3.39     3.38     3.37
%τO     87.0     86.3     85.6     86.2     86.2     84.9     87.7
%τS     16.7     39.2     21.3     31.1     25.9     26.9     20.5
%τR     72.3     77.3     66.1     75.1     72.5     72.9     68.7

Claims (5)

1.高折射的光致变色玻璃,含有作为光致变色载体的银、卤素和氧化铜,具有的密度≤3.5g/cm3,其特征在于:
玻璃的折射率≥1.69,色散本领倒数≥35,它含有(用氧化物重量百分比表示):SiO2                    15-33B2O3                   12-22∑SiO2+B2O3           30-50Li2O                    0.5-5.0Na2O                    0-3K2O                     0-12∑碱金属氧化物            4-12BaO                      0-23SrO                      0-23∑SrO+BaO                0-23ZrO2                    5-14Nb2O5                  15-24Ta2O5                  2-11以及向玻璃粉组合物中添加的作为光致变色性的载体:Ag2O                   0.10-0.35Cl                      0.15-0.65Br                      0.15-0.45CuO                     0.005-0.030%(重量)。
2.根据权利要求1的高折射光致变色玻璃,其特征在于:玻璃粉组合物具有(用%重量表示):SiO2                    20-29B2O3                   14-18∑SiO2+B2O3               38-47Li2O                        0.5-4Na2O                        0-3K2O                         1-6∑R2O                       4-12SrO                          17-23ZrO2                        5-8Nb2O5                      18-22Ta2O5                      5-10.5。
3.根据权利要求1的高折射光致变色玻璃,其特征在于:为了在曝光的状态下使其变成棕色,可添加1-3ppm的金或一种或多种铂系金属。
4.根据权利要求2的高折射光致变色玻璃,其特征在于:为了在曝光的状态下使其变成棕色,可添加1-3ppm的金或一种或多种铂系金属。
5.根据权利要求1-3之任一项的高折射光致变色玻璃,其特征在于:含有至多2%(重量)的着色氧化物。
CN95100972A 1994-03-11 1995-03-08 高折射光致变色玻璃 Expired - Fee Related CN1039405C (zh)

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DE4408190A DE4408190C1 (de) 1994-03-11 1994-03-11 Hochbrechendes phototropes Glas
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US5424255A (en) 1995-06-13
DE4408190C1 (de) 1995-08-03
JPH0859288A (ja) 1996-03-05
BR9500836A (pt) 1995-10-17
CN1112526A (zh) 1995-11-29
GB2287245B (en) 1997-08-06
FR2717170A1 (fr) 1995-09-15
GB9425653D0 (en) 1995-02-22
GB2287245A (en) 1995-09-13

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