CN1832804A - 光催化剂构件 - Google Patents

光催化剂构件 Download PDF

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CN1832804A
CN1832804A CNA2004800225921A CN200480022592A CN1832804A CN 1832804 A CN1832804 A CN 1832804A CN A2004800225921 A CNA2004800225921 A CN A2004800225921A CN 200480022592 A CN200480022592 A CN 200480022592A CN 1832804 A CN1832804 A CN 1832804A
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photocatalyst
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CN100482346C (zh
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安崎利明
木岛义文
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Nippon Sheet Glass Co Ltd
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Abstract

本发明的目的在于提供不进行热处理也有实用价值的光催化剂构件。本发明的光催化剂构件在基材表面隔着底涂层形成光催化剂层。所述底涂层以结晶性锆化合物尤其单斜晶系锆化合物为主成分，所述光催化剂层由晶相构成，例如以正方晶系氧化钛为主成分。还有，所述基材包含耐热性低的要素。

Description

光催化剂构件
技术领域
本发明涉及建筑用玻璃、汽车用玻璃、显示器用玻璃、生物芯片、化学芯片、电子器件、光器件、玻璃纤维、玻璃片等，特别涉及为防污、亲水、防雾、有机物分解等目的而应用光催化剂的应用领域。
背景技术
众所周知，锥型钛白粉等光催化剂通过紫外线的照射发挥分解有机物的防污效果、抗菌性及亲水性。另外最近由可见光发挥催化功能的光催化剂倍受关注。
形成氧化钛膜，且作为提高其催化活性的手段，公开了通过在形成膜时或形成膜后，在空气中或真空中进行热处理，提高其结晶性等并提高光催化剂活性的具有实用价值的物体。
专利文献1：特许第2517874号公报(第2页～第4页)
发明的公开
但是，一旦实施这样的热处理，虽能提高光催化剂的性能，但成为基材的材料或在该基材上已经形成的其它功能性膜等，因该热量而引起变形或氧化、胶体化等，存在其形状或光学特性等会恶化的问题。
特别是，树脂基板或树脂膜、耐热性低的玻璃或采用其它材料、一般耐热性低的银等材料的热线反射膜(所谓Low-E膜)等容易受热处理的影响，尤其在具备这些材料的基材上形成实用的光催化剂层时出现问题。
本发明鉴于上述问题构思而成，旨在提供不进行热处理也有实用价值的光催化剂构件。
为解决上述课题，本发明人研究了不经热处理也能得到高活性的光催化剂层的手段。结果发现：通过在某一特定的底涂层上形成光催化剂层，在一贯的低温工序也得到高活性的光催化剂层。具体地说，在包含耐热性低的要素的基材上以非加热方式成膜以结晶性锆化合物尤其单斜晶系锆化合物为主成分的底涂层，然后以非加热方式形成以由晶相构成的氧化钛为主成分的光催化剂层。
上述基材可采用耐热性低的玻璃、耐热性低的金属、树脂基体、树脂膜、有机无机复合基体等，也可设有非耐热性薄膜。本发明可适用于700℃以下耐热温度的基材，特别是，有效适用于在可享受本发明效果的500℃以下、还有在传统技术中难以形成高活性光催化剂层的300℃以下耐热温度的基材。还有，耐热温度指的是在该温度下在空气中进行30分钟热处理时，其光学透射率、反射率、形状上无5％以上变化的上限温度。
另外，作为上述非耐热性薄膜，例如有使用银的热线反射膜，或者使用电介质层/银层/电介质层的层叠膜的热线反射膜，或者使用电介质层/银层/电介质层/银层/电介质层的层叠膜的热线反射膜等。
当形成上述层叠膜时，为在后面工序中产生的等离子体中保护银层，可在形成银层后设置由Zn、Ti、Sn、Nb等构成的牺牲层。
另外，本发明的光催化剂构件中，可在基材表面设置以至少包含硅和锡中之一的氧化物、氮氧化物及以氮化物为主成分的剥离防止层。在该剥离防止层上隔着结晶性底涂层形成光催化剂层，并且在上述底涂层与光催化剂层之间基本不存在失效层(不能识别柱状粒子结构的非晶层)。还有，上述剥离防止层的厚度为2nm～200nm，最好为5nm～50nm。若剥离防止层的厚度薄于2nm，则膜剥离或缺点发生的抑制效果并不充分而不理想。另外厚度厚于200nm时，所述膜剥离或缺点发生的抑制效果也不会提高很多，因此从经济的观点来说，剥离防止层厚度的上限最好为200nm。若剥离防上层厚度厚于5nm，则对于水的截断效果变大，更加理想。另外超过50nm时，非晶质膜的应力变大，容易剥离，因此剥离防止层厚度的更加理想的上限为50nm。
另外，本发明的光催化剂构件的一个形态中，在基材表面隔着结晶性底涂层形成光催化剂层，并且基材是用浮法玻璃法制作的玻璃基板，且该玻璃基板的包含非耐热性薄膜的面或该面的相反侧的面上设有所述底涂层。
通过设置结晶性底涂层，能够提高光催化剂层的结晶性，并可高速将光催化剂层表面超亲水化。还有，通过在基材和结晶性底涂层之间设置剥离防止层，能够抑制从基材开始的底涂层的剥离或缺点的发生。
上述剥离防止层截断来自表面的氯离子或水分，防止这些离子或分子到达玻璃基板(基材)，并可抑制从基板开始的底涂层的剥离。另外，防止外来的二氧化碳或水分与玻璃基板的碱成分反应而形成斑点或缺点。
上述光催化剂层的厚度最好为1nm～1000nm。当薄于1nm时膜的连续性恶化且光催化剂活性并不充分，而厚于1000nm时激励光(紫外线)传不到光催化剂膜的里面，即便增大膜厚，光催化剂活性也不会变大。特别是，在1nm～500nm的范围可观察到底涂层的效果明显。即，以相同膜厚进行比较时，观察到比不设底涂层的场合大的光催化剂活性，因此1nm～500nm的范围更理想。
即便光催化剂层的厚度薄致1nm～1000nm，只要构成光催化剂层的粒子从与底涂层的界面到光催化剂层表面连续形成，也能进行结晶生长，并可充分发挥光催化剂活性。
构成光催化剂层的粒子在与基板平行的方向的宽度最好为5nm以上。这是由于粒子宽度小于5nm时结晶性低，且光催化剂活性不充分。
作为底涂层，采用所述单斜晶系氧化锆，此外还采用微量添加了氮的氧化锆、氮氧化锆及将铌(Nb)添加0.1～10atm％的氧化锆。尤其采用添加了铌的靶进行溅镀时，能够防止发生击穿和为此而作的非本意的功率控制及由此产生的成膜率的下降。
另外，作为光催化剂层最好采用正方晶系氧化钛，尤其锥型钛白粉具有高的光催化剂活性而理想。除了锥型钛白粉外，还可采用金红石型氧化钛、钛与锡的复合氧化物以及钛和锡的混合氧化物、微量添加氮的氧化钛或氮氧化钛。
底涂层的厚度最好为1nm以上500nm以下。当薄于1nm时底涂层的作为膜的连续性消失，成为岛状且耐久性降低而不理想。而且，厚于500nm时，对光催化剂层的影响几乎不变，因此增大膜厚对经济性而言成为浪费，并不理想。更理想的底涂层的厚度为2～50nm。当薄于2nm时，底涂层的结晶性低，且光催化剂层的结晶生长促进效果小。当厚于50nm时，对应于膜厚变动的光学特性(色调、反射率)的变动变大，因此不理想。
作为上述非耐热性薄膜、底涂层及光催化剂层的形成方法，可采用液相法(溶胶凝胶法、液相析出法、喷涂法、热溶胶法)、气相法(溅镀法、真空蒸镀法、CVD法)等任一方法，虽可以确认底涂层的光催化剂层的结晶性提高效果，但伴有结晶生长，因此本发明中还是适合采用可确认看到显著效果的溅镀法或蒸镀法等的气相法。
另外，能够通过在上述光催化剂层的表面形成具有亲水性的薄膜来提高亲水效果。具有亲水性的薄膜最好是从由氧化硅、氧化锆、氧化锗、氧化铝构成的组中选择的至少一种氧化物。其中，基于亲水性提高效果和耐久性的观点，最常用氧化硅。具有亲水性的薄膜最好为多孔状。由于是多孔状，提高了保水效果，不仅提高了亲水性的维持性能，而且通过照射紫外线来光催化剂层表面发生的活性氧等的活性种子能够通过孔到达物品表面，因此不会对光催化剂层的光催化剂活性产生大破坏。
作为形成多孔状亲水性薄膜的方法，采用液相法(溶胶凝胶法、液相析出法、喷涂法、溶胶凝胶法)或气相法(溅镀法、真空蒸镀法、CVD法)。若采用一般公知的溶胶凝胶法，可简单地制造多孔状薄膜，但可通过在溶胶凝胶法的原料液中添加有机高分子或高级醇，更加容易地得到多孔质薄膜。在溅镀法等的气相法中，能够通过提升溅镀时的气压、减少气体中氧含量等，增加氧化物的悬空键(danglingbond)来调整成膜条件，制作多孔状薄膜。
上述具有亲水性的薄膜的厚度最好为1nm以上30nm以下。当薄于1nm时，赋予的亲水性并不充分，而厚于30nm时破坏光催化剂层的光催化剂活性，因此不理想。另外，该厚度更好的范围是1nm以上20nm以下。在该范围，光照不到时的亲水性维持性能高。
特别在减压气氛中用蒸镀法或溅镀法等成膜锆化合物底涂层时，即便在低温也成为其本身以单斜晶系为首的结晶性的薄膜。该结晶性底涂层对其上形成的以氧化钛为首的光催化剂的膜生长起到一种种子(seed)层的作用，因此不加热也能容易得到结晶性高的光催化剂层。作为光催化剂层采用氧化钛时，往往生长为锥型结晶，通过该方法能以非加热方式获得非常高活性的光催化剂层。
这样，依据本发明，以非加热方式能够将具有高光催化剂活性的光催化剂层形成在耐热性低的基材上或薄膜上，可进行与耐热性低的构件的组合。另外，也适用于在均匀加热或加热冷却时以难以抑制破坏的玻璃为首的大尺寸基材上的成膜。
发明效果
如以上说明，依据本发明，在基材表面上隔着以结晶性锆化合物为主成分的底涂层形成光催化剂层，所述底涂层提高所述光催化剂层的结晶性，并提高光催化剂活性，因此不需要光催化剂层形成后的热处理。因而能够向建筑用窗玻璃、显示器用玻璃板、DNA分析用玻璃基板、信息便携机器、卫生设备、医疗设备、电子机器、活体/医疗用检查芯片、氢/氧发生装置用材料等所有构件，尤其向耐热性低的构件赋予高的光催化剂活性及防污性，并能进行迄今未能容易获得的非耐热性构件与具有高的光催化剂活性的光催化剂层的组合。
另外，也可适用于以均匀加热或加热冷却时难以抑制破坏的玻璃为首的大尺寸基材上的制膜。
附图的简单说明
图1是本发明的光催化剂构件具体例的剖视图。
图2是本发明的光催化剂构件具体例的剖视图。
图3是本发明的光催化剂构件具体例的剖视图。
实施本发明的最佳方式
以下参照附图，就本发明的实施方式进行说明。这里，图1至图3是表示本发明的光催化剂构件具体例的剖视图，在图1所示的具体例中，基材即玻璃板表面上形成的非耐热性薄膜相反面的表面上作为底涂层形成单斜晶系ZrO2层，而且其上作为光催化剂层形成结晶性TiO2层。还有，可在基板和底涂层之间形成剥离防止层(未图示)，也可在结晶性TiO2层上形成用以提高亲水性的多孔状SiO2层(未图示)。
图2所示的具体例中，在基材即玻璃板表面依次形成非耐热性薄膜、作为底涂层的单斜晶系ZrO2层、作为光催化剂层的结晶性TiO2层。还有，可在基板和底涂层之间形成剥离防止层(未图示)，也可在结晶性TiO2层上形成用以提高亲水性的多孔状SiO2层。
在图3所示的具体例中，在非耐热性基材即基板表面上作为底涂层形成单斜晶系ZrO2层，该单斜晶ZrO2层上作为光催化剂层还形成结晶性TiO2层。还有，可在基板和底涂层之间形成剥离防止层(未图示)，也可在结晶性TiO2层上形成用以提高亲水性的多孔状SiO2层。
上述非耐热性薄膜、ZrO2层、TiO2层及SiO2层用溅镀法形成。作为非耐热性薄膜，例示了如电介质层/银层/电介质层/银层/电介质层那样的多层膜。
在以下的表1和表2中汇总了实施例1～4的非耐热性薄膜、底涂层、光催化剂层及剥离防止层的结构，光催化剂特性，以及光学特性的评价结果。还有，作为比较，还示出比较例1～6的热处理工序、光催化剂层和剥离防止层的形成方法、光触媒特性及光学特性的评价结果。
[表1]
[表2]
Figure A20048002259200111
实施例1
使用在线型磁控管溅镀装置，在纵1m×横1m、厚度3mm的碱石灰玻璃基板上交替层叠氧化锌层和银层，形成基板/氧化锌层40nm/银层10nm/氧化锌层80nm/银层10nm/氧化锌层40nm结构的多层膜。氧化锌层采用添加了铝的氧化锌靶，另外银层采用银靶，分别在减压氩气氛中采用非加热方式来形成。该氧化锌和银的多层膜具有热线反射功能，但耐热性低，所述定义的耐热温度为150℃，若曝露在超过该耐热温度的温度中，则银凝聚而变黑。
接着与上述工序连续并在相同的在线型磁控管溅镀装置内后级的容器内(氩与氧的等量混合气氛，0.93Pa)，该碱石灰玻璃基板的上述氧化锌和银的多层膜(非耐热性薄膜)相反侧的面上，依次形成氧化硅层5nm/单斜晶系氧化锆层5nm/锥型钛白粉层5nm。各膜分别采用硅靶、锆靶、钛靶，用非加热的反应性溅镀法来形成。
从而，在碱石灰玻璃基板的一面得到由氧化锌和银的多层膜构成的热线反射膜在其相反面形成光催化剂层的具有非耐热性功能的光催化剂玻璃。这时，一概不经过加热工序，因此不引起银的凝聚，得到可见光透射率高的物品。将可见光透射率的测定结果表示在表1中。可见光透射率是采用D65光源，并按照JIS R3106记载的“板玻璃类的透射率、反射率、放射率、日射热取得率的实验方法”进行测定。
另外，用亲水性化性能的指标评价光催化剂层的光催化剂活性。在形成光催化剂层后，在光达不到的暗处将多层膜物品放置14天，使空气中的碳氢化合物沉积到表面上，使表面的亲水性下降。然后，用黑光(black light)，对氧化钛层表面照射1小时强度为1mW/cm2的紫外线，根据照射后的水滴接触角，进行以下的评价。
  水滴接触角(°)   光催化剂活性评价
  0～910～19   ◎(优)○(良)
  20～2930以上   △(差)×(坏)
在评价上述物品的氧化钛层光催化剂活性的结果，示出良好的性能。
将该碱石灰玻璃基板的形成热线反射膜的一侧作为内侧，用其它碱石灰玻璃和该玻璃，实施多层玻璃加工处理，得到在屋外侧玻璃内面形成热线反射膜、屋外侧玻璃的外面形成光催化剂防污膜的具有防污功能的热线反射型多层玻璃。
实施例2
使用在线型磁控管溅镀装置，在纵1m×横1m、厚度3mm的丙烯树脂基板上，形成单斜晶系氧化锆层10nm/锥型钛白粉层20nm。各膜分别采用锆靶、钛靶，在氩和氧的等量混合气氛(0.93Pa)中，用非加热的反应性溅镀法形成。
丙烯树脂耐热性低，所述定义的耐热温度为230℃。若曝露在高于该温度的温度，则着色成黄色。在上述光催化剂层成膜工序中，一概不用加热工序，因此丙烯树脂基板不变黄，成膜前后的丙烯树脂的光学特性完全不变。
该非耐热性光催化剂玻璃基板可作为显示器用基板加以使用。
实施例3
使用在线型磁控管溅镀装置，在纵1m×横1m、厚度3mm的聚对苯二甲酸乙酯(PET)膜基板上，交替层叠铟锡氧化物(ITO)层和银层，得到基板/ITO层45nm/银层10nm/ITO层40nm结构的多层膜。ITO层采用ITO靶，另外银层采用银靶，在减压氩气氛中以非加热方式形成。该ITO与银的多层膜具有热线反射功能但耐热性低，所述定义的耐热温度为150℃，若曝露在超过该耐热温度的温度，银凝聚而变黑。另外，PET膜本身的耐热温度也180℃，一旦越过该温度就显著地软化变形。
接着与上述工序连续并在相同在线型磁控管溅镀装置内后级的容器内(氩与氧的等量混合气氛，0.93Pa)，在该ITO与银的多层膜上，依次形成单斜晶系氧化锆层10nm/锥型钛白粉层10nm。各膜分别采用锆靶、钛靶，用非加热的反应性溅镀法来形成。所得物品的氧化钛层具有非常高的光催化剂活性。
PET膜基板及银层含有耐热性低的要素，但所述成膜工序一概不采用加热工序，因此不会看到它们的恶化，得到光学特性良好的物品。
该光催化剂基板可作为具有电磁屏蔽功能的防污膜使用。
实施例4
使用在线型磁控管溅镀装置，在纵1m×横1m、厚度1mm的薄板碱石灰玻璃基板上，形成氧化硅层10nm/单斜晶系氧化锆层10nm/掺铌锥型钛白粉层10nm。氧化硅层及单斜晶系氧化锆层分别采用硅靶、锆靶，在氩与氧的等量混合气氛(0.93Pa)中，用非加热的反应性溅镀法来形成。另外，掺Nb锥型钛白粉层采用钛-铌氧化物靶，在氩气氛(0.93Pa)中，用非加热的溅镀法来形成。所得物品的铌氧化钛层具有良好的光催化剂活性。
厚度1mm的薄板碱石灰玻璃基板一旦曝露在高温中就容易变形，所述定义的耐热温度为500℃。由于在所述成膜中无需经过加热工序，成膜前后完全看不到基板的变形。
该光催化剂基板可作为生物化学芯片使用。
比较例1
除不形成氧化锆层以外，以与实施例1相同的条件进行各膜的成膜。所得物品的可见光透射率高达73％而优秀，但氧化钛层的光催化剂活性的评价为“×”。
比较例2
将比较例1的物品在空气中以400℃加热30分钟，进行了氧化钛膜的热处理。该热处理后，评价的光催化剂活性为“○”，但热线反射膜的银凝聚而降低了可见光透射率(由加热前73％降低到加热后54％)。
比较例3
除不形成氧化锆层以外，以与实施例2相同的条件进行各膜的成膜。在评价所得物品的氧化钛层光催化剂活性的结果，评价为“×”。
比较例4
将比较例3的物品在空气中以350℃加热30分钟，进行了氧化钛膜的热处理。该热处理后，评价的光催化剂活性为“○”，但基板的丙烯树脂变黄而降低了可见光透射率(由加热前92％下降到加热后75％)。
比较例5
除不形成氧化锆层以外，以与实施例4相同的条件进行各膜的成膜。在评价所得物品的氧化钛层光催化剂活性的结果，评价为“×”。
比较例6
将比较例5的物品在空气中以600℃加热30分钟，进行了氧化钛膜的热处理。该热处理后，评价的光催化剂活性为“○”，但基板变形较大而得知不能用作商品。

Claims (18)

1.一种光催化剂构件，其特征在于：在基材表面上隔着底涂层形成光催化剂层，所述底涂层以结晶性锆化合物为主成分，所述光催化剂层由晶相构成，且所述基材包含耐热性低的要素。
2.如权利要求1所述的光催化剂构件，其特征在于：所述结晶性锆化合物包含单斜晶系氧化锆结晶。
3.如权利要求1或2所述的光催化剂构件，其特征在于：所述基材是耐热性低的玻璃。
4.如权利要求1或2所述的光催化剂构件，其特征在于：所述基材是树脂基体。
5.如权利要求1或2所述的光催化剂构件，其特征在于：所述基材是树脂膜。
6.如权利要求1或2所述的光催化剂构件，其特征在于：所述基材是有机无机复合基体。
7.如权利要求1或2所述的光催化剂构件，其特征在于：所述基材是耐热性低的金属。
8.如权利要求1至7中任一项所述的光催化剂构件，其特征在于：所述基材包含非耐热性薄膜。
9.如权利要求8所述的光催化剂构件，其特征在于：所述非耐热性薄膜为使用银的热线反射膜。
10.如权利要求9所述的光催化剂构件，其特征在于：所述非耐热性薄膜是使用电介质层/银层/电介质层的层叠膜的热线反射膜。
11.如权利要求9所述的光催化剂构件，其特征在于：所述非耐热性薄膜是使用电介质层/银层/电介质层/银层/电介质层的层叠膜的热线反射膜。
12.如权利要求1至11中任一项所述的光催化剂构件，其特征在于：所述基材的耐热温度为700℃以下。
13.如权利要求1至11中任一项所述的光催化剂构件，其特征在于：所述基材的耐热温度为500℃以下。
14.如权利要求1至13中任一项所述的光催化剂构件，其特征在于：所述光催化剂层以钛化合物为主成分。
15.如权利要求14所述的光催化剂构件，其特征在于：所述钛化合物为正方晶系氧化钛。
16.如权利要求14或15所述的光催化剂构件，其特征在于：所述钛化合物为锥型钛白粉。
17.如权利要求1至16中任一项所述的光催化剂构件，其特征在于：所述非耐热性薄膜、底涂层及光催化剂层通过气相法来形成。
18.如权利要求17所述的光催化剂构件，其特征在于：所述气相法为溅镀法。
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