CN107828413A - 一种发射白光的长余辉荧光粉及其制备方法 - Google Patents
一种发射白光的长余辉荧光粉及其制备方法 Download PDFInfo
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- CN107828413A CN107828413A CN201711061715.8A CN201711061715A CN107828413A CN 107828413 A CN107828413 A CN 107828413A CN 201711061715 A CN201711061715 A CN 201711061715A CN 107828413 A CN107828413 A CN 107828413A
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- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- ZBZHVBPVQIHFJN-UHFFFAOYSA-N trimethylalumane Chemical compound C[Al](C)C.C[Al](C)C ZBZHVBPVQIHFJN-UHFFFAOYSA-N 0.000 description 1
- UWSCPROMPSAQOL-UHFFFAOYSA-N trimethylazanium;sulfate Chemical compound CN(C)C.CN(C)C.OS(O)(=O)=O UWSCPROMPSAQOL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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- 239000001018 xanthene dye Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
- C09K11/7712—Borates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/22—Luminous paints
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/50—Wavelength conversion elements
- H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder
- H01L33/502—Wavelength conversion materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
本发明公开了一种发射白光的长余辉荧光粉及其制备方法,旨在提供一种具有白色长余辉发光性能的荧光粉材料,属于荧光粉技术领域。该荧光粉的化学组成通式为Sr1‑x Al2‑y BySiO6:xDy3+,x和y的取值范围分别为:0.01≤x≤0.1,0.5≤y≤1.5。该荧光粉的发光中心为Dy3+离子,利用Dy3+离子在蓝光和黄光区域的双峰发射组合成白光,通过Al和B元素之间相互取代引起晶格缺陷,为Dy3+发光提供缺陷能级,有效增强其白光长余辉发光效果。本发明提供的长余辉荧光粉具有余辉亮度高、余辉时间长、余辉颜色稳定等特点,可用于安全消防、应急照明指示等领域。
Description
技术领域
本发明属于荧光粉技术领域,特别是涉及一种发射白光的长余辉荧光粉及其制备方法。
背景技术
物质在受到外界光照的作用下,吸收光的能量,然后产生发光的现象叫做光致发光,被吸收的外界光能量可以是不同波长的光波,如可见光、近紫外光、近红外光等。发光材料在受到外界光波激发停止后,会继续发光,这种发光就称为余辉。而余辉会随着时间慢慢减弱,直至停止发光为止,这个过程称为衰减过程。如果某种材料的余辉时间很长,达到几秒甚至几个小时,这种材料就被称之为长余辉发光材料。长余辉发光材料具有节能环保的特点,它可在自然光或其他人造光源照射下,吸收外界光辐射能量,然后可以缓慢地以可见光的形式释放这些存储的能量。长余辉发光材料的现象出现已久,从中国古代的“鬼火”,到夜明珠的发光,这些都是长余辉发光现象。长余辉发光材料真正成为一门科学被研究的时间并不是很长,但是发展速度非常迅速,到现在为止,已经出现了不同基质不同颜色的各种长余辉发光材料。
到了21世纪,长余辉发光材料的颜色已经涉及到可见光的各个区域,其中红色和蓝色,绿色的发展也越来越成熟。但是,在长余辉发光材料的研究中,最适合作为照明光源的白色发光,却还属于初步的认识阶段。在传统的制备工艺中,白色光是由红绿蓝三基色复合而成,但是由于长余辉发光材料是出现衰减的,而通常情况下,三基色的衰减是不同步的,所以在这一研究背景下,新的白色长余辉发光材料的制备方法就进入了人们的研究范围。
白光是一种复合光,若要让材料发出白光,必定需要其他单色光的复合,而在色度学中,我们讨论的单色光就是指可见光。这些可见光的波长在380nm到780nm。众所周知,白光是由七种颜色的可见光复合而成,而七种颜色中,又有红绿蓝三基色,这三种颜色可以复合成白光。然而白光并不需要完全是三基色来组成,在色度的研究中,两种光色的互补,就可以复合成白光来。在最初研究白色长余辉发光材料的时候,人们只是按照光色互补的原理,将两种发不同颜色、而且互补光色的材料进行复合,从而发出白光。但是由于不同发光材料的光色衰减不同,就会导致随着时间的变化,发光的颜色会发生变化,而不能保持白光。所以若要保证白色长余辉发光材料中白光保持不变,就要使得单色光的衰减一致,所以若要制备出良好发光性能的白色长余辉发光材料,就不能通过两种发光材料的混合来实现,必须在单一的基质中的互补光色来达到发白光的目的。这些条件确实给研究者提高了困难。对于白色长余辉发光材料的报道,也是近几年才开始出现,虽然余辉时间和亮度还不尽如人意,却也为大部分的研究者提供了一个新的思路,开拓了一个新的局面。
发明内容
为了克服上述现有技术中发射白光的长余辉材料余辉亮度低、余辉时间短、颜色不稳定等缺点,本发明提供了一种新型发射白光的长余辉荧光粉及其制备方法,该荧光粉具有余辉亮度高、余辉时间长、余辉颜色稳定等优点,可用于安全消防、应急照明指示等领域。
由于长余辉发光材料的种类较多,不同的材料具有不同的发光机制,而有些材料的发光机理目前还不太清楚,因此,寻求合适的基质和激活离子对于新型长余辉材料的开发至关重要。此外,由于长余辉发光材料的制备方法较多,而且存在各自的优缺点,因此对各种长余辉发光材料的制备方法的优化组合也将对长余辉发光材料的推广应用起到很关键的作用。
为解决上述现有技术的不足,本发明所采用的技术方案如下:
一种发射白光的长余辉荧光粉,所述荧光粉的化学组成通式为Sr1-x Al2-y BySiO6: xDy3 +,x和y的取值范围分别为:0.01≤x≤0.1,0.5≤y≤1.5。特别地,所述荧光粉的发光中心为Dy3+离子,利用Dy3+离子在蓝光和黄光区域的双峰发射组合成白光,必须同时含有Al和B元素,通过Al和B元素之间相互取代引起晶格缺陷,为Dy3+发光提供缺陷能级,有效增强其白光长余辉发光效果。
一种发射白光的长余辉荧光粉的制备方法,其特征在于包括以下步骤:
(1)以高纯度的SrCO3、Al2O3、SiO2、H3BO3和Dy2O3作为原料,按照化学组成通式Sr1-x Al2- y BySiO6: xDy3+,中各元素的配比,精确称取各原料;
(2)将各原料同时放入玛瑙研钵中,并通过手工研磨的方式将其混合均匀,每个样品的研磨时间为20~30min;
(3)将上述混合均匀的原料放入刚玉坩埚,并在高温管式炉中进行烧结,烧结温度为1000~1300℃,烧结时间为2~6小时,升温速率为10℃/min,烧结气氛为空气气氛,烧结完成后随炉冷却至室温,获得烧结体;
(4)将步骤(3)获得的烧结体进行研磨粉碎,即得所述发射白光的长余辉荧光粉。
与现有技术相比,本发明的有益效果是:
(1)本发明提供的长余辉荧光粉化学组成通式为Sr1-x Al2-y BySiO6: xDy3+,利用Dy3+离子在蓝光和黄光区域的双峰发射组合成白光,发光颜色稳定;
(2)本发明提供的长余辉荧光粉必须同时含有Al和B元素,通过Al和B元素之间相互取代引起晶格缺陷,为Dy3+发光提供缺陷能级,有效增强其白光长余辉发光效果,余辉亮度高、余辉时间长;
本发明还公开了一种发射白光的长余辉发光元件,采用上述的发射白光的长余辉荧光粉制成的基片。
本发明还公开了一种发射白光的长余辉发光元件,包括基底和附着在基底上的长余辉发光薄膜,所述的长余辉发光薄膜为上述的发射白光的长余辉荧光粉粉末或发射白光的长余辉荧光粉薄片。
本发明还公开了一种发射白光的长余辉发光元件,包括基底和附着在基底上的长余辉发光薄膜,所述的长余辉发光薄膜为发射白光的长余辉荧光粉粉末或发射白光的长余辉荧光粉薄片。
作为优选,长余辉发光薄膜的厚度为1-10mm。
本发明的基底,可以为刚性基底,也可以为柔性基底。作为优选,所述刚性基底可以选自玻璃、硅、钢铁、陶瓷、水泥、木材和石头,所述柔性基底可以选自PDMS(聚二甲基硅氧烷)膜、PET(聚对苯二甲酸乙二醇酯)膜、PS(聚苯乙烯)膜、PU(聚氨酯)膜、PI(聚酰亚胺)膜和PVA(聚乙烯醇)薄膜。
上述的发射白光的长余辉发光元件制备方法,包括:将如上所述的发射白光的长余辉荧光粉粉末颗粒的悬浮液涂覆于如上所述的基底上。
尽管将如上所述的发射白光的长余辉荧光粉粉末颗粒悬浮液溶剂中制备成悬浮液,然后涂覆于所述基底上即可制备出满足本发明要求的发光元件,但当所述悬浮液中还含有高分子物质时,最终所制备的发光元件的灵敏度和精准度会得到进一步提升。
所述发射白光的长余辉荧光粉粉末颗粒的含量也可以在较宽的范围内变化,优选情况下,基于100重量份的所述悬浮液,所述发射白光的长余辉荧光粉粉末颗粒的含量为0.5-10重量份,优选为1-5重量份。
优选的,所述高分子物质选自PVA、EVA(乙烯-乙酸乙烯共聚物)、PDMS、PU、PMMA(聚甲基丙烯酸甲酯)、PAM(聚丙烯酰胺)、PVP(聚乙烯吡咯烷酮)、淀粉、纤维素、植物胶、动物胶、羧甲基淀粉、醋酸淀粉、羟甲基纤维素和羧甲基纤维素中的一种或多种。
根据本发明,所述高分子物质的含量也可以在较宽的范围内变化,优选情况下,基于100重量份的所述悬浮液,所述高分子的含量为1-10重量份,优选为3-8重量份。
根据本发明,所述溶剂可以为本领域常规使用的各种溶剂,优选选自水、甲醇、乙醇、丙酮、乙二醇、异丙醇、二甘醇、乙二醇甲醚、乙二醇乙醚、乙二醇丁醚、乙二醇苯醚、乙二醇苄醚、康醇、二甘醇甲醚、二甘醇乙醚、二甘醇丁醚、三甘醇甲醚、双丙酮醇、十三醇、十四醇、邻苯二甲酸二辛酯、醋酸乙酯、醋酸丁酯、环己酮、二甲苯、联二环己烷、环己烷、正丁醇、丁酮、邻苯二甲酸二甲酯和山梨糖醇中的一种或多种。
根据本发明,将所述发射白光的长余辉荧光粉粉末颗粒的悬浮液涂覆在所述基底表面上的方法可以为本领域常规的选择,例如,可以采用喷涂、旋涂等涂覆方法,也可以采用打印技术。本发明在此优选打印技术将发射白光的长余辉荧光粉粉末颗粒的悬浮液印在基底的表面上,从而使得制备得到的传感器的灵敏度和精准度得到进一步提升。其中,所述打印技术可以选自点胶、喷墨打印、水转印、丝网印刷和卷对卷印刷中的一种。当采用打印技术将所述发射白光的长余辉荧光粉粉末颗粒的悬浮液印在基底的表面上时,优选将所述悬浮液制备成墨水,所述墨水的制备方法是通过将所述悬浮液共混搅拌或共混超声分散得到。
本发明还公开了一种发射白光的长余辉发光元件,该发射白光的长余辉发光元件包括高分子材料和所述的发射白光的长余辉荧光粉粉末,发射白光的长余辉荧光粉粉末均匀分布在高分子材料中,发射白光的长余辉荧光粉粉末的加入量为1~90%;优选为10~80%。高分子材料可以选自PDMS(聚二甲基硅氧烷)、PET(聚对苯二甲酸乙二醇酯)、PS(聚苯乙烯)、PU(聚氨酯)、PI(聚酰亚胺)和PVA(聚乙烯醇)薄。适度的为了改善加工的性能,该薄膜材料还可以加入偶联剂、润滑剂、增塑剂等。
本发明还公开了一种油墨,该油墨包括油墨常规成分和所述的发射白光的长余辉荧光粉粉末,发射白光的长余辉荧光粉粉末均匀分布在油墨常规成分中,发射白光的长余辉荧光粉粉末的加入量为1~30%;优选为5~10%。油墨树脂体系可以是聚酰胺,氯化聚丙稀,聚氨酯或丙稀酸。既可以是油性油墨也可以是水性油墨。
本发明还公开了一种涂料,该涂料包括涂料常规成分和所述的发射白光的长余辉荧光粉粉末,发射白光的长余辉荧光粉粉末均匀分布在涂料常规成分中,发射白光的长余辉荧光粉粉末的加入量为1~30%;优选为5~10%。涂料树脂体系可以是聚酰胺,氯化聚丙稀,聚氨酯或丙稀酸。既可以是油性涂料也可以是水性涂料。
另外,通过将包含发射白光的长余辉荧光粉形成于通常的纸、合成纸、或环氧树脂、聚乙烯、聚对苯二甲酸乙二醇酯、聚酯、聚丙烯、聚氯乙烯等高分子原材料、天然橡胶或合成橡胶、玻璃、陶瓷、金属、木、人工纤维或天然纤维、混凝土、或它们的组合以及它们的加工制品等的外饰表面,或通过在内部含有发射白光的长余辉荧光粉。
本发明发射白光的长余辉发光元件可以作为照明、用于安全的显示的利用。例如为:器件振动灯、风力灯等照明器具;紧急、异常报知、非常用具、危险显示、非常灯、非常用标识、救命工具用的标识、招牌、显示装置;安全栏、悬挂于工厂建筑物周围的紧张绳、动物防护栏;阶梯的踏板、扶手、和在半埋入于道路等的状态下设置的目地用线条体;健康器具、步行辅助器具(步行辅助用手杖、发光报知天线等);耳环、项链等首饰;支撑旗的支柱、铁道等的截路机的截路棒、自行车、汽车、电车、船、飞机等的外饰用部件或内置部件、钓鱼用具(模拟饵、钓竿、捕鱼用网等;发光性纤维结构体、发光性渔具、钓丝、渔网等)、浮标(浮子、浮标);人、狗、猫等宠物、牛、猪、羊、鸡等家畜等的位置显示;风扇(风力发电、扇风机等的叶片等)、服装(鞋子、运动服、人工发光布匹、人工发光丝、人工发光纤维等);包装(箱、支架、器、信封、厚纸、外皮包装、外部覆膜)、医疗品(呼吸援助器具、试验研究用器材)机器人(人工发光毛发结构体、人工发光皮肤、人工发光身体)等。作为涂料组合物、墨组合物、接合剂、表面覆盖剂中含有发射白光的长余辉荧光粉的运用例,可以举出:金融组织、公共组织、信用卡公司、流通业界等中使用的、粘贴用的粘接剂中含有发射白光的长余辉荧光粉的压接明信片片材等邮寄物;椅子、床等家具;地板材料、瓷砖、墙壁材料、预制板材料、铺路材料、木材·钢铁·混凝土等建材;搭载于车辆的自动导航系统装置;用于操作音频装置和空调等的操作装置;家电制品、便携式机器、电子计算机等输入装置;数码相机、CCD相机、薄膜、照片、影像等图像存储手段等。
通过使发射白光的长余辉荧光粉发光而可以产生新的外观,因此也考虑向玩具、活动商品等娱乐商品、生活用品的展开。例如可以举出:动态玩具、风筝、鲤鱼形旗等风幡、秋千、快速滑行车、旋转木马、弓箭等;通过风力同时产生声和光的无电源型发光装置(风铃等)。发光球(高尔夫球、棒球的球、乒乓球用球、台球的球等)、发光机制的风车;气球;片状结构物为纸的、卷取笛、折纸、纸气球、折扇、贺年片、绘本;运动用品(撑杆跳用杆、击剑、弓箭等长尺寸物体等);高尔夫球棒的得分确认用压敏密封件、网球场用线路试验器、动态装饰体、动态雕刻、动态纪念物;动态展示装置;发光装饰装置;扬声器等音响装置、乐器(小提琴、吉他等弦乐器、木琴、鼓等打击乐器、小号、长笛等管乐器、玻璃等光阑)、音叉等;活动商品等娱乐商品;水族馆的观赏用水槽等的水草、容器;发光手表、发光砂计时器或砂计时器型发光装置;发光型模拟蜡烛装置;能够发光的人工植物;人工眼;含有附着性聚合物的化妆品组合物、在目视状态下能够辨别伪造的印刷物和有价证券、含有长余辉发光颗粒的印刷墨、票据、支票、股票、债券、各种证券、商品券、图书券、交通组织的车票、收费设施、项目的入场券、彩票、公共体育比赛的投票券的中奖券等、纸币、身份证、票、通行证等、护照、书写有机密文书的印刷物、或封缄密封件等。
利用伴随着长余辉荧光粉的发光,使附着于发射白光的长余辉荧光粉表面的光催化剂活化而得到的、长余辉发光体-光催化剂复合体可以用于:抗菌、杀菌、对非人动物的治疗、车辆的扶手带、把手等抗菌性物品的污垢净化、利用位于暗处的配管等内部壁面的流动物的流动能量的净化。长余辉发光物质通过发光,使高分子树脂中的光交联剂活化,也可以促进交联。
通过将本发明的发射白光的长余辉荧光粉配混于树脂中,可以形成本发明的树脂组合物。
另外,通过在本发明的树脂组合物中进一步加入其他无机材料或有机材料形成复合材料,也可以形成本发明的长余辉发光体。
例如,树脂为环氧树脂、丙烯酸类树脂等的情况下,相对于树脂100质量份配混上述发射白光的长余辉荧光粉1~200份,树脂为聚乙烯树脂、软质氯乙烯树脂等的情况下,相对于树脂100质量份配混上述发射白光的长余辉荧光粉30~300质量份。配混物可以通过使用锥型混合机、V型混合机、螺带式混合机、亨舍尔混合机、班伯里混合机、三辊磨等混合机来制作树脂组合物。
另外,由该树脂组合物形成长余辉发光体的情况下,例如得到片状的长余辉发光体时,例如相对于聚氯乙烯树脂100重量份,配混上述发射白光的长余辉荧光粉50~200质量份、钙-锌系稳定剂3~5质量份、作为增塑剂的邻苯二甲酸二辛酯30~100质量份,用两辊磨在150~200℃下进行混炼,从而可以得到具有可挠性的片状的长余辉发光体。
得到薄膜状的长余辉发光体时,例如相对于聚对苯二甲酸乙二醇酯树脂100质量份,配混上述发射白光的长余辉荧光粉20~50质量份,用双螺杆挤出机、吹胀加工机在250~300℃下进行混炼、成型,从而可以得到薄膜状的长余辉发光体。
得到其他形状的长余辉发光体时,例如相对于聚丙烯树脂100质量份,配混发射白光的长余辉荧光粉5~100质量份,用双螺杆挤出机在170~200℃下进行混炼、成型,从而可以得到带状、板状、棒状、粒料状的长余辉发光体。另外,通过使用注射成型机在170~200℃下对粒料状的长余辉发光体进行加工成型,可以得到立体形状的长余辉发光体。
作为上述树脂或其他有机材料,可以举出:热塑性树脂、热固性树脂那样的树脂。作为热塑性树脂,例如可以举出:低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、线型低密度聚乙烯等聚乙烯、聚丙烯、聚苯乙烯、聚氯乙烯、聚氟乙烯、聚偏二氯乙烯、丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)等苯乙烯聚合物或共聚物、6-尼龙、66-尼龙、12-尼龙等聚酰胺、聚酰胺酰亚胺、聚酰亚胺、聚醚酰亚胺、聚氨酯、聚甲基丙烯酸甲酯等丙烯酸类树脂、聚乙酸乙烯酯、乙烯-乙酸乙烯酯共聚物、聚偏二氟乙烯、聚四氟乙烯等氟树脂、烯基芳香族树脂、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚萘二甲酸乙二醇酯、聚乳酸等聚酯、双酚A系聚碳酸酯等聚碳酸酯、聚缩醛、聚苯硫醚、聚甲基戊烯、纤维素、聚乙烯醇、聚乙酸乙烯酯、聚丙烯腈等聚丙烯酸、苯乙烯-丙烯腈共聚物(AS树脂)、聚苯醚(PPE)、改性PPE、聚芳酯、聚苯硫醚、聚砜、聚醚砜、聚醚腈、聚醚酮、聚酮、液晶聚合物乙烯与丙烯的共聚物、乙烯或丙烯与其他α-烯烃(1-丁烯、1-戊烯、1-己烯、4-甲基-1-戊烯等)的共聚物、乙烯与其他烯属不饱和单体(乙酸乙烯酯、丙烯酸、丙烯酸酯、甲基丙烯酸、甲基丙烯酸酯、乙烯醇等)的共聚物等。
热塑性树脂可以单独使用或组合2种以上使用。需要说明的是,热塑性树脂为共聚物时,可以为无规共聚物、嵌段共聚物等任意形态的共聚物。作为热固性树脂,可以举出:酚醛树脂、尿素树脂、三聚氰胺树脂、不饱和聚酯树脂、邻苯二甲酸二烯丙酯树脂、环氧树脂、有机硅树脂、醇酸树脂、聚酰亚胺、聚氨基双马来酰亚胺、酪素树脂、呋喃树脂、聚氨酯树脂等。此外还可以举出:利用紫外线、辐射线固化的树脂。
进而,可以举出:天然橡胶、聚异戊二烯橡胶、丁苯橡胶、聚丁二烯橡胶、乙烯-丙烯-二烯橡胶、丁基橡胶、氯丁橡胶、丙烯腈丁二烯橡胶、硅橡胶等橡胶系材料。
除此之外,可以将颜料、染料、润滑剂、抗氧化剂、紫外线吸收剂、光稳定剂、抗静电剂、阻燃剂、杀菌剂、抗菌剂、固化用催化剂、光聚合引发剂等与本发明的发射白光的长余辉荧光粉一起混合,成型为棒状、板状、薄膜状、纤维状、膜状、针状、球状、箔状、颗粒状、砂状、鳞片状、片状、液态、凝胶状、溶胶状、悬浮液、聚集体、胶囊型等任意形状。
作为颜料,可以举出无机颜料、有机颜料。
作为无机颜料,可以举出:氧化钛、硫酸钡、碳酸钙、氧化锌、硫酸铅、黄色铅、锌黄、胭脂(红色氧化铁(III))、镉红、群青、深蓝、氧化铬绿、钴绿、赭石色、钛黑、合成铁黑、炭黑、云母、由氧化钛、氧化铁覆盖的氧化铝、由氧化钛、氧化铁覆盖的云母、玻璃鳞片、全息颜料等。除此之外,作为金属粉末颜料,可以举出:铝粉末、铜粉末、不锈钢粉末、金属胶体、作为有干涉作用的透明珍珠云母、着色云母、干涉云母、干涉氧化铝、干涉二氧化硅(干涉玻璃)等。
作为有机颜料,可以举出:偶氮系颜料(单偶氮黄、缩合偶氮黄、偶氮甲碱黄等)、黄色氧化铁、钛黄、钒酸铋、苯并咪唑酮、异吲哚啉酮、异吲哚啉、喹酞酮、联苯胺黄、永久黄等黄色颜料;永久橙等橙色颜料;红色氧化铁、萘酚AS系偶氮红、蒽嵌蒽醌、蒽醌红、芘红褐、喹吖啶酮红、二酮基吡咯并吡咯红、永久红等红色颜料;钴紫、喹吖啶酮紫、二噁嗪紫等紫色颜料;钴蓝、酞菁系颜料(酞菁蓝等)、蒽蓝等蓝色颜料;酞菁绿等绿色颜料、偶氮系分散染料、蒽醌系分散染料等有机染料等。
作为染料,可以举出:偶氮染料、蒽醌染料、靛蓝染料、硫化染料、三苯基甲烷染料、吡唑啉酮染料、茋染料、二苯基甲烷染料、氧杂蒽染料、茜素染料、吖啶染料、醌亚胺染料(嗪染料、噁嗪染料、噻嗪染料)、噻唑染料、甲炔染料、硝基染料、和亚硝基染料等。
作为抗氧化剂,可以举出:受阻酚系化合物、亚磷酸酯系化合物、亚膦酸酯系化合物、和硫醚系化合物等。
作为受阻酚系化合物,可以举出:α-生育酚、丁基羟基甲苯、芥子醇、维生素E、正十八烷基-β-(4’-羟基-3’,5’-二叔丁基苯基)丙酸酯、2-叔丁基-6-(3’-叔丁基-5’-甲基-2’-羟基苄基)-4-甲基苯基丙烯酸酯、2,6-二叔丁基-4-(N,N-二甲基氨基甲基)苯酚、3,5-二叔丁基-4-羟基苄基膦酸二乙基酯、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)、4,4’-亚甲基双(2,6-二叔丁基苯酚)、2,2’-亚甲基双(4-甲基-6-环己基苯酚)、2,2’-二亚甲基-双(6-α-甲基-苄基-对甲酚)2,2’-乙叉基-双(4,6-二叔丁基苯酚)、2,2’-丁叉基-双(4-甲基-6-叔丁基苯酚)、4,4’-丁叉基双(3-甲基-6-叔丁基苯酚)、三乙二醇-N-双-3-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯、1,6-己二醇双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、双[2-叔丁基-4-甲基6-(3-叔丁基-5-甲基-2-羟基苄基)苯基]对苯二甲酸酯、3,9-双{2-[3-(3-叔丁基-4-羟基-5-甲基苯基)丙酰基氧基]-1,1-二甲基乙基}-2,4,8,10-四氧杂螺[5,5]十一烷、4,4’-硫代双(6-叔丁基-间甲酚)、4,4’-硫代双(3-甲基-6-叔丁基苯酚)、2,2’-硫代双(4-甲基-6-叔丁基苯酚)、双(3,5-二叔丁基-4-羟基苄基)硫醚、4,4’-二硫代双(2,6-二叔丁基苯酚)、4,4’-三硫代双(2,6-二叔丁基苯酚)、2,2-硫代二亚乙基双-[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2,4-双(正辛硫基)-6-(4-羟基-3’,5’-二叔丁基苯胺基)-1,3,5-三嗪、N,N’-六亚甲基双-(3,5-二叔丁基-4-羟基氢化肉桂酰胺)、N,N’-双[3-(3,5-二叔丁基-4-羟基苯基)丙酰基]肼、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、1,3,5-三甲基-2,4,6-三(3,5-二叔丁基-4-羟基苄基)苯、三(3,5-二叔丁基-4-羟基苯基)异氰脲酸酯、三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、1,3,5-三(4-叔丁基-3-羟基-2,6-二甲基苄基)异氰脲酸酯、1,3,5-三2[3-(3,5-二叔丁基-4-羟基苯基)丙酰基氧基]乙基异氰脲酸酯和四[亚甲基-3-(3’,5’-二叔丁基-4-羟基苯基)丙酸酯]甲烷等。
作为亚磷酸酯系化合物,可以举出亚磷酸三苯酯、亚磷酸三(壬基苯基)酯、亚磷酸三癸基酯、亚磷酸三辛基酯、亚磷酸三(十八烷基)酯、亚磷酸二癸基单苯基酯、亚磷酸二辛基单苯基酯、亚磷酸二异丙基单苯基酯、亚磷酸单丁基二苯基酯、亚磷酸单癸基二苯基酯、亚磷酸单辛基二苯基酯、亚磷酸三(二乙基苯基)酯、亚磷酸三(二异丙基苯基)酯、亚磷酸三(二正丁基苯基)酯、亚磷酸三(2,4-二叔丁基苯基)酯、亚磷酸三(2,6-二叔丁基苯基)酯、二硬脂基季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-乙基苯基)季戊四醇二亚磷酸酯、双{2,4-双(1-甲基-1-苯基乙基)苯基}季戊四醇二亚磷酸酯、苯基双酚A季戊四醇二亚磷酸酯、双(壬基苯基)季戊四醇二亚磷酸酯和二环己基季戊四醇二亚磷酸酯等。作为其他亚磷酸酯系化合物,可以举出与二元苯酚类反应从而具有环状结构的亚磷酸酯系化合物。
作为亚膦酸酯系化合物,可以举出:四(2,4-二叔丁基苯基)-4,4’-亚联苯基二亚膦酸酯、四(2,4-二叔丁基苯基)-4,3’-亚联苯基二亚膦酸酯、四(2,4-二叔丁基苯基)-3,3’-亚联苯基二亚膦酸酯、四(2,6-二叔丁基苯基)-4,4’-亚联苯基二亚膦酸酯、四(2,6-二叔丁基苯基)-4,3’-亚联苯基二亚膦酸酯、四(2,6-二叔丁基苯基)-3,3’-亚联苯基二亚膦酸酯、双(2,4-二叔丁基苯基)-4-苯基-苯基亚膦酸酯、双(2,4-二叔丁基苯基)-3-苯基-苯基亚膦酸酯、双(2,6-二正丁基苯基)-3-苯基-苯基亚膦酸酯、双(2,6-二叔丁基苯基)-4-苯基-苯基亚膦酸酯和双(2,6-二叔丁基苯基)-3-苯基-苯基亚膦酸酯等。
作为硫醚系化合物,可以举出:硫代二丙酸二月桂基酯、硫代二丙酸二(十三烷基)酯、硫代二丙酸二肉豆蔻基酯、硫代二丙酸二硬脂基酯、季戊四醇-四(3-月桂基硫代丙酸酯)、季戊四醇-四(3-十二烷基硫代丙酸酯)、季戊四醇-四(3-十八烷基硫代丙酸酯)、季戊四醇四(3-肉豆蔻基硫代丙酸酯)和季戊四醇-四(3-硬脂基硫代丙酸酯)等。作为包含紫外线吸收剂的光稳定剂,可以举出:二苯甲酮系化合物、苯并三唑系化合物、芳香族苯甲酸酯系化合物、草酰苯胺系化合物、氰基丙烯酸酯系化合物和受阻胺系化合物等。
作为二苯甲酮系化合物,可以举出:二苯甲酮、2,4-二羟基二苯甲酮、2,2’-二羟基二苯甲酮、2,2’,4,4’-四羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2,2’-二羟基-4,4’-二甲氧基二苯甲酮、2,2’-二羟基-4,4’-二甲氧基-5-磺酰基二苯甲酮、2-羟基-4-辛氧基二苯甲酮、2-羟基-4-十二烷氧基二苯甲酮、2-羟基-4-辛氧基二苯甲酮、2-羟基-4-甲氧基-5-磺酰基二苯甲酮、5-氯-2-羟基二苯甲酮、2-羟基-4-辛氧基二苯甲酮、2-羟基-4-甲氧基-2’-羧基二苯甲酮和2-羟基-4-(2-羟基-3-甲基-丙烯酰氧基异丙氧基)二苯甲酮等。
作为苯并三唑系化合物,可以举出:2-(5-甲基-2-羟基苯基)苯并三唑、2-(3,5-二叔丁基-2-羟基苯基)苯并三唑、2-(3,5-二叔戊基-2-羟基苯基)苯并三唑、2-(3’,5’-二叔丁基-4’-甲基-2’-羟基苯基)苯并三唑、2-(3,5-二叔戊基-2-羟基苯基)-5-氯苯并三唑、2-(5-叔丁基-2-羟基苯基)苯并三唑、2-[2’-羟基-3’,5’-双(α,α-二甲基苄基)苯基]苯并三唑、2-[2’-羟基-3’,5’-双(α,α-二甲基苄基)苯基]-2H-苯并三唑和2-(4’-辛氧基-2’-羟基苯基)苯并三唑等。
作为芳香族苯甲酸酯系化合物,可以举出:水杨酸对叔丁基苯基酯、水杨酸对辛基苯基酯等水杨酸烷基苯基酯类等。
作为草酰苯胺系化合物,可以举出:2-乙氧基-2’-乙基草酰二苯胺、2-乙氧基-5-叔丁基-2’-乙基草酰二苯胺和2-乙氧基-3’-十二烷基草酰二苯胺等。
作为氰基丙烯酸酯系化合物,可以举出:乙基-2-氰基-3,3’-二苯基丙烯酸酯、2-乙基己基-氰基-3,3’-二苯基丙烯酸酯等。
作为受阻胺系化合物,可以举出:4-乙酰氧基-2,2,6,6-四甲基哌啶、4-硬脂酰氧基-2,2,6,6-四甲基哌啶、4-丙烯酰氧基-2,2,6,6-四甲基哌啶、4-(苯基乙酰氧基)-2,2,6,6-四甲基哌啶、4-苯甲酰氧基-2,2,6,6-四甲基哌啶、4-甲氧基-2,2,6,6-四甲基哌啶、4-十八烷基氧基-2,2,6,6-四甲基哌啶、4-环己基氧基-2,2,6,6-四甲基哌啶、4-苄基氧基-2,2,6,6-四甲基哌啶、4-苯氧基-2,2,6,6-四甲基哌啶、4-(乙基氨基甲酰氧基)-2,2,6,6-四甲基哌啶、4-(环己基氨基甲酰氧基)-2,2,6,6-四甲基哌啶、4-(苯基氨基甲酰氧基)-2,2,6,6-四甲基哌啶、双(2,2,6,6-四甲基-4-哌啶基)碳酸酯、双(2,2,6,6-四甲基-4-哌啶基)草酸酯、双(2,2,6,6-四甲基-4-哌啶基)丙二酸酯、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(2,2,6,6-四甲基-4-哌啶基)己二酸酯、双(2,2,6,6-四甲基-4-哌啶基)对苯二甲酸酯、1,2-双(2,2,6,6-四甲基-4-哌啶基氧基)-乙烷、α,α’-双(2,2,6,6-四甲基-4-哌啶基氧基)-对二甲苯、双(2,2,6,6-四甲基-4-哌啶基)-甲代亚苯基-2,4-二氨基甲酸酯、双(2,2,6,6-四甲基-4-哌啶基)-六亚甲基-1,6-二氨基甲酸酯、三(2,2,6,6-四甲基-4-哌啶基)-苯-1,3,5-三羧酸酯、三(2,2,6,6-四甲基-4-哌啶基)-苯-1,3,4-三羧酸酯、1,2-{3-(3,5-二叔丁基-4-羟基苯基)丙酰基氧基}-2,2,6,6-四甲基哌啶以及1,2,3,4-丁烷四羧酸和1,2,2,6,6-五甲基-4-羟基哌啶和β,β,β’,β’-四甲基-3,9-[2,4,8,10-四氧杂螺(5,5)十一烷]二甲醇的缩合物等。
作为抗静电剂,可以举出:炭黑、石墨等碳粉体、锡·锑复合氧化物、锑·铟·锡复合氧化物、铟·锡复合氧化物、掺杂了Sn、F、Cl等的导电性氧化铟、氧化锡、氧化锌等金属氧化物、铜、镍、银、金、铝等各种金属颗粒(粉体)或金属纤维等无机系抗静电剂、以及(β-月桂酰胺丙酰基)三甲基硫酸铵、十二烷基苯磺酸钠等季铵盐系、磺酸盐系化合物、烷基磷酸酯系化合物等有机系的抗静电剂等。
作为阻燃剂,可以举出:溴系阻燃剂、磷系阻燃剂、氯系阻燃剂、三嗪系阻燃剂、以及磷酸与哌嗪的盐等其它无机系阻燃剂等。
作为溴系阻燃剂,可以举出:溴化聚苯乙烯、溴化聚丙烯酸酯、溴化聚苯醚、溴化双酚A型环氧树脂、溴化双酚A型环氧树脂的分子链末端的缩水甘油基的一部分或全部经过封端的改性物、以溴化双酚A作为原料合成的聚碳酸酯低聚物、溴化二邻苯二甲酰亚胺化合物、溴化联苯醚和1,2-二(五溴苯基)乙烷等溴化二苯基烷等化合物。其中,可以举出:聚三溴苯乙烯等溴化聚苯乙烯、聚(二溴苯醚)、十溴二苯基醚、双(三溴苯氧基)乙烷、1,2-二(五溴苯基)乙烷、乙烯-双-(四溴邻苯二甲酰亚胺)、四溴双酚A、溴化聚碳酸酯低聚物、聚三溴苯乙烯等溴化聚苯乙烯、1,2-二(五溴苯基)乙烷等。
作为磷系阻燃剂,可以举出:磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三(2-乙基己基)酯、磷酸三丁氧基乙酯、磷酸三苯酯、磷酸三甲苯基酯、磷酸三(二甲苯基)酯、磷酸三(异丙基苯基)酯、磷酸三(苯基苯基)酯、磷酸三萘基酯、磷酸甲苯基二苯基酯、磷酸二甲苯基二苯基酯、磷酸二苯基(2-乙基己基)酯、磷酸二(异丙基苯基)苯基酯、磷酸单异癸基酯、2-丙烯酰氧基乙基酸式磷酸酯、2-甲基丙烯酰氧基乙基酸式磷酸酯、二苯基-2-丙烯酰氧基乙基磷酸酯、二苯基-2-甲基丙烯酰氧基乙基磷酸酯、三聚氰胺磷酸酯、二(三聚氰胺)磷酸酯、三聚氰胺焦磷酸酯、三苯基氧化膦、三甲苯基氧化膦、甲烷膦酸二苯酯、苯基膦酸二乙酯等磷酸酯、间苯二酚聚苯基磷酸酯、1,3-亚苯基双(2,6-二甲基苯基磷酸酯)、间苯二酚聚(二-2,6-二甲苯基)磷酸酯、双酚A聚甲苯基磷酸酯、双酚A聚苯基磷酸酯、氢醌聚(2,6-二甲苯基)磷酸酯以及它们的缩合物等芳香族缩合磷酸酯等缩合磷酸酯等。
作为氯系阻燃剂,可以举出:五氯五环癸烷、六氯苯、五氯甲苯、四氯双酚A和聚氯苯乙烯等。作为三嗪系阻燃剂,可以举出:三聚氰胺、甲基胍胺、苯并胍胺、丙烯酰胍胺、2,4-二氨基-6-壬基-1,3,5-三嗪、2,4-二氨基-6-羟基-1,3,5-三嗪、2-氨基-4,6-二羟基-1,3,5-三嗪、2,4-二氨基-6-甲氧基-1,3,5-三嗪、2,4-二氨基-6-乙氧基-1,3,5-三嗪、2,4-二氨基-6-丙氧基-1,3,5-三嗪、2,4-二氨基-6-异丙氧基-1,3,5-三嗪、2,4-二氨基-6-巯基-1,3,5-三嗪和2-氨基-4,6-二巯基-1,3,5-三嗪等。
作为磷酸与哌嗪的盐,可以举出:正磷酸哌嗪、焦磷酸哌嗪和多磷酸哌嗪等。
作为无机系阻燃剂,可以举出:三氧化锑、五氯化锑等锑化合物、硼酸锌、硼酸钠、氢氧化铝、氢氧化镁和红磷等。
作为杀菌剂,可以举出:喹啉铜等铜杀菌剂、代森锌(Zineb)、代森锰(Maneb)等有机硫杀菌剂、克菌丹、百菌清等有机氯系杀菌剂、甲基硫菌灵、苯来特、多菌灵、噻苯咪唑等苯并咪唑系杀菌剂、异菌脲、乙烯菌核利、腐霉利等二羧基酰亚胺系杀菌剂、呋吡菌胺等酰胺系杀菌剂、咯菌腈等苯基吡咯系杀菌剂、烯酰吗啉等吗啉系杀菌剂、嘧菌酯、醚菌酯、ORIBRIGHT等甲氧基丙烯酸酯系杀菌剂、嘧菌胺、嘧菌环胺、嘧霉胺等苯胺基嘧啶系杀菌剂、三唑酮、氟菌唑等麦角甾醇生物合成抑制剂、三氯硝基甲烷、PCNB等土壤杀菌剂、以及氟啶胺、邻苯基苯酚(OPP)、二苯基、氯二苯基、甲酚、1,2-双(溴乙酰氧基)乙烷、肉桂醛、乙酸苯酯、异硫氰酸烯丙酯、α-甲基苯乙酮、百里酚、全氯环戊二烯、溴乙酸、2,2-二溴-3-腈基丙酰胺、氯乙酸乙酯、氯乙酸丁酯、氯乙酸甲酯、5-氯-2-甲基异噻唑啉-3-酮、戊二醛、和桧木醇等。
作为抗菌剂,可以举出:使银、锌、铜的一种或2种以上的抗菌性金属负载于无机化合物而得到的无机系粉体。作为负载体,可以举出:沸石、磷灰石、磷酸锆、氧化钛、二氧化硅凝胶、铝硫酸盐氢氧化物、磷酸钙、硅酸钙等。另外还可以举出:在以磷酸系、硼酸系、硅酸系的各系玻璃的一种或2种以上作为玻璃形成成分的玻璃中含有银、锌、铜的一种或2种以上的抗菌性金属而得到的抗菌性玻璃粉体。
作为润滑剂,可以举出:脂肪酸、脂肪酸金属盐、氧代脂肪酸、石蜡、低分子量的聚烯烃、脂肪酰胺、亚烷基双脂肪酰胺、脂肪族酮、脂肪酸部分皂化酯、脂肪酸低级醇酯、脂肪酸多元醇酯、脂肪酸聚乙醇酯和改性有机硅等。
作为脂肪酸,可以举出:油酸、硬脂酸、月桂酸、羟基硬脂酸、山萮酸、花生四烯酸、亚油酸、亚麻酸、蓖麻醇酸、棕榈酸、褐煤酸和它们的混合物等碳数6~40的脂肪酸。作为脂肪酸金属盐,可以举出:月桂酸钠、月桂酸钾、月桂酸镁、月桂酸钙、月桂酸锌、月桂酸钡、硬脂酸钠、硬脂酸钾、硬脂酸镁、硬脂酸钙、硬脂酸锌、硬脂酸钡、山萮酸钠、山萮酸钾、山萮酸镁、山萮酸钙、山萮酸锌、山萮酸钡、褐煤酸钠和褐煤酸钙等碳数6~40的脂肪酸的碱(土)金属盐。
作为氧代脂肪酸,可以举出:1,2-氧代硬脂酸等。
作为石蜡,可以举出:液体石蜡、天然石蜡、微晶蜡和凡士林等碳数18以上的石蜡。
作为低分子量的聚烯烃,可以举出:聚乙烯蜡、马来酸改性聚乙烯蜡、氧化型聚乙烯蜡、氯化聚乙烯蜡和聚丙烯蜡等分子量5000以下的聚烯烃。作为脂肪酰胺,具体而言可以举出:油酰胺、芥酰胺、山萮酰胺等碳数6以上的脂肪酰胺。
作为亚烷基双脂肪酰胺,可以举出:亚甲基双硬脂酰胺、亚乙基双硬脂酰胺和N,N-双(2-羟基乙基)硬脂酰胺等碳数6以上的亚烷基双脂肪酰胺。
作为脂肪族酮,可以举出:高级脂肪族酮等碳数6以上的脂肪族酮。 作为脂肪酸部分皂化酯,可以举出:褐煤酸部分皂化酯等。
作为脂肪酸低级醇酯,可以举出:硬脂酸酯、油酸酯、亚油酸酯、亚麻酸酯、己二酸酯、山萮酸酯、花生四烯酸酯、褐煤酸酯和异硬脂酸酯等。
作为脂肪酸多元醇酯,可以举出:丙三醇三硬脂酸酯、丙三醇二硬脂酸酯、丙三醇单硬脂酸酯、季戊四醇四硬脂酸酯、季戊四醇三硬脂酸酯、季戊四醇二肉豆蔻酸酯、季戊四醇单硬脂酸酯、季戊四醇己二酸酯硬脂酸酯和失水山梨醇单山萮酸酯等。
作为脂肪酸聚乙醇酯,可以举出:聚乙二醇脂肪酸酯、聚三亚甲基二醇脂肪酸酯和聚丙二醇脂肪酸酯等。
作为改性有机硅,可以举出:聚醚改性有机硅、高级脂肪酸烷氧基改性有机硅、含有高级脂肪酸的有机硅、高级脂肪酸酯改性有机硅、甲基丙烯酸类改性有机硅和氟改性有机硅等。
作为固化用催化剂,可以举出:(过氧化苯甲酸叔丁酯、过氧化苯甲酰、过氧化甲乙酮等)和偶氮化合物(偶氮二异丁腈和偶氮二异戊腈等)等有机过氧化物、辛基酸锡、二丁基锡二(2-乙基己酸酯)、二辛基锡二(2-乙基己酸酯)、二辛基锡二乙酸酯、二丁基锡二月桂酸酯、二辛基锡二月桂酸酯、二丁基氧化锡、二辛基氧化锡、二丁基锡脂肪酸盐、2-乙基己酸铅、辛酸锌、环烷酸锌、脂肪酸锌类、环烷酸钴、辛酸钙、环烷酸铜、2-乙基己酸铅辛酸铅和四正丁基钛酸酯等金属与有机和无机酸的盐等有机金属衍生物、盐酸、硝酸、硫酸等无机酸、对甲苯磺酸、十二烷基苯磺酸、二壬基萘磺酸、二壬基萘二磺酸等磺酸化合物、磺酸化合物的胺中和物、三乙基胺等有机胺、磷酸、焦磷酸等、磷酸单酯或磷酸二酯等。作为磷酸单酯,例如可以举出:磷酸单辛酯、磷酸单丙酯和磷酸单月桂酯等。作为磷酸二酯,例如可以举出:磷酸二辛酯、磷酸二丙酯和磷酸二月桂酯等。进而,可以举出:单(2-(甲基)丙烯酰氧基乙基)酸式磷酸酯等磷酸化合物、二氮杂双环十一碳烯系催化剂、路易斯酸和酸酐等。
作为光聚合引发剂,可以举出:羟基苯甲酰化合物(2-羟基-2-甲基-1-苯基丙烷-1-酮、1-羟基环己基苯基酮、苯偶姻烷基醚等)、苯甲酰甲酸酯化合物(甲基苯甲酰甲酸酯等)、噻吨酮化合物(异丙基噻吨酮等)、二苯甲酮化合物(二苯甲酮等)、磷酸酯化合物(1,3,5-三甲基苯甲酰二苯基氧化膦等)和苯偶酰二甲基缩酮等。
进而,通过将本发明的发射白光的长余辉荧光粉配混于涂料从而也可以制成本发明的长余辉发光性涂料组合物。
本发明的长余辉发光性涂料组合物可以涂布其他材料的表面。
另外,含有本发明的发射白光的长余辉荧光粉的本发明的长余辉发光性涂料组合物的发光亮度高,因此可以进行可视性高的涂装。
作为涂料组合物,可以使用含有覆膜形成性树脂的涂料组合物。涂料组合物中,根据需要也可以含有:溶剂、分散剂、填充剂、增稠剂、流平剂、固化剂、交联剂、颜料、消泡剂、抗氧化剂、包含紫外线吸收剂的光稳定剂、阻燃剂、固化用催化剂、杀菌剂和抗菌剂等涂料用添加剂。
作为涂料组合物中使用的材料,也可以使用热固性树脂、常温固化性树脂、紫外线固化性树脂、辐射线固化性树脂等各种树脂,例如可以举出:丙烯酸类树脂、醇酸树脂、聚氨酯树脂、聚酯树脂、氨基树脂等、有机硅酸酯、有机钛酸酯等。
作为墨膜形成材料,可以举出:聚氨酯树脂、丙烯酸类树脂、聚酰胺树脂、氯乙烯-乙酸乙烯酯树脂和氯化丙烯树脂等。
作为溶剂,可以举出:脂肪族烃类、芳香族烃(C7~10、例如甲苯、二甲苯和乙基苯)、酯或醚酯(C4~10、例如甲氧基丁基乙酸酯)、醚(C4~10、例如四氢呋喃、EG的单乙基醚、EG的单丁基醚、PG的单甲基醚和DEG的单乙基醚)、酮(C3~10、例如甲基异丁基酮、二正丁基酮)、醇(C1~10、例如甲醇、乙醇、正丙醇和异丙醇、正丁醇、异丁醇、仲丁醇和叔丁醇、2-乙基己基醇)、酰胺(C3~6、例如二甲基甲酰胺、二甲基乙酰胺、N-甲基吡咯烷酮等)、亚砜(C2~4、例如二甲基亚砜)、和它们的2种以上的混合溶剂、水或前述混合溶剂等。作为分散剂,只要为高分子分散剂即可,可以举出:萘磺酸盐[碱金属(Na和K等)盐、铵盐等]的福尔马林缩合物、聚苯乙烯磺酸盐(与上述相同)、聚丙烯酸盐(与上述相同)、聚(2~4)羧酸(马来酸/甘油/单烯丙基醚共聚物等)盐(与上述相同)、羧甲基纤维素(Mn2000~10000)和聚乙烯醇(Mn2000~100000)等。
作为低分子分散剂,可以举出下述物质。
(1)聚氧亚烷基型
脂肪族醇(C4~30)、[烷基(C1~30)]苯酚、脂肪族(C4~30)胺和脂肪族(C4~30)酰胺的AO(C2~4)1~30摩尔加成物。
作为脂肪族醇,有正丁醇、异丁醇、仲丁醇和叔丁醇、辛醇、十二烷醇等;作为(烷基)苯酚,有苯酚、甲基苯酚和壬基苯酚等;作为脂肪族胺,有月桂基胺和甲基硬脂基胺等;和作为脂肪族酰胺,有硬脂酰胺等。
(2)多元醇型
C4~30的脂肪酸(月桂酸、硬脂酸等)与多元(2~6或其以上)醇(例如GR、PE、山梨糖醇和失水山梨醇)的单酯化合物。
(3)羧酸盐型
C4~30的脂肪酸(与上述相同)的碱金属(与上述相同)盐。
(4)硫酸酯型
C4~30的脂肪族醇(与上述相同)和脂肪族醇的AO(C2~4)1~30摩尔加成物的硫酸酯碱金属(与上述相同)盐等。
(5)磺酸盐型
[烷基(C1~30)]苯酚(与上述相同)的磺酸碱金属(与上述相同)盐。
(6)磷酸酯型
C4~30的脂肪族醇(与上述相同)和脂肪族醇的AO(C2~4)1~30摩尔加成物的单磷酸酯或二磷酸酯的盐[碱金属(与上述相同)盐、季铵盐等]。
(7)伯~叔胺盐型
C4~30的脂肪族胺[伯胺(月桂基胺等)、仲胺(二丁基胺等)和叔胺(二甲基硬脂基胺等)]盐酸盐、三乙醇胺与C4~30的脂肪酸(与上述相同)的单酯的无机酸(盐酸、硫酸、硝酸和磷酸等)盐。
(8)季铵盐型
C4~30的季铵(丁基三甲基铵、二乙基月桂基甲基铵、二甲基二硬脂基铵等)的无机酸(与上述相同)盐等。
作为无机分散剂,可以举出:多磷酸的碱金属(与上述相同)盐和磷酸系分散剂(磷酸、单烷基磷酸酯和二烷基磷酸酯等)等。
作为填充剂,可以举出:以二氧化硅、氧化铝、氧化锆、云母为代表的氧化物系无机物、碳化硅、氮化硅等非氧化物系无机物的微粉、或丙烯酸类树脂、氟树脂等有机化合物。另外,根据用途还可以添加铝、锌、铜等金属粉末。进而,作为填充剂的具体例,可以举出:二氧化硅溶胶、氧化锆溶胶、氧化铝溶胶、二氧化钛溶胶等溶胶;硅砂、石英、均密石英盐、硅藻土等二氧化硅系物质;合成无定形二氧化硅;高岭石、云母、滑石、硅灰石、石棉、硅酸钙、硅酸铝等硅酸盐;玻璃粉末、玻璃球、中空玻璃球、玻璃鳞片、泡玻璃球等玻璃体;氮化硼、碳化硼、氮化铝、碳化铝、氮化硅、碳化硅、硼化钛、氮化钛、碳化钛等非氧化物系无机物;碳酸钙;氧化锌、氧化铝、氧化镁、氧化钛、氧化铍等金属氧化物:硫酸钡、二硫化钼、二硫化钨、氟化碳等无机物;铝、青铜、铅、不锈钢、锌等金属粉末;和炭黑、焦炭、石墨、热分解碳、中空碳球等碳体等。
作为增稠剂,可以举出:蒙脱石系粘土矿物、包含这些矿物的膨润土、胶体状氧化铝等无机填充剂系增稠剂、甲基纤维素、羧甲基纤维素、己基甲基纤维素、羟乙基纤维素、羟丙基纤维素等纤维素系增稠剂、聚氨酯树脂系增稠剂、聚乙烯醇、聚乙烯吡咯烷酮、聚乙烯苄基醚共聚物等聚乙烯系增稠剂、聚醚二烷基酯、聚醚二烷基醚、聚醚环氧改性物等聚醚树脂系增稠剂、氨基甲酸酯改性聚醚系等缔合型增稠剂、聚醚多元醇系聚氨酯树脂系等特殊高分子非离子型增稠剂、非离子系等表面活性剂系增稠剂、酪素、酪素酸钠、酪素酸铵等蛋白质系增稠剂、和藻酸钠等丙烯酸系增稠剂等。
作为流平剂,可以举出:PEG型非离子表面活性剂(壬基苯酚EO1~40摩尔加成物、硬脂酸EO1~40摩尔加成物等)、多元醇型非离子表面活性剂(失水山梨醇棕榈酸单酯、失水山梨醇硬脂酸单酯、失水山梨醇硬脂酸三酯等)、含氟表面活性剂(全氟烷基EO1~50摩尔加成物、全氟烷基羧酸盐、全氟烷基甜菜碱等)、和改性硅油[聚醚改性硅油、(甲基)丙烯酸酯改性硅油等]等。
对于固化剂,作为多元醇类的固化剂,可以举出:六亚甲基二异氰酸酯、三甲基六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、氢化二苯基甲烷二异氰酸酯、二苯基甲烷二异氰酸酯、苯二甲撑二异氰酸酯、氢化苯二甲撑二异氰酸酯、甲代亚苯基二异氰酸酯、氢化甲代亚苯基二异氰酸酯、赖氨酸二异氰酸酯、多异氰酸酯化合物的nurate体、buret体、多异氰酸酯化合物与乙二醇、丙二醇、三羟甲基丙烷那样的多元醇的加成体、经过嵌段化的多异氰酸酯固化剂等单体或2种以上的混合物、它们的多元醇加成物、它们的共聚物、嵌段聚合物等那样在常温下能够固化的异氰酸酯类。作为环氧树脂类的固化剂,可以举出:酸酐、酚醛树脂、聚酰胺树脂、胺加成物、尿素树脂、三聚氰胺树脂和异氰酸酯类等。
作为交联剂,可以举出:三聚氰胺树脂、尿素树脂、多异氰酸酯化合物、嵌段多异氰酸酯化合物、环氧化合物或树脂、含羧基化合物或树脂、酸酐、含烷氧基硅烷基化合物或树脂、以及六甲氧基甲基化三聚氰胺、N,N,N’,N’-四羟基甲基琥珀酰胺、四甲氧基甲基化尿素、2,4,6-四羟基甲基化苯酚等具有羟基甲基、和甲氧基甲基、或乙氧基甲基等的化合物。
作为颜料,除了前述颜料以外,还可以举出:五氧化钒、钒酸钙、钒酸镁和偏钒酸铵等钒化合物;磷酸镁、磷酸镁·铵共析物、磷酸一氢镁、磷酸二氢镁、磷酸镁·钙共析物、磷酸镁·钴共析物、磷酸镁·镍共析物、亚磷酸镁、亚磷酸镁·钙共析物、三多磷酸二氢铝、三多磷酸镁、三多磷酸二氢铝的氧化镁处理物、三多磷酸二氢锌的氧化镁处理物等磷酸金属盐的含镁化合物的处理物、进而二氧化硅改性磷酸镁等那样的磷酸镁的二氧化硅改性化合物等磷酸盐系防锈颜料;磷酸锌等含有锌成分的防锈颜料、镁处理三多磷酸二氢铝、钙处理磷酸钙等无锌防锈颜料;包含正硅酸钙成分或偏硅酸钙成分的复合硅酸钙等硅酸钙;钙离子交换二氧化硅、镁离子交换二氧化硅等金属离子交换二氧化硅;和包含六价铬、铅等的防锈颜料等。
作为消泡剂,例如可以举出:硅油、二甲基聚硅氧烷、有机改性聚硅氧烷、氟改性聚硅氧烷等有机硅系消泡剂、矿物油系消泡剂、非有机硅·聚合物系消泡剂、包含选自有机改性氟化合物和聚氧亚烷基化合物中的至少1种的消泡剂、以及包含碳数18以上的脂肪族醇的消泡剂等。
对于抗氧化剂、包含紫外线吸收剂的光稳定剂、阻燃剂、固化用催化剂、杀菌剂、和抗菌剂等,可以举出前述物质。
附图说明
图1为本发明提供的实施例1~3样品的发射光谱;
图2为本发明提供的实施例4~6样品的发射光谱;
图3为本发明提供的实施例1~3样品的余辉强度测试结果;
图4为本发明提供的实施例4~6样品的余辉强度测试结果。
具体实施方式
下面结合附图1-4和具体实施例对本发明作进一步详细说明。
实施例1
一种发射白光的长余辉荧光粉,化学组成为Sr0.99Al1.5B0.5SiO6: 0.01Dy3+。
制备过程:以高纯度的SrCO3、Al2O3、SiO2、H3BO3和Dy2O3作为原料,按照化学组成Sr0.99Al1.5B0.5SiO6: 0.01Dy3+中各元素的配比,精确称取各原料;将各原料同时放入玛瑙研钵中,并通过手工研磨的方式将其混合均匀,每个样品的研磨时间为30min;将上述混合均匀的原料放入刚玉坩埚,并在高温管式炉中进行烧结,烧结温度为1100℃,烧结时间为4小时,升温速率为10℃/min,烧结气氛为空气气氛,烧结完成后随炉冷却至室温,获得烧结体;将获得的烧结体进行研磨粉碎,即得一种发射白光的长余辉荧光粉。
实施例2
一种发射白光的长余辉荧光粉,化学组成为Sr0.98Al1.2B0.8SiO6: 0.02Dy3+。
制备过程:以高纯度的SrCO3、Al2O3、SiO2、H3BO3和Dy2O3作为原料,按照化学组成Sr0.98Al1.2B0.8SiO6: 0.02Dy3+中各元素的配比,精确称取各原料;将各原料同时放入玛瑙研钵中,并通过手工研磨的方式将其混合均匀,每个样品的研磨时间为20min;将上述混合均匀的原料放入刚玉坩埚,并在高温管式炉中进行烧结,烧结温度为1000℃,烧结时间为6小时,升温速率为10℃/min,烧结气氛为空气气氛,烧结完成后随炉冷却至室温,获得烧结体;将获得的烧结体进行研磨粉碎,即得一种发射白光的长余辉荧光粉。
实施例3
一种发射白光的长余辉荧光粉,化学组成为Sr0.94AlBSiO6: 0.06Dy3+。
制备过程:以高纯度的SrCO3、Al2O3、SiO2、H3BO3和Dy2O3作为原料,按照化学组成Sr0.94AlBSiO6: 0.06Dy3+中各元素的配比,精确称取各原料;将各原料同时放入玛瑙研钵中,并通过手工研磨的方式将其混合均匀,每个样品的研磨时间为25min;将上述混合均匀的原料放入刚玉坩埚,并在高温管式炉中进行烧结,烧结温度为1300℃,烧结时间为4小时,升温速率为10℃/min,烧结气氛为空气气氛,烧结完成后随炉冷却至室温,获得烧结体;将获得的烧结体进行研磨粉碎,即得一种发射白光的长余辉荧光粉。
实施例4
一种发射白光的长余辉荧光粉,化学组成为Sr0.92Al0.5B1.5SiO6: 0.08Dy3+。
制备过程:以高纯度的SrCO3、Al2O3、SiO2、H3BO3和Dy2O3作为原料,按照化学组成Sr0.92Al0.5B1.5SiO6: 0.08Dy3+中各元素的配比,精确称取各原料;将各原料同时放入玛瑙研钵中,并通过手工研磨的方式将其混合均匀,每个样品的研磨时间为20min;将上述混合均匀的原料放入刚玉坩埚,并在高温管式炉中进行烧结,烧结温度为1300℃,烧结时间为2小时,升温速率为10℃/min,烧结气氛为空气气氛,烧结完成后随炉冷却至室温,获得烧结体;将获得的烧结体进行研磨粉碎,即得一种发射白光的长余辉荧光粉。
实施例5
一种发射白光的长余辉荧光粉,化学组成为Sr0.9Al0.8B1.2SiO6: 0.1Dy3+。
制备过程:以高纯度的SrCO3、Al2O3、SiO2、H3BO3和Dy2O3作为原料,按照化学组成Sr0.9Al0.8B1.2SiO6: 0.1Dy3+中各元素的配比,精确称取各原料;将各原料同时放入玛瑙研钵中,并通过手工研磨的方式将其混合均匀,每个样品的研磨时间为30min;将上述混合均匀的原料放入刚玉坩埚,并在高温管式炉中进行烧结,烧结温度为1200℃,烧结时间为3小时,升温速率为10℃/min,烧结气氛为空气气氛,烧结完成后随炉冷却至室温,获得烧结体;将获得的烧结体进行研磨粉碎,即得一种发射白光的长余辉荧光粉。
实施例6
一种发射白光的长余辉荧光粉,化学组成为Sr0.96Al1.3B0.7SiO6: 0.04Dy3+。
制备过程:以高纯度的SrCO3、Al2O3、SiO2、H3BO3和Dy2O3作为原料,按照化学组成Sr0.96Al1.3B0.7SiO6: 0.04Dy3+中各元素的配比,精确称取各原料;将各原料同时放入玛瑙研钵中,并通过手工研磨的方式将其混合均匀,每个样品的研磨时间为25min;将上述混合均匀的原料放入刚玉坩埚,并在高温管式炉中进行烧结,烧结温度为1250℃,烧结时间为4小时,升温速率为10℃/min,烧结气氛为空气气氛,烧结完成后随炉冷却至室温,获得烧结体;将获得的烧结体进行研磨粉碎,即得一种发射白光的长余辉荧光粉。
图1和图2分别为本发明提供的实施例1~3和实施例4~6的发射光谱图,激发波长为350nm,从图中可以看出,所有样品的发射光谱由两个发射峰组成,其峰值波长分别位于470nm的蓝光和573nm的黄光区域,通过改变Dy3+离子的掺杂浓度及Al和B之间的元素比,可以调控光谱中蓝光和黄光的组成比例,以获得不同色温的白光。
图3和图4分别为实施例1~3和实施例4~6的余辉强度测试结果,余辉监控波长为573nm的黄光,从图中可以看出,Dy3+离子的掺杂浓度及Al和B之间的元素比对样品的初始荧光强度及余辉强度和余辉时间均由重要影响,通过Al和B元素之间相互取代引起晶格缺陷,为Dy3+发光提供缺陷能级,有效增强其白光长余辉发光效果。
Claims (2)
1. 一种发射白光的长余辉荧光粉,其特征在于,所述荧光粉的化学组成通式为Sr(Al2-y By)SiO6: xDy3+,x和y的取值范围分别为:0.01≤x≤0.1,0.5≤y≤1.5。
2.一种发射白光的长余辉荧光粉的制备方法,其特征在于包括以下步骤:
(1)以高纯度的SrCO3、Al2O3、SiO2、H3BO3和Dy2O3作为原料,按照化学组成通式Sr1-x Al2- y BySiO6: xDy3+,中各元素的配比,精确称取各原料;
(2)将各原料同时放入玛瑙研钵中,并通过手工研磨的方式将其混合均匀,每个样品的研磨时间为20~30min;
(3)将上述混合均匀的原料放入刚玉坩埚,并在高温管式炉中进行烧结,烧结温度为1000~1300℃,烧结时间为2~6小时,升温速率为10℃/min,烧结气氛为空气气氛,烧结完成后随炉冷却至室温,获得烧结体;
(4)将步骤(3)获得的烧结体进行研磨粉碎,即得所述发射白光的长余辉荧光粉。
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CN113755171A (zh) * | 2021-09-23 | 2021-12-07 | 五邑大学 | 一种宽带发射红外荧光粉及其制备方法 |
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