CN1204226C - 涂覆有防潮层的发红光磷光体 - Google Patents
涂覆有防潮层的发红光磷光体 Download PDFInfo
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- CN1204226C CN1204226C CNB998120723A CN99812072A CN1204226C CN 1204226 C CN1204226 C CN 1204226C CN B998120723 A CNB998120723 A CN B998120723A CN 99812072 A CN99812072 A CN 99812072A CN 1204226 C CN1204226 C CN 1204226C
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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
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/567—Chalcogenides with alkaline earth metals
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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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
- C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
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- 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
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- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
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Abstract
将一种粘附的、透明的防潮层涂覆至碱土硫化物磷光体颗粒上,其是通过在含有浓度不超过0.02摩尔的氟化剂化合物的无水极性溶剂中搅拌直至透明含氟防潮涂层涂覆至所述颗粒上。将极性溶剂除去并干燥经涂层后的颗粒。也可涂覆第二个防潮层以确保磷光体对潮气降解的长期耐受性。
Description
本申请要求1998年10月15日递交的临时申请60/104,368作为优先权。
本发明涉及制备防潮的发红光磷光体的方法。更具体地说,本发明涉及对发红光磷光体颗粒进行涂层以提供防潮性的方法。
发明背景
据目前所知发红光磷光体是稀有的,且它们不具有长余辉。Royce等人的US5,650,094公开了稀土活化的二价钛酸盐磷光体,如CaTiO3或Ca-Zn-Mg-TiO3,但是它们只能发几分钟可见光。Lindmayer在US5043096中报道了一种用三种稀土以其氧化物形式活化且与一种卤化物如LiF混熔的硫化锶基磷光体。然而这种焙烧后的氟化物磷光体是被高度烧结的,必须粉碎以得到可用的粉末原料。然而粉碎使其发光能力减弱,因此该磷光体必须加热或退火以修补结晶缺陷。然而其发光能力无法完全恢复。据称,这些磷光体适用于油漆配方中。
碱土硫化物,例如硫化钙、硫化锶、硫化镁和硫化钡,具有长余辉,但它们在暴露与潮气之后发生降解。硫化钙与水具有最低反应性,而硫化钡与水具有最高反应性。当暴露于高湿度空气中或含水的液体中时,硫化物发生降解。这些材料可用于制备发光材料例如磷光体。然而,因为它们对湿气的敏感性,它们作为磷光体的应用是受限制的。它们必须用聚合物或塑料进行包封,或与防水材料例如涂料进行混合以改进它们的防潮性。
长余辉发红光磷光体例如硫化钙或硫化锶是用二价稀土元素铕和三价稀土元素例如镨(Pr)、钕(Nd)、钐(Sm)、铈(Ce)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)和镥(Lu)进行活化。类似的但不具有长余辉特性的磷光体是可用于电场致发光器件和阴极射线管中。然而显示器件中的长余辉引起移动物体的轮廓模糊。
如Yocom等人在US4,725,344所述,这些磷光体可通过如下方法制得:将碱土金属卤化物和活化剂加热至卤化物的熔融温度,并将熔融卤化物与硫化氢接触。所得碱土金属硫化物在较低温度下可制成密实的、高结晶的层。由此这种方法可在玻璃基材上形成磷光体薄膜。
粉末状卤化物磷光体可与延缓磷光体的烧结以形成粉末状磷光体的粉末状氧化铝混合。可将这个粉末添加至包封或包裹该磷光体以保护它们不受潮气影响的基体材料中,例如粉末状或熔融的塑料、纤维等中。
活化的硫化锶磷光体也可通过在约1200℃从碳源上通过汽化硫而焙烧成。这种方法形成一个二硫化碳气氛。得到微细粒径的磷光体。
长余辉磷光体指的是磷光体材料的光谱发射,这种材料在用光激发后,移走光源后,发射几个小时红色或橙红色光线。此种磷光体具有许多用途且例如对安全设备是极其受欢迎的。
因此一直在寻找用于发红光磷光体的有效防潮阻隔层。大多数有机材料例如聚合物和塑料是透水的,所以它们是不能单独形成持久的磷光体防潮涂层。也曾尝试过从含水介质中涂覆氟化物涂层,但它们可降低磷光体的发光性能。由此极其需要一种涂覆碱土类磷光体颗粒的方法,其提供防潮层但不降低磷光体颗粒的发光性能。
发明综述
将碱土磷光体分散在含有低浓度的反应性氟化物的极性无水溶剂中以在磷光体颗粒上涂布粘附的、透明的氟化物涂层。该涂层不降低磷光体的发光性能。在暴露之后,用纯净无水溶剂洗涤磷光体颗粒并干燥。所得的磷光体颗粒具有极佳的长期稳定性。
发明的详细描述
基于碱土硫化物的磷光体,例如硫化锶、硫化钡和硫化钙具有许多极佳的性能,特别是发出长余辉红光。然而,尽管需要此种磷光体,但它们的应用是受限制的,因为当它们暴露至潮气下发生降解。曾提议将磷光体颗粒嵌入至塑料中,但是因为所有塑料均是稍微透过水分的,因此这在商业上不是可行的方案。其它涂层是不透明的,且由此将降低发光性能或甚至降低磷光体的显色。
由此根据本发明的方法,通过将发红光的磷光体颗粒分散在含有低浓度的反应性氟化物的无水极性溶剂中从而将透明的氟化物涂层涂覆至该颗粒上。
合适的反应性氟化物可选自于氟化铵(NH4F)、二氟氢铵(NH4HF2)、氟代硅酸铵(NH4SiO3F)等。这些氟化物可溶解在无水有机极性溶剂中且添加量为使形成的氟化物浓度最高为约10-2M,且优选是低于约10-3M的溶液。酸性氟化物,例如氟化铵可与硫化物磷光体反应形成对应的氟化物,但是通过保持低浓度的氟化物,使得氟化物和硫化物磷光体颗粒之间的反应足够慢以致于形成氟化物涂层而不明显地破坏硫化物磷光体。
将约10重量份硫化物磷光体适当地分散在添加了氟化铵或其它合适氟化剂的无水极性溶剂中以达到约0.001摩尔浓度。温和地搅拌分散体约10分钟,且将溶剂除去。用纯净的溶剂洗涤这些刚涂层磷光体颗粒一次或多次并干燥。如果需要,可重复这个涂层方法,或可将其它有机类材料涂覆至磷光体颗粒上以得到对潮气降解的耐受性。
优选的极性溶剂包括具有通式R-OH的溶剂,其中R是最高为8个碳原子的烷基或链烯基。最优选的溶剂是甲醇和乙醇。
按这种方式涂覆至磷光体颗粒上的氟化物涂层是很透明的、不溶解的材料,其涂覆和保护磷光体颗粒免于潮气降解,且不影响该磷光体的发光性能。
也可在含氟涂层上涂覆透明有机材料的第二个涂层,例如丙烯酸酯等的透明聚合物涂层。
虽然以上就特定的溶剂和氟化物浓度对本发明的方法进行了描述,但正如本领域熟练人员所知,也意欲将其它溶剂和氟化剂以及其它氟化物浓度在此包括。本发明意欲仅受所附权利要求书的范围的限制。
Claims (10)
1、一种对发红光的碱土硫化物磷光体颗粒进行处理以提供防潮性的方法,其包括:
(a)将所述磷光体颗粒分散在无水极性有机溶剂中,该有机溶剂含有摩尔浓度为0.01摩尔/升以下的溶解的氟化剂,该氟化剂是酸性氟化物;
(b)将所得的分散体搅拌足够长的时间以在磷光体颗粒上形成防潮的氟化涂层;和
(c)除去溶剂和多余的氟化剂;
其中所述碱土硫化物中的碱土金属是钙、锶或钡。
2、根据权利要求1的方法其中氟化剂化合物的摩尔浓度是0.001摩尔/升以下。
3、根据权利要求1的方法,其中所述碱土硫化物中的碱土金属是钙或锶。
4、根据权利要求1的方法,其中所述溶剂是通式为ROH的醇,其中R是最高为8个碳原子的烷基或链烯基。
5、根据权利要求4的方法,其中R是甲基。
6、根据权利要求4的方法,其中R是乙基。
7、根据权利要求1的方法,其中在用氟化剂涂覆磷光体颗粒之后,用另外的无水极性溶剂洗涤该颗粒。
8、根据权利要求1的方法,其中所述酸性氟化物是氟化铵、二氟氢铵或氟代硅酸铵。
9、根据权利要求1的方法,其中在将氟化物涂层施加至磷光体颗粒上之后,在其上涂覆一个透明的有机聚合物涂层。
10、根据权利要求9的方法,其中所述透明有机聚合物涂层是含有丙烯酸酯的聚合物。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10436898P | 1998-10-15 | 1998-10-15 | |
US60/104,368 | 1998-10-15 |
Publications (2)
Publication Number | Publication Date |
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CN1323336A CN1323336A (zh) | 2001-11-21 |
CN1204226C true CN1204226C (zh) | 2005-06-01 |
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Application Number | Title | Priority Date | Filing Date |
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CNB998120723A Expired - Fee Related CN1204226C (zh) | 1998-10-15 | 1999-10-15 | 涂覆有防潮层的发红光磷光体 |
Country Status (10)
Country | Link |
---|---|
US (1) | US6346326B1 (zh) |
EP (1) | EP1124913B1 (zh) |
JP (1) | JP2002527570A (zh) |
KR (1) | KR20010075615A (zh) |
CN (1) | CN1204226C (zh) |
AT (1) | ATE407989T1 (zh) |
AU (1) | AU1113600A (zh) |
DE (1) | DE69939546D1 (zh) |
TW (1) | TWI237053B (zh) |
WO (1) | WO2000022065A1 (zh) |
Families Citing this family (20)
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US6787988B2 (en) * | 2001-11-13 | 2004-09-07 | Durel Corporation | Process for treating previously coated phosphor particles |
US6734466B2 (en) * | 2002-03-05 | 2004-05-11 | Agilent Technologies, Inc. | Coated phosphor filler and a method of forming the coated phosphor filler |
EP1659306B1 (de) | 2004-11-23 | 2008-11-12 | BorgWarner Inc. | Reiblamelle sowie Verfahren zum Einbringen einer Nut in den Reibbelag einer Reiblamelle |
DE102009044255A1 (de) | 2009-10-15 | 2011-04-28 | Leuchtstoffwerk Breitungen Gmbh | Erdalkalimetallsilikat-Leuchtstoffe und Verfahren zur Verbesserung ihrer Langzeitstabilität |
US8057706B1 (en) * | 2010-07-27 | 2011-11-15 | General Electric Company | Moisture-resistant phosphor and associated method |
DE102010034322A1 (de) | 2010-08-14 | 2012-02-16 | Litec-Lp Gmbh | Oberflächenmodifizierter Silikatleuchtstoffe |
US9234129B2 (en) | 2010-08-14 | 2016-01-12 | Seoul Semiconductor Co., Ltd. | Surface-modified quantum dot luminophores |
US9196785B2 (en) | 2010-08-14 | 2015-11-24 | Seoul Semiconductor Co., Ltd. | Light emitting device having surface-modified quantum dot luminophores |
US9614129B2 (en) | 2010-08-14 | 2017-04-04 | Seoul Semiconductor Co., Ltd. | Light emitting device having surface-modified luminophores |
US8252613B1 (en) * | 2011-03-23 | 2012-08-28 | General Electric Company | Color stable manganese-doped phosphors |
CN103597054B (zh) | 2011-08-11 | 2015-03-18 | 三井金属矿业株式会社 | 红色荧光体和发光元件 |
WO2014065292A1 (ja) | 2012-10-23 | 2014-05-01 | 三井金属鉱業株式会社 | 蛍光体、led発光素子及び光源装置 |
WO2014128676A1 (en) * | 2013-02-25 | 2014-08-28 | Koninklijke Philips N.V. | A coated luminescent particle, a luminescent converter element, a light source, a luminaire and a method of manufacturing a coated luminescent particle |
US9871173B2 (en) | 2015-06-18 | 2018-01-16 | Cree, Inc. | Light emitting devices having closely-spaced broad-spectrum and narrow-spectrum luminescent materials and related methods |
KR102397910B1 (ko) | 2015-07-06 | 2022-05-16 | 삼성전자주식회사 | 불화물계 형광체, 불화물계 형광체 제조방법 및 발광장치 |
US10253257B2 (en) | 2015-11-25 | 2019-04-09 | Intematix Corporation | Coated narrow band red phosphor |
US10217907B2 (en) | 2016-02-29 | 2019-02-26 | Nichia Corporation | Method of producing nitride fluorescent material, nitride fluorescent material, and light emitting device using the same |
JP6443417B2 (ja) * | 2016-02-29 | 2018-12-26 | 日亜化学工業株式会社 | 窒化物蛍光体の製造方法、窒化物蛍光体及び発光装置 |
US10541353B2 (en) | 2017-11-10 | 2020-01-21 | Cree, Inc. | Light emitting devices including narrowband converters for outdoor lighting applications |
KR102454269B1 (ko) * | 2020-06-30 | 2022-10-14 | 욱성화학주식회사 | 가수분해 안정성이 향상된 축광성 형광체의 제조방법 |
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US2372071A (en) | 1942-01-26 | 1945-03-20 | Gen Electric | Luminescent material |
US2527365A (en) | 1945-05-22 | 1950-10-24 | Rca Corp | Doubly activated infrared phosphors |
US2522074A (en) | 1946-05-03 | 1950-09-12 | Univ Rochester | Method of rendering infrared radiation visible employing doubly activated alkaline earth sulfide phosphors |
US2521124A (en) | 1946-08-09 | 1950-09-05 | Neville F Miller | Infrared strontium sulfide phosphors |
US2979467A (en) | 1958-06-30 | 1961-04-11 | Ibm | Infrared stimulable phosphors |
US3617332A (en) | 1969-06-24 | 1971-11-02 | Westinghouse Electric Corp | Method for stabilizing alkaline-earth metal sulfide phosphors |
US3791844A (en) * | 1972-05-02 | 1974-02-12 | Radium Corp | Phosphors for multi-color displays |
GB1581830A (en) | 1976-06-01 | 1980-12-31 | Secr Defence | Phosphors |
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US5650094A (en) | 1995-06-06 | 1997-07-22 | Royce; Martin R. | Red emitting long decay phosphors |
-
1999
- 1999-03-10 US US09/266,062 patent/US6346326B1/en not_active Expired - Lifetime
- 1999-10-15 AT AT99954906T patent/ATE407989T1/de not_active IP Right Cessation
- 1999-10-15 EP EP99954906A patent/EP1124913B1/en not_active Expired - Lifetime
- 1999-10-15 JP JP2000575961A patent/JP2002527570A/ja active Pending
- 1999-10-15 DE DE69939546T patent/DE69939546D1/de not_active Expired - Fee Related
- 1999-10-15 TW TW088117869A patent/TWI237053B/zh not_active IP Right Cessation
- 1999-10-15 CN CNB998120723A patent/CN1204226C/zh not_active Expired - Fee Related
- 1999-10-15 WO PCT/US1999/023927 patent/WO2000022065A1/en not_active Application Discontinuation
- 1999-10-15 AU AU11136/00A patent/AU1113600A/en not_active Abandoned
- 1999-10-15 KR KR1020017004536A patent/KR20010075615A/ko not_active Application Discontinuation
Also Published As
Publication number | Publication date |
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JP2002527570A (ja) | 2002-08-27 |
EP1124913A1 (en) | 2001-08-22 |
US6346326B1 (en) | 2002-02-12 |
DE69939546D1 (de) | 2008-10-23 |
EP1124913B1 (en) | 2008-09-10 |
WO2000022065A1 (en) | 2000-04-20 |
AU1113600A (en) | 2000-05-01 |
CN1323336A (zh) | 2001-11-21 |
TWI237053B (en) | 2005-08-01 |
EP1124913A4 (en) | 2005-02-02 |
ATE407989T1 (de) | 2008-09-15 |
KR20010075615A (ko) | 2001-08-09 |
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