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Publication numberCN100333895 C
Publication typeGrant
Application numberCN 02827279
PCT numberPCT/US2002/037246
Publication date29 Aug 2007
Filing date19 Nov 2002
Priority date20 Nov 2001
Also published asCN1615218A, US6833191, US7297404, US8003211, US8394497, US20040130045, US20050042452, US20080064789, US20090140207, US20120068219, WO2003043813A1
Publication number02827279.X, CN 02827279, CN 100333895 C, CN 100333895C, CN-C-100333895, CN02827279, CN02827279.X, CN100333895 C, CN100333895C, PCT/2002/37246, PCT/US/2/037246, PCT/US/2/37246, PCT/US/2002/037246, PCT/US/2002/37246, PCT/US2/037246, PCT/US2/37246, PCT/US2002/037246, PCT/US2002/37246, PCT/US2002037246, PCT/US200237246, PCT/US2037246, PCT/US237246
Inventors罗伯特G贝利斯
Applicant罗伯特G贝利斯
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Microencapsulated particles and process for manufacturing same
CN 100333895 C
Abstract  translated from Chinese
通过在成膜的可交联水解聚合物中对粒子进行微囊化,可制备抗湿气性有所改进且具有缓释性能的微囊化粒子。 In the film formation by hydrolysis of the crosslinkable polymer to microencapsulated particles can be prepared by moisture resistance and having improved release properties of microencapsulated particles.
Claims(31)  translated from Chinese
1.一种使电致发光物质微囊化的方法,其特征在于,所述的方法包括如下步骤:A.将成膜的可交联水解聚合物和该聚合物的有机非极性溶剂相混合,其中该溶剂不是该物质粒子的溶剂;B.搅拌该混合物,在溶剂中形成聚合物的溶液;C.在继续搅拌的条件下向该溶液中加入物质粒子,其中该物质粒子分散于溶液中;D.诱发溶液进行相分离,其中该聚合物由溶液中分离出,形成膜状的聚合物外壳,并包覆于每一物质粒子上;及E.在继续搅拌的条件下向该溶液中加入交联剂,其中每一物质粒子上的膜状外壳围绕每一物质粒子发生交联并硬化,由此,该微囊化的物质粒子与用其他成膜聚合物进行微囊化的物质粒子相比,对湿气的不渗透性有所改进。 An electroluminescent substances so that the method of microencapsulation, characterized in that the method comprises the steps of:. A crosslinkable hydrolyzable organic polymer and the polymer film forming a non-polar solvent phase mixing, wherein the solvent is not the solvent material particle;. B The mixture was stirred, solution of the polymer in a solvent is formed;. C material particles added to the solution under continued stirring, wherein the substance particles are dispersed in a solution in;. D solution induced phase separation, wherein the polymer separated out from the solution, forming a film of the polymer shell, and coated on each of the material particles; and E. Under continued stirring this solution adding a crosslinking agent, wherein the film-like shell material particles in each material particle on the surrounding each crosslinked and hardened, whereby the microencapsulated material particles and the film-forming polymer be microencapsulated with other substances Compared to the particles, for improved moisture impermeability.
2.根据权利要求1所述的方法,其特征在于,所述的物质是磷光体。 2. A method according to claim 1, wherein said substance is a phosphor.
3.根据权利要求1所述的方法,其特征在于,所述的物质是聚合物发光二极管。 3. The method according to claim 1, wherein said substance is a polymer light-emitting diodes.
4.根据权利要求1所述的方法,其特征在于,所述的物质是有机发光二极管。 4. The method according to claim 1, wherein said substance is an organic light emitting diode.
5.根据权利要求1-4中任一项所述的方法,其特征在于,所述的成膜的可交联水解聚合物是聚(乙烯-乙酸乙烯酯)。 5. A method according to any one of claims 1-4 claim, characterized in that the film-forming crosslinkable hydrolyzable polymer is said poly (ethylene - vinyl acetate).
6.根据权利要求1-4中任一项所述的方法,其特征在于,所述的有机非极性溶剂是甲苯。 6. The method according to any one of claims 1-4 claims, characterized in that said organic non-polar solvent is toluene.
7.根据权利要求1-4中任一项所述的方法,其特征在于,所述的相分离由加入棉子油,玉米油,亚麻子油,大豆油或二种或两种以上的此类油的混合物诱发。 7. The method as claimed in any one of claims 1-4, characterized in that the phase separation by added cottonseed oil, corn oil, linseed oil, soybean oil, or of two or more of the said a mixture of oils induced.
8.根据权利要求1-4中任一项所述的方法,其特征在于,所述的交联剂是二异氰酸酯或多异氰酸酯。 8. The method of any one of 1 to 4 according to claim, wherein said crosslinking agent is a diisocyanate or polyisocyanate.
9.根据权利要求1-4中任一项所述的方法,其特征在于,所述的交联剂是甲苯二异氰酸酯。 9. A method according to any one of claims 1-4 claims, characterized in that said cross-linking agent is toluene diisocyanate.
10.根据权利要求1-4中任一项所述的方法,其特征在于,所述的交联剂是甲苯二异氰酸酯-三羟甲基丙烷加合物。 10. A method according to any one of claims 1-4 claims, characterized in that said crosslinking agent is a toluene diisocyanate - trimethylolpropane adduct.
11.根据权利要求1-4中任一项所述的方法,其特征在于,所述的聚合物的水解程度为44%-46%。 11. A method according to any one of claims 1-4 claim, characterized in that the degree of hydrolysis of the polymer was 44% -46%.
12.根据权利要求1-4中任一项所述的方法,其特征在于,所述的各步骤是连续的。 12. The method according to any one of claims 1-4 claim, characterized in that each said step is continuous.
13.一种对湿气的不渗透性有所改进的微囊化电致发光物质,其特征在于,所述的微囊化电致发光物质由包括下述步骤的方法制备:A.将成膜的可交联水解聚合物和该聚合物的有机非极性溶剂相混合,其中该溶剂不是该物质粒子的溶剂;B.搅拌该混合物,在溶剂中形成聚合物的溶液;C.在继续搅拌的条件下向该溶液中加入物质粒子,其中该物质粒子分散于溶液中;D.诱发溶液进行相分离,其中该聚合物由溶液中分离出,形成膜状的聚合物外壳,并包覆于每一物质粒子上;及E.在继续搅拌的条件下向该溶液中加入交联剂,其中每一物质粒子上的膜状外壳围绕每一物质粒子发生交联并硬化,由此,该微囊化的物质粒子与用其他成膜聚合物进行微囊化的物质粒子相比,对湿气的不渗透性有所改进。 13. A method for improved moisture impermeability microencapsulated electroluminescent substances, characterized in that the microencapsulated electroluminescent substances by the method comprising the steps of preparing:. A will become crosslinkable hydrolyzable organic polymer and the polymer film is a non-polar solvent is mixed, wherein the solvent is not a solvent for the material particle;. B The mixture was stirred, solution of the polymer is formed in a solvent; C continued. Under stirring the solution was added material particles, wherein the material particles dispersed in the solution;. D solution induced phase separation, wherein the polymer is separated from the solution, forming a film of the polymer shell, and coated and E. To this solution was added under continued stirring crosslinking agent, wherein the film-like shell material particles in each material particle on the surrounding each crosslinked and hardened, whereby the; on each of the material particles microencapsulated material particle as compared with other film-forming polymer material particle be microencapsulated, for improved moisture impermeability.
14.根据权利要求13所述的微囊化电致发光物质,其特征在于,所述的成膜的可交联水解聚合物是聚(乙烯-乙酸乙烯酯)。 14. The microencapsulated electroluminescent material as claimed in claim 13, characterized in that the film-forming crosslinkable hydrolyzable polymer is said poly (ethylene - vinyl acetate).
15.根据权利要求13所述的微囊化电致发光物质,其特征在于,所述的有机非极性溶剂是甲苯。 15. The 13 of the microencapsulated electroluminescent substances claim, wherein said organic non-polar solvent is toluene.
16.根据权利要求13所述的微囊化电致发光物质,其特征在于,所述的相分离由加入棉子油,玉米油,亚麻子油,大豆油或二种或两种以上的此类油的混合物诱发。 16. The microencapsulated electroluminescent material as claimed in claim 13, characterized in that the phase separation by added cottonseed oil, corn oil, linseed oil, soybean oil, or two or more kinds of this a mixture of oils induced.
17.根据权利要求13所述的微囊化电致发光物质,其特征在于,所述的交联剂是二异氰酸酯或多异氰酸酯。 17. The microencapsulated electroluminescent material as claimed in claim 13, wherein said crosslinking agent is a diisocyanate or polyisocyanate.
18.根据权利要求17所述的微囊化电致发光物质,其特征在于,所述的交联剂是甲苯二异氰酸酯。 18. The microencapsulated electroluminescent material according to claim 17, wherein said cross-linking agent is toluene diisocyanate.
19.根据权利要求17所述的微囊化电致发光物质,其特征在于,所述的交联剂是甲苯二异氰酸酯-三羟甲基丙烷加合物。 19. The microencapsulated electroluminescent material according to claim 17, wherein said crosslinking agent is a toluene diisocyanate - trimethylolpropane adduct.
20.根据权利要求13所述的微囊化电致发光物质,其特征在于,所述的聚合物的水解程度为44%-46%。 20. The microencapsulated electroluminescent material as claimed in claim 13, wherein the degree of hydrolysis of the polymer was 44% -46%.
21.根据权利要求13所述的微囊化电致发光物质,其特征在于,所述的物质是磷光体。 21. The microencapsulated electroluminescent material as claimed in claim 13, wherein said substance is a phosphor.
22.根据权利要求13所述的微囊化电致发光物质,其特征在于,所述的物质是聚合物发光二极管。 22. The microencapsulated electroluminescent material as claimed in claim 13, wherein said substance is a polymer light-emitting diodes.
23.根据权利要求13所述的微囊化电致发光物质,其特征在于,所述的物质是有机发光二极管。 23. The microencapsulated electroluminescent material as claimed in claim 13, wherein said substance is an organic light emitting diode.
24.一种对湿气的不渗透性有所改进的微囊化电致发光物质,其特征在于,所述的微囊化物质被包括防潮湿性树脂的组合物包封,所述的防潮湿性树脂包括(a)成膜的可交联部分水解聚合物和(b)交联剂构成的混合物,其中所述的聚合物的水解程度为44%-46%。 24. A moisture impermeable improved microencapsulated electroluminescent substances, characterized in that the microencapsulated material is a composition comprising the encapsulated moisture wet resin, said moisture wet resin comprising (a) a crosslinkable film-forming polymer and a partially hydrolyzed mixture (b) a crosslinking agent, and wherein the degree of hydrolysis of the polymer is 44% -46%.
25.根据权利要求24所述的微囊化电致发光物质,其特征在于,所述成膜的可交联部分水解聚合物是聚(乙烯-乙酸乙烯酯)。 25. The microencapsulated electroluminescent material according to claim 24, wherein said film-forming crosslinkable polymer is partially hydrolyzed poly (ethylene - vinyl acetate).
26.根据权利要求24所述的微囊化电致发光物质,其特征在于,所述的交联剂是二异氰酸酯或多异氰酸酯。 26. The microencapsulated electroluminescent material according to claim 24, wherein said crosslinking agent is a diisocyanate or polyisocyanate.
27.根据权利要求24所述的微囊化电致发光物质,其特征在于,所述的交联剂是甲苯二异氰酸酯。 27. The microencapsulated electroluminescent material according to claim 24, wherein said cross-linking agent is toluene diisocyanate.
28.根据权利要求24所述的微囊化电致发光物质,其特征在于,所述的交联剂是甲苯二异氰酸酯-三羟甲基丙烷加合物。 28. The microencapsulated electroluminescent material according to claim 24, wherein said crosslinking agent is a toluene diisocyanate - trimethylolpropane adduct.
29.根据权利要求24所述的微囊化电致发光物质,其特征在于,所述的物质是磷光体。 29. The microencapsulated electroluminescent material according to claim 24, wherein said substance is a phosphor.
30.根据权利要求24所述的微囊化电致发光物质,其特征在于,所述的物质是直径为1-15,000微米的粒子。 30. The microencapsulated electroluminescent material according to claim 24, wherein said substance is 1-15,000 microns in diameter.
31.根据权利要求24所述的微囊化电致发光物质,其特征在于,所述的物质是直径为5-2500微米的粒子。 31. The microencapsulated electroluminescent material according to claim 24, wherein said substance having a diameter of 5-2500 microns.
Description  translated from Chinese
微囊化粒子及其制备方法 Microencapsulated particles and preparation method

技术领域 FIELD

本发明涉及微囊化粒子。 The present invention relates to microencapsulated particles. 更具体地,本发明涉及在电致发光应用中的微囊化粒子。 More particularly, the present invention relates to an electroluminescent applications microencapsulated particles. 本发明也涉及这些粒子的微囊化方法。 The present invention also relates to a method of microencapsulation of these particles.

本发明将具体以磷光体粒子的微囊化作详细说明。 The invention will be specific to the microcapsules turned phosphor particles in detail. 然而,应该理解到本发明也可用于其他粒子,如药物,有机溶剂,有机油,颜料,染料,环氧树脂,无机盐等的微囊化。 However, it should be understood that the present invention may also be used for other particles, such as drugs, organic solvents, organic oil, a pigment, a dye, an epoxy resin, an inorganic salt such as microencapsulated.

此外,本发明可用于聚合物(或聚合物的)发光二极管(也称作PLEDs)的微囊化及其用于有机发光二极管(或称作OLEDs)的微囊化。 Further, the present invention can be used in the polymer (or polymer) light-emitting diodes (also called PLEDs) microencapsulated and used in organic light emitting diodes (or called OLEDs) are microencapsulated.

在一般术语中,PLEDs是这样的薄膜显示器,其由在相距短距离的两个合适电极之间夹入一层无掺杂的共轭聚合物构成。 In general terms, PLEDs is such that the thin film display, which consists of between two suitable electrodes separated by a short distance sandwiching a layer of undoped conjugated polymer. 此聚合物在曝露于电时即发光。 The polymer that is luminescent when exposed to electricity. PLEDs能构成全光谱彩色显像器。 PLEDs can constitute a full spectrum of color imaging devices.

在一般术语中,OLEDs是这样的显像器装置,其在两个带电的电极夹入了碳-基膜,所述电极中一个为金属阴极,一个为透明阳极,通常为玻璃。 In general terms, OLEDs is such developing apparatus, in which two charged electrodes sandwiching the carbon - base film, the metal electrode is a cathode, an anode is transparent, usually glass. 有机膜由空穴注入层(hole-injection layer),空穴传输层(hole-transport layer),发光层及电子传输层构成。 The organic film is made of a hole injection layer (hole-injection layer), a hole transport layer (hole-transport layer), a light emitting layer and the electron transport layer. 当对OLED元件(cell)施加电压时,注入的正电荷和负电荷即在发光层内重组并产生电致发光。 When an OLED element (cell) voltage is applied, the injected positive and negative charges, that is, within the light emitting layer and produce recombinant electroluminescence.

发明背景微囊化粒子在现有技术中是公知的。 BACKGROUND OF THE INVENTION microencapsulated particles in the prior art are known. Bayless等于美国专利3,674,704号(1972)中揭示了一种于液体制造载体中一同制造微胶囊的方法,其中该胶囊含水或水溶液。 Bayless equal U.S. Patent (1972) No. 3,674,704 discloses a method for manufacturing a liquid carrier together producing microcapsules, wherein the capsule or aqueous solution. 该专利揭示了一种制造微胶囊的特殊方法,其中胶囊壁材料是聚(乙烯-醋酸乙烯酯),其发生狭窄的特定程度的水解(38-50%水解)。 This patent discloses a particular method of manufacturing the microcapsules, wherein the capsule wall material is poly (ethylene - vinyl acetate), with its narrow specific hydrolysis degree (38-50% hydrolysis) occurs.

Bayless的美国专利4,107,071号(1978)揭示了一种微胶囊,其具有被相对不渗透的致密性保护壁围绕的胶囊核材料,也揭示了制造此类微胶囊的方法。 Bayless U.S. Patent 4,107,071 (1978) discloses a microcapsule having a protective wall is relatively dense impermeable material around the core capsule, also discloses a process for producing such microcapsules.

使用液-液相分离法提供对胶囊核材料进行封装的胶囊壁材料的一般成囊方法于Miller等的美国专利3,155,590号;Powell等的美国专利3,415,758号;以及Wagner等的美国专利3,748,277号中有所公开。 Using liquid - liquid phase separation to provide a core capsule capsule wall material encapsulating material is generally a method in Miller et sac U.S. Patent No. 3,155,590; Powell et al, U.S. Patent No. 3,415,758; and Wagner et al, U.S. Patent No. 3,748,277 there is The disclosed.

其他的现有技术参考文献揭示了电致发光磷光体的胶囊化方法,例如参见Budd的美国专利5,968,698号(1999)。 Other prior art references discloses a method for encapsulating electrical actuation emitting phosphor, see, e.g., Budd U.S. Patent No. 5,968,698 (1999). 此外,现有技术揭示了用含二氧化硅的覆盖层对萤光粉进行包覆的方法,见Opitz等的美国专利5,744,233号(1998)。 In addition, the prior art discloses the use of silica-containing coating layer on the phosphor coating technique, see Opitz U.S. Patent No. 5,744,233, etc. (1998).

磷光体粒子有多种用途,如用于平板显像器及装饰品,阴极射线管,萤光照明固定装置等。 Phosphor particles have a variety of uses, such as for flat panel imaging devices and decorations, cathode ray tubes, fluorescent lighting fixtures and the like. 以磷光体粒子发光(luminescence)或光发射(lightemission)可由热(热致发光),光(光致发光),高能放射(例如x-射线或电子束(e-beam))和电场(电致发光)激发。 In the phosphor particles emitting (luminescence) or a light-emitting (lightemission) by heat (thermoluminescence), light (photoluminescence), high energy radiation (e.g., x- rays, or electron beam (e-beam)) and the electric field (electroluminescence light) excitation.

由于各种原因,现有技术不能提供具有不渗透湿气以及缓释性能的微囊化粒子。 For various reasons, the prior art does not provide a moisture impermeable and sustained release properties of microencapsulated particles. 因此,工业上需要一种性质明显改进的微囊化粒子。 Therefore, a significant improvement of one property microencapsulated particles industrially.

发明概述简言之,本发明提供一种微囊化粒子,其对湿气的不良影响有高抗性,并能长时间发挥作用(即缓释性能)。 SUMMARY OF THE INVENTION Briefly, the present invention provides a microencapsulated particle, its adverse effects on a high moisture resistance, and can play a role (i.e., release properties) long. 本发明也提供一种此种粒子的微囊化方法。 The present invention also provides a method of microencapsulation of such particles.

与按照现有技术制造的类似微囊化粒子(即并非按照本发明方法所制者)相比,本发明微囊化粒子的上述优点是显而易见的。 Compared with the above-mentioned advantages of microencapsulated particles according to the prior art is similar to the manufacturing (i.e. not in accordance with the present invention is prepared by the method), microencapsulated particles of the present invention is obvious.

本申请中采用的各术语具有如下的定义:“对湿气的不渗透性”-防止或基本上排除湿气进入,从而避免了湿气的不良影响。 Each term used in this application have the following definition: "moisture impermeability" - preventing or substantially exclude moisture from entering, thereby avoiding the adverse effects of moisture.

“有所改进的”-指与现有技术所揭示的,以及并非是按照本发明进行微囊化的微囊化粒子相比而言。 "Somewhat improved" - refers to the prior art disclosed, and microencapsulated particles according to the present invention is not microencapsulated of comparison.

如由下述详细说明所示,本发明的微囊化粒子具有其他的特征,这些特征或相当于或明显地胜过现有技术中微囊化粒子的对应特性。 As shown by the following detailed description, microencapsulated particles of the present invention have other features, such features or equivalent or clearly better than the corresponding properties of the prior art microencapsulated particles.

因此,本发明的目的在提供微囊化粒子。 Accordingly, an object of the invention is to provide microencapsulated particles.

本发明另一目的在于提供对湿气的不渗透性有所改进的微囊化粒子。 Another object of the present invention is to provide an improved moisture impermeability of microencapsulated particles.

本发明另一目的在于提供有缓释性能的微囊化粒子。 Another object of the present invention to provide sustained-release properties of microencapsulated particles.

本发明另一目的在于提供微囊化磷光体粒子。 Another object of the present invention is to provide microencapsulated phosphor particles.

本发明另一目的在于提供微囊化聚合物发光二极管。 Another object of the present invention to provide a polymer encapsulated light emitting diode.

本发明另一目的在于提供微囊化有机发光二极管。 Another object of the present invention is to provide microencapsulated organic light emitting diode.

本发明又一目的在于提供对湿气的不渗透性有所改进的微囊化磷光体粒子。 A further object of the present invention is to provide an improved moisture impermeability microencapsulated phosphor particles.

本发明又一目的在于提供具有缓释性能的微囊化磷光体粒子。 A further object of the present invention to provide encapsulated phosphor particles have sustained release properties.

本发明又一目的在于提供使粒子微囊化的方法。 A further object of the present invention to provide a method the particles microencapsulated.

本发明又一目的在于提供使粒子微囊化的方法,以生产对湿气的不渗透性有所改进的微囊化粒子。 A further object of the present invention to provide the particles microencapsulation methods to produce moisture impermeability improvement of microencapsulated particles.

本发明又一目的在于提供使粒子微囊化的方法,以生产具有缓释性能的微囊化粒子。 A further object of the present invention to provide a method of making microencapsulated particles to produce microencapsulated particles having a sustained release properties.

本发明又一目的在于提供使磷光体粒子微囊化的方法。 A further object of the present invention is to provide a phosphorescent particles microencapsulation method.

本发明又一目的在于提供使聚合物发光二极管微囊化的方法。 A further object of the present invention to provide a polymer light emitting diode microencapsulation method.

本发明又一目的在于提供使有机发光二极管微囊化的方法。 A further object of the present invention to provide an organic light emitting diode microencapsulation method.

本发明又一目的在于提供使磷光体粒子微囊化,以产生对湿气的不渗透性有所改进的微囊化磷光体粒子的方法。 A further object of the present invention to provide phosphor particles microencapsulated so as to produce a method for improved moisture impermeability microencapsulated phosphor particles.

本发明又的目的在于提供使磷光体粒子微囊化,以产生具有缓释性能的微囊化磷光体粒子的方法。 Another object of the present invention is to provide phosphor particles microencapsulated so as to produce a method having the sustained release property of microencapsulated phosphor particles.

本发明这些及其他目的,特点及优点可从如下详细说明中明显看出。 The present invention These and other objects, features and advantages will be apparent from the following detailed description.

附图简述图1显示了曝露(以小时测定)对微囊化的电致发光磷光体及未进行微囊化的电致发光磷光体的亮度(以英尺朗伯测定)的影响。 1 is a graph showing exposure (measured in hours) of electricity to the brightness of the microencapsulated electroluminescent phosphor and encapsulated electro-luminescent phosphor not performed (in feet measured Lambert) effects.

参见图1,在湿度箱中测试1,000小时时,含有按照本发明进行微囊化后的磷光体的灯只衰减34%,这比含有未进行微囊化的磷光体的电致发光灯表现出的衰减少60%。 Referring to Figure 1, in the humidity cabinet test for 1,000 hours, the in accordance with the present invention comprising microencapsulated lamp phosphors only after attenuation of 34%, this ratio containing microencapsulated electroluminescent lamp phosphors not subjected to exhibit The decline by 60%.

此外,在采用含有按照本发明进行微囊化后的磷光体的电致发光灯及白炽照明设备作跑道灯时,电致发光灯不产生灯晕或眩光,且在比白炽照明设备几乎远3倍处仍然可见。 In addition, the use of electrically microencapsulated containing phosphors according to the present invention, when the electroluminescent lamp and incandescent lighting equipment for runway lights, electroluminescent lamps do not produce light halo or glare, and in almost farther than incandescent lighting apparatus 3 still visible at times. 在极冷的条件(artic condition)下也测得了相同结果。 In extremely cold conditions (artic condition) has been measured the same result.

图2是胶囊品质和部分水解的聚(乙烯-醋酸乙烯酯)的水解百分比之间的关系图示。 Figure 2 is a capsule quality and partially hydrolyzed poly - relationship diagram (ethylene vinyl acetate) between the percentage of hydrolysis. 有些原因尚不完全明了,但品质随水解的百分比变化而发生变化是十分确切而明显的。 Some of the reasons are not fully understood, but the quality is the percentage change in the hydrolysis occurs with change is very precise and clear. 在水解少于38%时,按照已确立的液-液相分离技术而制备的分离相的粘性不足以形成有用的胶囊壁,所形成的壁发粘,通常不能分离出胶囊。 In the hydrolysis of less than 38%, the solution according to the established - the viscous liquid prepared in a separate phase separation techniques useful enough to form the capsule wall, the wall formed tacky, generally can not be separated out of the capsule. 以水解小于38%的材料所制造的胶囊,在微囊化的过程中有发生凝集的趋势,原因在于缺少乙烯醇基团,阻止了各羟基间发生交联。 In the material of less than 38% hydrolysis of the manufactured capsule, there occurs aggregation tendency in the process of microencapsulation because of the lack of vinyl alcohol groups, preventing crosslinking between the hydroxy group.

在水解大于55%时,分离相会太粘,且成为半固体的,有黏丝的,易沉淀(precipitous)的相。 When more than 55% hydrolysis, separation meet too viscous and to become semi-solid, there is sticky wire, easy precipitation (precipitous) phase. 由“好”变成“不好”是突然发生的,在几个百分比间即可完成。 From "good" to "bad" is the sudden, the percentage can be completed in a few.

在水解介于约38%至46%间时,可在靠近43%水解时制备成品质改进的胶囊。 When hydrolysis between about 38 to 46% between, and close to 43% can be hydrolyzed in a quality improvement of the preparation of capsules.

在水解约42%到约53%之间,本发明胶囊品质极佳,此种胶囊特别适合于含磷光体,极性液体及其他延长使用时间的物质粒子。 Termination of water between 42% to about 53%, excellent quality capsules present invention is particularly suitable for such a capsule containing a phosphor, polar liquid and other material particles to extend the use of time.

在水解约53%至54或55%间,胶囊品质快速降低,在水解约56%时,不再能成功地生产出好品质的胶囊。 In hydrolysed 53% to 54 or 55% of the inter-capsule quality and rapid reduction, when in 56% hydrolysed, no longer able to successfully produce a good quality capsules.

如图2所示,在水解约44%至约46%间时,本发明胶囊品质达到最佳。 As shown in Figure 2, when the cancellation of 44% water to about 46% between the capsule of the present invention to achieve the best quality. 此水解范围内的确切胶囊品质值尚未测出,但比在此水解范围以下胶囊品质有明显的改进,如图2所示。 The exact capsule quality value within this range has not been measured hydrolysis, but this hydrolysis than the scope of the following capsule quality significantly improved, as shown in Fig.

发明详述本发明涉及微囊化粒子,特别是微囊化胶的磷光体粒子,其制造方法包括下列步骤:将成膜的可交联性水解聚合物与该聚合物的有机非极性溶剂相混合,其中该溶剂不是物质粒子的溶剂;搅拌该混合物,在溶剂中生成溶液;在继续搅拌的条件下向溶液中加入物质粒子,其中该物质粒子分散于溶液中; DETAILED DESCRIPTION The present invention relates to microencapsulated particles, in particular rubber microencapsulated phosphor particles, which method comprises the steps of: forming a film of crosslinkable polymer and the polymer is hydrolyzed non-polar organic solvent are mixed, wherein the solvent is not a solvent material particle; The mixture was stirred, the resulting solution in a solvent; material particles added to the solution under continued stirring, wherein the material particles dispersed in the solution;

诱发溶液发生相分离,其中聚合物从溶液中分离出来,形成膜状的聚合物外壳,且包覆于每一物质粒子上;及在继续搅拌的条件下向该溶液中加入交联剂,其中每一物质粒子上的膜状外壳围绕每一物质粒子发生交联并硬化。 Solution induced phase separation, wherein the polymer is separated from the solution, forming a film of the polymer shell, and coated on each of the material particles; and the crosslinking agent added to the solution under continued stirring, wherein Each film-like material particle shell surrounding each material particle on the crosslinked and hardened.

根据本发明方法生产的微囊化粒子,与根据现有技术以其他成膜聚合物进行微囊化的物质粒子相比,对湿气的不渗透性有所改进。 The method according to the present invention for producing microencapsulated particles, as compared with other film-forming according to the prior art microencapsulated polymer particles of matter, moisture impermeability improved.

如上所述,本发明将以具体以磷光体粒子作详细说明,但本发明也可有效地用于使上述的其它物质粒子进行微囊化。 As described above, the present invention is specific to the phosphor particles will be described in detail, but the present invention can be effectively used to carry out the above-described other material particles microencapsulated.

本发明微囊化的磷光体包括一般是微粒形式的由磷光体形成的核,以及包围该核的膜状外壳。 The present invention comprises microencapsulated phosphor core is generally formed by the phosphor in particulate form, and a film-like shell surrounding the core. 该外壳包括水解的交联聚合物,其足以防止湿气(特别是水)渗透,从而保护曝露于湿气的磷光体不致变坏,但该交联的聚合物足可让照明能量通过以激活磷光体到发光状态。 The housing includes a cross-linked polymer hydrolysis, which is sufficient to prevent moisture (especially water) penetration, thereby protecting the phosphor is exposed to moisture from being deteriorated, but the crosslinked polymer is capable of allowing light energy to activate by phosphor to the light emitting state. 因此,本发明的微胶囊特别适合于发光应用。 Hence, microcapsules of the invention is particularly suitable for lighting applications.

于本发明方法中,磷光体粒子与成膜聚合物及液体载体相混合,其中该液体载体是聚合物的溶剂但不是磷光体粒子的溶剂。 In the process of the present invention, the phosphor particles and the film-forming polymer and a liquid carrier are mixed, wherein the liquid carrier is a solvent for the polymer solvent but not the phosphor particles. 搅拌混合物,使聚合物溶解于液体载体中,并使磷光体粒子分散于整个溶液中。 The mixture was stirred to dissolve the polymer in a liquid carrier, and the phosphor particles are dispersed throughout the solution. 用凝聚法使溶液发生相分离,从液体载体中分离出聚合物,并使聚合物膜状外壳包覆于磷光体粒子上。 By coacervation phase separation of the solution, the polymer was separated from the liquid carrier, and the polymer coated on the film-like shell phosphor particles. 然后磷光体粒子周围的聚合物外壳发生交联以硬化聚合物,使得聚合物外壳不可渗透,从而保护磷光体粒子曝露于湿气而不致变坏。 Then the phosphor particles of the crosslinked polymer shell surrounding occur to harden the polymer, such that the polymer shell is not permeable, thereby protecting the phosphor particles are exposed to moisture from being deteriorated. 然后从溶液中分离出聚合物封装的磷光体粒子,冲洗,并在必要时进行干燥。 Is then separated from the solution of polymer encapsulated phosphor particles, rinsed, and dried when necessary.

在此过程中分离出磷光体胶囊时,优选将聚合物外壳与卤化烃相接触,使聚合物外壳包覆磷光体粒子而增强聚合物外壳对水的不渗透性。 A separation of the phosphor in this process the capsule, the polymer shell is preferably contacted with the halogenated hydrocarbon, the polymer shell-coated phosphor particles with a polymer shell of enhanced water impermeability. 优选的卤化烃是1,1,2-三氯-1,2,2-三氟乙烷及二溴四氟乙烷。 The preferred halogenated hydrocarbon is 1,1,2-trichloro-1,2,2-trifluoroethane and dibromotetrafluoroethane.

成膜的可交联性水解聚合物聚合物应是基本绝缘的,优选介电常数小于约2.2,较佳是在约1.8至约2.2之间。 Film-forming polymer cross-linkable polymer hydrolysis should be basic insulation, preferably a dielectric constant of less than about 2.2, preferably between about 1.8 to about 2.2. 可采用各种聚合物生成微胶囊的保护膜状外壳。 Various polymers can be used to generate the microcapsules protect the film-like shell. 优选的聚合物是可水解的可交联性乙烯-醋酸乙烯酯聚合物。 Preferred polymers are hydrolyzable crosslinkable ethylene - vinyl acetate polymer. 在某些应用中,该聚合物应是可热解的。 In some applications, the polymer should be pyrolysis.

用于本发明的优选成膜聚合物是聚(乙烯-醋酸乙烯酯),其含有约60至88摩尔百分比的乙烯,具有约38至约55百分比(优选约42至46百分比)的醋酸乙烯酯基团,该醋酸乙烯酯基团水解成乙烯醇,以提供交联的反应位。 Preferably the film-forming polymer used in the present invention are poly (ethylene - vinyl acetate), which comprises about 60 to 88 mole percent ethylene, having from about 38 to about 55 percent (preferably from about 42 to 46 percent) of vinyl acetate group, the vinyl acetate groups hydrolyzed to vinyl alcohol to provide a reaction site crosslinked. 优选的溶解聚合物的液体载体为甲苯。 A preferred liquid carrier polymer is dissolved in toluene.

聚合物胶囊壁材料可以是润湿磷光体核材料的任何成膜聚合物材料。 Polymeric capsule wall material may be wetted phosphor of any nuclear material film-forming polymer material. 胶囊壁材料优选为部分水解的聚(乙烯-醋酸乙烯酯),其中某些醋酸乙烯酯基团水解生成乙烯醇基团,从而提供后继交联反应所需的反应位。 Capsule wall material is preferably partially hydrolyzed poly (ethylene - vinyl acetate), wherein the hydrolysis of certain groups generate vinyl acetate vinyl alcohol groups, thus providing the subsequent crosslinking reaction the desired reaction site. 生成聚(乙烯-醋酸乙烯酯)壁的材料的水解度范围较宽,约38至约55百分比,优选为约44至约46百分比。 Generating Poly - a degree of hydrolysis range (ethylene vinyl acetate) material of the walls is wide, from about 38 to about 55 percentage, preferably about 44 to about 46 percentage.

因此,乙烯合附醋酸乙烯酯的部分水解聚合物含有乙烯基团,醋酸乙烯酯基团及乙烯醇基团,可以如下通式表示: Thus, ethylene vinyl acetate co-attached and partially hydrolyzed polymers containing vinyl groups, vinyl acetate groups and vinyl alcohol group, can be represented by the formula: 其中x,y及z分别代表乙烯,乙烯醇及醋酸乙烯酯的摩尔分数。 Wherein x, y and z represent, vinyl alcohol and vinyl acetate mole fraction. 对于水解度,乙烯醇与乙烯醇基团和醋酸乙烯酯基团的总量的摩尔比为约0.15至约0.7。 For the degree of hydrolysis, vinyl alcohol and vinyl acetate, the total amount of vinyl alcohol groups and ester groups in a molar ratio of from about 0.15 to about 0.7. 乙烯基团的量也是重要的,可为约60至约88摩尔百分比。 Amount of vinyl groups is also important, for about 60 to about 88 mole percent. 换句话说,乙烯基团与乙烯基团,乙烯醇基团和醋酸乙烯酯基团的总量的摩尔比可为约0.6至约0.88。 In other words, the molar ratio of vinyl groups and vinyl groups, vinyl alcohol group and vinyl acetate groups of the total may be about 0.6 to about 0.88.

适于实践本发明的部分水解聚(乙烯-醋酸乙烯酯)的分子量为约50,000,熔融指数(于190℃使用2160克力,10分钟)为约5至约70,优选熔融指数为约35至约45。 Suitable for the practice of the present invention, the partially hydrolyzed poly (ethylene - vinyl acetate) of molecular weight of about 50,000, a melt index (at 190 ℃ using 2160 grams force, 10 minutes) is about 5 to about 70, preferably a melt index of about 35 to about 45. 共聚合物的分子量并不十分重要,只是在分子量太大时,共聚合物在构成微胶囊系统主要部分的液体载体中相对不溶解。 The molecular weight of the copolymer is not critical, but when the molecular weight is too large, copolymers relatively insoluble in the liquid carrier constituting the main part of the microcapsule system. 如果共聚合物的分子量太低,则难以在微囊化中进行相分离。 If the molecular weight of the copolymer is too low, it is difficult to perform the phase separation microencapsulation. 其他合适的聚合物壁材料有聚(乙烯-缩甲醛),乙酰化纤维素(例如醋酸丁酸纤维素)等。 Other suitable polymeric wall materials are poly (ethylene - formals), acetylated cellulose (e.g., cellulose acetate butyrate) or the like.

有机非极性溶剂可用作本发明制法中液体载体的,典型并具说明性的与水不混溶液体是聚合物壁材料的溶剂,包括液体芳香族烃如甲苯,二甲苯,苯,氯苯等;及液体卤化烃如三氯乙烯,四氯乙烯,四氯化碳,甲基氯等。 The organic non-polar solvent may be used in the present invention is prepared by the liquid carrier, a typical and illustrative of the water-immiscible liquid is a solvent for the polymer wall material, comprising a liquid aromatic hydrocarbons such as toluene, xylene, benzene, chlorobenzene and the like; and a liquid halogenated hydrocarbons such as trichlorethylene, tetrachlorethylene, carbon tetrachloride, methyl chloride and the like. 也适宜的溶剂有环己醇,甲基异丁基酮,1-甲基-2-吡咯烷酮,丁醇等。 Suitable solvents also have cyclohexanol, methyl isobutyl ketone, 1-methyl-2-pyrrolidone and butanol.

被微囊化的物质粒子优选地,用于本发明的磷光体粒子为微粒形式,其横截面一般为约1至约100微米,优选为约5至约50微米。 Microencapsulated substance particles Preferably, the phosphor particles of the present invention is in particulate form, in cross-section is generally from about 1 to about 100 microns, preferably from about 5 to about 50 microns. 在制成初步的混合物时,磷光体粒子,聚合物及液体载体是相对成比例的,以使液体载体构成系统的主要成分,聚合物构成系统的最少成分。 When the initial mixture formed, phosphor particles, the polymer and the liquid carrier is relatively proportional to the liquid carrier constituting the main component of the system, at least a polymer component constituting the system.

如上所述,根据本发明所生产的微胶囊具有这样的核,其含有以不透水的聚合物材料保护壁或外壳包覆的磷光体粒子。 As described above, has a core according to the present invention produced microcapsules containing a water impermeable protective wall or shell polymeric material coated phosphor particles. 此种微胶囊可用于照明路标,交叉路口,门牌号码,仪表板,航空器内部,表盘,计算器显示器,阴极射线管等。 Such microcapsules can be used to illuminate signs, intersections, house number, instrument panels, aircraft interior, dial, calculator displays, cathode ray tubes.

根据所采用的进行微囊化的不同磷光粉,可用电流,电子轰击,吸收电磁辐射,或以其他活化手段将微胶囊激活至其磷光状态。 According to the different microencapsulated phosphor powder employed, the available current, electron bombardment, electromagnetic radiation absorption, or other activation means to activate the microcapsules its phosphorescent state.

典型的磷光体包括氧占主导的磷光体,如:CaWO4:Pb MgWO4Zn2SiO4:MnCaSiO3:Pb,Mn (MgO)X(As2O5)X:Mn Ca5F(PO4)3:Sb,MnCa5Cl(PO4)3:Sb,Mn BaSi2O5:Pb Ca3(PO4)2:TISrHPO4Sn Y2O3:Eu(III) YVO4:EuZn2GeO4:Mn (BaZnMg)3Si2O7;金刚石晶格的磷光体,如锌、镉及汞的硫化物,硒化物及碲化物,例子有ZnS:AgCl,ZnS:CuCl,ZnS:MnCl和以其他活化剂如Mn(II),P,As,Sb,V,Fe及Ti与共活化剂如卤素,Al,Ga,In进行活化的ZnS,及以稀土与Ag或Cu联合活化的ZnS,及以与上述ZnS的相同活化剂与共活化剂进行活化的CdS;碱土硫化物,例如CaS,SrS等,其含铕,铯,铜,锰,钐,或铋,SiC,AiN,GaP;以及有机磷光体如芪,萘,蒽,及菲。 Typical phosphors include oxygen dominated phosphors, such as: CaWO4: Pb MgWO4Zn2SiO4: MnCaSiO3: Pb, Mn (MgO) X (As2O5) X: Mn Ca5F (PO4) 3: Sb, MnCa5Cl (PO4) 3: Sb, Mn BaSi2O5: Pb Ca3 (PO4) 2: TISrHPO4Sn Y2O3: Eu (III) YVO4: EuZn2GeO4: Mn (BaZnMg) 3Si2O7; diamond lattice of the phosphor, such as zinc, cadmium and mercury sulfides, selenides and tellurides, Examples of ZnS: AgCl, ZnS: CuCl, ZnS: MnCl and other activators such as Mn (II), P, As, Sb, V, Fe and Ti co activators such as halogen, Al, Ga, In activation of ZnS , rare earth and combined with Ag or Cu-activated ZnS, and ZnS is the same as in the above activator co activators activated CdS; alkaline earth sulfides, such as CaS, SrS, etc., which contains europium, cerium, copper, manganese, samarium, or bismuth, SiC, AiN, GaP; and organic phosphors such as stilbene, naphthalene, anthracene, and phenanthrene.

磷光体的详细说明见Kirk-Othmer,Encyclopedia of ChemicalTechnology,John Wiley & Sons,(2ed.1967)第616-631页,其讨论列入本申请以供参考。 See a detailed description of the phosphor Kirk-Othmer, Encyclopedia of ChemicalTechnology, John Wiley & amp; Sons, (2ed.1967) p. 616-631, its discussions included in this application by reference. 有关磷光体理论方面的讨论及一些常见磷光体及其性质见Theculis,Encyclopedic Dictionary of Physics,(Pergamon Press,Oxford 1962)第368-372页,其讨论列入本申请以供参考。 Discuss theoretical aspects of phosphors and phosphor and some common properties see Theculis, Encyclopedic Dictionary of Physics, (Pergamon Press, Oxford 1962) p. 368-372, the discussion included in this application by reference.

在需要以电致发光(其定义为通过电子和空穴流的辐射重组直接将电能转为光能)激发微囊化磷光体时,优选用硫化锌(特别以铜活化剂制备的,铜活化剂中部分铜以硫化铜的第二相终止)作为核心材料。 Need to electroluminescent (which is defined as the electrical energy into light energy directly by radiation recombination of electrons and holes flow) excitation microencapsulated phosphor, zinc sulfide is preferably used (particularly in the preparation of a copper activator, copper activated agent part of the copper to copper sulfide terminated second phase) as the core material. 电致发光过程的发光与紫外线激发下所见到的光致发光相似。 Electroluminescent process Luminescence and UV excitation photoluminescence seen similar. 厚度小于1/32英寸的伸缩性电致发光灯应用于许多场合中,包括读出器,仪表板照明,信号标记等。 Scalability of thickness less than 1/32 inches electroluminescent lamps used in many occasions, including the reader, dashboard lighting, signal markings.

对于电致发光的全面评论参见HFlvy,IRE Trans.Electron Devices6,203(1959);J.Electronchem.Sec.108,590(1961);Electrochem.Technol 1.42(1963);HKHenisch,Electroluminescence,Pergamon Press,New York,1962;及HFlvey,Electroluminescence and Related Effects,Academic Press,Inc.,New York,1963。 For a comprehensive review of electroluminescent see HFlvy, IRE Trans.Electron Devices6,203 (1959); J.Electronchem.Sec.108,590 (1961); Electrochem.Technol 1.42 (1963); HKHenisch, Electroluminescence, Pergamon Press, New York, 1962; and HFlvey, Electroluminescence and Related Effects, Academic Press, Inc., New York, 1963. 电致发光也见于其它化合物中AnS:Cu;ZnTe:Cu;SiC:Gap;及GaAs的单晶中。 Electroluminescent also found in other compounds AnS: Cu; ZnTe: Cu; SiC: Gap; and single crystals of GaAs. 于这些许多实例中,激发归因于pn连接处的载体注入。 In many of these instances, the excitation vector pn junction due to the injection.

此微胶囊一般在基体中得到支撑,其中包围磷光体粒子的基体介质的绝缘常数应在约10至约20的范围内,这样可避免磷光体被电场活化。 The microcapsules obtained are generally supported in the matrix, wherein the matrix surrounding the dielectric constant of the medium of the phosphor particles should be in the range of from about 10 to about 20, so that an electric field can be avoided phosphor activated.

对基体和典型信号的罩子上施加交流电会产生电磁场,因而使支撑基体中微胶囊内的磷光体粒子遭受电磁波能量而导致磷光体发光。 On the cover of the substrate and a typical signal will produce alternating electromagnetic field is applied, thus making the phosphor particles in supporting matrix microcapsules suffer electromagnetic energy caused by light-emitting phosphor. 微胶囊内磷光体粒子的这种电致发光产生了信息形式的照明显示器,本领域的技术人员承认并理解该信息在相当远的距离处以及在如雾,雨或雪的情形下是易见的。 This electrical microcapsules electroluminescent phosphor particles generated information in the form of lighting displays, skilled personnel to recognize and understand the information at a considerable distance and in fog, rain or snow scenario is easy to see a. 在显示器使用于无交流电的环境时,可使用直流电,如来自电池的直流电,经变换器将电能转换成交流电后施加于此基体及罩子。 In the display used in the non-AC environment, you can use direct current, such as direct current from the battery, the converter is applied to the substrate and cover this electrical energy is converted into alternating current post.

本发明微囊化的磷光体也可沉积在屏幕上,如在阴极射线管内,之后再用如热解或燃烧方法将壁或外壳的聚合物材料破坏。 The present invention microencapsulated phosphor can be deposited on the screen, such as in a cathode ray tube, and then after the pyrolysis or combustion processes such as the wall or shell of polymeric material damage. 结果是在屏幕上沉积可未封装的磷光体。 The result is the deposition may be unencapsulated phosphor on the screen. 在磷光体以控制的方式沉积时即可采用这种沉积磷光体的方法。 When the phosphor is deposited in a controlled manner to adopt this method for phosphor deposition. 在此情形下,壁材料必须是在低温下可热解破坏的,这样才不会对磷光体有不良影响。 In this case, the wall material must be at a low temperature pyrolysis can be destroyed, so as not to adversely affect the phosphor. 乙烯-醋酸乙烯酯共聚物及其他可选的聚合物可用于此目的。 Ethylene - vinyl acetate copolymer and optional other polymers used for this purpose.

基本上,含磷光体粒子的微胶囊可通过将(a)磷光体,(b)成膜聚合物材料及(c)与水不混溶的,能溶解聚合物材料但不溶解磷光体的液体载体相混合而生产。 Basically, microcapsules containing a phosphor particles can be obtained by (a) phosphor, (b) film-forming polymeric material and (c) water-immiscible, but does not dissolve the phosphor material a liquid capable of dissolving the polymer mixing carrier production. 于较佳具体实施方式中,磷光体的形式为磷光体粒子,其平均直径在约1微米至约100微米间,优选在约5微米至约50微米间。 In the preferred embodiment, the form of the phosphor of the phosphor particles having an average diameter of about 1 micron to about 100 microns, preferably from about 5 microns to about 50 microns.

磷光体材料可以液体形式进行微囊化,这是利用有机磷光体的有用方法。 The phosphor material may be microencapsulated liquid form, this is a useful way of using an organic phosphor. 搅拌所得混合物使磷光体粒子在整个液体载体中分散成为单个微小的成核实体以形成搅拌系统,该系统中液体载体构成此系统的主要成分。 The resulting mixture was stirred to make the phosphor particles dispersed throughout the liquid carrier into a single minute to verify the body to form a mixing system, the system liquid carrier constituting the main components of this system. 然后将聚合物成膜材料溶于液体载体内。 The polymer was then dissolved in a liquid film-forming material within the vector. 在搅拌过的系统内进行相分离,从液体载体中分离出聚合物材料,并在磷光体粒子核周围形成聚合物材料的膜状外壳。 In a stirred system, phase separation, separating out from the liquid carrier polymer material, and a film forming polymeric material in the shell around the core particles of the phosphor. 然后,使外壳内的聚合物材料交联,在磷光体核周围生成保护壁。 Then, the polymer material is cross-linked within the housing, to form a protective wall around the core phosphor. 最后,可将保护壁与卤化烃接触足够的时间,以增强壁的抗水性,然后再进行洗涤和干燥。 Finally, the protective wall with a halogenated hydrocarbon for a time sufficient to enhance the water resistance wall, and then washed and dried.

使磷光体粒子如掺杂铜的硫化锌进行微囊化的优选方法,包括将磷光体粒子进行液-液相分离型的凝聚微囊化,使用有机液体载体及部分水解的乙烯-醋酸乙烯共聚物为成膜的壁材料。 So that the phosphor particles, such as copper-doped zinc sulfide microencapsulated preferred method, the phosphor particles comprising liquid - liquid phase separation type flocculating microencapsulated using an organic liquid carrier and partially hydrolyzed ethylene - vinyl acetate copolymer a film-forming composition of the wall material. 然后通过交联使由该方法制成的微胶囊的膜状聚合物壁硬化,并可使其与低沸点的烃接触以增强抗水性。 Then the microcapsules prepared by the method of a film by crosslinking the polymer walls harden, and can make contact with the low-boiling hydrocarbons to enhance the water resistance. 优选地,再以细碎粒的硅胶处理该微胶囊体,以增强其在干燥及过滤过程中的抗凝集性。 Preferably, the finely divided particles of silica gel and then treated with the microcapsules body to enhance its anti-aggregation properties in drying and filtration process.

溶液的相分离本发明认为相分离可以各种方法引起,典型的是于此混合物中引入诱发相分离的材料。 Solution of the present invention recognizes that the phase separation phase separation may cause a variety of methods, this mixture is typically introduced to induce phase separation material. 例如,可将对磷光体粒子亲合性小于对成膜聚合物亲合性的补充聚合物材料溶于液体载体内,使成膜聚合物优先包覆于磷光体粒子上。 For example, the phosphor particles will be less than the affinity of the film-forming polymer affinity for complementary polymer material dissolved in a liquid carrier, a film-forming polymer is preferentially coated on the phosphor particles.

或者,也可用并非是成膜聚合物或磷光体粒子的溶剂的非聚合物材料作为诱发相分离的材料。 Alternatively, non-polymeric material can be used is not a solvent or a phosphor film-forming polymer particles as a material-induced phase separation. 于另一方法中,通过调节系统温度至成膜聚合物一般不溶于液体载体的某一温度,在向系统引入或者不引入任何相分离诱发材料的情况下诱发相分离。 In another method, by adjusting the temperature of the system to a film-forming polymer is generally insoluble in the liquid carrier of a certain temperature, in the case of the introduction of the system or do not introduce any phase separation inducing material-induced phase separation. 可以理解的是,根据所用的成膜聚合物不同,该方法的这一步骤可包括冷却或加热系统。 Be appreciated that, depending on the film-forming polymer used, this step of the method may include cooling or heating system.

当使用诱发相分离的材料时,可于开始混合步骤期间或之后将诱发相分离的材料引入系统中。 When using induced phase separation of materials, during or after the beginning of the mixing step induced phase separation of the material introduced into the system. 再有一种方法是开始时即可将成膜聚合物和诱发相分离的材料彼此混合,然后再与液体载体及磷光体粒子相混合。 Yet another method is to be at the beginning of the film-forming polymer and induced phase separation material mixed with each other, and then mixed with the liquid carrier and the phosphor particles.

用于本发明的合适的诱发相分离的材料是溶于液体载体及于系统内对胶囊核材料比对聚合物成膜材料的亲合性更低的聚合物材料,因而使聚合物成膜材料优先沉积于分散核的周围。 Suitable for the present invention is to induce phase separation of the material is soluble in the liquid carrier and the capsule in the system of the nuclear material than the polymeric material of the affinity of a lower polymer material, thus making the polymer film-forming material preferentially deposited around the dispersed nuclei. 换句话说,诱发相分离的材料与聚合物成膜材料不相容。 In other words, with the polymeric material to induce phase separation of incompatible materials. 这种类型的诱发相分离的材料例子是聚合物材料,如硅油,具体如聚二甲基硅氧烷等;聚烯烃,例如分子量为约8,000至约10,000的聚丁二烯,分子量为约330至约780的聚丁烯;未水解的乙烯-醋酸乙烯酯共聚物;天然蜡;等等。 Examples of this type of material to induce phase separation is a polymeric material, such as silicone oils, such as polydimethylsiloxane concrete like; polyolefins, e.g., a molecular weight of from about 8,000 to about 10,000 polybutadiene, molecular weight of about 330 to about 780 polybutene; unhydrolyzed ethylene - vinyl acetate copolymer; natural waxes; and the like. 此类型的聚合物材料有时在本领域中称为“补充性聚合物材料”。 This type of polymer material is sometimes referred to as "supplemental polymeric material" in the art.

另一类用于开始即生成微胶囊壁或外壳的诱发相分离的材料是非聚合物液体,此液体不是聚合物成膜材料及胶囊核材料的溶剂,但可与液体载体混溶。 Another class of non-polymeric material is used to start liquid evoked i.e. generating the microcapsule wall or shell phase separation, the liquid polymeric material and a solvent is not a capsule nuclear material, but is miscible with the liquid carrier. 此类示例性的非溶剂型诱发相分离的材料有植物油,例如半干的油,具体有棉子油或玉米油,及干燥油如亚麻子油,大豆油等。 Exemplary of such non-solvent induced phase separation materials are vegetable oils, such as semi-dry oils, specifically cottonseed oil or corn oil, and drying oils such as linseed oil, soybean oil. 其他此类示例性的非溶剂型材料有矿物油,卤化矿物油,液体饱和脂环烃如环己烷,环庚烷等,液体饱和的直链脂肪烃如n-己烷,n-庚烷等。 Exemplary of such other non-solvent materials are mineral oils, halogenated mineral oil, liquid saturated alicyclic hydrocarbons such as cyclohexane, cycloheptane, etc., a liquid straight-chain aliphatic saturated hydrocarbons such as n- hexane, n- heptane and so on. 通常,相分离由加入棉子油,玉米油,亚麻子油,大豆油或二种或两种以上的此类油的混合物诱发。 Typically, phase separation from cotton seed oil was added, the mixture was induced corn oil, linseed oil, soybean oil, or two or more kinds of such oils.

为达到相分离及伴随形成外壳或微胶囊,可以任何方便的顺序合并成膜聚合物材料,诱发相分离的材料及溶剂(该溶剂用作系统的液体载体)。 To achieve phase separation and the accompanying formation of the housing or microcapsules, combined in any convenient order may be film-forming polymeric material, a material-induced phase separation and solvent (liquid carrier is used as the solvent system). 优选地,先制备聚合物成膜材料的稀溶液,然后在约30℃或更高温度下加入诱发相分离的材料以进行液-液相分离。 Preferably, the first polymeric material of the dilute solution was prepared, and then added to induce phase separation of the material at a temperature of about 30 ℃ or higher for liquid - liquid phase separation.

但加入顺序也可相反。 However, the order of addition may be reversed. 另一种方法中,将成膜聚合物材料,诱发相分离的材料及液体载体同时合并。 Another method, the film-forming polymeric material, to induce phase separation of the liquid carrier material and simultaneously merge.

成膜聚合物材料和诱发相分离的材料间的量关系视所用的具体材料及胶囊磷光体核所需的保护壁或膜状外壳的厚度而定。 Film-like protective wall or shell thickness depending on the relationship between the amount of the specific materials and film-forming polymeric material to induce phase separation between the materials used and the capsule core phosphor may be required. 一般而言,成膜聚合物构成总系统容积的约0.5至约5百分比(优选约1至约2百分比),诱发相分离的材料构成总系统容积的约0.5至25百分比(优选约8至约12百分比),分散的胶囊核材料体构成总系统容积的约2至约30百分比(优选约15至约20百分比)。 In general, the film-forming polymer constituting the total system volume of about 0.5 to about 5 percent (preferably from about 1 to about 2 percent), to induce phase separation of the material constituting from about 0.5 to 25 percentage of the total system volume (preferably from about 8 to about 12 percent), dispersed capsule nucleus material body constituting the total system volume of about 2 to about 30 percent (preferably from about 15 to about 20 percent). 在这种方式中,本发明所制得的微胶囊中磷光体核与起保护作用的聚合物壁或外壳的相比率较高,典型为约3∶1至约20∶1,优选在该方位的上端部分。 In this manner, the present invention is prepared microcapsules was higher phosphor core and protective polymeric wall or shell compared to, typically about 3 to about 20, preferably at the position The upper end portion.

或者是,可先于预定的溶解温度下在液体载体内制备成膜聚合物材料(即形成微胶囊壁的材料)的溶液,然后再通过加热或冷却改变所得溶液的温度到至少一部分已溶解的聚合物材料不溶解的温度,从而诱发相分离。 Alternatively, the film-forming polymeric material may be dissolved at a predetermined temperature in a liquid carrier the preparation of (i.e., the formation of microcapsule wall material) was added, and then changing the temperature by heating or cooling the resulting solution to at least a portion of the dissolved insoluble polymeric material temperature, thereby inducing phase separation. 一般是将溶液温度降低约10℃,在分散于溶液中的磷光体核的周围形成微胶囊壁。 Temperature of the solution is generally reduced by about 10 ℃, dispersed in the solution around the phosphor core forming microcapsule walls. 但在聚合物材料在液体载体内的溶解度随温度的增加而降低时,相分离是通过升高聚合物材料溶液温度而诱发。 However, when the solubility of the polymeric material within the liquid carrier decreases with the increase of temperature, the phase separation by increasing solution temperature induced polymer material.

也可接合使用这些诱发相分离的技术。 These may also be used to induce phase separation bonding techniques.

成膜的可交联水解聚合物的交联用于硬化本发明微胶囊的合适交联剂包括二异氰酸酯或多异氰酸酯,例如甲苯二异氰酸酯,催化剂可存在或不存在。 Crosslinkable hydrolyzable polymer suitable crosslinking agent for hardening the microcapsules of the present invention comprises a film-forming diisocyanate or polyisocyanate, such as toluene diisocyanate, the catalyst may be present or absent. 特别优选的是甲苯二异氰酸酯-羟甲基丙烷加合物,其通常溶于液体载体的等分试样中。 Particularly preferred are toluene diisocyanate - trimethylolpropane adduct, which is generally dissolved in an aliquot of a liquid carrier. 也可用作交联剂的是二酸卤化物,如丙二酰氯,草酰氯,磺酰氯,亚硫酰氯等;及双官能氢化物。 Also be used as the crosslinking agent is acid halide, such as malonyl chloride, oxalyl chloride, sulfuryl chloride, thionyl chloride and the like; and difunctional hydride. 另一组合适的硬化剂是醇碱金属盐如钠、钾、锂及铯的甲醇盐,乙醇盐,丙醇盐等。 Another group of suitable curing agents are the alkali metal salts of alcohols such as sodium, potassium, lithium and cesium methoxide, ethoxide, propoxide and the like.

为使形成的外壳进行化学硬化并因此提供保护的胶囊壁时,可将交联或硬化剂溶于液体载体或另一种相容的溶剂的等分试样中,再加于到包覆外壳的胶囊核的悬浮液中。 To the housing is formed of chemically hardened and thus provide protection capsule wall, it can be dissolved in a crosslinking or hardening agent or another compatible liquid carrier aliquot solvent, together with the housing in the covering The core capsule suspension. 然后于约0℃至5℃温度范围内进行交联约5分钟至约20小时,视所用的交联剂而定。 Then cross-linked about 5 minutes to about 20 hours in the range of about 0 ℃ to 5 ℃ temperature range, depending on the used crosslinking agent may be. 如是使用二酸卤化物,交联时间可为约5至约15分钟,如是使用二氰酸酯,交联时间可为约5至约15小时,视反应条件而定。 The case of using acid halide, crosslinking time may be from about 5 to about 15 minutes, in the case using two diisocyanate, crosslinking time may be from about 5 to about 15 hours, depending on the reaction conditions.

通过使外壳曝露于高能离子射线下,如加速电子,X-射线,γ射线,α粒子,中子等,可使微胶囊外壳硬化或交联。 By making the housing is exposed to high-energy ion rays, such as accelerated electrons, X- rays, γ-rays, α particles, neutrons, etc., can microcapsule shell hardening or crosslinking.

微胶囊保护壁的渗透性相当大程度上取决于所实现的交联度,通过控制交联度,可于保护壁内建立如特定的最终用途所需的渗透性。 Depending on the degree of crosslinking achieved microcapsule protective wall permeability to a large extent, by controlling the degree of crosslinking, can be established as the intended end use desired permeability in the protective wall.

聚合物的交联也可不同方式完成。 Crosslinked polymer may also be done differently. 典型的是将交联剂加于系统内,优选的交联剂有二异氰酸酯,多异氰酸酯,二酸卤化物,双官能氢化物及醇碱金属盐。 Typically the crosslinking agent is added to the system, the crosslinking agent is preferably a diisocyanate, polyisocyanate, acid halide, difunctional hydride and an alkali metal salt of an alcohol. 或者,也可向系统施加射线以引发交联。 Alternatively, radiation may be applied to the system to initiate the crosslinking.

实施本发明时可制备各种尺寸的微胶囊,且该尺寸可从直径约1微米或更小延伸至约数千微米或更大。 Various sizes can be prepared microcapsules practice of the present invention, and the size can be from about 1 micron in diameter or less extending to several thousand micrometers or more. 所制得的微胶囊的一般尺寸以平均直径计,为约1微米至约15,000微米,优选为约5微米至约2,500微米。 Microcapsule prepared generally as an average diameter size from about 1 micron to about 15,000 microns, preferably from about 5 microns to about 2,500 microns. 同样,可制成含不同量的磷光体核材料的微胶囊,其中磷光体核材料最多可占每一微胶囊总重量的99%或更多。 Similarly, can be made containing varying amounts of nuclear material phosphor microcapsules, wherein the phosphor core material may constitute up to 99% of the total weight of each microcapsule or more. 优选地,该核材料构成每一微胶囊总重的约50至约97%。 Preferably, the core material of the total weight of each of the microcapsules of about 50 to about 97%.

为说明本发明的方法,于高溶解温度,较合适的是约70℃以上,优选约75℃至约100℃的温度下制备液体载体和成膜聚合物材料的溶液,其中所述的液体载体如甲苯,所述的成膜聚合物材料含有部分水解的乙烯-醋酸乙烯酯共聚物(HEVA),其中约38%至约55%,优选约44%至约46%的醋酸乙烯酯基团水解成乙烯醇基团。 For the process of the present invention will be described, the high dissolution temperature, suitably not less than about 70 ℃, the solution preferably to a temperature of about 75 ℃ about 100 ℃ of preparing a liquid carrier and film-forming polymeric material, wherein said liquid carrier such as toluene, the film-forming polymeric material comprises partially hydrolysed ethylene - vinyl acetate copolymer (HEVA), wherein from about 38% to about 55%, preferably hydrolyzed vinyl ester groups of acetic acid from about 44% to about 46% a vinyl alcohol group. 然后制得的溶液准备接受磷光体核材料。 The resulting solution is then ready to accept the phosphor nuclear material. 优选地,使溶液冷却至分散温度约30℃至约65℃。 Preferably, the solution was cooled to a temperature of about 30 ℃ dispersion to about 65 ℃. 然后将直径平均约5至约50微米的磷光体粒子在剧烈搅拌下加入HEVA-甲苯溶液中,使作为核材料体的磷光体粒子分散于整个HEVA-甲苯溶液内。 Then the average phosphor particle diameter of about 5 to about 50 microns in toluene was added with vigorous stirring HEVA- solution so as phosphor particles of nuclear material body is dispersed throughout a toluene solution HEVA-.

然后,通过加入相分离诱发剂如棉子油,于甲苯溶液中诱发HEVA共聚物进行液-液相分离,然后再将所得混合物冷至约15℃至约50℃,优选约20℃至约30℃的相分离温度,同时继续搅拌以维持核材料磷光体粒子分散。 Then, by adding a phase separation inducing agent, such as cottonseed oil, evoked in the toluene solution HEVA copolymer liquid - liquid phase separation, and then the resulting mixture was cooled to about 15 ℃ to about 50 ℃, preferably from about 30 to about 20 ℃ phase separation temperature ℃ while stirring was continued to maintain the nuclear material phosphor particle dispersion. 但相分离诱发剂也可在磷光体核之前加入。 However, phase separation inducing agent may also be added prior to phosphor core. 当相分离在系统内诱发后,成壁的NEVA共聚物材料即作为另一不连续相即第三相分离,润湿磷光体核并形成外壳或胶囊壁。 After phase separation induced in the system, wall-forming material, i.e., as a copolymer of NEVA another discontinuous phase i.e. the third phase separation, wetting phosphor core and forming a housing or a capsule wall. 此第三相为较浓的溶液或聚合物凝胶,比连续相更粘,尽管有时需剪切力以维持各独立的核成分散状态,其粘度足以在各磷光体核周围形成基本连续的外壳。 This third phase is more concentrated solution or a polymer gel, more viscous than the continuous phase, although sometimes required shear forces to maintain the separate core into the dispersed state, a viscosity in the nuclear around each sufficient to form a substantially continuous phosphor shell.

然后,将交联剂,如与三羟甲基丙烷加合的甲苯二异氰酸酯(TDI)的甲苯溶液,加入冷却的混合物内进行交联并硬化HEVA外壳,该外壳由于加入相分离诱发剂棉子油而沉积于磷光体核周围。 Then, the cross-linking agent, such as a toluene solution and trimethylolpropane adduct of toluene diisocyanate (TDI), and the mixture was added to the cooled and hardened HEVA crosslinking a housing due to the phase separation inducing agent is added raffinose deposition in oil around the core phosphor. 在加入TDI加合物后,再将制得的混合物进一步冷至约0℃至20℃的温度范围内,然后任其升温至环境温度,同时继续搅拌。 After the addition of TDI adduct, and then the resulting mixture was further cooled to a temperature in the range of from about 0 ℃ to 20 ℃, and then allowed to warm to ambient temperature while stirring was continued. 继续搅拌至交联完成。 Continue stirring the crosslinking is complete. 然后收取制得的微胶囊,洗涤并干燥。 Then charged microcapsules prepared, washed and dried.

然后,如有需要,再使微胶囊与卤化烃接触,如将微胶囊悬浮于1,1,2-三氯-1,2,2-三氟乙烷内。 Then, if necessary, and then the microcapsules in contact with the halogenated hydrocarbon, such as the microcapsules are suspended in 1,1,2-trichloro-1,2,2-trifluoroethane. 该洗涤使微胶囊的外壳或壁收紧并防止微胶囊发生凝集。 The washing of the microcapsules and to prevent tightening housing or wall microcapsules agglutination. 最后,将微胶囊干燥,并优选用微米级粒子形式的硅胶进行处理以防止聚集。 Finally, the microcapsules are dried, and is preferably used in the form of micron-sized silica particles may be treated to prevent aggregation.

本发明将通过以下的实施例加以说明,这些实施例是某些实施方式的例证,以教导普通技术人员如何实施本发明,并代表实施本发明的最佳方式。 The present invention will now be illustrated by the following examples, these examples are illustrative of certain embodiments, in order to teach one of ordinary skill how to implement the present invention and the best mode embodiment of the present invention is represented.

实施例1将其中44-52%的醋酸乙烯酯基团已水解成乙烯醇,熔融指数为35-37的六十克水解乙烯-醋酸乙烯酯共聚合物(HEVA,Mitsui公司以商标Japan 8出售)加入于4升烧瓶内的2400毫升甲苯中,该烧瓶于配备有由可变速搅拌马达操作的4-寸涡轮叶轮。 Example 1 wherein 44-52% of the vinyl acetate groups have been hydrolysed to vinyl alcohol, a melt index of 35-37 sixty grams hydrolyzed ethylene - vinyl acetate copolymer (HEVA, Mitsui Company sold under the trademark Japan 8 ) was added to 4 liters 2,400 ml of toluene in the flask, the flask was equipped with a variable-speed stirring motor operation by 4 inch turbine wheel. 将溶液加热至85℃,并搅拌15分钟使HEVA溶解于甲苯中。 The solution was heated to 85 ℃, and stirred for 15 minutes HEVA dissolved in toluene. 然后,移去热源,使得温度降至58℃。 Then, the heat is removed, so that the temperature dropped to 58 ℃. 此时,在搅拌器增至480rpm强烈搅拌下于HEVA共聚物的甲苯溶液中加入900克平均直径约10至约40微米的绿磷光体粒子,使磷光体粒子基本均匀地分散于甲苯溶液内。 At this time, 900 g average diameter of the stirrer increased to 480rpm toluene solution with vigorous stirring at HEVA copolymer from about 10 to about 40 microns in the green phosphor particles, so that the phosphor particles are substantially uniformly dispersed in a toluene solution. 大约与此同时,于甲苯溶液中加入棉子油(其量足以生成11%重量比的棉子油溶液)以诱发液-液相分离。 About the same time, cotton seed oil was added to the toluene solution (an amount sufficient to form 11% by weight of cotton seed oil solution ratio) to induce liquid - liquid phase separation. 于42℃将搅拌器减速至430rpm,将烧瓶置于冰浴内。 At 42 ℃ decelerate the agitator to 430rpm, the flask was placed in an ice bath. 然后将制得的混合物冷至约22℃,同时继续搅拌使磷光体粒子分散于悬浮液内。 The resulting mixture is then cooled to about 22 ℃, while continuing stirring to make the phosphor particles are dispersed in the suspension.

将71.4克与三羟甲基丙烷加合的甲苯二异氰酸酯的甲苯溶液(MobayChemicals以商标Mondur CB-75出售)加入冷却的混合物中进行交联,由此使由于添加棉子油而沉积于核材料周围的HEVA外壳发生固化。 The crosslinking (MobayChemicals the trademark Mondur CB-75 sold) was added to the cooled mixture and a toluene solution of 71.4 g of trimethylolpropane adduct of toluene diisocyanate in, whereby the addition of cotton seed oil deposition in nuclear material HEVA shell around curing. 加入二异氰酸酯加合物后,再将所得混合物进一步冷却至约10℃,然后任其升温至环境温度,同时继续搅拌。 After addition of diisocyanate adduct, and the resulting mixture was further cooled to about 10 ℃, and then allowed to warm to ambient temperature while stirring was continued. 搅拌持续至交联完成。 Stirring was continued for the crosslinking is complete.

然后过滤收取所得的微胶囊,用甲苯洗涤,再悬浮于1250毫升1,1,2-三氯-1,2,2-三氟乙烷内达5至1 0分钟,使微胶囊壁或外壳收紧而提高抗水性,并防止在过滤及干燥过程中微胶囊发生聚集。 Was collected by filtration and then the resulting microcapsules, washed with toluene, and then suspended in 1250 ml of 1,1,2-trichloro-1,2,2-by five to ten minutes in a trifluoroethane, so that the microcapsule wall or housing tightening improve water resistance, and to prevent aggregation of the microcapsules occurs in the filtration and drying process. 重复该悬浮三次,然后滤出微胶囊,再用少量1,1,2-三氟-1,2,2-三氟乙烷再次洗涤。 The suspension was repeated three times, and then the microcapsules were filtered off, and then a small amount of 1,1,2-trifluoro-1,2,2-trifluoroethane and washed again. 然后将胶囊与细碎的硅胶(WRGrace公司以商标Syloid 74出售)混合,帮助防止微胶囊聚集。 Then the capsule with the finely divided silica (WRGrace sold under the trademark Syloid 74) mix to help prevent aggregation of the microcapsules. 用500微米的筛筛过Syloid/微胶囊混合物,再用106微米筛筛过,然后再散布于盘上干燥。 With 500 micron sieve over Syloid / microcapsule mixture and 106 micron sieve over, and then spread to the disc dry. 收率约80%。 The yield of about 80%.

实施例2用900克平均直径约10微米至约40微米的蓝色磷光体粒子成功地重复实施例1的方法。 Successful method of Example 1 was repeated blue phosphor particles in Example 2 with 900 g average diameter of about 10 microns to about 40 microns.

实施例3用600克平均直径约10微米至约40微米的黄色磷光体粒子成功地重复实例1的方法。 Successful method of Example 1 was repeated yellow phosphor particles in Example 3 using 600 g average diameter of about 10 microns to about 40 microns.

实施例4用其中44-46%的醋酸乙烯酯基团已水解成乙烯醇基团的水解乙烯-醋酸乙烯酯共聚物成功地重复实例1的方法。 Example 4 in which 44-46% of the vinyl acetate groups have been hydrolysed to vinyl alcohol groups of hydrolyzed ethylene - vinyl acetate copolymer successful method of Example 1 was repeated.

本领域的技术人员者所容易理解的是,本发明能用于多方面。 Those skilled in the art will be readily understood that the present invention can be used in many ways. 除本申请所述的具体实施方式之外,本发明许多具体实施方式和修改以及多种变化都可从本发明及前述说明书中明显地得到或合理地暗示出来,但仍不背离本发明内容或范围。 In addition to the specific embodiments described herein, many embodiments and that various changes and modifications of the present invention can be clearly obtained from the present invention and the foregoing description or reasonably implied out, but still departing from the present invention, or range. 前述公开并不意图,也不应被认作是对本发明的限制或排除任何其他的具体实施方式,修改和变化,本发明只受如以下权利要求所限定的发明精神和范围的限制。 The foregoing disclosure is not intended to, and should not be construed as a limitation or exclusion of any other specific embodiments, modifications and variations of the present invention, the present invention is limited only by the following claims as defined by the spirit and scope of the invention.

Classifications
International ClassificationB01J13/02, H05B33/14, H01L51/50, B01J13/06, A61K9/50, H05B33/20, B01J13/04, B32B15/02
Cooperative ClassificationY10T428/2985, B01J13/06, Y10T428/2982, Y10T428/2991, Y10T428/2984, Y10T428/2989, B01J13/14
European ClassificationB01J13/14, B01J13/06
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