JP2007160519A

JP2007160519A - Single-layer phosphor fine particle film, phosphor fine particle film laminate, manufacturing method of them, display device and photosensitive body using them and sensor

Info

Publication number: JP2007160519A
Application number: JP2005355934A
Authority: JP
Inventors: Kazufumi Ogawa; 小川　　一文
Original assignee: Kagawa University NUC
Current assignee: Kagawa University NUC
Priority date: 2005-12-09
Filing date: 2005-12-09
Publication date: 2007-06-28

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a film uniform in thickness on a particle size level using phosphor fine particles because micron- or nano-sized phosphor fine particles are numerously developed and manufactured but it is necessary to form the phosphor fine particles into a film uniform in thickness in order to effectively utilize the original function possessed by those phosphor fine particles. <P>SOLUTION: One film of the phosphor fine particles is formed on the surface of a base material. The single-layer phosphor fine particle films are covalently bonded mutually through a first organic film wherein one film of phosphor fine particles formed on one side of the base material is formed on the surface of the base material and the second organic film formed on the surfaces of the fine phosphor particles. The first organic film formed on the surface of the base material and the second organic film formed on the surfaces of the fine phosphor particles are different mutually. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、膜厚が均一な単層蛍光体微粒子膜や前記単層蛍光体微粒子膜を積層した蛍光体微粒子膜積層体、およびそれらを用いた表示装置と感光体とセンサーに関するものである。 The present invention relates to a single-layer phosphor fine particle film having a uniform film thickness, a phosphor fine particle film laminate in which the single-layer phosphor fine particle films are laminated, and a display device, a photoreceptor and a sensor using the same.

本発明において、「蛍光体微粒子」には、主として、アルカリハライド、希土類イオン蛍光体、マンガン蛍光体、硫化物蛍光体が含まれる。また、ここでいう蛍光体微粒子には、いわゆるＥＬ材料も含まれる。 In the present invention, “phosphor fine particles” mainly include alkali halides, rare earth ion phosphors, manganese phosphors, and sulfide phosphors. Moreover, what is called EL material is also contained in the fluorescent substance fine particle here.

従来から、両親媒性の有機分子を用い、水面上で分子を並べて基板表面に単分子膜を累積するラングミュアー・ブロジェット（ＬＢ）法が知られている。また、界面活性剤を溶かした溶液中で化学吸着法を用いて単分子膜を累積する化学吸着（ＣＡ）法が知られている。
例えば、参考特許として以下のものがある
特開2001-279471号公報 Conventionally, a Langmuir-Blodget (LB) method is known in which amphiphilic organic molecules are used, molecules are arranged on the water surface, and a monomolecular film is accumulated on the substrate surface. Further, a chemical adsorption (CA) method is known in which monomolecular films are accumulated using a chemical adsorption method in a solution in which a surfactant is dissolved.
For example, there are the following as reference patents:
JP 2001-279471 A

しかしながら、任意の基材表面に蛍光体微粒子を１層のみ並べた粒子サイズレベルで均一厚みの被膜（以下、単層蛍光体微粒子膜という。）や蛍光体微粒子を１層のみ並べた膜を複数層累積した被膜（以下、蛍光体微粒子膜積層体という。）、及び、それらの製造方法は、未だ開発、提供されていなかった。 However, a plurality of films having a uniform thickness (hereinafter referred to as a single-layer phosphor fine particle film) or a single layer of phosphor fine particles arranged on a surface of an arbitrary substrate with a single particle size level of phosphor fine particles. A layer-accumulated film (hereinafter referred to as a phosphor fine particle film laminate) and a production method thereof have not yet been developed and provided.

従来から、ミクロンサイズ、あるいは、ナノサイズの蛍光体微粒子は数々開発製造されている。しかしながら、それら蛍光体微粒子が持つ本来の機能を有効に利用するには、蛍光体微粒子を均一な膜厚の被膜にする必要があるが、それら蛍光体微粒子を用いて粒子サイズレベルで均一厚みの被膜を製造するという思想はなかった。 Conventionally, many micron-sized or nano-sized phosphor fine particles have been developed and manufactured. However, in order to effectively use the original functions of the phosphor fine particles, it is necessary to form the phosphor fine particles into a film having a uniform film thickness. There was no idea of producing a coating.

本発明は、蛍光体微粒子を用い、各種蛍光体微粒子本来の機能を損なうことなく、任意の基材表面に蛍光体微粒子を１層のみ並べた粒子サイズレベルで均一厚みの被膜（単層蛍光体微粒子膜）や蛍光体微粒子を１層のみ並べた膜を複数層累積した被膜（蛍光体微粒子膜積層体）、及び、それらの製造方法を提供することを目的とする。 The present invention uses phosphor fine particles, and a coating (single layer phosphor) having a uniform thickness at a particle size level in which only one layer of phosphor fine particles is arranged on the surface of an arbitrary substrate without impairing the original functions of various phosphor fine particles. It is an object of the present invention to provide a coating film (phosphor fine particle film laminated body) in which a plurality of films each including only one layer of a fine particle film or phosphor fine particles are accumulated, and a method for manufacturing the same.

前記課題を解決するための手段として提供される第一の発明は、基材表面に１層形成された蛍光体微粒子の膜が当該基材表面に形成された第１の有機膜と蛍光体微粒子表面に形成された第２の有機膜を介して互いに共有結合している単層蛍光体微粒子膜である。 A first invention provided as a means for solving the above-described problems is that a phosphor fine particle film formed on one surface of a substrate surface is formed with a first organic film and phosphor particles formed on the substrate surface. This is a single-layer phosphor fine particle film that is covalently bonded to each other via a second organic film formed on the surface.

第二の発明は、第１の発明に於いて、基材表面に形成された第１の有機被膜と蛍光体微粒子表面に形成された第２の有機膜が互いに異なる単層蛍光体微粒子膜である。 The second invention is the single-layer phosphor fine particle film according to the first invention, wherein the first organic film formed on the substrate surface and the second organic film formed on the phosphor fine particle surface are different from each other. is there.

第三の発明は、第１の発明に於いて、共有結合が、エポキシ基とイミノ基の反応で形成された−Ｎ−Ｃ−の結合である単層蛍光体微粒子膜である。 A third invention is the single-layer phosphor fine particle film according to the first invention, wherein the covalent bond is a —N—C— bond formed by a reaction between an epoxy group and an imino group.

第四の発明は、第二の発明に於いて、基材表面に形成された第１の有機被膜と蛍光体微粒子表面に形成された第２の有機膜が単分子膜で構成されている単層蛍光体微粒子膜である。 According to a fourth invention, in the second invention, the first organic film formed on the surface of the substrate and the second organic film formed on the surface of the phosphor fine particles are formed of a monomolecular film. This is a single layer phosphor fine particle film.

第五の発明は、第一乃至四の発明の蛍光体微粒子膜を使用した表示装置である。 A fifth invention is a display device using the phosphor fine particle film of the first to fourth inventions.

第六の発明は、第一乃至四の発明の蛍光体微粒子膜を使用したことを特徴とする感光体である。 A sixth invention is a photoconductor characterized by using the phosphor fine particle film of the first to fourth inventions.

第七の発明は、第一乃至四の発明の蛍光体微粒子膜を使用したことを特徴とするセンサーである。 A seventh invention is a sensor characterized by using the phosphor fine particle film of the first to fourth inventions.

第八の発明は、基材表面を少なくとも第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程と、蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて蛍光体微粒子表面に第２の反応性の有機膜を形成する工程と、第１の反応性の有機膜が形成された基材表面に第２の反応性の有機膜で被覆された蛍光体微粒子を接触させて反応させる工程と、余分な第２の反応性の有機膜で被覆された蛍光体微粒子を洗浄除去する単層蛍光体微粒子膜の製造方法である。 In the eighth invention, the surface of the substrate is brought into contact with a chemical adsorption solution prepared by mixing at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the substrate surface are reacted. And a step of forming a first reactive organic film on the surface of the substrate, and a chemisorbed liquid prepared by mixing phosphor fine particles with at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent A step of forming a second reactive organic film on the surface of the phosphor fine particles by allowing the alkoxysilane compound and the surface of the phosphor fine particles to react with each other, and a substrate on which the first reactive organic film is formed A step of bringing phosphor particles coated with the second reactive organic film into contact with the surface for reaction, and a single-layer fluorescence for washing and removing the phosphor particles coated with the extra second reactive organic film Small body It is a method of manufacturing a child film.

第九の発明は、第八の発明に於いて、基材表面を少なくとも第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程、および蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて蛍光体微粒子表面に第２の反応性の有機膜を形成する工程の後に、それぞれ基材および蛍光体微粒子表面を有機溶剤で洗浄して基材及び蛍光体微粒子表面に共有結合した第１、及び、第２の反応性の単分子膜を形成する単層蛍光体微粒子膜の製造方法である。 According to a ninth invention, in the eighth invention, the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and then alkoxylated. A step of reacting the silane compound with the surface of the substrate to form a first reactive organic film on the surface of the substrate; and phosphor fine particles comprising at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. After the step of forming a second reactive organic film on the surface of the phosphor fine particles by reacting the alkoxysilane compound and the surface of the phosphor fine particles by dispersing in a chemisorption liquid prepared by mixing, the substrate and the fluorescence Method for producing single-layer phosphor fine particle film in which first and second reactive monomolecular films are formed by washing body fine particle surface with organic solvent and covalently bonding to substrate and phosphor fine particle surface A.

第十の発明は、第八の発明に於いて、第１の反応性の有機膜がエポキシ基を含み第２の反応性の有機膜がイミノ基を含むか、第１の反応性の有機膜がイミノ基を含み第２の反応性の有機膜がエポキシ基を含む単層蛍光体微粒子膜の製造方法である。 In a tenth aspect based on the eighth aspect, the first reactive organic film contains an epoxy group and the second reactive organic film contains an imino group, or the first reactive organic film Is a method for producing a single-layer phosphor fine particle film that contains an imino group and the second reactive organic film contains an epoxy group.

第十一の発明は、第九の発明に於いて、第１の反応性の単分子膜がエポキシ基を含み第２の反応性の単分子膜がイミノ基を含むか、第１の反応性の単分子 In an eleventh aspect based on the ninth aspect, the first reactive monomolecular film contains an epoxy group and the second reactive monomolecular film contains an imino group, or the first reactivity Single molecule

膜がイミノ基を含み第２の反応性の単分子膜がエポキシ基を含む単層蛍光体微粒子膜の製造方法である。 This is a method for producing a single-layer phosphor fine particle film in which the film contains an imino group and the second reactive monomolecular film contains an epoxy group.

第十二の発明は、基材表面に層状に累積され蛍光体微粒子が蛍光体微粒子表面に形成された有機被膜を介して層間で互いに共有結合している蛍光体微粒子膜積層体。 A twelfth aspect of the invention is a phosphor fine particle film laminate in which phosphor fine particles are accumulated in layers on the surface of a substrate and are covalently bonded to each other through an organic film formed on the surface of the fine phosphor particles.

第十三の発明は、第十二の発明に於いて、蛍光体微粒子表面に形成された有機被膜が２種類有り、第１の有機膜が形成された蛍光体微粒子と第２の有機膜が形成された蛍光体微粒子とが交互に積層されている蛍光体微粒子膜積層体である。 According to a thirteenth invention, in the twelfth invention, there are two types of organic coatings formed on the surface of the phosphor fine particles, and the phosphor fine particles on which the first organic film is formed and the second organic film are The phosphor fine particle film laminate in which the formed phosphor fine particles are alternately laminated.

第十四の発明は、第十三の発明に於いて、第１の有機膜と第２の有機膜が反応して共有結合を形成している蛍光体微粒子膜積層体である。 A fourteenth invention is the phosphor fine particle film laminate according to the thirteenth invention, wherein the first organic film and the second organic film react to form a covalent bond.

第十五の発明は、第十二の発明に於いて、共有結合が、エポキシ基とイミノ基の反応で形成された−Ｎ−Ｃ−の結合である蛍光体微粒子膜積層体である。 A fifteenth invention is the phosphor fine particle film laminate according to the twelfth invention, wherein the covalent bond is a —N—C— bond formed by a reaction between an epoxy group and an imino group.

第十六の発明は、第十二乃至第十五の発明の蛍光体微粒子膜積層体を使用した表示装置である。 A sixteenth invention is a display device using the phosphor fine particle film laminate of the twelfth to fifteenth inventions.

第十七の発明は、第十二乃至第十五の発明の蛍光体微粒子膜積層体を使用した感光体である。 The seventeenth invention is a photoconductor using the phosphor fine particle film laminate of the twelfth to fifteenth inventions.

第十八の発明は、第十二乃至第十五の発明の蛍光体微粒子膜積層体を使用したセンサーである。 The eighteenth invention is a sensor using the phosphor fine particle film laminate of the twelfth to fifteenth inventions.

第十九の発明は、少なくとも基材表面を第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程と、第１の蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて第１の蛍光体微粒子表面に第２の反応性の有機膜を形成する工程と、第１の反応性の有機膜が形成された基材表面に第２の反応性の有機膜で被覆された第１の蛍光体微粒子を接触させて反応させる工程と、余分な第２の反応性の有機膜で被覆された第１の蛍光体微粒子を洗浄除去して第１の単層蛍光体微粒子膜を形成する工程と、第２の蛍光体微粒子を少なくとも第３のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて第２の蛍光体微粒子表面に第３の反応性の有機膜を形成する工程と、第２の反応性の有機膜で被覆された第１の単層蛍光体微粒子膜が形成された基材表面に第３の反応性の有機膜で被覆された第２の蛍光体微粒子を接触させて反応させる工程と、余分な第３の反応性の有機膜で被覆された第２の蛍光体微粒子を洗浄除去して第２の単層蛍光体微粒子膜を形成する工程を用いた蛍光体微粒子膜積層体の製造方法である。 In the nineteenth invention, at least the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing the first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the substrate surface are brought into contact with each other. A step of forming a first reactive organic film on the surface of the substrate by reacting, and a first phosphor fine particle is prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent A step of forming a second reactive organic film on the surface of the first fluorescent fine particles by dispersing the alkoxysilane compound and the surface of the fluorescent fine particles so as to be dispersed in the chemisorbed liquid, and the first reactive organic A step of bringing the first phosphor fine particles coated with the second reactive organic film into contact with the surface of the substrate on which the film is formed and reacting with the substrate, and an extra second reactive organic film coated First phosphor fine particles A step of forming a first single-layer phosphor fine particle film by washing and removing, and a chemical produced by mixing the second phosphor fine particle with at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of forming a third reactive organic film on the surface of the second phosphor fine particles by allowing the alkoxysilane compound and the surface of the phosphor fine particles to react with each other by dispersing in an adsorbing liquid; and a second reactive organic film A step of bringing the second phosphor fine particles coated with the third reactive organic film into contact with the surface of the base material on which the coated first single-layer phosphor fine particle film is formed, and reacting, 3 is a method for manufacturing a phosphor fine particle film laminate using a step of forming a second single layer phosphor fine particle film by washing and removing the second phosphor fine particles coated with the reactive organic film of No. 3.

第二十の発明は、第十九の発明に於いて、第１の反応性の有機膜と第３の反応性の有機膜が同じものである蛍光体微粒子膜積層体の製造方法である。 The 20th invention is the method for producing a phosphor fine particle film laminate according to the 19th invention, wherein the first reactive organic film and the third reactive organic film are the same.

第二十一の発明は、第十九の発明に於いて、第２の単層蛍光体微粒子膜を形成する工程の後、同様に第１の単層蛍光体微粒子膜を形成する工程と第２の単層蛍光体微粒子膜を形成する工程を繰り返し行う多層構造の蛍光体微粒子膜積層体の製造方法である。 According to a twenty-first aspect, in the nineteenth aspect, after the step of forming the second single-layer phosphor fine particle film, the step of similarly forming the first single-layer phosphor fine particle film and the first step 2 is a method for producing a multilayered phosphor fine particle film laminate in which the step of forming a single-layer phosphor fine particle film is repeated.

第二十二の発明は、第十九の発明に於いて、第１〜３の反応性の有機膜を形成する工程の後に、それぞれ基材、あるいは、蛍光体微粒子表面を有機溶剤で洗浄して基材や蛍光体微粒子表面に共有結合した第１〜３の反応性の単分子膜を形成する蛍光体微粒子膜積層体の製造方法である。 According to a twenty-second invention, in the nineteenth invention, after the steps of forming the first to third reactive organic films, the substrate or the surface of the phosphor fine particles is washed with an organic solvent, respectively. And a phosphor fine particle film laminate for forming first to third reactive monomolecular films covalently bonded to the surface of the substrate and the fine phosphor particles.

第二十三の発明は、第十九の発明に於いて、第１および３の反応性の有機膜がエポキシ基を含み第２の反応性の有機膜がイミノ基を含むか、第１および３の反応性の有機膜がイミノ基を含み第２の反応性の有機膜がエポキシ基を含む蛍光体微粒子膜積層体の製造方法である。 According to a twenty-third aspect, in the nineteenth aspect, the first and third reactive organic films contain an epoxy group and the second reactive organic film contains an imino group, 3 is a method for producing a phosphor fine particle film laminate in which the reactive organic film 3 contains an imino group and the second reactive organic film contains an epoxy group.

第二十四の発明は、第五および第十九の発明に於いて、シラノール縮合触媒の代わりに、ケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物を用いる単層蛍光体微粒子膜および蛍光体微粒子膜積層体の製造方法である。 The twenty-fourth invention uses a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound in place of the silanol condensation catalyst in the fifth and nineteenth inventions. This is a method for producing a single-layer phosphor fine particle film and a phosphor fine particle film laminate.

第二十五の発明は、第五および第十九の発明に於いて、シラノール縮合触媒に助触媒としてケチミン化合物、又は、有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物から選ばれる少なくとも１つを混合して用いる蛍光体微粒子膜積層体の製造方法である。
さらに、本発明に関してその要旨を説明する。 According to a twenty-fifth invention, in the fifth and nineteenth inventions, from a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound as a co-catalyst for a silanol condensation catalyst. This is a method of manufacturing a phosphor fine particle film laminate using a mixture of at least one selected.
Further, the gist of the present invention will be described.

本発明は、基材表面を少なくとも第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程と、蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて蛍光体微粒子表面に第２の反応性の有機膜を形成する工程と、第１の反応性の有機膜が形成された基材表面に第２の反応性の有機膜で被覆された蛍光体微粒子を接触させて反応させる工程と、余分な第２の反応性の有機膜で被覆された蛍光体微粒子を洗浄除去する工程とにより、基材表面に１層形成された蛍光体微粒子の膜が基材表面に形成された第１の有機膜と蛍光体微粒子表面に形成された第２の有機膜を介して互いに共有結合している単層蛍光体微粒子膜を提供することを要旨とする。 In the present invention, the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the substrate surface are reacted. A step of forming a first reactive organic film on the surface of the substrate; and a chemisorption liquid prepared by mixing phosphor fine particles with at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of dispersing and reacting the alkoxysilane compound and the surface of the phosphor fine particles to form a second reactive organic film on the surface of the phosphor fine particles; and a surface of the substrate on which the first reactive organic film is formed. A step of bringing the phosphor fine particles coated with the second reactive organic film into contact with each other and a step of washing and removing the phosphor fine particles coated with the extra second reactive organic film; A single layer in which a layer of phosphor fine particles formed on the surface is covalently bonded to each other via a first organic film formed on the surface of the substrate and a second organic film formed on the surface of the phosphor fine particles The gist is to provide a phosphor fine particle film.

このとき、基材表面を少なくとも第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程、および蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて蛍光体微粒子表面に第２の反応性の有機膜を形成する工程の後に、それぞれ基材および蛍光体微粒子表面を有機溶剤で洗浄して基材及び蛍光体微粒子表面に共有結合した第１及び第２の反応性の単分子膜を形成すると単層蛍光体微粒子膜の膜厚制御を容易にできて都合がよい。 At this time, the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the substrate surface are reacted to form a group. A step of forming a first reactive organic film on the surface of the material, and phosphor fine particles dispersed in a chemical adsorption solution prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent After the step of reacting the alkoxysilane compound with the phosphor fine particle surface to form the second reactive organic film on the phosphor fine particle surface, the substrate and the phosphor fine particle surface are washed with an organic solvent, respectively. Forming the first and second reactive monomolecular films covalently bonded to the surface of the material and the phosphor fine particles is convenient because it is easy to control the film thickness of the single-layer phosphor fine particle film.

さらに、第１の反応性の有機膜にエポキシ基を含め第２の反応性の有機膜にイミノ基を含めておくか、第１の反応性の有機膜にイミノ基を含め第２の反応性の有機膜にエポキシ基を含めておくと、基材表面に共有結合した単層蛍光体微粒子膜を作製する上で都合がよい。
また、第１の反応性の単分子膜にエポキシ基を含め第２の反応性の単分子膜がイミノ基を含めておくか、第１の反応性の単分子膜がイミノ基を含め第２の反応性の単分子膜がエポキシ基を含めておくと基材表面に共有結合した単層蛍光体微粒子膜を作製する上で都合がよい。 Further, an epoxy group is included in the first reactive organic film and an imino group is included in the second reactive organic film, or an imino group is included in the first reactive organic film. Including an epoxy group in the organic film is convenient for producing a single-layer phosphor fine particle film covalently bonded to the substrate surface.
In addition, the first reactive monomolecular film includes an epoxy group and the second reactive monomolecular film includes an imino group, or the first reactive monomolecular film includes an imino group and the second reactive monomolecular film includes an imino group. When the reactive monomolecular film includes an epoxy group, it is convenient to produce a single-layer phosphor fine particle film covalently bonded to the substrate surface.

さらにまた、シラノール縮合触媒の代わりに、ケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物を用いると製膜時間を短縮する上で都合がよい。
また、シラノール縮合触媒に助触媒としてケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物から選ばれる少なくとも１つを混合して用いるとさらに製膜時間を短縮できて都合がよい。 Furthermore, it is convenient to use a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound in place of the silanol condensation catalyst for shortening the film formation time.
In addition, the use of a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound as a co-catalyst as a co-catalyst for the silanol condensation catalyst can further reduce the film formation time. convenient.

またここで、蛍光体微粒子表面に形成された第１の有機被膜と基材表面に形成された第２の有機膜が互いに異ならせておけば、単層蛍光体微粒子膜を基材表面に１層のみ結合させる上で都合がよい。 Here, if the first organic film formed on the phosphor fine particle surface and the second organic film formed on the substrate surface are different from each other, the single-layer phosphor fine particle film is formed on the substrate surface. Convenient for bonding only the layers.

さらに、共有結合としてエポキシ基とイミノ基の反応で形成された−Ｎ−Ｃ−の結合を用いると、基材に対して密着強度が優れた単層蛍光体微粒子膜を提供する上で都合がよい。
また、蛍光体微粒子表面に形成された第１の有機被膜と基材表面に形成された第２の有機膜が単分子膜で構成されていると膜厚均一性を改善する上で都合がよい。 Furthermore, using a —N—C— bond formed by the reaction of an epoxy group and an imino group as a covalent bond is advantageous in providing a single-layer phosphor fine particle film having excellent adhesion strength to a substrate. Good.
In addition, it is convenient to improve the film thickness uniformity when the first organic film formed on the surface of the phosphor fine particles and the second organic film formed on the surface of the substrate are formed of a monomolecular film. .

さらに、本発明は、少なくとも基材表面を第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程と、第１の蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて第１の蛍光体微粒子表面に第２の反応性の有機膜を形成する工程と、第１の反応性の有機膜が形成された基材表面に第２の反応性の有機膜で被覆された第１の蛍光体微粒子を接触させて反応させる工程と、余分な第２の反応性の有機膜で被覆された第１の蛍光体微粒子を洗浄除去して第１の単層蛍光体微粒子膜を形成する工程と、第２の蛍光体微粒子を少なくとも第３のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて第２の蛍光体微粒子表面に第３の反応性の有機膜を形成する工程と、第２の反応性の有機膜で被覆された第１の単層蛍光体微粒子膜が形成された基材表面に第３の反応性の有機膜で被覆された第２の蛍光体微粒子を接触させて反応させる工程と、余分な第３の反応性の有機膜で被覆された第２の蛍光体微粒子を洗浄除去して第２の単層蛍光体微粒子膜を形成する工程とにより、基材表面に層状に累積され蛍光体微粒子が蛍光体微粒子表面に形成された有機被膜を介して層間で互いに共有結合している蛍光体微粒子膜積層体を提供することを要旨とする。 Furthermore, the present invention makes the alkoxysilane compound react with the substrate surface by contacting at least the substrate surface with a chemical adsorption solution prepared by mixing the first alkoxysilane compound, the silanol condensation catalyst, and the non-aqueous organic solvent. And forming the first reactive organic film on the surface of the substrate, and forming the first phosphor fine particles by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of forming a second reactive organic film on the surface of the first phosphor fine particles by dispersing in the chemical adsorption solution and reacting the alkoxysilane compound with the surface of the phosphor fine particles, and the first reactive organic film A step of bringing the first phosphor fine particles coated with the second reactive organic film into contact with the surface of the substrate on which the second reactive organic film is formed, and reacting with the first phosphor fine particles coated with the extra second reactive organic film. 1 phosphor fine particles The first phosphor fine particle film is formed by washing and removing, and the second phosphor fine particles are prepared by mixing at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of forming a third reactive organic film on the surface of the second phosphor fine particles by reacting the alkoxysilane compound with the surface of the phosphor fine particles by dispersing in the chemical adsorption solution; and a second reactive organic film. A step of bringing the second phosphor fine particles coated with the third reactive organic film into contact with the surface of the base material on which the first single-layer phosphor fine particle film coated with is reacted, The second phosphor fine particles coated with the third reactive organic film are washed and removed to form a second single-layer phosphor fine particle film, and the phosphor fine particles are accumulated in layers on the substrate surface. Through an organic coating formed on the surface of the phosphor particles And gist thereof is to provide a fluorescent fine particle film laminate which is covalently bonded to one another in layers.

このとき、第１の反応性の有機膜と第３の反応性の有機膜に同じものを用いると蛍光体微粒子膜積層体の製造方法を単層純化する上で都合がよい。
また、第２の単層蛍光体微粒子膜を形成する工程の後、同様に第１の単層蛍光体微粒子膜を形成する工程と第２の単層蛍光体微粒子膜を形成する工程を繰り返し行えば、多層構造の蛍光体微粒子膜積層体を容易に製造できる。 At this time, it is convenient to purify the phosphor fine particle film laminate by using the same one for the first reactive organic film and the third reactive organic film.
Further, after the step of forming the second single-layer phosphor fine particle film, the step of similarly forming the first single-layer phosphor fine particle film and the step of forming the second single-layer phosphor fine particle film are repeated. For example, a phosphor fine particle film laminate having a multilayer structure can be easily produced.

さらに、第１〜３の反応性の有機膜を形成する工程の後に、それぞれ基材あるいは蛍光体微粒子表面を有機溶剤で洗浄して基材や蛍光体微粒子表面に共有結合した第１〜３の反応性の単分子膜を形成すると、蛍光体微粒子膜積層体の膜厚を均一化する上で都合がよい。 Further, after the steps of forming the first to third reactive organic films, the substrate or phosphor fine particle surface is washed with an organic solvent to be covalently bonded to the substrate or phosphor fine particle surface, respectively. Forming a reactive monomolecular film is convenient for making the film thickness of the phosphor fine particle film laminate uniform.

さらにまた、第１および３の反応性の有機膜がエポキシ基を含み第２の反応性の有機膜がイミノ基を含むか、第１および３の反応性の有機膜がイミノ基を含み第２の反応性の有機膜がエポキシ基を含んでいると、エポキシ基とイミノ基の反応で層間で共有結合した蛍光体微粒子膜積層体を製造する上で都合がよい。 Furthermore, the first and third reactive organic films contain an epoxy group and the second reactive organic film contains an imino group, or the first and third reactive organic films contain an imino group and the second reactive organic film contains an imino group. When the reactive organic film contains an epoxy group, it is convenient for producing a phosphor fine particle film laminate in which an epoxy group and an imino group are covalently bonded to each other.

さらにまた、シラノール縮合触媒の代わりに、ケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物を用いると製膜時間を短縮する上で都合がよい。
また、シラノール縮合触媒に助触媒としてケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物から選ばれる少なくとも１つを混合して用いるとさらに製膜時間を短縮できて都合がよい。
またここで、蛍光体微粒子表面に形成された有機被膜を２種類用い、第１の有機膜が形成された蛍光体微粒子と第２の有機膜が形成された蛍光体微粒子とを交互に積層すると多層の蛍光体微粒子膜積層体を単層純なプロセスで製造する上で都合がよい。 Furthermore, it is convenient to use a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound in place of the silanol condensation catalyst for shortening the film formation time.
In addition, the use of a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound as a co-catalyst as a co-catalyst for the silanol condensation catalyst can further reduce the film formation time. convenient.
Further, here, when two types of organic coatings formed on the surface of the phosphor fine particles are used, the phosphor fine particles on which the first organic film is formed and the phosphor fine particles on which the second organic film is formed are alternately laminated. This is convenient for producing a multilayer phosphor fine particle film laminate by a single-layer pure process.

さらに、第１の有機膜と第２の有機膜が反応して共有結合を形成していると密着強度が優れた蛍光体微粒子膜積層体を提供する上で都合がよい。また、共有結合として、エポキシ基とイミノ基の反応で形成された−Ｎ−Ｃ−の結合を用いると、強度の点で優れた蛍光体微粒子膜積層体を提供する上で都合がよい。 Furthermore, when the first organic film and the second organic film are reacted to form a covalent bond, it is convenient to provide a phosphor fine particle film laminate having excellent adhesion strength. In addition, when a —NC— bond formed by a reaction between an epoxy group and an imino group is used as a covalent bond, it is convenient to provide a phosphor fine particle film laminate excellent in strength.

以上説明したとおり、本発明によれば、蛍光体微粒子を用い、各種蛍光体微粒子本来の機能を損なうことなく、任意の基材表面に蛍光体微粒子を１層のみの並べた粒子サイズレベルで均一厚みの被膜（単層蛍光体微粒子膜）や蛍光体微粒子を１層のみの並べた膜を複数層累積した被膜（蛍光体微粒子膜積層体）及びそれらの製造方法を低コストで提供できる格別の効果がある。 As described above, according to the present invention, phosphor fine particles are used, and uniform at a particle size level in which only one layer of phosphor fine particles is arranged on the surface of an arbitrary substrate without impairing the original functions of various phosphor fine particles. A coating with a thickness (single-layer phosphor fine particle film), a film in which a plurality of layers of phosphor fine particles arranged in a single layer (phosphor fine particle film laminate), and a manufacturing method thereof can be provided at low cost. effective.

本発明は、少なくとも基材表面を第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程と、第１の蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて第１の蛍光体微粒子表面に第２の反応性の有機膜を形成する工程と、第１の反応性の有機膜が形成された基材表面に第２の反応性の有機膜で被覆された第１の蛍光体微粒子を接触させて反応させる工程と、余分な第２の反応性の有機膜で被覆された第１の蛍光体微粒子を洗浄除去して第１の単層蛍光体微粒子膜を形成する工程と、第２の蛍光体微粒子を少なくとも第３のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて第２の蛍光体微粒子表面に第３の反応性の有機膜を形成する工程と、第２の反応性の有機膜で被覆された第１の単層蛍光体微粒子膜が形成された基材表面に第３の反応性の有機膜で被覆された第２の蛍光体微粒子を接触させて反応させる工程と、余分な第３の反応性の有機膜で被覆された第２の蛍光体微粒子を洗浄除去して第２の単層蛍光体微粒子膜を形成する工程とにより、基材表面に層状に累積され蛍光体微粒子が蛍光体微粒子表面に形成された有機被膜を介して層間で互いに共有結合している蛍光体微粒子膜積層体を用いた表示装置や感光体、センサーを提供するものである。 In the present invention, at least the substrate surface is brought into contact with a chemical adsorption solution prepared by mixing a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the substrate surface are reacted. A step of forming a first reactive organic film on the surface of the substrate; and a chemical adsorption formed by mixing the first phosphor fine particles with at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of dispersing the alkoxysilane compound and the surface of the phosphor fine particles to form a second reactive organic film on the surface of the first phosphor fine particles, and forming a first reactive organic film; A step of bringing the first phosphor fine particles coated with the second reactive organic film into contact with the surface of the substrate that has been reacted, and a first of the first coated with the extra second reactive organic film Cleaning phosphor particles A step of forming a first single-layer phosphor fine particle film, and a chemical adsorption produced by mixing the second phosphor fine particles with at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent A step of forming a third reactive organic film on the surface of the second phosphor fine particles by reacting the alkoxysilane compound with the surface of the phosphor fine particles by dispersing in the liquid, and coating with the second reactive organic film A step of bringing the second phosphor fine particles coated with the third reactive organic film into contact with the surface of the substrate on which the first single-layer phosphor fine particle film thus formed is brought into contact, and an extra third The second phosphor fine particles coated with the reactive organic film are washed and removed to form a second single-layer phosphor fine particle film, and the phosphor fine particles are accumulated in layers on the substrate surface. Between layers through organic coatings formed on the surface of body particles Display device and the photosensitive member using a fluorescent fine particle film laminate that is covalently bonded to have, there is provided a sensor.

したがって、本発明では、２種類の被膜で被われた２種類の蛍光体微粒子を用いることにより、各種蛍光体微粒子本来の機能を損なうことなく、任意の基材表面に蛍光体微粒子を１層のみの並べた粒子サイズレベルで均一厚みの被膜（単層蛍光体微粒子膜）や蛍光体微粒子を１層のみの並べた膜を複数層累積した被膜（蛍光体微粒子膜積層体）を用いた製品を提供し、それらを簡便で低コストに製造できる方法を提供できる作用がある。 Therefore, in the present invention, by using two kinds of phosphor fine particles covered with two kinds of coatings, only one layer of phosphor fine particles is formed on the surface of an arbitrary substrate without impairing the original functions of the various phosphor fine particles. A product using a film with a uniform thickness (single layer phosphor fine particle film) and a film in which a plurality of films with only one layer of phosphor fine particles are accumulated (phosphor fine particle film laminate) There is an effect that it is possible to provide a method that can be produced easily and at low cost.

以下、本願発明の詳細を実施例を用いて説明するが、本願発明は、これら実施例によって何ら限定されるものではない。 Hereinafter, although the detail of this invention is demonstrated using an Example, this invention is not limited at all by these Examples.

また、本発明に関する単層蛍光体微粒子膜や蛍光体微粒子膜積層体の蛍光体微粒子には、主として、アルカリハライド、希土類イオン蛍光体、マンガン蛍光体、硫化物蛍光体等があるが、まず、代表例として硫化亜鉛の微粒子状の蛍光体を取り上げて説明する。 The phosphor fine particles of the single-layer phosphor fine particle film and phosphor fine particle film laminate according to the present invention mainly include alkali halides, rare earth ion phosphors, manganese phosphors, sulfide phosphors, etc. As a representative example, a zinc sulfide fine particle phosphor will be described.

まず、大きさが１００ｎｍ程度の無水の硫化亜鉛微粒子１を用意し、よく乾燥した。次に、化学吸着剤として機能部位に反応性の官能基、例えば、エポキシ基あるいはイミノ基と他端にアルコキシシリル基を含む薬剤、例えば、下記式（化１）あるいは（化２）に示す薬剤を９９重量％、シラノール縮合触媒として、例えば、ジブチル錫ジアセチルアセトナート、あるいは有機酸である酢酸を１重量％となるようそれぞれ秤量し、シリコーン溶媒、例えば、ヘキサメチルジシロキサンとジメチルホルムアミド（５０：５０）混合溶媒に１重量％程度の濃度（好ましくい化学吸着剤の濃度は、０．５〜３％程度）になるように溶かして化学吸着液を調製した。 First, anhydrous zinc sulfide fine particles 1 having a size of about 100 nm were prepared and dried well. Next, as a chemical adsorbent, a functional group having a reactive functional group such as an epoxy group or imino group and an alkoxysilyl group at the other end, such as a chemical represented by the following formula (Chemical Formula 1) or (Chemical Formula 2) As a silanol condensation catalyst, for example, dibutyltin diacetylacetonate or acetic acid as an organic acid is weighed to 1% by weight, respectively, and a silicone solvent such as hexamethyldisiloxane and dimethylformamide (50: 50) A chemisorbed solution was prepared by dissolving in a mixed solvent to a concentration of about 1% by weight (preferably the concentration of the chemical adsorbent is about 0.5 to 3%).

この吸着液に無水の硫化亜鉛微粒子１を混入撹拌して普通の空気中で（相対湿度４５％）で２時間程度反応させた。このとき、無水の硫化亜鉛微粒子表面のダングリングボンドには水酸基２が多数含まれているの（図１（ａ））で、前記化学吸着剤の−Ｓｉ（ＯＣＨ_３）基と前記水酸基がシラノール縮合触媒あるいは有機酸である酢酸の存在下で脱アルコール（この場合は、脱ＣＨ_３ＯＨ）反応し、下記式（化３）あるいは（化４）に示したような結合を形成し、蛍光体微粒子表面全面に亘り表面と化学結合したエポキシ基を含む化学吸着単分子膜３あるいはアミノ基を含む化学吸着膜４が約１ナノメートル程度の膜厚で形成された（図１（ｂ）、１（ｃ））。なお、ここで、アミノ基を含む吸着剤を使用する場合には、スズ系の触媒では沈殿が生成するので、酢酸等の有機酸を用いた方がよかった。また、アミノ基はイミノ基を含んでいるが、アミノ基以外にイミノ基を含む物質には、ピロール誘導体や、イミダゾール誘導体等がある。さらに、ケチミン誘導体を用いれば、被膜形成後、加水分解により容易にアミノ基を導入できた。 Anhydrous zinc sulfide fine particles 1 were mixed in the adsorbed liquid and stirred, and reacted in ordinary air (relative humidity 45%) for about 2 hours. At this time, since the dangling bonds on the surface of the anhydrous zinc sulfide fine particles contain a large number of hydroxyl groups 2 (FIG. 1 (a)), the —Si (OCH ₃ ) group of the chemical adsorbent and the hydroxyl group are silanols. A dealcoholization (in this case, de-CH ₃ OH) is reacted in the presence of a condensation catalyst or acetic acid, which is an organic acid, to form a bond as shown in the following formula (Chemical Formula 3) or (Chemical Formula 4). A chemisorption monomolecular film 3 containing an epoxy group chemically bonded to the surface over the entire surface of the fine particle or a chemisorption film 4 containing an amino group was formed with a film thickness of about 1 nanometer (FIG. 1 (b), 1 (C)). Here, when an adsorbent containing an amino group is used, since a precipitate is generated with a tin-based catalyst, it is better to use an organic acid such as acetic acid. The amino group contains an imino group, but substances containing an imino group in addition to the amino group include pyrrole derivatives and imidazole derivatives. Furthermore, when a ketimine derivative was used, an amino group could be easily introduced by hydrolysis after film formation.

その後、塩素系溶媒であるクロロホルムを添加して撹拌洗浄する（この実施例ではトリクレン等）と、表面に反応性の官能基、例えばエポキシ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子５、あるいはアミノ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子６をそれぞれ作製できた。 Thereafter, chloroform, which is a chlorinated solvent, is added and washed with stirring (in this example, trichlene, etc.), and zinc sulfide fine particles covered with a chemically adsorbed monomolecular film having a reactive functional group such as an epoxy group on the surface. 5 or zinc sulfide fine particles 6 covered with a chemisorption monomolecular film having an amino group could be produced.

なお、この被膜はナノメートルレベルの膜厚で極めて薄いため、粒子径を損なうことはなかった。
一方、洗浄せずに空気中に取り出すと、反応性はほぼ変わらないが、溶媒が蒸発し粒子表面に残った化学吸着剤が表面で空気中の水分と反応して、単分子膜に比べるとやや厚いが、表面に前記化学吸着剤よりなる極薄のポリマー膜が形成された蛍光体微粒子が得られた。 Note that this film was extremely thin with a nanometer-level film thickness, so the particle diameter was not impaired.
On the other hand, when it is taken out into the air without washing, the reactivity is almost the same, but the chemical adsorbent remaining on the particle surface reacts with the moisture in the air due to the evaporation of the solvent, compared with the monomolecular film. Although slightly thick, phosphor fine particles were obtained in which an ultrathin polymer film made of the chemical adsorbent was formed on the surface.

この方法の特徴は、脱アルコール反応であるため、蛍光体微粒子が有機物であったとしても使用可能であり、適用範囲が広い。 Since this method is characterized by a dealcoholization reaction, it can be used even if the phosphor fine particles are organic, and has a wide range of applications.

実施例１と同様に、まず、ガラス基材１１を用意し、よく乾燥した。次に、化学吸着剤として機能部位に反応性の官能基、例えば、エポキシ基あるいはイミノ基と他端にアルコキシシリル基を含む薬剤、例えば、前記式（化１）（あるいは（化２））に示す薬剤を９９重量％、シラノール縮合触媒として、例えば、ジブチル錫ジアセチルアセトナートを１重量％となるようそれぞれ秤量し、シリコーン溶媒、例えば、ヘキサメチルジシロキサン溶媒に１重量％程度の濃度（好ましくい化学吸着剤の濃度は、０．５〜３％程度）になるように溶かして化学吸着液を調製した。 As in Example 1, first, a glass substrate 11 was prepared and thoroughly dried. Next, as a chemical adsorbent, a functional group reactive at the functional site, for example, an epoxy group or imino group and an agent containing an alkoxysilyl group at the other end, such as the above formula (Formula 1) (or (Formula 2)) 99% by weight of the drug to be used and 1% by weight of dibutyltin diacetylacetonate as a silanol condensation catalyst, for example, are weighed to a concentration of about 1% by weight in a silicone solvent such as hexamethyldisiloxane solvent (preferably A chemical adsorption solution was prepared by dissolving so that the concentration of the chemical adsorbent was about 0.5 to 3%.

次に、この吸着液に、ガラス基材１１を漬浸して普通の空気中で（相対湿度４５％）で２時間程度反応させた。このとき、ガラス基材１１表面には水酸基１２が多数含まれているの（図２（ａ））で、前記化学吸着剤の−Ｓｉ（ＯＣＨ_３）基と前記水酸基がシラノール縮合触媒の存在下で脱アルコール（この場合は、脱ＣＨ_３ＯＨ）反応し、前記式（化３）（あるいは（化４））に示したような結合を形成し、ガラス基材１１表面全面に亘り表面と化学結合したエポキシ基を含む化学吸着単分子膜１３（図２（ｂ））（あるいはアミノ基を含む化学吸着膜１４（図２（ｃ）））が約１ナノメートル程度の膜厚で形成される。 Next, the glass substrate 11 was immersed in this adsorbing solution and reacted in ordinary air (relative humidity 45%) for about 2 hours. At this time, since the surface of the glass substrate 11 contains a large number of hydroxyl groups 12 (FIG. 2A), the —Si (OCH ₃ ) group of the chemical adsorbent and the hydroxyl group are present in the presence of a silanol condensation catalyst. To deal with alcohol (in this case, de-CH ₃ OH) to form a bond as shown in the above formula (Chem. 3) (or (Chem. 4)). A chemically adsorbed monomolecular film 13 containing bonded epoxy groups (FIG. 2B) (or a chemically adsorbed film 14 containing amino groups (FIG. 2C)) is formed with a film thickness of about 1 nanometer. .

その後、塩素系溶媒であるクロロホルムを用いて洗浄する（本実施例では、トリクレン）と、表面に反応性の官能基、例えばエポキシ基を有する化学吸着単分子膜で被われたガラス基材１５、あるいは、アミノ基を有する化学吸着単分子膜で被われたガラス基材１６がそれぞれ作製できた。（図２（ｂ）、２（ｃ）） Thereafter, the glass substrate 15 covered with a chemisorbed monomolecular film having a reactive functional group, for example, an epoxy group on the surface is washed with chloroform, which is a chlorinated solvent (in this embodiment, trichlene). Alternatively, each of the glass substrates 16 covered with a chemically adsorbed monomolecular film having an amino group could be produced. (Fig. 2 (b), 2 (c))

なお、この被膜はナノメートルレベルの膜厚で極めて薄いため、ガラス基材の透明性を損なうことはなかった。
一方、洗浄せずに空気中に取り出すと、反応性はほぼ変わらないが、溶媒が蒸発しガラス基材表面に残った化学吸着剤が表面で空気中の水分と反応して、表面に前記化学吸着剤よりなる極薄のポリマー膜が形成されたガラス基材が得られた。 In addition, since this film was extremely thin with a film thickness of nanometer level, the transparency of the glass substrate was not impaired.
On the other hand, when it is taken out into the air without washing, the reactivity is not substantially changed, but the chemical adsorbent remaining on the glass substrate surface reacts with the moisture in the air on the surface, and the chemical is adsorbed on the surface. A glass substrate on which an extremely thin polymer film made of an adsorbent was formed was obtained.

次ぎに、前記エポキシ基を有する化学吸着単分子膜で被われたガラス基材１５表面に、アミノ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子６（前記アミノ基を有する化学吸着単分子膜で被われたガラス基材表面に、エポキシ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子の組み合わせでもよい。）をアルコールに分散させて塗布し加熱する（本実施例では、１００℃）と、ガラス基材表面のエポキシ基と接触している硫化亜鉛微粒子表面のアミノ基が下記式（化５）に示したような反応で付加して蛍光体微粒子とガラス基材は二つの単分子膜を介して結合固化した。なお、このとき、超音波を当てながらアルコールを蒸発させると、被膜の膜厚均一性を向上できた。 Next, on the surface of the glass substrate 15 covered with the chemisorption monomolecular film having the epoxy group, the zinc sulfide fine particles 6 covered with the chemisorption monomolecular film having the amino group (the chemisorption single molecule having the amino group). A glass substrate surface covered with a molecular film may be a combination of zinc sulfide fine particles covered with a chemisorbed monomolecular film having an epoxy group) dispersed in alcohol and heated (in this embodiment, 100 ° C.) and an amino group on the surface of the zinc sulfide fine particle in contact with the epoxy group on the surface of the glass substrate are added by the reaction shown in the following formula (Chemical Formula 5). It was solidified through two monolayers. At this time, when the alcohol was evaporated while applying ultrasonic waves, the film thickness uniformity of the coating could be improved.

そこで、再びアルコールで基材表面を洗浄し、余分な未反応のアミノ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子を洗浄除去すると、ガラス基材表面１５に共有結合したアミノ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子が１層のみ並べた状態で、且つ粒子サイズレベルで均一厚みの単層蛍光体微粒子膜１７が形成できた。（図３（ａ））

Therefore, the surface of the substrate is again washed with alcohol, and the zinc sulfide fine particles covered with the chemisorption monomolecular film having an extra unreacted amino group are washed and removed, whereby the amino group covalently bonded to the glass substrate surface 15 is removed. A single-layer phosphor fine particle film 17 having a uniform thickness at the particle size level could be formed in a state where only one layer of zinc sulfide fine particles covered with the chemisorbed monomolecular film had been arranged. (Fig. 3 (a))

一方、アミノ基を有する化学吸着単分子膜で被われたガラス基材表面に、エポキシ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子の被膜を形成した場合には、ガラス基材表面に共有結合したエポキシ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子が１層のみ並べた状態で、且つ粒子サイズレベルで均一厚みの単層蛍光体微粒子膜が形成できた。
なお、硫化亜鉛微粒子の単層蛍光体微粒子膜の厚みが１００ｎｍ程度であり、極めて均一性が良かったので、干渉色も全く見えなかった On the other hand, when a coating of zinc sulfide fine particles covered with a chemical adsorption monomolecular film having an epoxy group is formed on the surface of a glass substrate covered with a chemical adsorption monomolecular film having an amino group, the surface of the glass substrate A single-layer phosphor fine particle film having a uniform thickness at the particle size level can be formed in a state in which only one layer of zinc sulfide fine particles covered with a chemisorption monomolecular film having an epoxy group covalently bonded to is arranged.
In addition, since the thickness of the single layer phosphor fine particle film of zinc sulfide fine particles was about 100 nm and the uniformity was very good, no interference color was seen at all.

さらに、蛍光体微粒子膜の膜厚を厚くしたい場合、実施例３に引き続き、共有結合したアミノ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子を１層のみ並べた状態で、且つ粒子サイズレベルで均一厚みの単層蛍光体微粒子膜１７が形成されたガラス基材表面１５に、エポキシ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子５をアルコールに分散させて塗布し加熱（本実施例では、１００℃）すると、アミノ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子の単層蛍光体微粒子膜が形成されたガラス基材表面のアミノ基と接触している硫化亜鉛微粒子表面のエポキシ基が前記式（化５）に示したような反応で付加して、ガラス基材表面でアミノ基を有する化学吸着単分子膜で被われた蛍光体微粒子とエポキシ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子は、二つの単分子膜を介して結合固化した。 Further, when it is desired to increase the thickness of the phosphor fine particle film, the zinc sulfide fine particles covered with the chemisorbed monomolecular film having a covalently bonded amino group are arranged in a state where only one layer is arranged as in the case of Example 3. Zinc sulfide fine particles 5 covered with a chemical adsorption monomolecular film having an epoxy group are dispersed in alcohol and applied to a glass substrate surface 15 on which a single-layer phosphor fine particle film 17 having a uniform thickness at a size level is formed and heated. (In this example, at 100 ° C.), it is in contact with the amino group on the surface of the glass substrate on which the monolayer phosphor fine particle film of zinc sulfide fine particles covered with the chemisorption monomolecular film having an amino group is formed. Epoxy groups on the surface of zinc sulfide fine particles are added by the reaction shown in the above formula (Chemical Formula 5), and phosphor fine particles and epoxy groups covered with a chemisorption monomolecular film having amino groups on the surface of the glass substrate. Have Zinc sulfide fine particles covered with Manabu monomolecular film were bonded and solidified through the two monolayers.

そこで、再びアルコールで基材表面を洗浄し、余分で未反応のエポキシ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子を洗浄除去すると、ガラス基材表面１５に共有結合した２層目の硫化亜鉛微粒子が１層のみ並んだ状態で、且つ粒子サイズレベルで均一厚みの２層構造の複層蛍光体微粒子膜１８が形成できた。（図３（ｂ））
以下同様に、アミノ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子とエポキシ基を有する化学吸着単分子膜で被われた硫化亜鉛微粒子を交互に積層すると、任意の厚みで且つ多層構造の蛍光体微粒子の被膜を累積製造できた。 Then, the surface of the base material is again washed with alcohol, and the zinc sulfide fine particles covered with the chemisorption monomolecular film having an extra unreacted epoxy group are removed by washing, whereby the second layer covalently bonded to the glass base material surface 15 is obtained. A multilayer phosphor fine particle film 18 having a two-layer structure with a uniform thickness at the particle size level was formed in a state where only one layer of zinc sulfide fine particles was arranged. (Fig. 3 (b))
Similarly, when zinc sulfide fine particles covered with a chemisorption monomolecular film having an amino group and zinc sulfide fine particles covered with a chemisorption monomolecular film having an epoxy group are alternately laminated, a multilayer structure having an arbitrary thickness is obtained. Thus, it was possible to cumulatively produce the phosphor fine particle coating.

なお、上記実施例１および２では、反応性基を含む化学吸着剤として式（化１）あるいは（化２）に示した物質を用いたが、上記のもの以外にも、下記（１）〜（１６）に示した物質が利用できた。
(１) （ＣＨ_２ＯＣＨ）ＣＨ₂Ｏ(ＣＨ₂)_７Ｓｉ(ＯＣＨ_３)₃
(２) （ＣＨ_２ＯＣＨ）ＣＨ₂Ｏ(ＣＨ₂)_１１Ｓｉ(ＯＣＨ_３)₃
(３) （ＣＨ_２ＣＨＯＣＨ（ＣＨ_２）_２）ＣＨ(ＣＨ₂)_２Ｓｉ(ＯＣＨ_３)₃
(４) （ＣＨ_２ＣＨＯＣＨ（ＣＨ_２）_２）ＣＨ(ＣＨ₂)_４Ｓｉ(ＯＣＨ_３)₃
(５) （ＣＨ_２ＣＨＯＣＨ（ＣＨ_２）_２）ＣＨ(ＣＨ₂)_６Ｓｉ(ＯＣＨ_３)₃
(６) （ＣＨ２ＯＣＨ）ＣＨ₂Ｏ(ＣＨ₂)_７Ｓｉ(ＯＣ_２Ｈ_５)₃
(７) （ＣＨ_２ＯＣＨ）ＣＨ₂Ｏ(ＣＨ₂)_１１Ｓｉ(ＯＣ_２Ｈ_５)₃
(８) （ＣＨ_２ＣＨＯＣＨ（ＣＨ_２）_２）ＣＨ(ＣＨ₂)_２Ｓｉ(ＯＣ_２Ｈ_５)₃
(９) （ＣＨ_２ＣＨＯＣＨ（ＣＨ_２）_２）ＣＨ(ＣＨ₂)_４Ｓｉ(ＯＣ_２Ｈ_５)₃
(１０) （ＣＨ_２ＣＨＯＣＨ（ＣＨ_２）_２）ＣＨ(ＣＨ₂)_６Ｓｉ(ＯＣ_２Ｈ_５)₃
(１１) Ｈ₂Ｎ (ＣＨ₂)_５Ｓｉ(ＯＣＨ_３)₃
(１２) Ｈ₂Ｎ (ＣＨ₂)_７Ｓｉ(ＯＣＨ_３)₃
(１３) Ｈ₂Ｎ (ＣＨ₂)_９Ｓｉ(ＯＣＨ_３)₃
(１４) Ｈ₂Ｎ (ＣＨ₂)_５Ｓｉ(ＯＣ_２Ｈ_５)₃
(１５) Ｈ₂Ｎ (ＣＨ₂)_７Ｓｉ(ＯＣ_２Ｈ_５)₃
(１６) Ｈ₂Ｎ (ＣＨ₂)_９Ｓｉ(ＯＣ_２Ｈ_５)₃ In Examples 1 and 2 described above, the substance represented by the formula (Chemical Formula 1) or (Chemical Formula 2) was used as the chemical adsorbent containing a reactive group. The substance shown in (16) was available.
(1) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(2) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OCH ₃ ) ₃
(3) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₂ Si (OCH ₃ ) ₃
_{_{(4) (CH 2 CHOCH (}} CH 2) 2) CH (CH 2) 4 Si (OCH 3) 3
_{_{(5) (CH 2 CHOCH (}} CH 2) 2) CH (CH 2) 6 Si (OCH 3) 3
_{(6) (CH2OCH) CH 2} O (CH 2) 7 Si (OC 2 H 5) 3
(7) (CH ₂ OCH) CH ₂ O (CH ₂ ) ₁₁ Si (OC ₂ H ₅ ) ₃
_{_{(8) (CH 2 CHOCH (}} CH 2) 2) CH (CH 2) 2 Si (OC 2 H 5) 3
_{_{(9) (CH 2 CHOCH (}} CH 2) 2) CH (CH 2) 4 Si (OC 2 H 5) 3
(10) (CH ₂ CHOCH (CH ₂ ) ₂ ) CH (CH ₂ ) ₆ Si (OC ₂ H ₅ ) ₃
(11) H ₂ N (CH ₂ ) ₅ Si (OCH ₃ ) ₃
(12) H ₂ N (CH ₂ ) ₇ Si (OCH ₃ ) ₃
(13) H ₂ N (CH ₂ ) ₉ Si (OCH ₃ ) ₃
(14) H ₂ N (CH ₂ ) ₅ Si (OC ₂ H ₅ ) ₃
(15) H ₂ N (CH ₂ ) ₇ Si (OC ₂ H ₅ ) ₃
(16) H ₂ N (CH ₂ ) ₉ Si (OC ₂ H ₅ ) ₃

ここで、（ＣＨ_２ＯＣＨ）−基は、下記式（化７）で表される官能基を表し、（ＣＨ_２ＣＨＯＣＨ（ＣＨ_２）_２）ＣＨ−基は、下記式（化８）で表される官能基を表す。 Here, the (CH ₂ OCH) — group represents a functional group represented by the following formula (Chemical Formula 7), and the (CH ₂ CHOCH (CH ₂ ) ₂ ) CH— group is represented by the following formula (Chemical Formula 8). Represents a functional group.

なお、実施例１および２に置いて、シラノール縮合触媒には、カルボン酸金属塩、カルボン酸エステル金属塩、カルボン酸金属塩ポリマー、カルボン酸金属塩キレート、チタン酸エステル及びチタン酸エステルキレート類が利用可能である。さらに具体的には、酢酸第１錫、ジブチル錫ジラウレート、ジブチル錫ジオクテート、ジブチル錫ジアセテート、ジオクチル錫ジラウレート、ジオクチル錫ジオクテート、ジオクチル錫ジアセテート、ジオクタン酸第１錫、ナフテン酸鉛、ナフテン酸コバルト、２−エチルヘキセン酸鉄、ジオクチル錫ビスオクチリチオグリコール酸エステル塩、ジオクチル錫マレイン酸エステル塩、ジブチル錫マレイン酸塩ポリマー、ジメチル錫メルカプトプロピオン酸塩ポリマー、ジブチル錫ビスアセチルアセテート、ジオクチル錫ビスアセチルラウレート、テトラブチルチタネート、テトラノニルチタネート及びビス（アセチルアセトニル）ジープロピルチタネートを用いることが可能であった。 In Examples 1 and 2, silanol condensation catalysts include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates. Is available. More specifically, stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, stannous dioctanoate, lead naphthenate, cobalt naphthenate , Iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate, dioctyltin maleate, dibutyltin maleate polymer, dimethyltin mercaptopropionate polymer, dibutyltin bisacetylacetate, dioctyltin bisacetyl Laurate, tetrabutyl titanate, tetranonyl titanate and bis (acetylacetonyl) dipropyl titanate could be used.

また、膜形成溶液の溶媒としては、水を含まない有機塩素系溶媒、炭化水素系溶媒、あるいは、フッ化炭素系溶媒やシリコーン系溶媒、あるいは、それら混合物を用いることが可能であった。なお、洗浄を行わず、溶媒を蒸発させて粒子濃度を上げようとする場合には、溶媒の沸点は５０〜２５０℃程度がよい。さらに、吸着剤がアルコキシシラン系の場合で且つ溶媒を蒸発させて有機被膜を形成する場合には、前記溶媒に加え、メタノール、エタノール、プロパノール等のアルコール系溶媒、あるいは、それら混合物が使用できた。 In addition, as a solvent for the film forming solution, it is possible to use an organic chlorine-based solvent, a hydrocarbon-based solvent, a fluorinated carbon-based solvent, a silicone-based solvent, or a mixture thereof that does not contain water. In addition, when it is going to raise particle concentration by evaporating a solvent, without wash | cleaning, the boiling point of a solvent is good at about 50-250 degreeC. Furthermore, when the adsorbent is an alkoxysilane type and the organic film is formed by evaporating the solvent, in addition to the solvent, an alcohol type solvent such as methanol, ethanol, propanol, or a mixture thereof can be used. .

具体的に使用可能なものは、クロロシラン系非水系の石油ナフサ、ソルベントナフサ、石油エーテル、石油ベンジン、イソパラフィン、ノルマルパラフィン、デカリン、工業ガソリン、ノナン、デカン、灯油、ジメチルシリコーン、フェニルシリコーン、アルキル変性シリコーン、ポリエーテルシリコーン、ジメチルホルムアミド等を挙げることができる。 Specifically usable are chlorosilane-based non-aqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosene, dimethyl silicone, phenyl silicone, alkyl modified Examples thereof include silicone, polyether silicone, and dimethylformamide.

また、フッ化炭素系溶媒には、フロン系溶媒や、フロリナート（３Ｍ社製品）、アフルード（旭ガラス社製品）等がある。なお、これらは１種単層独で用いても良いし、良く混ざるものなら２種以上を組み合わせてもよい。さらに、クロロホルム等有機塩素系の溶媒を添加しても良い。 Fluorocarbon solvents include fluorocarbon solvents, Fluorinert (product of 3M), Afludo (product of Asahi Glass). These may be used alone or in combination of two or more if mixed well. Further, an organic chlorine solvent such as chloroform may be added.

一方、上述のシラノール縮合触媒の代わりに、ケチミン化合物又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物を用いた場合、同じ濃度でも処理時間を半分〜２／３程度まで短縮できた。 On the other hand, when a ketimine compound or organic acid, aldimine compound, enamine compound, oxazolidine compound, aminoalkylalkoxysilane compound is used instead of the above-mentioned silanol condensation catalyst, the treatment time is reduced to about half to 2/3 even at the same concentration. did it.

さらに、シラノール縮合触媒とケチミン化合物、又は、有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物を混合（１：９〜９：１範囲で使用可能だが、通常１：１前後が好ましい。）して用いると、処理時間をさらに数倍早く（３０分程度まで）でき、製膜時間を数分の一まで短縮できる。 Furthermore, a silanol condensation catalyst and a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound can be used in a range of 1: 9 to 9: 1. When used, the processing time can be further several times faster (up to about 30 minutes), and the film forming time can be reduced to a fraction of a minute.

例えば、シラノール触媒であるジブチル錫オキサイドをケチミン化合物であるジャパンエポキシレジン社のＨ３に置き換え、その他の条件は同一にしてみたが、反応時間を１時間程度にまで短縮できた他は、ほぼ同様の結果が得られた。 For example, dibutyltin oxide, which is a silanol catalyst, was replaced with H3 from Japan Epoxy Resin, which is a ketimine compound, and the other conditions were the same, but the reaction time was reduced to about 1 hour. Results were obtained.

さらに、シラノール触媒を、ケチミン化合物であるジャパンエポキシレジン社のＨ３と、シラノール触媒であるジブチル錫ビスアセチルアセトネートの混合物（混合比は１：１）に置き換え、その他の条件は同一にしてみたが、反応時間を３０分程度に短縮できた他は、ほぼ同様の結果が得られた。 Furthermore, the silanol catalyst was replaced with a mixture of ketimine compound Japan Epoxy Resin H3 and silanol catalyst dibutyltin bisacetylacetonate (mixing ratio is 1: 1), and other conditions were the same. The same results were obtained except that the reaction time could be shortened to about 30 minutes.

したがって、以上の結果から、ケチミン化合物や有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物がシラノール縮合触媒より活性が高いことが明らかとなった。 Therefore, the above results revealed that ketimine compounds, organic acids, aldimine compounds, enamine compounds, oxazolidine compounds, and aminoalkylalkoxysilane compounds are more active than silanol condensation catalysts.

さらにまた、ケチミン化合物や有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物の内の１つとシラノール縮合触媒を混合して用いると、さらに活性が高くなることが確認された。 Furthermore, it was confirmed that the activity is further increased when one of a ketimine compound, an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound is mixed with a silanol condensation catalyst.

なお、ここで、利用できるケチミン化合物は特に限定されるものではないが、例えば、２，５，８−トリアザ−１，８−ノナジエン、３，１１−ジメチル−４，７，１０−トリアザ−３，１０−トリデカジエン、２，１０−ジメチル−３，６，９−トリアザ−２，９−ウンデカジエン、２，４，１２，１４−テトラメチル−５，８，１１−トリアザ−４，１１−ペンタデカジエン、２，４，１５，１７−テトラメチル−５，８，１１，１４−テトラアザ−４，１４−オクタデカジエン、２，４，２０，２２−テトラメチル−５，１２，１９−トリアザ−４，１９−トリエイコサジエン等がある。 Here, the ketimine compound that can be used is not particularly limited. For example, 2,5,8-triaza-1,8-nonadiene, 3,11-dimethyl-4,7,10-triaza-3 , 10-tridecadiene, 2,10-dimethyl-3,6,9-triaza-2,9-undecadiene, 2,4,12,14-tetramethyl-5,8,11-triaza-4,11-pentadeca Diene, 2,4,15,17-tetramethyl-5,8,11,14-tetraaza-4,14-octadecadiene, 2,4,20,22-tetramethyl-5,12,19-triaza- 4,19-trieicosadiene and the like.

また、利用できる有機酸としても特に限定されるものではないが、例えば、ギ酸、あるいは酢酸、プロピオン酸、ラク酸、マロン酸等があり、ほぼ同様の効果があった。
さらにまた、単層の蛍光体微粒子膜や蛍光体微粒子膜積層体を使用すると、明るさの均一性が優れた表示装置や表示均一性に優れた感光板や感度均一性に優れたセンサーを製造できた。 Further, the organic acid that can be used is not particularly limited, but there are, for example, formic acid, acetic acid, propionic acid, lactic acid, malonic acid, and the like, which have almost the same effects.
Furthermore, when a single-layer phosphor particle film or phosphor particle film laminate is used, a display device with excellent brightness uniformity, a photosensitive plate with excellent display uniformity, and a sensor with excellent sensitivity uniformity are manufactured. did it.

上記実施例１〜４では、蛍光体として硫化亜鉛微粒子とガラス基材を例として説明したが、他にアルカリハライド、希土類イオン蛍光体、マンガン蛍光体、硫化物蛍光体等に適用可能である。また、表面に水酸基やイミノ基の様な活性水素を含む有機蛍光体にも適用可能である。
さらに、本発明の用途は、ディスプレー、蛍光灯、表示板、Ｘ線等の感光板、光記録媒体、電子写真イメージバー、ガス濃度センサー等がある。 In Examples 1 to 4 described above, the zinc sulfide fine particles and the glass base material have been described as examples of the phosphor. However, the present invention can be applied to alkali halides, rare earth ion phosphors, manganese phosphors, sulfide phosphors, and the like. Moreover, it is applicable also to the organic fluorescent substance which contains active hydrogen like a hydroxyl group or an imino group on the surface.
Furthermore, applications of the present invention include displays, fluorescent lamps, display plates, photosensitive plates such as X-rays, optical recording media, electrophotographic image bars, gas concentration sensors, and the like.

本発明の第１の実施例における蛍光体微粒子表面の反応を分子レベルまで拡大した概念図であり、（ａ）は反応前の硫化亜鉛蛍光体微粒子表面の図、（ｂ）は、エポキシ基を含む単分子膜が形成された後の図、（ｃ）は、アミノ基を含む単分子膜が形成された後の図を示す。It is the conceptual diagram which expanded the reaction of the phosphor fine particle surface in the 1st Example of this invention to the molecular level, (a) is the figure of the zinc sulfide phosphor fine particle surface before reaction, (b) is an epoxy group. The figure after the monomolecular film containing a film is formed, (c) shows the figure after the monomolecular film containing an amino group is formed. 本発明の第２の実施例におけるガラス基材表面の反応を分子レベルまで拡大した概念図であり、（ａ）は反応前の表面の図、（ｂ）は、エポキシ基を含む単分子膜が形成された後の図、（ｃ）は、アミノ基を含む単分子膜が形成された後の図を示す。It is the conceptual diagram which expanded reaction of the glass substrate surface in the 2nd Example of this invention to the molecular level, (a) is the figure of the surface before reaction, (b) is a monomolecular film containing an epoxy group. The figure after formation, (c) shows the figure after the monomolecular film containing an amino group is formed. 本発明の第３および第４の実施例におけるガラス基材表面の反応を分子レベルまで拡大した概念図であり、（ａ）は単層の硫化亜鉛蛍光体微粒子膜が形成された基材表面の図、（ｂ）は、単層の硫化亜鉛蛍光体微粒子膜が２層形成された基材表面の図を示す。It is the conceptual diagram which expanded the reaction of the glass substrate surface in the 3rd and 4th Example of this invention to the molecular level, (a) of the substrate surface in which the single layer zinc sulfide fluorescent substance fine particle film was formed FIG. 4B is a diagram showing the surface of a base material on which two layers of a single-layer zinc sulfide phosphor fine particle film are formed.

符号の説明Explanation of symbols

１硫化亜鉛微粒子
２水酸基
３エポキシ基を含む単分子膜
４アミノ基を含む単分子膜
５エポキシ基を含む単分子膜で被われた硫化亜鉛微粒子
６アミノ基を含む単分子膜で被われた硫化亜鉛微粒子
１１ガラス基材
１２水酸基
１３エポキシ基を含む単分子膜
１４アミノ基を含む単分子膜
１５エポキシ基を含む単分子膜で被われたガラス基材
１６アミノ基を含む単分子膜で被われたガラス基材
１７単層蛍光体微粒子膜
１８２層構造の複層蛍光体微粒子膜 1 Zinc sulfide fine particle 2 Hydroxyl group 3 Monomolecular film containing epoxy group 4 Monomolecular film containing amino group
5 Zinc sulfide fine particles covered with monomolecular film containing epoxy group
Zinc sulfide fine particles covered with monomolecular film containing 6 amino group 11 Glass substrate 12 Hydroxyl group
13 Monomolecular film containing an epoxy group 14 Monomolecular film containing an amino group
Glass substrate covered with a monomolecular film containing 15 epoxy groups
Glass substrate covered with monomolecular film containing 16 amino groups
17 single layer phosphor fine particle film
18 Double-layer phosphor fine particle film having two-layer structure

Claims

基材表面に１層形成された蛍光体微粒子の膜が当該基材表面に形成された第１の有機膜と蛍光体微粒子表面に形成された第２の有機膜を介して互いに共有結合していることを特徴とする単層蛍光体微粒子膜。 The phosphor fine particle film formed on the surface of the substrate is covalently bonded to each other through the first organic film formed on the surface of the substrate and the second organic film formed on the surface of the phosphor fine particle. A single-layer phosphor fine particle film characterized by comprising:

基材表面に形成された第１の有機被膜と蛍光体微粒子表面に形成された第２の有機膜が互いに異なることを特徴とする請求項１記載の単層蛍光体微粒子膜。 2. The single-layer phosphor fine particle film according to claim 1, wherein the first organic film formed on the substrate surface and the second organic film formed on the phosphor fine particle surface are different from each other.

共有結合が、エポキシ基とイミノ基の反応で形成された−Ｎ−Ｃ−の結合であることを特徴とする請求項１記載の単層蛍光体微粒子膜。 The single-layer phosphor fine particle film according to claim 1, wherein the covalent bond is a -NC- bond formed by a reaction between an epoxy group and an imino group.

基材表面に形成された第１の有機被膜と蛍光体微粒子表面に形成された第２の有機膜が単分子膜で構成されていることを特徴とする請求項１および２記載の単層蛍光体微粒子膜。 3. The single-layer fluorescence according to claim 1 or 2, wherein the first organic film formed on the substrate surface and the second organic film formed on the phosphor fine particle surface are formed of a monomolecular film. Body fine particle film.

請求項1から請求項4記載の蛍光体微粒子膜を使用したことを特徴とする表示装置。 5. A display device using the phosphor fine particle film according to claim 1.

請求項1から請求項4記載の蛍光体微粒子膜を使用したことを特徴とする感光体。 5. A photoconductor using the phosphor fine particle film according to claim 1.

請求項1から請求項4記載の蛍光体微粒子膜を使用したことを特徴とするセンサー。 5. A sensor using the phosphor fine particle film according to claim 1.

基材表面を少なくとも第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程と、蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて蛍光体微粒子表面に第２の反応性の有機膜を形成する工程と、第１の反応性の有機膜が形成された基材表面に第２の反応性の有機膜で被覆された蛍光体微粒子を接触させて反応させる工程と、余分な第２の反応性の有機膜で被覆された蛍光体微粒子を洗浄除去することを特徴とする単層蛍光体微粒子膜の製造方法。 The substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to cause the alkoxysilane compound and the substrate surface to react with each other. A step of forming a first reactive organic film, and phosphor fine particles dispersed in a chemical adsorption solution prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to obtain an alkoxy A step of forming a second reactive organic film on the surface of the phosphor fine particles by reacting the silane compound with the surface of the phosphor fine particles, and a second reaction on the surface of the substrate on which the first reactive organic film is formed. A single-layer phosphor, characterized in that a phosphor fine particle coated with a reactive organic film is brought into contact and reacted, and the phosphor fine particle coated with an extra second reactive organic film is washed away Method for producing a particle film.

基材表面を少なくとも第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程、および蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて蛍光体微粒子表面に第２の反応性の有機膜を形成する工程の後に、それぞれ基材および蛍光体微粒子表面を有機溶剤で洗浄して基材及び蛍光体微粒子表面に共有結合した第１及び第２の反応性の単分子膜を形成することを特徴とする請求項８記載の単層蛍光体微粒子膜の製造方法。 The substrate surface is brought into contact with a chemical adsorption solution prepared by mixing at least a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent to cause the alkoxysilane compound and the substrate surface to react with each other. A step of forming a first reactive organic film, and phosphor particles dispersed in a chemical adsorption solution prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, After the step of reacting the silane compound with the surface of the phosphor fine particles to form the second reactive organic film on the surface of the phosphor fine particles, the substrate and the surface of the phosphor fine particles are washed with an organic solvent, respectively. 9. The method for producing a single-layer phosphor fine particle film according to claim 8, wherein the first and second reactive monomolecular films covalently bonded to the surface of the fine particle are formed.

第１の反応性の有機膜がエポキシ基を含み第２の反応性の有機膜がイミノ基を含むか、第１の反応性の有機膜がイミノ基を含み第２の反応性の有機膜がエポキシ基を含むことを特徴とする請求項８記載の単層蛍光体微粒子膜の製造方法。 The first reactive organic film contains an epoxy group and the second reactive organic film contains an imino group, or the first reactive organic film contains an imino group and the second reactive organic film is 9. The method for producing a single-layer phosphor fine particle film according to claim 8, comprising an epoxy group.

第１の反応性の単分子膜がエポキシ基を含み第２の反応性の単分子膜がイミノ基を含むか、第１の反応性の単分子膜がイミノ基を含み第２の反応性の単分子膜がエポキシ基を含むことを特徴とする請求項９記載の単層蛍光体微粒子膜の製造方法。 The first reactive monolayer contains an epoxy group and the second reactive monolayer contains an imino group, or the first reactive monolayer contains an imino group and the second reactive monolayer The method for producing a single-layer phosphor fine particle film according to claim 9, wherein the monomolecular film contains an epoxy group.

基材表面に層状に累積され蛍光体微粒子が蛍光体微粒子表面に形成された有機被膜を介して層間で互いに共有結合していることを特徴とする蛍光体微粒子膜積層体。 A phosphor fine particle film laminate, wherein the phosphor fine particles are accumulated in layers on the surface of a substrate and are covalently bonded to each other through an organic film formed on the surface of the phosphor fine particles.

蛍光体微粒子表面に形成された有機被膜が２種類有り、第１の有機膜が形成された蛍光体微粒子と第２の有機膜が形成された蛍光体微粒子とが交互に積層されていることを特徴とする請求項１２記載の蛍光体微粒子膜積層体。 There are two types of organic coatings formed on the surface of the phosphor fine particles, and the phosphor fine particles on which the first organic film is formed and the phosphor fine particles on which the second organic film is formed are alternately laminated. 13. The phosphor fine particle film laminate according to claim 12,

第１の有機膜と第２の有機膜が反応して共有結合を形成していることを特徴とする請求項１３記載の蛍光体微粒子膜積層体。 14. The phosphor fine particle film laminate according to claim 13, wherein the first organic film and the second organic film react to form a covalent bond.

共有結合が、エポキシ基とイミノ基の反応で形成された−Ｎ−Ｃ−の結合であることを特徴とする請求項１２記載の蛍光体微粒子膜積層体。 13. The phosphor fine particle film laminate according to claim 12, wherein the covalent bond is a —N—C— bond formed by a reaction between an epoxy group and an imino group.

請求項１２乃至請求項１５記載の蛍光体微粒子膜積層体を使用したことを特徴とする表示装置。 16. A display device using the phosphor fine particle film laminate according to claim 12.

請求項１２乃至請求項１５記載の蛍光体微粒子膜積層体を使用したことを特徴とする感光体。 16. A photoconductor using the phosphor fine particle film laminate according to claim 12.

請求項１２乃至請求項１５記載の蛍光体微粒子膜積層体を使用したことを特徴とするセンサー。 16. A sensor using the phosphor fine particle film laminate according to claim 12.

少なくとも基材表面を第１のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に接触させてアルコキシシラン化合物と基材表面を反応させて基材表面に第１の反応性の有機膜を形成する工程と、第１の蛍光体微粒子を少なくとも第２のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて第１の蛍光体微粒子表面に第２の反応性の有機膜を形成する工程と、第１の反応性の有機膜が形成された基材表面に第２の反応性の有機膜で被覆された第１の蛍光体微粒子を接触させて反応させる工程、余分な第２の反応性の有機膜で被覆された第１の蛍光体微粒子を洗浄除去して第１の単層蛍光体微粒子膜を形成する工程と、第２の蛍光体微粒子を少なくとも第３のアルコキシシラン化合物とシラノール縮合触媒と非水系の有機溶媒を混合して作成した化学吸着液中に分散させてアルコキシシラン化合物と蛍光体微粒子表面を反応させて第２の蛍光体微粒子表面に第３の反応性の有機膜を形成する工程と、第２の反応性の有機膜で被覆された第１の単層蛍光体微粒子膜が形成された基材表面に第３の反応性の有機膜で被覆された第２の蛍光体微粒子を接触させて反応させる工程と、余分な第３の反応性の有機膜で被覆された第２の蛍光体微粒子を洗浄除去して第２の単層蛍光体微粒子膜を形成する工程とを含むことを特徴とする蛍光体微粒子膜積層体の製造方法。 At least the base material surface is brought into contact with a chemical adsorption solution prepared by mixing a first alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent, and the alkoxysilane compound and the base material surface are reacted to form a base material surface. A step of forming a first reactive organic film, and a first phosphor fine particle dispersed in a chemical adsorption solution prepared by mixing at least a second alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent A step of reacting the alkoxysilane compound with the surface of the phosphor fine particles to form a second reactive organic film on the surface of the first phosphor fine particles, and a substrate on which the first reactive organic film is formed A step of bringing the first phosphor fine particles coated with the second reactive organic film into contact with the surface and reacting; and washing the first phosphor fine particles coated with the extra second reactive organic film Removed first A step of forming a single-layer phosphor fine particle film, and the second phosphor fine particles are dispersed in a chemical adsorption solution prepared by mixing at least a third alkoxysilane compound, a silanol condensation catalyst, and a non-aqueous organic solvent. A step of forming a third reactive organic film on the surface of the second phosphor fine particle by reacting the alkoxysilane compound with the surface of the phosphor fine particle; and a first unit coated with the second reactive organic film. A step of bringing the second phosphor fine particles coated with the third reactive organic film into contact with the surface of the base material on which the layer phosphor fine particle film is formed and reacting, and an extra third reactive organic film And a step of forming a second single-layer phosphor fine particle film by washing and removing the second phosphor fine particles coated with (1).

第１の反応性の有機膜と第３の反応性の有機膜が同じものであることを特徴とする請求項１９記載の蛍光体微粒子膜積層体の製造方法。 20. The method of manufacturing a phosphor fine particle film laminate according to claim 19, wherein the first reactive organic film and the third reactive organic film are the same.

第２の単層蛍光体微粒子膜を形成する工程の後、同様に第１の単層蛍光体微粒子膜を形成する工程と第２の単層蛍光体微粒子膜を形成する工程を繰り返し行うことを特徴とする請求項１９に記載の多層構造の蛍光体微粒子膜積層体の製造方法。 After the step of forming the second single-layer phosphor fine particle film, the step of similarly forming the first single-layer phosphor fine particle film and the step of forming the second single-layer phosphor fine particle film are repeated. The method for producing a phosphor fine particle film laminate having a multilayer structure according to claim 19.

第１〜３の反応性の有機膜を形成する工程の後に、それぞれ基材あるいは蛍光体微粒子表面を有機溶剤で洗浄して基材や蛍光体微粒子表面に共有結合した第１〜３の反応性の単分子膜を形成することを特徴とする請求項１９記載の蛍光体微粒子膜積層体の製造方法。 After the steps of forming the first to third reactive organic films, the first to third reactivity in which the surface of the base material or phosphor fine particle is washed with an organic solvent and covalently bonded to the surface of the base material or phosphor fine particle, respectively. 20. The method for producing a phosphor fine particle film laminate according to claim 19, wherein the monomolecular film is formed.

第１および３の反応性の有機膜がエポキシ基を含み第２の反応性の有機膜がイミノ基を含むか、第１および３の反応性の有機膜がイミノ基を含み第２の反応性の有機膜がエポキシ基を含むことを特徴とする請求項１９記載の蛍光体微粒子膜積層体の製造方法。 The first and third reactive organic films contain an epoxy group and the second reactive organic film contains an imino group, or the first and third reactive organic films contain an imino group and the second reactivity The method for producing a phosphor fine particle film laminate according to claim 19, wherein the organic film contains an epoxy group.

シラノール縮合触媒の代わりに、ケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物を用いることを特徴とする請求項５および１９に記載の単層蛍光体微粒子膜および蛍光体微粒子膜積層体の製造方法。 20. The single-layer phosphor fine particle film according to claim 5 or 19, wherein a ketimine compound, or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, or an aminoalkylalkoxysilane compound is used in place of the silanol condensation catalyst. A method for producing a phosphor fine particle film laminate.

シラノール縮合触媒に助触媒としてケチミン化合物、又は有機酸、アルジミン化合物、エナミン化合物、オキサゾリジン化合物、アミノアルキルアルコキシシラン化合物から選ばれる少なくとも１つを混合して用いることを特徴とする請求項５および１９に記載の単層蛍光体微粒子膜および蛍光体微粒子膜積層体の製造方法。
A mixture of at least one selected from a ketimine compound or an organic acid, an aldimine compound, an enamine compound, an oxazolidine compound, and an aminoalkylalkoxysilane compound as a co-catalyst for the silanol condensation catalyst. A method for producing the single-layer phosphor fine particle film and the phosphor fine particle film laminate described