WO2008149471A1 - Fluor fine particle, manufacturing method thereof, and fluor covering film using them - Google Patents

Fluor fine particle, manufacturing method thereof, and fluor covering film using them Download PDF

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Publication number
WO2008149471A1
WO2008149471A1 PCT/JP2007/061948 JP2007061948W WO2008149471A1 WO 2008149471 A1 WO2008149471 A1 WO 2008149471A1 JP 2007061948 W JP2007061948 W JP 2007061948W WO 2008149471 A1 WO2008149471 A1 WO 2008149471A1
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Prior art keywords
fluor
fine particle
compound
functional group
group
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PCT/JP2007/061948
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French (fr)
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Kazufumi Ogawa
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Kazufumi Ogawa
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Priority to PCT/JP2007/061948 priority Critical patent/WO2008149471A1/en
Publication of WO2008149471A1 publication Critical patent/WO2008149471A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/301—Details of OLEDs
    • H10K2102/331—Nanoparticles used in non-emissive layers, e.g. in packaging layer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to a fluor fine particle, more specifically, relates to the fluor fine particle, of which surfaces are stabilized or surfaces are given with heat-reactivity or photoreactivity or radical reactivity or ion reactivity, and the covering film thereof.
  • the "fluor fine particle” includes mainly an alkali halide, rare earth ion fluor, manganese fluor, and sulfide fluor.
  • fluor fine particle mentioned herewith includes so-called EL film.
  • the fluor fine particle emitting a fluorescent light has been abundantly developed and manufactured.
  • a purpose of improving a dispersibility of the fluor fine particle in a solution or a plastic medium there are many known methods for adding a surfactant to a solution prepared by mixing the fluor fine particle with a solvent and a mixture of the fluor fine particle and a plastic (e.g., Japanese Published Patent Application No. 2005-514531 and No. 2002-80607).
  • the present invention aims to provide the fluor fine particles given with the function of inacrivating the surface keeping the shape and functions inherent in the fluor, the function of improving dispersibility in the solvent, and a variety of reaction functions by covering the surface of the fluor fine particles with the organic thin film such as a high performance monomolecular film containing a high performance functional group such as an inactive group having a 25 mN/ m or smaller of critical surface energy or a reactive functional group.
  • the organic thin film such as a high performance monomolecular film containing a high performance functional group such as an inactive group having a 25 mN/ m or smaller of critical surface energy or a reactive functional group.
  • a first invention provided as a means of solving the problem as described above is a fluor fine particle covered with an organic thin film having a covalent bond to a surface.
  • a second invention according to the first invention is the fluor fine particle, wherein the organic thin film having the covalent bond to the surface contains a high performance functional group in an end and the other end is composed of a molecule having the covalent bond to a particle surface via Si.
  • a third invention according to the second invention is the fluor fine particle, wherein a high performance functional group is an inactive group having a 25 mN/ m or smaller of critical surface energy or a reactive functional group.
  • a fourth invention according to the third invention is the fluor fine particle, wherein the inactive group having a 25 mN/ m or smaller of critical surface energy contains -CF3 or -CH 3 .
  • a fifth invention according to the third invention is the fluor fine particle, wherein the reactive functional group is heat-reactive or photoreactive or radical reactive or ion reactive functional group.
  • a sixth invention according to the fourth invention is the fluor fine particle, wherein the reactive functional group is an epoxy group and an imino group or a calconyl group.
  • a seventh invention according to the first invention and second invention is the fluor fine particle, wherein an organic thin film having a covalent bond to the surface is composed of a monomolecular film.
  • a eighth invention is a manufacturing method of the fluor fine particle, containing a step of reacting a chlorosilane compound to the surface of the fluor fine particle by dispersing the fiuor fine particle in a chemical adsorption solution prepared by mixing at least the chlorosilane compound with a nonaqueous organic solvent.
  • a ninth invention is the manufacturing method of the fluor fine particle, containing the step of reacting an alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution prepared by mixing at least the alkoxysilane compound, a silanol condensation catalyst, the nonaqueous organic solvent.
  • a tenth invention is the manufacturing method of the fluor fine particle, wherein following the step of reacting the chlorosilane compound or the alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution, the surface of the fluor fine particle is washed with an organic solvent to form a monomolecular film having the covalent bond to the surface of the fluor fine particle.
  • An eleventh invention according to the ninth invention is the manufacturing method of the fluor fine particle, wherein in a replacement of the silanol condensation catalyst, a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.
  • a twelfth invention according to the ninth invention is the manufacturing method of the fluor fine particle, wherein the ketimine compound or at least one selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound is blended with the silanol condensation catalyst for use as a promoter.
  • a thirteenth invention is a fluor covering film, wherein a surface of a base material covered with an organic thin film containing a reactive functional group on the surface has a covalent bond to the fluor fine particle covered with the organic thin film containing a functional group reactive to the reactive functional group through each organic thin film to make hardening and molding.
  • a fourteenth invention according to the thirteenth invention is the fluor covering film, containing the epoxy group and the imino group or the calconyl group as the reactive functional group.
  • a fifteenth invention is the manufacturing method of the fluor covering film, containing a step of blending the fluor fine particle having a first reactivity with the fluor fine particle having a second reactivity in an organic solvent for preparing a paste, the step of application to the surface of the base material, and the step of hardening.
  • a sixteenth invention according to the fourteenth invention is the manufacturing method of the fluor covering film, wherein the organic thin film having the functional group reactive to the fluor fine particle having the first reactivity or the fluor fine particle having the second reactivity is previously formed on the surface of a base material before application.
  • the present invention provides essentially a fluor fine particle given with a function of forming the organic thin film such as a high performance monomolecular film having the covalent bond to the surface of the fluor fine particle to improve solvent dispersibility keeping almost the function inherent in the fluor fine particle by reacting the chlorosilane compound to the surface of the fluor fine particle through dispersing the fluor fine particle in the chemical adsorption solution prepared by mixing at least the chlorosilane compound with the nonaqueous organic solvent, and a variety of reaction functions.
  • the present invention provides essentially the fluor fine particle given with the function of forming a covering film composed of a molecule having the covalent bond to the surface of the fluor fine particle by reacting the alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution prepared by mixing at least the alkoxysilane compound, the silanol condensation catalyst, and the nonaqueous organic solvent to improve solvent dispersibility keeping almost the function inherent in the fluor fine particle, and the variety of chemical reaction functions.
  • the present invention provides essentially the fluor fine particle given with the function of stabilizing the particle keeping almost completely a shape and function inherent in the fluor fine particle, the function of improving the dispersibility, and the variety of chemical reaction functions by washing the fluor fine particle with the organic solvent to wash and remove an excessive compounds to cover with a chemically adsorbed monomolecular film following reacting the chlorosilane compound or the alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution.
  • the silanol condensation catalyst can be replaced by the ketimine compound or the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound.
  • the ketimine compound or at least one selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound as the promoter by blending with the silanol condensation catalyst is preferable for shortening a reaction time.
  • the present invention provides essentially the hardened and formed fluor covering film having a high antiremoval resistance caused by having the covalent bond of the surface of the base material, which is covered with the organic thin film containing the reactive functional group on the surface, to the fluor fine particle, which is covered with the organic thin film containing the functional group reactive to the reactive functional group, through the each organic thin film.
  • the organic thin film having the functional group reactive to the fluor fine particle having the first reactivity or the fluor fine particle having the second reactivity on the surface of the base material before application is preferable for improving antiremoval resistance.
  • using the epoxy group and the imino group or the calconyl group as the reactive functional group is preferable for making the covalent bond to improve antiremoval resistance.
  • the present invention has an effect of providing the fluor fine particle given with the function of stabilizing the fluor fine particle keeping almost the inherent function, the function of improving the dispersibility in the variety of solvents, and the variety of chemical reaction functions. Furthermore, the present invention has the prominent effect of the function of stabilizing the fluor fine particle keeping almost completely the shape and function inherent in the fluor fine particle, the function of improving the dispersibility, and the variety of chemical reaction functions by covering with the chemically adsorbed monomolecular film. Moreover, the present invention has the effect of providing the fluor covering film excellent in antiremoval resistance performance.
  • FIG. 1 is a conceptual rendering made by enlarging the reaction of the fluor fine particle in the first example according to the present invention to a molecular level
  • FIG. 1A is a figure of the surface of the fluor fine particle before the reaction
  • FIG. 1 B the figure after the monomolecular film was formed
  • FIG. 2 is the conceptual rendering made by enlarging the reaction of the fluor fine particle in the second example according to the present invention to the molecular level
  • FIG. 2A is the figure of the surface of the fluor fine particle before the reaction
  • FIG. 2B the figure after the monomolecular film containing the epoxy group was formed
  • FIG. 2C the figure after the monomolecular film containing the amino group was formed.
  • the present invention provides the fluor fine particle, in which a molecule having the covalent bond to the surface has the reactive functional group such as heat-reactive or photoreactive or radical reactive or ion reactive functional groups and the fluor fine particle composes the monomolecular film, and the fluor covering film made by using them. Consequently, the present invention has the performance of providing the function of stabilizing the surface of the particle itself keeping almost completely the shape and function inherent in
  • the fluor fine particle includes mainly the alkali halide, rare earth ion fluor, manganese fluor, and sulfide fluor.
  • a zinc sulfate-based fluor fine particle will be described below as a typical example.
  • zinc sulfate fluor fine particle 1 with a 100 nm mean grain size was prepared (FIG. 1) and dried well.
  • a carbon fluoride group (functional site,) of which critical surface energy becomes 25 or smaller mN/ m by making the monomolecular film, and a chemical adsorbent such as CF3(CF 2 )7(CH 2 )2SiCl3 containing a chlorosilyl group (active site) are dissolved in the nonaqueous solvent (for example, dehydrated nonane) in a concentration of about 0.1 weight percents to prepare the chemical adsorption solution (hereafter adsorption solution.)
  • the zinc sulfate fluor fine particle is soaked in this adsorption solution, stir, and reacted in a dried atmosphere (relative humidity was preferably 30% or lower.)
  • Many hydroxyl groups (OH) 2 have bonded to a dangling bond on the surface of zinc sulfate fluor fine particle 1 (FIG.
  • the critical surface energy of the monomolecular film formed on the surface of the fluor fine particle becomes about 6 mN/ m and, hence, this pigment fluor fine particle became to disperse well in the freon-based solvent and a silicone-based solvent or a fluorine resin that has a small critical surface energy.
  • This chemical adsorption film has a very strong covalent bond to the surface of the fluor fine particle and, therefore, was not removed by a normal reaction. Furthermore, a film thickness is of a single molecule length (about 1 nm) and, thus, using the fluor fine particle (nano particle) having a particle size of about some ten nanometers caused no loss of the shape.
  • the shown example was the drug used as the chemical adsorbent, which has the carbon fluoride-based functional group having a surface energy reducible function in a functional site.
  • the drug such as CH3(CF2)7(CH2) 2 SiC
  • the obtained covering film had the critical surface energy of about 25 mN/ m.
  • using these drugs by blending arbitrarily enabled to control arbitrarily the critical surface energy of the covering film over the prepared fluor fine particle surface in a range between 6 and 25 mN/ m.
  • changing some functional groups in the functional site enables to give a new function and fabricate the fluor fine particle, of which surface energy is regulated to a target value, without the loss of the shape inherent in the fluor fine particles.
  • hydrochloric acid occurs in formation of the covering film to injure slightly the surface of the fluor fine particle.
  • hydrochloric acid occurred was a very little amount and, hence, no problem arose.
  • the fluor fine particle covered with the monomolecular film in such the way for example, the fluor fine particle covered with the hydrocarbon-based monomolecular film with the critical surface energy of about 25 mN/ m, could be dispersed in a very good condition for the hydrocarbon-based solvent and a hydrocarbon-based or acrylic plastic by inhibiting coagulation.
  • Example 1 as the carbon fluoride-based chemical adsorbent, CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl3 was used. However, substances, other than the above described materials, enumerated in the following (1 ) to (12) were usable including hydrocarbon-based substances. (I) CF 3 CH 2 O(CH 2 )I 5 SICI 3
  • an anhydrous cadmium sulfate fluor fine particle 11 was prepared and dried well.
  • the drug which contains the reactive functional group such as the epoxy group and the imino group in the functional site and an alkoxysilyl group in the other end, as the chemical adsorbent, exemplified by the drug shown in the following formula (Chemical formula C2) or (Chemical formula C3) was weighed to make a 99 weight percents and dibutyltin diacetyl acetonate or acetic acid being an organic acid, for example, as the silanol condensation catalyst was also weighed to make a 1 weight percents to dissolve in the solvent, which was prepared by mixing the same amounts of silicone and dimethyl formamide, such as the solution prepared by mixing hexamethyl disiloxane (50%) and dimethyl formamide (50%) to make about 1 weight percent concentration (a preferable concentration of the chemical adsorbent ranged from 0.5 to 3 percents) for preparation of the chemical adsorption solution.
  • the anhydrous cadmium sulfate fluor fine particle is dispersed and stirred in this adsorption solution and reacted in normal air (relative humidity 55%) for about 2 hours. At this time, many hydroxyl groups 12 has bonds to the dangling bond of the surface of the anhydrous cadmium sulfate fluor fine particle (FIG.
  • the amino group contains the imino group and substances, which contain the imino group other than the amino group, include pyrrole derivatives and irnidazol derivatives. Furthermore, using ketimine derivatives enabled to introduce easily the amino group by hydrolysis after the formation of the covering film.
  • the covering film is very thin in a nanometer order film thickness and, thus, the particle size was not affected.
  • This method in comparison with Example 1 , is characterized in no need of dried air to require no specially isolated room and, therefore, is excellent in mass producibility.
  • this method employs dealcohol reaction and not dehydrochlorination reaction and, hence, even if the fluor fine particle is a substance breakable largely by hydrochloric acid, can be used in a wide range of applications.
  • the organic thin film having the reactive functional group is previously formed on the surface of the base material by the same method, the organic thin film on the surface of the fluor fine particle react also to the organic thin film on the surface of the surface of the base material to enable to fabricate the fluor covering film having high antiremoval resistance.
  • Example 2 the materials shown in formulae (Chemical formula C2 or Chemical formula C3) were used as the chemical adsorbent containing the reactive group. Materials, other than the above described materials, shown by the following (21 ) to (36) were usable.
  • (CH 2 OCH)- group represents the functional group expressed by the following formula (Chemical formula C7) and (CH 2 CHOCH(CH 2 ) 2 )CH- represents the functional group expressed by the following formula (Chemical formula C8.) [C7]
  • the chemical adsorbent containing the functional group reactive to an energy beam such as a light or electron beam
  • the substances shown by the following (41 ) to (46) were usable. In this case, naturally, hardening simply requires irradiation of such energy beam as the light or electron beam.
  • usable silanol condensation catalysts are a metal salt of a carboxylic acid, the metal salt of a carboxylic acid ester, a polymer of the metal salt of the carboxylic acid, a chelate of the metal salt of the carboxylic acid, titanic acid ester, and chelates of the titanic acid ester.
  • usable materials were stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, tin dioctanoate, lead naphtenate, cobalt naphtenate, iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate ester salt, dioctyltin maleate ester salt, dibutyltin maleate salt polymer, dimetyltin mercaptopropionate salt polymer, dibutyltin bisacetyl acetate, dioctyltin bisacetyl laurate, tetrabutyl titanate, tetranonyl titanate, and bis (acetyl acetonyl
  • Usable solvents for a film forming solution were an organic chlorine-based solvent, hydrocarbon-based solvent, or carbon fluoride-based solvent, and silicone-based solvent or a mixture thereof, that contain no water in either of alkoxysilane or chlorosilane based chemical adsorbents.
  • a boiling point of the solvent ranges preferably from about 50 to 250 0 C.
  • Usable solvents include specifically an organic chlorine-based solvent, nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzin, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosine, dimethyl silicone, phenyl silicone, alkyl denatured silicone, polyether silicone, and dimethyl formamide.
  • adsorbent is alcoxysilane-based and the organic covering film is formed by evaporating the solvent, additionally to the solvent as described above, alcohol-based solvents such as methanol, ethanol, and propanol or the mixture thereof were used.
  • Still further carbon fluoride-based solvent are a freon-based solvent Frorinate (made by Sumitomo 3M Limited,) and Alfude (Asahi Glass Co. made.) These materials may be singly used and, if they can be blended well, may be used in a combination of two kinds.
  • the organic chlorine-based solvent such as chloroform may be added.
  • silanol condensation catalysts as described above were replaced for use by the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound, a process time could be shorten to make a half to 2/ 3 of the time necessary for the same concentration.
  • silanol condensation catalyst by mixing (a range from 1 : 9 to 9: 1 can be applied, but normally around 1 : 1 is preferable) with the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound can make the process time fast several-fold (up to about 30 minutes) resulting in shortening of the time for making the film up to several-fold decrease.
  • dibutyltin oxide being the silanol catalyst was replaced by Japan Epoxy Resin Co. made H3 being the ketimine compound under the same condition. Almost same result was obtained except that the reaction time became short to about 1 hour.
  • the silanol catalyst was replaced by the mixture (mixture ratio was
  • ketimine compounds are not specially restricted, but include, for example, 2,5,8-triaza-1 ,8-nonadiene,
  • Usable organic acids are not specially restricted, but include, for example, formic acid, or acetic acid, propionic acid, butyric acid, and malonic acid and showed the almost same effect.
  • the present invention can be applied to any inorganic fluor being the fluor fine particle containing active hydrogen such as the hydrogen of a hydroxy! group on the surface thereof.
  • the present invention can be applied to an organic fluor containing the active hydrogen such as the hydrogen of the hydroxyl group on the surface thereof.
  • the present invention can be applied to an alkali halide, rare earth ion fluor, manganese fluor, and sulfide fluor and is also applicable to the organic fluor containing the active hydrogen such as the hydrogen of the hydroxyl group on the surface thereof.
  • its usage includes a display, fluorescent light, indication board, and X-ray photographic plate.

Abstract

The present invention aims to provide the fluor fine particle given with the function of improving a solvent dispersibility and a variety of chemical reaction functions by covering the surface of the fluor fine particle with the organic thin film through dispersing the particle in the chemical adsorption solution prepared by mixing a silane compound with a nonaqueous organic solvent.

Description

DESCRIPTION
FLUOR FINE PARTICLE, MANUFACTURING METHOD THEREOF, AND FLUOR
COVERING FILM USING THEM
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a fluor fine particle, more specifically, relates to the fluor fine particle, of which surfaces are stabilized or surfaces are given with heat-reactivity or photoreactivity or radical reactivity or ion reactivity, and the covering film thereof.
According to the present invention, the "fluor fine particle" includes mainly an alkali halide, rare earth ion fluor, manganese fluor, and sulfide fluor. In addition, fluor fine particle mentioned herewith includes so-called EL film.
Description of Related Art
Conventionally, the fluor fine particle emitting a fluorescent light has been abundantly developed and manufactured. On the other hand, with a purpose of improving a dispersibility of the fluor fine particle in a solution or a plastic medium, there are many known methods for adding a surfactant to a solution prepared by mixing the fluor fine particle with a solvent and a mixture of the fluor fine particle and a plastic (e.g., Japanese Published Patent Application No. 2005-514531 and No. 2002-80607).
SUMMARY OF THE INVENTION
However, there has been no thought of giving further a new function almost without a loss of a function and shape inherent in those fluor fine particles.
Moreover, no new fluor fine particle, which is given with a variety of functions without the loss of the function inherent in the fluor fine particles by covering the fluor fine particles with an organic film such as a functional monomolecular film chemically adsorbed (having a covalent bond) to a surface of the fluor fine particle itself, and the manufacturing method thereof and a fluor covering film using them have been developed and provided so far.
The present invention aims to provide the fluor fine particles given with the function of inacrivating the surface keeping the shape and functions inherent in the fluor, the function of improving dispersibility in the solvent, and a variety of reaction functions by covering the surface of the fluor fine particles with the organic thin film such as a high performance monomolecular film containing a high performance functional group such as an inactive group having a 25 mN/ m or smaller of critical surface energy or a reactive functional group.
A first invention provided as a means of solving the problem as described above is a fluor fine particle covered with an organic thin film having a covalent bond to a surface.
A second invention according to the first invention is the fluor fine particle, wherein the organic thin film having the covalent bond to the surface contains a high performance functional group in an end and the other end is composed of a molecule having the covalent bond to a particle surface via Si.
A third invention according to the second invention is the fluor fine particle, wherein a high performance functional group is an inactive group having a 25 mN/ m or smaller of critical surface energy or a reactive functional group.
A fourth invention according to the third invention is the fluor fine particle, wherein the inactive group having a 25 mN/ m or smaller of critical surface energy contains -CF3 or -CH3.
A fifth invention according to the third invention is the fluor fine particle, wherein the reactive functional group is heat-reactive or photoreactive or radical reactive or ion reactive functional group. A sixth invention according to the fourth invention is the fluor fine particle, wherein the reactive functional group is an epoxy group and an imino group or a calconyl group.
A seventh invention according to the first invention and second invention is the fluor fine particle, wherein an organic thin film having a covalent bond to the surface is composed of a monomolecular film.
A eighth invention is a manufacturing method of the fluor fine particle, containing a step of reacting a chlorosilane compound to the surface of the fluor fine particle by dispersing the fiuor fine particle in a chemical adsorption solution prepared by mixing at least the chlorosilane compound with a nonaqueous organic solvent.
A ninth invention is the manufacturing method of the fluor fine particle, containing the step of reacting an alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution prepared by mixing at least the alkoxysilane compound, a silanol condensation catalyst, the nonaqueous organic solvent.
A tenth invention is the manufacturing method of the fluor fine particle, wherein following the step of reacting the chlorosilane compound or the alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution, the surface of the fluor fine particle is washed with an organic solvent to form a monomolecular film having the covalent bond to the surface of the fluor fine particle.
An eleventh invention according to the ninth invention is the manufacturing method of the fluor fine particle, wherein in a replacement of the silanol condensation catalyst, a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.
A twelfth invention according to the ninth invention is the manufacturing method of the fluor fine particle, wherein the ketimine compound or at least one selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound is blended with the silanol condensation catalyst for use as a promoter.
A thirteenth invention is a fluor covering film, wherein a surface of a base material covered with an organic thin film containing a reactive functional group on the surface has a covalent bond to the fluor fine particle covered with the organic thin film containing a functional group reactive to the reactive functional group through each organic thin film to make hardening and molding.
A fourteenth invention according to the thirteenth invention is the fluor covering film, containing the epoxy group and the imino group or the calconyl group as the reactive functional group.
A fifteenth invention is the manufacturing method of the fluor covering film, containing a step of blending the fluor fine particle having a first reactivity with the fluor fine particle having a second reactivity in an organic solvent for preparing a paste, the step of application to the surface of the base material, and the step of hardening. A sixteenth invention according to the fourteenth invention is the manufacturing method of the fluor covering film, wherein the organic thin film having the functional group reactive to the fluor fine particle having the first reactivity or the fluor fine particle having the second reactivity is previously formed on the surface of a base material before application. Below, the present invention is described in detail.
The present invention provides essentially a fluor fine particle given with a function of forming the organic thin film such as a high performance monomolecular film having the covalent bond to the surface of the fluor fine particle to improve solvent dispersibility keeping almost the function inherent in the fluor fine particle by reacting the chlorosilane compound to the surface of the fluor fine particle through dispersing the fluor fine particle in the chemical adsorption solution prepared by mixing at least the chlorosilane compound with the nonaqueous organic solvent, and a variety of reaction functions.
The present invention provides essentially the fluor fine particle given with the function of forming a covering film composed of a molecule having the covalent bond to the surface of the fluor fine particle by reacting the alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution prepared by mixing at least the alkoxysilane compound, the silanol condensation catalyst, and the nonaqueous organic solvent to improve solvent dispersibility keeping almost the function inherent in the fluor fine particle, and the variety of chemical reaction functions.
At this time, for the purpose of improving dispersibility of the organic solvent and the plastic in the organic matter medium, using a drug to make critical surface energy of a particle surface in 25 mN/ m or smaller is preferable for improving dispersibility in the medium. Meanwhile, for giving the reactivity, using the drug containing the epoxy group and the imino group or the calconyl group is preferable for giving reactivity to the particle itself. Furthermore, the present invention provides essentially the fluor fine particle given with the function of stabilizing the particle keeping almost completely a shape and function inherent in the fluor fine particle, the function of improving the dispersibility, and the variety of chemical reaction functions by washing the fluor fine particle with the organic solvent to wash and remove an excessive compounds to cover with a chemically adsorbed monomolecular film following reacting the chlorosilane compound or the alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution.
In case of using the alkoxysilane compound, the silanol condensation catalyst can be replaced by the ketimine compound or the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound. On the other hand, using the ketimine compound or at least one selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound as the promoter by blending with the silanol condensation catalyst is preferable for shortening a reaction time.
By the step of blending the fluor fine particle having the first reactivity with the fluor fine particle having second reactivity in the organic solvent to make the paste, the step of application to the surface of the base material, and the step of hardening, the present invention provides essentially the hardened and formed fluor covering film having a high antiremoval resistance caused by having the covalent bond of the surface of the base material, which is covered with the organic thin film containing the reactive functional group on the surface, to the fluor fine particle, which is covered with the organic thin film containing the functional group reactive to the reactive functional group, through the each organic thin film. At this time, forming previously the organic thin film having the functional group reactive to the fluor fine particle having the first reactivity or the fluor fine particle having the second reactivity on the surface of the base material before application is preferable for improving antiremoval resistance. On the other hand, using the epoxy group and the imino group or the calconyl group as the reactive functional group is preferable for making the covalent bond to improve antiremoval resistance.
As described above, the present invention has an effect of providing the fluor fine particle given with the function of stabilizing the fluor fine particle keeping almost the inherent function, the function of improving the dispersibility in the variety of solvents, and the variety of chemical reaction functions. Furthermore, the present invention has the prominent effect of the function of stabilizing the fluor fine particle keeping almost completely the shape and function inherent in the fluor fine particle, the function of improving the dispersibility, and the variety of chemical reaction functions by covering with the chemically adsorbed monomolecular film. Moreover, the present invention has the effect of providing the fluor covering film excellent in antiremoval resistance performance.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing aspects and many of the attendant advantages of this invention will become more readily appreciated as the same becomes better understood by reference to the following detailed description, when taken in conjunction with the accompanying drawings, wherein like reference numerals refer to like parts throughout the various views unless otherwise specified:
FIG. 1 is a conceptual rendering made by enlarging the reaction of the fluor fine particle in the first example according to the present invention to a molecular level, FIG. 1A is a figure of the surface of the fluor fine particle before the reaction, and FIG. 1 B the figure after the monomolecular film was formed
FIG. 2 is the conceptual rendering made by enlarging the reaction of the fluor fine particle in the second example according to the present invention to the molecular level, FIG. 2A is the figure of the surface of the fluor fine particle before the reaction, FIG. 2B the figure after the monomolecular film containing the epoxy group was formed, FIG. 2C the figure after the monomolecular film containing the amino group was formed.
DETAILED DESCRIPTION
By the method of washing with the organic solvent following the step of reacting the chlorosilane compound to the surface of the fluor fine particle through dispersing the fluor fine particle in the chemical adsorption solution prepared by mixing at least the chlorosilane compound with the nonaqueous organic solvent or by the method of washing with the organic solvent following the step of reacting the alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution prepared by mixing at least the alkoxysilane compound, the silanol condensation catalyst, and the nonaqueous organic solvent, the present invention provides the fluor fine particle, in which a molecule having the covalent bond to the surface has the reactive functional group such as heat-reactive or photoreactive or radical reactive or ion reactive functional groups and the fluor fine particle composes the monomolecular film, and the fluor covering film made by using them. Consequently, the present invention has the performance of providing the function of stabilizing the surface of the particle itself keeping almost completely the shape and function inherent in the fluor fine particle, the function of improving the dispersibility, and the variety of chemical reaction functions.
Details of the present invention will be described as follows with reference to examples. However, the present invention is not restricted by these examples.
According to the present invention, the fluor fine particle includes mainly the alkali halide, rare earth ion fluor, manganese fluor, and sulfide fluor. A zinc sulfate-based fluor fine particle will be described below as a typical example. [Example 1] First, zinc sulfate fluor fine particle 1 with a 100 nm mean grain size was prepared (FIG. 1) and dried well. Next, a carbon fluoride group (functional site,) of which critical surface energy becomes 25 or smaller mN/ m by making the monomolecular film, and a chemical adsorbent such as CF3(CF2)7(CH2)2SiCl3 containing a chlorosilyl group (active site) are dissolved in the nonaqueous solvent (for example, dehydrated nonane) in a concentration of about 0.1 weight percents to prepare the chemical adsorption solution (hereafter adsorption solution.) The zinc sulfate fluor fine particle is soaked in this adsorption solution, stir, and reacted in a dried atmosphere (relative humidity was preferably 30% or lower.) Many hydroxyl groups (OH) 2 have bonded to a dangling bond on the surface of zinc sulfate fluor fine particle 1 (FIG. 1A) and, thus, the chlorosilyl group (SiCI) of the chemical adsorbent reacts to the hydroxyl group on the surface of the fluor fine particle, a dehydrochlorination reaction occurred, and the bond expressed by the following formula (Chemical formula C1) is formed across a whole surface of the zinc sulfate fluor fine particle. Then, adding a freon-based solvent, stirring, and washing gave the zinc sulfate fluor fine particle 4 covered with the monomolecular film 3 composed of the chemical adsorbent. [C1]
O —
CF3(CF2MCH2J2Si — O — O—
At this time, the critical surface energy of the monomolecular film formed on the surface of the fluor fine particle becomes about 6 mN/ m and, hence, this pigment fluor fine particle became to disperse well in the freon-based solvent and a silicone-based solvent or a fluorine resin that has a small critical surface energy.
This chemical adsorption film has a very strong covalent bond to the surface of the fluor fine particle and, therefore, was not removed by a normal reaction. Furthermore, a film thickness is of a single molecule length (about 1 nm) and, thus, using the fluor fine particle (nano particle) having a particle size of about some ten nanometers caused no loss of the shape.
Then, exposing to air without washing caused almost no change of dispersibility and evaporation of the solvent resulting in reaction of the chemical adsorbent left on the surface of the particle to water in air on the surface of the particle to give the fluor fine particle, on which particle surface had the formed very thin chemically adsorbed polymer film composed of the chemical adsorbent.
In the example as described above, the shown example was the drug used as the chemical adsorbent, which has the carbon fluoride-based functional group having a surface energy reducible function in a functional site. In case of using the drug such as CH3(CF2)7(CH2)2SiC|3 containing a hydrocarbon group (-CH3 group) in the functional site, the obtained covering film had the critical surface energy of about 25 mN/ m. On the other hand, using these drugs by blending arbitrarily enabled to control arbitrarily the critical surface energy of the covering film over the prepared fluor fine particle surface in a range between 6 and 25 mN/ m. Where, changing some functional groups in the functional site enables to give a new function and fabricate the fluor fine particle, of which surface energy is regulated to a target value, without the loss of the shape inherent in the fluor fine particles.
According to this method, hydrochloric acid occurs in formation of the covering film to injure slightly the surface of the fluor fine particle. However, in Example 1 , hydrochloric acid occurred was a very little amount and, hence, no problem arose. The fluor fine particle covered with the monomolecular film in such the way, for example, the fluor fine particle covered with the hydrocarbon-based monomolecular film with the critical surface energy of about 25 mN/ m, could be dispersed in a very good condition for the hydrocarbon-based solvent and a hydrocarbon-based or acrylic plastic by inhibiting coagulation.
In Example 1 as described above, as the carbon fluoride-based chemical adsorbent, CF3(CF2)7(CH2)2SiCl3 was used. However, substances, other than the above described materials, enumerated in the following (1 ) to (12) were usable including hydrocarbon-based substances. (I) CF3CH2O(CH2)I5SICI3
(2) CF3(CH2)3Si(CH3)2(CH2)15SiCI3 (3) CF3(CF2)5(CH2)2Si(CH3)2(CH2)9SiCI3 (4) CF3(CF2)7(CH2)2Si(CH3)2(CH2)9SiCI3 (5) CF3COO(CH2)I5SiCI3 (6) CF3(CF2)5(CH2)2SiCl3
(7) CH3CH2O(CH2)I5SiCI3 (8) CH3(CH2)3Si(CH3)2(CH2)i5SiCl3
(9) CH3(CH2)5Si(CH3)2(CH2)9SiCl3
(10) CH3(CH2)7Si(CH3)2(CH2)9SiCl3 (11 ) CH3COO(CH2)I5SiCI3
Figure imgf000010_0001
[Example 2]
First, an anhydrous cadmium sulfate fluor fine particle 11 was prepared and dried well. Next, the drug, which contains the reactive functional group such as the epoxy group and the imino group in the functional site and an alkoxysilyl group in the other end, as the chemical adsorbent, exemplified by the drug shown in the following formula (Chemical formula C2) or (Chemical formula C3) was weighed to make a 99 weight percents and dibutyltin diacetyl acetonate or acetic acid being an organic acid, for example, as the silanol condensation catalyst was also weighed to make a 1 weight percents to dissolve in the solvent, which was prepared by mixing the same amounts of silicone and dimethyl formamide, such as the solution prepared by mixing hexamethyl disiloxane (50%) and dimethyl formamide (50%) to make about 1 weight percent concentration (a preferable concentration of the chemical adsorbent ranged from 0.5 to 3 percents) for preparation of the chemical adsorption solution. [C2]
O OCH3
CH2-CHCH2O(CH2)SSi -OCH3
OCH3
[C3]
OCH3
H2N(CH2)3Si —OCH3 OCH3
The anhydrous cadmium sulfate fluor fine particle is dispersed and stirred in this adsorption solution and reacted in normal air (relative humidity 55%) for about 2 hours. At this time, many hydroxyl groups 12 has bonds to the dangling bond of the surface of the anhydrous cadmium sulfate fluor fine particle (FIG. 2A) and, thus, -Si- (OCH3) group of the chemical adsorbent makes a dealcohol (in this case, deCH3OH) reaction to the hydroxyl groups in the presence of the silanol condensation catalyst or the organic acid to make the bond shown in the following formula (chemical formula C4) or (chemical formula C5) resulting in formation of the chemical adsorption monomolecular film 13, which contains the epoxy group chemically bonded to the surface across all the surface of the fluor fine particle, or the chemical adsorption film 14, which contains the amino group, in the film thickness of about 1 nanometer (FIG. 2B, 2C).
Where, in case of using the adsorbent containing the amino group, a precipitation occurs in a tin-based catalyst and, therefore, the organic acid such as acetic acid should have been used. Meanwhile, the amino group contains the imino group and substances, which contain the imino group other than the amino group, include pyrrole derivatives and irnidazol derivatives. Furthermore, using ketimine derivatives enabled to introduce easily the amino group by hydrolysis after the formation of the covering film.
Thereafter, adding a chlorine-based solvent (for example, chloroform) followed by stirring and washing allowed, similar to Example 1 , preparing the cadmium sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the reactive functional group such as the epoxy group or the amino group on the surface. [C4]
O O—
CH2- CHCH2O(CH2)3Si — O —
O—
[C5]
O—
H2N(CH2)3Si — O — O—
In this processing step, similar to Example 1 , the covering film is very thin in a nanometer order film thickness and, thus, the particle size was not affected.
Exposing to air without washing caused almost no change of reactivity and evaporation of the solvent resulting in reaction of the chemical adsorbent left on the surface of the particle to water in air on the surface of the particle to give the fluor fine particle, on which particle surface had the formed very thin polymer film composed of the chemical adsorbent.
This method, in comparison with Example 1 , is characterized in no need of dried air to require no specially isolated room and, therefore, is excellent in mass producibility. On the other hand, this method employs dealcohol reaction and not dehydrochlorination reaction and, hence, even if the fluor fine particle is a substance breakable largely by hydrochloric acid, can be used in a wide range of applications.
Next, an identical amount was measured for each of the cadmium sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the epoxy group or the cadmium sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the amino group and blended enough in isopropyl alcohol to make the paste, applied to an inside wall of a glass tube, and heated to a temperature of about 50 to 100 0C to add the epoxy group and the amino group by the reaction shown by the following formula (Chemical formula C6) resulting in binding and hardening of the fluor fine particle allowing carrying out the application of the fluor without not any binder contained.
At this time, if the organic thin film having the reactive functional group is previously formed on the surface of the base material by the same method, the organic thin film on the surface of the fluor fine particle react also to the organic thin film on the surface of the surface of the base material to enable to fabricate the fluor covering film having high antiremoval resistance.
[C6]
O
/ \ -(CH2)CH-CH2 + H2NCH2 —
► - (CH2)CHCH2-NHCH2 -
OH
In Example 2 as described above, the materials shown in formulae (Chemical formula C2 or Chemical formula C3) were used as the chemical adsorbent containing the reactive group. Materials, other than the above described materials, shown by the following (21 ) to (36) were usable.
(21 ) (CH2OCH)CH2O(CH2)7Si(OCH3)3
(22) (CH2OCH)CH2O(CH2)Ii Si(OCHa)3 (23) (CH2CHOCH(CH2)2)CH(CH2)2Si(OCH3)3 (24) (CH2CHOCH(CH2)2)CH(CH2)4Si(OCH3)3
(25) (CH2CHOCH(CH2)2)CH(CH2)6Si(OCH3)3 (26) (CH2OCH)CH2O(CH2)7Si(OC2H5)3 (2Z) (CH2OCH)CH2O(CH2)IiSi(OC2Hs)3 (28) (CH2CHOCH(CH2)2)CH(CH2)2Si(OC2H5)3 (29) (CH2CHOCH(CH2)2)CH(CH2)4Si(OC2H5)3 (30) (CH2CHOCH(CH2)2)CH(CH2)6Si(OC2H5)3 (31 ) H2N(CH2)5Si(OCH3)3
(32) H2N(CH2)TSi(OCHs)3
(33) H2N(CH2)9Si(OCH3)3
(34) H2N(CH2)SSi(OC2Hs)3
(35) H2N(CHz)7Si(OC2Hs)3 (36) H2N(CH2)9Si(OC2H5)3
Where, (CH2OCH)- group represents the functional group expressed by the following formula (Chemical formula C7) and (CH2CHOCH(CH2)2)CH- represents the functional group expressed by the following formula (Chemical formula C8.) [C7]
O
/ \
CH2-CH
[C8]
O — CH-CH2
\ / \
CH CH
\ /
CH2 -CH2
In addition, as the chemical adsorbent containing the functional group reactive to an energy beam such as a light or electron beam, the substances shown by the following (41 ) to (46) were usable. In this case, naturally, hardening simply requires irradiation of such energy beam as the light or electron beam. (41 ) CH≡C-C≡C-(CH2)15SiCI3 (42) CH≡C-C≡C-(CH2)2Si(CH3)2(CH2)15SiCI3 (43) CH≡C-C≡C-(CH2)2Si(CH3)2(CH2)9SiCI3 (44) (C6H5)(CH)2CO(C6H4)O(CH2)6OSi(OCH3)3 (45) (C6H5)(CH)2CO(C6H4)O(CH2)6OSi(OC2H5)3 (46) (C6H5)CO(CH)2(C6H4)O(CH2)6OSi(OCH3)3 Where, (C6H5)(CH)2CO(C6H4)- and (C6H5)CO(CH)2(C6H4)- express the calconyl group.
In Example 2, usable silanol condensation catalysts are a metal salt of a carboxylic acid, the metal salt of a carboxylic acid ester, a polymer of the metal salt of the carboxylic acid, a chelate of the metal salt of the carboxylic acid, titanic acid ester, and chelates of the titanic acid ester. More specifically, usable materials were stannous acetate, dibutyltin dilaurate, dibutyltin dioctate, dibutyltin diacetate, dioctyltin dilaurate, dioctyltin dioctate, dioctyltin diacetate, tin dioctanoate, lead naphtenate, cobalt naphtenate, iron 2-ethylhexenoate, dioctyltin bisoctylthioglycolate ester salt, dioctyltin maleate ester salt, dibutyltin maleate salt polymer, dimetyltin mercaptopropionate salt polymer, dibutyltin bisacetyl acetate, dioctyltin bisacetyl laurate, tetrabutyl titanate, tetranonyl titanate, and bis (acetyl acetonyl) dipropyl titanate.
Usable solvents for a film forming solution were an organic chlorine-based solvent, hydrocarbon-based solvent, or carbon fluoride-based solvent, and silicone-based solvent or a mixture thereof, that contain no water in either of alkoxysilane or chlorosilane based chemical adsorbents. In case of increasing a particle concentration by evaporating the solvent without washing, a boiling point of the solvent ranges preferably from about 50 to 250 0C.
Usable solvents include specifically an organic chlorine-based solvent, nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzin, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosine, dimethyl silicone, phenyl silicone, alkyl denatured silicone, polyether silicone, and dimethyl formamide. Furthermore, in the case where the adsorbent is alcoxysilane-based and the organic covering film is formed by evaporating the solvent, additionally to the solvent as described above, alcohol-based solvents such as methanol, ethanol, and propanol or the mixture thereof were used.
Still further carbon fluoride-based solvent are a freon-based solvent Frorinate (made by Sumitomo 3M Limited,) and Alfude (Asahi Glass Co. made.) These materials may be singly used and, if they can be blended well, may be used in a combination of two kinds. In addition, the organic chlorine-based solvent such as chloroform may be added. On the other hand, when silanol condensation catalysts as described above were replaced for use by the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound, a process time could be shorten to make a half to 2/ 3 of the time necessary for the same concentration. Moreover, using the silanol condensation catalyst by mixing (a range from 1 : 9 to 9: 1 can be applied, but normally around 1 : 1 is preferable) with the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound can make the process time fast several-fold (up to about 30 minutes) resulting in shortening of the time for making the film up to several-fold decrease.
For example, dibutyltin oxide being the silanol catalyst was replaced by Japan Epoxy Resin Co. made H3 being the ketimine compound under the same condition. Almost same result was obtained except that the reaction time became short to about 1 hour. In addition, the silanol catalyst was replaced by the mixture (mixture ratio was
1 : 1) of Japan Epoxy Resin Co. made H3 being the ketimine compound and dibutyltin bisacetyl acetonate being the silanol catalyst and other conditions were set identical. Almost same result was obtained except that the reaction time became short to about 30 minutes. Consequently, from the results as described above, it found that the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound has a higher activity than that of the silanol condensation catalyst.
Furthermore, it was observed that using one of the ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound by mixing with the silanol condensation catalyst shows further higher activity. Where, usable ketimine compounds are not specially restricted, but include, 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 -pentadecadiene, 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.
Usable organic acids are not specially restricted, but include, for example, formic acid, or acetic acid, propionic acid, butyric acid, and malonic acid and showed the almost same effect.
In the two examples as described above, descriptions were made for the zinc sulfate fluor fine particle and the cadmium sulfate fluor fine particle as examples.
The present invention can be applied to any inorganic fluor being the fluor fine particle containing active hydrogen such as the hydrogen of a hydroxy! group on the surface thereof. On the other hand, the present invention can be applied to an organic fluor containing the active hydrogen such as the hydrogen of the hydroxyl group on the surface thereof.
Specifically, the present invention can be applied to an alkali halide, rare earth ion fluor, manganese fluor, and sulfide fluor and is also applicable to the organic fluor containing the active hydrogen such as the hydrogen of the hydroxyl group on the surface thereof. In addition, its usage includes a display, fluorescent light, indication board, and X-ray photographic plate.

Claims

1. A fluor fine particle covered with an organic thin film having a covalent bond to a surface.
2. The fluor fine particle according to claim 1 , wherein the organic thin film having the covalent bond to the surface contains a high performance functional group in an end and the other end is composed of a molecule having the covalent bond to a particle surface via Si.
3. The fluor fine particle according to claim 2, wherein a high performance functional group is an inactive group having a 25 mN/ m or smaller of critical surface energy or a reactive functional group.
4. The fluor fine particle according to claim 3, wherein the inactive group having a 25 mN/ m or smaller of critical surface energy contains -CF3 or -CH3.
5. The fluor fine particle according to claim 3, wherein the reactive functional group is heat-reactive or photoreactive or radical reactive or ion reactive functional group.
6. The fluor fine particle according to claim 4, wherein the reactive functional group is an epoxy group and an imino group or a calconyl group.
7. The fluor fine particle according to claim 1 or 2, wherein an organic thin film having a covalent bond to the surface is composed of a monomolecular film.
8. The manufacturing method of the fluor fine particle, containing a step of reacting a chlorosilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in a chemical adsorption solution prepared by mixing at least the chlorosilane compound with a nonaqueous organic solvent.
9. The manufacturing method of the fluor fine particle, containing the step of reacting an alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution prepared by mixing at least the alkoxysilane compound, a silanol condensation catalyst, the nonaqueous organic solvent.
10. The manufacturing method of the fluor fine particle according to claim 8 or 9, wherein following the step of reacting the chlorosilane compound or the alkoxysilane compound to the surface of the fluor fine particle by dispersing the fluor fine particle in the chemical adsorption solution, the surface of the fluor fine particle is washed with an organic solvent to form a monomolecular film having the covalent bond to the surface of the fluor fine particle.
11. The manufacturing method of the fluor fine particle according to claim 9, wherein in a replacement of the silanol condensation catalyst, a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.
12. The manufacturing method of the fluor fine particle according to claim 9, wherein the ketimine compound or at least one selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound is blended with the silanol condensation catalyst for use as a promoter.
13. A fluor covering film, wherein a surface of a base material covered with an organic thin film containing a reactive functional group on the surface has a covalent bond to the fluor fine' particle covered with the organic thin film containing a functional group reactive to the reactive functional group through each organic thin film to make hardening and molding.
14. The fluor covering film according to claim 13, containing the epoxy group and the imino group or the calconyl group as the reactive functional group.
15. The manufacturing method of the fluor covering film, containing a step of blending the fluor fine particle having a first reactivity with the fluor fine particle having a second reactivity in an organic solvent for preparing a paste, the step of application to the surface of the base material, and the step of hardening.
16. The manufacturing method of the fluor covering film according to claim 15, wherein the organic thin film having the functional group reactive to the fluor fine particle having the first reactivity or the fluor fine particle having the second reactivity is previously formed on the surface of a base material before application.
PCT/JP2007/061948 2007-06-07 2007-06-07 Fluor fine particle, manufacturing method thereof, and fluor covering film using them WO2008149471A1 (en)

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