WO2008149469A1 - Pattern-like fluor fine particle film and manufacturing method thereof - Google Patents
Pattern-like fluor fine particle film and manufacturing method thereof Download PDFInfo
- Publication number
- WO2008149469A1 WO2008149469A1 PCT/JP2007/061945 JP2007061945W WO2008149469A1 WO 2008149469 A1 WO2008149469 A1 WO 2008149469A1 JP 2007061945 W JP2007061945 W JP 2007061945W WO 2008149469 A1 WO2008149469 A1 WO 2008149469A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluor
- fine particle
- film
- pattern
- organic film
- Prior art date
Links
- 239000010419 fine particle Substances 0.000 title claims abstract description 331
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 119
- 239000002356 single layer Substances 0.000 claims abstract description 77
- 239000010410 layer Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims description 90
- -1 ketimine compound Chemical class 0.000 claims description 59
- 238000001179 sorption measurement Methods 0.000 claims description 49
- 150000001875 compounds Chemical class 0.000 claims description 48
- 239000003054 catalyst Substances 0.000 claims description 42
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 41
- 238000009833 condensation Methods 0.000 claims description 38
- 230000005494 condensation Effects 0.000 claims description 38
- 125000003700 epoxy group Chemical group 0.000 claims description 38
- 238000002156 mixing Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 24
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 19
- 150000007524 organic acids Chemical class 0.000 claims description 14
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 6
- 238000013517 stratification Methods 0.000 claims description 4
- 230000000415 inactivating effect Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- FMNJXQFKUYRRPZ-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Zn+2].[F] Chemical compound S(=O)(=O)([O-])[O-].[Zn+2].[F] FMNJXQFKUYRRPZ-UHFFFAOYSA-L 0.000 description 38
- 239000002904 solvent Substances 0.000 description 24
- 125000003277 amino group Chemical group 0.000 description 19
- 239000011521 glass Substances 0.000 description 19
- 239000003463 adsorbent Substances 0.000 description 17
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 125000000524 functional group Chemical group 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- 229960001763 zinc sulfate Drugs 0.000 description 4
- 229910000368 zinc sulfate Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 238000004904 shortening Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- HGQSXVKHVMGQRG-UHFFFAOYSA-N dioctyltin Chemical compound CCCCCCCC[Sn]CCCCCCCC HGQSXVKHVMGQRG-UHFFFAOYSA-N 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 2
- 229940073561 hexamethyldisiloxane Drugs 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical class CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical class C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- CJAGRJAFLCPABV-UHFFFAOYSA-N 2-(4-methylpentan-2-ylideneamino)-n-[2-(4-methylpentan-2-ylideneamino)ethyl]ethanamine Chemical compound CC(C)CC(C)=NCCNCCN=C(C)CC(C)C CJAGRJAFLCPABV-UHFFFAOYSA-N 0.000 description 1
- NOJHYEMRGGBHOI-UHFFFAOYSA-N 2-(butan-2-ylideneamino)-n-[2-(butan-2-ylideneamino)ethyl]ethanamine Chemical compound CCC(C)=NCCNCCN=C(C)CC NOJHYEMRGGBHOI-UHFFFAOYSA-N 0.000 description 1
- CLSFJOSFPTTYLQ-UHFFFAOYSA-N 2-(methylideneamino)-n-[2-(methylideneamino)ethyl]ethanamine Chemical compound C=NCCNCCN=C CLSFJOSFPTTYLQ-UHFFFAOYSA-N 0.000 description 1
- FPHDXPRLWRPJNS-UHFFFAOYSA-N 2-(propan-2-ylideneamino)-n-[2-(propan-2-ylideneamino)ethyl]ethanamine Chemical compound CC(C)=NCCNCCN=C(C)C FPHDXPRLWRPJNS-UHFFFAOYSA-N 0.000 description 1
- ZHJFAUWFPQHZFH-UHFFFAOYSA-L 2-ethylhex-2-enoate iron(2+) Chemical compound [Fe+2].CCCC=C(CC)C([O-])=O.CCCC=C(CC)C([O-])=O ZHJFAUWFPQHZFH-UHFFFAOYSA-L 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZGMQJOYUICXLDZ-UHFFFAOYSA-N 6-(4-methylpentan-2-ylideneamino)-n-[6-(4-methylpentan-2-ylideneamino)hexyl]hexan-1-amine Chemical compound CC(C)CC(C)=NCCCCCCNCCCCCCN=C(C)CC(C)C ZGMQJOYUICXLDZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 208000031481 Pathologic Constriction Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- CQQXCSFSYHAZOO-UHFFFAOYSA-L [acetyloxy(dioctyl)stannyl] acetate Chemical compound CCCCCCCC[Sn](OC(C)=O)(OC(C)=O)CCCCCCCC CQQXCSFSYHAZOO-UHFFFAOYSA-L 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- IFSWBZCGMGEHLE-UHFFFAOYSA-L cobalt(2+);naphthalene-2-carboxylate Chemical compound [Co+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 IFSWBZCGMGEHLE-UHFFFAOYSA-L 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- JQZRVMZHTADUSY-UHFFFAOYSA-L di(octanoyloxy)tin Chemical compound [Sn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O JQZRVMZHTADUSY-UHFFFAOYSA-L 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000004658 ketimines Chemical class 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- 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
-
- 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
Definitions
- the present invention relates to a pattern-like monolayer fluor fine particle film, a pattern-like layered fluor fine particle film and a manufacturing method thereof. More specifically, the present invention relates to the pattern-like monolayer fluor fine particle film, the pattern-like layered fluor fine particle film, which are made by using fluor fine particles, of which surface is gave with hot-reactivity or photoreactivity or radical reactivity or ion reactivity, and a manufacturing method thereof and a display device and a television, which use the film and the method.
- "fluor fine particle film” includes an inorganic fluor fine particle film, an organic fluor fine particle film or an organic-inorganic hybrid fluor fine particle film.
- the fluor fine particle film mentioned here includes so-called EL film.
- LB Langmuir-Blodgett
- CA chemical adsorption
- Patent document 1 Japanese Published Unexamined Patent Application No. 2001-323387.
- a covering film (pattern-like monolayer fluor fine particle film) having even thickness in a molecular size level, which is made by arranging only a monolayer of fluor fine particles on an arbitrary base material surface
- the covering film (pattern-like layered fluor fine particle films) made by layering a plurality of layers of the film, which is made by arranging fluor fine particles as only a monolayer, in a pattern-like shape, and the manufacturing method thereof have not been yet developed and provided.
- the present invention aims to provide, the covering film (pattern-like monolayer fluor fine particle film) having even thickness in the molecular size level, which is made by arranging only a single layer of fluor fine particles on the arbitrary base material surface in the pattern-like form, the covering film (pattern-like layered fluor fine particle films) made by layering the plurality of layers of the film, which is made by arranging fluor fine particles only as the monolayer, and the manufacturing method thereof and a display device and a television, which use the film and the method.
- the covering film pattern-like monolayer fluor fine particle film having even thickness in the molecular size level, which is made by arranging only a single layer of fluor fine particles on the arbitrary base material surface in the pattern-like form
- the covering film (pattern-like layered fluor fine particle films) made by layering the plurality of layers of the film, which is made by arranging fluor fine particles only as the monolayer, and the manufacturing method thereof and a display device and a television, which use the film
- a first invention provided as means for solving the problem is a pattern-like monolayer fluor fine particle film having a covalent bond of a film of a monolayer of a fluor fine particle formed selectively on a surface of a base material to a first organic film formed selectively on the surface of the base material, through a second organic film formed on the surface of the fluor fine particle.
- a second invention according to the first invention is the pattern-like monolayer fluor fine particle film according to claim 1 , wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are different from each other.
- a third invention according to the first invention is the pattern-like monolayer fluor fine particle film, wherein the covalent bond is a -N-C- bond formed by a reaction of an epoxy group and an imino group.
- a fourth invention according to the first and the second invention is the pattern-like monolayer fluor fine particle film, wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are constituted from a monomolecular film.
- a fifth invention according to the first invention is the pattern-like monolayer fluor fine particle film, wherein a reactive group of the second organic film located in the surface of the fluor fine particle other than the covalent bond part is inactivated or a third nonreactive organic film bound to the second organic film is formed.
- a sixth invention is a manufacturing method for the pattern-like monolayer fluor fine particle film, comprising: a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material; a step of processing the first reactive organic film to make a predetermined pattern; a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; a step of contacting, for a selective reaction, the fluor fine particle covered with the second reactive organic film to the surface of the base material having the
- a seventh invention according to sixth invention is the manufacturing method for the pattern-like layered fluor fine particle film, comprising: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material and a step of forming the second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle, followed by washing each of the base material and the surface of the fluor fine particle with an organic solvent to form a first and second reactive monomolecular films having the covalent bond to the base material and the surface of the fluor fine particle.
- An eighth invention according to sixth invention is the manufacturing method for the pattern-like monolayer fluor fine particle film, wherein the first reactive organic film contains an epoxy group and the second reactive organic film contains an imino group.
- a ninth invention according to seventh invention is the manufacturing method for the pattern-like monolayer fluor fine particle film according to claim 7, wherein the first reactive monomolecular film contains an epoxy group and the second reactive monomolecular film contains an imino group.
- a tenth invention according to sixth invention is the manufacturing method for the pattern-like monolayer fluor fine particle film, wherein following the step of washing and removing the fluor fine particle covered with an excessive second reactive organic film, a step is carried out for inactivating a reactive group of the second organic film located in the surface of the fluor fine particle other than the covalent bond part or binding a third nonreactive organic film to the second organic film located on the surface of the fluor fine particle other than the covalent bond part.
- An eleventh invention is a pattern-like layered fluor fine particle film, wherein the fluor fine particle films layered as stratification selectively on the surface of the base material has the covalent bond between layers through an organic covering film formed on the surface of the fluor fine particle.
- a twelfth invention according to eleventh invention is the pattern-like layered fluor fine particle film, wherein the first organic film is selectively formed on the surface of the base material and the fluor fine particle film having the second organic film and the fluor fine particle film having the third organic film are layered alternately via the first organic film.
- a thirteenth invention according to twelfth invention is the pattern-like layered fluor fine particle film, wherein a part of the first, second, and third organic film react each other to form the covalent bond.
- a fourteenth invention according to thirteenth invention is the pattern-like layered fluor fine particle film, wherein the covalent bond is the -N-C- bond formed by the reaction of the epoxy group to the imino group.
- a fifteenth invention according to fourteenth invention is the pattern-like monolayer fluor fine particle film, wherein a reactive group of the organic film located on the surface of the fluor fine particle on an outermost surface is inactivated or a fourth nonreactive organic film bound to the organic film on the surface of the fluor fine particle on the outermost surface is formed.
- a sixteenth invention is a manufacturing method for the pattern-like layered fluor fine particle film comprising: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of processing the first reactive organic film to make the predetermined pattern; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting the first fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; the step of washing and removing the
- a seventeenth invention according to sixteenth invention is the manufacturing method for the pattern-like layered fluor fine particle film, wherein the first reactive organic film is identical to the third reactive organic film.
- a eighteenth invention according to sixteenth invention is the manufacturing method for the pattern-like layered fluor fine particle film of a multilayer structure, wherein, following the step of forming the second pattern-like monolayer fluor fine particle film, similarly, the step of forming the first pattern-like monolayer fluor fine particle film and the step of forming the second pattern-like monolayer fluor fine particle film are repeated.
- a nineteenth invention according to sixteenth invention is the manufacturing method for the pattern-like layered fluor fine particle film, wherein, following the step of forming the first to third reactive organic films, for each of their steps, the surfaces of the base material or the fluor fine particle are washed with the organic solvent to form the first to third reactive monomolecular films having the covalent bond to the surface of the base material and the fluor fine particle.
- a twentieth invention according to sixteenth invention is the manufacturing method for the pattern-like layered fluor fine particle film, wherein the first and third reactive organic films contain the epoxy group and the second reactive organic film contains the imino group.
- a twenty-first invention according to sixth and sixteenth invention is the manufacturing method for the pattern-like monolayer fluor fine particle film and the pattern-like layered fluor fine particle film, wherein, replacing the silanol condensation catalyst with a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.
- a twenty-second invention according to sixth and sixteenth invention is the manufacturing method for the pattern-like monolayer fluor fine particle film and the pattern-like layered fluor fine particle film, wherein the silanol condensation catalyst is blended with ketimine compound or at least one selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound for use as a promoter.
- a twenty-third invention is a display device, wherein a film of a single layer of the pattern-like fluor fine particle formed selectively in a pixel portion of a device has the covalent bond to the first organic film formed selectively on the surface of the base material via the second organic film formed on the surface of the fluor fine particle.
- a twenty-fourth invention is a display device, wherein a plurality of layers of the pattern-like fluor fine particle film formed selectively in the pixel portion of the device has the covalent bond to each other between layers via the organic film formed on the surface of the fluor fine particle.
- a twenty-fifth invention according to twenty-third and twenty- fourth inventions is the display device, wherein each of the pattern-like fluor fine particle film contains a red, blue, or green luminescent fluor fine particle.
- a twenty-sixth invention is a television using the display device, wherein the film of the single layer of the pattern-like fluor fine particle formed selectively in the pixel portion of a device has the covalent bond to the first organic film formed selectively on the surface of the base material via the second organic film formed on the surface of the fluor fine particle.
- a twenty-seventh invention is the television using the display device, wherein the plurality of layers of the pattern-like fluor fine particle film formed selectively in the pixel portion of the device has the covalent bond to each other between layers via the organic film formed on the surface of the fluor fine particle.
- the present invention aims to provide the pattern-like monolayer fluor fine particle film, wherein the monolayer film of the fluor fine particle, which is formed selectively on the surface of the base material, has the mutual covalent bond to the first organic film, which is formed selectively on the surface of the base material, through the second organic film formed on the surface of the fluor fine particle, by a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material, a step of processing the first reactive organic film to make a predetermined pattern, a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation
- Difference between the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle is preferable for preparing the monolayer fluor fine particle film by selectively reacting the first organic film formed on the surface of the base material to the second organic film formed on the surface of the fluor fine particle.
- the covalent bond made by -N-C bond formed by the reaction of the epoxy group to the imino group is preferable for obtaining a stable adhesive force.
- the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle, which are constituted by monomolecular film, is preferable for making a binder component least.
- the inactivated reactive group of the second organic film located on the surface of the fluor fine particle other than the covalent bond part or the third nonreactive organic film formed by binding to the second organic film is preferable for preparing a plurality of places of the pattern-like monolayer fluor fine particle film on an identical base material.
- the binder component least that, following a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material and a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle, washing each of the surface of the base material and the surface of the fluor fine particle with an organic solvent to form a first and second reactive monomolecular films having the covalent bond to the surface of the base material and the surface of the fluor fine particle.
- containing an epoxy group in the first reactive organic film and containing an imino group in the second reactive organic film are preferable for reacting selectively the organic film on the surface of the fine particle to the organic film on the surface of the base material.
- conducting the step of inactivating the reactive group of the second organic film located on the surface of the fluor fine particle other than the covalent bond part or binding the third nonreactive organic film to the second organic film located on the surface of the fluor fine particle other than the covalent bond part is preferable for preparing the plurality of pattern-like monolayer fluor fine particle film to the surface of the identical base material.
- the present invention aims to provide the pattern-like layered fluor fine particle film having the covalent bond of the fluor fine particle film, which is made by layering selectively on the surface of the base material in stratification, between each other layer through the organic film formed on the surface of the fluor fine particle by: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of processing the first reactive organic film to make the predetermined pattern; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor
- the first reactive organic film which is formed selectively on the surface of the base material, and the fluor fine particle film having the second organic film and the fluor fine particle film having the third organic film, which are alternately layered via the first organic film, are preferable for improving antiremoval strength of the pattern-like layered fluor fine particle film.
- the covalent bond made by reaction of a part of the first, second, and third organic films to each other is preferable for layering the pattern-like fluor fine particle film.
- the covalent bond made by -N-C bond formed by the reaction of the epoxy group to the imino group is preferable for obtaining the stable adhesive force.
- the inactivated reactive group of the organic film located on the surface of the fluor fine particle located on the outermost surface or the fourth nonreactive organic film formed by binding to the organic film located on the surface of the fluor fine particle located on the outermost surface is preferable for preparing the plurality of places of the pattern-like monolayer fluor fine particle film on the identical base material.
- the first reactive organic film identical to the third reactive organic film is preferable for simplifying manufacturing steps.
- step of forming the second pattern-like monolayer fluor fine particle film similarly, repeating the step of forming the first pattern-like monolayer fluor fine particle film and the step of forming the second pattern-like monolayer fluor fine particle film is preferable for thickening a thickness of the layered fine particle film.
- the step of forming the first to third reactive organic films each, washing the surface of the base material or the fluor fine particle with the organic solvent to form the first to third reactive monomolecular films having the covalent bond to the surface of the base material and the fluor fine particle is preferable for making the binder component least.
- the first and the third reactive organic films containing the epoxy group and the second reactive organic film containing the imino group is preferable for making the organic film on the fine particle react selectively to the organic film to the surface of the base material.
- ketimine compound or the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound is preferable for shortening the time for fabricating the covering film.
- ketimine compound or at least one selected from the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound is preferable for shortening further the time for fabricating the covering film.
- the present invention provides essentially a display device, in which the single layer of the pattern-like fluor fine particle film formed selectively on a pixel portion of the device has the covalent bond to the first organic film, which is formed selectively on the surface of the base material, via the second organic film formed on the surface of the fluor fine particle.
- the present invention provides essentially the display device, in which the plurality of the pattern-like fluor fine particle films selectively layered on the pixel portion of the device have covalent bonds between their layers via the organic film formed on the surface of the fluor fine particle.
- each of the pattern-like fluor fine particle films containing the red, blue, or green luminescent fluor fine particle is preferable for providing the display device capable of color display.
- the present invention provides essentially a television using the display device, in which the film of the pattern-like fluor fine particle selectively and singly formed on the pixel portion of the device has the covalent bond to the first organic film formed selectively on the surface of the base material via the second organic film formed on the surface of the fluor fine particle.
- the plurality of the pattern-like fluor fine particle films, which is selectively layered on the pixel portion of the device has the covalent bonds between their layers via the organic film formed on the surface of the fluor fine particle, is preferable for providing the television using the display device excellent in reliability.
- each of the pattern-like fluor fine particle films containing the red, blue, or green luminescent fluor fine particle is preferable for providing the television capable of color display.
- the covering film (the pattern-like monolayer fluor fine particle film) made by the pattern-like arrangement of only one layer of fluor fine particles on a surface of the arbitrary base material and having an even thickness in a particle size level; the covering film (the pattern-like layered fluor fine particle film) made by layering the plurality of films made by arranging only one layer of fluor fine particles; manufacturing methods thereof; and the display device and the television using them.
- FIG. 1 is a conceptual rendering made by enlarging the reaction of the surface of the TFT array base material in the first example according to the present invention to a molecular level
- 1A is a figure of the surface before the reaction
- 1B the figure after the monomolecular film containing the epoxy group was formed
- 1C the figure after the monomolecular film containing the amino group was formed.
- Fig. 2 is the conceptual rendering made by enlarging the reaction of the surface of the red zinc sulfate fluor fine particle in the second example according to the present invention to the molecular level
- 2A is the figure of the surface of the red zinc sulfate fluor fine particle before the reaction
- 2B the figure after the monomolecular film containing the epoxy group was formed
- 2C the figure after the monomolecular film containing the amino group was formed.
- Fig. 3 is the conceptual rendering made by enlarging the reaction of the surface of the glass base material in the third and fourth examples according to the present invention to the molecular level
- 3A shows the figure of the surface of the base material formed as the pattern-like monolayer red zinc sulfate fluor fine particle film
- 3B shows the figure of the surface of the base material, on which two layers of the pattern-like monolayer red zinc sulfate fluor fine particle film were formed.
- Fig. 4 is a conceptual figure, which is enlarged to a molecular level, showing the reaction of the surface of the glass base material, on which the TFT array mentioned in the fifth example according to the present invention has been formed, 4A a sectional conceptual figure of the surface of the base material after the organic film on the surface of the red pattern-like zinc sulfate layered fluor fine particle film is inactivated, 4B the sectional conceptual figure of the surface of the base material, on which the green pattern-like zinc sulfate layered fluor fine particle film has been formed, and 4C the sectional conceptual figure of the surface of the base material, on which the green pattern-like zinc sulfate layered fluor fine particle film has been formed.
- the present invention provides the pattern-like layered fluor fine particle film having the covalent bond of fluor fine particles, which is made by layering on the surface of the base material in stratification, between each other layer through the organic film, which is formed on the surface of the fluor fine particle, and a high performance display device and the television using the pattern-like layered fluor fine particle film by: the step of forming the first reactive organic film on the surface of the base material by contacting at least the surface of the base material with the chemical adsorption solution prepared by blending the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of processing the first reactive organic film to make the predetermined pattern; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation
- the pattern-like monolayer fluor fine particle film made by the pattern-like arrangement of only one layer of fluor fine particles on a surface of the arbitrary base material and having an even thickness in a particle size level
- the pattern-like layered fluor fine particle film made by layering the plurality of films made by arranging only one layer of fluor fine particles; manufacturing methods for them; and manufacturing the high performance display device and the television using them at the low cost.
- norganic fluor fine particle, organic fluor fine particle, and organic-inorganic hybrid fluor fine particle film can be used.
- a zinc sulfate-based fluor fine particle film will be described below as the typical example.
- a functional group such as the epoxy group having reactivity in a functional site and a drug containing an alkoxy silyl group, which is exemplified by the drug shown by the following formula (chemical formula 1 ,) in the other terminal were weighed to make 99 weight percent each, and, as a silanol condensation catalyst, dibutyltin diacetylacetonate, for example, is weighed to make about 1 weight percent. All these drugs were dissolved in a silicon solvent, for example, hexamethyl disiloxane solvent to make about 1 weight percent concentration (preferable concentration of the chemical adsorbent solution ranges from about 0.5 to 3%) to prepare a chemical adsorbent solution. [Chemical formula 1]
- glass base material 1 was soaked in this adsorbent solution to react in normal air (relative humidity 45%) for 2 hours.
- the surface of the glass base material 1 contains many hydroxyl group 2 (Fig. 1A) and, thus, -Si (OCH 3 ) of the chemical adsorbent makes dealcohol reaction (in this case, deCH 3 OH) to the hydroxyl group in the presence of the silanol condensation catalyst to make a bond shown in the following formula (chemical formula 2) resulting in formation of a chemical adsorption monomolecular film 3, which contains the epoxy group chemically bonded to the surface across all the surface of glass base material 1 , in the film thickness of about 1 nanometer.
- chemical formula 2 O O O -
- This covering film is very thin in the thickness of a nanometer order and, hence, did not cause a loss of transparency of the glass base material.
- an excimer laser and a mask are used for selective irradiation (e.g., irradiating the monomolecular film other than the portion predetermined for forming a red EL layer.) of an unnecessary portion on the surface of the base material to remove the reactive monomolecular film by abrasion
- a cation-based polymerization initiator such as IRGACURE 250 made by Ciba Specialty Chemicals was applied to the surface of the epoxy-covering film by diluting with methylethyl ketone to open selectively the epoxy group as shown in Fig. 1 D for polymerization by exposing selectively to a far ultraviolet ray resulting in pattern-like inactivation.
- IRGACURE 250 made by Ciba Specialty Chemicals
- anhydrous a red zinc sulfate fluor (ZnS: Mn) fine particle 11 with an about 10 nm size was prepared and dried well.
- a functional group such as the epoxy group or an imino group, which has reactivity in a functional site, and a drug containing an alkoxy silyl group, which is exemplified by the drug shown by the formula (chemical formula 1) or the following formula (chemical formula 3)
- acetic acid being the organic acid, for example, is weighed to make about 1 weight percent.
- Anhydrous red zinc sulfate fluor fine particle 11 was mixed with this adsorbent solution, stirred, and reacted in normal air (relative humidity 45%) for about 2 hours.
- the surface of the anhydrous red zinc sulfate fluor fine particle contains many hydroxyl groups 12 (Fig. 2A) and, thus, -Si (OCH 3 ) group of the chemical adsorbent makes dealcohol (in this case, deCH 3 OH) reaction to the hydroxyl groups in the presence of the acetic acid as the organic acid to make the bond shown in the formula (chemical formula 2) or the following formula (chemical formula 4) resulting in formation of the chemical adsorption monomolecular film 13
- the second reactive organic film or the third reactive organic film which contains the epoxy group chemically bonded to the surface across all the surface of the red zinc sulfate fluor fine particle, or the chemical adsorption film 14 (the third reactive organic film or the second reactive organic film), which contains the amino group, in the film thickness of about 1 nanometer (Fig. 2B, 2C).
- the amino group contains the imino group and other substances containing the imino group other than the amino group includes a pyrrole derivative and imidazol derivative.
- using a ketimine derivative allows easily introducing the amino group by hydrolysis following formation of the covering film.
- This covering film having the film thickness is very thin on the nanometer level and, therefore, showed no loss of the particle size.
- red zinc sulfate fluor fine particle 23 which was covered with the chemical adsorption monomolecular film having the amino group, was applied to the surface of glass base material 22, which was covered selectively with ITO electrodes formed of chemical adsorption monomolecular film 21 having the epoxy group, by dispersing in alcohol and heated at 100 0 C.
- the amino group on the surface of the red zinc sulfate fluor fine particle contacting to the epoxy group on the surface of the glass base material was added by the reaction shown in the following formula (chemical formula 5) to make selectively the bond of the red zinc sulfate fluor fine particle to the glass base material via two monomolecular films.
- evaporating alcohol by irradiating of an ultrasonic wave allowed improving the evenness of film thickness of the covering film.
- the thickness of pattern-like monolayer red zinc sulfate fluor fine particle film is about 10 nm and showed very good evenness.
- Example 4 in addition, in case of desiring to make the thickness of the red zinc sulfate fluor fine particle film thicker to improve a light emitting performance, following Example 3, in the state of pattern-like arrangement of only one layer of the red zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having amino groups having the covalent bond, red zinc sulfate fluor fine particle 25, which was covered with the chemical adsorption monomolecular film having the epoxy group, was applied to the surface of glass base material, on which the pattern-like monolayer red zinc sulfate fluor fine particle film 24 was formed having the even thickness in the particle size level, by dispersing in alcohol and heated at 100 0 C.
- the surface of the base material was again washed with alcohol to wash out for removing the red zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having excessive and unreacted epoxy groups.
- the pattern-like layered red zinc sulfate fluor fine particle film 26 of a double layer stricture was formed having the even thickness in the particle size level (Fig. 3B).
- the pattern-like zinc sulfate fluor fine particle film expressing an another luminescent color was formed by the following steps according to Example 4: the amino group or the epoxy group on the surface of the particle of the outermost surface of the layered films of the red zinc sulfate fluor fine particle film having the patterned multilayer structure, or the TFT array, was soaked into a chemical adsorption agent containing no any active functional group, e.
- adsorption solution a chemical adsorption agent (hereinafter called as adsorption solution) prepared by dissolving CH 3 CH 2 -CH 2 SiCI 3 , in a nonaqueous solvent (for example, dehydrated nonane) in a concentration of about 0.1 weight percent, in a dry atmosphere (relative humidity was preferably 30 or smaller percents) for reaction.
- adsorption solution a chemical adsorption agent prepared by dissolving CH 3 CH 2 -CH 2 SiCI 3 , in a nonaqueous solvent (for example, dehydrated nonane) in a concentration of about 0.1 weight percent, in a dry atmosphere (relative humidity was preferably 30 or smaller percents) for reaction.
- the epoxy group or the imino group contained in the organic film on the outermost surface of the layered films of the red zinc sulfate fluor fine particle film having the patterned multilayer structure made a dehydrochlorination reaction to generate a bond shown in the following formula (Chemical formula 6 or 7)
- CH 3 CH 3 group is inactive to the epoxy group or the imino group and, therefore, no layering is carried out in the subsequent layering steps.
- the pattern-like organic film containing the epoxy group is newly formed in the portion, in which the red layering films have not been formed, by the method similar to that of Example 1 followed by Examples 3 and 4 were operated to form the layered films 28 of the fluor fine particle film such as a pattern-like green zinc sulfate fluor fine particle (ZnS: Tb) film expressing the second luminescent color resulting in an inactivated surface (Fig. 4B).
- the fluor fine particle film such as a pattern-like green zinc sulfate fluor fine particle (ZnS: Tb) film expressing the second luminescent color resulting in an inactivated surface (Fig. 4B).
- (CH 2 OCH)- group represents the functional group expressed by the following formula (Chemical formula 8) and (CH 2 CHOCH (CH 2 ) 2 ) CH- group represents the functional group expressed by the following formula (Chemical formula 9).
- Example 5 CH 3 CH 2 CH 2 Si(CH 3 ) 2 CI was used. On the other hand, additionally to the substances described above, the following substances (21) to (28) were also usable. (2I) CH 3 CH 2 Si(CHs) 2 CI (22) CH 3 (CH 2 ) 4 Si(CH 3 ) 2 CI
- usable silanol condensation catalysts include a metal salt of a carboxylic acid, the metal salt of a carboxylic acid ester, 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 solvents for a film formation solution were an organic chlorine-based solvent containing no water, hydrocarbon-based solvent, or carbon fluoride-based solvent, and silicone-based solvent, or a mixture thereof.
- a boiling point of the solvent ranges preferably from about 50° to 25O 0 C.
- alcohol-based solvents such as methanol, ethanol, and propanol or the mixture thereof could be used.
- Specifically usable solvents include a chlorosilane-based nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosine, dimethyl silicone, phenyl silicone, alkyl denatured silicone, polyether silicone, and dimethyl formamide.
- Carbon fluoride-based solvents include freon-based solvent, Frorinate (made by Sumitomo 3M Limited), and Afrude (Asahi Glass Co. made.). These may be singly used as the pattern-like monolayer and, if they are blended well, may be used in a combination of two or more 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 short 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 ketimine compound or the organic acid, the aldimine compound, enamine compound, oxazolidine compound, and aminoaikyl 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.
- usable 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 glass base material, on which the TFT array used for the EL display has been formed, and the red, blue, and green luminescent fluor fine particles were described as examples.
- the present invention can be applied to any occasions, when the fluor is needed to apply in a pattern.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Biophysics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Optical Filters (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Using the fluor fine particle, without a loss of the inherent function of a variety of fluor fine particles, the following effects are provided: a covering film (the pattern-like monolayer fluor fine particle film) made by the pattern-like arrangement of an only one layer of fluor fine particles on a surface of the arbitrary base material and having an even thickness in a particle size level; the covering film (the pattern-like layered fluor fine particle film) made by layering the plurality of films made by arranging only one layer of fluor fine particles; a manufacturing method for them; and the display device and the television using them.
Description
DESCRIPTION
PATTERN-LIKE FLUOR FINE PARTICLE FILM AND MANUFACTURING METHOD
THEREOF
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a pattern-like monolayer fluor fine particle film, a pattern-like layered fluor fine particle film and a manufacturing method thereof. More specifically, the present invention relates to the pattern-like monolayer fluor fine particle film, the pattern-like layered fluor fine particle film, which are made by using fluor fine particles, of which surface is gave with hot-reactivity or photoreactivity or radical reactivity or ion reactivity, and a manufacturing method thereof and a display device and a television, which use the film and the method. According to the present invention, "fluor fine particle film" includes an inorganic fluor fine particle film, an organic fluor fine particle film or an organic-inorganic hybrid fluor fine particle film. In addition, the fluor fine particle film mentioned here includes so-called EL film.
Description of Related Art
Conventionally, there is a known method called Langmuir-Blodgett (LB) method for layering a monomolecular film on a surface of a substrate by arranging molecules on a water surface by using both amphipatic organic molecules. On the other hand, there is a known method called chemical adsorption (CA) for layering the monomolecular film in a solution, in which a surfactant has been solved, by using the chemical adsorption method.
[Patent document 1] Japanese Published Unexamined Patent Application No. 2001-323387.
However, a covering film (pattern-like monolayer fluor fine particle film) having even thickness in a molecular size level, which is made by arranging only a monolayer of fluor fine particles on an arbitrary base material surface, the covering film (pattern-like layered fluor fine particle films) made by layering a plurality of layers
of the film, which is made by arranging fluor fine particles as only a monolayer, in a pattern-like shape, and the manufacturing method thereof have not been yet developed and provided.
Conventionally, micrometer-sized or nanometer-sized fluor fine particles have been abundantly developed and manufactured. Applying effectively inherent functions of these fluor fine particles requires making fluor fine particles in a covering film having an even thickness. However, there was no idea of manufacturing the covering film having an even thickness on a particle size level by using these fluor fine particles. Using fluor fine particle and without a loss of a function inherent in a variety of fluor fine particles, the present invention aims to provide, the covering film (pattern-like monolayer fluor fine particle film) having even thickness in the molecular size level, which is made by arranging only a single layer of fluor fine particles on the arbitrary base material surface in the pattern-like form, the covering film (pattern-like layered fluor fine particle films) made by layering the plurality of layers of the film, which is made by arranging fluor fine particles only as the monolayer, and the manufacturing method thereof and a display device and a television, which use the film and the method.
SUMMARY OF THE INVENTION
A first invention provided as means for solving the problem is a pattern-like monolayer fluor fine particle film having a covalent bond of a film of a monolayer of a fluor fine particle formed selectively on a surface of a base material to a first organic film formed selectively on the surface of the base material, through a second organic film formed on the surface of the fluor fine particle.
A second invention according to the first invention is the pattern-like monolayer fluor fine particle film according to claim 1 , wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are different from each other. A third invention according to the first invention is the pattern-like monolayer fluor fine particle film, wherein the covalent bond is a -N-C- bond formed by a reaction of an epoxy group and an imino group.
A fourth invention according to the first and the second invention is the pattern-like monolayer fluor fine particle film, wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are constituted from a monomolecular film. A fifth invention according to the first invention is the pattern-like monolayer fluor fine particle film, wherein a reactive group of the second organic film located in the surface of the fluor fine particle other than the covalent bond part is inactivated or a third nonreactive organic film bound to the second organic film is formed.
A sixth invention is a manufacturing method for the pattern-like monolayer fluor fine particle film, comprising: a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material; a step of processing the first reactive organic film to make a predetermined pattern; a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; a step of contacting, for a selective reaction, the fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; and washing and removing the fluor fine particle covered with an excessive second reactive organic film.
A seventh invention according to sixth invention is the manufacturing method for the pattern-like layered fluor fine particle film, comprising: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react an alkoxysilane
compound to the surface of the base material and a step of forming the second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle, followed by washing each of the base material and the surface of the fluor fine particle with an organic solvent to form a first and second reactive monomolecular films having the covalent bond to the base material and the surface of the fluor fine particle.
An eighth invention according to sixth invention is the manufacturing method for the pattern-like monolayer fluor fine particle film, wherein the first reactive organic film contains an epoxy group and the second reactive organic film contains an imino group. A ninth invention according to seventh invention is the manufacturing method for the pattern-like monolayer fluor fine particle film according to claim 7, wherein the first reactive monomolecular film contains an epoxy group and the second reactive monomolecular film contains an imino group.
A tenth invention according to sixth invention is the manufacturing method for the pattern-like monolayer fluor fine particle film, wherein following the step of washing and removing the fluor fine particle covered with an excessive second reactive organic film, a step is carried out for inactivating a reactive group of the second organic film located in the surface of the fluor fine particle other than the covalent bond part or binding a third nonreactive organic film to the second organic film located on the surface of the fluor fine particle other than the covalent bond part.
An eleventh invention is a pattern-like layered fluor fine particle film, wherein the fluor fine particle films layered as stratification selectively on the surface of the base material has the covalent bond between layers through an organic covering film formed on the surface of the fluor fine particle. A twelfth invention according to eleventh invention is the pattern-like layered fluor fine particle film, wherein the first organic film is selectively formed on the surface of the base material and the fluor fine particle film having the second organic
film and the fluor fine particle film having the third organic film are layered alternately via the first organic film.
A thirteenth invention according to twelfth invention is the pattern-like layered fluor fine particle film, wherein a part of the first, second, and third organic film react each other to form the covalent bond.
A fourteenth invention according to thirteenth invention is the pattern-like layered fluor fine particle film, wherein the covalent bond is the -N-C- bond formed by the reaction of the epoxy group to the imino group.
A fifteenth invention according to fourteenth invention is the pattern-like monolayer fluor fine particle film, wherein a reactive group of the organic film located on the surface of the fluor fine particle on an outermost surface is inactivated or a fourth nonreactive organic film bound to the organic film on the surface of the fluor fine particle on the outermost surface is formed.
A sixteenth invention is a manufacturing method for the pattern-like layered fluor fine particle film comprising: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of processing the first reactive organic film to make the predetermined pattern; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting the first fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; the step of washing and removing the first fluor fine particle covered with the excessive second reactive organic film to form selectively the first pattern-like
monolayer fluor fine particle film; the step of forming the third reactive organic film on the surface of the second fluor fine particle by dispersing the second fluor fine particle film in the chemical adsorption solution prepared by blending at least the third alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the second fluor fine particle; the step of contacting and reacting the second fluor fine particle covered with the third reactive organic film to the surface of the base material having the first pattern-like monolayer fluor fine particle film covered with the second reactive organic film; and the step of washing and removing the second fluor fine particle covered with the excessive third reactive organic film to form selectively the second pattern-like monolayer fluor fine particle film.
A seventeenth invention according to sixteenth invention is the manufacturing method for the pattern-like layered fluor fine particle film, wherein the first reactive organic film is identical to the third reactive organic film.
A eighteenth invention according to sixteenth invention is the manufacturing method for the pattern-like layered fluor fine particle film of a multilayer structure, wherein, following the step of forming the second pattern-like monolayer fluor fine particle film, similarly, the step of forming the first pattern-like monolayer fluor fine particle film and the step of forming the second pattern-like monolayer fluor fine particle film are repeated.
A nineteenth invention according to sixteenth invention is the manufacturing method for the pattern-like layered fluor fine particle film, wherein, following the step of forming the first to third reactive organic films, for each of their steps, the surfaces of the base material or the fluor fine particle are washed with the organic solvent to form the first to third reactive monomolecular films having the covalent bond to the surface of the base material and the fluor fine particle.
A twentieth invention according to sixteenth invention is the manufacturing method for the pattern-like layered fluor fine particle film, wherein the first and third reactive organic films contain the epoxy group and the second reactive organic film contains the imino group.
A twenty-first invention according to sixth and sixteenth invention is the manufacturing method for the pattern-like monolayer fluor fine particle film and the pattern-like layered fluor fine particle film, wherein, replacing the silanol condensation catalyst with a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.
A twenty-second invention according to sixth and sixteenth invention is the manufacturing method for the pattern-like monolayer fluor fine particle film and the pattern-like layered fluor fine particle film, wherein the silanol condensation catalyst is blended with ketimine compound or at least one selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound for use as a promoter.
A twenty-third invention is a display device, wherein a film of a single layer of the pattern-like fluor fine particle formed selectively in a pixel portion of a device has the covalent bond to the first organic film formed selectively on the surface of the base material via the second organic film formed on the surface of the fluor fine particle.
A twenty-fourth invention is a display device, wherein a plurality of layers of the pattern-like fluor fine particle film formed selectively in the pixel portion of the device has the covalent bond to each other between layers via the organic film formed on the surface of the fluor fine particle.
A twenty-fifth invention according to twenty-third and twenty- fourth inventions is the display device, wherein each of the pattern-like fluor fine particle film contains a red, blue, or green luminescent fluor fine particle.
A twenty-sixth invention is a television using the display device, wherein the film of the single layer of the pattern-like fluor fine particle formed selectively in the pixel portion of a device has the covalent bond to the first organic film formed selectively on the surface of the base material via the second organic film formed on the surface of the fluor fine particle.
A twenty-seventh invention is the television using the display device, wherein the plurality of layers of the pattern-like fluor fine particle film formed selectively in the pixel portion of the device has the covalent bond to each other between layers via the organic film formed on the surface of the fluor fine particle.
The content of the present invention will be further described below.
The present invention aims to provide the pattern-like monolayer fluor fine particle film, wherein the monolayer film of the fluor fine particle, which is formed selectively on the surface of the base material, has the mutual covalent bond to the first organic film, which is formed selectively on the surface of the base material, through the second organic film formed on the surface of the fluor fine particle, by a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material, a step of processing the first reactive organic film to make a predetermined pattern, a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle, a step of contacting, for a selective reaction, the fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon, and a step of washing and removing the fluor fine particle covered with an excessive second reactive organic film.
Difference between the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle is preferable for preparing the monolayer fluor fine particle film by selectively reacting the first organic film formed on the surface of the base material to the second organic film formed on the surface of the fluor fine particle.
In addition, the covalent bond made by -N-C bond formed by the reaction of the epoxy group to the imino group is preferable for obtaining a stable adhesive force.
Further, the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle, which are constituted by monomolecular film, is preferable for making a binder component least.
Moreover, the inactivated reactive group of the second organic film located on the surface of the fluor fine particle other than the covalent bond part or the third nonreactive organic film formed by binding to the second organic film is preferable for preparing a plurality of places of the pattern-like monolayer fluor fine particle film on an identical base material.
Where, it is preferable for making the binder component least that, following a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material and a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle, washing each of the surface of the base material and the surface of the fluor fine particle with an organic solvent to form a first and second reactive monomolecular films having the covalent bond to the surface of the base material and the surface of the fluor fine particle.
Furthermore, containing an epoxy group in the first reactive organic film and containing an imino group in the second reactive organic film are preferable for reacting selectively the organic film on the surface of the fine particle to the organic film on the surface of the base material. Moreover, following the step of washing and removing the fluor fine particle covered with excessive second reactive organic film, conducting the step of inactivating the reactive group of the second organic film located on the surface of the fluor fine particle other than the covalent bond part or binding the third nonreactive organic film to the second organic film located on the surface of the fluor fine particle other than the covalent bond part is preferable for preparing the plurality of pattern-like monolayer fluor fine particle film to the surface of the identical base material.
Further, the present invention aims to provide the pattern-like layered fluor fine particle film having the covalent bond of the fluor fine particle film, which is made by layering selectively on the surface of the base material in stratification, between each other layer through the organic film formed on the surface of the fluor fine particle by: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of processing the first reactive organic film to make the predetermined pattern; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting, for the reaction, the first fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; the step of washing and removing the first fluor fine particle covered with the excessive second reactive organic film to form selectively the first pattern-like monolayer fluor fine particle film; the step of forming the third reactive organic film on the surface of the second fluor fine particle by dispersing the second fluor fine particle in the chemical adsorption solution prepared by blending at least the third alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting and reacting the second fluor fine particle covered with the third reactive organic film to the surface of the base material having the first pattern-like monolayer fluor fine particle film covered with the second reactive organic film; and
the step of washing and removing the second fluor fine particle covered with the excessive third reactive organic film to form selectively the second pattern-like monolayer fluor fine particle film.
The first reactive organic film, which is formed selectively on the surface of the base material, and the fluor fine particle film having the second organic film and the fluor fine particle film having the third organic film, which are alternately layered via the first organic film, are preferable for improving antiremoval strength of the pattern-like layered fluor fine particle film.
The covalent bond made by reaction of a part of the first, second, and third organic films to each other is preferable for layering the pattern-like fluor fine particle film.
Still further, the covalent bond made by -N-C bond formed by the reaction of the epoxy group to the imino group is preferable for obtaining the stable adhesive force. Still further, the inactivated reactive group of the organic film located on the surface of the fluor fine particle located on the outermost surface or the fourth nonreactive organic film formed by binding to the organic film located on the surface of the fluor fine particle located on the outermost surface is preferable for preparing the plurality of places of the pattern-like monolayer fluor fine particle film on the identical base material.
At this time, the first reactive organic film identical to the third reactive organic film is preferable for simplifying manufacturing steps.
On the other hand, following the step of forming the second pattern-like monolayer fluor fine particle film, similarly, repeating the step of forming the first pattern-like monolayer fluor fine particle film and the step of forming the second pattern-like monolayer fluor fine particle film is preferable for thickening a thickness of the layered fine particle film.
Furthermore, following the step of forming the first to third reactive organic films, each, washing the surface of the base material or the fluor fine particle with the organic solvent to form the first to third reactive monomolecular films having the covalent bond to the surface of the base material and the fluor fine particle is preferable for making the binder component least.
In addition, the first and the third reactive organic films containing the epoxy group and the second reactive organic film containing the imino group is preferable for making the organic film on the fine particle react selectively to the organic film to the surface of the base material. Moreover, using the ketimine compound or the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound as a replacement of the silanol condensation catalyst is preferable for shortening the time for fabricating the covering film.
Using the ketimine compound or at least one selected from the organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound as the promoter for blending with the silanol condensation catalyst is preferable for shortening further the time for fabricating the covering film.
Additionally, the present invention provides essentially a display device, in which the single layer of the pattern-like fluor fine particle film formed selectively on a pixel portion of the device has the covalent bond to the first organic film, which is formed selectively on the surface of the base material, via the second organic film formed on the surface of the fluor fine particle.
The present invention provides essentially the display device, in which the plurality of the pattern-like fluor fine particle films selectively layered on the pixel portion of the device have covalent bonds between their layers via the organic film formed on the surface of the fluor fine particle.
Each of the pattern-like fluor fine particle films containing the red, blue, or green luminescent fluor fine particle is preferable for providing the display device capable of color display. On the other hand, the present invention provides essentially a television using the display device, in which the film of the pattern-like fluor fine particle selectively and singly formed on the pixel portion of the device has the covalent bond to the first organic film formed selectively on the surface of the base material via the second organic film formed on the surface of the fluor fine particle. The plurality of the pattern-like fluor fine particle films, which is selectively layered on the pixel portion of the device has the covalent bonds between their layers via the organic film formed on the surface of the fluor fine particle, is preferable for
providing the television using the display device excellent in reliability.
Each of the pattern-like fluor fine particle films containing the red, blue, or green luminescent fluor fine particle is preferable for providing the television capable of color display. As described above, according to the present invention, using the fluor fine particle, without loss of the inherent function of a variety of fluor fine particles, the following prominent effects can be provided at a low cost: the covering film (the pattern-like monolayer fluor fine particle film) made by the pattern-like arrangement of only one layer of fluor fine particles on a surface of the arbitrary base material and having an even thickness in a particle size level; the covering film (the pattern-like layered fluor fine particle film) made by layering the plurality of films made by arranging only one layer of fluor fine particles; manufacturing methods thereof; and the display device and the television using them.
BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual rendering made by enlarging the reaction of the surface of the TFT array base material in the first example according to the present invention to a molecular level, 1A is a figure of the surface before the reaction, 1B the figure after the monomolecular film containing the epoxy group was formed, and 1C the figure after the monomolecular film containing the amino group was formed.
Fig. 2 is the conceptual rendering made by enlarging the reaction of the surface of the red zinc sulfate fluor fine particle in the second example according to the present invention to the molecular level, 2A is the figure of the surface of the red zinc sulfate fluor fine particle before the reaction, 2B the figure after the monomolecular film containing the epoxy group was formed, 2C the figure after the monomolecular film containing the amino group was formed.
Fig. 3 is the conceptual rendering made by enlarging the reaction of the surface of the glass base material in the third and fourth examples according to the present invention to the molecular level, 3A shows the figure of the surface of the base material formed as the pattern-like monolayer red zinc sulfate fluor fine particle film, 3B shows the figure of the surface of the base material, on which two layers of
the pattern-like monolayer red zinc sulfate fluor fine particle film were formed.
Fig. 4 is a conceptual figure, which is enlarged to a molecular level, showing the reaction of the surface of the glass base material, on which the TFT array mentioned in the fifth example according to the present invention has been formed, 4A a sectional conceptual figure of the surface of the base material after the organic film on the surface of the red pattern-like zinc sulfate layered fluor fine particle film is inactivated, 4B the sectional conceptual figure of the surface of the base material, on which the green pattern-like zinc sulfate layered fluor fine particle film has been formed, and 4C the sectional conceptual figure of the surface of the base material, on which the green pattern-like zinc sulfate layered fluor fine particle film has been formed.
DETAILED DESCRIPTION The present invention provides the pattern-like layered fluor fine particle film having the covalent bond of fluor fine particles, which is made by layering on the surface of the base material in stratification, between each other layer through the organic film, which is formed on the surface of the fluor fine particle, and a high performance display device and the television using the pattern-like layered fluor fine particle film by: the step of forming the first reactive organic film on the surface of the base material by contacting at least the surface of the base material with the chemical adsorption solution prepared by blending the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of processing the first reactive organic film to make the predetermined pattern; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting, for the selective reaction, the first fluor fine particle covered
with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; the step of washing and removing the first fluor fine particle covered with the excessive second reactive organic film to form the first pattern-like monolayer fluor fine particle film; the step of forming the third reactive organic film on the surface of the second fluor fine particle by dispersing the second fluor fine particle in the chemical adsorption solution prepared by blending at least the third alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting and reacting selectively the second fluor fine particle covered with the third reactive organic film to the surface of the base material having the first pattern-like monolayer fluor fine particle film covered with the second reactive organic film; and the step of washing and removing the second fluor fine particle covered with the excessive third reactive organic film to form the second pattern-like monolayer fluor fine particle film.
Consequently, according to the present invention, using the fluor fine particle, without loss of the inherent function of a variety of fluor fine particles, the following effects can be provided: the pattern-like monolayer fluor fine particle film made by the pattern-like arrangement of only one layer of fluor fine particles on a surface of the arbitrary base material and having an even thickness in a particle size level; the pattern-like layered fluor fine particle film made by layering the plurality of films made by arranging only one layer of fluor fine particles; manufacturing methods for them; and manufacturing the high performance display device and the television using them at the low cost.
Details of the present invention will be described as follows with reference to examples. However, the present invention is not restricted by these examples.
For preparation of the pattern-like monolayer fluor fine particle film and the pattern-like layered fluor fine particle film according to the present invention,
norganic fluor fine particle, organic fluor fine particle, and organic-inorganic hybrid fluor fine particle film can be used. A zinc sulfate-based fluor fine particle film will be described below as the typical example. [Example 1] First, a glass base material 1 , on which a TFT array had been previously formed, was prepared and dried well. Subsequently, as the chemical adsorbent, a functional group such as the epoxy group having reactivity in a functional site and a drug containing an alkoxy silyl group, which is exemplified by the drug shown by the following formula (chemical formula 1 ,) in the other terminal were weighed to make 99 weight percent each, and, as a silanol condensation catalyst, dibutyltin diacetylacetonate, for example, is weighed to make about 1 weight percent. All these drugs were dissolved in a silicon solvent, for example, hexamethyl disiloxane solvent to make about 1 weight percent concentration (preferable concentration of the chemical adsorbent solution ranges from about 0.5 to 3%) to prepare a chemical adsorbent solution. [Chemical formula 1]
O O C H 3
C H 2- C H C H2O ( C H2) g S i — O C H 3
I
O C H g
Next, glass base material 1 was soaked in this adsorbent solution to react in normal air (relative humidity 45%) for 2 hours. At this time, the surface of the glass base material 1 contains many hydroxyl group 2 (Fig. 1A) and, thus, -Si (OCH3) of the chemical adsorbent makes dealcohol reaction (in this case, deCH3OH) to the hydroxyl group in the presence of the silanol condensation catalyst to make a bond shown in the following formula (chemical formula 2) resulting in formation of a chemical adsorption monomolecular film 3, which contains the epoxy group chemically bonded to the surface across all the surface of glass base material 1 , in the film thickness of about 1 nanometer. [Chemical formula 2]
O O -
/ \ 1
C H2-C H C H2O (CH2) aS i — O -
! o-
Following this step, washing with a chlorine-based solvent, chloroform, allowed preparing each of glass base material 4 covered with the chemical adsorption monomolecular film (the first reactive organic film) having the reactive functional group such as the epoxy group on the surface (Fig. 1 B).
This covering film is very thin in the thickness of a nanometer order and, hence, did not cause a loss of transparency of the glass base material.
On the other hand, exposing in air without washing showed almost no change of transparency and reactivity, but caused evaporation of the solvent. As the result, the chemical adsorbent left on the surface of the glass base material reacted to water in air on the surface to gave the glass base material, on which a very thin, reactive, polymer film composed of the chemical adsorbent was formed on the surface.
In case of manufacturing an EL display, an excimer laser and a mask are used for selective irradiation (e.g., irradiating the monomolecular film other than the portion predetermined for forming a red EL layer.) of an unnecessary portion on the surface of the base material to remove the reactive monomolecular film by abrasion
(Fig. 1C) or a ring of the epoxy group is opened to be inactivated (Fig. 1 D). Thus, the base material 6 and 6', of which the surface of the glass base material is covered selectively with pattern-like covering films 5 and 5' having the epoxy group was fabricated.
As another method, a cation-based polymerization initiator such as IRGACURE 250 made by Ciba Specialty Chemicals was applied to the surface of the epoxy-covering film by diluting with methylethyl ketone to open selectively the epoxy group as shown in Fig. 1 D for polymerization by exposing selectively to a far ultraviolet ray resulting in pattern-like inactivation. [Example 2]
Similar to Example 1 , first, anhydrous a red zinc sulfate fluor (ZnS: Mn) fine
particle 11 with an about 10 nm size was prepared and dried well. Subsequently, as the chemical adsorbent, a functional group such as the epoxy group or an imino group, which has reactivity in a functional site, and a drug containing an alkoxy silyl group, which is exemplified by the drug shown by the formula (chemical formula 1) or the following formula (chemical formula 3), in the other terminal are weighed to make 99 weight percent each, and, as a silanol condensation catalyst, acetic acid being the organic acid, for example, is weighed to make about 1 weight percent. All these drugs were dissolved in a silicon solvent, for example, hexamethyl disiloxane and dimethyl formamide (50: 50) mixture solvent to make about 1 weight percent concentration (preferable concentration of the chemical adsorbent solution ranges from about 0.5 to 3%) to prepare a chemical adsorbent solution. [Chemical formula 3]
O C H3
1
H 2 N CC H2) a S ϊ - O CH 3
I
O C H 3
Anhydrous red zinc sulfate fluor fine particle 11 was mixed with this adsorbent solution, stirred, and reacted in normal air (relative humidity 45%) for about 2 hours. At this time, the surface of the anhydrous red zinc sulfate fluor fine particle contains many hydroxyl groups 12 (Fig. 2A) and, thus, -Si (OCH3) group of the chemical adsorbent makes dealcohol (in this case, deCH3OH) reaction to the hydroxyl groups in the presence of the acetic acid as the organic acid to make the bond shown in the formula (chemical formula 2) or the following formula (chemical formula 4) resulting in formation of the chemical adsorption monomolecular film 13
(the second reactive organic film or the third reactive organic film), which contains the epoxy group chemically bonded to the surface across all the surface of the red zinc sulfate fluor fine particle, or the chemical adsorption film 14 (the third reactive organic film or the second reactive organic film), which contains the amino group, in the film thickness of about 1 nanometer (Fig. 2B, 2C).
[Chemical formula 4]
i
H2 N ( C H2) 3 S J — O -
I o—
Here, in case of using the chemical adsorbent containing the amino group, a tin-based catalyst causes precipitation and, hence, it was better to use the organic acid such as the acetic acid. In addition, the amino group contains the imino group and other substances containing the imino group other than the amino group includes a pyrrole derivative and imidazol derivative. Moreover, using a ketimine derivative allows easily introducing the amino group by hydrolysis following formation of the covering film.
Thereafter, stirring and washing after adding the chlorine-based solvent, chloroform, allowed preparing each of red zinc sulfate fluor fine particle 15 covered with the chemical adsorption monomolecular film (the second reactive organic film or the third reactive organic film) having the reactive functional group such as the epoxy group on the surface, or, red zinc sulfate fluor fine particle 16 covered with the chemical adsorption monomolecular film (the third reactive organic film or the second reactive organic film) having the amino group.
This covering film having the film thickness is very thin on the nanometer level and, therefore, showed no loss of the particle size.
On the other hand, exposing to air without washing caused almost no change of reactivity and evaporation of the solvent. As the result, the chemical adsorbent left on the surface of the particle reacted to water in air on the surface to gave the red zinc sulfate fluor fine particle, on which the very thin (in comparison with the monomolecular film, slightly thicker), reactive, polymer film composed of the chemical adsorbent was formed on the surface.
Features of this method using the dealcohol reaction is that the fluor fine particle of an organic material or a metal oxide can be used to enable to apply to a wide range of application fields. [Example 3]
Next, red zinc sulfate fluor fine particle 23, which was covered with the
chemical adsorption monomolecular film having the amino group, was applied to the surface of glass base material 22, which was covered selectively with ITO electrodes formed of chemical adsorption monomolecular film 21 having the epoxy group, by dispersing in alcohol and heated at 1000C. As the result, the amino group on the surface of the red zinc sulfate fluor fine particle contacting to the epoxy group on the surface of the glass base material was added by the reaction shown in the following formula (chemical formula 5) to make selectively the bond of the red zinc sulfate fluor fine particle to the glass base material via two monomolecular films. At this time, evaporating alcohol by irradiating of an ultrasonic wave allowed improving the evenness of film thickness of the covering film. [Chemical formula 5] o /• \
- ( C H2) C H- C H2 + H 2 N CH2 -
→ - (CH2) C H C H2 - N H C Hj -
1
O H
Then, the surface of the base material was again washed with alcohol and the red zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having excessive amino groups, which had not reacted to the surface of the base material, was washed and removed. As the result, in the state of arranging selectively only one layer of the red zinc sulfate fluor fine particle film 23 covered with the chemical adsorption monomolecular film having amino groups, which had the covalent bond to the surface of glass base material 22, a pattern-like monolayer red zinc sulfate fluor fine particle film 24 can be formed having the even thickness in the particle size level (Fig. 3A).
Here, the thickness of pattern-like monolayer red zinc sulfate fluor fine particle film is about 10 nm and showed very good evenness. [Example 4] In addition, in case of desiring to make the thickness of the red zinc sulfate fluor fine particle film thicker to improve a light emitting performance, following Example 3, in the state of pattern-like arrangement of only one layer of the red zinc
sulfate fluor fine particle covered with the chemical adsorption monomolecular film having amino groups having the covalent bond, red zinc sulfate fluor fine particle 25, which was covered with the chemical adsorption monomolecular film having the epoxy group, was applied to the surface of glass base material, on which the pattern-like monolayer red zinc sulfate fluor fine particle film 24 was formed having the even thickness in the particle size level, by dispersing in alcohol and heated at 1000C. As the result, the epoxy group on the surface of the red zinc sulfate fluor fine particle contacting to the amino group of the part, which was formed in a pattern-like monolayer of the red zinc sulfate fluor fine particle film covered with the chemical adsorption monomolecular film having the amino group, was added by the reaction shown in the formula (chemical formula 5). Finally, the red zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the amino group was selectively bonded to the red zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the epoxy group via two monomolecular films on the surface of the glass base material resulting in hardening.
Then, the surface of the base material was again washed with alcohol to wash out for removing the red zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having excessive and unreacted epoxy groups. As the result, in the state of arranging only one layer of the red zinc sulfate fluor fine particle film of the second layer having the covalent bond to the surface of the glass base material 22 via the red zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having epoxy groups, the pattern-like layered red zinc sulfate fluor fine particle film 26 of a double layer stricture was formed having the even thickness in the particle size level (Fig. 3B). Similarly, layering alternately the red zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the amino group and the red zinc sulfate fluor fine particle covered with the chemical adsorption monomolecular film having the epoxy group allowed fabricating the layered covering films of the red zinc sulfate fluor fine particle having the patterned multilayer structure. [Example 5]
Further, the pattern-like zinc sulfate fluor fine particle film expressing an another luminescent color was formed by the following steps according to Example 4:
the amino group or the epoxy group on the surface of the particle of the outermost surface of the layered films of the red zinc sulfate fluor fine particle film having the patterned multilayer structure, or the TFT array, was soaked into a chemical adsorption agent containing no any active functional group, e. g., a chemical adsorption agent (hereinafter called as adsorption solution) prepared by dissolving CH3CH2-CH2SiCI3, in a nonaqueous solvent (for example, dehydrated nonane) in a concentration of about 0.1 weight percent, in a dry atmosphere (relative humidity was preferably 30 or smaller percents) for reaction. Then, the epoxy group or the imino group contained in the organic film on the outermost surface of the layered films of the red zinc sulfate fluor fine particle film having the patterned multilayer structure made a dehydrochlorination reaction to generate a bond shown in the following formula (Chemical formula 6 or 7) across the whole surface of the fine particle layer. In addition, stirring and washing by adding a freon-based solvent resulted in formation of inactive monomolecular film 27 made of the chemical adsorption agent to make the amino group or the epoxy group inactive (Fig.4A). [Chemical formula 6]
O
/ \ CH3CH2CH2S i (CHg) 2C I + CH2-CH (CH2) -
C H3 CH3
\/
→ CH3CH2CH2S i O
I
CH2C I -CH (CH2) —
[Chemical formula 7]
CHaCH2CH2S i CH3C l 2 + H2N (CH2) 3—
-* CH3CH2CH2S I=N (CH2) 3— +2HC I
I
CH3 CH3 group is inactive to the epoxy group or the imino group and, therefore,
no layering is carried out in the subsequent layering steps.
Then, the pattern-like organic film containing the epoxy group is newly formed in the portion, in which the red layering films have not been formed, by the method similar to that of Example 1 followed by Examples 3 and 4 were operated to form the layered films 28 of the fluor fine particle film such as a pattern-like green zinc sulfate fluor fine particle (ZnS: Tb) film expressing the second luminescent color resulting in an inactivated surface (Fig. 4B).
Finally, by the similar method, the layered films 29 of a pattern-like blue zinc sulfate fluor fine particle (Mg, Ba) AbS4: Eu films wad formed to make the surface inactive resulting in a fabricated an EL display device capable of full color display (Fig. 4C).
This device never has uneven film thickness of fluor fine particles in a display screen and, hence, distinct improvement of display evenness in the screen enables its application to the display device for the television. In Examples 1 and 2 as described above, substances shown in formula
(Chemical formula 1) or (Chemical formula 3) were used as the chemical adsorbent containing the reactive group. Other substances, which were shown in the following (1) to (16), than those as described above were usable.
(I) (CH2OCH) CH2O (CH2)7 Si(OCH3)3 (2) (CH2OCH) CH2O (CHz)11 Si(OCH3)3
(3) (CH2CHOCH (CHz)2) CH(CH2)2 Si(OCH3)3
(4) (CH2CHOCH (CH2J2) CH(CH2)4 Si(OCH3)3
(5) (CH2CHOCH (CH2J2) CH(CH2)6 Si(OCH3)3
(6) (CH2OCH) CH2O (CH2)7 Si(OC2H5)3 (7) (CH2OCH) CH2O (CHs)11 Si(OC2Hs)3
(8) (CH2CHOCH (CH2)2)CH (CH2)2 Si(OC2Hs)3
(9) (CH2CHOCH (CHz)2)CH (CH2)4 Si(OC2Hs)3
(10) (CH2CHOCH (CH2)2)CH (CH2)6 Si(OC2Hs)3
(II) H2N (CH2) 5Si (OCH3)3 (12) H2N (CH2) 7Si (OCHs)3
(13) H2N (CH2) 9Si (OCH3)3
(14) H2N (CH2) 5Si (OC2Hs)3
(15) H2N (CH2) 7Si (OC2Hg)3
(16) H2N (CH2) 9Si (OC2Hg)3
Here, (CH2OCH)- group represents the functional group expressed by the following formula (Chemical formula 8) and (CH2CHOCH (CH2)2) CH- group represents the functional group expressed by the following formula (Chemical formula 9). [Chemical formula 8]
O
/ X
C H 2- C H -
[Chemical formula 9] O C H — C H 2
\ / \
C H C H -
\ /
C H 2-C H 2
In Example 5 as described above, CH3CH2CH2Si(CH3)2CI was used. On the other hand, additionally to the substances described above, the following substances (21) to (28) were also usable. (2I) CH3CH2Si(CHs)2CI (22) CH3(CH2)4Si(CH3)2CI
(23) CF3(CHs)2Si(CHs)2CI
(24) CF3(CF2)6(CH2)2Si(CH3)2CI
(25) CH3CH2SiCH3CI2
(26) CH3(CHs)4SiCH3CI2 (27) CF3(CHs)2SiCH3CI2
(28) CF3(CH2)6(CH2)2SiCH3CI2
In Examples 1 and 2, usable silanol condensation catalysts include a metal salt of a carboxylic acid, the metal salt of a carboxylic acid ester, 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, 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 were usable.
Usable solvents for a film formation solution were an organic chlorine-based solvent containing no water, hydrocarbon-based solvent, or carbon fluoride-based solvent, and silicone-based solvent, or a mixture thereof. In the case of attempting to increase a particle concentration by evaporating the solvent without washing, a boiling point of the solvent ranges preferably from about 50° to 25O0C. In addition, in the case where the adsorbent is assumed as an alkoxysilane-based and the organic covering film is formed by evaporating the solvent, in addition to the solvents as described above, alcohol-based solvents such as methanol, ethanol, and propanol or the mixture thereof could be used.
Specifically usable solvents include a chlorosilane-based nonaqueous petroleum naphtha, solvent naphtha, petroleum ether, petroleum benzine, isoparaffin, normal paraffin, decalin, industrial gasoline, nonane, decane, kerosine, dimethyl silicone, phenyl silicone, alkyl denatured silicone, polyether silicone, and dimethyl formamide.
Carbon fluoride-based solvents include freon-based solvent, Frorinate (made by Sumitomo 3M Limited), and Afrude (Asahi Glass Co. made.). These may be singly used as the pattern-like monolayer and, if they are blended well, may be used in a combination of two or more 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 short 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 aminoaikyl 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- tetramethy 1-5,8, 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 Examples 1 to 5 as described above, the glass base material, on which the TFT array used for the EL display has been formed, and the red, blue, and green luminescent fluor fine particles were described as examples. The present invention can be applied to any occasions, when the fluor is needed to apply in a pattern.
Claims
1. A pattern-like monolayer fluor fine particle film having a covalent bond of a film of a monolayer of a fluor fine particle formed selectively on a surface of a base material to a first organic film formed selectively on the surface of the base material, through a second organic film formed on the surface of the fluor fine particle.
2. The pattern-like monolayer fluor fine particle film according to claim 1 , wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are different from each other.
3. The pattern-like monolayer fluor fine particle film according to claim 1 , wherein the covalent bond is a -N-C- bond formed by a reaction of an epoxy group and an imino group.
4. The pattern-like monolayer fluor fine particle film according to claim 1 or claim 2, wherein the first organic film formed on the surface of the base material and the second organic film formed on the surface of the fluor fine particle are constituted from a monomolecular film.
5. The pattern-like monolayer fluor fine particle film according to claim 1 , wherein a reactive group of the second organic film located in the surface of the fluor fine particle other than the covalent bond part is inactivated or a third nonreactive organic film bound to the second organic film is formed.
6. A manufacturing method for the pattern-like monolayer fluor fine particle film, comprising: a step of forming a first reactive organic film on the surface of the base material by contacting the surface of the base material with a chemical adsorption solution prepared by blending at least a first alkoxysilane compound and a silanol condensation catalyst and a nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material; a step of processing the first reactive organic film to make a predetermined pattern; a step of forming a second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least a second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; a step of contacting, for a selective reaction, the fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; and washing and removing the fluor fine particle covered with an excessive second reactive organic film.
7. The manufacturing method for the pattern-like layered fluor fine particle film according to claim 6, comprising: the step of forming the first reactive organic film on the surface of the base material by contacting the surface of the base material with the chemical adsorption solution prepared by blending at least the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react an alkoxysilane compound to the surface of the base material and a step of forming the second reactive organic film on the surface of the fluor fine particle by dispersing the fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle, followed by washing each of the base material and the surface of the fluor fine particle with an organic solvent to form a first and second reactive monomolecular films having the covalent bond to the base material and the surface of the fluor fine particle.
8. The manufacturing method for the pattern-like monolayer fluor fine particle film according to claim 6, wherein the first reactive organic film contains an epoxy group and the second reactive organic film contains an imino group.
9. The manufacturing method for the pattern-like monolayer fluor fine particle film according to claim 7, wherein the first reactive monomolecular film contains an epoxy group and the second reactive monomolecular film contains an imino group.
10. The manufacturing method for the pattern-like monolayer fluor fine particle film according to claim 6, wherein following the step of washing and removing the fluor fine particle covered with an excessive second reactive organic film, a step is carried out for inactivating a reactive group of the second organic film located in the surface of the fluor fine particle other than the covalent bond part or binding a third nonreactive organic film to the second organic film located in the surface of the fluor fine particle other than the covalent bond part.
11. A pattern-like layered fluor fine particle film layered as stratification selectively on the surface of the base material, wherein the fluor fine particle has the covalent bond between layers through an organic covering film formed on the surface of the fluor fine particle.
12. The pattern-like layered fluor fine particle film according to claim 11, wherein the first organic film is formed on the surface of the base material and the fluor fine particle film having the second organic film and the fluor fine particle film having the third organic film are layered alternately via the first organic film.
13. The pattern-like layered fluor fine particle film according to claim 12, wherein a part of the first, second, and third organic film react each other to form the covalent bond.
14. The pattern-like layered fluor fine particle film according to claim 13, wherein the covalent bond is the -N-C- bond formed by the reaction of the epoxy group to the imino group.
15. The pattern-like monolayer fluor fine particle film according to claim 14, wherein a reactive group of the organic film located on the surface of the fluor fine particle on an outermost surface is inactivated or the a fourth nonreactive organic film bound to the organic film on the surface of the fluor fine particle on the outermost surface is formed.
16. A manufacturing method for the pattern-like layered fluor fine particle film comprising: the step of forming the first reactive organic film on the surface of the base material by contacting at least the surface of the base material with the chemical adsorption solution prepared by blending the first alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the base material; the step of processing the first reactive organic film to make the predetermined pattern; the step of forming the second reactive organic film on the surface of the first fluor fine particle by dispersing the first fluor fine particle in chemical adsorption solution prepared by blending at least the second alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the fluor fine particle; the step of contacting the first fluor fine particle covered with the second reactive organic film to the surface of the base material having the first reactive organic film formed thereon; the step of washing and removing the first fluor fine particle covered with the excessive second reactive organic film to form selectively the first pattern-like monolayer fluor fine particle film; the step of forming the third reactive organic film on the surface of the second fluor fine particle by dispersing the second fluor fine particle film in the chemical adsorption solution prepared by blending at least the third alkoxysilane compound and the silanol condensation catalyst and the nonaqueous organic solvent to react the alkoxysilane compound to the surface of the second fluor fine particle; the step of contacting and reacting the second fluor fine particle covered with the third reactive organic film to the surface of the base material having the first pattern-like monolayer fluor fine particle film covered with the second reactive organic film; and the step of washing and removing the second fluor fine particle covered with the excessive third reactive organic film to form selectively the second pattern-like monolayer fluor fine particle film.
17. The manufacturing method for the pattern-like layered fluor fine particle film according to claim 16, wherein the first reactive organic film is identical to the third reactive organic film.
18. The manufacturing method for the pattern-like layered fluor fine particle film of a multilayer structure according to claim 16, wherein, following the step of forming the second pattern-like monolayer fluor fine particle film, similarly, the step of forming the first pattern-like monolayer fluor fine particle film and the step of forming the second pattern-like monolayer fluor fine particle film are repeated.
19. The manufacturing method for the pattern-like layered fluor fine particle film according to claim 16, wherein, following the step of forming the first to third reactive organic films, for each of their steps, surfaces of the base material or the fluor fine particle are washed with the organic solvent to form the first to third reactive monomolecular films having the covalent bond to the surface of the base material and the fluor fine particle.
20. The manufacturing method for the pattern-like layered fluor fine particle film according to claim 16, wherein the first and third reactive organic films contain the epoxy group and the second reactive organic film contains the imino group.
21. The manufacturing method for the pattern-like monolayer fluor fine particle film and the pattern-like layered fluor fine particle film according to claim 6 or claim 16, wherein, replacing to the silanol condensation catalyst, a ketimine compound or an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound are used.
22. The manufacturing method for the pattern-like monolayer fluor fine particle film and the pattern-like layered fluor fine particle film according to claim 6 or claim 16, wherein the silanol condensation catalyst is blended with ketimine compound or at least one selected from an organic acid, aldimine compound, enamine compound, oxazolidine compound, and aminoalkyl alkoxy silane compound for use as a promoter.
23. A display device, wherein a film of a single layer of the pattern-like fluor fine particle formed selectively in a pixel portion of a device has the covalent bond to the first organic film formed selectively on the surface of the base material via the second organic film formed on the surface of the fluor fine particle.
24. A display device, wherein a plurality of layers of the pattern-like fluor fine particle film formed selectively in the pixel portion of the device has the covalent bond to each other between layers via the organic film formed on the surface of the fluor fine particle.
25. The display device according to claim 23 or claim 24, wherein each of the pattern-like fluor fine particle film contains a red, blur, or green luminescent fluor fine particle.
26. A television using the display device, wherein the film of the single layer of the pattern-like fluor fine particle formed selectively in the pixel portion of a device has the covalent bond to the first organic film formed selectively on the surface of the base material via the second organic film formed on the surface of the fluor fine particle.
27. The television using the display device, wherein the plurality of layers of the pattern-like fluor fine particle film formed selectively in the pixel portion of the device has the covalent bond to each other between layers via the organic film formed on the surface of the fluor fine particle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2007/061945 WO2008149469A1 (en) | 2007-06-07 | 2007-06-07 | Pattern-like fluor fine particle film and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2007/061945 WO2008149469A1 (en) | 2007-06-07 | 2007-06-07 | Pattern-like fluor fine particle film and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2008149469A1 true WO2008149469A1 (en) | 2008-12-11 |
Family
ID=40093304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2007/061945 WO2008149469A1 (en) | 2007-06-07 | 2007-06-07 | Pattern-like fluor fine particle film and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2008149469A1 (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6221151A (en) * | 1985-07-19 | 1987-01-29 | Matsushita Electric Ind Co Ltd | Pattern formation method |
| WO2006008987A1 (en) * | 2004-07-15 | 2006-01-26 | Idemitsu Kosan Co., Ltd. | Organic el display |
| JP2007118276A (en) * | 2005-10-26 | 2007-05-17 | Kagawa Univ | Single-layer fine particle film, cumulative fine particle film, and production method thereof. |
-
2007
- 2007-06-07 WO PCT/JP2007/061945 patent/WO2008149469A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6221151A (en) * | 1985-07-19 | 1987-01-29 | Matsushita Electric Ind Co Ltd | Pattern formation method |
| WO2006008987A1 (en) * | 2004-07-15 | 2006-01-26 | Idemitsu Kosan Co., Ltd. | Organic el display |
| JP2007118276A (en) * | 2005-10-26 | 2007-05-17 | Kagawa Univ | Single-layer fine particle film, cumulative fine particle film, and production method thereof. |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2008068873A1 (en) | Monolayer nanoparticle film, multilayer nanoparticle film, and manufacturing method thereof | |
| JP5487460B2 (en) | Silicon fine particles, production method thereof, solar cell using the same, and production method thereof | |
| JP2007118276A (en) | Single-layer fine particle film, cumulative fine particle film, and production method thereof. | |
| JP5087764B2 (en) | Silicon fine particles, production method thereof, solar cell using the same, and production method thereof | |
| JP4848502B2 (en) | WIRING, MANUFACTURING METHOD THEREOF, AND ELECTRONIC COMPONENT AND ELECTRONIC DEVICE USING THEM | |
| US9580645B2 (en) | Fluorescent pastes and films | |
| JP5050190B2 (en) | Fine particles and production method thereof | |
| JP2007117827A (en) | Patterned fine particle film and manufacturing method thereof. | |
| JP2007119545A (en) | Fine particle film and manufacturing method thereof | |
| JP2007220883A (en) | WIRING, MANUFACTURING METHOD THEREOF, AND ELECTRONIC COMPONENT AND ELECTRONIC DEVICE USING THEM | |
| JP4993700B2 (en) | Protective film and method for producing the same | |
| WO2008149469A1 (en) | Pattern-like fluor fine particle film and manufacturing method thereof | |
| US20100143665A1 (en) | Patterned fine particle film structures | |
| JP5594806B2 (en) | Phosphor fine particle film, method for producing the same, and display device using the phosphor fine particle film | |
| JP4868496B2 (en) | Solar cell and manufacturing method thereof | |
| JP2007161748A (en) | Phosphor fine particles, method for producing the same, and phosphor coating using the same | |
| JP2010129619A (en) | Solar cell using silicon particulate, optical sensor, and method of manufacturing them | |
| JP5167528B2 (en) | Chemisorption solution | |
| WO2008149470A1 (en) | Monolayer fluor fine particle film, fluor fine particle film-layered body, and manufacturing method thereof and display device and photoreceptor and sensor, which are made by using them | |
| JP2008221369A (en) | Particulate membrane and method of manufacturing the same | |
| JP5200244B2 (en) | Fine particle film and manufacturing method thereof | |
| WO2008136129A1 (en) | Pattern-like fine particle film and manufacturing method | |
| WO2008139634A1 (en) | Insulant fine particle film, a method of manufacturing the same, and a capacitor made thereof | |
| JP5750706B2 (en) | TFT using Si fine particles, manufacturing method thereof, TFT array using the same, and display device | |
| JP2007161749A (en) | Patterned phosphor fine particle film and manufacturing method thereof. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07767112 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |
|
| 122 | Ep: pct application non-entry in european phase |
Ref document number: 07767112 Country of ref document: EP Kind code of ref document: A1 |