JP4447354B2 - Manufacturing method of fine particle fixed body - Google Patents
Manufacturing method of fine particle fixed body Download PDFInfo
- Publication number
- JP4447354B2 JP4447354B2 JP2004074089A JP2004074089A JP4447354B2 JP 4447354 B2 JP4447354 B2 JP 4447354B2 JP 2004074089 A JP2004074089 A JP 2004074089A JP 2004074089 A JP2004074089 A JP 2004074089A JP 4447354 B2 JP4447354 B2 JP 4447354B2
- Authority
- JP
- Japan
- Prior art keywords
- fine particles
- thin film
- resin
- silane coupling
- coupling agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010419 fine particle Substances 0.000 title claims description 178
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 239000000758 substrate Substances 0.000 claims description 73
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 63
- 229920005989 resin Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 60
- 239000010409 thin film Substances 0.000 claims description 51
- 238000010559 graft polymerization reaction Methods 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 21
- 230000005855 radiation Effects 0.000 claims description 19
- 125000000524 functional group Chemical group 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 44
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 42
- 239000000463 material Substances 0.000 description 27
- 239000000835 fiber Substances 0.000 description 25
- 239000000377 silicon dioxide Substances 0.000 description 20
- 229920006267 polyester film Polymers 0.000 description 17
- -1 acryloxy group Chemical group 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000010894 electron beam technology Methods 0.000 description 12
- 239000010408 film Substances 0.000 description 12
- 239000004575 stone Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 230000003100 immobilizing effect Effects 0.000 description 9
- 230000001678 irradiating effect Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000011859 microparticle Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- 239000004744 fabric Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 125000005372 silanol group Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
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- 239000011230 binding agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000006482 condensation reaction Methods 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
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- 238000007645 offset printing Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
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- 125000004432 carbon atom Chemical group C* 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
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- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000025 natural resin Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000002285 radioactive effect Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-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
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 229910004158 TaO Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- IKNAJTLCCWPIQD-UHFFFAOYSA-K cerium(3+);lanthanum(3+);neodymium(3+);oxygen(2-);phosphate Chemical compound [O-2].[La+3].[Ce+3].[Nd+3].[O-]P([O-])([O-])=O IKNAJTLCCWPIQD-UHFFFAOYSA-K 0.000 description 1
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- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- RMTGISUVUCWJIT-UHFFFAOYSA-N n-[3-[3-aminopropoxy(dimethoxy)silyl]propyl]-1-phenylprop-2-en-1-amine;hydrochloride Chemical compound Cl.NCCCO[Si](OC)(OC)CCCNC(C=C)C1=CC=CC=C1 RMTGISUVUCWJIT-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、基体表面上に微粒子が固定化されることで様々な用途に応用可能な微粒子固定化体の製造方法に関する。 The present invention relates to a method for producing a fine particle immobilized body that can be applied to various uses by immobilizing fine particles on a substrate surface.
最近、微粒子を基材上に固定化した粒子集積体への関心が高まってきており、新たな特性を有する機能材料の開発の手段として、さらには、それらのデバイスへの応用が期待されている。微粒子を基体表面に集積して固定化する方法としては、単分散性に優れたコロイド状のポリマー粒子や無機、金属粒子を沈降させて溶媒を加熱乾燥などにより除去することで容易に得られる。しかしながら、得られた微粒子の固定化体では、固定化された微粒子が非常に弱い静電結合やイオン結合などで基体表面に固定化されていることから、微粒子固定化体を様々な環境で使用すると、環境によっては固定化した微粒子が脱離して、発現する機能が消失してしまう問題が発生する。したがって、微粒子を固定化して微粒子の特性や新たに発現する効果を利用するためには、様々な環境でも固定化した微粒子の脱離が発生し難い微粒子固定化体の製造技術を確立することが必要となってきている。 Recently, interest in particle aggregates in which fine particles are immobilized on a substrate has been increasing, and as a means of developing functional materials having new characteristics, further application to these devices is expected. . As a method of collecting and fixing the fine particles on the substrate surface, it can be easily obtained by precipitating colloidal polymer particles having excellent monodispersibility, inorganic or metal particles, and removing the solvent by heating and drying. However, in the obtained immobilized microparticles, the immobilized microparticles are used in various environments because the immobilized microparticles are immobilized on the substrate surface by very weak electrostatic bonds or ionic bonds. Then, depending on the environment, there arises a problem that the immobilized fine particles are detached and the function to be expressed is lost. Therefore, in order to immobilize the microparticles and utilize the characteristics of the microparticles and the newly developed effect, it is necessary to establish a technique for producing a microparticle immobilization body in which desorption of the immobilized microparticles hardly occurs even in various environments It has become necessary.
これまでに微粒子を固定化する方法としては、様々な方法が提案されており、例えば、ガラス表面にＳｉＯ2薄膜で微粒子を固定化する方法（例えば、特許文献１参照。）、カチオン重合性のモノマーを主成分とするバインダー成分により微粒子を固定化する方法（例えば、特許文献２参照。）、レーザーを照射して微粒子を基体表面に固定化する方法（例えば、特許文献３、特許文献４参照。）、放射線を照射して基体表面に微粒子を固定化する方法（例えば、特許文献５参照。）、微粒子表面に官能基を導入して粒子表面に存在する官能基同士を結合させて微粒子を集積して固定化する方法（例えば、特許文献６参照。）などが挙げられる。
しかしながら、上記の微粒子を固定化する方法としては、以下のような様々な問題がある。例えば、特開平０１−１５４４４４号公報記載の技術では、ガラス基体表面にＳｉＯ2の薄膜でＳｉＯ2からなる微粒子を固定化しており、基体の表面が少なくとも樹脂からなる場合ではＳｉＯ2薄膜自体が樹脂表面に接着しないことから、ＳｉＯ2からなる微粒子を固定化することは不可能である。また、特開平０６−１５５６５２号公報記載の技術では、紫外線重合可能なカチオン重合性のモノマーを主成分とするバインダー成分により固定化する方法であるが、この場合、基体が樹脂でも微粒子を固定化することは可能であるが、金属やそれらの酸化物からなる微粒子では紫外線がこれらの材料を透過し難い為に、充分な強度で固定化することは困難であり、さらに、機能性を有する微粒子では、条件によってはカチオン性重合性モノマーで微粒子が覆われることから、微粒子が持つ機能が損なわれる問題が発生する。また、特開２００１−１４９７７４号公報や特開２００２−０８８４８７号公報記載の技術では、固定化の原理がレーザー照射により固定化しようとする金属微粒子を溶融して基体表面に固定化することから、金属以外の酸化物や窒化物、炭化物、ほう化物、天然の鉱物などからなる高融点材料では微粒子の固定化は不可能であり、さらに、レーザー光を透過しない基体では微粒子の固定化も不可能である。また、特開２００３−３４２７４８号公報に記載の技術においては、レーザー光が透過しない材料に対してＸ線を照射することにより金属微粒子を固定化する方法が提案されているが、固定化の原理は金属微粒子の融解によることが開示されており、固定化する基体が樹脂の場合では、金属微粒子が接触している場所の樹脂が融解熱により分解して金属微粒子が固定されないと推察される。さらに、特開２００２−３４１１６１号公報に記載の技術においては、微粒子同士の化学結合は開示されているものの基体への微粒子の固定化に関しては開示されておらず、実用面、製造面または耐久性において問題があると考えられる。 However, the method for immobilizing the above fine particles has the following various problems. For example, in the technique of JP-A-01-154444 JP, the fine particles comprising SiO 2 with a thin film of SiO 2 on the glass substrate surface have been fixed, the SiO 2 thin film itself in the case the surface of the substrate comprising at least a resin resin Since it does not adhere to the surface, it is impossible to immobilize fine particles made of SiO 2 . The technique described in Japanese Patent Application Laid-Open No. 06-155562 is a method of fixing with a binder component mainly composed of a cationically polymerizable monomer capable of UV polymerization. In this case, fine particles are fixed even if the substrate is a resin. While it is possible to, for difficult to transmit these materials ultraviolet in fine particles of metal or oxides thereof, it is difficult to immobilize with charging and partial intensity, further, it has a functional In the case of fine particles, since the fine particles are covered with a cationic polymerizable monomer depending on conditions, there is a problem that the function of the fine particles is impaired. Further, in the techniques described in Japanese Patent Application Laid-Open Nos. 2001-149774 and 2002-088487, the fixing principle is that the fine metal particles to be fixed by laser irradiation are melted and fixed on the substrate surface. High-melting-point materials made of oxides other than metals, nitrides, carbides, borides, natural minerals, etc. cannot immobilize fine particles. In addition, fine particles cannot be immobilized on substrates that do not transmit laser light. It is. Further, in the technique described in JP-A-2003-342748, a method of immobilizing the metal fine particles has been proposed by irradiating X-rays for the material which the laser beam is not transmitted, the principle of immobilized Is disclosed by melting of metal fine particles, and when the substrate to be immobilized is a resin, it is assumed that the resin at the place where the metal fine particles are in contact is decomposed by the heat of fusion and the metal fine particles are not fixed. Further, in the technique described in JP-A No. 2002-341161, although chemical bonding between fine particles is disclosed, the immobilization of fine particles to a substrate is not disclosed, and practical use, production, or durability is not disclosed. There seems to be a problem.
本発明は、上述した従来技術の問題を解決し、繊維やフィルム、布などからなる少なくとも表面が樹脂からなる基材の風合いや、様々な機能を有する微粒子の特性を損なわずに微粒子を固定化する方法を提供することを目的とする。 The present invention solves the above-mentioned problems of the prior art, and immobilizes fine particles without impairing the texture of the substrate made of resin, at least on the surface consisting of fibers, films, fabrics, etc. and the characteristics of fine particles having various functions. It aims to provide a way to do.
本発明者らは、鋭意研究を重ねた結果、反応性に優れた不飽和結合を有するシランカップリング剤を用いることにより、様々な材料からなる微粒子を、それらの微粒子が有する機能や特性を極力損なわずに、基材の表面に強固に、且つ、風合いを損ねない程度の量として結合させる方法を見出し、これにより固定化する微粒子の機能や特性を最大限発揮できることが可能となる知見を得るに至り、新規な微粒子固定化体の製造方法を創出した。 As a result of intensive research, the present inventors have used silane coupling agents having an unsaturated bond with excellent reactivity, so that the functions and characteristics of these fine particles can be reduced as much as possible. Finding a method for binding to the surface of the substrate firmly and in an amount that does not impair the texture without damaging it, and obtaining knowledge that can maximize the functions and characteristics of the fixed fine particles As a result, a novel method for producing a fine particle-immobilized body was created.
すなわち、第一の発明は、少なくとも基体表面が樹脂からなる微粒子固定化体の製造方法であって、微粒子表面に不飽和結合を有するシランカップリング剤の薄膜を形成し、前記基体表面の樹脂と前記微粒子表面に形成した薄膜とを接触させ、前記基体表面の樹脂表面と前記微粒子表面の薄膜に存在する不飽和結合とを放射線グラフト重合させてなる微粒子固定化体の製造方法を提供するものである。
That is, the first invention is a method for producing a fine particle immobilization body in which at least the surface of a substrate is made of a resin, wherein a thin film of a silane coupling agent having an unsaturated bond is formed on the surface of the fine particle, those wherein a thin film formed on the particle surface is contacted, provides a method for producing an unsaturated bond and consisting by radiation grayed rAFT polymerization particulate immobilized body present in the thin film of the resin surface of the substrate surface the fine particle surface It is.
また、第二の発明は、少なくとも基体表面が樹脂からなる微粒子固定化体の製造方法であって、微粒子に不飽和結合を有するシランカップリング剤の薄膜を形成し、前記薄膜を形成した微粒子からなるコーティング薄膜を前記基体表面に形成し、前記の微粒子と同種または異種の微粒子に不飽和結合を有するシランカップリング剤の薄膜を形成し、前記基体表面に形成した微粒子からなるコーティング薄膜と薄膜を形成した微粒子とを接触させて、コーティング薄膜に存在する不飽和結合と微粒子の薄膜に存在する不飽和結合とを、放射線グラフト重合させてなる積層された微粒子固定化体の製造方法を提供するものである。
The second invention is a method for producing a fine particle immobilization body in which at least the surface of a substrate is made of a resin, wherein a thin film of a silane coupling agent having an unsaturated bond is formed on the fine particles, and from the fine particles on which the thin film is formed. Forming a coating thin film on the substrate surface, forming a thin film of a silane coupling agent having an unsaturated bond on the same kind or different kind of fine particles as the fine particles, and forming the coating thin film and the thin film comprising fine particles formed on the substrate surface. Provided is a method for producing a laminated fine particle immobilization product obtained by bringing a formed fine particle into contact with each other and subjecting an unsaturated bond present in a coating thin film and an unsaturated bond present in the fine particle thin film to radiation graft polymerization. It is.
さらに、第三の発明は、少なくとも基体表面が樹脂からなる微粒子固定化体の製造方法であって、不飽和結合を有するシランカップリング剤からなるコーティング薄膜を前記基体表面にグラフト重合で形成し、微粒子表面に不飽和結合を有するシランカップリング剤の薄膜を形成し、前記コーティング薄膜と前記薄膜を形成した微粒子とを接触させ、コーティング薄膜に存在する官能基と、微粒子の薄膜に存在する官能基とを、放射線グラフト重合させてなる微粒子固定化体の製造方法を提供するものである。
Further, the third invention is a method for producing a fine particle immobilization body having at least a substrate surface made of a resin, wherein a coating thin film made of a silane coupling agent having an unsaturated bond is formed on the substrate surface by graft polymerization, A thin film of a silane coupling agent having an unsaturated bond is formed on the surface of the fine particles, the coating thin film is contacted with the fine particles forming the thin film, and the functional groups present in the coating thin film and the functional groups present in the thin film of the fine particles And a method for producing a fine particle-immobilized body obtained by radiation graft polymerization.
さらにまた、第四の発明は、上記第一乃至第三のいずれかの方法において、微粒子表面に不飽和結合を有するシランカップリング剤の薄膜を、微粒子の重量に対して０．０１〜５重量％のシランカップリング剤を使用して形成する微粒子固定化体の製造方法を提供するものである。
Still further, a fourth invention is the method according to any one of the first to third methods, wherein the thin film of the silane coupling agent having an unsaturated bond on the surface of the fine particles is 0.01 to 5 wt. It provides a method for producing a fine particle immobilization product formed by using% silane coupling agent .
本発明によれば、少なくとも基体表面が樹脂からなる粒子固定化体の製造方法であって、基体の表面に対して、様々な機能や特性を有する微粒子が、シランカップリング剤を介した化学結合によって固定化されるため、基体に対する微粒子は、余剰のモノマーやオリゴマーなどのバインダーに覆われることなく充分な耐久性を保持して固定化できるものである。 According to the present invention, there is provided a method for producing a particle-immobilized body having at least a substrate surface made of a resin, and fine particles having various functions and properties are chemically bonded to the substrate surface via a silane coupling agent. particles because, to the substrate is immobilized by is one that can be immobilized by retaining sufficient durability without being covered with the binder, such as excess monomers and oligomers.
したがって、本発明によれば、様々な機能を有する材料からなる微粒子が各種の基材の表面に強固に結合された耐久性に優れた微粒子固定化体を提供することが可能となる。また、微粒子がバインダーで覆われることなく基材の表面に配置されるので、微粒子が持つ機能や特性を最大限に効率良く発揮することが可能となり、さらに、微粒子は島状、単粒子膜状にも繊維やフィルム、布などからなる基材に固定化できるので、これらの基材の風合いを損なわないことから、様々な分野で応用できる材料を提供することが可能となる。 Therefore, according to the present invention, it is possible to provide a fine particle fixed body having excellent durability in which fine particles made of materials having various functions are firmly bonded to the surfaces of various substrates. In addition, since the fine particles are arranged on the surface of the base material without being covered with a binder, it is possible to maximize the functions and properties of the fine particles with maximum efficiency, and the fine particles are in the form of islands or single particles. In addition, since it can be fixed to a substrate made of fiber, film, cloth or the like, the texture of these substrates is not impaired, and thus it is possible to provide materials applicable in various fields.
なお、本発明の基体の形態としては、例えば、フィルム状、繊維状、布状、メッシュ状、ハニカム状など、使用目的に合った様々な形態（形状、大きさ等）に適応可能であり、これら様々な形態の各種基体に固定化する微粒子が持つ機能や特性を付加することが可能となる。 In addition, as the form of the substrate of the present invention, for example, it can be applied to various forms (shape, size, etc.) suitable for the purpose of use, such as film form, fiber form, cloth form, mesh form, honeycomb form, etc. It becomes possible to add the functions and characteristics of the fine particles to be immobilized on these various types of substrates.
以下に本発明についてさらに詳述する。 The present invention is described in further detail below.
本発明に用いられる様々な機能を有する微粒子の材料としては、用途に応じて適宜選択されるものであり、例えば、酸化チタン、酸化亜鉛、酸化タングステン、酸化鉄、チタン酸ストロンチウム、硫化カドミウム、セレン化カドミウムなどの金属化合物半導体からなる光触媒機能を発現する材料、銀、銅、亜鉛などの金属およびそれらの化合物からなる抗菌性を有する材料および一般に市販されている抗菌性を有する材料、例えば、東亞合成（株）製「ノバロン」、（株）シナネンゼオミック製「ゼオミック」、（株）サンギ製「アパタイザーA」、大日精化工業（株）製「ダイキラー」、松下電器産業（株）製「アメニトップ」、触媒化成工業（株）製「アトミーボール」、カネボウ化成（株）製「バクテキラー」など、デービト鉱、センウラン鉱、ブランネル石、ニンギョウ石、リンカイウラン石、カルノー石、ツャムン石、メタチャムン石、フランセビル石、トール石、コフィン石、サマルスキー石、トリウム石、トロゴム石、サマルスキー石、トリウム石、トロゴム石、モナズ石、タンタル石、バデライト、イルメナイトなどの放射性希有元素を微量含有する天然放射性希有元素鉱物や、これらの鉱物の一部を精製して得られる電融ジルコニアなどのマイナスイオンを放出する材料、Ａｌ2Ｏ３、ＴｉＯ2、ＺｒＯ2、ＳｉＯ2、Ｆｅ2Ｏ３、ＣｏＯ、ＣｕＯ、ＭｇＯなどの金属酸化物やこれらの混合物、例えば、コージライト、βスポジューメン、チタン酸アルミニウムなどの遠赤外線を放出する材料および市販されている遠赤外線セラミックス、例えば、OKトレーディング製セラジット、水澤化学工業株式会社製シルトンＦＩ−８５など、ＳｉＯ2、ＴｉＯ2、ＴａＯ５、ＺｒＯ2、ＳｎＯ2、Ｉｎ2Ｏ３などの反射防止や赤外線反射等の特性を有する材料、Ａｕ、Ａｇ、Ｐｔ、Ｐｄなどの触媒活性を有する貴金属材料およびこれら貴金属の酸化物、ＬａＢ６、ＣｅＢ６、ＮｄＢ６、ＳｎＯ２、Ｉｎ２Ｏ３、酸化ルテニウム、酸化レニウムなどの近赤外線を吸収する材料、ＴａＮ、ＴｉＮ、ＣｒＮなどの金属窒化物、ＴａＣ、ＴｉＣ、ＷＣ、ＭｏＣなどの金属炭化物などからなる導電性金属化合物、グラファイト、活性炭、フラーレン、カーボンナノチューブなどの炭素化合物などを挙げることができる。なお、微粒子の径については特に限定されないが、グラフト重合を好適に行うには、平均粒子径が５００ｎｍ以下とすることが好ましく、さらに平均粒子径が３００ｎｍ以下であれば、基体へのより強固な結合が達成されるため、耐久性の点より一層好適である。 As a material of fine particles having various functions used in the present invention, which is applied Yichun selected depending on the application, for example, titanium oxide, zinc oxide, tungsten oxide, iron oxide, strontium titanate, cadmium sulfide, Materials having a photocatalytic function composed of a metal compound semiconductor such as cadmium selenide, materials having antibacterial properties composed of metals such as silver, copper, and zinc and their compounds, and materials having antibacterial properties which are generally commercially available, for example, “Novalon” manufactured by Toagosei Co., Ltd. “Zeomic” manufactured by Sinanen Zeomic Co., Ltd. “Appaizer A” manufactured by Sangi Co., Ltd. “Daikyler” manufactured by Dainichi Seika Kogyo Co., Ltd. “Made by Matsushita Electric Industrial Co., Ltd.” "Ameni Top", "Atomy Ball" manufactured by Catalytic Kasei Kogyo Co., Ltd., "Bactekiller" manufactured by Kanebo Kasei Co., Ltd., etc. Orbital, Blannel, Ningyo, Rinkai uranium, Carnotite, Chamun stone, Metachamun stone, Franceville stone, Tall stone, Coffin stone, Samarsky stone, Thorium stone, Trogam stone, Samarsky stone, Thorium stone, Trogam stone, monazite, tantalum stone, baddeleyite, materials radioactive rare element emits and natural radioactive rare chromatic element mineral containing trace amounts, negative ions, such as fused zirconia obtained by refining some of these minerals, such as ilmenite, Far-infrared rays such as Al 2 O 3 , TiO 2 , ZrO 2 , SiO 2 , Fe 2 O 3 , CoO, CuO, MgO and other metal oxides and mixtures thereof such as cordierite, β-spodumene, aluminum titanate Emission material and commercially available far-infrared ceramics, eg OK trading Grayed made Serajitto, Mizusawa Industrial Chemicals, such as Co. Silton FI-85, a material having antireflection and characteristics of the infrared reflection such as such as SiO 2, TiO 2, TaO 5 , ZrO 2, SnO 2, In 2 O 3, Au , Ag, Pt, Pd and other noble metal materials and oxides of these noble metals, LaB 6 , CeB 6 , NdB 6 , SnO 2 , In 2 O 3 , ruthenium oxide, rhenium oxide, etc. Examples thereof include conductive materials such as materials, metal nitrides such as TaN, TiN, and CrN, metal carbides such as TaC, TiC, WC, and MoC, and carbon compounds such as graphite, activated carbon, fullerene, and carbon nanotubes. . The diameter of the fine particles is not particularly limited, but in order to carry out graft polymerization suitably, the average particle diameter is preferably 500 nm or less, and if the average particle diameter is 300 nm or less, the substrate is stronger. Since the bonding is achieved, it is more preferable from the viewpoint of durability.
本発明では、様々な機能を有する材料の微粒子を、不飽和結合を有するシランカップリング剤により、樹脂基体上に化学結合により固定するものである。具体的なシランカップリング剤が有する不飽和結合としては、ビニル基、エポキシ基、スチリル基、メタクリロ基、アクリロキシ基、イソシアネート基などが挙げられる。本発明は、反応性に優れたシランカップリング剤を用いることで、様々な機能を有する微粒子を、シランカップリング剤が有するシラノール基の脱水縮合反応による微粒子の化学結合と前記官能基の基体樹脂表面へのグラフト重合による化学結合により、基体表面に結合せしめた微粒子固定化体の製造方法である。 In the present invention, fine particles of materials having various functions are fixed on a resin substrate by chemical bonds with a silane coupling agent having an unsaturated bond. Specific examples of the unsaturated bond of the silane coupling agent include a vinyl group, an epoxy group, a styryl group, a methacrylo group, an acryloxy group, and an isocyanate group. The present invention uses a silane coupling agent having excellent reactivity to form fine particles having various functions, a chemical bond of fine particles by a dehydration condensation reaction of silanol groups of the silane coupling agent, and a base resin of the functional group. This is a method for producing an immobilized fine particle bonded to the surface of a substrate by chemical bonding by graft polymerization to the surface.
本発明で用いられるシランカップリング剤の一例としては、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン、N−（ビニルベンジル）−２−アミノエチル−３−アミノプロピルトリメトキシシランの塩酸塩、２−（３、４エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリメトキシシラン、３−グリシドキシプロピルメチルジエトキシシラン、３−グリシドキシプロピルトリエトキシシラン、ｐ−スチリルトリメトキシシラン、３−メタクリロキシプロピルメチルジメトキシシラン、３−メタクリロキシプロピルトリメトキシシラン、３−メタクリロキシプロピルメチルジエトキシシラン、３−メタクリロキシプロピルトリエトキシシラン、３−アクリロキシプロピルトリメトキシシラン、３−イソシアネートプロピルトリエトキシシランなどが挙げられる。 As an example of the silane coupling agent used in the present invention, vinyl-trimethoxysilane, vinyl triethoxysilane, vinyl triacetoxy silane, N-β- (N- vinylbenzylaminoethyl)-.gamma.-aminopropyltrimethoxysilane N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Jeet Shishiran, 3-methacryloxypropyl triethoxysilane, 3-acryloxy propyl trimethoxy silane, 3-isocyanate propyl triethoxysilane and the like.
これらのシランカップリング剤は一種もしくは二種以上混合して用いられる。その使用形態としては、必要量のシランカップリング剤をメタノールやエタノール、アセトン、トルエン、キシレンなどの有機溶剤に溶解し、必要に応じて加水分解に必要な水を加えて用いられる。また、分散性を改善するために塩酸、硝酸などの鉱酸などが加えられる。用いられる溶剤としては、エタノール、メタノール、プロパノールやブタノールなどの低級アルコール類、蟻酸やプロピオン酸などの低級アルキルカルボン酸類、トルエンやキシレンなどの芳香族化合物、酢酸エチルや酢酸ブチルなどのエステル類、メチルセルソルブやエチルセルソルブなどのセロソルブ類を単独または複数組み合わせて用いても良い。さらに、シランカップリング剤を水溶液の状態で使用しても良く、水への溶解性が悪い場合では、酢酸を添加してｐＨを弱酸性に調整してアルコキシシランの加水分解性を促進し、水溶性を上げて用いられる。 These silane coupling agents are used alone or in combination. As a form of use, a necessary amount of a silane coupling agent is dissolved in an organic solvent such as methanol, ethanol, acetone, toluene, xylene, and water necessary for hydrolysis is added as necessary. In addition, mineral acids such as hydrochloric acid and nitric acid are added to improve dispersibility. Solvents used include ethanol, methanol, lower alcohols such as propanol and butanol, lower alkyl carboxylic acids such as formic acid and propionic acid, aromatic compounds such as toluene and xylene, esters such as ethyl acetate and butyl acetate, methyl Cellosolves such as cellosolve and ethylcellosolve may be used alone or in combination. Furthermore, the silane coupling agent may be used in the state of an aqueous solution, and in the case where the solubility in water is poor, acetic acid is added to adjust the pH to weak acidity to promote the hydrolyzability of alkoxysilane, Used with increased water solubility.
本発明に用いられる様々な機能を有する微粒子は、前述したシランカップリング剤の溶液に分散した状態で製造に用いられる。様々な機能を有する微粒子の分散は、ホモミキサーやマグネットスターラーなどを用いた撹拌分散や、ボールミル、サンドミル、高速回転ミル、ジェットミルなどを用いた粉砕・分散、超音波を用いた分散などにより行われる。 The fine particles having various functions used in the present invention are used for production in a state dispersed in the above-mentioned solution of the silane coupling agent. Dispersion of fine particles having various functions is performed by stirring and dispersing using a homomixer or a magnetic stirrer, pulverizing / dispersing using a ball mill, sand mill, high-speed rotating mill, jet mill, etc., or using ultrasonic waves. Is called.
また、様々な機能を有する微粒子は、分散したコロイド状分散液や、粉砕により微粒子化して得られた分散液の状態で微粒子固定体の製造に用いられる。様々な機能を有する微粒子の分散液は、コロイド状分散液や粉砕して得られた分散液にシランカップリング剤を加え、その後、還流下で加熱させながら微粒子表面にシランカップリング剤を脱水縮合反応により結合させてシランカップリング剤からなる薄膜を形成する。還流下で微粒子に反応結合させるシランカップリング剤の量は、微粒子の平均粒子径にもよるが、反応結合させる微粒子の重量に対して０．０１％重量から５．０重量％であれば微粒子の結合強度は実用上問題ない。また、結合に預からない余剰のシランカップリング剤があっても良い。 The fine particles having various functions are used in the production of a fine particle fixed body in the form of a dispersed colloidal dispersion or a dispersion obtained by pulverization. For fine particle dispersions with various functions, a silane coupling agent is added to a colloidal dispersion or a dispersion obtained by pulverization, and then the silane coupling agent is dehydrated and condensed on the surface of the fine particles while heating under reflux. Bonding by reaction forms a thin film made of a silane coupling agent. The amount of the silane coupling agent to be reactively bonded to the fine particles under reflux depends on the average particle diameter of the fine particles, but if the amount is 0.01% to 5.0% by weight with respect to the weight of the fine particles to be reactively bonded, There is no practical problem with the bond strength. Moreover, there may be an excess silane coupling agent that is not deposited in the bond.
特に様々な機能を有する微粒子からなる薄膜が厚くなると、前記薄膜の応力や使用環境によっては凝集破壊により微粒子薄膜が劣化することもあるので、還流処理後必要に応じて不飽和結合を有するシランカップリング剤や、Si（OR1）4（式中、Ｒ1は炭素数1〜４のアルキル基を示す）で示されるアルコキシシラン化合物、一例として、テトラメトキシシラン、テトラエトキシシランなどや、Ｒ2nSi（OR3）4-n（式中、Ｒ2は炭素数1〜６の炭化水素基、Ｒ3は炭素数1〜４のアルキル基、ｎは１〜３の整数を示す）で示されるアルコキシシラン化合物、一例として、メチルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ヘキサメチルジシラザン、ヘキシルトリメトキシシランなど、他にアルコキシオリゴマーなどが添加されて用いられる。 In particular, when the thin film composed of fine particles having various functions becomes thick, the fine particle thin film may be deteriorated due to cohesive failure depending on the stress and use environment of the thin film. Therefore, a silane cup having an unsaturated bond as necessary after the reflux treatment. A ring agent, an alkoxysilane compound represented by Si (OR 1 ) 4 (wherein R 1 represents an alkyl group having 1 to 4 carbon atoms), for example, tetramethoxysilane, tetraethoxysilane, etc., R 2n Si (OR 3 ) 4-n (wherein R 2 is a hydrocarbon group having 1 to 6 carbon atoms, R 3 is an alkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 3). Alkoxysilane compounds such as methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, hexyltrimethoxysilane And other alkoxy oligomer is used are added.
本発明の微粒子固定化体の製造に用いられる基体を構成する材料としては、不飽和結合を有するシランカップリング剤による化学結合が可能なものであれば良く、このような材料としては、例えば、各種樹脂や、合成繊維、天然繊維などが挙げられる。また、本発明の微粒子固定化体の製造に用いられる基体は、少なくともその表面が樹脂からなるものであれば良い。 The material constituting the substrate used in the production of the fine particle immobilized body of the present invention may be any material that can be chemically bonded by a silane coupling agent having an unsaturated bond. Examples of such a material include: Examples include various resins, synthetic fibers, and natural fibers. Further, the substrate used in the production of the fine particle fixed body of the present invention may be any one as long as its surface is made of a resin.
ここで、基体の表面乃至全体を構成する樹脂としては、合成樹脂や天然樹脂が用いられ、その一例としては、ポリエチレン樹脂、ポリプロピレン樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ＥＶＡ樹脂、ポリメチルペンテン樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリアクリル酸メチル樹脂、ポリ酢酸ビニル樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリカーボネート樹脂、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、ポリアセタール樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリフッ化ビニリデン樹脂、ＰＴＦＥなどの熱可塑性樹脂や、ポリ乳酸樹脂、ポリヒドロキシブチレート樹脂、修飾でんぷん樹脂、ポリカプロラクト樹脂、ポリブチレンサクシネート樹脂、ポリブチレンアジペートテレフタレート樹脂、ポリブチレンサクシネートテレフタレート樹脂、ポリエチレンサクシネート樹脂などの生分解性樹脂、フェノール樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、ジアリルフタレート樹脂、エポキシ樹脂、エポキシアクリレート樹脂、ケイ素樹脂、アクリルウレタン樹脂、ウレタン樹脂などの熱硬化性樹脂や、シリコーン樹脂、ポリスチレンエラストマー、ポリエチレンエラストマー、ポリプロピレンエラストマー、ポリウレタンエラストマーなどのエラストマー、漆などの天然樹脂、などが挙げられる。 Here, as the resin constituting the surface or the whole of the substrate, synthetic resin or natural resin is used, and examples thereof include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, EVA resin, polymethylpentene. Resin, polyvinyl chloride resin, polyvinylidene chloride resin, polymethyl acrylate resin, polyvinyl acetate resin, polyamide resin, polyimide resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacetal resin, polyarylate resin, polysulfone resin , Thermoplastic resins such as polyvinylidene fluoride resin and PTFE, polylactic acid resin, polyhydroxybutyrate resin, modified starch resin, polycaprolacto resin, polybutylene succinate resin, polybutylene adip Biodegradable resins such as terephthalate resin, polybutylene succinate terephthalate resin, polyethylene succinate resin, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin, silicon resin, Thermosetting resins such as acrylic urethane resins and urethane resins, elastomers such as silicone resins, polystyrene elastomers, polyethylene elastomers, polypropylene elastomers and polyurethane elastomers, natural resins such as lacquer, and the like can be mentioned.
本発明方法では、これらの樹脂の形態は、板状、フィルム状、繊維状、布状、メッシュ状、ハニカム状など、使用目的に合った種々の形状及びサイズ等のものが適用でき、特に制限されるものではない。また、これらの樹脂は、基体の主要部がアルミニウムやマグネシウム、鉄などの金属材料や、ガラス、セラミックスなどの無機材料である場合には、これら各材料の表面に、フィルム状に積層されたり、吹き付け塗装や浸漬塗装、静電塗装などの塗装法や、スクリーン印刷やオフセット印刷などの印刷法により薄膜として形成されたものであっても良い。さらに、これらの樹脂は、顔料や染料などにより着色されてあっても良く、シリカ、アルミナ、珪藻土、マイカなどの無機材料が充填されてあっても良い。 In the method of the present invention, these resins can be applied in various shapes and sizes suitable for the purpose of use, such as plate, film, fiber, cloth, mesh, and honeycomb. Is not to be done. In addition, these resins are laminated in the form of a film on the surface of each material when the main part of the base is a metal material such as aluminum, magnesium, iron, or an inorganic material such as glass or ceramics. It may be formed as a thin film by a coating method such as spray coating, immersion coating or electrostatic coating, or a printing method such as screen printing or offset printing. Furthermore, these resins may be colored with pigments, dyes, or the like, or may be filled with inorganic materials such as silica, alumina, diatomaceous earth, and mica.
また、基体は、合成樹脂からなる繊維（合成繊維、化学繊維）であっても良く、基体を構成する合成繊維の例としては、ポリエステル繊維、ポリアミド繊維、ポリビニルアルコール繊維、アクリル繊維、塩化ビニル繊維、塩化ビニリデン繊維、ポリオレフィン繊維、ポリカーボネイト繊維、フッソ繊維、ポリ尿素繊維、エラストマー繊維、また、これら繊維を構成する材料と前記樹脂材料との複合繊維などが挙げられる。なお、本願発明方法においては、上述のように基体表面が樹脂であれば良いので、基体材料に合成樹脂以外の繊維を用いる場合には、樹脂を上述した各種塗装法で繊維表面に塗装することで、樹脂を薄膜として形成しておけば良い。したがって、天然繊維の例として、綿、麻、絹、天然繊維から得られた和紙なども、基体の材料として用いることが可能である。 The substrate may be a fiber made of synthetic resin (synthetic fiber, chemical fiber). Examples of the synthetic fiber constituting the substrate include polyester fiber, polyamide fiber, polyvinyl alcohol fiber, acrylic fiber, and vinyl chloride fiber. , Vinylidene chloride fiber, polyolefin fiber, polycarbonate fiber, fluorine fiber, polyurea fiber, elastomer fiber, and composite fiber of the material constituting these fibers and the resin material. In the method of the present invention, since the substrate surface may be a resin as described above, when a fiber other than a synthetic resin is used as the substrate material, the resin is applied to the fiber surface by the various coating methods described above. Thus, the resin may be formed as a thin film. Therefore, as examples of natural fibers, cotton, hemp, silk, Japanese paper obtained from natural fibers, and the like can be used as the base material.
本発明方法におけるグラフト重合としては、例えばパーオキサイド触媒を用いるグラフト重合、熱や光エネルギーを用いるグラフト重合、放射線によるグラフト重合、などが挙げられ、このうち重合プロセスの簡便性、生産スピード等の観点より、放射線グラフト重合が特に適している。ここで、グラフト重合において用いられる放射線としては、α線、β線、γ線、電子線、紫外線などを挙げることができるが、本発明において用いるのには、γ線、電子線、紫外線が特に適している。 The graft polymerization in the method of the present invention, for example, the graph preparative polymerization using a peroxide catalyst, graft polymerization using heat or light energy, graft polymerization by radiation, and the like, ease of these polymerization processes, such as production speed From the viewpoint, radiation graft polymerization is particularly suitable. Here, examples of the radiation used in the graft polymerization include α rays, β rays, γ rays, electron rays, ultraviolet rays, and the like. In the present invention, γ rays, electron rays, and ultraviolet rays are particularly used. Is suitable.
本発明でのグラフト重合を用いた微粒子固定化体の製造方法は、以下に記した方法により好適に製造される。第一の発明における第一の好適な方法としては、シランカップリング剤が結合された前述した様々な機能を有する微粒子が分散した溶液を、結合しようとする基体表面（樹脂面）に塗布し、必要に応じて溶剤を加熱乾燥などの方法により除去した後、γ線、電子線、紫外線などの放射線を、シランカップリング剤が結合した微粒子が塗布された基体表面に照射することで、シランカップリング剤を基体表面にグラフト重合させると同時に微粒子を結合させる、所謂同時照射グラフト重合により製造される。 The manufacturing method of the fine particle fixed body using graft polymerization in the present invention is preferably manufactured by the method described below. As a first preferred method in the first invention, a solution in which fine particles having various functions described above, to which a silane coupling agent is bound, is dispersed is applied to a substrate surface (resin surface) to be bound, If necessary, the solvent is removed by a method such as heat drying, and then the silane cup is irradiated with γ-rays, electron beams, ultraviolet rays, or other radiation on the surface of the substrate coated with fine particles bound with the silane coupling agent. It is produced by so-called simultaneous irradiation graft polymerization in which a ring agent is graft-polymerized on the surface of a substrate and fine particles are bonded at the same time.
また第一の発明における第二の好適な方法としては、予め基体表面にγ線、電子線、紫外線などの放射線を照射した後に、シランカップリング剤が結合された微粒子が分散した溶液を塗布して、シランカップリング剤と基体とを反応させると同時に微粒子を結合させる所謂前照射グラフト重合により製造される。 In the second preferred method of the first invention, the surface of the substrate is previously irradiated with radiation such as γ rays, electron beams, and ultraviolet rays, and then a solution in which fine particles combined with a silane coupling agent are dispersed is applied. Thus, it is produced by so-called pre-irradiation graft polymerization in which a silane coupling agent and a substrate are reacted and at the same time fine particles are bonded.
第二の発明における好適な方法としては、シランカップリング剤が結合された微粒子が分散した溶液を基体表面（樹脂面）に塗布し、必要に応じて溶剤を加熱乾燥などの方法により除去して微粒子からなるコーティング薄膜を形成した後に、前記の微粒子と同種または異種の微粒子にシランカップリング剤の薄膜を形成させるために、この微粒子が分散した溶液を、前記のコーティング薄膜表面上に塗布して新たな薄膜を形成し、放射線を照射することにより、前記微粒子で形成されたコーティング薄膜と基材および前記微粒子と同種または異種の微粒子に形成したシランカップリング剤とを一度にグラフト重合させることにより結合させる方法により製造される。 As a suitable method in the second invention, a solution in which fine particles to which a silane coupling agent is bonded is dispersed is applied to the substrate surface (resin surface), and the solvent is removed by a method such as heat drying if necessary. After forming a coating thin film composed of fine particles, in order to form a silane coupling agent thin film on the same kind or different kind of fine particles as described above, a solution in which the fine particles are dispersed is applied onto the surface of the coating thin film. By forming a new thin film and irradiating with radiation, the coating thin film formed of the fine particles, the base material, and the silane coupling agent formed on the same kind or different kind of fine particles of the fine particles are grafted at a time. Manufactured by a method of bonding.
この場合でも、第一の微粒子層を基体表面に塗布した後に基体表面に放射線を照射することで、グラフト重合により基体表面にシランカップリング剤を介して第一の微粒子層を結合させてから、前記微粒子と同種または異種の微粒子層を形成することで、より強固な積層された微粒子固定化体を製造することが可能である。また、第一の微粒子層を形成する方法として、第一の発明における第二法で用いた前照射を採用することも可能である。 Even in this case, after the first fine particle layer is applied to the substrate surface, the first fine particle layer is bonded to the surface of the substrate via the silane coupling agent by irradiating the surface of the substrate with radiation, By forming a fine particle layer of the same kind or different kind from the fine particles, it is possible to produce a stronger laminated fine particle fixed body. Further, as the method for forming the first fine particle layer, the pre-irradiation used in the second method in the first invention can be employed.
第三の発明における好適な方法としては、予め基体表面にシランカップリング剤を、γ線、電子線、紫外線などの放射線の同時照射法や前照射法によりグラフト重合してシランカップリング剤からなるコーティング被膜を形成した後、シランカップリング剤が結合された微粒子が分散した溶液を、前記基体表面のコーティング被膜上に塗布し、その後、放射線を照射することにより、グラフト重合により微粒子を基体表面に結合させる方法により製造される。この場合でも、シランカップリング剤を基体表面に塗布し、必要に応じて溶剤を加熱乾燥などの方法により除去したコーティング被膜上に、シランカップリング剤が結合された微粒子が分散した溶液を塗布し、放射線を照射することにより、グラフト重合により微粒子を基体表面に結合させる方法で製造することも可能である。 As a preferred method in the third invention, a silane coupling agent is previously formed by graft polymerization of a silane coupling agent on the surface of a substrate in advance by a simultaneous irradiation method or pre-irradiation method of radiation such as γ rays, electron beams, and ultraviolet rays. After forming the coating film, a solution in which fine particles to which the silane coupling agent is bonded is dispersed is applied onto the coating film on the surface of the substrate, and then irradiated with radiation, whereby the fine particles are applied to the surface of the substrate by graft polymerization. Manufactured by a method of bonding. Even in this case, the silane coupling agent is applied to the surface of the substrate, and if necessary, a solution in which the fine particles with the silane coupling agent are dispersed is applied onto the coating film from which the solvent has been removed by a method such as heat drying. It is also possible to manufacture by a method in which fine particles are bonded to the substrate surface by graft polymerization by irradiating with radiation.
第四の発明における好適な方法としては、予め基体表面に不飽和結合を有するシランカップリング剤を、γ線、電子線、紫外線などの放射線の同時照射法や前照射法によりグラフト重合した後、微粒子が分散した溶液を、前記シランカップリング剤がグラフト重合された基体表面に塗布し、その後、加熱などのエネルギーを加えて、グラフト重合により基体表面に導入したシラノール基と微粒子表面に存在する水酸基との脱水縮合反応により、光触媒微粒子を基体表面に結合させる方法により製造される。 As a preferred method in the fourth invention, a silane coupling agent having an unsaturated bond on the substrate surface in advance, after graft polymerization by a simultaneous irradiation method or a pre-irradiation method of radiation such as γ rays, electron beams, and ultraviolet rays, The solution in which the fine particles are dispersed is applied to the surface of the substrate on which the silane coupling agent has been graft-polymerized, and then, by applying energy such as heating, the silanol groups introduced on the surface of the substrate by graft polymerization and the hydroxyl groups present on the surface of the fine particles Is produced by a method in which the photocatalyst fine particles are bonded to the substrate surface by a dehydration condensation reaction.
本実施形態では、上述したように、固定化する微粒子が分散した溶液を、固定化する基体表面に塗布して微粒子固定化体を製造するが、具体的な微粒子の分散液の塗布方法としては、一般に行われているスピンコート法、ディップコート法、スプレーコート法、キャストコート法、バーコート法、マイクログラビアコート法、グラビアコート法、または部分的に塗布する方法として、スクリーン印刷法、パッド印刷法、オフセット印刷法、ドライオフセット印刷法、フレキソ印刷法、インクジェット印刷法などの様々な方法が用いられ、目的に合った塗布ができれば特に限定されない。 In this embodiment, as described above, a solution in which fine particles to be immobilized are dispersed is applied to the surface of a substrate to be immobilized to produce a fine particle fixed body. As a specific method for applying a fine particle dispersion, As a general spin coating method, dip coating method, spray coating method, cast coating method, bar coating method, micro gravure coating method, gravure coating method, or partial coating method, screen printing method, pad printing Various methods such as an offset printing method, an offset printing method, a dry offset printing method, a flexographic printing method, and an ink jet printing method are used, and the coating is not particularly limited as long as it can be applied in accordance with the purpose.
また、シランカップリング剤のグラフト重合を効率良く、かつ、均一に行わせるためには、予め、樹脂基体表面がコロナ放電処理やプラズマ放電処理、火炎処理、クロム酸や過塩素酸などの酸化性酸水溶液や水酸化ナトリウムなどを含むアルカリ性水溶液による化学的な処理などにより親水化処理されてあっても良い。 In addition, in order to carry out graft polymerization of the silane coupling agent efficiently and uniformly, the surface of the resin substrate is previously subjected to corona discharge treatment, plasma discharge treatment, flame treatment, oxidizing properties such as chromic acid and perchloric acid. Hydrophilic treatment may be performed by chemical treatment with an alkaline aqueous solution containing an acid aqueous solution or sodium hydroxide.
本発明によれば、前述したように、フィルム状、繊維状、布状、メッシュ状、ハニカム状など、使用目的に合った様々な形態（形状、大きさ等）に様々な機能を有する微粒子が固定化できるので、外壁材、サッシ、ドア、ブラインドなどの建装材、壁紙、カーペット、樹脂タイルなどの内装材、衣類、インナーウェア、靴下、手袋、靴等の履物、該履物用の中敷、パジャマ、マット、シーツ、枕、枕カバー、毛布、タオルケット、蒲団および蒲団カバーなどの寝装材、帽子、ハンカチ、タオル、絨毯、カーテン、フィルターまたは防虫網などに様々な機能を付加できることが可能となる。従って、本発明は、様々な分野に優れた各種製品を提供することができる有用な方法である。 According to the present invention, as described above, fine particles having various functions in various forms (shape, size, etc.) suitable for the purpose of use, such as film, fiber, cloth, mesh, and honeycomb. Because it can be fixed, building materials such as exterior wall materials, sashes, doors, blinds, interior materials such as wallpaper, carpets, resin tiles, clothing, innerwear, socks, gloves, shoes, etc., insoles for the footwear Various functions can be added to bedding materials such as pajamas, mats, sheets, pillows, pillow covers, blankets, towels, quilts and quilt covers, hats, handkerchiefs, towels, carpets, curtains, filters or insect screens It becomes. Therefore, the present invention is a useful method capable of providing various products excellent in various fields.
また、本発明によれば、様々な機能を有する微粒子を化学結合により基体上に強固に固定できることから、紡糸後に製品形状とした後で、または、製品化の過程で行うことが可能であり、このため、様々な機能を有する微粒子の存在が紡糸性に影響しない、というメリットがある。 In addition, according to the present invention, fine particles having various functions can be firmly fixed on a substrate by chemical bonding, and thus can be performed after forming into a product shape after spinning or in the process of commercialization. For this reason, there exists a merit that presence of the microparticles | fine-particles which have various functions does not affect spinnability.
次に、実施例を挙げて本発明をより具体的に説明する。ただし、本発明はこれらの実施例のみに限定されるものではない。 Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to only these examples.
本発明方法による下記実施例１〜実施例３の微粒子固定化体の製造にあたっては、岩崎電気株式会社製、エレクトロカーテン型電子線照射装置、ＣＢ２５０／１５／１８０Ｌ、を用い、電子線グラフト重合により実施した。これに対して、各比較例の光触媒体の製造にあたっては、電子線は用いず、塗布後加熱、乾燥の方法とした。 In the production of the fixed microparticles of the following Examples 1 to 3 according to the method of the present invention, an electron curtain type electron beam irradiation device, CB250 / 15 / 180L, manufactured by Iwasaki Electric Co., Ltd. Carried out. On the other hand, in the production of the photocatalyst of each comparative example, an electron beam was not used, and a post-application heating and drying method was used.
実施例１：
平均粒子径７０〜１００ｎｍのシリカ微粒子が５重量％分散したイソプロピルアルコール（日産化学工業株式会社製ＩＰＡ−ＳＺ−ＺＬ）に不飽和結合を持つ３−メタクリロキシプロピルトリエトキシシラン（信越化学工業株式会社製、ＫＢＭ−５０３）をシリカ微粒子に対して１．０重量％加えた後、冷却管を備えたフラスコに移し、その後フラスコをオイルバスで加熱し、４時間還流下で処理することによりシリカ微粒子表面にシランカップリング剤を脱水縮合反応により結合させた。
Example 1:
3-Methacryloxypropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) having an unsaturated bond in isopropyl alcohol (IPA-SZ-ZL manufactured by Nissan Chemical Industries, Ltd.) in which 5% by weight of silica fine particles having an average particle size of 70 to 100 nm are dispersed. Manufactured by KBM-503), 1.0% by weight with respect to the silica fine particles, and then transferred to a flask equipped with a cooling tube. Thereafter, the flask is heated in an oil bath and treated under reflux for 4 hours. A silane coupling agent was bonded to the surface by a dehydration condensation reaction.
また、１２５μmのポリエステルフィルム（ルミラー（東レ(株)登録商標））の表面に、前記シランカップリング剤が結合したシリカ微粒子分散イソプロピルアルコール溶液をバーコーターで塗布し、１２０℃、３分間乾燥した。次に、イソプロピルアルコール溶液を塗布したポリエステルフィルムに電子線を２００ｋＶの加速電圧で５Ｍｒａｄ照射することで、シリカ微粒子をシランカップリング剤のグラフト重合によりポリエステルフィルム表面に結合させることでリシカ微粒子固定化体を得た。
Furthermore, the surface of the polyester film of 125 [mu] m (Le mirrors (Toray TM)), silica fine particles dispersed isopropyl alcohol solution in which the silane coupling agent bound with a bar coater, and dried 120 ° C., 3 minutes . Next, the silica film is bonded to the polyester film surface by graft polymerization of a silane coupling agent by irradiating the polyester film coated with the isopropyl alcohol solution with an electron beam at an acceleration voltage of 200 kV for 5 Mrad, thereby fixing the silica particles. Got.
得られた微粒子固定化体の表面を走査型電子顕微鏡で観察したところ、球状のシリカ微粒子が単層に配列して固定化されていることが確認された。配列した微粒子は、微粒子固定化体をイソプロピルアルコールに浸漬して超音波を１時間照射しても脱離することがなく、強固にポリエステルフィルム表面に固定化されていた。 When the surface of the obtained fine particle fixed body was observed with a scanning electron microscope, it was confirmed that spherical silica fine particles were arranged and fixed in a single layer. The arranged fine particles were firmly fixed on the surface of the polyester film without being detached even when the fine particle fixed body was immersed in isopropyl alcohol and irradiated with ultrasonic waves for 1 hour.
また、得られた微粒子固定化体の反射率は分光光度計を用いて測定した。微粒子固定化体に５５０ｎｍの波長の光を微粒子固定化体に１５°の入射角で入射させて測定したところ、反射率は２．３％であり、反射防止効果に優れていることが確認された。 Further, the reflectance of the obtained fine particle immobilized body was measured using a spectrophotometer. When light having a wavelength of 550 nm was incident on the fine particle immobilization body and incident on the fine particle immobilization body at an incident angle of 15 °, the reflectance was 2.3%, and it was confirmed that the antireflection effect was excellent. It was.
実施例２：
実施例１で基体に用いたポリエステルフィルムに、電子線を２００ｋＶの加速電圧で１０Ｍｒａｄ照射した後、実施例１で調整したシランカップリング剤が結合したシリカ微粒子分散イソプロピルアルコール溶液に電子線を照射したポリエステルフィルムを浸漬して電子線照射によりフィルム表面および内部に発生したラジカルによりシランカップリング剤をポリエステルフィルム表面にグラフト重合させることでシリカ微粒子を固定化し、その後、余分の分散液を洗浄により除去し乾燥することで微粒子固定化体を得た。
Example 2:
The polyester film used for the substrate in Example 1 was irradiated with an electron beam at an acceleration voltage of 200 kV for 10 Mrad, and then the silica particle-dispersed isopropyl alcohol solution combined with the silane coupling agent prepared in Example 1 was irradiated with the electron beam. The silica fine particles are fixed by graft polymerization of the silane coupling agent onto the polyester film surface by radicals generated on the film surface and inside by immersing the polyester film and irradiating the electron beam, and then the excess dispersion is removed by washing. The fine particle fixed body was obtained by drying.
得られた微粒子固定化体の表面を走査型電子顕微鏡で観察したところ、球状のシリカ微粒子が単層に配列して固定化されていることが確認された。配列した微粒子は、微粒子固定化体をイソプロピルアルコールに浸漬して超音波を１時間照射しても脱離することがなく、強固にポリエステルフィルム表面に固定化されていた。また、実施例１と同様の方法で反射率を測定したところ、反射率は２．１％であり、反射防止効果に優れていることも確認された。 When the surface of the obtained fine particle fixed body was observed with a scanning electron microscope, it was confirmed that spherical silica fine particles were arranged and fixed in a single layer. The arranged fine particles were firmly fixed on the surface of the polyester film without being detached even when the fine particle fixed body was immersed in isopropyl alcohol and irradiated with ultrasonic waves for 1 hour. Further, when the reflectance was measured by the same method as in Example 1, it was confirmed that the reflectance was 2.1% and the antireflection effect was excellent.
実施例３：
実施例１で用いたポリエステルフィルムに電子線を２００ｋＶの加速電圧で１５Ｍｒａｄ照射した後に、実施例１で用いたシランカップリング剤をイソプロピルアルコールに１．０重量％溶解した溶液をスプレーにて塗布し、３分間放置することでシランカップリング剤をポリエステルフィルム表面にグラフト重合させることにより、シラノール基を導入させた。次に、余分のシランカップリング剤をイソプロピルアルコールにより除去した後に、シランカップリング剤のグラフト重合によりシラノール基が導入されたポリエステルフィルム表面に、実施例１で用いたシリカ微粒子分散イソプロピルアルコールをバーコーターで塗布した後、１２０℃、１０分間加熱処理した。その後、結合していない過剰のシリカ微粒子を水洗により洗浄除去することで、シリカ微粒子がシランカップリング剤でポリエステルフィルム表面に固定化されてなる微粒子固定化体を得た。
Example 3:
After irradiating the polyester film used in Example 1 with an electron beam at an acceleration voltage of 200 kV for 15 Mrad, a solution obtained by dissolving 1.0% by weight of the silane coupling agent used in Example 1 in isopropyl alcohol was applied by spraying. Silanol groups were introduced by allowing the silane coupling agent to graft onto the polyester film surface by leaving it for 3 minutes. Next, after removing excess silane coupling agent with isopropyl alcohol, the silica fine particle-dispersed isopropyl alcohol used in Example 1 was applied to the surface of the polyester film into which silanol groups were introduced by graft polymerization of the silane coupling agent. Then, the coating was heated at 120 ° C. for 10 minutes. Thereafter, excess silica fine particles that were not bonded were washed and removed by washing with water to obtain a fine particle fixed body in which the silica fine particles were fixed on the surface of the polyester film with a silane coupling agent.
得られた微粒子固定化体の表面を走査型電子顕微鏡で観察したところ、球状のシリカ微粒子が単層に配列して固定化されていることが確認された。配列した微粒子は、微粒子固定化体をイソプロピルアルコールに浸漬して超音波を１時間照射しても脱離することがなく、強固にポリエステルフィルム表面に固定化されていた。また、実施例１と同様の方法で反射率を測定したところ、反射率は２．０％であり、反射防止効果に優れていることも確認された。 When the surface of the obtained fine particle fixed body was observed with a scanning electron microscope, it was confirmed that spherical silica fine particles were arranged and fixed in a single layer. The arranged fine particles were firmly fixed on the surface of the polyester film without being detached even when the fine particle fixed body was immersed in isopropyl alcohol and irradiated with ultrasonic waves for 1 hour. Further, when the reflectance was measured by the same method as in Example 1, it was confirmed that the reflectance was 2.0% and the antireflection effect was excellent.
比較例１：
実施例１で用いたシリカ微粒子分散イソプロピルアルコール溶液を、バーコーターを用いて実施例１で用いたポリエステルフィルム表面に塗布した後、１２０℃、３分間乾燥することでシリカ微粒子を固定化した微粒子固定化体を得た。得られた微粒子固定体表面を走査型電子顕微鏡で観察したところ、シリカ微粒子は無秩序に島状、多層粒子層を形成して固定化されていた。次に、微粒子固定化体をイソプロピルアルコールに浸漬して超音波を１時間照射したところ、ポリエステルフィルム表面に固定化されていたシリカ微粒子は全て脱離していた。
Comparative Example 1:
The silica fine particle-dispersed isopropyl alcohol solution used in Example 1 was applied to the surface of the polyester film used in Example 1 using a bar coater and then dried at 120 ° C. for 3 minutes to fix the fine silica particles. The chemical was obtained. When the surface of the obtained fine particle fixed body was observed with a scanning electron microscope, the silica fine particles were fixed in an orderly manner by forming islands and multilayer particle layers. Next, when the fine particle immobilized body was immersed in isopropyl alcohol and irradiated with ultrasonic waves for 1 hour, all silica fine particles immobilized on the polyester film surface were detached.
比較例２：
実施例１で用いたシランカップリング剤が結合したシリカ微粒子が分散したイソプロピルアルコール溶液を実施例１で用いたポリエステルフィルム表面にバーコーターを用いて塗布した後、１２０℃、３分間乾燥することでシリカ微粒子を固定化した微粒子固定化体を得た。得られた微粒子固定体表面を走査型電子顕微鏡で観察したところ、シリカ微粒子が単層で規則的に配列していることが確認された。次に、微粒子固定化体をイソプロピルアルコールに浸漬して超音波を１時間照射したところ、ポリエステルフィルム表面に固定化されていたシリカ微粒子はほとんど脱離していた。
Comparative Example 2:
By applying the isopropyl alcohol solution in which the silica fine particles bound with the silane coupling agent used in Example 1 are dispersed to the surface of the polyester film used in Example 1 using a bar coater, drying is performed at 120 ° C. for 3 minutes. A fine particle fixed body in which silica fine particles were fixed was obtained. When the surface of the obtained fine particle fixed body was observed with a scanning electron microscope, it was confirmed that the silica fine particles were regularly arranged in a single layer. Next, when the fine particle immobilized body was immersed in isopropyl alcohol and irradiated with ultrasonic waves for 1 hour, the silica fine particles immobilized on the surface of the polyester film were almost detached.
本発明の製造方法で得られた微粒子固定化体は、実施例１〜３の結果が示すように、得られた固定化体をアルコールに浸漬して超音波を長時間照射しても固定化された微粒子の脱離は認められず、耐久性に優れていることが実証された。これらの結果に対し、電子線を照射しない各比較例では、得られた微粒子固定化体をアルコールに浸漬して超音波を照射すると、固定化された微粒子のほとんどが脱離することが確認され、耐久性に乏しいことが確認された。 As shown in the results of Examples 1 to 3, the fine particle immobilized body obtained by the production method of the present invention is immobilized even if the obtained immobilized body is immersed in alcohol and irradiated with ultrasonic waves for a long time. No desorption of the fine particles was observed, demonstrating excellent durability. In contrast to these results, it was confirmed that in each of the comparative examples in which the electron beam was not irradiated, when the obtained fine particle immobilized body was immersed in alcohol and irradiated with ultrasonic waves, most of the immobilized fine particles were detached. It was confirmed that the durability was poor.
以上説明したように、本発明の製造方法は、シランカップリング剤のグラフト重合により様々な機能を有する微粒子を樹脂表面に固定化する方法であり、シランカップリング剤のアルコキシ基の加水分解により生成したシラノール基が、様々な機能を有する微粒子の表面に脱水縮合反応で強固に化学的に結合し、さらに、シランカップリング剤のビニル基、エポキシ基、スチリル基、メタクリロ基、アクリロキシ基、イソシアネート基などの不飽和結合を有する官能基が、放射線の照射により生成したラジカルによるグラフト重合で樹脂基体表面に化学的に結合することによってなされている。よって、様々な機能を有する微粒子は樹脂基体表面にシランカップリング剤により化学的な結合で強固に結合させることから、本発明方法によれば、過酷な環境で使用しても様々な機能を有する微粒子の脱離などが起こり難い耐久性に優れた微粒子固定化体を供給することが可能となる。また、本発明では、様々な機能を有する微粒子が繊維や樹脂フィルムの表面にシランカップリング剤によって固定させることから、微粒子が基体上に島状乃至薄膜の形態で形成しても微粒子表面が高分子などで覆われていないので微粒子が有する機能が最大限発揮できるため、繊維やそれらからなる構造体の風合いを損なうことが無いなど、様々な分野に応用できる実用性に優れた微粒子固定化体を提供できる極めて有用な微粒子固定化体の製造方法を提供することが可能となる。 As described above, the production method of the present invention is a method of immobilizing fine particles having various functions on the resin surface by graft polymerization of a silane coupling agent, and is produced by hydrolysis of alkoxy groups of the silane coupling agent. The silanol group is strongly chemically bonded to the surface of fine particles having various functions by a dehydration condensation reaction, and further, vinyl group, epoxy group, styryl group, methacrylo group, acryloxy group, isocyanate group of the silane coupling agent. Such a functional group having an unsaturated bond is chemically bonded to the surface of the resin substrate by graft polymerization with radicals generated by irradiation with radiation. Therefore, since the fine particles having various functions are firmly bonded to the resin substrate surface by a chemical bond by the silane coupling agent, the method of the present invention has various functions even when used in a harsh environment. It is possible to supply a fine particle immobilization body having excellent durability in which fine particles are not easily detached. In the present invention, fine particles having various functions are fixed to the surface of the fiber or resin film by a silane coupling agent. Therefore, even if the fine particles are formed on the substrate in the form of islands or thin films, the fine particle surface is high. Since it is not covered with molecules, the fine particle functions can be exhibited to the maximum, so that the texture of the fiber and the structure composed thereof is not impaired. It is possible to provide a method for producing a very useful fine particle immobilized body that can provide
Claims (4)
微粒子表面に不飽和結合を有するシランカップリング剤の薄膜を形成し、
前記基体表面の樹脂と前記微粒子表面に形成した薄膜とを接触させ、
前記基体表面の樹脂表面と前記微粒子表面の薄膜に存在する不飽和結合とを放射線グラフト重合させる微粒子固定化体の製造方法。 A method for producing a fine particle fixed body having at least a substrate surface made of a resin,
Forming a thin film of a silane coupling agent having an unsaturated bond on the surface of the fine particles,
Contacting the resin on the surface of the substrate with the thin film formed on the surface of the fine particles,
Method for producing an unsaturated bond and a particulate immobilized body to radiation grayed rafts polymerization existing in the thin film of the resin surface of the substrate surface the fine particle surface.
微粒子に不飽和結合を有するシランカップリング剤の薄膜を形成し、
前記薄膜を形成した微粒子からなるコーティング薄膜を前記基体表面に形成し、前記の微粒子と同種または異種の微粒子に不飽和結合を有するシランカップリング剤の薄膜を形成し、
前記基体表面に形成した微粒子からなるコーティング薄膜と薄膜を形成した微粒子とを接触させて、
コーティング薄膜に存在する不飽和結合と微粒子の薄膜に存在する不飽和結合とを、放射線グラフト重合させてなる積層された微粒子固定化体の製造方法。 A method for producing a fine particle fixed body having at least a substrate surface made of a resin,
Forming a silane coupling agent thin film with an unsaturated bond in the fine particles,
Forming a coating thin film composed of fine particles forming the thin film on the surface of the substrate, forming a thin film of a silane coupling agent having an unsaturated bond to the same kind or different kinds of fine particles as the fine particles,
The coating thin film made of fine particles formed on the surface of the substrate is brought into contact with the fine particles forming the thin film,
A method for producing a laminated fine particle immobilization product obtained by subjecting an unsaturated bond present in a coating thin film and an unsaturated bond present in a fine particle thin film to radiation graft polymerization.
不飽和結合を有するシランカップリング剤からなるコーティング薄膜を前記基体表面にグラフト重合で形成し、
微粒子表面に不飽和結合を有するシランカップリング剤の薄膜を形成し、
前記コーティング薄膜と前記薄膜を形成した微粒子とを接触させ、
コーティング薄膜に存在する官能基と、微粒子の薄膜に存在する官能基とを、放射線グラフト重合させてなる微粒子固定化体の製造方法。 A method for producing a fine particle fixed body having at least a substrate surface made of a resin,
Forming a coating thin film comprising a silane coupling agent having an unsaturated bond on the surface of the substrate by graft polymerization;
Forming a thin film of a silane coupling agent having an unsaturated bond on the surface of the fine particles,
Bringing the coating thin film into contact with the fine particles forming the thin film;
A method for producing a fine particle immobilization product obtained by subjecting a functional group present in a coating thin film and a functional group present in a fine particle thin film to radiation graft polymerization.
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