JP4965628B2 - Method for producing antibacterial member - Google Patents
Method for producing antibacterial member Download PDFInfo
- Publication number
- JP4965628B2 JP4965628B2 JP2009244235A JP2009244235A JP4965628B2 JP 4965628 B2 JP4965628 B2 JP 4965628B2 JP 2009244235 A JP2009244235 A JP 2009244235A JP 2009244235 A JP2009244235 A JP 2009244235A JP 4965628 B2 JP4965628 B2 JP 4965628B2
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- fine particles
- silane coupling
- coupling agent
- substrate
- 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
- 230000000844 anti-bacterial effect Effects 0.000 title claims description 158
- 238000004519 manufacturing process Methods 0.000 title claims description 40
- 239000010419 fine particle Substances 0.000 claims description 84
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 57
- 229920005989 resin Polymers 0.000 claims description 51
- 239000011347 resin Substances 0.000 claims description 51
- 239000000758 substrate Substances 0.000 claims description 51
- -1 silane compound Chemical class 0.000 claims description 36
- 239000000835 fiber Substances 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 18
- 229910000077 silane Inorganic materials 0.000 claims description 16
- 230000005855 radiation Effects 0.000 claims description 14
- 230000000845 anti-microbial effect Effects 0.000 claims description 13
- 238000010559 graft polymerization reaction Methods 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000004599 antimicrobial Substances 0.000 claims description 5
- 238000003851 corona treatment Methods 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 208000028659 discharge Diseases 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 description 77
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 22
- 239000003242 anti bacterial agent Substances 0.000 description 20
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- 238000010894 electron beam technology Methods 0.000 description 13
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
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- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000003385 bacteriostatic effect Effects 0.000 description 5
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- 241000191967 Staphylococcus aureus Species 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
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- 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
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 241000238631 Hexapoda Species 0.000 description 2
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- 239000004743 Polypropylene Substances 0.000 description 2
- 206010041925 Staphylococcal infections Diseases 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- FUWUEFKEXZQKKA-UHFFFAOYSA-N beta-thujaplicin Chemical compound CC(C)C=1C=CC=C(O)C(=O)C=1 FUWUEFKEXZQKKA-UHFFFAOYSA-N 0.000 description 2
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- 238000006297 dehydration reaction Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
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- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
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- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 description 2
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- 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
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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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- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
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- HMDRAGZZZBGZJC-UHFFFAOYSA-N n-[3-[3-aminopropoxy(dimethoxy)silyl]propyl]-1-phenylprop-2-en-1-amine Chemical compound NCCCO[Si](OC)(OC)CCCNC(C=C)C1=CC=CC=C1 HMDRAGZZZBGZJC-UHFFFAOYSA-N 0.000 description 1
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- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
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- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
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- 235000019260 propionic acid Nutrition 0.000 description 1
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- 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
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- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052613 tourmaline Inorganic materials 0.000 description 1
- 229940070527 tourmaline Drugs 0.000 description 1
- 239000011032 tourmaline Substances 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- 229960003500 triclosan Drugs 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 229920006312 vinyl chloride fiber Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
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- 239000011787 zinc oxide Substances 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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- 229930007845 β-thujaplicin Natural products 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、抗菌性を有する材料の微粒子が、基体上に固定されてなる抗菌性を有する部材の製造方法に関する。 The present invention relates to a method for producing an antibacterial member in which fine particles of an antibacterial material are fixed on a substrate.
壁紙などの内装材やカーテン、絨毯などのインテリア材、コートや背広、下着などの衣類などは、カビや細菌などの微生物の繁殖により悪臭を放ったり、変色の発生原因になることから、最近ではこれらの製品にカビや細菌などの微生物の繁殖を抑制するため、抗菌性を付与することが行われている。また、病院や診療所においては、保菌者あるいは感染者によって院内へ持ち込まれたMRSA（抗生物質耐性菌）や抗生剤投与によってメチシリン感受性黄色ブドウ球菌からMRSAへと変異した株が、患者から直接あるいは医療従事者または、白衣やパジャマ、シーツなどの使用物品、壁やエアコンなどの設備を含む環境を介して、患者・医療従事者に接触感染を生じる院内感染が社会的にも大きな問題になってきており、院内感染を防止するためには、病院内における使用物品や設備に抗菌性を付与することが求められてきている。 Interior materials such as wallpaper, interior materials such as curtains and carpets, clothing such as coats, suits, and underwear may cause odors and discoloration due to the growth of microorganisms such as mold and bacteria. In order to suppress the growth of microorganisms such as mold and bacteria, antibacterial properties are imparted to these products. In hospitals and clinics, MRSA (antibiotic-resistant bacteria) brought into the hospital by carriers or infected individuals, and strains that have been mutated from methicillin-sensitive Staphylococcus aureus to MRSA by administration of antibiotics are directly or from patients. Nosocomial infections that cause contact infections to patients and health care workers have become a major social problem through the environment including health care workers or items such as lab coats, pajamas and sheets, and equipment such as walls and air conditioners. In order to prevent nosocomial infections, it has been demanded to impart antibacterial properties to articles and equipment used in hospitals.
抗菌性を有する材料としては、有機系、天然有機系、無機系に分類することができる。ここで、有機系の一例としては、トリクロサン、クロロヘキシジン、ジンクピリチオン、塩化ベンザルコニウム、塩化ベンゼトニウム、塩化セチルピリジウム、アルキルトリメチルアンモニウム塩などが知られており、また、天然有機系としては、キトサン、カテキン、ヒノキチオール、カラシ、ワサビ精油などが知られている。これら有機系や天然有機系の抗菌性を有する材料は、抗菌性が要求される基体の表面に吸着させて用いられるが、単なる吸着では基体表面への固着性に問題があり、洗濯や洗浄などにより容易に除去されてしまうことから、抗菌効果の永続的な維持は困難である。 Antibacterial materials can be classified into organic, natural organic and inorganic materials. Here, as an example of an organic system, triclosan, chlorohexidine, zinc pyrithione, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, alkyltrimethylammonium salt, and the like are known, and natural organic systems include chitosan, Catechin, hinokitiol, mustard, wasabi essential oil and the like are known. These organic and natural organic antibacterial materials are used by adsorbing to the surface of the substrate where antibacterial properties are required, but mere adsorption has a problem with the adherence to the substrate surface, and washing, washing, etc. It is difficult to maintain the antibacterial effect permanently.
さらに、無機系の抗菌性を有する材料としては、銀、銅、亜鉛、錫、鉛およびこれらの化合物などが通常知られているが、特にその中でも、銀、銅、亜鉛およびそれらの化合物から選ばれる1種以上の抗菌性を有する材料は、抗菌特性や人体への安全性などの観点から様々な分野で利用されている。これらの金属およびそれらの化合物は、単体としても用いられるが、材料によっては変色したり抗菌性を付与する材料の着色の原因となることから、無機材料の微粒子に担持して使用されている。 Furthermore, silver, copper, zinc, tin, lead and their compounds are generally known as inorganic antibacterial materials, and among these, silver, copper, zinc and their compounds are particularly selected. One or more kinds of materials having antibacterial properties are used in various fields from the viewpoint of antibacterial properties and safety to the human body. These metals and their compounds are used as simple substances, but depending on the material, they may cause discoloration or coloring of the material imparting antibacterial properties, so that they are used supported on fine particles of inorganic materials.
かかる抗菌性を有する銀、銅、亜鉛金属およびそれらの化合物と無機材料から構成された抗菌性を有する材料の微粒子による、樹脂や繊維への抗菌性付与の方法としては、様々な方法が提案されており、例えば、羊毛などの天然繊維の表面に存在する空孔や空隙に、抗菌性を有する微粒子を還元剤の作用により固定する方法（例えば、特許文献１参照。）、染め吸尽加工法やスプレー法による繊維表面への抗菌性を有する微粒子の固定（例えば、特許文献２参照。）、バインダーによる繊維表面への抗菌性を有する微粒子の固定（例えば、特許文献３、特許文献４参照。）、合成樹脂に抗菌性を有する微粒子を充填する方法（例えば、特許文献５、特許文献６参照。）、繊維を芯・鞘構造となし、鞘部に抗菌性を有する微粒子含有ポリマーを配置した複合繊維（例えば、特許文献７参照。）、などが挙げられる。 Various methods have been proposed for imparting antibacterial properties to resins and fibers using fine particles of such antibacterial materials composed of silver, copper, zinc metal and their compounds and inorganic materials having antibacterial properties. For example, a method in which fine particles having antibacterial properties are fixed to pores or voids existing on the surface of natural fibers such as wool by the action of a reducing agent (see, for example, Patent Document 1), a dye exhaust process And fixing fine particles having antibacterial properties to the fiber surface by a spray method (for example, see Patent Document 2), and fixing fine particles having antibacterial properties to the fiber surface by using a binder (for example, see Patent Documents 3 and 4). ), A method of filling fine particles having antibacterial properties in a synthetic resin (see, for example, Patent Document 5 and Patent Document 6), a fiber having a core / sheath structure, and a fine particle-containing polymer having antibacterial properties in the sheath portion. Location composite fibers (e.g., see Patent Document 7.), And the like.
しかしながら、上記抗菌性を有する樹脂や繊維などでは、以下のような様々な問題がある。例えば、特開昭５４−０８２５００号公報や特開平１０−２８０２７０号公報記載の技術では、抗菌性を有する微粒子は繊維表面に吸着、吸尽により固定されていることから、抗菌性に優れているものの、洗濯などにより容易に抗菌性を有する微粒子が脱離することから抗菌効果の永続的な維持は困難であり、また、材料の種類によっては抗菌性を有する微粒子を吸着・固定することも困難である。さらに、特開昭０９−０１３２７９号公報や特開平１０−１１０３８８号公報記載の技術では、バインダーの種類や基体樹脂の種類によっては、抗菌性を有する微粒子が分散したバインダーの剥離や繊維の風合いが損なわれるなどの問題がある。また、特開昭０２−２５５８４４号公報や特開平０３−０８４０６６号公報に記載の技術においては、樹脂や繊維に抗菌性を有する材料を充填することから、必要以上の抗菌性を有する微粒子の充填が必要になったり、充填方法や条件によっては抗菌性を有する微粒子がスキン層で覆われて十分な抗菌性を発揮しないなどの問題がある。さらに、特開平０９−０１３２２５号公報に記載の技術においては、鞘部に充填された抗菌性を有する微粒子は紡糸条件によっては表面に露出しないことから、十分な抗菌性が発揮されない問題があった。 However, the antibacterial resins and fibers have the following various problems. For example, in the techniques described in JP-A-54-082500 and JP-A-10-280270, the antibacterial microparticles are fixed on the fiber surface by adsorption and exhaustion, and thus have excellent antibacterial properties. However, it is difficult to permanently maintain the antibacterial effect because the antibacterial microparticles are easily detached by washing, and it is also difficult to adsorb and fix the antibacterial microparticles depending on the type of material. It is. Furthermore, in the techniques described in JP-A-09-013279 and JP-A-10-110388, depending on the type of the binder and the type of the base resin, the peeling of the binder in which antibacterial fine particles are dispersed and the texture of the fiber may occur. There are problems such as damage. In the technique described in JP-A-02-255844 and JP-A-03-084066, a resin or fiber is filled with an antibacterial material. Depending on the filling method and conditions, fine particles having antibacterial properties are covered with a skin layer and sufficient antibacterial properties are not exhibited. Furthermore, in the technique described in Japanese Patent Application Laid-Open No. 09-013225, the antibacterial fine particles filled in the sheath portion are not exposed on the surface depending on the spinning conditions, and thus there is a problem that sufficient antibacterial properties are not exhibited. .
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、布などからなる基材の風合いを損なわずに、抗菌効果に優れ、かつ、簡易で耐久性に優れた抗菌性を有する部材の製造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 has an excellent antibacterial effect without compromising the texture of the substrate made of fiber, film, cloth, etc., and has a simple and excellent antibacterial property. It aims at providing the manufacturing method of.
本発明者らは、鋭意研究を重ねた結果、シラン化合物の化学結合を用いることにより、抗菌性を有する材料の微粒子を、細菌や微生物と最も効率良く接触させるため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ことを見出し、これにより上述の課題を解決できるとの知見を得るに至り、新規な抗菌性を有する部材の製造方法を創出した。 As a result of intensive research, the present inventors have used a chemical bond of a silane compound to firmly attach microparticles of an antibacterial material to the surface of a substrate in order to make contact with bacteria and microorganisms most efficiently. And it discovered that it couple | bonds as a quantity which does not impair a texture, and came to obtain the knowledge that the above-mentioned subject could be solved by this, and created the manufacturing method of the member which has a novel antibacterial property.
すなわち、本発明は、抗菌性を有する材料の微粒子が、基体の表面上に、シラン化合物の基体表面への化学結合により結合されてなる抗菌性を有する部材の製造方法であって、基体表面に抗菌性を有する微粒子を分散したシランカップリング剤溶液を塗布する工程と、微粒子を分散したシランカップリング剤溶液が塗布された基体表面に放射線を照射する工程とを含み、シラン化合物の基体表面への化学結合が放射線グラフト重合であることを特徴とする抗菌性を有する部材の製造方法を第１の発明として提供するものである。 That is, the present invention provides particulate materials having antimicrobial properties, on the surface of the substrate, a manufacturing method of a member having an antimicrobial comprising a more attached to the chemical bond to the substrate surface of the silane-compounds, base A substrate of a silane compound comprising a step of applying a silane coupling agent solution in which fine particles having antibacterial properties are dispersed on the surface, and a step of irradiating the surface of the substrate coated with the silane coupling agent solution in which fine particles are dispersed. A first aspect of the present invention provides a method for producing an antibacterial member, characterized in that the chemical bond to the surface is radiation graft polymerization .
また、本発明は、上記第１の発明において、前記基体表面に抗菌性を有する微粒子を分散したシランカップリング剤溶液を塗布した後に放射線を照射することを特徴とする抗菌性を有する部材の製造方法を第２の発明として提供するものである。 Further, the present invention is the first invention, the member having an antimicrobial you and irradiating radiation after coating dispersed silane coupling agent solution the fine particles having antimicrobial properties to the substrate surface A manufacturing method is provided as the second invention .
さらに、本発明は、上記第１の発明において、前記基体表面に放射線を照射した後に、抗菌性を有する微粒子を分散したシランカップリング剤溶液を塗布することを特徴とする抗菌性を有する部材の製造方法を第３の発明として提供するものである。 Furthermore, the present invention on the first aspect, after the radiation to the substrate surface, the member having an antimicrobial you characterized by applying the dispersed silane coupling agent solution microparticles having antimicrobial This manufacturing method is provided as a third invention .
さらにまた、本発明は、上記第３の発明において、前記基体表面にシランカップリング剤を塗布し、その表面に放射線を照射してシランカップリング剤をグラフト重合させた後に、抗菌性を有する微粒子を分散したシランカップリング剤溶液を塗布することを特徴とする抗菌性を有する部材の製造方法を第４の発明として提供するものである。 Furthermore, the present invention provides the fine particles having antibacterial properties after applying a silane coupling agent to the surface of the substrate and irradiating the surface with radiation to graft polymerize the silane coupling agent. the it is to provide a method of manufacturing a member having an antimicrobial you characterized by applying the dispersed silane coupling agent solution as a fourth invention.
さらにまた、本発明は、上記第１乃至第４のいずれかの発明において、前記基体表面を予め親水化処理を行うことを特徴とする抗菌性を有する部材の製造方法を第５の発明として提供するものである。 Furthermore, the present invention is the first to fourth any one of the method for manufacturing the member having antimicrobial you and performing pre-hydrophilization treatment of the substrate surface as a fifth aspect of the invention It is to provide.
さらにまた、本発明は、上記第５の発明において、前記親水化処理が、コロナ放電処理、プラズマ放電処理、火炎処理、酸化性酸水溶液による化学的な処理の何れかを含むことを特徴とする抗菌性を有する部材の製造方法を第６の発明として提供するものである。 Furthermore, the present invention is characterized in that, in the fifth invention, the hydrophilization treatment includes any one of corona discharge treatment, plasma discharge treatment, flame treatment, and chemical treatment with an oxidizing acid aqueous solution. The manufacturing method of the member which has antibacterial property is provided as 6th invention .
さらにまた、本発明は、上記第１乃至第６のいずれかの発明において、前記抗菌性を有する微粒子の平均粒子径が０．００５μm〜３．０μmであることを特徴とする抗菌性を有する部材の製造方法を第７の発明として提供するものである。 Furthermore, the present invention provides the antibacterial member according to any one of the first to sixth inventions, wherein the antibacterial fine particles have an average particle diameter of 0.005 μm to 3.0 μm. This manufacturing method is provided as a seventh invention .
また、本発明は、上記第１乃至第７のいずれかの発明において、前記基体の少なくとも表面が樹脂であることを特徴とする抗菌性を有する部材の製造方法を第８の発明として提供するものである。According to the present invention, in any one of the first to seventh inventions, an eighth aspect of the present invention provides a method for producing an antibacterial member, wherein at least the surface of the substrate is a resin. It is.
さらに、本発明は、上記第１乃至第８のいずれかの発明において、前記基体が、樹脂であることを特徴とする抗菌性を有する部材の製造方法を第９の発明として提供するものである。Furthermore, the present invention provides, as a ninth invention, a method for producing an antibacterial member, characterized in that, in any of the first to eighth inventions, the substrate is a resin. .
さらにまた、本発明は、上記第１乃至第９のいずれかの発明において、前記基体が、繊維構造体であることを特徴とする抗菌性を有する部材の製造方法を第１０の発明として提供するものである。 Furthermore, the present invention provides, as a tenth invention, a method for producing an antibacterial member according to any one of the first to ninth inventions, wherein the substrate is a fiber structure. Is.
本発明の製造方法によれば、基体の表面に対して、抗菌性を有する微粒子が、シラン化合物を介した化学結合によって、強固に結合された状態となっている。このため、基体に対する微粒子は、充分な耐久性を保持している。 According to the production method of the present invention, the fine particles having antibacterial properties are firmly bonded to the surface of the substrate by chemical bonding via the silane compound. For this reason, the microparticles | fine-particles with respect to a base | substrate hold | maintain sufficient durability.
したがって、本発明の製造方法によれば、抗菌性を有す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抗菌性を有する部材を提供することが可能となる。また、微粒子が基材の表面に配置され、微量にて効率良く細菌や微生物と接触するので、それらの増殖を抑制でき、繊維やフィルム、布などからなる基材の風合いを損なわずに、抗菌性を有する部材を提供することが可能となる。 Therefore, according to the production method of the present invention , it is possible to provide an antibacterial member having excellent durability in which antibacterial fine particles are firmly bonded to the surfaces of various substrates. In addition, fine particles are arranged on the surface of the base material and efficiently come into contact with bacteria and microorganisms in a small amount, so that their growth can be suppressed and antibacterial properties can be maintained without impairing the texture of the base material made of fiber, film, cloth, etc. It becomes possible to provide the member which has property.
なお、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）とすることができるので、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の用途に好適であり、これら各種製品での細菌や微生物の付着・増殖に伴う悪臭や変色、さらには院内感染を防止できるものとして提供することができる。 In addition, as a form of a base | substrate, since it can be set as various forms (a shape, a magnitude | size, etc.) suitable for a use purpose, such as a film form, a fiber form, a cloth form, a mesh form, and a honeycomb form, it is an outer wall material Building materials such as sashes, doors, blinds, interior materials such as wallpaper, carpets, resin tiles, footwear such as clothing, innerwear, socks, gloves, shoes, insoles for the footwear, pajamas, mats, sheets, Suitable for pillows, pillow covers, blankets, towels, bedding materials such as quilts and quilt covers, hats, handkerchiefs, towels, carpets, curtains, filters or insect screens. It can be provided as one that can prevent malodor and discoloration associated with adhesion and proliferation, as well as nosocomial infections.
以下に本発明の抗菌性を有する部材の製造方法についてさらに詳述する。 The method for producing the antibacterial member of the present invention will be described in detail below.
本発明で用いられる抗菌性を有する材料としては、抗菌効果が認められる材料であれば特に限定されない。具体的な抗菌性を示す材料としては、特開２００２−６０３０９号公報に開示されている茶ポリフェノール類やキトサンなどの天然材料、銀、銅、亜鉛などの金属およびそれらの化合物から選ばれる1種以上の抗菌性を有する材料が挙げられる。 The antibacterial material used in the present invention is not particularly limited as long as the material has an antibacterial effect. Specific materials exhibiting antibacterial properties include natural materials such as tea polyphenols and chitosan disclosed in JP-A-2002-60309, metals such as silver, copper, and zinc, and one compound selected from these compounds The material which has the above antibacterial property is mentioned.
これらの抗菌性を有する材料は、使用する環境や材料によっては変色したり抗菌性を付与する材料の着色の原因となることから、無機材料の微粒子に担持して使用される。無機材料としては、例えばイオン交換性を有する無機材料として、高シリカゼオライト、ソーダライト、モルデナイト、アナルサイト、エリナイトなどのゼオライト類、ハイドロキシアパタイトなどのアパタイト類などが挙げられ、他の一般的な無機材料としては、二酸化チタン、二酸化ケイ素、酸化アルミナ、酸化マグネシウム、酸化カルシウム、炭酸カルシウム、硫酸バリウム、酸化ジルコニウム、チタン酸バリウム、リン酸ジルコニウムなどが挙げられる。そして、本発明では、抗菌性を有する材料を担持させた後の無機微粒子の平均粒子径は、０．００５μmから３．０μmの間であれば良い。平均粒子径が３．０μmよりも大きくなると、これらの微粒子の固定能が低下して基材樹脂表面から脱離し易くなると共に、繊維や布の風合いを損なうので好ましくない。一方、粒子径を０．００５μmよりも小さくすることは技術的困難が伴い、また製造コスト上の観点からも好ましくない。 These antibacterial materials are used by being supported on fine particles of an inorganic material because they may cause discoloration or coloring of the material imparting antibacterial properties depending on the environment or material used. Examples of inorganic materials include ion-exchangeable inorganic materials such as zeolites such as high silica zeolite, sodalite, mordenite, analsite, and elite, apatites such as hydroxyapatite, and other common inorganic materials. Examples of the material include titanium dioxide, silicon dioxide, alumina oxide, magnesium oxide, calcium oxide, calcium carbonate, barium sulfate, zirconium oxide, barium titanate, and zirconium phosphate. In the present invention, the average particle size of the inorganic fine particles after supporting the antibacterial material may be between 0.005 μm and 3.0 μm. When the average particle diameter is larger than 3.0 μm, the fixing ability of these fine particles is lowered, and the fine particles are easily detached from the surface of the base resin, and the texture of the fibers and cloth is impaired. On the other hand, it is technically difficult to make the particle diameter smaller than 0.005 μm, and it is not preferable from the viewpoint of manufacturing cost.
また、一般に市販されている抗菌性を有する材料の微粒子、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」なども、これらを単一または２種以上組み合わせて用いることもできる。 Fine particles of antibacterial materials that are generally available on the market, such as “Novaron” manufactured by Toagosei Co., Ltd., “Zeomic” manufactured by Sinanen Zeomic Co., Ltd., “Apatizer A” manufactured by Sangi Co., Ltd. “Dai Killer” manufactured by Kogyo Co., Ltd., “Ameni Top” manufactured by Matsushita Electric Industrial Co., Ltd., “Atomy Ball” manufactured by Catalytic Chemical Industry Co., Ltd., “Bacter Killer” manufactured by Kanebo Kasei Co., Ltd. Alternatively, two or more kinds can be used in combination.
さらに、抗菌性を有する材料の微粒子とともに、光触媒機能を有する材料の微粒子や遠赤外線を放射する材料の微粒子、或いはマイナスイオンを放出する材料の微粒子などを混合して用いても良い。 Further, together with fine particles of a material having antibacterial properties, fine particles of a material having a photocatalytic function, fine particles of a material that emits far infrared rays, fine particles of a material that emits negative ions, or the like may be mixed and used.
ここで、光触媒機能を発現する微粒子としては、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公知の金属化合物半導体が挙げられ、これらの材料を単一または２種以上組み合わせて用いることができる。 Here, examples of the fine particles exhibiting a photocatalytic function include known metal compound semiconductors such as titanium oxide, zinc oxide, tungsten oxide, iron oxide, strontium titanate, cadmium sulfide, and cadmium selenide, and these materials. Can be used singly or in combination of two or more.
また、遠赤外線を放射する材料としては、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セラミックスや、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などが挙げられ、これらは単一または２種以上組み合わせて用いることができる。 The material that emits far infrared, Al 2 O 3, TiO 2 , ZrO 2, SiO 2, Fe 2 O 3, CoO, CuO, metal oxide or mixtures thereof, such as MgO, for example, cordierite, β-spodumene, ceramics such as aluminum titanate, and commercially available far-infrared ceramics, for example, OKTRADING SERAJIT, Mizusawa Chemical Industry Co., Ltd. Shiruton FI-85, and these are single or a combination of two or more Can be used.
さらに、マイナスイオンを発生させる材料としては、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稀有元素鉱物や、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が挙げられ、さらに、安全性を考慮して天然放射性稀有元素鉱物の使用量を少なくするために、トルマリンなどの自発分極を有する材料や、BaTiO３、PbZrO３、Pb(Zr,Ti)O３、KnbO３、KtaO３、K(Ta,Nb)O３、LiNbO３などの強誘電体を一種以上混合して用いることができる。 In addition, the materials that generate negative ions include davitite, senurite, blannelite, gingko, linca uranium, carnotite, tzamunite, metachamunite, francesvilleite, tall stone, coffinite, samarskiite, thorium. Obtained by refining natural radioactive rare element minerals containing trace amounts of radioactive rare elements such as stone, trogamite, samarsky stone, thorium stone, trogamite, monazite, tantalum stone, badelite, ilmenite, and some of these minerals In order to reduce the amount of natural radioactive rare element minerals used in consideration of safety, materials having spontaneous polarization such as tourmaline, BaTiO 3 , PbZrO 3 , Pb (Zr , Ti) O 3 , KnbO 3 , KtaO 3 , K (Ta, Nb) O 3 , LiNbO 3 You can.
本発明では、抗菌性を有する材料の微粒子をシラン化合物により、樹脂基体上に化学結合と同時に架橋により固定するものである。具体的なシラン化合物としては、X−Si（OR）3の一般式で示されるシランカップリング剤が挙げられる。なお、Xは有機物と反応する官能基でビニル基、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、ポリスルフィド基、アミノ基、メルカプト基、クロル基などであり、Rは加水分解可能なメトキシ基、エトキシ基などである。これらのメトキシ基やエトキシ基からなるアルコキシ基は加水分解してシラノール基を生ずる。このシラノール基やビニル基やエポキシ基、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などを有する官能基は、反応性が高いことが知られている。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、抗菌性を有する材料の微粒子を、化学結合およびシラン化合物の架橋により、基体表面に結合せしめたものである。 In the present invention, fine particles of a material having antibacterial properties are fixed on a resin substrate by crosslinking simultaneously with chemical bonding with a silane compound. Specific examples of the silane compound include a silane coupling agent represented by a general formula of X—Si (OR) 3 . X is a functional group that reacts with organic matter, such as vinyl group, epoxy group, styryl group, methacrylo group, acryloxy group, isocyanate group, polysulfide group, amino group, mercapto group, chloro group, and R is hydrolyzable. A methoxy group, an ethoxy group, and the like. These alkoxy groups composed of methoxy groups and ethoxy groups are hydrolyzed to form silanol groups. It is known that functional groups having an unsaturated bond such as silanol group, vinyl group, epoxy group, styryl group, methacrylo group, acryloxy group, and isocyanate group have high reactivity. In the present invention, by using a silane coupling agent having excellent reactivity, fine particles of an antibacterial material are bonded to the surface of a substrate by chemical bonding and crosslinking of a silane compound.
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、ビニルトリクロロシラン、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、ビス（トリエトキシシリルプロピル）テトラスルフィド、３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−トリエトキシシリル−Ｎ−（１、３−ジメチル−ブチリデン）プロピルアミン、Ｎ−フェニル−３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルメチルジメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリメトキシシラン、Ｎ−２（アミノエチル）３−アミノプロピルトリエトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシランなどが挙げられる。 Examples of silane coupling agents used in the present invention include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl. Trimethoxysilane, 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-methacrylo Cypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3- Aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3-aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-merca Examples thereof include puttopropyltrimethoxysilane.
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などの溶剤に溶解し、必要に応じて加水分解に必要な水を加えて用いられる。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 a solvent such as methanol or ethanol, and water necessary for hydrolysis is added as necessary. 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.
本発明では、前述したシランカップリング剤の溶液に、必要に応じて、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が、添加されて用いられる。 In the present invention, an alkoxysilane compound represented by Si (OR1) 4 (wherein R1 represents an alkyl group having 1 to 4 carbon atoms), as an example, is added to the solution of the silane coupling agent described above, if necessary. , Tetramethoxysilane, tetraethoxysilane, and the like, R 2 nSi (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, n represents an integer of 1 to 3, for example, methyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexamethyldisilazane, hexyltrimethoxysilane, etc. Is added and used.
本発明での抗菌性を有する部材は、前述したシランカップリング剤の溶液に抗菌性を有する材料の微粒子を分散した溶液を用いて製造される。抗菌性を有する材料の微粒子の分散は、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 antibacterial member in the present invention is manufactured using a solution in which fine particles of an antibacterial material are dispersed in the above-described silane coupling agent solution. Fine particles of antibacterial materials can be dispersed by stirring / dispersing using a homomixer or a magnetic stirrer, grinding / dispersing using a ball mill, sand mill, high-speed rotating mill, jet mill, etc. Done.
また、抗菌性を有する材料の微粒子が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にシランカップリング剤を加え、還流下で加熱させながら脱水縮合反応により抗菌性を有する材料の微粒子表面にシランカップリング剤を結合させて得られた分散液を用いて製造される。尚、分散液には過剰のシランカップリング剤が含まれてあっても良い。 In addition, it has antibacterial properties by adding a silane coupling agent to a colloidal dispersion in which fine particles of antibacterial material are dispersed, or a dispersion obtained by pulverization to form fine particles, and heating the mixture under reflux. It is manufactured using a dispersion obtained by bonding a silane coupling agent to the surface of fine particles of the material. The dispersion may contain an excessive silane coupling agent.
本発明の抗菌性を有する部材の製造方法に用いられる基体を構成する材料としては、シラン化合物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。 The material constituting the substrate used in the method for producing an antibacterial member of the present invention may be any material that can be chemically bonded with a silane compound. Examples of such a material include various resins and synthetic materials. Examples thereof include fibers and natural fibers.
本発明の抗菌性を有する部材の製造方法に用いられる基体を樹脂とする場合には、少なくとも基体表面が樹脂からなるものであれば良い。 When the substrate used in the method for producing an antibacterial member of the present invention is a resin, it is sufficient that at least the substrate surface is made of a resin.
ここで、基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, a synthetic resin or a natural resin is used as the resin constituting the substrate. Examples of the resin include a polyethylene resin, a polypropylene resin, a polystyrene resin, an ABS resin, an AS resin, an EVA resin, a polymethylpentene resin, and a polychlorinated resin. Vinyl 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, polyvinylidene fluoride Resin, PTFE and other thermoplastic resins, polylactic acid resin, polyhydroxybutyrate resin, modified starch resin, polycaprolacto resin, polybutylene succinate resin, polybutylene adipate terephthalate Resins, polybutylene succinate terephthalate resin, polyethylene succinate resin and other biodegradable resins, phenol resin, urea resin, melamine resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, epoxy acrylate resin, silicon resin, acrylic resin Thermosetting resins such as 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.
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、使用目的に合った形状及びサイズ等であれば良く、本発明では特に問わない。また、これらの樹脂は、アルミニウムやマグネシウム、鉄などの金属材料表面や、ガラス、セラミックスなどの無機材料表面に、フィルム状で積層されたり、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。 The form of these resins is not particularly limited in the present invention as long as it has a shape and size suitable for the purpose of use, such as plate, film, fiber, cloth, mesh, and honeycomb. In addition, these resins are laminated in the form of a film on the surface of metal materials such as aluminum, magnesium, and iron, or on the surface of inorganic materials such as glass and ceramics, or by coating methods such as spray coating, immersion coating, and electrostatic coating. Alternatively, it may be formed as a thin film by 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.
一方、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を挙げることができ、天然繊維の例としては、綿、麻、絹、などが挙げられる。 On the other hand, examples of synthetic fibers constituting the substrate include polyester fibers, polyamide fibers, polyvinyl alcohol fibers, acrylic fibers, vinyl chloride fibers, vinylidene chloride fibers, polyolefin fibers, polycarbonate fibers, fluorine fibers, polyurea fibers, elastomer fibers, Moreover, the composite fiber of the material which comprises these fibers, and the said resin material etc. can be mentioned, As an example of a natural fiber, cotton, hemp, silk, etc. are mentioned.
本発明に係る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、紫外線が適している。 Examples of the radiation used in the graft polymerization according to the present invention include α rays, β rays, γ rays, electron beams, ultraviolet rays, etc., but for use in the present invention, γ rays, electron beams, ultraviolet rays are used. Is suitable.
また、本発明でのグラフト重合を用いた抗菌性を有する部材は、以下に記した方法により製造される。第一の方法は、前述した抗菌性を有する材料の微粒子を分散したシランカップリング剤溶液またはシランカップリング剤が結合された抗菌性を有する材料の微粒子が分散した溶液を、結合しようとする基体表面に塗布し、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後、γ線、電子線、紫外線などの放射線を、抗菌性を有する材料の微粒子とシランカップリング剤の混合物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抗菌性を有する材料の微粒子を結合させることで行われる所謂同時照射グラフト重合により製造される。 Moreover, the member which has antimicrobial property using the graft polymerization in this invention is manufactured by the method described below. The first method is to combine a silane coupling agent solution in which fine particles of the antibacterial material are dispersed or a solution in which fine particles of the antibacterial material to which the silane coupling agent is dispersed is to be bonded. After applying to the surface and removing the solvent by heat drying if necessary, a mixture of fine particles of antibacterial material and silane coupling agent is applied with radiation such as γ rays, electron beams, ultraviolet rays, etc. By irradiating the surface of the substrate, the silane coupling agent is graft-polymerized on the surface of the substrate, and at the same time, it is produced by so-called simultaneous irradiation graft polymerization performed by binding fine particles of an antibacterial material.
第二の方法は、予め抗菌性を有する材料の微粒子を結合しようとする基体表面にγ線、電子線、紫外線などの放射線を照射した後、抗菌性を有する材料の微粒子が分散したシランカップリング剤溶液またはシランカップリング剤が結合された抗菌性を有する材料の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抗菌性を有する材料の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。 The second method is a silane coupling in which fine particles of antibacterial material are dispersed after irradiating the surface of the substrate to which fine particles of the antibacterial material are bonded in advance with radiation such as γ rays, electron beams, and ultraviolet rays. A so-called agent solution or a solution in which fine particles of an antibacterial material to which a silane coupling agent is bonded is applied to react the silane coupling agent with the substrate and simultaneously bind the fine particles of the antibacterial material. Manufactured by pre-irradiation graft polymerization.
第三の方法は、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た後、抗菌性を有する材料の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抗菌性を有する材料の微粒子表面に存在する水酸基との脱水縮合反応により、抗菌性を有する材料の微粒子を基体表面に結合させる方法により製造される。 In the third method, fine particles of antibacterial material are dispersed after graft polymerization of a silane coupling agent on the surface of the substrate in advance by a simultaneous irradiation method or a pre-irradiation method of radiation such as γ rays, electron beams, or ultraviolet rays. The solution is applied to the surface of the substrate on which the silane coupling agent has been graft-polymerized, and then applied to the surface of the fine particles of silanol groups and antibacterial materials introduced to the surface of the substrate by applying heat and other energy. It is produced by a method in which fine particles of an antibacterial material are bonded to the substrate surface by a dehydration condensation reaction with a hydroxyl group.
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 acid aqueous solution.
本発明では、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）とすることができるので、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の用途に好適であり、これら各種製品での細菌や微生物の付着・増殖に伴う悪臭や変色、さらには院内感染を防止できるものとして提供することができる。 In the present invention, as described above, various forms (shape, size, etc.) suitable for the purpose of use, such as a film shape, a fiber shape, a cloth shape, a mesh shape, and a honeycomb shape, can be used. Building materials such as sashes, doors, blinds, interior materials such as wallpaper, carpets, resin tiles, clothing, innerwear, socks, gloves, shoes, etc., insoles for the footwear, pajamas, mats, sheets, pillows Suitable for bedding such as pillowcases, blankets, towels, quilts and quilt covers, hats, handkerchiefs, towels, carpets, curtains, filters or insect screens, and adheres to bacteria and microorganisms in these various products -It can be provided as something that can prevent malodor and discoloration associated with proliferation, as well as hospital infection.
また、本発明では、抗菌性を有する材料の微粒子の化学結合による固着については、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、抗菌性を有する材料の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。 Further, in the present invention, the adhesion of the fine particles of the antibacterial material by chemical bonding can be performed after spinning into a product shape or in the process of commercialization. There is an advantage that the presence of fine particles of the material does not affect the spinnability.
次に、実施例を挙げて本発明の抗菌性を有する部材の製造方法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, an example is given and the manufacturing method of the member which has antibacterial property of the present invention is explained more concretely. However, the present invention is not limited to only these examples.
＜抗菌性を有する部材の作製＞
本発明での抗菌性を有する部材の作製は、電子線照射装置として岩崎電気株式会社製、エレクトロカーテン型、ＣＢ２５０／１５／１８０Ｌ、を用いて実施した。
実施例１：
コロイド状無機抗菌剤（触媒化成工業株式会社製、商品名：アトミーボール−Ｓ）にメタノールを加えてコロイド状無機抗菌剤濃度を０．２重量％に希釈し、コロイド状無機抗菌剤分散メタノール溶液にシランカップリング剤として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、コロイド状無機抗菌剤重量に対して１．０重量％加えた。次に、調整したコロイド状無機抗菌剤分散メタノール溶液を、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コロイド状無機抗菌剤の表面にシランカップリング剤を結合させた。
<Production of antibacterial member>
Production of the antibacterial member in the present invention was carried out using an Iwazaki Electric Co., Ltd., electro curtain type, CB250 / 15 / 180L as an electron beam irradiation device.
Example 1:
Methanol is added to a colloidal inorganic antibacterial agent (trade name: Atomy Ball-S, manufactured by Catalyst Kasei Kogyo Co., Ltd.) to dilute the colloidal inorganic antibacterial agent concentration to 0.2% by weight, and colloidal inorganic antibacterial agent dispersed methanol As a silane coupling agent, 3-methacryloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503) was added to the solution at 1.0% by weight based on the weight of the colloidal inorganic antibacterial agent. Next, the prepared colloidal inorganic antibacterial agent-dispersed methanol solution is transferred to a flask equipped with a cooling tube, and then the flask is heated in an oil bath and treated under reflux for 4 hours on the surface of the colloidal inorganic antibacterial agent. A silane coupling agent was bound.
また、ポリエステル不織布（旭化成株式会社製、エルタスＥ０１０４０）の表面を大気中でコロナ放電処理した後、シランカップリング剤が固定されたコロイド状無機抗菌剤を含むメタノール溶液をスプレーにて塗布した。１１０℃、３分間乾燥した後、メタノール溶液を塗布したポリエステル不織布に電子線を２００ｋＶの加速電圧で１０Ｍｒａｄ照射することで、抗菌性を有する材料の微粒子がシランカップリング剤でポリエステル不織布上に結合されてなる抗菌性を有する部材（以下、検体とも言う。）を得た。 Further, the surface of a polyester non-woven fabric (manufactured by Asahi Kasei Co., Ltd., ELTAS E01040) was subjected to corona discharge treatment in the air, and then a methanol solution containing a colloidal inorganic antibacterial agent having a silane coupling agent fixed thereto was applied by spraying. After drying at 110 ° C. for 3 minutes, the polyester nonwoven fabric coated with methanol solution is irradiated with an electron beam at an acceleration voltage of 200 kV for 10 Mrad, so that the fine particles of the antibacterial material are bonded onto the polyester nonwoven fabric with a silane coupling agent. An antibacterial member (hereinafter also referred to as a specimen) was obtained.
実施例２：
実施例１で基体に用いたポリエステル不織布をコロナ放電処理後、電子線を２００ｋＶの加速電圧で１０Ｍｒａｄ照射した後、その表面に、実施例１で調整したシランカップリング剤が固定されたコロイド状無機抗菌剤を含むメタノール溶液をスプレーで塗布した。次に、３分間放置後、過剰のコロイド状無機抗菌剤を含むメタノール溶液を水洗により除去することで、抗菌性を有する材料の微粒子がシランカップリング剤でポリエステル不織布上に結合されてなる抗菌性を有する部材（検体）を得た。
Example 2:
After the corona discharge treatment of the polyester nonwoven fabric used for the substrate in Example 1, the electron beam was irradiated with 10 Mrad at an acceleration voltage of 200 kV, and then the colloidal inorganic in which the silane coupling agent prepared in Example 1 was fixed on the surface A methanol solution containing an antibacterial agent was applied by spraying. Next, after leaving for 3 minutes, the methanol solution containing an excess of colloidal inorganic antibacterial agent is removed by washing with water so that the antibacterial material fine particles are bonded onto the polyester nonwoven fabric with a silane coupling agent. A member (specimen) having was obtained.
実施例３：
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。実施例１で用いた不織布に電子線を２００ｋＶの加速電圧で１５Ｍｒａｄ照射した後、シランカップリング剤を溶解したイソプロピルアルコール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不織布の表面にグラフト重合した。次に、余分のシランカップリング剤を水洗により除去した後、シランカップリング剤がグラフト重合された不織布の表面にコロイド状無機抗菌剤を１．０重量％含む水溶液をスプレーにて塗布した後、１２０℃、１０分間加熱処理した。その後、結合していない過剰のコロイド状無機抗菌剤を水洗にて洗浄除去することで、抗菌性を有する材料の微粒子がシランカップリング剤でポリエステル不織布上に結合されてなる抗菌性を有する部材（検体）を得た。
Example 3:
The silane coupling agent used in Example 1 was dissolved in 1.0% by weight in isopropyl alcohol. After irradiating the nonwoven fabric used in Example 1 with an electron beam for 15 Mrad at an acceleration voltage of 200 kV, isopropyl alcohol in which the silane coupling agent was dissolved was applied by spraying and left standing for 3 minutes to remove the silane coupling agent from the nonwoven fabric. Graft polymerized on the surface. Next, after removing the excess silane coupling agent by washing with water, after applying an aqueous solution containing 1.0% by weight of a colloidal inorganic antibacterial agent on the surface of the nonwoven fabric graft-polymerized with the silane coupling agent, Heat treatment was performed at 120 ° C. for 10 minutes. Thereafter, an excess colloidal inorganic antibacterial agent that has not been bonded is washed and removed by washing with water, so that the antibacterial member is formed by binding fine particles of the antibacterial material on the polyester nonwoven fabric with a silane coupling agent ( Specimen).
実施例４：
実施例１で用いたコロイド状無機抗菌剤にイソプロピルアルコールを加えてコロイド状無機抗菌剤の濃度を０．１重量％に希釈した後、γ−アクリロシキプロピルトリメトキシシラン（信越化学工業株式会社製、ＫＢＭ−５１０３）をコロイド状無機抗菌剤重量に対して３．０重量％加え１時間撹拌することで、シランカップリング剤の一部を加水分解すると共に、シランカップリング剤をコロイド状無機抗菌剤の表面に吸着させた。
Example 4:
After adding isopropyl alcohol to the colloidal inorganic antibacterial agent used in Example 1 to dilute the colloidal inorganic antibacterial agent concentration to 0.1% by weight, γ-acryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Manufactured by KBM-5103) is added to 3.0% by weight of the colloidal inorganic antibacterial agent and stirred for 1 hour to hydrolyze a part of the silane coupling agent and to convert the silane coupling agent to colloidal inorganic. Adsorbed on the surface of the antibacterial agent.
また、１２５μmのポリエステルフィルム（パナック株式会社製、ルミラー）の表面に、前記シランカップリング剤を固定したコロイド状無機抗菌剤が分散されたイソプロピルアルコール溶液をスプレーにて塗布し、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、抗菌性を有する材料の微粒子がシランカップリング剤でポリエステル不織布上に結合されてなる抗菌性を有する部材（検体）を得た。 In addition, an isopropyl alcohol solution in which a colloidal inorganic antibacterial agent having the silane coupling agent fixed is dispersed is applied to the surface of a 125 μm polyester film (Plumac Corp., Lumirror) by spraying, at 120 ° C. for 3 minutes. Dried. Next, the polyester film coated with the isopropyl alcohol solution is irradiated with an electron beam at an acceleration voltage of 200 kV for 5 Mrad, so that the antibacterial property is obtained by binding fine particles of the antibacterial material on the polyester nonwoven fabric with a silane coupling agent. A member (specimen) was obtained.
実施例５：
綿で織られた布に電子線を２００ｋＶの加速電圧で５Ｍｒａｄ照射した後、その表面に、実施例４で調整したシランカップリング剤を固定したコロイド状無機抗菌剤が分散されたイソプロピルアルコール溶液をスプレーにて塗布し、１２０℃、３分間乾燥した。その後、結合していない過剰のシランカップリング剤が固定されたコロイド状無機抗菌剤を水洗により除去することで、抗菌性を有する材料の微粒子がシランカップリング剤で綿製布上に結合されてなる抗菌性を有する部材（検体）を得た。
Example 5:
After irradiating a cloth woven with cotton with an electron beam at an acceleration voltage of 200 kV for 5 Mrad, an isopropyl alcohol solution in which a colloidal inorganic antibacterial agent fixed with the silane coupling agent prepared in Example 4 is dispersed is applied to the surface. It was applied by spraying and dried at 120 ° C. for 3 minutes. After that, the colloidal inorganic antibacterial agent to which excess unbonded silane coupling agent is fixed is removed by washing with water, so that the fine particles of the antibacterial material are bonded onto the cotton cloth with the silane coupling agent. An antibacterial member (specimen) was obtained.
実施例６：
粉末状の抗菌性を有する微粒子（触媒化成工業株式会社製、商品名：アトミーボール−ＵＡ）をイソプロピルアルコールに５．０重量％加えた後、ビーズミルにて３時間処理することにより平均粒子径０．０５μｍに粉砕した。得られた抗菌性を有する微粒子が分散したイソプロピルアルコール溶液にＮ−（ビニルベンジル）−２−アミノエチルー３−アミノプロピルトリメトキシシラン（信越化学工業株式会社製、ＫＢＭ−５７５）を、抗菌性を有する微粒子の固形分に対して１．０重量％加えた。次に、抗菌性を有する微粒子が分散したイソプロピルアルコール溶液を、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抗菌性を有する微粒子の表面にシランカップリング剤を結合させた。
Example 6:
After adding 5.0% by weight of powdery antibacterial fine particles (manufactured by Catalyst Kasei Kogyo Co., Ltd., trade name: ATOMY BALL-UA) to isopropyl alcohol, the average particle size is treated by a bead mill for 3 hours. It grind | pulverized to 0.05 micrometer. N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-575) has antibacterial properties in the obtained isopropyl alcohol solution in which fine particles having antibacterial properties are dispersed. 1.0% by weight was added to the solid content of the fine particles. Next, the surface of the fine particles having antibacterial properties is transferred by transferring the isopropyl alcohol solution in which the fine particles having antibacterial properties are dispersed to a flask equipped with a cooling tube, and then heating the flask in an oil bath and treating it under reflux for 4 hours. A silane coupling agent was bound to the.
また、５５μmのポリエステルフィラメントで作製した２００メッシュのメッシュクロスに電子線を２００ｋＶの加速電圧で１０Ｍｒａｄ照射した後、前記シランカップリング剤を固定した抗菌性を有する微粒子のイソプロピルアルコール分散溶液に、電子線を照射したメッシュクロスを３分間浸漬した。その後、流水中で水洗して過剰の抗菌性微粒子のイソプロピルアルコール分散溶液を除去することで、抗菌性を有する材料の微粒子がシランカップリング剤でポリエステルメッシュクロス上に結合されてなる抗菌性を有する部材（検体）を得た。 Further, after irradiating a 200 mesh mesh cloth made of 55 μm polyester filament with an electron beam at an acceleration voltage of 200 kV for 10 Mrad, an antibacterial fine particle having an antibacterial property fixed thereto with an isopropyl alcohol dispersion solution. The mesh cloth irradiated with was immersed for 3 minutes. After that, it is washed with running water to remove the isopropyl alcohol dispersion solution of excess antibacterial fine particles, so that the antibacterial material fine particles are bonded on the polyester mesh cloth with a silane coupling agent. A member (specimen) was obtained.
実施例７：
厚さ１．０mmのアルミニウム板を公知の方法で脱脂し、１５重量％硫酸水溶液中に浸漬し、１．５Ａ／ｄｍ２の電流密度で３０分間、陽極酸化することによりアルミニウム板表面に１５μmの酸化皮膜を形成した。さらに、このアルミニウム板を水洗して乾燥後、熱硬化型アクリル系塗料（関西ペイント株式会社製、ＭＧ１０００）をスプレーにて塗布した後１８０℃、３０分間乾燥することで、厚さ１５μmの厚さの塗膜が形成された塗膜被覆アルミニウム板を得た。次に、実施例６で調整したシランカップリング剤を固定した抗菌性を有する微粒子のイソプロピルアルコール分散溶液をスプレーにて塗布し、１３０℃、３分間乾燥した後、電子線を２４０ｋＶの加速電圧で２０Ｍｒａｄ照射することで、抗菌性を有する材料の微粒子がシランカップリング剤で塗膜被覆アルミニウム板上に結合されてなる抗菌性を有する部材（検体）を得た。
Example 7:
An aluminum plate having a thickness of 1.0 mm is degreased by a known method, immersed in a 15% by weight sulfuric acid aqueous solution, and anodized at a current density of 1.5 A / dm 2 for 30 minutes. An oxide film was formed. Further, the aluminum plate was washed with water and dried, and then a thermosetting acrylic paint (MG1000, manufactured by Kansai Paint Co., Ltd.) was applied by spraying and then dried at 180 ° C. for 30 minutes to obtain a thickness of 15 μm. A coating-coated aluminum plate on which the coating film was formed was obtained. Next, an isopropyl alcohol dispersion solution of antibacterial fine particles having the silane coupling agent prepared in Example 6 fixed thereon is applied by spraying and dried at 130 ° C. for 3 minutes, and then the electron beam is applied at an acceleration voltage of 240 kV. By irradiating with 20 Mrad, an antibacterial member (specimen) obtained by binding fine particles of an antibacterial material on a coating-coated aluminum plate with a silane coupling agent was obtained.
比較例１：
実施例１で用いたコロイド状無機抗菌剤（触媒化成工業株式会社製、商品名：アトミーボール−Ｓ）にメタノールを加えてコロイド状無機抗菌剤濃度を０．２重量％に調整し、コロナ放電処理したポリエステル不織布（旭化成株式会社製、エルタスＥ０１０４０）の表面にスプレーにより塗布し、１２０℃、２０分間加熱処理することで、抗菌性を有する材料の微粒子が付着した抗菌性を有する部材（検体）を得た。
Comparative Example 1:
Methanol was added to the colloidal inorganic antibacterial agent (catalyst chemical industry Co., Ltd., trade name: ATOMY BALL-S) used in Example 1 to adjust the colloidal inorganic antibacterial agent concentration to 0.2% by weight. An antibacterial member (specimen) in which fine particles of an antibacterial material are attached by applying the sprayed polyester non-woven fabric (manufactured by Asahi Kasei Co., Ltd., Eltus E01040) by spraying and heat-treating at 120 ° C. for 20 minutes. )
比較例２：
ポリエステル樹脂（日本ユニペット株式会社製）に、実施例６で用いた粉末状の抗菌性を有する微粒子を２軸混練機により０．１重量％充填してペレットを作製した。次に、得られたペレットを用いて溶融紡糸装置によりポリエステルフィラメントを紡糸し、さらに延伸加工することで、径が８０μmのポリエステルフィラメントを得た。得られたポリエステルフィラメントを用い、２００メッシュの抗菌性を有する材料の微粒子が充填されたメッシュクロスからなる抗菌性を有する部材（検体）を得た。
Comparative Example 2:
A polyester resin (manufactured by Nippon Unipet Co., Ltd.) was filled with 0.1% by weight of the powdery antibacterial fine particles used in Example 6 by a biaxial kneader to produce pellets. Next, a polyester filament having a diameter of 80 μm was obtained by spinning a polyester filament with a melt spinning apparatus using the obtained pellets and further drawing. Using the obtained polyester filament, an antibacterial member (specimen) made of mesh cloth filled with 200 mesh fine particles of antibacterial material was obtained.
＜抗菌性の試験及び評価＞
本発明者らは、上述の製法にて得られた各実施例１〜７及び比較例１，２の各部材（検体）に対して、ＪＩＳ Ｌ １９０２に基づく抗菌性についての試験及び評価を行った。尚、試験対象菌種としては、黄色ぶどう球菌Staphylococcus aureus ATCC 6538Pと、大腸菌Escherichia coli NBRC 3301を用いた。また、抗菌性の指標としては、殺菌活性値と静菌活性値を求めた。ここで、殺菌活性値および静菌活性値は、植菌時の菌体数をAとし、抗菌性を施していない検体での植菌１８時間後の菌体数をB、抗菌性を施している検体での植菌18時間後の菌体数をＣとして、以下に示した式により求めた。
殺菌活性値＝ｌｏｇＡ−ｌｏｇＣ
静菌活性値＝ｌｏｇＢ−ｌｏｇＣ
<Antimicrobial test and evaluation>
The present inventors conducted tests and evaluations on antibacterial properties based on JIS L 1902 for each member (specimen) of each of Examples 1 to 7 and Comparative Examples 1 and 2 obtained by the above-described production method. It was. As test species, Staphylococcus aureus ATCC 6538P and Escherichia coli NBRC 3301 were used. Further, as an antibacterial index, a bactericidal activity value and a bacteriostatic activity value were determined. Here, the bactericidal activity value and the bacteriostatic activity value are as follows: A is the number of cells at the time of inoculation, B is the number of cells after 18 hours inoculation in a sample that has not been antibacterial, The number of bacterial cells 18 hours after inoculation in a given sample was defined as C, and was calculated according to the following formula.
Bactericidal activity value = log A−log C
Bacteriostatic activity value = log B-log C
＜微粒子の固着性の試験及び評価＞
また、本発明者らは、上述の製法にて得られた各実施例１〜７及び比較例１，２の各部材（検体）に対して、抗菌性を有する材料の微粒子の固着性についての試験及び評価を以下のように行った。すなわち、各検体につき、試験対象菌種として上記の大腸菌Escherichia coli NBRC 3301を用い、蒸留水中で超音波洗浄処理を１０分間行うとともに、蒸留水を新たに交換して、同様に超音波洗浄処理を合計２０回繰り返し行った後に、検体の大腸菌についての殺菌活性値を上記式により求めて評価した。これら各試験結果を表１に示す。
<Test and evaluation of adhesion of fine particles>
In addition, the present inventors are concerned with the adhesion of fine particles of antibacterial material to each member (specimen) of each of Examples 1 to 7 and Comparative Examples 1 and 2 obtained by the above-described production method. Tests and evaluations were performed as follows. That is, for each specimen, the above Escherichia coli NBRC 3301 was used as the test species, and ultrasonic cleaning treatment was performed in distilled water for 10 minutes, and distilled water was newly replaced and ultrasonic cleaning treatment was similarly performed. After a total of 20 repetitions, the bactericidal activity value for the E. coli sample was determined by the above formula and evaluated. These test results are shown in Table 1.
表１の結果から分かるように、本発明の実施例１〜７における放射線グラフト重合で得られた抗菌性を有する部材（検体）では、大腸菌および黄色ぶどう球菌での殺菌活性値がいずれも２．５以上と高い値を示した。ここで、殺菌活性値が２．５以上であることは植菌した微生物の９９．５％以上が殺菌されたことを示すものであり、これにより各実施例における抗菌性を有する部材は優れた殺菌性を有することが確認された。また、各実施例１〜７の検体では、静菌活性値についても５．５以上と高い値を示しており、微生物の増殖を抑制する能力に優れていることが確認された。これらの結果より、本発明の抗菌性を有する部材は、抗菌活性に優れた部材であることが実証された。
As can be seen from the results in Table 1, the antibacterial members (specimens) obtained by the radiation graft polymerization in Examples 1 to 7 of the present invention each have a bactericidal activity value in Escherichia coli and Staphylococcus aureus of 2. A high value of 5 or more was shown. Here, the bactericidal activity value of 2.5 or more indicates that 99.5% or more of the inoculated microorganisms were sterilized, and thus the antibacterial member in each example was excellent. It was confirmed to have bactericidal properties. Moreover, in the sample of each Example 1-7, the bacteriostatic activity value also showed a high value of 5.5 or more, and it was confirmed that the ability to suppress the growth of microorganisms was excellent. From these results, it was demonstrated that the antibacterial member of the present invention is a member excellent in antibacterial activity.
さらに、表１の結果に示されるように、各実施例１〜７の検体では、超音波洗浄後の殺菌活性値は超音波洗浄前と比較してほとんど変化していないことから、本発明の抗菌性を有する部材では、基体表面に対する抗菌性材料の微粒子の固着性が優れていることが確認された。これより、本発明の抗菌性を有する部材は、洗濯などの耐久性に優れていることも示唆された。 Furthermore, as shown in the results of Table 1, in the specimens of Examples 1 to 7, the bactericidal activity value after ultrasonic cleaning is hardly changed compared with that before ultrasonic cleaning. It was confirmed that the antibacterial member has excellent adhesion of the fine particles of the antibacterial material to the substrate surface. From this, it was also suggested that the antibacterial member of the present invention is excellent in durability such as washing.
これらの結果に対し、シラン化合物の化学結合を用いなかった各比較例の抗菌性を有する部材（検体）では、殺菌活性値および静菌活性値共に実施例と比較して低い値を示しており、抗菌活性に関して劣っていることが分かる。さらに、微粒子の固着性の試験結果では、超音波洗浄後の殺菌活性値につき、比較例２の検体については超音波洗浄前の値と比較して変化が少なかったが、比較例１の検体については大幅に値が低下していることから、固着法によっては抗菌耐久性に乏しいことが示された。 In contrast to these results, the antibacterial member (specimen) of each comparative example that did not use a chemical bond of a silane compound showed a low value for both the bactericidal activity value and the bacteriostatic activity value compared to the examples. It can be seen that the antibacterial activity is inferior. Furthermore, in the test result of the adhesion of fine particles, the bactericidal activity value after ultrasonic cleaning was less changed for the sample of Comparative Example 2 than the value before ultrasonic cleaning, but for the sample of Comparative Example 1 Since the value of A was significantly reduced, it was shown that the antibacterial durability was poor depending on the fixing method.
以上説明したように、本発明の製造方法を適用した、シラン化合物のグラフト重合により抗菌性を有する材料の微粒子を樹脂基体表面へ結合させた抗菌性を有する部材は、シラン化合物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、抗菌性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、シラン化合物のビニル基、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、ポリスルフィド基などが、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、抗菌性を有する微粒子は樹脂基体表面にシラン化合物により化学的な結合で強固に結合されていることから、本発明の製造方法による抗菌性を有する部材は、様々な環境で使用しても抗菌性を有する材料の微粒子の脱離などが起こり難い耐久性に優れたものである。また、本発明の製造方法によれば、抗菌性を有する材料の微粒子が繊維や樹脂フィルムの表面にシラン化合物によって固定されていることから、細菌や微生物と効率良く接触し、抗菌効果に優れたものであり、さらに、抗菌性を有する材料の微粒子が基体上に島状乃至薄膜の形態で形成されていることから、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極めて有用なものである。 As described above, the antibacterial member obtained by binding the fine particles of the antibacterial material to the surface of the resin substrate by graft polymerization of the silane compound to which the production method of the present invention is applied is a hydrolyzed alkoxy group of the silane compound. Silanol groups generated by decomposition are firmly chemically bonded to the surface of antibacterial fine particles by dehydration condensation reaction, and further, vinyl group, epoxy group, styryl group, methacrylo group, acryloxy group, isocyanate group of silane compound Polysulfide groups and the like are formed by chemically bonding to the resin substrate surface by graft polymerization with radicals generated by irradiation with radiation. Therefore, since the antibacterial fine particles are firmly bonded to the resin substrate surface by a chemical bond with the silane compound, the antibacterial member produced by the production method of the present invention can be used in various environments. It is excellent in durability in which detachment of fine particles of an antibacterial material is difficult to occur. Further , according to the production method of the present invention , since the fine particles of the antibacterial material are fixed to the surface of the fiber or the resin film by the silane compound, it is in efficient contact with bacteria and microorganisms and has an excellent antibacterial effect. In addition, since the fine particles of the antibacterial material are formed in the form of islands or thin films on the substrate, the texture of the fibers and the structures composed thereof is not impaired. It is extremely useful because of its practical utility that can be applied to.
Claims (10)
基体表面に抗菌性を有する微粒子を分散したシランカップリング剤溶液を塗布する工程と、
微粒子を分散したシランカップリング剤溶液が塗布された基体表面に放射線を照射する工程とを含み、
シラン化合物の基体表面への化学結合が放射線グラフト重合であることを特徴とする抗菌性を有する部材の製造方法。 Fine member having antimicrobial properties, on the surface of the substrate, the chemical bonding to the substrate surface of the silane compound be more combined method of manufacturing a member having an antimicrobial comprising,
Applying a silane coupling agent solution in which fine particles having antibacterial properties are dispersed on the substrate surface;
Irradiating a substrate surface coated with a silane coupling agent solution in which fine particles are dispersed, and
A method for producing an antibacterial member, wherein a chemical bond of a silane compound to a substrate surface is radiation graft polymerization .
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| JP2021181632A (en) * | 2018-06-12 | 2021-11-25 | 花王株式会社 | Antibacterial fiber and clothing |
| KR102085193B1 (en) * | 2018-11-19 | 2020-03-05 | 영남대학교 산학협력단 | Fabrics with improved antimicrobial and photodegradable properties and the manufacturing method thereof |
| KR102140408B1 (en) * | 2019-11-19 | 2020-08-03 | 주식회사 포머스 | Eco-friendly LPM furniture with excellent antibacterial and adhesive properties, and method of manufacturing thereof |
| CN114182435B (en) * | 2021-12-10 | 2023-03-17 | 太原理工大学 | Polylactic acid antibacterial composite fiber membrane and preparation method and application thereof |
| JP2024064699A (en) * | 2022-10-28 | 2024-05-14 | 信越ポリマー株式会社 | Medical device and its manufacturing method |
| CN119041212B (en) * | 2024-11-04 | 2025-03-04 | 福建大方睡眠科技股份有限公司 | Skin-friendly non-sense cotton and preparation method thereof |
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| JP2621580B2 (en) * | 1990-05-22 | 1997-06-18 | 東レ株式会社 | Antibacterial and deodorant colored polyester fiber structure and method for producing the same |
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