JP2009167572A - Antioxidant fabric, clothing, and bedding, and method for producing them - Google Patents
Antioxidant fabric, clothing, and bedding, and method for producing them Download PDFInfo
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- 239000004744 fabric Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 230000003078 antioxidant effect Effects 0.000 title abstract description 27
- 239000003963 antioxidant agent Substances 0.000 title abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 219
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 110
- 239000002105 nanoparticle Substances 0.000 claims abstract description 103
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 26
- 239000004094 surface-active agent Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims description 20
- 239000000835 fiber Substances 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012080 ambient air Substances 0.000 abstract 1
- 239000003223 protective agent Substances 0.000 description 13
- 229920000742 Cotton Polymers 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000003064 anti-oxidating effect Effects 0.000 description 4
- MGJZITXUQXWAKY-UHFFFAOYSA-N diphenyl-(2,4,6-trinitrophenyl)iminoazanium Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1N=[N+](C=1C=CC=CC=1)C1=CC=CC=C1 MGJZITXUQXWAKY-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229920003043 Cellulose fiber Polymers 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- HHEAADYXPMHMCT-UHFFFAOYSA-N dpph Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1[N]N(C=1C=CC=CC=1)C1=CC=CC=C1 HHEAADYXPMHMCT-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- -1 aminopectin Polymers 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000000338 in vitro Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920002972 Acrylic fiber Polymers 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920000433 Lyocell Polymers 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000002292 Radical scavenging effect Effects 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000003396 thiol group Chemical class [H]S* 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は、抗酸化性を有する白金ナノ粒子を担持した布帛及び衣類、寝装品及びその製造方法に関する。 The present invention relates to a fabric, clothing, bedding, and a method for producing the same, which carry platinum nanoparticles having antioxidant properties.
近年、白金ナノ粒子の持つ抗酸化性能に着目した提案がされている。白金のコロイド中において、白金ナノ粒子は、保護剤に包囲された状態で１〜１００ｎｍ（ナノメーター）の粒径の懸濁液として存在し（以下、ナノ粒子とその周囲の保護剤との結合体をコロイド液と称する場合がある）、燃料電池用触媒、自動車用排ガス処理触媒に使用することが知られている（特許文献１）。この白金ナノ粒子は、還元性があることから、活性酸素の還元と、抗酸化性作用に着目して、化粧品に混合する提案もある（特許文献２〜３）。又、白金ナノ粒子の繊維への適用として、セルロース繊維に白金ナノ粒子を含有させた提案もある（特許文献４）。
従来、繊維束になった状態のセルロース繊維に白金ナノ粒子を担持させ、それを煙草フィルタープラグとして使用する試みはあった。しかし、白金ナノ粒子を直接担持した下着、肌着、パジャマ、シャツなどの衣類、シーツ、寝具類、タオル等の寝装品及び白金ナノ粒子を直接担持させた布帛を使った前記衣類や前記寝装品の提案はなされてこなかった。 Conventionally, attempts have been made to support platinum nanoparticles on cellulose fibers in a fiber bundle and use it as a tobacco filter plug. However, underwear, underwear, pajamas, shirts and other clothing that directly carries platinum nanoparticles, bedding such as sheets, bedding, towels, etc. It hasn't been done.
当初、本発明者は、市販されているポリアクリル酸塩を保護剤とした白金ナノ粒子を使い布帛に担持させてみたものの、バインダーを使用しなければ脱落が多くて抗酸化性について満足する結果を得ることができなかった。そこで、鋭意研究の結果、白金ナノ粒子とそれを保護する保護剤の種類及び保護剤の配合割合に着目し、その保護剤の種類及びその保護剤の配合割合によっては、抗酸化性を有する布帛等が得られることを見出し本発明に至った。即ち、本発明は、白金ナノ粒子を担持させた抗酸化性のある布帛、及びこれを用いた衣類、寝装品並びに白金ナノ粒子を担持させた抗酸化性のある衣類、寝装品を提供する。
本発明の布帛は、水溶性高分子及び／又は界面活性剤で保護した白金ナノ粒子を直接担持した布帛であって、白金ナノ粒子１に対して水溶性高分子及び／又は界面活性剤が質量比で０．５〜２であることを特徴とする。又、本発明の布帛は、布帛１ｇに対して前記白金ナノ粒子を乾燥質量で０．１μｇ以上担持させたことをも特徴とする。即ち、本発明は、水溶性高分子及び／又は界面活性剤で保護した白金ナノ粒子を担持した布帛であって、前記白金ナノ粒子と水溶性高分子及び／又は界面活性剤の配合割合が、白金ナノ粒子：水溶性高分子及び／又は界面活性剤＝１：２〜１：０．５であり、前記布帛１ｇに対して前記白金ナノ粒子を乾燥質量で０．１μｇ以上直接担持させたことを特徴とする。本発明の衣類、寝装品は、前記の白金ナノ粒子を担持した布帛で形成されていてもよいし、前記白金ナノ粒子を直接、衣類又は寝装品に担持させていてもよい。
本発明の布帛は、布帛を、布帛１ｇに対して０．６μｇ以上の白金ナノ粒子を含み、バインダーを含まない処理液中に浴比１：３〜４０の範囲内で浸漬させ、布帛に白金ナノ粒子を選択吸着させた後に乾燥させることにより製造することができる。又、白金ナノ粒子を布帛染色後に担持させてもよいし、白金ナノ粒子をイオン性物質がない状態に精製する工程を含んでもよい。
Initially, the present inventor tried to carry on a fabric using platinum nanoparticles having a protective agent made of a commercially available polyacrylate, but if the binder was not used, the result was that there was a lot of dropping and the antioxidant was satisfied. Could not get. Therefore, as a result of earnest research, we focused on the type of platinum nanoparticles and the protective agent that protects them, and the blending ratio of the protective agent. Depending on the type of protective agent and the blending ratio of the protective agent, the fabric has an antioxidant property. Etc. were found and the present invention was achieved. That is, the present invention provides an antioxidant fabric carrying platinum nanoparticles, and clothing, bedding using the same, and antioxidant clothing and bedding using platinum nanoparticles.
The fabric of the present invention is a fabric in which platinum nanoparticles protected with a water-soluble polymer and / or a surfactant are directly supported, and the water-soluble polymer and / or the surfactant is in a mass relative to the platinum nanoparticles 1. The ratio is 0.5-2. The fabric of the present invention is also characterized in that the platinum nanoparticles are supported in a dry mass of 0.1 μg or more per 1 g of the fabric. That is, the present invention is a fabric carrying platinum nanoparticles protected with a water-soluble polymer and / or surfactant, wherein the blending ratio of the platinum nanoparticles and the water-soluble polymer and / or surfactant is: Platinum nanoparticles: water-soluble polymer and / or surfactant = 1: 2 to 1: 0.5, and the platinum nanoparticles were directly supported by 0.1 g or more in dry mass on 1 g of the fabric. It is characterized by. The clothing and bedding of the present invention may be formed of a cloth carrying the platinum nanoparticles, or the platinum nanoparticles may be directly carried on the clothing or bedding.
The fabric according to the present invention includes 0.6 μg or more of platinum nanoparticles with respect to 1 g of the fabric, and is immersed in a treatment solution containing no binder within a range of a bath ratio of 1: 3 to 40 so that the fabric is platinum. It can be produced by selectively adsorbing nanoparticles and then drying them. Further, the platinum nanoparticles may be supported after the fabric is dyed, or a step of purifying the platinum nanoparticles to be free of ionic substances may be included.
本発明の布帛は、水溶性高分子及び／又は界面活性剤で保護した白金ナノ粒子を直接担持し、前記白金ナノ粒子１に対して水溶性高分子及び／又は界面活性剤が質量比で０．５〜２であり、前記布帛１ｇに対して前記白金ナノ粒子を乾燥質量で０．１μｇ以上担持させたことにより、抗酸化性のある布帛とすることができる。 The fabric of the present invention directly carries platinum nanoparticles protected with a water-soluble polymer and / or a surfactant, and the water-soluble polymer and / or surfactant is 0 by mass with respect to the platinum nanoparticles 1. 0.5 to 2 and by supporting 0.1 μg or more of the platinum nanoparticles in a dry mass with respect to 1 g of the fabric, an anti-oxidation fabric can be obtained.
本発明の衣類、寝装品は、前記の白金ナノ粒子を担持した布帛で形成されていることにより、身体周囲の空気層から身体に悪影響を及ぼすといわれている活性酸素やフリーラジカルを分解する効果が期待できる。又、衣類、寝装品に白金ナノ粒子を直接担持することによっても身体周囲の空気層から身体に悪影響を及ぼすといわれている活性酸素やフリーラジカルを分解する効果が期待できる。 The clothes and bedding of the present invention are formed of the above-described fabric carrying platinum nanoparticles, and thus have an effect of decomposing active oxygen and free radicals, which are said to adversely affect the body from the air layer around the body. I can expect. Moreover, the effect of decomposing active oxygen and free radicals, which are said to adversely affect the body from the air layer around the body, can be expected by directly supporting platinum nanoparticles on clothes and bedding.
本発明で用いられる白金ナノ粒子は、例えば、ＷＯ２００５／０１８５９８号公報記載の方法にて提供され、その平均粒径は、１〜５ｎｍであることが好ましく、１〜３ｎｍであるのがより好ましく、１．５〜２．５ｎｍであるのが特に好ましい。又、９０質量％以上の白金ナノ粒子の粒径が０．１〜１０ｎｍの範囲に入るのが好ましく、１〜３ｎｍの範囲に入るのがより好ましい。このように白金ナノ粒子の粒径分布が狭く、かつその平均粒径が１〜５ｎｍの範囲であると、白金ナノ粒子の個数割合が高く、良好な抗酸化性を有する。前記白金ナノ粒子は、イオン性物質は含まない状態が好ましい。白金ナノ粒子は、白金ナノコロイドとして作成する。その際に、酸根などが残らないように精製し、イオン性物質はない状態にするのが好ましい。 The platinum nanoparticles used in the present invention are provided by, for example, the method described in WO2005 / 018598, and the average particle diameter is preferably 1 to 5 nm, more preferably 1 to 3 nm, A thickness of 1.5 to 2.5 nm is particularly preferable. Moreover, it is preferable that the particle diameter of 90 mass% or more of platinum nanoparticles falls within the range of 0.1 to 10 nm, and more preferably within the range of 1 to 3 nm. Thus, when the particle size distribution of the platinum nanoparticles is narrow and the average particle size is in the range of 1 to 5 nm, the number ratio of the platinum nanoparticles is high and the antioxidant property is good. The platinum nanoparticles preferably do not contain an ionic substance. Platinum nanoparticles are prepared as platinum nanocolloids. At that time, it is preferable to purify the acid radicals and the like so that no ionic substances are present.
本発明の白金ナノ粒子を担持した布帛は抗酸化性を有する。抗酸化性の測定方法は後に説明する。本発明の布帛が抗酸化性を有することにより、前記特許文献２〜３に提案されているような化粧品と同様な人体に対する好ましい抗酸化性を発揮することが推定されるほか、布帛自体の劣化も抑えることが期待できる。又、白金ナノ粒子が触媒的に機能するため長期間使用することが可能となる。 本発明において布帛とは、編み物、織物、不織布等をいう。布帛は衣類、あるいは寝装品の素材ともなる。本発明の衣類は、下着、肌着、パジャマ、シャツ、帽子、セーター、ベスト、上着、コートなど様々なものがある。又、本発明の寝装品は、シーツ、布団側地、タオルケット、毛布、タオル、ハンカチなど様々なものがある。 The fabric carrying the platinum nanoparticles of the present invention has antioxidant properties. The method for measuring antioxidant properties will be described later. The anti-oxidation property of the fabric of the present invention is presumed to exhibit a preferable anti-oxidation property to the human body similar to the cosmetics proposed in Patent Documents 2 to 3, and the fabric itself is deteriorated. Can also be expected. Moreover, since platinum nanoparticles function as a catalyst, they can be used for a long time. In the present invention, the fabric refers to knitted fabric, woven fabric, non-woven fabric, and the like. The fabric is also a material for clothing or bedding. The clothing of the present invention includes various items such as underwear, underwear, pajamas, shirts, hats, sweaters, vests, outerwear, and coats. Also, the bedding of the present invention includes various items such as sheets, futon sides, towels, blankets, towels and handkerchiefs.
本発明においては、保護剤として水溶性高分子及び／又は界面活性剤を使用し、その質量割合は、白金ナノ粒子１に対して水溶性高分子及び／又は界面活性剤が質量比で０．５〜２の範囲が適切である。白金ナノ粒子１質量部に対して水溶性高分子及び／又は界面活性剤が０．５質量部未満ではコロイドが安定せず、白金ナノ粒子の凝集・沈殿が起こりやすくなる。また、白金ナノ粒子１質量部に対して水溶性高分子及び／又は界面活性剤が２質量部を超えると抗酸化性が低くなる傾向となる。白金ナノ粒子の保護剤としては水溶性高分子及び／又は界面活性剤が使用される。これらは、白金の親溶媒性を向上させる働きをする。水溶性高分子としてはポリビニルピロリドン、ポリビニルアルコール、ポリアクリル酸、ポリアクリル酸塩、シクロデキストリン、アミノペクチン、又はメチルセルロース等が挙げられる。これらを二種以上組み合わせて使用しても良い。中でもポリビニルピロリドンが選択的に好ましい。又、チオール系保護剤のような界面活性剤を使用することもできる。又、クエン酸塩を保護剤として使用することもできる。 In the present invention, a water-soluble polymer and / or surfactant is used as a protective agent, and the mass ratio of the water-soluble polymer and / or surfactant to the platinum nanoparticle 1 is 0.00. A range of 5 to 2 is appropriate. If the water-soluble polymer and / or the surfactant is less than 0.5 parts by mass with respect to 1 part by mass of the platinum nanoparticles, the colloid is not stable, and aggregation / precipitation of the platinum nanoparticles easily occurs. Moreover, when the water-soluble polymer and / or the surfactant exceeds 2 parts by mass with respect to 1 part by mass of the platinum nanoparticles, the antioxidant property tends to be lowered. A water-soluble polymer and / or a surfactant is used as a protective agent for the platinum nanoparticles. These serve to improve the solvophilicity of platinum. Examples of the water-soluble polymer include polyvinyl pyrrolidone, polyvinyl alcohol, polyacrylic acid, polyacrylate, cyclodextrin, aminopectin, and methylcellulose. Two or more of these may be used in combination. Of these, polyvinylpyrrolidone is selectively preferred. A surfactant such as a thiol-based protective agent can also be used. Citrate can also be used as a protective agent.
前記布帛１ｇに対して前記白金ナノ粒子を乾燥質量で０．１μｇ以上担持させる。担持量が０．１μｇ以上であれば好ましい抗酸化性を有する。担持量が０．１μｇ／ｇ未満では抗酸化性と洗濯耐久性は低い傾向となる。また、担持量が２μｇ／ｇを超えると、抗酸化性は有するが、コストが高くなる傾向となると共に色のくすみともなることから、０．１〜２μｇ／ｇの範囲が好ましい。
前記布帛は、セルロース系繊維３０〜１００質量％で構成するのが好ましい。ここで、セルロース系繊維としては、綿、麻等の天然繊維、レーヨン、キュプラ、リヨセル等の再生セルロース繊維又はアセテート等の半合成繊維が挙げられ、これらは単独又は混用したものであっても構わない。この場合、セルロース系繊維は綿繊維を通常５０％以上のものが好ましい。綿は肌にやさしいからである。混紡する繊維としては、ポリエステル、ナイロン、アクリル系繊維等の合成繊維やシルク、ウール等の天然繊維等が挙げられ、用途に応じて適宜、選択することができる。
The platinum nanoparticles are supported in an amount of 0.1 μg or more on a dry mass basis with respect to 1 g of the fabric. When the loading amount is 0.1 μg or more, preferable antioxidant properties are obtained. When the supported amount is less than 0.1 μg / g, the antioxidant property and the washing durability tend to be low. Further, when the loading amount exceeds 2 μg / g, it has antioxidant properties, but it tends to increase the cost and also becomes dull in color, so the range of 0.1 to 2 μg / g is preferable.
The fabric is preferably composed of 30 to 100% by mass of cellulosic fibers. Here, examples of the cellulosic fibers include natural fibers such as cotton and hemp, regenerated cellulose fibers such as rayon, cupra, and lyocell, and semi-synthetic fibers such as acetate. These may be used singly or in combination. Absent. In this case, the cellulosic fiber is preferably 50% or more of cotton fiber. This is because cotton is gentle on the skin. Examples of the fiber to be blended include synthetic fibers such as polyester, nylon, and acrylic fibers, and natural fibers such as silk and wool, and can be appropriately selected depending on the application.
本発明において白金ナノ粒子を布帛に担持させる方法は、吸尽法である。ここで、吸尽法とは、仕上げ剤の希薄溶液を用い、温度及び浸せき時間、液循環回数等の条件を設定して、仕上げ剤を繊維に選択吸着させることで吸尽させる方法である。本発明の布帛は、布帛を、布帛１ｇに対して０．６μｇ以上の白金ナノ粒子を含み、バインダーを含まない処理液中に浴比１：３〜４０の範囲内で浸漬させ、布帛に白金ナノ粒子を選択吸着させた後に乾燥させることにより製造することができる。浴比が１：３未満であると白金ナノ粒子の担持ムラが発生し易くなると共に布帛のこすれが発生し、浴比が１：４０を超えると白金ナノ粒子をムラなく担持し易くなるものの資源やエネルギーのロスが大きくなる傾向がある。又、処理温度及び処理時間については、経済的な範囲で設定すればよい。本発明の布帛は、白金ナノ粒子とセルロース系繊維との親和性を利用して吸着させることで、洗濯耐久性を高めつつ、バインダー樹脂を使用しないで、白金ナノ粒子を繊維表面に存在するナノオーダーの微細孔に直接担持させることができる。又、本発明において白金ナノ粒子を直接、衣類或いは寝装品に担持させる方法も前記と同様に行うことができる。 In the present invention, the method of supporting platinum nanoparticles on a fabric is an exhaust method. Here, the exhaust method is a method of exhausting by using a dilute solution of the finishing agent, setting conditions such as temperature, immersion time, number of times of liquid circulation, and the like, and selectively adsorbing the finishing agent on the fiber. The fabric according to the present invention includes 0.6 μg or more of platinum nanoparticles with respect to 1 g of the fabric, and is immersed in a treatment solution containing no binder within a range of a bath ratio of 1: 3 to 40 so that the fabric is platinum. It can be produced by selectively adsorbing nanoparticles and then drying them. When the bath ratio is less than 1: 3, uneven support of the platinum nanoparticles is likely to occur, and the fabric is rubbed. When the bath ratio exceeds 1:40, the platinum nanoparticles are easily supported without unevenness. And energy loss tends to increase. The processing temperature and processing time may be set within an economical range. The fabric of the present invention is made by adsorbing using the affinity between platinum nanoparticles and cellulosic fibers, thereby improving washing durability and using platinum nanoparticles on the fiber surface without using a binder resin. It can be directly supported on the micropores of the order. In the present invention, the method of directly supporting platinum nanoparticles on clothes or bedding can also be performed in the same manner as described above.
前記白金ナノ粒子は、布帛染色完了後に担持することが好ましい。この場合、柔軟剤等の仕上剤を併用してもよい。セルロース系繊維本来の肌へのやさしさを生かすため、吸水性を損なわないように仕上げるのが好ましい。布帛染色完了後に白金ナノ粒子を担持すると最終製品にもそのままの状態で残る。糸の染色後に白金ナノ粒子を担持させることもでき、靴下やスカーフ等の繊維製品を作製することができる。但し、原綿又は原糸の状態で白金ナノ粒子を担持すると、布帛形成工程や精練晒染色工程で白金ナノ粒子が脱落する可能性がある。 The platinum nanoparticles are preferably supported after the fabric dyeing is completed. In this case, a finishing agent such as a softening agent may be used in combination. In order to make use of the gentleness of the cellulosic fibers inherent to the skin, it is preferable to finish so as not to impair the water absorption. When the platinum nanoparticles are supported after the fabric dyeing is completed, they remain in the final product as they are. After dyeing the yarn, platinum nanoparticles can be supported, and textile products such as socks and scarves can be produced. However, if the platinum nanoparticles are supported in the state of raw cotton or raw yarn, the platinum nanoparticles may fall off in the fabric forming process or the scouring bleaching dyeing process.
以下、実施例を用いて本発明をさらに具体的に説明する。なお、本発明は下記の実施例に限定されるものではない。
１．抗酸化性（ＤＰＰＨ法）
抗酸化性をインビトロ（試験管内）で分析を行う場合、ＤＰＰＨラジカル試薬を使う方法の利便性が高いことが知られている。本実施例では、１，１−ジフェニル−２−ピクリルヒドラジル（ＤＰＰＨ）ラジカル消去法を使用した。測定手順は次のとおりである。
（１）ＤＰＰＨラジカル試験液の調製
ＤＰＰＨ２５μＭ（マイクロモル）アルコール溶液を作成する。液は紫色を呈する。
（２）加工および未加工布帛を５ｃｍ×５ｃｍの大きさを採取した後、細かく裁断し試験管に入れる。サンプル数はｎ＝２とする。
（３）上記の比色管へＤＰＰＨラジカル試験液１０ｍｌを注入する。
（４）上部をシールした後、十分に振とうして静置する。時々振とうしながら液の色を観察する。ラジカルが減少すれば、紫色が薄くなる。
（５）紫色が薄くなり、加工および未加工布帛（又は、綿１００％染色堅牢度試験添付布）で明確な色差が確認できれば、抗酸化性ＤＰＰＨラジカル消去能ありと判定した（２４時間以内）。
２．抗酸化性（Ｈ2Ｏ2法）
測定手順は以下のとおりである。
（１）１質量％の過酸化水素液を調製する。
（２）加工および未加工布帛を１ｃｍ×１ｃｍの大きさに裁断し試験管に採取する。サンプル数はｎ＝２とする。
（３）上記の試験管へ過酸化水素液１０ｍｌを注入し、静置する。
（４）加工および未加工布帛で明確な泡の出方に差が確認できれば、抗酸化性ありと判定した（２４時間以内）。（効果があれば、通常は多量の泡により浮上する。）
（実施例１）
（１）白金ナノ粒子
白金ナノ粒子が平均粒径２ｎｍ（電子顕微鏡（ＳＥＭ）写真による判定）で、保護剤としてポリビニルピロリドン（ＰＶＰ）を使用し、その質量比を白金ナノ粒子１に対して０．５〜２の範囲で変化させた白金ナノコロイド液を準備した。また、白金ナノコロイドを作成する際には、酸根などが残らないように精製し、イオン性物質はない状態にしている。性状は淡黒色液体であり、水に易溶であった。この白金ナノ粒子の濃度は２００ｐｐｍであった。
（２）布帛への担持
染色後の織物生地（綿１００質量％、綿番手３０番、平織組織、目付け１２０ｇ／ｍ2）に対し、吸尽法担持処理−水洗−遠心脱水−乾燥（７０℃、３０分）を行い、白金ナノ粒子を担持させた。担持処理条件は、浴比を布帛：処理液＝１：３０とし、温度は５０℃、時間２０分とした。得られた布帛の評価結果と併せて表１に示す。
Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example.
1. Antioxidant (DPPH method)
When analyzing antioxidant properties in vitro (in vitro), it is known that the method using DPPH radical reagent is highly convenient. In this example, a 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging method was used. The measurement procedure is as follows.
(1) Preparation of DPPH radical test solution A DPPH 25 μM (micromolar) alcohol solution is prepared. The liquid is purple.
(2) After collecting a 5 cm × 5 cm size of processed and unprocessed fabric, it is cut into small pieces and put into a test tube. The number of samples is n = 2.
(3) Inject 10 ml of DPPH radical test solution into the above colorimetric tube.
(4) After sealing the upper part, shake it well and leave it to stand. Observe the color of the liquid with occasional shaking. As radicals decrease, the purple color fades.
(5) If the purple color becomes thin and a clear color difference can be confirmed between the processed and unprocessed fabric (or the fabric attached to the 100% cotton dyeing fastness test), it is determined that the antioxidant DPPH radical can be eliminated (within 24 hours). .
2. Antioxidant (H 2 O 2 method)
The measurement procedure is as follows.
(1) A 1% by mass hydrogen peroxide solution is prepared.
(2) The processed and unprocessed fabric is cut into a size of 1 cm × 1 cm and collected in a test tube. The number of samples is n = 2.
(3) Inject 10 ml of hydrogen peroxide solution into the above test tube and leave it to stand.
(4) If there was a difference in the way bubbles were clearly formed between the processed and unprocessed fabrics, it was determined that there was an antioxidant property (within 24 hours). (If it is effective, it usually floats with a lot of bubbles.)
Example 1
(1) Platinum nanoparticle The platinum nanoparticle has an average particle diameter of 2 nm (determined by an electron microscope (SEM) photograph), polyvinylpyrrolidone (PVP) is used as a protective agent, and its mass ratio is 0 with respect to the platinum nanoparticle 1. A platinum nanocolloid solution changed in the range of 5 to 2 was prepared. Moreover, when producing platinum nanocolloid, it refine | purifies so that an acid radical etc. may not remain, and it is set as the state without an ionic substance. The property was a light black liquid and was easily soluble in water. The concentration of the platinum nanoparticles was 200 ppm.
(2) woven fabric after carrying staining the fabric (100% by weight of cotton, cotton count No.30, plain weave, basis weight 120 g / m 2) with respect to, the exhaust process carried process - washing - centrifugal dehydration - drying (70 ° C. , 30 minutes), and platinum nanoparticles were supported. The supporting treatment conditions were such that the bath ratio was fabric: treatment liquid = 1: 30, the temperature was 50 ° C., and the time was 20 minutes. It shows in Table 1 together with the evaluation result of the obtained fabric.
（備考）owfはon the weight of fiberの略。 (Remarks) owf is an abbreviation for on the weight of fiber.
表１から、実験番号１〜７の布帛は、抗酸化性が合格であった。この布帛を男性用下着に縫製し、２０〜４０歳台の男性１０名に着用試験してもらったところ、いずれも着心地が良く、肌荒れもないとの感想を得た。又、実験番号８の布帛は、抗酸化性は合格であるものの、コストが非常に高くなる傾向になった。 From Table 1, the fabrics of Experiment Nos. 1 to 7 passed the antioxidant property. This fabric was sewed on male underwear and subjected to a wear test by 10 males in the 20 to 40-year-old range, and they all felt that they were comfortable and there was no rough skin. Moreover, although the fabric of experiment number 8 passed the antioxidant property, the cost tended to be very high.
（実施例２）
（１）白金ナノ粒子
実施例１と同様の白金ナノコロイド液を準備した。
（２）女性用下着への担持
女性用下着（組成が綿５０％、ナイロン４０％、ポリウレタン１０％、綿番手で６０番相当、フライス編、目付け２００ｇ／ｍ2）に対し、染色処理後、吸尽法担持処理−水洗−遠心脱水−乾燥（７０℃ ３０分）を行い、白金ナノ粒子を担持させた。担持処理条件は、実施例１と同様とした。得られた女性用下着の評価結果と併せて表２に示す。
(Example 2)
(1) Platinum nanoparticle The same platinum nanocolloid liquid as Example 1 was prepared.
(2) Carrying on women's underwear For women's underwear (composition 50% cotton, nylon 40%, polyurethane 10%, cotton count equivalent to No. 60, milling knitting, basis weight 200 g / m 2 ) Exhaust method supporting treatment—washing with water—centrifugal dehydration—drying (70 ° C., 30 minutes) was performed to support platinum nanoparticles. The supporting treatment conditions were the same as in Example 1. It shows in Table 2 together with the evaluation result of the obtained underwear for women.
表２から、実験番号１〜３の女性用下着は、抗酸化性が合格であった。又、洗濯１０回後（１０３法）の抗酸化性も合格であった。 From Table 2, the underwear for women of Experiment Nos. 1-3 passed the antioxidant property. Further, the antioxidant property after 10 washings (103 method) was also acceptable.
（比較例１）
（１）白金ナノ粒子
白金ナノ粒子が平均粒径２ｎｍ（電子顕微鏡（ＳＥＭ）写真による判定）で、保護剤としてポリビニルピロリドン（ＰＶＰ）を使用し、その質量比を白金ナノ粒子１に対して０．３及び３の白金ナノコロイド液を準備した。また、白金ナノコロイドを作成する際には、酸根などが残らないように精製し、イオン性物質はない状態にしている。性状は淡黒色液体であり、水に易溶であった。この白金ナノ粒子の濃度は２００ｐｐｍであった。
（２）布帛への担持
布帛として、実施例１と同様の布帛を使用し、実施例１と同様に白金ナノ粒子を担持させた。繰り返し３回実施した。得られた布帛の評価結果と併せて表３に示す。
(Comparative Example 1)
(1) Platinum nanoparticles The platinum nanoparticles have an average particle diameter of 2 nm (determined by an electron microscope (SEM) photograph), polyvinyl pyrrolidone (PVP) is used as a protective agent, and the mass ratio thereof is 0 with respect to the platinum nanoparticles 1. 3 and 3 platinum nanocolloid solutions were prepared. Moreover, when producing platinum nanocolloid, it refine | purifies so that an acid radical etc. may not remain, and it is set as the state without an ionic substance. The property was a light black liquid and was easily soluble in water. The concentration of the platinum nanoparticles was 200 ppm.
(2) Supporting to fabric The same fabric as in Example 1 was used as the fabric, and platinum nanoparticles were supported in the same manner as in Example 1. Repeated three times. It shows in Table 3 together with the evaluation result of the obtained fabric.
表３から、実験番号１（比較例）は、白金ナノ粒子１質量部に対してポリビニルピロリドン（ＰＶＰ）が０．５質量部未満であったのでコロイドが安定せず、白金ナノ粒子の凝集・沈殿が起こりやすく、抗酸化性がばらつくため、合格とは認められなかった。また、実験番号２（比較例）も抗酸化性がばらつくため、合格とは認められなかった。 From Table 3, experiment number 1 (comparative example) shows that the colloid is not stable because polyvinylpyrrolidone (PVP) was less than 0.5 parts by mass with respect to 1 part by mass of the platinum nanoparticles, and the aggregation / Precipitation was likely to occur and the antioxidant properties varied, so it was not accepted. In addition, Experiment No. 2 (Comparative Example) was not accepted as the antioxidation property varied.
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| WO2021241551A1 (en) * | 2020-05-26 | 2021-12-02 | 株式会社荏原製作所 | Metal-supporting nonwoven fabric and production method thereof, catalyst, unsaturated compound hydrogenation method, and carbon-carbon bond forming method |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04313340A (en) * | 1991-04-12 | 1992-11-05 | Toda Kogyo Corp | Noble metal hydrosol and its production |
| JP2000051848A (en) * | 1998-08-05 | 2000-02-22 | Nippon Denshi Keiraku Kenkokai:Kk | Ceramic powder, thread, cloth, molded item, water quality improver, and soil conditioner |
| JP2001114671A (en) * | 1999-10-15 | 2001-04-24 | Otsuka Yakuhin Kogyo Kk | Cataplasm |
| JP2004162223A (en) * | 2002-11-15 | 2004-06-10 | Katsuhiro Yoshie | Negative ion generation material |
| JP2005245258A (en) * | 2004-03-02 | 2005-09-15 | Shetech:Kk | Filter tip containing platinum nano particles, and smoking object having the filter tip or solution of platinum nanoparticles |
| JP2005281637A (en) * | 2004-03-31 | 2005-10-13 | Fukui Prefecture | Anti-oxidizing agent |
| JP2006035205A (en) * | 2004-06-25 | 2006-02-09 | Mitsubishi Materials Corp | Stable metal colloid and usage of the same |
| JP2008178295A (en) * | 2001-02-23 | 2008-07-31 | Black & Decker Inc | Cylinder/magneto assembly for field assemblies of electric device, its manufacturing method, and electric motor and power tool in which cylinder/magneto assembly have been arranged |
-
2008
- 2008-01-18 JP JP2008009442A patent/JP4928475B2/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04313340A (en) * | 1991-04-12 | 1992-11-05 | Toda Kogyo Corp | Noble metal hydrosol and its production |
| JP2000051848A (en) * | 1998-08-05 | 2000-02-22 | Nippon Denshi Keiraku Kenkokai:Kk | Ceramic powder, thread, cloth, molded item, water quality improver, and soil conditioner |
| JP2001114671A (en) * | 1999-10-15 | 2001-04-24 | Otsuka Yakuhin Kogyo Kk | Cataplasm |
| JP2008178295A (en) * | 2001-02-23 | 2008-07-31 | Black & Decker Inc | Cylinder/magneto assembly for field assemblies of electric device, its manufacturing method, and electric motor and power tool in which cylinder/magneto assembly have been arranged |
| JP2004162223A (en) * | 2002-11-15 | 2004-06-10 | Katsuhiro Yoshie | Negative ion generation material |
| JP2005245258A (en) * | 2004-03-02 | 2005-09-15 | Shetech:Kk | Filter tip containing platinum nano particles, and smoking object having the filter tip or solution of platinum nanoparticles |
| JP2005281637A (en) * | 2004-03-31 | 2005-10-13 | Fukui Prefecture | Anti-oxidizing agent |
| JP2006035205A (en) * | 2004-06-25 | 2006-02-09 | Mitsubishi Materials Corp | Stable metal colloid and usage of the same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021241551A1 (en) * | 2020-05-26 | 2021-12-02 | 株式会社荏原製作所 | Metal-supporting nonwoven fabric and production method thereof, catalyst, unsaturated compound hydrogenation method, and carbon-carbon bond forming method |
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