JP2006132059A - Animal hair fiber product - Google Patents
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- JP2006132059A JP2006132059A JP2004325240A JP2004325240A JP2006132059A JP 2006132059 A JP2006132059 A JP 2006132059A JP 2004325240 A JP2004325240 A JP 2004325240A JP 2004325240 A JP2004325240 A JP 2004325240A JP 2006132059 A JP2006132059 A JP 2006132059A
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- 229920000642 polymer Polymers 0.000 claims abstract description 27
- NJNWCIAPVGRBHO-UHFFFAOYSA-N 2-hydroxyethyl-dimethyl-[(oxo-$l^{5}-phosphanylidyne)methyl]azanium Chemical group OCC[N+](C)(C)C#P=O NJNWCIAPVGRBHO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000470 constituent Substances 0.000 claims abstract description 3
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- 239000011347 resin Substances 0.000 claims description 13
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- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 7
- 239000004952 Polyamide Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 6
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- 239000004753 textile Substances 0.000 claims description 6
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
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- 238000005406 washing Methods 0.000 abstract description 15
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- ZJXZSIYSNXKHEA-UHFFFAOYSA-N ethyl dihydrogen phosphate Chemical compound CCOP(O)(O)=O ZJXZSIYSNXKHEA-UHFFFAOYSA-N 0.000 abstract description 2
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- 238000011156 evaluation Methods 0.000 description 6
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- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- 206010015150 Erythema Diseases 0.000 description 4
- -1 azetidinium cation Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
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- 241001494479 Pecora Species 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 239000002085 irritant Substances 0.000 description 2
- 231100000021 irritant Toxicity 0.000 description 2
- QAVIDTFGPNJCCX-UHFFFAOYSA-N n'-(2-aminoethyl)ethane-1,2-diamine;2-(chloromethyl)oxirane;hexanedioic acid Chemical compound ClCC1CO1.NCCNCCN.OC(=O)CCCCC(O)=O QAVIDTFGPNJCCX-UHFFFAOYSA-N 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
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- ZSZRUEAFVQITHH-UHFFFAOYSA-N 2-(2-methylprop-2-enoyloxy)ethyl 2-(trimethylazaniumyl)ethyl phosphate Chemical compound CC(=C)C(=O)OCCOP([O-])(=O)OCC[N+](C)(C)C ZSZRUEAFVQITHH-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 241000282836 Camelus dromedarius Species 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000005529 alkyleneoxy group Chemical group 0.000 description 1
- 210000000077 angora Anatomy 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- CEJLBZWIKQJOAT-UHFFFAOYSA-N dichloroisocyanuric acid Chemical compound ClN1C(=O)NC(=O)N(Cl)C1=O CEJLBZWIKQJOAT-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 210000000245 forearm Anatomy 0.000 description 1
- 238000009975 hank dyeing Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 210000000050 mohair Anatomy 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000001953 sensory effect Effects 0.000 description 1
- 208000017520 skin disease Diseases 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 230000003813 thin hair Effects 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000009969 top dyeing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009970 yarn dyeing Methods 0.000 description 1
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- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は肌に接する衣料に適した獣毛繊維製品に関する。 The present invention relates to an animal hair fiber product suitable for clothing that contacts the skin.
肌に接する衣服には吸放湿性や肌触りなどの快適性のほか、十分な安全性が求められている。しかし、時には衣服が皮膚障害の原因となるケースがあり、下記非特許文献１には、その原因は物理的刺激または化学的刺激であることが示されている。従って、安全な衣服を得るためこれらの原因を取り除くことが強く求められている。羊毛等の獣毛繊維は、吸放湿性が大きいことや人間の肌に近いケラチン蛋白からできているなど肌に接する衣料に適した性質を持っていることは良く知られている（下記非特許文献１）。 Clothes that come into contact with the skin are required to have sufficient safety in addition to comfort such as moisture absorption and desorption. However, there are cases where clothes cause skin disorders, and Non-Patent Document 1 below shows that the cause is physical stimulation or chemical stimulation. Therefore, there is a strong demand to eliminate these causes in order to obtain safe clothing. It is well known that animal hair fibers such as wool have properties suitable for clothing that touches the skin, such as high moisture absorption and release and made of keratin protein close to human skin. Reference 1).
羊毛は、一般にチクチク感といわれる物理的刺激のために肌に接する衣料での使用は限られている。チクチク感は、原料繊維の繊度に大きく影響を受け、繊度が小さくなるほど減少し、平均平均直径２０．０μｍ以下では少なくなることが下記非特許文献２に報告されている。しかし、２０．０μｍ以下の獣毛を用いても物理的な刺激抑制に効果があるだけで、化学的な刺激から肌を保護する効果は得られない。一方、近年刺激物質から肌を保護する効果がある繊維処理剤の研究開発が行われており、特許文献１〜５にはホスホリルコリン基含有単量体及び重合体を主成分とする繊維処理剤及び処理方法が開示されている。しかし、これらの方法で獣毛繊維を処理した場合、バインダー樹脂を併用しないと処理剤が洗濯により容易に脱落する問題があった。洗濯耐久性を向上させるためにバインダー樹脂を併用する場合は、風合いが硬化するという問題があった。
本発明は前記従来の問題を改善し、肌に対する物理的及び化学的な刺激の抑制効果があり、洗濯耐久性を有し、かつ風合いの良好な、肌に接する衣料に適した獣毛繊維製品を提供する。 The present invention improves the above-mentioned conventional problems, has an effect of suppressing physical and chemical irritation to the skin, has washing durability, and has a good texture, and is suitable for clothing that touches the skin. I will provide a.
本発明の獣毛繊維製品は、構成繊維の平均直径が２０．０μｍ以下の獣毛繊維を含む繊維製品であって、前記獣毛繊維を親水化した後に、ホスホリルコリン基含有重合体を前記獣毛繊維表面に固定したことを特徴とする。 The animal hair fiber product of the present invention is a fiber product including animal hair fibers having an average diameter of constituent fibers of 20.0 μm or less, and after hydrophilizing the animal hair fibers, the phosphorylcholine group-containing polymer is added to the animal hair. It is fixed to the fiber surface.
本発明は平均直径２０．０μｍ以下の獣毛繊維を原料とすることで肌への物理的刺激を抑制すると同時に、前記獣毛繊維を親水化した後にホスホリルコリン基含有重合体を前記獣毛繊維に固定したことにより、肌に対する物理的及び化学的な刺激の抑制効果があり、洗濯耐久性を有し、かつ風合いも良好で、肌に接する衣料に適した獣毛繊維製品を提供できる。 The present invention uses animal hair fibers having an average diameter of 20.0 μm or less as a raw material to suppress physical irritation to the skin, and at the same time, hydrophilizes the animal hair fibers and then converts the phosphorylcholine group-containing polymer into the animal hair fibers. By fixing, it has the effect of suppressing physical and chemical irritation to the skin, has washing durability, has a good texture, and can provide an animal hair fiber product suitable for clothing touching the skin.
本発明は、獣毛繊維を含む繊維製品である。獣毛繊維は２０重量％含まれているのが好ましく、より好ましくは３０重量％以上である。獣毛繊維１００重量％製品はもちろん含まれる。本発明の獣毛繊維製品とは、ウール・カシミヤ・モヘヤ・キャメル・アンゴラ等の毛繊維を含有する製品をいう。他の繊維と混紡する場合は、ポリエステル繊維、ナイロン繊維、アクリル系繊維等の合成繊維、レーヨン等の化学繊維、コットン、麻、絹等の天然繊維を使用できる。 The present invention is a textile product containing animal hair fibers. The animal hair fiber is preferably contained in an amount of 20% by weight, more preferably 30% by weight or more. Of course, a 100% animal fiber product is included. The animal hair fiber product of the present invention refers to a product containing hair fibers such as wool, cashmere, mohair, camel, and angora. When blended with other fibers, synthetic fibers such as polyester fibers, nylon fibers and acrylic fibers, chemical fibers such as rayon, and natural fibers such as cotton, hemp and silk can be used.
獣毛繊維の平均直径は２０．０μｍ以下である。これにより、繊維が肌を物理的に刺激することはなく、チクチク感を防止できる。好ましい平均直径は１９．０μｍ以下である。平均直径は２０．０μｍ以下の獣毛繊維を選択するには、羊の場合、細い毛の取れる羊の種類を選択するのが好ましい。 The average diameter of animal hair fibers is 20.0 μm or less. Thereby, a fiber does not irritate | stimulate skin physically and it can prevent a tingling feeling. A preferred average diameter is 19.0 μm or less. In order to select animal hair fibers having an average diameter of 20.0 μm or less, in the case of sheep, it is preferable to select the kind of sheep that can take thin hair.
前記獣毛繊維は親水化した後に、ホスホリルコリン基含有重合体を表面に固定する。親水化により獣毛繊維に水酸基、カルボキシル基、スルホン酸基等の活性基が付与されるか又は内部から現れ、前記活性基にホスホリルコリン基含有重合体がイオン結合などにより固定される。親水化前の未処理羊毛の臨界表面張力は約４５dyne/cmであるが、親水化処理後の好ましい臨界表面張力は５０dyne/cmが好ましく、さらに好ましくは６０dyne/cm以上、特に好ましくは約６５dyne/cm以上である。 After the animal hair fibers are hydrophilized, the phosphorylcholine group-containing polymer is fixed to the surface. Hydrophilicity imparts an active group such as a hydroxyl group, a carboxyl group, or a sulfonic acid group to the animal hair fiber, or appears from the inside, and the phosphorylcholine group-containing polymer is fixed to the active group by an ionic bond or the like. The critical surface tension of untreated wool before hydrophilization is about 45 dyne / cm, but the preferred critical surface tension after hydrophilization is preferably 50 dyne / cm, more preferably 60 dyne / cm or more, particularly preferably about 65 dyne / cm. More than cm.
前記親水化は、前記獣毛製品を塩素系化合物、モノ過硫酸、過マンガン酸塩及びオゾンから選ばれる少なくとも一つによる酸化によるものが好ましい。この酸化により、獣毛繊維の少なくとも外皮エピクチクル層が除去され、エキソチクル層又はエンドチクル層が現れる。このエキソチクル層又はエンドチクル層に含まれる活性基にホスホリルコリン基含有重合体をイオン結合などにより固定してもよい。別な方法としては、前記酸化の後に、前記獣毛繊維にポリアミドエピクロルヒドリン樹脂を共有結合し防縮処理した後に、ホスホリルコリン基含有重合体をイオン結合などにより固定してもよい。 The hydrophilization is preferably performed by oxidizing the animal hair product with at least one selected from a chlorine compound, monopersulfuric acid, permanganate and ozone. This oxidation removes at least the epidermal layer of animal hair fibers and reveals an exolayer or an endicle layer. The phosphorylcholine group-containing polymer may be fixed to the active group contained in the exoicle layer or the endicle layer by ionic bonding or the like. As another method, after the oxidation, a polyamide epichlorohydrin resin may be covalently bonded to the animal hair fiber and subjected to shrinkage treatment, and then the phosphorylcholine group-containing polymer may be fixed by ionic bonding or the like.
別の親水化は、アルカリ性水溶液による処理である。 Another hydrophilization is treatment with an alkaline aqueous solution.
さらに別の親水化は、低温プラズマ及びコロナ放電から選ばれる少なくとも一つによる放電である。この処理の場合は、外皮エピクチクル層の分子が分断され、活性基が付与される。 Yet another hydrophilization is discharge by at least one selected from low-temperature plasma and corona discharge. In the case of this treatment, molecules of the outer epidermal layer are fragmented and active groups are imparted.
本発明において親水化処理自体は知られており、例えば改森道信，「染色工業」Ｖｏｌ．４１，Ｎｏ．７，３４７−３５６頁，１９９３年に記載されている表面改質方法の中で、過マンガン酸塩、モノ過硫酸、アルカリ性水溶液による処理法や塩素化法、酸化法、塩素化／樹脂法等の防縮加工方法がある。また、唐川忠志，梅原亮，「繊維機械学会誌」Ｖｏｌ．５５，Ｎｏ．９，３４０−３４４頁，２００２年に記載されているオゾン法、改森道信，「染色工業」Ｖｏｌ．４１，Ｎｏ．１１，５６６−５６９頁，１９９３年に記載されている脱スケール法及び改森道信，「染色工業」Ｖｏｌ．４１，Ｎｏ．１１，５６９−５７７頁，１９９３年に記載されている低温プラズマ処理やコロナ放電処理を使用できる。 In the present invention, the hydrophilization treatment itself is known. For example, Michinobu Kaimori, “Dyeing Industry” Vol. 41, no. 7, 347-356, 1993, surface modification methods described in 1993, treatment methods with permanganate, monopersulfuric acid, alkaline aqueous solution, chlorination method, oxidation method, chlorination / resin method, etc. There is a shrink-proofing method. Also, Tadashi Karagawa and Ryo Umehara, “Journal of the Textile Machinery Society” Vol. 55, no. 9, pp. 340-344, 2002, the ozone method, Michinobu Kaimori, “Dyeing Industry” Vol. 41, no. 11, pages 566-569, 1993, descaling method and Michinobu Kaimori, “Dyeing Industry” Vol. 41, no. 11, 569-577, 1993, low temperature plasma treatment and corona discharge treatment can be used.
本発明のホスホリルコリン基含有重合体を主成分とする繊維処理剤自体も知られており、例えば、日本油脂株式会社製"Lipidure"（商品名）で各種グレードが市販されている。 The fiber treating agent itself containing the phosphorylcholine group-containing polymer of the present invention as a main component is also known, and various grades are commercially available, for example, “Lipidure” (trade name) manufactured by NOF Corporation.
上記繊維処理剤の処理装置は浸漬処理の可能な装置であれば何でも良く、製品の形態に応じ、トップ染め機、かせ染め機、糸染め機、反染め機等の一般的な染色機を用いることができる。浴比は１：１０〜１：３０が好ましいが、処理装置の形態次第でどのような浴比でも処理することはできる。 The fiber treatment agent treatment apparatus may be any apparatus capable of immersion treatment, and a general dyeing machine such as a top dyeing machine, a skein dyeing machine, a yarn dyeing machine, or an anti-dyeing machine is used according to the form of the product. be able to. The bath ratio is preferably 1:10 to 1:30, but any bath ratio can be used depending on the form of the processing apparatus.
ホスホリルコリン基含有重合体の使用濃度は０．１％ｏｗｆ〜５０％ｏｗｆ（owfはon the weight of fiberの略）の範囲が好ましく、コストと効果を考えると２％ｏｗｆ〜１０％ｏｗｆの範囲がより好ましい。 The concentration of the phosphorylcholine group-containing polymer is preferably in the range of 0.1% owf to 50% owf (owf is an abbreviation for on the weight of fiber), and considering the cost and effect, the range is 2% owf to 10% owf. More preferred.
処理温度は２５℃〜６０℃が好ましい。処理温度が低すぎると、年間を通してエネルギー的に安価にかつ安定して処理を行うのが困難であるし、高すぎるとホスホリルコリン基含有重合体の吸着が低下する。また、処理ｐＨは４〜１１が好ましく、低すぎると吸着が低下し、高すぎると獣毛繊維の品質が劣化する。 The treatment temperature is preferably 25 ° C to 60 ° C. If the treatment temperature is too low, it is difficult to carry out the treatment inexpensively and stably throughout the year, and if it is too high, the adsorption of the phosphorylcholine group-containing polymer decreases. Further, the treatment pH is preferably 4 to 11, and if it is too low, the adsorption is lowered, and if it is too high, the quality of the animal hair fiber is deteriorated.
本発明により洗濯耐久性に優れた皮膚刺激抑制効果が得られる理由は十分解明するに至っていないが、概ね次のように考えられる。即ち、疎水性の獣毛の表面を改質し親水化することにより繊維表面にカルボキシル基、スルホン酸基又は水酸基が露出する。これらの活性基は等電点以上のｐＨでイオン化し負電荷を持つ。一方、ホスホリルコリン基含有重合体の第４級アンモニウム基は正電荷を持つ。従って、親水化された獣毛繊維とホスホリルコリン基含有重合体は第４級アンモニウム塩となり、イオン的に強固に結合し、高い洗濯耐久性が得られると考えられる。 The reason why the skin irritation inhibitory effect excellent in washing durability can be obtained by the present invention has not been fully elucidated, but is generally considered as follows. That is, by modifying and hydrophilizing the surface of hydrophobic animal hair, a carboxyl group, a sulfonic acid group or a hydroxyl group is exposed on the fiber surface. These active groups are ionized at a pH higher than the isoelectric point and have a negative charge. On the other hand, the quaternary ammonium group of the phosphorylcholine group-containing polymer has a positive charge. Therefore, it is considered that the animal hair fiber and the phosphorylcholine group-containing polymer that have been hydrophilized become a quaternary ammonium salt, and are strongly ionically bonded to obtain high washing durability.
前記繊維製品は、綿、トップ、糸、織物、編物、フェルト及び不織布から選ばれる少なくとも一つであることが好ましい。 The fiber product is preferably at least one selected from cotton, top, yarn, woven fabric, knitted fabric, felt and non-woven fabric.
前記繊維製品は、肌に直接又は間接に接触する用途に好適であり、スポーツ衣料品、肌着、シャツ、手袋、靴下又は寝具等に使用するのが好ましい。 The textile product is suitable for use in direct or indirect contact with the skin, and is preferably used for sports clothing, underwear, shirts, gloves, socks or bedding.
（実施の形態）
図１に非特許文献１の995頁に記載されている羊毛繊維の構造を示す。本発明の一実施形態においては、塩素化処理により、疎水性の高い脂肪酸のエピクチクル層を除去する。一部エキソクチクル層を除去しても良い。この処理により、下記化学式１〜２に示すような反応が起こり、ペプタイド結合が開裂してカルボキシル基（−ＣＯＯＨ）とアミノ基（−ＮＨ2）が形成され、ジサルファイド結合の酸化によりスルホン酸基（−ＳＯ3Ｈ）が形成される。
(Embodiment)
FIG. 1 shows the structure of the wool fiber described on page 995 of Non-Patent Document 1. In one embodiment of the present invention, the highly hydrophobic fatty acid epiicle layer is removed by chlorination. A portion of the exoicle layer may be removed. By this treatment, reactions as shown in the following chemical formulas 1 and 2 occur, the peptide bond is cleaved to form a carboxyl group (—COOH) and an amino group (—NH 2 ), and a sulfonic acid group is formed by oxidation of the disulfide bond. (-SO 3 H) is formed.
本発明ではこの状態でホスホリルコリン基含有重合体を結合させても良い。また、次に説明するようにポリアミドエピクロルヒドリン樹脂を結合させて防縮処理した後にホスホリルコリン基含有重合体を結合させても良い。 In the present invention, the phosphorylcholine group-containing polymer may be bound in this state. Further, as will be described below, after the polyamide epichlorohydrin resin is bonded and subjected to an anti-shrink treatment, the phosphorylcholine group-containing polymer may be bonded.
前記カルボキシル基（−ＣＯＯＨ）とスルホン酸基（−ＳＯ3Ｈ）はｐＨが６．５を超えるとイオン化し、負に帯電する。この負に帯電した基は、下記化学式３に示すようにポリアミドエピクロルヒドリン樹脂等のカチオン性樹脂を繊維表面に引き付け結合する。 The carboxyl group (—COOH) and the sulfonic acid group (—SO 3 H) are ionized and negatively charged when the pH exceeds 6.5. The negatively charged group attracts and bonds a cationic resin such as polyamide epichlorohydrin resin to the fiber surface as shown in the following chemical formula 3.
ペプタイド結合の開烈により生成したアミノ基（−ＮＨ2）は、ポリアミドエピクロルヒドリン樹脂を構成しているアゼチジニウムカチオンと反応し、共有結合を形成する。さらに羊毛のチオール基（−ＳＨ）もアゼチジニウムカチオンと共有結合を形成する。またジサルファイド結合、ペプタイド結合の開裂によって生成したカルボキシル基とスルホン酸基もアゼチジニウムカチオンと共有結合を形成する。 The amino group (—NH 2 ) generated by the cleavage of the peptide bond reacts with the azetidinium cation constituting the polyamide epichlorohydrin resin to form a covalent bond. In addition, the wool thiol group (-SH) also forms a covalent bond with the azetidinium cation. In addition, carboxyl groups and sulfonic acid groups generated by cleavage of disulfide bonds and peptide bonds also form covalent bonds with azetidinium cations.
前記防縮加工に用いるポリアミドエピクロルヒドリン樹脂は、ディックハーキュレス社製、商品名“ハーコセット(Hercosett) 57”又は東邦化学工業社製、商品名“ポーラミン(Pollamin) E-10"として販売されている。“ハーコセット(Hercosett) 57”の構造式を下記化学式５に示す。 The polyamide epichlorohydrin resin used for the shrink-proofing process is sold under the trade name “Hercosett 57” manufactured by Dick Hercules Co., Ltd. or the trade name “Pollamin E-10” manufactured by Toho Chemical Industry Co., Ltd. The structural formula of “Hercosett 57” is shown in Chemical Formula 5 below.
次に本発明で使用するホスホリルコリン基含有重合体を下記化学式６に示す。このホスホリルコリン基含有重合体は、日本油脂株式会社製"Lipidure"（商品名）で各種グレードが市販されている。 Next, the phosphorylcholine group-containing polymer used in the present invention is shown in the following chemical formula 6. Various grades of this phosphorylcholine group-containing polymer are commercially available from Nippon Oil & Fats Co., Ltd. “Lipidure” (trade name).
（但し、Ｘは−ＣＯＯ−，−Ｏ−，−Ｃ6Ｈ4−等の２価の有機残基、Ｙは炭素数１〜６のアルキレンオキシ基、Ｚは水素原子もしくはＲ5−Ｏ−（Ｃ＝Ｏ）−（但し、Ｒ5は炭素数１〜１０のアルキル基又は炭素数１〜１０のヒドロキシアルキル基を示す。）、Ｒ1は水素原子もしくはメチル基を示す。Ｒ2，Ｒ3及びＲ4は同一もしくは異なる基であって、炭素数１〜６のアルキル基又はヒドロキシアルキル基を示す。ｍは０又は１，ｎは１〜４の整数である。）で表わされるホスホリルコリン類似基含有単量体（例えば２−[（メタ）アクリロイルオキシエチル−２’−（トリメチルアンモニオ）エチルホスフェート]）２０〜９０mol%と、メタクリル酸アルキルエステル等の疎水性単量体２〜８０mol%を重合して、平均分子量100,000〜2,000,000としたポリマーである。このポリマーは、２−メタクリロイルオキシエチルホスホリルコリンとも呼ばれる。 (Where X is a divalent organic residue such as —COO—, —O—, —C 6 H 4 —, Y is an alkyleneoxy group having 1 to 6 carbon atoms, Z is a hydrogen atom or R 5 —O— (C = O) - (. However, R 5 is showing a hydroxyalkyl group having 1 to 10 carbon alkyl group or C 1 to 10 carbon atoms), R 1 represents a hydrogen atom or a methyl group .R 2, R 3 and R 4 are the same or different groups and each represents an alkyl group or a hydroxyalkyl group having 1 to 6 carbon atoms, m is 0 or 1, and n is an integer of 1 to 4. Group-containing monomer (for example, 2-[(meth) acryloyloxyethyl-2 ′-(trimethylammonio) ethyl phosphate]) 20 to 90 mol% and hydrophobic monomer 2 to 80 mol% such as alkyl methacrylate ester And average molecular weight 100,000 to 2,000,000 It is a polymer. This polymer is also called 2-methacryloyloxyethyl phosphorylcholine.
次に、実施例により本発明を具体的に説明する。本発明は下記の実施例に限定されるものではない。
（１）物理的刺激の評価方法
物理的刺激（チクチク感）の評価は非特許文献２の方法に準拠した官能試験を用いた。判定者６人（女性３人、男性３人）が、温度２０℃、相対湿度６５％ＲＨの恒温恒湿室内で、試料を首や前腕に触れさせチクチク感を判定する。判定基準は下記の５段階基準とし、下記の計算式に従いチクチク指数を算出した。チクチク指数が低い方ほど物理的刺激が少ないことを意味する。
判定基準 評点
全くチクチクしない ０
わずかにチクチクする １
チクチクする ２
かなりチクチクする ３
強くチクチクする ４
チクチク指数＝総評点和／判定者数
（２）化学的刺激の評価方法
化学的刺激の評価は刺激物質を染込ませた試料を２４時間皮膚に貼り付けた後、剥離１時間後と２４時間後の皮膚の状態を観察するパッチテストを用いた。刺激物質としてＳＤＳ（ドデシル硫酸ナトリウム）の１．０％、３．０％水溶液を２０μＬ使用した。被験者は男性５人で下記の本邦基準に従い判定し、下記の計算式に従い皮膚刺激指数を算出した。皮膚刺激指数は低いほど皮膚刺激が低いことを意味する。
基準 反応 評点
− 反応なし ０
± わずかな紅斑 ０．５
＋ 明らかな紅斑 １．０
＋＋ 紅斑＋浮腫、丘疹 ２．０
＋＋＋ 紅斑＋浮腫、丘疹＋小水疱 ３．０
＋＋＋＋ 大水疱 ４．０
皮膚刺激指数＝総評点和／被験者数×１００
（３）洗濯耐久性評価方法
表面分析装置（ＥＳＣＡ）を用い表面に存在するリン原子を分析し、基質の炭素原子とリン原子の割合Ｐ／Ｃ値を求める。数値が高いほどホスホリルコリン基含有重合体の表面濃度が高いことを示す。洗濯はＪＩＳ Ｌ０２１７ １０５法に従い１０回繰り返し、洗濯前後でのＰ／Ｃ値を求めて耐久性を評価した。
（４）風合い評価
ＫＥＳ−Ｆ計測システムを用いて風合い評価を行った。ここでＫＥＳ−Ｆ計測システムとは、布の力学特性や風合いを評価する際に、当業界で一般的に行われている測定方法で、日本家政学会編「被服の資源と被服材料」、５７−８４頁、１９８９年１２月１０日、朝倉書店発行に記載されている。
Next, the present invention will be described specifically by way of examples. The present invention is not limited to the following examples.
(1) Evaluation Method of Physical Stimulation A sensory test based on the method of Non-Patent Document 2 was used for the evaluation of physical stimulation (feeling of tingling). Six assessors (three women and three men) judge the tingling sensation by touching the sample to the neck or forearm in a constant temperature and humidity chamber at a temperature of 20 ° C. and a relative humidity of 65% RH. The judgment criteria were the following five-step criteria, and the tingling index was calculated according to the following formula. A lower tingling index means less physical stimulation.
Judgment criteria Grade No tingling at all 0
Slightly tingling 1
Tingling 2
I feel pretty tingling 3
Strongly tingling 4
Tick index = sum of total scores / number of judges (2) Evaluation method of chemical irritation Chemical irritation is evaluated by applying a sample impregnated with an irritant to the skin for 24 hours, and then 1 hour after peeling and 24 hours. A patch test was used to observe the skin condition later. 20 μL of a 1.0% and 3.0% aqueous solution of SDS (sodium dodecyl sulfate) was used as a stimulating substance. The test subjects were five men and judged according to the following Japanese standards, and the skin irritation index was calculated according to the following formula. A lower skin irritation index means lower skin irritation.
Standard Response Score-No response 0
± slight erythema 0.5
+ Clear erythema 1.0
++ Erythema + edema, papules 2.0
+++ Erythema + Edema, papules + small blisters 3.0
++++ Great blister 4.0
Skin irritation index = total score / number of subjects × 100
(3) Washing durability evaluation method Phosphorus atoms present on the surface are analyzed using a surface analyzer (ESCA) to determine the ratio P / C value of carbon atoms and phosphorus atoms of the substrate. The higher the value, the higher the surface concentration of the phosphorylcholine group-containing polymer. Washing was repeated 10 times according to JIS L0217 105 method, and durability was evaluated by obtaining P / C values before and after washing.
(4) Texture evaluation Texture evaluation was performed using the KES-F measurement system. Here, the KES-F measurement system is a measurement method commonly used in the industry when evaluating the mechanical properties and texture of a fabric. The Japan Society for Home Economics “Clothing resources and clothing materials”, 57 -84, December 10, 1989, published by Asakura Shoten.
（実施例１）
平均繊維直径１８．５μｍの羊毛トップを有効塩素濃度２．０％ｏｗｆの次亜塩素酸ナトリウム溶液の槽に浸漬し、次いで重亜硫酸ナトリウム４％ｏｗｆ、酢酸４％ｏｗｆの槽で脱塩素処理を行い、水で洗浄した後、”ハーコセット１２５”（商品名、ポリアミドエピクロルヒドリン樹脂、ハーキュレス社製）２％ｏｗｆ、４０℃の槽に通して乾燥し、塩素化／樹脂防縮法による親水化羊毛トップを作成した。この親水化羊毛トップを原料とした糸番手２／８０、平織り、目付け１５０ｇ／ｍ2の羊毛１００％織物に”Ｌｉｐｉｄｕｒｅ ＣＦ７２”（商品名、日本油脂株式会社製）３％ｏｗｆ、浴比１：２０、ｐＨ６で３０℃３０分間処理を行った。処理後ホフマンプレス仕上げを行い、肌への刺激抑制効果をもつ織物を得た。
Example 1
A wool top having an average fiber diameter of 18.5 μm is dipped in a sodium hypochlorite solution bath having an effective chlorine concentration of 2.0% owf, and then dechlorinated in a bath of sodium bisulfite 4% owf and acetic acid 4% owf. After performing and washing with water, "Hercoset 125" (trade name, polyamide epichlorohydrin resin, Hercules Co., Ltd.) 2% owf, dried through a bath at 40 ° C, and dried the hydrophilic wool top by the chlorination / resin shrinkage method. Created. "Lipidure CF72" (trade name, manufactured by Nippon Oil & Fats Co., Ltd.) 3% owf, bath ratio 1: on yarn 100% wool fabric with a yarn count of 2/80, plain weave, and a basis weight of 150 g / m 2 Treatment at 30 ° C. for 30 minutes at 20, pH 6. After the treatment, a Hoffman press finish was performed to obtain a woven fabric having a skin irritation suppressing effect.
（実施例２）
平均繊維直径１８．５μｍ、糸番手２／８０、平織り、目付け１５０ｇ／ｍ2の羊毛１００％織物をユニテックス社の低温プラズマ加工機で反物速度１０ｍ／分で処理して親水化した後、”Ｌｉｐｉｄｕｒｅ ＣＦ７２”（商品名、日本油脂株式会社製）３％ｏｗｆ、浴比１：２０、ｐＨ６で３０℃３０分間処理を行った。処理後ホフマンプレス仕上げを行い、肌への刺激抑制効果をもつ織物を得た。
(Example 2)
A 100% wool fabric with an average fiber diameter of 18.5 μm, yarn count of 2/80, plain weave, and basis weight of 150 g / m 2 was treated with a low temperature plasma processing machine from Unitex at a fabric speed of 10 m / min to make it hydrophilic. CF72 ″ (trade name, manufactured by NOF Corporation) 3% owf, bath ratio 1:20, pH 6 and 30 ° C. for 30 minutes. After the treatment, a Hoffman press finish was performed to obtain a woven fabric having a skin irritation suppressing effect.
（実施例３）
実施例２で使用した平均繊度１８．５μｍの羊毛１００％織物を“ハイライト"（日産化学製、ジクロロイソシアヌル酸ナトリウム）５％ｏｗｆ、酢酸２％ｏｗｆ、浴比１：２０で４０℃、３０分間処理することで親水化した後、“Lipidure CF72"（日本油脂株式会社製）３％ｏｗｆ、浴比１：２０、ｐＨ５で３０℃、３０分間処理を行った。処理後ホフマンプレス仕上げを行い、肌への刺激抑制効果をもつ織物を得た。
(Example 3)
The 100% wool fabric with an average fineness of 18.5 μm used in Example 2 is “highlight” (Nissan Chemical, sodium dichloroisocyanurate) 5% owf, acetic acid 2% owf, bath ratio 1:20 at 40 ° C., 30 After hydrophilizing by treating for 30 minutes, treatment was performed at 30 ° C. for 30 minutes at “Lipidure CF72” (manufactured by NOF Corporation) 3% owf, bath ratio 1:20, pH 5. After the treatment, a Hoffman press finish was performed to obtain a woven fabric having a skin irritation suppressing effect.
（比較例１）
実施例２で用いた織物の未処理品を比較例１とした。
(Comparative Example 1)
The untreated fabric used in Example 2 was referred to as Comparative Example 1.
（比較例２）
実施例２で用いた織物に親水化処理を行わずに、“Lipidure CF72"（日本油脂株式会社製）３％ｏｗｆ、浴比１：２０、ｐＨ５で３０℃、３０分間処理を行った。処理後ホフマンプレス仕上げを行い、比較例２の織物を得た。
(Comparative Example 2)
The woven fabric used in Example 2 was treated with “Lipidure CF72” (manufactured by NOF Corporation) 3% owf, bath ratio 1:20, pH 5 at 30 ° C. for 30 minutes. After the treatment, Hoffman press finishing was performed to obtain a fabric of Comparative Example 2.
（比較例３）
塩素化／樹脂防縮法で親水化された平均繊度２１．５μｍの羊毛１００％織物に“Lipidure CF72"（日本油脂株式会社製）３％ｏｗｆ、浴比１：２０、ｐＨ５で３０℃、３０分間処理を行った。処理後ホフマンプレス仕上げを行い、比較例３の織物を得た。
(Comparative Example 3)
"Lipidure CF72" (manufactured by Nippon Oil & Fats Co., Ltd.) 3% owf, 100% wool fabric with an average fineness of 21.5μm, hydrophilized by chlorination / resin shrinkage method, bath ratio 1:20, pH 5 at 30 ° C, 30 minutes Processed. After the treatment, Hoffman press finishing was performed to obtain a fabric of Comparative Example 3.
（比較例４）
実施例１で用いた織物に“Lipidure MF3"（日本油脂株式会社製）５％（ｗ／ｗ）、“ガブセンＳＲ１５０"（ナガセケムテックス株式会社製・ポリエステル樹脂）２％（ｗ／ｗ）、絞り率６０％でパディング処理を行い、１５０℃で３分間キュアリングした。処理後ホフマンプレス仕上げを行い、比較例４の織物を得た。
(Comparative Example 4)
“Lipidure MF3” (manufactured by NOF Corporation) 5% (w / w), “Gabsen SR150” (manufactured by Nagase ChemteX Corporation / polyester resin) 2% (w / w), Padding was performed at a drawing ratio of 60%, and curing was performed at 150 ° C. for 3 minutes. After the treatment, a Hoffman press finish was performed to obtain a fabric of Comparative Example 4.
本発明の実施例１〜３と比較例１〜４の測定結果を表１〜２にまとめて示す。 The measurement result of Examples 1-3 of this invention and Comparative Examples 1-4 is put together in Tables 1-2, and is shown.
本発明の実施例１〜３、比較例１と比較例３のチクチク指数の結果より明らかなとおり、平均繊度が２０μｍ以下の実施例１〜３、比較例１は平均繊度が２０μｍ以上の比較例３より物理的刺激が抑制されていることが確認できた。 As is apparent from the results of the ticks index of Examples 1 to 3 and Comparative Examples 1 and 3 of the present invention, Examples 1 to 3 and Comparative Example 1 having an average fineness of 20 μm or less are Comparative Examples having an average fineness of 20 μm or more. 3 confirmed that physical stimulation was suppressed.
実施例１〜３、比較例３と比較例１の皮膚刺激指数の結果から、ホスホリルコリン基含有重合体処理を行った実施例１〜３、比較例３は行わなかった比較例１に比べて明らかに化学的皮膚刺激が抑制されていることが確認できた。 From the results of the skin irritation index of Examples 1 to 3, Comparative Example 3 and Comparative Example 1, it is clear that Examples 1 to 3 and Comparative Example 3 subjected to the phosphorylcholine group-containing polymer treatment were compared with Comparative Example 1 which was not performed. It was confirmed that chemical skin irritation was suppressed.
実施例１〜３と比較例２のＰ／Ｃ値（洗濯前後）の結果からは、親水化前処理を行った実施例１〜３は行わなかった比較例２に比べて、明らかにホスホリルコリン基含有重合体の初期吸着量及び洗濯後の残留が大きいこと、すなわち洗濯耐久性に優れることが確認できた。 From the results of the P / C values (before and after washing) of Examples 1 to 3 and Comparative Example 2, the phosphorylcholine group was clearly compared with Comparative Example 2 in which Examples 1 to 3 which had been subjected to hydrophilization pretreatment were not performed. It was confirmed that the initial adsorption amount of the contained polymer and the residue after washing were large, that is, the washing durability was excellent.
実施例１と比較例４のＫＥＳ測定値を比べると実施例１はバインダーを併用した比較例４に比べて明らかに、柔らかく柔軟な風合いであることが確認できた。 When the KES measurement values of Example 1 and Comparative Example 4 were compared, it was clearly confirmed that Example 1 had a soft and soft texture as compared with Comparative Example 4 in which a binder was used.
以上から本発明の平均直径２０．０μｍの獣毛繊維を原料とすることで肌への物理的刺激を抑制すると同時に、前記獣毛繊維を親水化した後にホスホリルコリン基含有重合体を前記獣毛繊維に固定したことにより、肌に対する物理的及び化学的な刺激の抑制効果があり、洗濯耐久性を有し、かつ風合いも良好で、肌に接する衣料に適した獣毛繊維製品が確認できた。 From the above, the animal hair fiber having an average diameter of 20.0 μm of the present invention is used as a raw material, and at the same time, physical stimulation to the skin is suppressed, and at the same time, the animal hair fiber is hydrophilized and then the phosphorylcholine group-containing polymer is converted to the animal hair fiber. As a result, it was possible to confirm an animal hair fiber product that has an effect of suppressing physical and chemical irritation to the skin, has washing durability, has a good texture, and is suitable for clothing in contact with the skin.
Claims (8)
前記獣毛繊維を親水化した後に、
ホスホリルコリン基含有重合体を前記獣毛繊維表面に固定したことを特徴とする獣毛繊維製品。 A fiber product comprising animal fibers having an average diameter of constituent fibers of 20.0 μm or less,
After hydrophilizing the animal hair fiber,
An animal hair fiber product, wherein a phosphorylcholine group-containing polymer is fixed to the surface of the animal hair fiber.
前記エピクチクル層より内層の表面に前記ホスホリルコリン基含有重合体を固定した請求項１〜４のいずれかに記載の獣毛繊維製品。 Removing at least the outer epidermal layer of animal hair fibers by the hydrophilization,
The animal hair fiber product according to any one of claims 1 to 4, wherein the phosphorylcholine group-containing polymer is fixed to the surface of the inner layer from the epicuticle layer.
The animal hair fiber product according to any one of claims 1 to 6, wherein the textile product is sports clothing, underwear, a shirt, gloves, socks, or bedding.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008202174A (en) * | 2007-02-21 | 2008-09-04 | Ist Corp | Water- and oil-repellent animal hair textile product |
| JP2009046619A (en) * | 2007-08-22 | 2009-03-05 | Nof Corp | Leather surface protective agent |
| JP2010037397A (en) * | 2008-08-01 | 2010-02-18 | Nissan Motor Co Ltd | Antifouling coating composition, coating film containing antifouling coating composition, method for forming coating film, and coated article |
| CN101424040B (en) * | 2008-10-28 | 2011-05-04 | 苏州大学 | Wool fiber modification treatment method |
| JP2017110132A (en) * | 2015-12-17 | 2017-06-22 | 国立大学法人室蘭工業大学 | Animal fiber molding and method for producing the same |
| CN108425237A (en) * | 2018-03-16 | 2018-08-21 | 浙江理工大学 | A kind of wool tops is without chlorine feld proofing technique |
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2004
- 2004-11-09 JP JP2004325240A patent/JP4369854B2/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008202174A (en) * | 2007-02-21 | 2008-09-04 | Ist Corp | Water- and oil-repellent animal hair textile product |
| JP2009046619A (en) * | 2007-08-22 | 2009-03-05 | Nof Corp | Leather surface protective agent |
| JP2010037397A (en) * | 2008-08-01 | 2010-02-18 | Nissan Motor Co Ltd | Antifouling coating composition, coating film containing antifouling coating composition, method for forming coating film, and coated article |
| CN101424040B (en) * | 2008-10-28 | 2011-05-04 | 苏州大学 | Wool fiber modification treatment method |
| JP2017110132A (en) * | 2015-12-17 | 2017-06-22 | 国立大学法人室蘭工業大学 | Animal fiber molding and method for producing the same |
| CN108425237A (en) * | 2018-03-16 | 2018-08-21 | 浙江理工大学 | A kind of wool tops is without chlorine feld proofing technique |
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