JP5536002B2 - Fabric, thread or floc surface treatment method - Google Patents
Fabric, thread or floc surface treatment method Download PDFInfo
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- JP5536002B2 JP5536002B2 JP2011207137A JP2011207137A JP5536002B2 JP 5536002 B2 JP5536002 B2 JP 5536002B2 JP 2011207137 A JP2011207137 A JP 2011207137A JP 2011207137 A JP2011207137 A JP 2011207137A JP 5536002 B2 JP5536002 B2 JP 5536002B2
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- 239000004744 fabric Substances 0.000 title claims description 28
- 238000000034 method Methods 0.000 title claims description 24
- 238000004381 surface treatment Methods 0.000 title claims description 9
- 235000015523 tannic acid Nutrition 0.000 claims description 51
- 229920002258 tannic acid Polymers 0.000 claims description 51
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 50
- 239000001263 FEMA 3042 Substances 0.000 claims description 50
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 50
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 50
- 229940033123 tannic acid Drugs 0.000 claims description 50
- 229920001864 tannin Polymers 0.000 claims description 40
- 235000018553 tannin Nutrition 0.000 claims description 40
- 239000001648 tannin Substances 0.000 claims description 40
- 239000007788 liquid Substances 0.000 claims description 29
- 239000000178 monomer Substances 0.000 claims description 21
- 229920001940 conductive polymer Polymers 0.000 claims description 16
- 239000011247 coating layer Substances 0.000 claims description 13
- 244000144992 flock Species 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 46
- 238000010306 acid treatment Methods 0.000 description 22
- 239000002657 fibrous material Substances 0.000 description 20
- 239000000835 fiber Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 229920002292 Nylon 6 Polymers 0.000 description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002759 woven fabric Substances 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 229920000128 polypyrrole Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920002770 condensed tannin Polymers 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 235000004515 gallic acid Nutrition 0.000 description 3
- 229940074391 gallic acid Drugs 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 229920000271 Kevlar® Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- -1 zirconium salt Chemical class 0.000 description 2
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- 101100087409 Arabidopsis thaliana RH18 gene Proteins 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 206010016807 Fluid retention Diseases 0.000 description 1
- 229920002670 Fructan Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012445 acidic reagent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229920001461 hydrolysable tannin Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Paints Or Removers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、フロック、糸、布帛（織物、不織布等）などの繊維素材の表面に導電性皮膜を形成するための表面処理方法に関する。 The present invention relates to a surface treatment method for forming a conductive film on the surface of a fiber material such as floc, yarn, and fabric (woven fabric, nonwoven fabric, etc.).
従来、繊維やフィルム等の表面にピロールを重合させて皮膜を形成し、導電性を得る方法が知られている（例えば、特許文献１〜３）。 Conventionally, a method is known in which pyrrole is polymerized on the surface of a fiber, a film, or the like to form a film to obtain conductivity (for example, Patent Documents 1 to 3).
特許文献１（特許第２９８６８５７号）は、ボビンに巻きつけた繊維基材を、ピロール（導電性高分子形成モノマー）と塩化第二鉄（酸化剤）とを含む処理液中に浸漬し、処理液中のモノマーが消失するか酸化剤の能力が消失するまで、処理液を循環させる方法を提案している。 Patent Document 1 (Patent No. 2986857) immerses a fiber substrate wound around a bobbin in a treatment liquid containing pyrrole (conductive polymer-forming monomer) and ferric chloride (oxidant), and treats the fiber substrate. A method of circulating the treatment liquid until the monomer in the liquid disappears or the ability of the oxidizing agent disappears is proposed.
特許文献２（特許第３２８４７０５号）は、短繊維を含む処理液中において、化学酸化重合剤（塩化第二鉄）を触媒として所望により添加されたドーパント，表面張力低下剤とともにピロールの重合反応を進行させる方法を提案している。 Patent Document 2 (Patent No. 3284705) discloses that a pyrrole polymerization reaction is carried out in a treatment liquid containing short fibers together with a dopant and a surface tension reducing agent which are optionally added using a chemical oxidation polymerization agent (ferric chloride) as a catalyst. Proposes a way to proceed.
特許文献３（特許第３６８２２３３号）は、樹脂フイルムの表面に、ピロールと樹脂バインダーとを含む塗料を塗布および乾燥して塗膜を形成し、さらに、この塗膜を有する樹脂フイルムを酸化性液体中に浸漬して酸化剤を作用させて塗膜中にポリピロールを生成させる導電性樹脂フイルム製造方法を提案している。 Patent Document 3 (Patent No. 3682233) discloses that a coating film is formed by applying and drying a coating containing pyrrole and a resin binder on the surface of a resin film, and further, the resin film having this coating film is formed into an oxidizing liquid. A method for producing a conductive resin film is proposed in which a polypyrrole is formed in a coating film by dipping in it to cause an oxidizing agent to act.
また、特許文献２（特許第３２８４７０５号）の従来技術に記載される様に、タンニン化合物の保水性を利用して表面の通電性を保つ方法も知られている（特許文献４〜７）。 In addition, as described in the prior art of Patent Document 2 (Patent No. 3284705), a method of maintaining the surface conductivity by utilizing the water retention of a tannin compound is also known (Patent Documents 4 to 7).
特許文献４（特許第３１７１６５４号）の実施例には、ポリエステル繊維の短繊維（パイル）を植毛に使用するために、パイル重量に対し０．５％のタンニン酸（フロクタンII：オムニケム社製）と９０％酢酸を、処理液１リットル当り１ミリリットルの割合で加えて作成した処理液を６０〜７０℃に保ち、この処理液中でパイルを約３０分間浸漬処理することで、６０メッシュの篩分選別機にかけたところ、通過率は９５％であったことが報告されている。 In Examples of Patent Document 4 (Patent No. 3171654), tannic acid of 0.5% with respect to the pile weight (Fructan II: manufactured by Omnichem) is used in order to use polyester short fibers (pile) for flocking. And 90% acetic acid added at a rate of 1 milliliter per liter of the treatment liquid, the treatment liquid prepared is kept at 60 to 70 ° C., and the pile is immersed in this treatment liquid for about 30 minutes to obtain a 60 mesh sieve. It has been reported that the passing rate was 95% when subjected to a fraction sorter.
特許文献５（特開平１１−２２９２７４）には、植毛密度が高く長期使用に耐える良質の導電性植毛製品を提供するために、ナイロン短繊維を染色した後、タンニン酸による電着処理（オムニケム社処方）を施して表面抵抗を１．０×１０８ ないし１．０×１０９ Ω／ｃｍに調整し、植毛用短繊維に加工し、アルミニウム管の表面に接着剤をスプレイコートし、静電植毛した植毛ロールを、ピロールと塩化鉄(III)を溶解して調合した導電処理液に浸漬し、回転させながら導電処理し、乾燥して帯電防止植毛ロールを製作する方法が記載されている。 In Patent Document 5 (Japanese Patent Laid-Open No. 11-229274), in order to provide a high-quality conductive flocking product having a high flocking density and withstanding long-term use, after short nylon fibers are dyed, electrodeposition treatment with tannic acid (Omnichem) The surface resistance is adjusted to 1.0 × 10 8 to 1.0 × 10 9 Ω / cm, processed into short fibers for flocking, spray coated with an adhesive on the surface of the aluminum tube, and electrostatically A method is described in which an implanted antistatic flocking roll is manufactured by immersing the implanted flocking roll in a conductive treatment solution prepared by dissolving pyrrole and iron (III) chloride, rotating the conductive treatment, and drying.
特許文献６（特開２０００−２６５３６７）は、第１段階：「硫酸塩の弱酸性水溶液処理」によって合成繊維表面を親水性雰囲気とし、第２段階：「タンニン処理」によって微細合成繊維の飛翔性を整え、第３段階：「硫酸塩処理」によってタンニン処理を安定化し、第４段階：「アニオン界面活性剤と硫酸アンモニウム塩の混合水溶液処理」により、微細合成繊維の飛翔を効果的に行うための条件を整えて得たフロックを用いて温かみのあるピーチ肌感触の布帛を得る方法が記載されている。 Patent Document 6 (Japanese Patent Laid-Open No. 2000-265367) discloses that the first stage: “sulphate treatment with weakly acidic aqueous solution” makes the surface of the synthetic fiber hydrophilic, and the second stage: “tannin treatment”. 3rd stage: Stabilization of tannin treatment by “sulfate treatment”, 4th step: “Effect of mixed aqueous solution of anionic surfactant and ammonium sulfate salt” for effective flight of fine synthetic fibers A method for obtaining a warm peach skin-like fabric using flock obtained by adjusting the conditions is described.
特許文献７（特許第４０２７８１０号）は、従来技術として特許文献５，６に記載されているタンニンによる電着処理方法を示しつつ、これら従来技術で所望の植毛適性が得られる程度の条件でタンニン処理を施したフロックを静電植毛に供すると、フロックが直立しすぎることから、「タンニンに接触させた繊維を、ジルコニウム塩に接触させる方法」を提案し、用い得るタンニンとして「ピロガロールタンニン等の加水分解型タンニン、カテコールタンニン等の縮合型タンニンの他、それらの誘導体等、広義のタンニン（または広義のタンニン酸）として知られているもの」を挙げている。 Patent Document 7 (Patent No. 4027810) shows an electrodeposition treatment method using tannin described in Patent Documents 5 and 6 as a conventional technique, and tannin under the condition that desired flocking suitability can be obtained with these conventional techniques. When the treated flocs are subjected to electrostatic flocking, the flocs are too upright. Therefore, the “method of bringing the fiber in contact with the tannin into contact with the zirconium salt” is proposed. In addition to condensed tannins such as hydrolyzed tannins and catechol tannins, derivatives thereof, etc., those known as tannins in a broad sense (or broadly defined tannic acids) are mentioned.
しかし、ピロールモノマーの重合被覆層を形成する方法によって製造した導電性繊維素材には、ピロールと繊維等との親和性が不十分な場合があり、使用中に脱落して導電性が低下するという問題がある。 However, the conductive fiber material produced by the method of forming a polymerized coating layer of pyrrole monomer may have insufficient affinity between pyrrole and fibers, etc. There's a problem.
また、タンニンで被覆を施す方法は、表面抵抗を１．０×１０８ 〜１．０×１０９ Ω／ｃｍ程度に調整してフロックの植毛を好適に行うには足りるものの使用中の導電性布帛等として使用するには不十分という問題がある。 In addition, the method of coating with tannin is sufficient to adjust the surface resistance to about 1.0 × 10 8 to 1.0 × 10 9 Ω / cm to suitably carry out flocking, but the conductivity during use is sufficient. There is a problem that it is insufficient for use as a fabric or the like.
そこで、本発明は、フロック、糸、布帛（織物、不織布等）などの繊維素材の表面に導電性モノマーの重合皮膜を形成してなる製品のさらなる導電性の向上と堅牢性の向上を目的とする。 Therefore, the present invention aims to further improve the conductivity and fastness of a product obtained by forming a polymerized film of a conductive monomer on the surface of a fiber material such as flock, yarn, and fabric (woven fabric, nonwoven fabric, etc.). To do.
上記目的を達成するためになされた本発明の布帛、糸、又はフロックに導電性皮膜を形成する方法であって、前記布帛、糸、又はフロックをタンニン酸を溶解した第１処理液に浸漬して前記布帛、糸、又はフロックの表面にタンニン被覆層を形成した後、さらに、当該布帛、糸、又はフロックを導電性高分子モノマーと酸化剤とを溶解した第２処理液に浸漬して導電性高分子モノマー重合被覆層を形成することを特徴とし、特に、前記第１処理液として、縮合型ではなく加水分解型のタンニン酸を溶解した処理液を用いることをも特徴とする。
より好ましくは、前記第１処理液として、加水分解型タンニン酸をｏｗｆ３％以上のタンニン濃度となる様に溶解した処理液を用いる。また、前記布帛、糸、又はフロックとしてタンニンに対する親和性を有する布帛、糸、又はフロックを用いると共に、前記第１処理液として加水分解型タンニン酸をｏｗｆ１％以上のタンニン濃度となる様に溶解した処理液を用いる。
A method for forming a conductive film on a fabric, yarn or floc of the present invention made to achieve the above object, wherein the fabric, yarn or floc is immersed in a first treatment solution in which tannic acid is dissolved. the fabric, after forming a yarn, or tannin coating layer on the surface of the floc Te, further, the fabric, yarn, or floc is immersed in a second treatment solution obtained by dissolving a conductive polymer monomer and an oxidizing agent conducting It is also characterized in that a coating layer of a polymerizable polymer monomer is formed, and in particular, as the first treatment liquid, a treatment liquid in which hydrolyzed tannic acid is dissolved instead of a condensation type is used.
More preferably, a treatment solution in which hydrolyzable tannic acid is dissolved to a tannin concentration of owf 3% or more is used as the first treatment solution. Moreover, while using the cloth, thread | yarn, or floc which has affinity for tannin as the said cloth, thread | yarn, or a flock , hydrolyzable tannic acid was melt | dissolved as the said 1st process liquid so that it might become a tannin density | concentration of owf1% or more. Use treatment solution .
本発明によれば、最初に第１処理液により、繊維素材にタンニン酸を付与するので、繊維素材には多くのフェノール性水酸基を有するタンニン被覆層が形成される。 According to the present invention, since tannic acid is first imparted to the fiber material by the first treatment liquid, a tannin coating layer having many phenolic hydroxyl groups is formed on the fiber material.
第２処理液による工程では、導電性高分子モノマーの酸化重合によって、エピタキシャル生長が行われる。この際、繊維素材の表面には多くのフェノール性水酸基を備えるタンニン被覆層が形成されているので、導電性高分子モノマーと繊維素材との結合が強くなるものと推定される。ここで、導電性高分子モノマーとしては、アニリン、チオフェン、ピロール或いは、これら誘導体を用いることができる。 In the process using the second treatment liquid, epitaxial growth is performed by oxidative polymerization of the conductive polymer monomer. At this time, since a tannin coating layer having many phenolic hydroxyl groups is formed on the surface of the fiber material, it is presumed that the bond between the conductive polymer monomer and the fiber material becomes strong. Here, aniline, thiophene, pyrrole, or derivatives thereof can be used as the conductive polymer monomer.
この結果、本発明により製造される導電性繊維素材（導電性布帛、導電性糸、導電性フロック）は、表面に形成されたタンニン被覆層のフェノール性水酸基に対して結合されつつ重合された導電性高分子モノマー重合被覆層を備え、高い導電性と、導電性に関する高い耐久性を示すものとなったと推定される。 As a result, the conductive fiber material (conductive fabric, conductive thread, conductive flock) produced by the present invention is polymerized while being bonded to the phenolic hydroxyl group of the tannin coating layer formed on the surface. It is presumed that the conductive polymer monomer polymerization coating layer is provided and exhibits high conductivity and high durability regarding conductivity.
ここで、特許文献５は、タンニン処理したフロックをアルミ管の表面に植毛した後にロール全体をピロール処理して表面抵抗を０．１×１０４ Ω／ｃｍとしているが、フロックの段階はタンニン処理されただけであるから、本発明の導電性フロックとは異なる。また、帯電防止ロールは素材がアルミ管であり、植毛部以外はピロール重合被覆層のみを有するだけであるから、本発明の新規な導電性布帛、導電性糸にも該当しない。加えて、表面抵抗の値も、アルミ管を主体とした製品における値であるから、加水分解型タンニン酸による処理に引き続いて導電性高分子モノマーによる処理を施した繊維素材がどの様な性質のものになるかを示唆するものともなっていない。 Here, Patent Document 5 describes that after the tannin-treated floc is implanted on the surface of the aluminum tube, the entire roll is pyrroled to have a surface resistance of 0.1 × 10 4 Ω / cm. This is different from the conductive floc of the present invention. Further, since the material of the antistatic roll is an aluminum tube and has only the pyrrole polymerization coating layer other than the flocked portion, it does not correspond to the novel conductive fabric or conductive yarn of the present invention. In addition, since the surface resistance value is the value for products mainly made of aluminum pipes, what kind of property is the fiber material treated with hydrolyzable tannic acid followed by treatment with a conductive polymer monomer? Nor does it suggest that it will be.
これに対し、本発明者は、後述実験例に示す通り加水分解型タンニン酸を溶解した第１処理液を用いた処理を行うことにより、かかる処理を行わないで導電性高分子モノマーによる処理を行った場合に比べて大幅に導電性が高まり、かつ、耐久性も高まることを実証して初めて、本発明を完成したものである。 On the other hand, the present inventor performs the treatment with the conductive polymer monomer without performing such treatment by performing the treatment using the first treatment liquid in which the hydrolyzable tannic acid is dissolved as shown in the following experimental examples. The present invention has been completed only after demonstrating that the conductivity is greatly increased and the durability is increased as compared with the case where the test is performed.
また、特許文献７が、タンニン処理には、加水分解型、縮合型等の種々のものを用いればよいとの認識であるのに対し、後述実験例に示す通り、縮合型タンニンでは本発明の効果が得られないことは、本発明が、従来のタンニン処理の延長上にそのまま乗った技術ではないことを示すものであり、かつ、本発明は、課題解決手段としてタンニン処理において加水分解型タンニン酸を用い、その後に導電性高分子モノマーによる処理を施すことにこそ技術的意義があるのだということを実証して初めて確立されたものである。 In addition, Patent Document 7 recognizes that various types such as a hydrolyzed type and a condensed type may be used for the tannin treatment, whereas as shown in an experimental example to be described later, the condensed tannins of the present invention are used. The fact that the effect is not obtained indicates that the present invention is not a technique that is directly applied to the extension of the conventional tannin treatment, and the present invention is a hydrolyzable tannin in tannin treatment as a problem solving means. It was established for the first time by demonstrating that it is technically meaningful to use an acid and then a treatment with a conductive polymer monomer.
この様に、本発明は、従来のタンニン処理と導電性高分子モノマーによる処理を単に組み合わせたものではなく、従来の常識だけでは完成することのできない有意義なる発明であって、後述の実験例に示す実験を繰り返して初めてなされたものなのである。 Thus, the present invention is not a simple combination of the conventional tannin treatment and the treatment with the conductive polymer monomer, and is a meaningful invention that cannot be completed by conventional common sense alone. It was the first time that the experiment shown was repeated.
ここで、本発明においては、前記繊維素材がタンニン酸に対して親和性を有する素材であることを特徴とする。 Here, in the present invention, the fiber material is a material having affinity for tannic acid.
本発明では、タンニン処理によって形成されたタンニン被覆層のフェノール性水酸基が導電性高分子モノマーのエピタキシャル生長において結合力を高める等の作用を果たしているものと推定されるからである。なお、繊維素材自体がタンニン酸に対する親和性を有しない場合も、後述実験例の様に、第１処理液をｏｗｆ３％以上のタンニン濃度とすれば、多少の効果が見られる。 This is because in the present invention, the phenolic hydroxyl group of the tannin coating layer formed by the tannin treatment is presumed to play an action such as increasing the binding force in the epitaxial growth of the conductive polymer monomer. Even when the fiber material itself does not have affinity for tannic acid, if the first treatment liquid has a tannin concentration of owf 3% or more as in the experimental example described later, some effects can be seen.
即ち、タンニン被覆層との結合及び繊維素材自体との結合という現象が本発明の表面処理において進行する結果、タンニン処理なしに導電性高分子モノマーによる処理をした場合に比べて大幅に導電性が向上し、導電性についての耐久性が向上するものと推定されるのである。 That is, the phenomenon of bonding with the tannin coating layer and bonding with the fiber material itself proceeds as a result of the surface treatment of the present invention. As a result, the conductivity is significantly higher than when the treatment with the conductive polymer monomer is performed without the tannin treatment. It is estimated that the durability is improved and the conductivity is improved.
なお、本発明の繊維素材の表面処理方法において、耐久性向上の観点からは、前記第１処理液は、タンニン酸をｏｗｆ３％以上の割合となる様に溶解した溶液であることがより望ましい。 In the fiber material surface treatment method of the present invention, from the viewpoint of improving durability, the first treatment liquid is more preferably a solution in which tannic acid is dissolved at a ratio of owf of 3% or more.
なお、ｏｗｆとは、「on weight of fiber」の略で、布（繊維）に対する洗剤や染料等の濃度をあらわす単位として用いられるものである。本願においても、タンニン酸の繊維素材に対する重量％を示す。 In addition, owf is an abbreviation for “on weight of fiber” and is used as a unit representing the concentration of detergent, dye, or the like with respect to the cloth (fiber). Also in this application, the weight% with respect to the fiber material of a tannic acid is shown.
本発明の表面処理方法によれば、高い導電性と導電性に関する高い耐久性を示す導電性繊維素材を提供することができる。また、本発明の導電性布帛、導電性糸、導電性フロックは、帯電防止、電磁波シールド等に好適な繊維素材となる。 According to the surface treatment method of the present invention, it is possible to provide a conductive fiber material that exhibits high conductivity and high durability related to conductivity. In addition, the conductive fabric, conductive yarn, and conductive floc of the present invention are suitable fiber materials for antistatic, electromagnetic shielding, and the like.
以下、本発明を実施するための形態を具体的な実施例に基づいて説明する。 Hereinafter, modes for carrying out the present invention will be described based on specific examples.
［実験例１］
東レ ナイロン６ ジャージー（（株）色染社 テスト用品番 ９０６０）を１０ｇ取り、タンニン酸（オムニケム社 フロクタンＩ）をｏｗｆで１％，３％，５％の割合となる様に溶解した第１処理液に浸漬し、この第１処理液をｐＨ３．２、温度６０±３℃に維持して３０分間のタンニン被覆層形成処理を実行し、水洗した。その後、ピロール３％（ｏｗｆ），塩化第二鉄１２％（ｏｗｆ）の水溶液を水に対して１：３０の液量となる様に溶解した第２処理液に浸漬し、１８±３℃で１８０分処理した後、水洗、ソーピング、乾燥を施した。
ソーピングの条件は、液量１：３０、ソーダ灰１ｇ／ｌ、センカノールＤＭ（センカ（株））１ｃｃ／ｌ、温度９０℃〜９５℃３０分である。
こうして処理したナイロン６ジャージーの導電度を測定した。測定機は、「ＴＯＡ ｅｌｅｃｔｒｏｎｉｃｓ． ＳＵＰＥＲ ＭＥＧＯＨＭＭＥＴＥＲ ＳＭ８２０３」で、６５％ＲＨ２４℃の環境下で測定した。
また、試料の明度をコニカミノルタ社のＢ：ｃｏｌｏｒ Ｅｙｅ ３０００ で測定した。その結果を表１に示す。なお、表１には、第２処理液による処理のみとした場合をタンニン酸処理０％として併記している。
[Experimental Example 1]
10% of Toray Nylon 6 Jersey (color dyeing company, test article No. 9060) was taken, and tannic acid (Omnichem Froktan I) was dissolved in owf to a ratio of 1%, 3%, and 5%. The first treatment solution was immersed in the solution, and the tannin coating layer forming treatment was performed for 30 minutes while maintaining the pH of 3.2 and the temperature of 60 ± 3 ° C., followed by washing with water. Thereafter, an aqueous solution of pyrrole 3% (owf) and ferric chloride 12% (owf) is immersed in a second treatment solution dissolved in water so as to have a liquid amount of 1:30. After treatment for 180 minutes, washing with water, soaping and drying were performed.
The conditions of the soaping are a liquid amount of 1:30, soda ash 1 g / l, Senkanol DM (Senka Co., Ltd.) 1 cc / l, and a temperature of 90 ° C. to 95 ° C. for 30 minutes.
The conductivity of the nylon 6 jersey thus treated was measured. The measuring instrument was “TOA electronics. SUPER MEGOHMMETER SM8203”, and measurement was performed in an environment of 65% RH at 24 ° C.
Moreover, the brightness of the sample was measured by K: minolta B: color Eye 3000. The results are shown in Table 1. In Table 1, the case where only the treatment with the second treatment solution is performed is also shown as 0% tannic acid treatment.
［実験例２］
ナイロン６６ジャージー（（株）色染社 品番 ５００００）を１０ｇ取り、次の処理を施した。
タンニン酸処理、ピロール処理、ソーピング等は実験例１と同様。また、測定機も同じである。
導電度・明度は次の通りである。
[Experiment 2]
10 g of nylon 66 jersey (color dye company number 50000) was taken and subjected to the following treatment.
Tannic acid treatment, pyrrole treatment, soaping, etc. are the same as in Experimental Example 1. The measuring machine is also the same.
The conductivity and brightness are as follows.
［実験例３］
ローディア社製 ナイロン６６のトウを切断し、３．３ｄＴｅｘ ０．８ｍｍ のカットファイバーを１０ｇ取り、実験例１と同じようにタンニン酸処理をｐＨ３．０で行い、次にピロール処理を２０±３度で１８０分行い、同一の測定機で測定した。
導電度・明度は次の通りである。
[Experiment 3]
Cut toe of nylon 66 made by Rhodia, take 10g of 3.3dTex 0.8mm cut fiber, perform tannic acid treatment at pH 3.0 as in Experimental Example 1, and then pyrrole treatment 20 ± 3 degrees For 180 minutes and measured with the same measuring machine.
The conductivity and brightness are as follows.
また、この短繊維についてフロックモーションテスター（Ｅｒｉｃｈ Ｓｃｈｅｎｋ社）で、飛翔性を測ると（４万ＫＶ×１０ｃｍ２ｇ）が飛散するまでの時間は、表４の通りであった。
Further, when the flying property of this short fiber was measured with a flock motion tester (Erich Schenk), the time required for scattering (40,000 KV × 10 cm 2 g) was as shown in Table 4.
［実験例４］
東レ・デュポン（株）の ケブラー織物＃２９７ を用いて同様のテストを行った。
＃２９７の織物の使用原糸は、３３００ｄｔｅｘ、平織り密度１７．５×１６．５本／インチ、厚さ０．７≠０．１ｍｍ、絶乾目付４４９±９ｇ／ｍ である。
この織物１０ｇを取り、実験例１と同じようにタンニン酸処理とピロール処理を行った。
導電度・明度は次の通りである。
[Experimental Example 4]
A similar test was conducted using Kevlar fabric # 297 from Toray DuPont.
The used yarn of the # 297 woven fabric is 3300 dtex, plain weave density is 17.5 × 16.5 pieces / inch, thickness is 0.7 ≠ 0.1 mm, and dryness is 449 ± 9 g / m 2.
10 g of this woven fabric was taken and subjected to tannic acid treatment and pyrrole treatment in the same manner as in Experimental Example 1.
The conductivity and brightness are as follows.
［実験例５］
三菱レイヨン（株） アクリルモスリン（（株）色染社 品番７５７３）を１０ｇ取り、実験例１と同様のテストを行った。
導電度・明度は次の通りである。
[Experimental Example 5]
10 g of Mitsubishi Rayon Co., Ltd. acrylic muslin (Colored Co., Ltd., product number 7573) was taken, and the same test as in Experimental Example 1 was performed.
The conductivity and brightness are as follows.
ピロール処理のｏｗｆ濃度を高める等の対応によって導電性は向上できるものと考える。
It is considered that the conductivity can be improved by measures such as increasing the owf concentration of the pyrrole treatment.
［実験例６］
（株）クラレ ビニロンブロード（（株）色染社 品番８３７５）を１０ｇ取り、実験例１と同様のテストを行った。
導電度・明度は次の通りである。
[Experimental Example 6]
10 g of Kuraray Vinylon Broad Co., Ltd. (Color Co., Ltd., product number 8375) was taken, and the same test as in Experimental Example 1 was performed.
The conductivity and brightness are as follows.
この場合も、ピロール処理のｏｗｆ濃度を高める等の対応によって導電性は向上できるものと考える。
Also in this case, it is considered that the conductivity can be improved by taking measures such as increasing the owf concentration of the pyrrole treatment.
［実験例７］
帝人（株）ポリエステルタフタ（（株）色染社 品番Ｔ３５５０）を１０ｇ取り、実験例１と同様のテストを行った。
タンニン酸の親和性のないポリエステルは、タンニン酸が付着しないので、ピロールの被膜形成もほとんど見られなかった。
[Experimental Example 7]
10 g of Teijin's Polyester Taffeta (color dye company, product number T3550) was taken, and the same test as in Experimental Example 1 was performed.
Polyester having no affinity for tannic acid did not adhere to tannic acid, so that almost no pyrrole film was formed.
［実験例８］
タンニンには、大別して縮合型と加水分解型とがあり、その効果は大きな差がある。縮合型の没食子酸は、効果が小さい。
縮合型としてキシダ化学の没食子酸試薬１級を、加水分解型としてオムニケム社製のフロクタンＩを加工して実験を行った。
タンニン酸・没食子酸の処理は、実験例１と同様、次にピロール処理を同一条件で行った。ピロールの重合温度が２０℃〜２５℃１８０分と高めであった。
[Experimental Example 8]
Tannins are roughly classified into a condensed type and a hydrolyzed type, and the effects are greatly different. Condensed gallic acid is less effective.
An experiment was conducted by processing Kishida Chemical gallic acid reagent grade 1 as the condensation type and Floktan I manufactured by Omnichem as the hydrolysis type.
In the same manner as in Experimental Example 1, the tannic acid / gallic acid treatment was followed by pyrrole treatment under the same conditions. The polymerization temperature of pyrrole was as high as 20 ° C. to 25 ° C. for 180 minutes.
［実験例９］
導電度の耐摩耗性を評価してみると、次のような結果になった。
東レ ナイロン プロミラン ２１５デニール ３６ｆ の糸を使用。
縦１７０本／インチ、横６０本／インチの織物を２０ｇ取り、タンニン酸（オムニケム社 フロクタンＩ）３％を液量１：３０ｐＨ３．２温度６０±３℃で３０分処理し水洗後、実験例１と同じ条件でピロール処理を行い、ポリピロールの皮膜を形成した。このものを常温で乾燥後、耐摩擦テストを行った。すなわち、染色堅牢度測定する 学振型摩擦テストのＡ−１エッヂ法の４５Ｒ法で測定した。摩擦布は綿布６号を用い、荷重５００ｇで５００回往復運動後の摩擦前後の導電率を測定した。
[Experimental Example 9]
When the wear resistance of conductivity was evaluated, the following results were obtained.
Toray nylon Promilan 215 denier 36f yarn is used.
20g of woven fabric of length 170 / inch, width 60 / inch, tannic acid (Omnichem Froktan I) 3% was treated for 30 minutes at 1:30 pH 3.2 temperature 60 ± 3 ° C, and washed with water. A pyrrole treatment was performed under the same conditions as in 1 to form a polypyrrole film. This was dried at room temperature and then subjected to a friction resistance test. That is, it was measured by the 45R method of the A-1 edge method of the Gakushin type friction test which measures the dyeing fastness. Cotton cloth No. 6 was used as the friction cloth, and the electrical conductivity before and after friction after 500 reciprocations with a load of 500 g was measured.
この時の導電率の測定は、ＴＯＡ ｅｌｅｃｔｒｏｎｉｃｓ． ＳＵＰＥＲ ＭＥＧＯＨＭＭＥＴＥＲ ＳＭ８２０３で、６５％ＲＨ１８℃の環境下で測定した。
The measurement of the conductivity at this time is performed by TOA electronics. The measurement was performed with a SUPER MEGOHMMETER SM8203 in an environment of 65% RH18 ° C.
［比較例１］
＜タンニン酸処理のみによる導電度の測定＞
試験布として実験例１と同じナイロン６ジャージー（（株）色染社 テスト用品番 ９０６０）を１０ｇ取り、次のテストを行った。
液量１：３０、ｐＨ３．１２、６０±５度、３０分処理後、水洗、乾燥後、導電度を測定。測定器は同一。温度３２度６０％ＲＨである。
[Comparative Example 1]
<Measurement of conductivity only by tannic acid treatment>
As a test cloth, 10 g of nylon 6 jersey (Test Co., Ltd., Color Dyeing Co., Ltd., Test Product No. 9060) as in Experimental Example 1 was taken, and the following test was performed.
Liquid volume 1:30, pH 3.12, 60 ± 5 degrees, after 30 minutes treatment, washed with water, dried and then measured for conductivity. The measuring instrument is the same. The temperature is 32 degrees 60% RH.
［実験例及び比較例に基づく考察］
各実験例において、「タンニン酸処理」の欄が「０％」となっているものは、タンニン酸処理をしなかったものを示している。
[Discussion based on experimental and comparative examples]
In each experimental example, the “tannic acid treatment” column with “0%” indicates that the tannic acid treatment was not performed.
実験例１〜６及び実験例９から分かる様に、タンニン酸処理をしなかったものに比べ、タンニン酸処理を行ったものの方が導電性において１オーダー以上の改善が見られることが分かる。特に、ケブラーを繊維素材として採用した実験例４は、３オーダー以上の改善を示し、導電性高分子モノマーによる処理を行う前にタンニン酸処理を行うことによる導電性付与の効果が格段に高くなることを示している。 As can be seen from Experimental Examples 1 to 6 and Experimental Example 9, it can be seen that the tannic acid treatment shows an improvement of one order or more in conductivity compared to the tannic acid treatment. In particular, Experimental Example 4 employing Kevlar as a fiber material shows an improvement of 3 orders or more, and the effect of imparting conductivity by performing the tannic acid treatment before the treatment with the conductive polymer monomer is remarkably increased. It is shown that.
また、実験例７は、タンニン酸に対する親和性のないポリエステルであっても、タンニン酸をｏｗｆ３％以上となる様に溶解した第１処理液を用いることによって、それなりに効果が発揮されることが分かる。このことは、繊維素材はタンニン酸に対する親和性を有するものが望ましいことと共に、仮にタンニン酸に対する親和性がない繊維素材であっても、タンニン酸処理における第１処理液中のタンニンのｏｗｆ％を３％以上とすれば、一応の効果を発揮するという見方もできる。 In addition, even if the experimental example 7 is a polyester having no affinity for tannic acid, the effect can be exhibited as it is by using the first treatment liquid in which tannic acid is dissolved so as to be owf 3% or more. I understand. This means that it is desirable that the fiber material has an affinity for tannic acid, and even if the fiber material does not have an affinity for tannic acid, owf% of tannin in the first treatment liquid in the tannic acid treatment is reduced. If it is set to 3% or more, it can be said that the effect will be exhibited.
一方、実験例８から、タンニン酸処理を施すとしても、縮合型タンニンの場合は効果が発現せず、加水分解型タンニンを用いるべきことを理解することができる。なお、実験例８以外の実験例１〜７及び実験例９は、全て加水分解型タンニンを用いたものである。 On the other hand, it can be understood from Experimental Example 8 that even if the tannic acid treatment is performed, the effect is not exhibited in the case of condensed tannin, and hydrolyzed tannin should be used. In addition, Experimental Examples 1-7 and Experimental Example 9 other than Experimental Example 8 all use hydrolyzed tannin.
実験例９は、タンニン処理を施さない場合には耐摩耗性試験を行った結果、２オーダーの導電性低下が見られるのに対し、タンニン処理を施した場合は、１オーダー程度の導電性低下で済んでいることが分かる。この結果、タンニン処理を事前に行った後に導電性高分子モノマーによる処理を施した場合には、導電性を長く保ち続けられることが判明した。 In Experimental Example 9, when the tannin treatment was not performed, the wear resistance test was performed. As a result, a two-order decrease in conductivity was observed, whereas when the tannin treatment was performed, the conductivity decreased by about one order. You can see that As a result, it has been found that when the treatment with the conductive polymer monomer is performed after the tannin treatment in advance, the conductivity can be kept long.
そして、比較例から分かる様に、タンニン処理のみを施してその後の導電性高分子モノマーによる処理を施さない場合には、導電性はほとんど付与されていないことが分かる。 As can be seen from the comparative example, when only the tannin treatment is performed and the subsequent treatment with the conductive polymer monomer is not performed, the conductivity is hardly imparted.
この比較例は、実験例１と同じ繊維素材によるものである。そこで、実験例１のタンニン酸処理０％、即ち、タンニン酸処理を施さない場合と共に考察すると、表１２の事実が判明する。 This comparative example is based on the same fiber material as in Experimental Example 1. Therefore, when considering together with 0% of the tannic acid treatment of Experimental Example 1, that is, without the tannic acid treatment, the facts of Table 12 are found.
即ち、ナイロン６ジャージーに対してタンニン酸処理をｏｗｆ５％で実施したとしても、それのみでは、表面電気抵抗は、0.3×10１１Ω／ｃｍである。また、ナイロン６ジャージーに対してタンニン酸処理を施すことなくピロール処理を施したものの表面電気抵抗は0.13×10８Ω／ｃｍである。これに対し、タンニン酸処理をｏｗｆ１％で施した上でピロール処理を施した場合には0.14×10７Ω／ｃｍとなっている。 That is, even if tannic acid treatment is performed on nylon 6 jersey at 5% owf, the surface electrical resistance is only 0.3 × 10 11 Ω / cm. The surface electrical resistance of nylon 6 jersey treated with pyrrole without tannic acid treatment is 0.13 × 10 8 Ω / cm. On the other hand, when the tannic acid treatment is performed at owf 1% and the pyrrole treatment is performed, it is 0.14 × 10 7 Ω / cm.
このことは、本発明は単なる足し算以上の導電性向上効果を発揮する画期的な表面処理方法であることを示しているといえる。 This can be said to indicate that the present invention is an epoch-making surface treatment method that exhibits an effect of improving conductivity more than mere addition.
以上、発明を実施するための形態として実施例にて多数の実験例を説明したが、本発明は、これらに限定されるものではなく、その要旨を逸脱しない範囲内における種々の態様での実施が可能である。 As described above, a number of experimental examples have been described as examples for carrying out the invention. However, the present invention is not limited to these examples, and can be implemented in various modes without departing from the scope of the invention. Is possible.
本発明によれば、帯電防止、電磁波シールド、電気メッキ等に好適な繊維素材を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the fiber raw material suitable for antistatic, electromagnetic wave shield, electroplating, etc. can be provided.
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