JP3023466B2 - Conductive adhesive - Google Patents
Conductive adhesiveInfo
- Publication number
- JP3023466B2 JP3023466B2 JP3246667A JP24666791A JP3023466B2 JP 3023466 B2 JP3023466 B2 JP 3023466B2 JP 3246667 A JP3246667 A JP 3246667A JP 24666791 A JP24666791 A JP 24666791A JP 3023466 B2 JP3023466 B2 JP 3023466B2
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- alkylene oxide
- polyol
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000853 adhesive Substances 0.000 title description 16
- 230000001070 adhesive effect Effects 0.000 title description 16
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 26
- 125000002947 alkylene group Chemical group 0.000 claims description 21
- 150000008040 ionic compounds Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 description 24
- 150000003077 polyols Chemical class 0.000 description 24
- 229920002635 polyurethane Polymers 0.000 description 22
- 239000004814 polyurethane Substances 0.000 description 22
- 239000005056 polyisocyanate Substances 0.000 description 10
- 229920001228 polyisocyanate Polymers 0.000 description 10
- 239000000203 mixture Substances 0.000 description 5
- -1 alkyl compound Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 208000010201 Exanthema Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 235000015125 Sterculia urens Nutrition 0.000 description 1
- 240000001058 Sterculia urens Species 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 201000005884 exanthem Diseases 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Landscapes
- Electrotherapy Devices (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、低周波治療器の導子等
に好適に使用される加温可能な導電性粘着剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heatable conductive pressure-sensitive adhesive suitably used for a conductor of a low-frequency treatment device.
【０００２】[0002]
【従来の技術】近時、導電性粘着剤にはいろいろな種類
のものが開発されている。例えばアクリル系のヒドロゲ
ルを用いたものや天然高分子に塩類微粒子、金属微粒子
などを混在させたもの等がある。2. Description of the Related Art Recently, various kinds of conductive adhesives have been developed. For example, there is a type using an acrylic hydrogel or a type obtained by mixing salt fine particles, metal fine particles, and the like with a natural polymer.
【０００３】また、本出願人は特願昭６０−２８１４０
７号においてイオン導電性高分子粘着剤を提案した。こ
のイオン導電性高分子粘着剤は柔軟で皮膚との密着性も
優れ、透明で良好な導電性を持つきわめて優れた特長を
有するものであり、低周波治療器やその他種々の医療用
電極材として使用されている。Further, the present applicant has filed Japanese Patent Application No. 60-28140.
No. 7 proposed an ionic conductive polymer adhesive. This ionic conductive polymer adhesive is flexible, has excellent adhesion to the skin, and has excellent features of transparency and good conductivity, and is used as a low-frequency therapeutic device and various other medical electrode materials. It is used.
【０００４】[0004]
【発明が解決しようとする課題】上記種々の粘着剤の中
で、アクリル系のヒドロゲルは残留モノマーが含有して
いる場合があり、人体への毒性、皮膚のかぶれ等の問題
がある。Among the above-mentioned various pressure-sensitive adhesives, acrylic hydrogels sometimes contain residual monomers, and have problems such as toxicity to the human body and rash on the skin.
【０００５】また、天然高分子多糖類の粘着剤は産地ロ
ットによって品質が異なる場合があり、また混在する金
属や塩類の微粒子は不連続な導電路を形成するため偶発
的に不均一な電解を生じ、長期保存中に変色して褐色不
透明になるため皮膚への接触という点で不快感を与えや
すい等の問題がある。[0005] In addition, the quality of the natural polymer polysaccharide adhesive may vary depending on the production lot, and mixed metal and salt fine particles form discontinuous conductive paths, so that accidental uneven electrolysis may occur. This causes discoloration and brown opacity during long-term storage, which causes problems such as easy contact with the skin and discomfort.
【０００６】一方、特願昭６０−２８１４０７号におい
て提案されたイオン導電性粘着剤は上記のような問題点
は解消されたものではあるが、一般に上述のような粘着
剤を寒い時期に人体、特に肩、首筋、腰等に貼着したと
き、非常に冷たくて不快感を与えるものであり、冬季の
肩こり時に低周波治療器を使用する場合などは、特にそ
の問題は重要視されるようになってきた。この問題は他
の素材を使用した場合も同様で、冬季に冷たい粘着剤を
使用することは、かなり抵抗があるものであった。On the other hand, the ionic conductive pressure-sensitive adhesive proposed in Japanese Patent Application No. 60-281407, although the above-mentioned problems have been solved, generally, the above-mentioned pressure-sensitive adhesive is applied to a human body in a cold season. Especially when applied to the shoulders, neck, waist, etc., it is very cold and gives discomfort, especially when using a low frequency treatment device during stiff shoulders in winter, so that the problem is particularly important It has become. The problem was similar when other materials were used, and the use of cold adhesives in winter was quite resistant.
【０００７】本発明は上記問題に鑑みてなされたもの
で、粘着剤を小さなエネルギーで４０〜６０℃程度まで
加温できる粘着剤を提供することを目的とする。The present invention has been made in view of the above problems, and has as its object to provide an adhesive capable of heating an adhesive to about 40 to 60 ° C. with small energy.
【０００８】[0008]
【課題を解決するための手段】本発明は上記目的を達成
するために鋭意研究を重ねた結果、イオン化合物が含有
されたアルキレンオキサイド鎖を有するウレタン樹脂粘
着剤を含水処理することにより、その粘着剤中の含水率
を２〜２０％に調整すれば、好適に加温可能であること
を見出し、発明を完成するに至った。Means for Solving the Problems According to the present invention, as a result of intensive studies for achieving the above object, the urethane resin pressure-sensitive adhesive having an alkylene oxide chain containing an ionic compound is subjected to a water-containing treatment, whereby the pressure-sensitive adhesive is obtained. It has been found that if the water content in the composition is adjusted to 2 to 20%, it is possible to suitably heat the solution, and the invention has been completed.
【０００９】本発明の導電性粘着剤は、アルキレンオキ
サイド鎖を有するポリウレタンポリオールプレポリマー
又は／及びアルキレンオキサイド鎖を有するポリオール
と、アルキレンオキサイド鎖を有するポリウレタンポリ
イソシアネートプレポリマーとを反応させ、それにイオ
ン化合物を含有させたウレタン樹脂粘着剤であって、含
水処理により含水率が２〜２０％に調整されたものであ
る。含水処理としては、後述するようにイオン化合物の
含有されたウレタン樹脂粘着剤を恒温、恒湿の雰囲気中
に静置するなどの処理が採用される。The conductive pressure-sensitive adhesive of the present invention is obtained by reacting a polyurethane polyol prepolymer having an alkylene oxide chain or / and a polyol having an alkylene oxide chain with a polyurethane polyisocyanate prepolymer having an alkylene oxide chain, and reacting with the ionic compound. Is a urethane resin pressure-sensitive adhesive having a water content adjusted to 2 to 20% by a water-containing treatment. As the water-containing treatment, a treatment such as leaving the urethane resin pressure-sensitive adhesive containing an ionic compound in a constant temperature and constant humidity atmosphere as described later is employed.
【００１０】本発明の粘着剤に用いられるポリウレタン
ポリオールプレポリマーは、例えば下記の構造式
（Ｉ）、ポリオールは例えば下記の構造式（II）〜（I
V）、またポリウレタンポリイソシアネートプレポリマ
ーは例えば下記の構造式（Ｖ）〜（IX）で示される構造
を備えた多官能の化合物で比較的低分子量領域では常温
で液体であり、いずれも主鎖中にアルキレンオキサイド
鎖［構造式（Ｉ）〜（IX）中、（ＡＯ）で表されてい
る］を有している。特に、ポリウレタンポリオールプレ
ポリマー及びポリオールは比較的高分子量領域では常温
で粘稠な樹脂液体ないし固体となり、これをポリウレタ
ンポリイソシアネートプレポリマーと反応させた場合、
粘着性のない固体樹脂となり、本発明の粘着剤としては
使用できない。The polyurethane polyol prepolymer used in the pressure-sensitive adhesive of the present invention is, for example, the following structural formula (I), and the polyol is, for example, the following structural formulas (II) to (I)
V) and the polyurethane polyisocyanate prepolymer are polyfunctional compounds having, for example, the structures represented by the following structural formulas (V) to (IX), and are liquid at room temperature in a relatively low molecular weight region. And an alkylene oxide chain [in the structural formulas (I) to (IX), represented by (AO)]. In particular, the polyurethane polyol prepolymer and polyol become a viscous resin liquid or solid at room temperature in a relatively high molecular weight region, and when this is reacted with a polyurethane polyisocyanate prepolymer,
It becomes a non-tacky solid resin and cannot be used as the pressure-sensitive adhesive of the present invention.
【００１１】また、ポリオールは低分子量領域では分子
鎖が短く、硬化し難く、高分子量領域ではポリウレタン
ポリオールと同様の挙動を示すので、粘着性発現のため
には各アルキレンオキサイド鎖及び全分子量の大きさが
規制されねばならない。このアルキレンオキサイド鎖
（ＡＯ）は親水性及び線状又は一部分枝を有するアルキ
レンオキサイドのコポリマーで、例えば次のもの等であ
る。Further, the polyol has a short molecular chain in a low molecular weight region and is hardly cured, and exhibits the same behavior as a polyurethane polyol in a high molecular weight region. Therefore, in order to develop tackiness, the size of each alkylene oxide chain and the total molecular weight is large. Must be regulated. The alkylene oxide chain (AO) is a copolymer of hydrophilic and linear or partially branched alkylene oxide, such as the following.
【００１２】[0012]
【化１】 Embedded image
【００１３】[0013]
【化２】 Embedded image
【００１４】[0014]
【化３】 Embedded image
【００１５】[0015]
【化４】 Embedded image
【００１６】[0016]
【化５】 Embedded image
【００１７】[0017]
【化６】 Embedded image
【００１８】いずれのアルキレンオキサイド鎖も（Ａ
Ｏ）で示すことが可能で、同じポリマー内においても１
種類のアルキレンオキサイド鎖に限定されるものではな
い。Any of the alkylene oxide chains (A
O), and even within the same polymer, 1
It is not limited to the type of alkylene oxide chain.
【００１９】[0019]
【化７】 Embedded image
【００２０】[0020]
【化８】 Embedded image
【００２１】[0021]
【化９】 Embedded image
【００２２】[0022]
【化１０】 Embedded image
【００２３】[0023]
【化１１】 Embedded image
【００２４】[0024]
【化１２】 Embedded image
【００２５】[0025]
【化１３】 Embedded image
【００２６】[0026]
【化１４】 Embedded image
【００２７】[0027]
【化１５】 （但しＲはアルキル化合物、脂環式化合物、芳香族化合
物のいずれかであり、（ＡＯ）はアルキレンオキサイド
鎖、Ｒ′は水素原子もしくはＲ同等、ｌ，ｍ，ｎは１以
上の整数である。）Embedded image (Where R is any one of an alkyl compound, an alicyclic compound, and an aromatic compound, (AO) is an alkylene oxide chain, R 'is a hydrogen atom or R equivalent, and l, m, and n are integers of 1 or more.) .)
【００２８】これらのポリウレタンポリオールプレポリ
マー（Ｉ）又は／及びポリオール（II）〜（IV）及びポ
リウレタンポリイソシアネートプレポリマー（Ｖ）〜
（IX）は、末端又は側鎖に反応性の官能基（−ＯＨ基あ
るいは−ＮＣＯ基）を有しており、この官能基が反応し
てウレタン結合することにより、粘着性を有する貫入型
のポリウレタンが形成される。These polyurethane polyol prepolymers (I) and / or polyols (II) to (IV) and polyurethane polyisocyanate prepolymers (V) to
(IX) has a reactive functional group (-OH group or -NCO group) at a terminal or a side chain, and the functional group reacts to form a urethane bond, thereby forming an intrusion type having adhesiveness. A polyurethane is formed.
【００２９】このポリウレタンのアルキレンオキサイド
鎖（ＡＯ）の部分は、イオン化合物が錯体を形成し易い
状態となっている。従って、イオン化合物を混入する
と、主としてこのアルキレンオキサイド鎖のところに複
合体又は固溶体が形成され、電位を与えるとイオン伝導
となって電流が流れ、良好な導電性（１０3 〜１０7 Ω
ｃｍ程度）を示すようになる。The portion of the alkylene oxide chain (AO) of this polyurethane is in a state where the ionic compound is likely to form a complex. Therefore, when an ionic compound is mixed, a complex or a solid solution is formed mainly at the alkylene oxide chain. When a potential is applied, the complex becomes a ionic conductor, a current flows, and a good conductivity (10 3 to 10 7 Ω) is obtained.
cm).
【００３０】また、混合するイオン化合物としては、例
えば塩化ナトリウム、塩化カリウム、塩化リチウム、過
塩素酸リチウム、塩化アンモニウム、塩素酸カリウム、
塩化アルミニウム、塩化銅、塩化第一鉄、塩化第二鉄、
硫酸アンモニウム、硝酸カリウム、硝酸ナトリウム、炭
酸ナトリウム、ホウ弗化リチウム、チオシアン酸ナトリ
ウム、トリフルオロメタンスルホン酸リチウムなどの無
機塩類、酢酸ナトリウム、アルギン酸ソーダ、ポリアク
リル酸ソーダ、リグニンスルホン酸ソーダ、トルエンス
ルホン酸ソーダなどの有機塩類が使用される。これらは
単独若しくは混合して使用してもよい。但し、生体電極
用の粘着剤とした場合は、人体に影響のないものが選ば
れる。Examples of the ionic compound to be mixed include sodium chloride, potassium chloride, lithium chloride, lithium perchlorate, ammonium chloride, potassium chlorate, and the like.
Aluminum chloride, copper chloride, ferrous chloride, ferric chloride,
Inorganic salts such as ammonium sulfate, potassium nitrate, sodium nitrate, sodium carbonate, lithium borofluoride, sodium thiocyanate, lithium trifluoromethanesulfonate, sodium acetate, sodium alginate, sodium polyacrylate, sodium ligninsulfonate, sodium toluenesulfonate, etc. Organic salts are used. These may be used alone or as a mixture. However, when the adhesive is used for a bioelectrode, one that does not affect the human body is selected.
【００３１】かかるイオン化合物は、ポリオールプレポ
リマー、ポリオール、ポリイソシアネートプレポリマー
の混合時に配合してもよいし、反応後に水溶液又は有機
溶液として含浸し溶媒を乾燥除去してもよい。Such an ionic compound may be added at the time of mixing the polyol prepolymer, the polyol, and the polyisocyanate prepolymer, or may be impregnated as an aqueous solution or an organic solution after the reaction, and the solvent may be removed by drying.
【００３２】ポリウレタンポリオール、ポリオール及び
ポリウレタンポリイソシアネートの各々の反応比は、末
端の官能基の比率によって規制でき、１≦［ＯＨ］／
［ＮＣＯ］＜５である必要がある。［ＯＨ］／［ＮＣ
Ｏ］＜１であれば、未反応の−ＮＣＯが残存し、後反応
が生じるため不適である。また［ＯＨ］／［ＮＣＯ］＞
５であれば、末端にＯＨ基を有するセグメントが過剰と
なり、熱や溶媒による溶出が起こり、好ましくない。The reaction ratio of each of the polyurethane polyol, the polyol and the polyurethane polyisocyanate can be regulated by the ratio of the terminal functional groups, and 1 ≦ [OH] /
[NCO] must be <5. [OH] / [NC
If O] <1, unreacted -NCO remains, which is not suitable because a post-reaction occurs. [OH] / [NCO]>
If it is 5, the segment having an OH group at the terminal becomes excessive, and elution by heat or a solvent occurs, which is not preferable.
【００３３】本発明の粘着剤を造るためのポリウレタン
ポリオール、ポリオール、ポリウレタンポリイソシアネ
ートの分子量の範囲は、アルキレンオキサイドやイソシ
アネートの種類、分子形状およびアルキレンオキサイド
がホモポリマーであるかコポリマーであるかによって広
い範囲で変わるが、ポリウレタンポリオールで大略１０
００〜１００００、ポリオールで大略１５０〜６００
０、ポリウレタンポリイソシアネートで大略５００〜１
００００であるが、好ましくは各々大略１４００〜６０
００、３００〜３０００、１０００〜６０００の範囲で
選択できる。The molecular weight range of the polyurethane polyol, polyol and polyurethane polyisocyanate for producing the pressure-sensitive adhesive of the present invention is broad depending on the type and molecular shape of the alkylene oxide or isocyanate and whether the alkylene oxide is a homopolymer or a copolymer. Although it varies depending on the range, it is roughly 10
00 to 10000, approximately 150 to 600 in polyol
0, approximately 500-1 with polyurethane polyisocyanate
0000, preferably about 1400 to 60 respectively.
00, 300 to 3000, 1000 to 6000.
【００３４】前記イオン化合物は、ポリオール等に溶か
して配合する場合、ポリオール等１００部に対して０．
１〜１００部、好ましくは０．５〜３０部である。０．
１部未満では充分なイオン伝導効果が得られず、１００
部を越えると、溶解させにくく、またイオン化合物混合
による著しい効果が期待されない。When the ionic compound is dissolved in a polyol or the like and blended, the ionic compound is added in an amount of 0.1 to 100 parts of the polyol or the like.
1 to 100 parts, preferably 0.5 to 30 parts. 0.
If it is less than 1 part, a sufficient ion conduction effect cannot be obtained, and
If the amount exceeds the above range, it is difficult to dissolve, and no remarkable effect by mixing the ionic compound is expected.
【００３５】なお、ジブチル錫ジラウレート等の触媒が
使用されるが、この触媒の配合量はポリウレタンポリオ
ールプレポリマー１００部に対して０．１〜５部、好ま
しくは０．５〜１．５部の範囲とされる。A catalyst such as dibutyltin dilaurate is used. The amount of the catalyst is 0.1 to 5 parts, preferably 0.5 to 1.5 parts, per 100 parts of the polyurethane polyol prepolymer. Range.
【００３６】本発明の導電性粘着剤はイオン化合物が含
有されたアルキレンオキサイド鎖を有するウレタン樹脂
粘着剤であって、含水処理により該粘着剤中に水分を２
〜２０％含有させたものである。粘着剤中の水分調整
は、ポリウレタンポリオールプレポリマー、ポリウレタ
ンポリイソシアネートプレポリマー、ポリオール及びイ
オン化合物を混合して反応させるか、或は前２〜３成分
を混合、反応させたのちイオン化合物を溶液として含浸
させるかによって得られた生成物（イオン化合物入りの
ウレタン樹脂粘着剤）を、恒温、恒湿の雰囲気中で５〜
２４時間静置するなどの含水処理を施すことによって行
われる。また、含水率をコントロールするためには、ウ
レタン樹脂中のアルキレンオキサイド鎖として親水性セ
グメントであるポリエチレンオキサイド鎖を３５〜８０
％の範囲で含有していることが望ましい。本発明におけ
るポリウレタン樹脂中のアルキレンオキサイド鎖につい
ては、何ら限定されるものではないが、粘着剤として柔
軟性があり、適度の粘着力があり、しかも保形性のある
ものにするためには、疎水性のセグメント鎖と親水性の
セグメント鎖のバランスがとれていることが重要であ
る。The conductive pressure-sensitive adhesive of the present invention is a urethane resin pressure-sensitive adhesive having an alkylene oxide chain containing an ionic compound.
-20%. The water content in the pressure-sensitive adhesive is adjusted by mixing a polyurethane polyol prepolymer, a polyurethane polyisocyanate prepolymer, a polyol and an ionic compound and reacting them, or by mixing and reacting two or three components before forming an ionic compound as a solution. The product (urethane resin adhesive containing an ionic compound) obtained by impregnation or is impregnated in an atmosphere of constant temperature and humidity for 5 to 5 minutes.
It is performed by performing a water-containing treatment such as standing for 24 hours. Further, in order to control the water content, a polyethylene oxide chain which is a hydrophilic segment as the alkylene oxide chain in the urethane resin is 35 to 80.
% Is desirable. The alkylene oxide chain in the polyurethane resin in the present invention is not particularly limited, but is flexible as an adhesive, has an appropriate adhesive strength, and in order to have a shape-retaining property, It is important that the hydrophobic segment chains and the hydrophilic segment chains are balanced.
【００３７】[0037]
【作用】本発明の導電性粘着剤は、貫入型ポリウレタン
の主としてアルキレンオキサイド鎖の部分にイオン化合
物が取り込まれて錯体を形成し、これに電位を与えると
イオン伝導によって電流が流れ、体積抵抗率が１０3 〜
１０7 Ωｃｍ程度の良好な導電性を示す。またアルキレ
ンオキサイド鎖を有するポリウレタン樹脂であるため、
可塑剤等を用いなくても柔軟な導電性粘着剤が得られ、
無毒性であり、皮膚との密着性もよく、透明できわめて
清潔感の良い粘着剤である。In the conductive pressure-sensitive adhesive of the present invention, an ionic compound is incorporated mainly into the alkylene oxide chain portion of the penetrating polyurethane to form a complex. When a potential is applied to the complex, a current flows by ionic conduction and the volume resistivity is increased. Is 10 3 or more
It shows good conductivity of about 10 7 Ωcm. Also, because it is a polyurethane resin having an alkylene oxide chain,
A flexible conductive adhesive can be obtained without using a plasticizer, etc.
It is non-toxic, has good adhesion to the skin, is transparent and has a very clean feeling.
【００３８】また、該粘着剤は含水率２〜２０％である
ため、通電した場合、粘着剤の全体が略均一に昇温で
き、温度が上昇するに従って抵抗値が小さくなり、昇温
速度も速くなるので極めて短時間に粘着剤全体を加温す
ることができるものである。Further, since the pressure-sensitive adhesive has a water content of 2 to 20%, the temperature of the entire pressure-sensitive adhesive can be substantially uniformly increased when current is applied, and the resistance value decreases as the temperature rises, and the rate of temperature rise also increases. Since the speed is increased, the entire pressure-sensitive adhesive can be heated in a very short time.
【００３９】[0039]
【実施例】前記構造式（Ｉ）（IV）におけるポリウレタ
ンポリオールプレポリマー（Ｐ．Ｕ．Ｐ−ＯＨ）および
ポリオール（Ｐ−ＯＨ）と、前記構造式（VII） におけ
るポリウレタンポリイソシアネートプレポリマー（Ｐ．
Ｕ．Ｐ−ＮＣＯ）とにジブチル錫ジラウレートを触媒と
して加え、さらにイオン化合物として過塩素酸リチウム
を加えて混合し、常温で厚さ２ｍｍのイオン導電性の粘
着剤Ａを得た。配合割合は次の通りである。 Ｐ．Ｕ．Ｐ−ＯＨ 分子量 セグメント構成 構成比率 １００重量部 １９００ Ｅ Ｐ Ｅ ４：３：４ Ｐ−ＯＨ 分子量 セグメント構成 ５０重量部 ２００ Ｅ Ｐ．Ｕ．Ｐ−ＮＣＯ 分子量 セグメント構成 １００重量部 １６００ Ｐ 触媒 ジブチル錫ジラウレート １重量部 イオン化合物 過塩素酸リチウム １０重量部 （但し、Ｅはポリエチレングリコールであり、Ｐはポリプロピレングリコール である。）The polyurethane polyol prepolymer (PUP-OH) and the polyol (P-OH) in the structural formulas (I) and (IV) and the polyurethane polyisocyanate prepolymer (P .
U. P-NCO) and dibutyltin dilaurate as a catalyst, and lithium perchlorate as an ionic compound was further added and mixed to obtain an ionic conductive pressure-sensitive adhesive A having a thickness of 2 mm at room temperature. The mixing ratio is as follows. P. U. P-OH molecular weight Segment composition Constituent ratio 100 parts by weight 1900 EP 4: 3: 4 P-OH molecular weight Segment composition 50 parts by weight 200 EP U. P-NCO molecular weight segment composition 100 parts by weight 1600 P catalyst dibutyltin dilaurate 1 part by weight ionic compound lithium perchlorate 10 parts by weight (provided that E is polyethylene glycol and P is polypropylene glycol)
【００４０】この粘着剤Ａを６０℃，９０％ＲＨの雰囲
気中で５〜２４時間静置して各々所定の含水率を有する
粘着剤Ａを調製した。これらの粘着剤Ａを一辺４ｃｍの
正方形に打ち抜くと共に、厚さ約１００μｍのポリエチ
レンテレフタレートシートの片面に銀・カーボンの導電
性インクを１０μｍの厚さで塗布して硬化させ、且つ一
隅にスナップ端子が具備された基材に導電性インク面が
前記粘着剤Ａと接するように貼合わせて積層体を造っ
た。The pressure-sensitive adhesive A was allowed to stand in an atmosphere of 60 ° C. and 90% RH for 5 to 24 hours to prepare a pressure-sensitive adhesive A having a predetermined water content. The adhesive A was punched into a square having a side of 4 cm, and a conductive ink of silver / carbon was applied on one side of a polyethylene terephthalate sheet having a thickness of about 100 μm to a thickness of 10 μm and cured, and a snap terminal was provided at one corner. A laminate was made by attaching the conductive ink surface to the pressure-sensitive adhesive A on the substrate provided.
【００４１】この積層体を約１ｍｍの厚さのステンレス
板上に張り合わせ、上記スナップ端子とステンレス板間
に家庭用の交番波電源を１０Ｖに降圧して通電させ、昇
温速度と繰り返し昇温適性を調べた。The laminated body was stuck on a stainless steel plate having a thickness of about 1 mm, a household alternating-current power supply was stepped down to 10 V between the snap terminal and the stainless steel plate, and electricity was supplied. Was examined.
【００４２】また、比較のために市販の天然多糖類ガム
であるカラヤゴム製の粘着剤Ｂ及びアクリルヒドロゲル
製の粘着剤Ｃをそれぞれ上記積層体と同様の構成にして
昇温速度と繰り返し昇温適性を調べた。その結果を表１
に示す。For comparison, a pressure-sensitive adhesive B made of karaya rubber and a pressure-sensitive adhesive C made of acryl hydrogel, which are commercially available natural polysaccharide gums, were each constructed in the same manner as the above-mentioned laminate, and the rate of temperature rise and suitability for temperature rise were repeated. Was examined. Table 1 shows the results.
Shown in
【００４３】[0043]
【表１】 [Table 1]
【００４４】[0044]
【発明の効果】本発明の導電性粘着剤は上述の説明から
明らかなように、通電することにより短時間で数十度に
加温できるため、寒冷地や寒い時期には該粘着剤を温め
て使用できるので、首や肩、腰等に貼った時頗る気持ち
良く、また電極材として優れ、柔軟性、密着性も良好で
あり、無毒性であるという著効を奏するものである。As is clear from the above description, since the conductive adhesive of the present invention can be heated to several tens of degrees in a short time by energizing, the adhesive can be heated in a cold region or a cold season. Since it can be used as such, it is extremely comfortable when applied to the neck, shoulders, waist, etc., and is excellent as an electrode material, has excellent flexibility and adhesion, and has a remarkable effect of being non-toxic.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭62−139628（ＪＰ，Ａ) 特開 昭58−183137（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) A61B 5/0408 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-62-139628 (JP, A) JP-A-58-183137 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) A61B 5/0408
Claims (1)
サイド鎖を有するウレタン樹脂粘着剤であって、含水処
理により含水率が２〜２０％に調整されていることを特
徴とする導電性粘着剤。An urethane resin pressure-sensitive adhesive having an alkylene oxide chain containing an ionic compound, wherein the water content is adjusted to 2 to 20% by a water-containing treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3246667A JP3023466B2 (en) | 1991-08-30 | 1991-08-30 | Conductive adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3246667A JP3023466B2 (en) | 1991-08-30 | 1991-08-30 | Conductive adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0556941A JPH0556941A (en) | 1993-03-09 |
| JP3023466B2 true JP3023466B2 (en) | 2000-03-21 |
Family
ID=17151825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3246667A Expired - Lifetime JP3023466B2 (en) | 1991-08-30 | 1991-08-30 | Conductive adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3023466B2 (en) |
-
1991
- 1991-08-30 JP JP3246667A patent/JP3023466B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0556941A (en) | 1993-03-09 |
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