JPH1171537A - Electroconductive coating material composition for floor and electroconductive floor material - Google Patents

Electroconductive coating material composition for floor and electroconductive floor material

Info

Publication number
JPH1171537A
JPH1171537A JP23354697A JP23354697A JPH1171537A JP H1171537 A JPH1171537 A JP H1171537A JP 23354697 A JP23354697 A JP 23354697A JP 23354697 A JP23354697 A JP 23354697A JP H1171537 A JPH1171537 A JP H1171537A
Authority
JP
Japan
Prior art keywords
weight
parts
conductive
floor
agent
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.)
Withdrawn
Application number
JP23354697A
Other languages
Japanese (ja)
Inventor
Hajime Osada
元 長田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Asahi Chemical Industry Co Ltd
Original Assignee
Asahi Chemical Industry Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Asahi Chemical Industry Co Ltd filed Critical Asahi Chemical Industry Co Ltd
Priority to JP23354697A priority Critical patent/JPH1171537A/en
Publication of JPH1171537A publication Critical patent/JPH1171537A/en
Withdrawn legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To obtain an electroconductive coating material composition for a floor, having stable antistatic effects, capable of being colored, and further capable of providing an antibacterial activities and/or antifungal activities. SOLUTION: This resin composition comprises 50-150 pts.wt. electroconductive zinc oxide having 2-20 μm particle diameter, 0.5-6 pts.wt. carbon fiber having 10-20 μm average diameter and 0.3-3 mm average length, 0.1-5 pts.wt. amidoamine-based disperser of a polyester acid, 0.1-5 pts.wt. antifoamer of a special modified vinylic polymer, and 0.01-0.1 pt.wt. antibacterial agent and/or 1-10 pts.wt. antifungal agent. The electroconductive floor material can be obtained by using the composition.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は、抗菌性または/お
よび防黴性付与可能な導電性床用塗材組成物、及び抗菌
性または/および防黴性付与可能な導電性床材に関し、
更に詳しくはクリーンルームや病院手術室、半導体工
場、食品工場、その他精密機械やコンピューター関連の
床に静電気除去の目的で使用する、抗菌性能または/お
よび防黴性能を有する導電性床用塗材組成物及び導電性
床材に関するものである。
The present invention relates to a conductive floor coating composition capable of imparting antibacterial and / or antifungal properties, and a conductive flooring capable of imparting antibacterial and / or antifungal properties.
More specifically, a conductive floor coating composition having antibacterial and / or antifungal properties for use in clean rooms, hospital operating rooms, semiconductor factories, food factories, and other precision machinery and computer-related floors for the purpose of removing static electricity. And a conductive flooring.

【0002】[0002]

【従来の技術】静電気障害を防止するためには、109
Ω以下のほぼ半導体領域の抵抗値(特に、105〜109
Ωが適切)があれば良いとされている。従来より、床材
に静電防止性を付与するには、被覆層を形成する塗材に
各種導電フィラーを混入して抵抗値を下げる手法が採ら
れてきた。それらの導電性フィラーとしては、形状が粉
末状のものでは、導電性カーボンブラック、グラファイ
ト、金属酸化物(酸化錫や酸化亜鉛)、金属粉(アルミ
ニウム、銅、銀)等があり、繊維状のものでは、炭素繊
維、金属繊維、金属コート繊維等がある。その他、粒状
のアルミニウムやステンレスのグリッドなどがある(特
公平2−2904号公報、特公平2−61799号公報
等参照)。
2. Description of the Related Art In order to prevent electrostatic interference, 10 9
Ω or less in a semiconductor region (especially, 10 5 to 10 9
Ω is appropriate). Conventionally, in order to impart antistatic properties to flooring materials, a technique of lowering the resistance value by mixing various conductive fillers into a coating material for forming a coating layer has been adopted. As the conductive fillers, those having a powdery shape include conductive carbon black, graphite, metal oxides (tin oxide and zinc oxide), metal powders (aluminum, copper, silver) and the like. Examples include carbon fibers, metal fibers, and metal-coated fibers. Other examples include grids of granular aluminum or stainless steel (see Japanese Patent Publication No. 2-2904, Japanese Patent Publication No. 2-61799, etc.).

【0003】しかるに、上記のような従来の静電気防止
性能を付与したいずれの床用塗材あるいは床材において
も、各種特性を満足するものではなかった。まず、色調
が黒色のカーボン系導電フィラーを用いたものは塗り床
材をカラー化できない欠点があり、金属系の導電フィラ
ーを用いたものは酸化により導電性が変化する欠点があ
る。更に、炭素繊維と金属繊維は上記欠点の他に分散性
にも問題があった。
[0003] However, none of the conventional floor coating materials or floor materials provided with the above-mentioned conventional antistatic performances satisfy the various characteristics. First, those using a carbon-based conductive filler having a black color have a drawback that the coated flooring material cannot be colored, and those using a metal-based conductive filler have a drawback that the conductivity changes due to oxidation. Further, carbon fibers and metal fibers have a problem in dispersibility in addition to the above-mentioned disadvantages.

【0004】次に、カラー化が容易な白色系導電フィラ
ーとしては、粉状の金属酸化物がある。しかし、粉状の
金属酸化物で導電性を得るためには極めて大量に添加す
る必要があり、塗材の機械的物性が極度に低下して、ク
ラックの発生や衝撃、荷重に弱い塗材に成らざるを得な
かった。一方、近年、厨房、食品加工場、病院、福祉施
設、医薬品工場、クリーンルーム、食品工場等の床で衛
生管理上の面から抗菌性能や防黴性能が要求されてお
り、抗菌性床材用として金属含有抗菌剤を使用したり
(特開平7−292288号公報、特開平7−2922
89号公報)、防黴材として珪酸アルカリ水溶液に亜硫
酸カルシウム等の無機質常温硬化剤を配合した組成物を
塗材、建材に使用したりすることが知られている(特公
昭59−40362号公報)。
[0004] As a white conductive filler which can be easily colored, there is a powdery metal oxide. However, in order to obtain conductivity with powdered metal oxides, it is necessary to add a very large amount, and the mechanical properties of the coating material are extremely deteriorated, so that the coating material is vulnerable to cracking, impact and load. I had to make it. On the other hand, in recent years, floors of kitchens, food processing plants, hospitals, welfare facilities, pharmaceutical factories, clean rooms, food factories, etc. have been required to have antibacterial performance and antifungal performance in terms of hygiene management, and are used for antibacterial flooring. Use of a metal-containing antibacterial agent (JP-A-7-292288, JP-A-7-2922)
No. 89), and it is known to use a composition prepared by blending an inorganic cold curing agent such as calcium sulfite in an aqueous alkali silicate solution as a fungicide for coating materials and building materials (Japanese Patent Publication No. 59-40362). ).

【0005】上述の床材としては、帯電防止性能に抗菌
性能または/および防黴性能を併せ持つ多機能性である
ことが望まれる。しかし、一般に床用塗材として使用さ
れる塗料は作業性が良好であることが要求される。ま
た、塗膜の性能として表面硬度や耐摩耗性等の機械的物
性や着色可能性、表面平滑性、脱泡性等の外観良好なる
ものが要求される。
[0005] It is desired that the above-mentioned flooring material be multifunctional having both antistatic performance and antibacterial performance and / or antifungal performance. However, paints generally used as floor coating materials are required to have good workability. Further, the coating film is required to have good mechanical properties such as surface hardness and abrasion resistance, and good appearance such as colorability, surface smoothness, and defoaming property.

【0006】このように作業性や塗膜の要求物性を維持
しつつ、帯電防止性能、抗菌および/または防黴性能と
いった多機能を付与した床材は実現されていなかった。
[0006] As described above, a flooring material having multifunctional properties such as antistatic performance, antibacterial and / or antifungal properties while maintaining workability and required physical properties of a coating film has not been realized.

【0007】[0007]

【発明が解決しようとする課題】本発明は、上記のよう
な問題点を解決し、安定した静電防止効果を有し、かつ
着色可能で抗菌性能または/および防黴性能を付与可能
な導電性床用塗材組成物及び導電性床材を提供すること
を目的とする。
DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems, has a stable antistatic effect, can be colored, and can impart antibacterial performance and / or antifungal performance. An object of the present invention is to provide a coating composition for conductive floors and a conductive flooring.

【0008】[0008]

【課題を解決するための手段】本発明者は、エポキシ樹
脂に導電性酸化亜鉛と抗菌剤または/および防黴剤を含
有させることで、作業性や塗膜の表面硬度、耐摩耗性、
着色可能等の塗膜の要求性能を満たしつつ、帯電防止と
抗菌性能または/および防黴性能を付与しうる多機能性
の床用塗材組成物が得られることを見出し、本発明を完
成した。
Means for Solving the Problems The present inventor has proposed that by adding conductive zinc oxide and an antibacterial agent and / or an antifungal agent to an epoxy resin, workability, surface hardness of a coating film, abrasion resistance, and the like can be improved.
It has been found that a multifunctional floor coating material composition capable of imparting antistatic and antibacterial performance or / and antifungal performance can be obtained while satisfying the required performance of a coating film such as a colorable film, and completed the present invention. .

【0009】すなわち、本発明は下記のとおりである。 1)エポキシ樹脂、導電性酸化亜鉛、抗菌剤または/お
よび防黴剤を必須成分とする導電性床用塗材組成物。 2)エポキシ樹脂100重量部に対して、導電性酸化亜
鉛50〜150部、抗菌剤0.01〜0.1重量部、ま
たは/および防黴剤1〜10重量部、分散剤0.1〜5
重量部、消泡剤0.1〜5重量部を含有することを特徴
とする上記1に記載の導電性床用塗材組成物。
That is, the present invention is as follows. 1) A conductive floor coating composition containing an epoxy resin, conductive zinc oxide, an antibacterial agent and / or a fungicide as essential components. 2) 100 to 100 parts by weight of epoxy resin, 50 to 150 parts of conductive zinc oxide, 0.01 to 0.1 part by weight of antibacterial agent, and / or 1 to 10 parts by weight of fungicide, 0.1 to 0.1 part by weight of dispersant. 5
The coating material composition for a conductive floor according to the above-mentioned item 1, comprising 0.1 part by weight and 0.1 to 5 parts by weight of an antifoaming agent.

【0010】3)エポキシ樹脂100重量部に対して、
粒子径2〜20μmの導電性酸化亜鉛50〜150重量
部、平均直径が10〜20μmで平均長さが0.3〜3
mmの炭素繊維0.5〜6重量部、抗菌剤0.01〜
0.1重量部、または/および防黴剤1〜10重量部、
ポリエステル酸のアマイドアミン系分散剤0.1〜5重
量部、特殊変性ビニル系重合物の消泡剤0.1〜5重量
部、を含有することを特徴とする上記1に記載の導電性
床用塗材組成物。
3) For 100 parts by weight of the epoxy resin,
50 to 150 parts by weight of conductive zinc oxide having a particle diameter of 2 to 20 μm, an average diameter of 10 to 20 μm, and an average length of 0.3 to 3
0.5 to 6 parts by weight of carbon fiber (mm), antimicrobial agent 0.01 to
0.1 part by weight, and / or 1 to 10 parts by weight of a fungicide,
2. The conductive floor according to the above item 1, comprising 0.1 to 5 parts by weight of an amide amine dispersant of a polyester acid and 0.1 to 5 parts by weight of an antifoaming agent of a specially modified vinyl polymer. Coating material composition.

【0011】4)上記1、2または3記載の組成物を被
覆層の少なくとも一部に有することを特徴とする導電性
床材。 以下、本発明につき詳述する。本発明で使用されるエポ
キシ樹脂は、1分子中に2個以上のエポキシ基を有する
ものであって、例えば、グリシジルエーテル類、グリシ
ジルエステル類、グリシジルアミン類、線状脂肪族エポ
キサイド類、脂環式エポキサイド類などが挙げられる。
[0011] 4) A conductive flooring material comprising the coating composition according to the above 1, 2 or 3 in at least a part of a coating layer. Hereinafter, the present invention will be described in detail. The epoxy resin used in the present invention has two or more epoxy groups in one molecule and includes, for example, glycidyl ethers, glycidyl esters, glycidylamines, linear aliphatic epoxides, and alicycles. Formula epoxides and the like.

【0012】グリシジルエーテル類としては、例えば、
ビスフェノールのジグリシジルエーテル、フェノールノ
ボラックのポリグリシジルエーテル、アルキレングリコ
ールまたはポリアルキレングリコールのジグリシジルエ
ーテルが挙げられる。該ビスフェノールのジグリシジル
エーテルとしては、例えば、ビスフェノールA、ビスフ
ェノールF、ビスフェノールAD、ビスフェノールS、
テトラメチルビスフェノールA、テトラブロモビスフェ
ノールAなどの二価フェノール類のジグリシジルエーテ
ルが、該フェノールノボラックのポリグリシジルエーテ
ルとしては、例えば、フェノールノボラック、クレゾー
ルノボラック、ブロム化フェノールノボラックなどのノ
ボラック樹脂のポリグリシジルエーテルが、該アルキレ
ングリコールまたはポリアルキレングリコールのジグリ
シジルエーテルとしては、例えば、ポリエチレングリコ
ール、ポリプロピレングリコール、ブタンジオールなど
のグリコール類のジグリシジルエーテルが挙げられる。
As glycidyl ethers, for example,
Examples include diglycidyl ether of bisphenol, polyglycidyl ether of phenol novolak, diglycidyl ether of alkylene glycol or polyalkylene glycol. Examples of the diglycidyl ether of bisphenol include bisphenol A, bisphenol F, bisphenol AD, bisphenol S,
Diglycidyl ethers of dihydric phenols such as tetramethylbisphenol A and tetrabromobisphenol A include polyglycidyl ethers of the phenol novolak, for example, polyglycidyl of novolak resins such as phenol novolak, cresol novolak, and brominated phenol novolak. Examples of the diglycidyl ether of the alkylene glycol or the polyalkylene glycol as the ether include diglycidyl ethers of glycols such as polyethylene glycol, polypropylene glycol, and butanediol.

【0013】また、前記グリシジルエステル類として
は、例えば、ヘキサヒドロフタル酸のジグリシジルエス
テル、ダイマー酸のジグリシジルエステルなどが挙げら
れる。グリシジルアミン類としては、例えば、テトラグ
リシジルジアミノジフェニルメタン、テトラグリシジル
イソシアヌレートなどが挙げられる。さらに線状脂肪族
エポキサイド類としては、例えば、エポキシ化ポリブタ
ジエン、エポキシ化大豆油などが挙げられる。脂環式エ
ポキサイド類としては、例えば、3,4−エポキシ−6
−メチルシクロヘキシルメチルカルボキシレート、3,
4−エポキシシクロヘキシルメチルカルボキシレートな
どが挙げられる。
The glycidyl esters include, for example, diglycidyl esters of hexahydrophthalic acid and diglycidyl esters of dimer acid. Examples of glycidylamines include tetraglycidyldiaminodiphenylmethane, tetraglycidyl isocyanurate, and the like. Further, examples of the linear aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil. Examples of alicyclic epoxides include 3,4-epoxy-6
-Methylcyclohexylmethyl carboxylate, 3,
4-epoxycyclohexylmethyl carboxylate and the like.

【0014】エポキシ樹脂はこれらに限定されるもので
はないが、好ましいエポキシ樹脂としてはグリシジルエ
ーテル類、グリシジルアミン類、グリシジルエステル類
であり、より好ましくはグリシジルエーテル類である。
グリシジルエーテル類で好ましいのはビスフェノール類
のジグリシジルエーテル類であり、特に好ましくはビス
フェノールA、ビスフェノールFのジグリシジルエーテ
ルである。エポキシ樹脂は単独で用いてもよく、2種以
上を組み合わせて用いてもよい。
The epoxy resin is not limited to these, but preferred epoxy resins are glycidyl ethers, glycidylamines and glycidyl esters, and more preferably glycidyl ethers.
Preferred among glycidyl ethers are diglycidyl ethers of bisphenols, and particularly preferred are diglycidyl ethers of bisphenol A and bisphenol F. The epoxy resins may be used alone or in combination of two or more.

【0015】エポキシ樹脂は、エポキシ当量100から
750の範囲のものが用いられ、好ましくは150から
300の範囲である。本発明においては、塗材のカラー
化を可能にし、かつ、安定した導電性を付与するため
に、導電性酸化亜鉛を使用する。本発明で使用される導
電性酸化亜鉛は、粒子径が2〜20μmのものが好まし
い。2μm未満のものは十分な導電性を得るためには配
合量を多くする必要があり、20μmを越えるものでは
塗材の安定性が低下し、塗膜の表面平滑性も不十分とな
る傾向がある。
An epoxy resin having an epoxy equivalent in the range of 100 to 750 is used, preferably in the range of 150 to 300. In the present invention, conductive zinc oxide is used in order to enable colorization of the coating material and to impart stable conductivity. The conductive zinc oxide used in the present invention preferably has a particle size of 2 to 20 μm. If it is less than 2 μm, it is necessary to increase the compounding amount in order to obtain sufficient conductivity. If it exceeds 20 μm, the stability of the coating material tends to decrease, and the surface smoothness of the coating film tends to be insufficient. is there.

【0016】導電性酸化亜鉛の配合量は、エポキシ樹脂
100重量部に対し50〜150重量部であることが好
ましい。導電性酸化亜鉛が150重量部を越えると粘度
が高くなり作業性が低下する傾向があり、50重量部未
満では導電性が必ずしも十分でない。本発明では、導電
性酸化亜鉛と炭素繊維を併用することが好ましい。併用
することにより、それぞれ単独では十分な抵抗値が得ら
れなかった配合量で導電性が確保できるとともに平滑性
のある優れた塗膜を得ることができる。また、併用する
ことにより、炭素繊維の配合量を少なくできるので、塗
り床材をカラー化することができる。本発明で使用され
る炭素繊維は、平均直径が10〜20μmで平均長さが
0.3〜3mmのものが良い。平均長さが0.3mm未
満のものを用いると導電性が不十分となり、また3mm
を越えた炭素繊維を用いると作業性が低下し、塗膜外観
が悪くなる傾向がある。
The amount of the conductive zinc oxide is preferably 50 to 150 parts by weight based on 100 parts by weight of the epoxy resin. If the conductive zinc oxide exceeds 150 parts by weight, the viscosity tends to increase and the workability tends to decrease. If the conductive zinc oxide is less than 50 parts by weight, the conductivity is not always sufficient. In the present invention, it is preferable to use conductive zinc oxide and carbon fiber in combination. By using them together, it is possible to secure conductivity and obtain a coating film having excellent smoothness at a compounding amount in which a sufficient resistance value was not obtained alone. In addition, the combined use can reduce the amount of carbon fiber blended, so that the coated flooring can be colored. The carbon fiber used in the present invention preferably has an average diameter of 10 to 20 μm and an average length of 0.3 to 3 mm. If the average length is less than 0.3 mm, the conductivity becomes insufficient, and 3 mm
When the carbon fiber exceeds the above, the workability tends to decrease and the appearance of the coating film tends to deteriorate.

【0017】炭素繊維の配合量は、エポキシ樹脂100
重量部に対し0.5〜6重量部であることが好ましい。
炭素繊維が6重量部を越えると着色が困難となったり、
粘度が高くなり作業性が低下する傾向があり、また、
0.5重量部未満では導電性が必ずしも十分でない。本
発明においては、必要に応じて着色剤を使用しうる。着
色剤としては、酸化チタン、酸化クロム、ベンガラ、カ
ーボンブラック等が例示される。
The compounding amount of the carbon fiber is 100
It is preferably 0.5 to 6 parts by weight based on parts by weight.
If the carbon fiber exceeds 6 parts by weight, coloring becomes difficult,
Viscosity tends to increase and workability tends to decrease, and
If it is less than 0.5 parts by weight, the conductivity is not always sufficient. In the present invention, a coloring agent may be used as necessary. Examples of the coloring agent include titanium oxide, chromium oxide, red iron oxide, and carbon black.

【0018】本発明においては、抗菌剤、防黴剤等を塗
料中で十分に分散させるためには分散剤を含有すること
が好ましい。使用される分散剤は種々の公知の分散剤を
配合することができる。例えば、脂肪族系多価カルボン
酸、高分子ポリエステルのアミン塩、ポリエーテル・エ
ステル型アニオン系界面活性剤、高分子量ポリカルボン
酸の長鎖アミン塩、長鎖ポリアミノアマイドと高分子ポ
リエステルの塩、長鎖ポリアミノアマイドのリン酸塩、
高分子量ポリエステル酸のアマイドアミン塩などが挙げ
られる。特に高分子量ポリエステル酸のアマイドアミン
塩は、炭素繊維の分散性を効果的に確保する。配合量は
エポキシ樹脂100重量部に対し、0.1〜5重量部で
あることが好ましい。0.1重量部未満では分散効果が
必ずしも十分ではなく、5重量部を越えると塗膜外観が
悪くなる傾向がある。
In the present invention, in order to sufficiently disperse an antibacterial agent, an antifungal agent and the like in a paint, it is preferable to contain a dispersant. As the dispersant to be used, various known dispersants can be blended. For example, aliphatic polycarboxylic acids, amine salts of high molecular weight polyesters, polyetherester type anionic surfactants, long chain amine salts of high molecular weight polycarboxylic acids, salts of long chain polyaminoamides and high molecular weight polyesters, Long-chain polyaminoamide phosphate,
Amideamine salts of high molecular weight polyester acids are exemplified. In particular, the amide amine salt of a high molecular weight polyester acid effectively secures the dispersibility of carbon fibers. The amount is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the epoxy resin. If it is less than 0.1 part by weight, the dispersing effect is not always sufficient, and if it exceeds 5 parts by weight, the appearance of the coating film tends to deteriorate.

【0019】本発明においては、塗膜の外観を良好にす
るために消泡剤を含有することが好ましい。本発明で使
用される消泡剤もまた種々の公知の消泡剤を配合するこ
とができる。例えば、特殊アクリル系重合物、シリコン
混合アクリル系重合物、特殊変性ビニル系重合物、特殊
高分子量シリコンなどがあげられる。特に、特殊変性ビ
ニル系重合物は塗膜の微小泡を除去する効果があり、塗
膜外観が良好となる。配合量は、エポキシ樹脂100重
量部に対し、0.1〜5重量部であることが好ましい。
0.1重量部未満では消泡効果が必ずしも十分ではな
く、5重量部を越えると塗膜外観が悪くなる傾向があ
る。
In the present invention, an antifoaming agent is preferably contained in order to improve the appearance of the coating film. The antifoaming agent used in the present invention can also contain various known antifoaming agents. For example, a special acrylic polymer, a silicone mixed acrylic polymer, a special modified vinyl polymer, a special high molecular weight silicon, and the like can be given. In particular, the specially modified vinyl polymer has an effect of removing fine bubbles from the coating film, and the coating film appearance is improved. The amount is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the epoxy resin.
If the amount is less than 0.1 part by weight, the defoaming effect is not always sufficient, and if it exceeds 5 parts by weight, the appearance of the coating film tends to deteriorate.

【0020】本発明で使用される抗菌剤は、種々の公知
の抗菌剤を一種または二種以上組み合わせて配合するこ
とができる。例えば、銀、銅、亜鉛等の金属粒子または
イオンもしくはその塩及び酸化物、銀ゼオライト、銀リ
ン酸塩系の無機系抗菌剤、有機系抗菌剤、天然物抗菌剤
などが挙げられる。特に、銀微粒子が効果の持続性から
好ましい。抗菌剤の形状、粒子径は、塗膜の表面の平滑
性に影響のない範囲で適宜選択すればよい。銀微粒子で
あれば、たとえば、特開平5−271718号公報に記
載の5〜10nmの超微粒などが好ましい。配合量は、
エポキシ樹脂100重量部に対し、0.01〜0.1重
量部が好ましい。
The antibacterial agent used in the present invention may be a mixture of various known antibacterial agents, alone or in combination of two or more. For example, metal particles such as silver, copper, zinc or the like or ions or salts and oxides thereof, silver zeolite, silver phosphate-based inorganic antibacterial agents, organic antibacterial agents, and natural product antibacterial agents are exemplified. In particular, silver fine particles are preferable from the viewpoint of persistence of the effect. The shape and particle size of the antibacterial agent may be appropriately selected within a range that does not affect the smoothness of the surface of the coating film. As silver fine particles, for example, ultrafine particles of 5 to 10 nm described in JP-A-5-271718 are preferable. The compounding amount is
0.01 to 0.1 part by weight is preferable for 100 parts by weight of the epoxy resin.

【0021】本発明で使用される防黴剤は、種々の公知
の防黴剤を一種または二種以上組み合わせて配合するこ
とができる。例えば、酸化珪素、ケイ酸ナトリウム、ケ
イ酸カリウム、ケイ酸カルシウム、ケイ酸マグネシウ
ム、ケイ酸アルミニウムなどのケイ酸塩、ベンズイミダ
ゾール系化合物やフタルイミド系化合物のような含窒素
芳香族化合物などがあげられるが、特にケイ酸カルシウ
ムおよび又はケイ酸マグネシウムが安全性の面から好ま
しい。たとえば、特公昭59−40362号公報に記載
のケイ酸アルカリ金属塩と酸化マグネシウムや酸化カル
シウム等の硬化剤との反応硬化物が使用できる。防黴剤
の形状、粒子径は、塗膜の表面の平滑性に影響のない範
囲で適宜選択すればよい。このましくは100メッシュ
アンダーである。配合量は、エポキシ樹脂100重量部
に対し、1〜10重量部が好ましい。
The antifungal agent used in the present invention may be a mixture of various known antifungal agents, alone or in combination of two or more. Examples thereof include silicates such as silicon oxide, sodium silicate, potassium silicate, calcium silicate, magnesium silicate, and aluminum silicate, and nitrogen-containing aromatic compounds such as benzimidazole compounds and phthalimide compounds. However, calcium silicate and / or magnesium silicate are particularly preferred from the viewpoint of safety. For example, a reaction cured product of an alkali metal silicate described in JP-B-59-40362 and a curing agent such as magnesium oxide or calcium oxide can be used. The shape and particle size of the fungicide may be appropriately selected within a range that does not affect the smoothness of the surface of the coating film. Preferably, it is under 100 mesh. The amount is preferably 1 to 10 parts by weight based on 100 parts by weight of the epoxy resin.

【0022】本発明で使用される抗菌剤と防黴剤とは、
目的に応じて、一方のみを用いてもよいし、両方を併用
してもよい。また、本発明においては、硬化剤としてポ
リアミンが用いられる。ポリアミンとしては、脂肪族ポ
リアミン、脂環族ポリアミン、芳香族ポリアミンなどの
未変性ポリアミンや、未変性ポリアミンを脂肪酸などと
重縮合したポリアミド、または、フェノール/ホルムア
ルデヒドなどと重縮合(マニッヒ)した変性ポリアミン
等が挙げられる。
The antibacterial agent and the antifungal agent used in the present invention are:
Depending on the purpose, only one of them may be used, or both may be used in combination. In the present invention, a polyamine is used as a curing agent. Examples of the polyamine include unmodified polyamines such as aliphatic polyamines, alicyclic polyamines, and aromatic polyamines, polyamides obtained by polycondensation of unmodified polyamines with fatty acids, and modified polyamines obtained by polycondensation (Mannich) with phenol / formaldehyde and the like. And the like.

【0023】脂肪族ポリアミンとしては、例えば、エチ
レンジアミン、ジエチレントリアミン、トリエチレンテ
トラミン、テトラエチレンペンタミン、ペンタエチレン
ヘキサミン、ヘキサメチレンジアミンなどが代表として
挙げられる。脂環族ポリアミンとしては、例えば、メン
センジアミン、イソホロンジアミン、N−アミンエチル
ピペラジン、ビス(4−アミノ−3−メチルシクロヘキ
シル)メタンなどが代表として挙げられる。また、芳香
族ポリアミンとしては、例えば、メタキシレンジアミ
ン、ジアミノジフェニルメタン、ジアミノジフェニルス
ルホン、m−フェニレンジアミンなどが代表として挙げ
られる。また、ポリアミドは、分子中に複数の活性なア
ミノ基をもち、同様にアミド基を1個以上もつものであ
る。例としては、天然の不飽和脂肪酸から作られる重合
脂肪酸(慣用的にはダイマー酸)と必要に応じて加えら
れる他の脂肪酸との混合物に未変性ポリアミンを縮合反
応させて作られるものが挙げられる。
Examples of the aliphatic polyamine include, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenediamine and the like. Representative alicyclic polyamines include, for example, mensendiamine, isophoronediamine, N-amineethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, and the like. Further, as the aromatic polyamine, for example, metaxylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, m-phenylenediamine and the like can be mentioned as representatives. Further, polyamide has a plurality of active amino groups in the molecule and similarly has one or more amide groups. Examples include those made by the condensation reaction of unmodified polyamines with a mixture of a polymerized fatty acid (conventionally dimer acid) made from natural unsaturated fatty acids and other fatty acids added as needed. .

【0024】本発明においては、必要に応じて硬化促進
剤を用いることも可能である。硬化促進剤としては、フ
ェノール、クレゾールなどのフェノール類やN,N’−
ジメチルピペラジン、2,4,6−トリス(ジメチルア
ミノメチル)フェノールなどの第3級アミン類を挙げる
ことができる。次に、本発明の導電性床材の製造方法で
あるが、前記の導電性塗材組成物の原材料を十分に混合
し、または分散させた後、床基材の表面に流し塗り、コ
テ塗り等で塗布し、膜化させる方法をとる。塗布に際し
ては、塗厚が1〜2mmとなるように行うのが一般的で
ある。
In the present invention, a curing accelerator can be used if necessary. Examples of the curing accelerator include phenols such as phenol and cresol, and N, N'-
Tertiary amines such as dimethylpiperazine and 2,4,6-tris (dimethylaminomethyl) phenol can be mentioned. Next, in the method for producing a conductive flooring material of the present invention, after thoroughly mixing or dispersing the raw materials for the conductive coating material composition, flow coating the surface of the floor base material, ironing Etc. and apply a film. In general, the coating is performed so that the coating thickness is 1 to 2 mm.

【0025】[0025]

【発明の実態の形態】以下、実施例により本発明を具体
的に説明するが、本発明は以下の実施例のみに限定され
るものではない。なお、得られた塗材の評価について
は、次の試験方法によった。 (a)表面漏洩抵抗値 910×910×5mmのスレート板に塗材を2kgコ
テ塗りで塗布し、翌日硬化後、NFPA法により測定し
た。
Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples. In addition, about the evaluation of the obtained coating material, the following test methods were used. (A) Surface Leakage Resistance The coating material was applied to a slate plate of 910 × 910 × 5 mm with a 2 kg iron coating, cured the next day, and measured by the NFPA method.

【0026】(b)機械的物性 [表面硬度]JIS K 7215に準拠して、ショア
ーDを測定した。[耐摩耗性]JIS K 7204に
準拠して、摩耗輪CS−17を用い測定した。測定値は
摩耗量(mg)で表す。 (c)抗菌試験 50×50mm、塗膜厚約1mmの試料を作成し、50
℃温水にて洗浄した後、これに黄色ブドウ球菌懸濁液
(約5×105 個/ミリリットル)または大腸菌(約5
×105 個/ミリリットル)を1ミリリットル滴下し、
30℃で24時間培養した。培養後、滅菌済み燐酸緩衝
液にて菌を洗い出し、この洗い出した液中の生存菌数
(個/ミリリットル)を菌数測定培地を用いて平板希釈
法にて測定した。
(B) Mechanical properties [Surface hardness] Shore D was measured according to JIS K 7215. [Abrasion resistance] Measured using a worn wheel CS-17 according to JIS K 7204. The measured value is represented by the amount of wear (mg). (C) Antibacterial test A sample having a size of 50 × 50 mm and a film thickness of about 1 mm was prepared,
After washing with warm water at room temperature, a suspension of S. aureus (about 5 × 10 5 cells / ml) or E. coli (about 5 × 10 5 cells / ml) was added thereto.
1 × 10 5 drops / ml)
The cells were cultured at 30 ° C. for 24 hours. After the culture, the bacteria were washed out with a sterilized phosphate buffer, and the number of surviving bacteria (cells / milliliter) in the washed-out solution was measured by a plate dilution method using a culture medium for measuring the number of bacteria.

【0027】(d)防黴試験 試料は抗菌試験に用いたのと同様に作成した。試験方法
はJIS Z 2911に準拠し、試験菌の胞子混合分
散液を平板上の試料と培地に吹き付け、30℃、湿度9
5%RHの条件で40日間培養した。カビ抵抗性の表示
は次の通り。 3:試料、又は試料片の接種した部分に菌糸の発育が認
められない。
(D) Antifungal test A sample was prepared in the same manner as used in the antibacterial test. The test method was based on JIS Z 2911, and a spore mixed dispersion of the test bacterium was sprayed on the sample and the medium on the plate, and the temperature was 30 ° C. and the humidity was 9
The cells were cultured for 40 days under the condition of 5% RH. The display of mold resistance is as follows. 3: No hyphal growth was observed in the inoculated portion of the sample or the sample piece.

【0028】2:試料、又は試料片の接種した部分に認
められる菌糸の発育部分の面積は、体の1/3を越えな
い。 1:試料、又は試料片の接種した部分に認められる菌糸
の発育部分の面積は、体の1/3を越える。 (e)作業性 910×910×5mmのスレート板に塗材を2kgコ
テ塗りで塗布した時の塗材の広がり具合から判断した。
2: The area of the hyphal growth area observed in the inoculated portion of the sample or the sample piece does not exceed 1/3 of the body. 1: The area of the hyphal growth part observed in the inoculated part of the sample or the sample piece exceeds one third of the body. (E) Workability Judgment was made based on the spread of the coating material when the coating material was applied on a 910 × 910 × 5 mm slate plate with a 2 kg iron coating.

【0029】極めて良好(◎)→良好(○)→やや気に
なる(△)→気になる(×) (f)塗膜の表面外観 910×910×5mmのスレート板に塗材を2kgコ
テ塗りで塗布し、翌日硬化後、肉眼により観察した。 [着色性]炭素繊維による黒ずみが全く気にならない
(◎)→ほとんど気にならない(○)→やや気になる
(△)→気になる(×) [表面平滑性]光沢があり極めて滑らか(◎)→光沢が
あり滑らか(○)→光沢あるもややザラツキ感あり
(△)→光沢なくザラツキ感あり(×) [脱泡性]ほぼ泡は残っていない(◎)→細かい泡が残
る程度(○)→多少泡が残る(△)→泡が残るか泡がは
じけて孔が残る(×) [炭素繊維の分散性]均一に分散(◎)→ほぼ均一に分
散(○)→多少塊となっているものも存在(△)→部分
的に集合し塊が目立つ(×)
Very good (◎) → good (○) → slightly anxious (△) → anxious (x) (f) Surface appearance of coating film A 910 × 910 × 5 mm slate plate is coated with 2 kg of coating material. It was applied with a coat and cured the next day, and visually observed. [Coloring property] Blackening due to carbon fiber is not bothersome (◎) → hardly bothersome (○) → slightly worrisome (△) → worrisome (×) [Surface smoothness] glossy and extremely smooth ( ◎) → glossy and smooth (○) → glossy and slightly rough (△) → glossy and rough (×) [Defoaming] Almost no bubbles remain (◎) → Fine bubbles remain (○) → Some bubbles remain (△) → Bubbles remain or bubbles pop out and holes remain (X) [Dispersibility of carbon fiber] Uniformly dispersed (◎) → Almost uniformly dispersed (○) → Some lump Also exist (△) → clusters are partially conspicuous and lump is conspicuous (×)

【0030】[0030]

【実施例1】表1に示した配合に従い、エポキシ当量1
90のビスフェノールAジグリシジルエーテル(旭チバ
社製、アラルダイトAER260)100重量部、平均
粒子径3〜6μmの酸化亜鉛(白水化学社製:PZ)1
00重量部、着色顔料20重量部を高速撹拌機で15分
間混合した後、平均長さ0.7mm、直径13mmの炭
素繊維(大阪ガス社製、ドナカーボS−244)4重量
部、ポリエステル酸のアマイドアミン系分散剤(楠本化
成社製、ディスパロンDA703−50)2重量部およ
び特殊変性ビニル系重合物の消泡剤(楠本化成社製、デ
ィスパロンP420)2重量部、抗菌剤として5〜10
nmの銀微粒子を0.05重量部投入し、高速撹拌機で
5分間混合した。
Example 1 According to the composition shown in Table 1, an epoxy equivalent of 1
90 parts by weight of bisphenol A diglycidyl ether (Alardite AER260, manufactured by Asahi Ciba Co., Ltd.) 100 parts by weight, zinc oxide (PZ) manufactured by Hakusui Chemical Co., Ltd.
After mixing 00 parts by weight and 20 parts by weight of the color pigment with a high-speed stirrer for 15 minutes, 4 parts by weight of carbon fiber (Donacarb S-244, manufactured by Osaka Gas Co., Ltd.) having an average length of 0.7 mm and a diameter of 13 mm, and a polyester acid 2 parts by weight of an amide amine-based dispersant (Kusumoto Kasei Co., Disparon DA703-50) and 2 parts by weight of a specially modified vinyl polymer defoamer (Kusumoto Kasei Co., Ltd., Disparon P420), 5 to 10 as antibacterial agents
0.05 parts by weight of silver fine particles having a diameter of 0.05 nm were charged, and mixed for 5 minutes by a high-speed stirrer.

【0031】この混合物に硬化剤として変性脂肪族ポリ
アミン(大日本インキ化学社製、ラッカマイドWGA2
81)40重量部を混合し、塗材組成物を得た。得られ
た塗膜の性能試験結果を表2に示す。
A modified aliphatic polyamine (Lacamide WGA2 manufactured by Dainippon Ink and Chemicals, Inc.) was used as a curing agent in this mixture.
81) 40 parts by weight were mixed to obtain a coating material composition. Table 2 shows the performance test results of the obtained coating films.

【0032】[0032]

【実施例2】表1に示すごとく、酸化亜鉛80重量部、
分散剤、消泡剤をそれぞれ3重量部とし、平均長さ3m
m、直径13mmの炭素繊維(大阪ガス社製、ドナカー
ボS−231)5重量部、防黴剤としてケイ酸塩系防黴
剤(ケイ酸カリウムと亜硫酸カルシウムとの反応硬化
物)4重量部を用いた以外は、実施例1と同様にして塗
材組成物を得た。得られた塗膜の性能試験結果を表2に
示す。
Example 2 As shown in Table 1, 80 parts by weight of zinc oxide
The dispersant and the defoamer are each 3 parts by weight, and the average length is 3 m
m, 5 parts by weight of carbon fiber having a diameter of 13 mm (Donacarbo S-231 manufactured by Osaka Gas Co., Ltd.), and 4 parts by weight of a silicate-based antifungal agent (reaction cured product of potassium silicate and calcium sulfite) as an antifungal agent Except for using, a coating material composition was obtained in the same manner as in Example 1. Table 2 shows the performance test results of the obtained coating films.

【0033】[0033]

【実施例3】表1に示すごとく、酸化亜鉛を120重量
部とし、炭素繊維量、分散剤量および消泡剤量を半分に
した。また抗菌剤として5〜10nmの銀微粒子を0.
05重量部、防黴剤としてケイ酸塩系防黴剤(ケイ酸ナ
トリウムと酸化マグネシウムとの反応硬化物)4重量部
を用いた以外は、実施例1と同様にして塗材組成物を得
た。得られた塗膜の性能試験結果を表2示す。
Example 3 As shown in Table 1, the amount of zinc oxide was 120 parts by weight, and the amounts of carbon fibers, dispersants and defoamers were halved. In addition, 5 to 10 nm of silver fine particles are used as an antibacterial agent.
A coating material composition was obtained in the same manner as in Example 1, except that 05 parts by weight and 4 parts by weight of a silicate-based antifungal agent (a reaction cured product of sodium silicate and magnesium oxide) were used as an antifungal agent. Was. Table 2 shows the performance test results of the obtained coating films.

【0034】[0034]

【実施例4】表1に示すごとく、分散剤および消泡剤を
添加しないこと以外は実施例1と同様にして、塗材組成
物を得た。得られた塗膜の性能試験結果を表2に示す。
Example 4 As shown in Table 1, a coating material composition was obtained in the same manner as in Example 1 except that no dispersant and defoaming agent were added. Table 2 shows the performance test results of the obtained coating films.

【0035】[0035]

【実施例5】表1に示すごとく、平均長さ0.13m
m、直径13mmの炭素繊維(大阪ガス社製、ドナカー
ボS−241)4重量部を用い、実施例1と同様にして
塗材組成物を得た。得られた塗膜の性能試験結果を表2
に示す。
Embodiment 5 As shown in Table 1, the average length is 0.13 m
A coating material composition was obtained in the same manner as in Example 1 using 4 parts by weight of carbon fiber (Donacarb S-241, manufactured by Osaka Gas Co., Ltd.) having a diameter of 13 mm. Table 2 shows the performance test results of the obtained coating films.
Shown in

【0036】[0036]

【実施例6】表1に示すごとく、分散剤を特殊変性ポリ
アマイド系分散剤(楠本化成社製、ディスパロンDA−
400N)とした他は実施例3と同様にして、塗材組成
物を得た。得られた塗膜の性能試験結果を表2に示す。
Example 6 As shown in Table 1, the dispersant was a specially modified polyamide-based dispersant (Kusumoto Kasei Co., Ltd., Dispalon DA-).
A coating material composition was obtained in the same manner as in Example 3 except that the pressure was set to 400 N). Table 2 shows the performance test results of the obtained coating films.

【0037】[0037]

【実施例7】表1に示すごとく、消泡剤を特殊アクリル
系の消泡剤(楠本化成社製、ディスパロン230)とし
た他は実施例3と同様にして、塗材組成物を得た。得ら
れた塗膜の性能試験結果を表2に示す。
Example 7 As shown in Table 1, a coating material composition was obtained in the same manner as in Example 3 except that a special acrylic defoaming agent (Kusumoto Kasei Co., Dispalon 230) was used as the defoaming agent. . Table 2 shows the performance test results of the obtained coating films.

【0038】[0038]

【実施例8】表1に示すごとく、消泡剤をシリコン系の
消泡剤(ダウコーニング社製、ペインダットS)とした
他は実施例3と同様にして、塗材組成物を得た。得られ
た塗膜の性能試験結果を表2に示す。
Example 8 As shown in Table 1, a coating material composition was obtained in the same manner as in Example 3, except that the defoaming agent was a silicone-based defoaming agent (Paindat S, manufactured by Dow Corning). Table 2 shows the performance test results of the obtained coating films.

【0039】[0039]

【比較例1】表1に示すごとく、炭素繊維、分散剤、消
泡剤、抗菌剤および防黴剤を添加しないで、酸化亜鉛2
00重量部のみを用い、実施例1と同様にして塗材組成
物を得た。得られた塗膜の性能試験結果を表2に示す。
Comparative Example 1 As shown in Table 1, zinc oxide 2 was added without adding carbon fibers, dispersants, defoaming agents, antibacterial agents and fungicides.
Using only 00 parts by weight, a coating material composition was obtained in the same manner as in Example 1. Table 2 shows the performance test results of the obtained coating films.

【0040】[0040]

【比較例2】表1に示すごとく、酸化亜鉛、炭素繊維、
分散剤、消泡剤および防黴剤を添加しないで、抗菌剤
0.05重量部のみを用い、実施例1と同様にして塗材
組成物を得た。得られた塗膜の性能試験結果を表2に示
す。
Comparative Example 2 As shown in Table 1, zinc oxide, carbon fiber,
A coating material composition was obtained in the same manner as in Example 1 except that only 0.05 parts by weight of the antibacterial agent was used without adding a dispersant, an antifoaming agent, and a fungicide. Table 2 shows the performance test results of the obtained coating films.

【0041】[0041]

【比較例3】表1に示すごとく、酸化亜鉛、炭素繊維、
分散剤、消泡剤および抗菌剤を添加しないで、防黴剤4
重量部のみを用い、実施例1と同様にして塗材組成物を
得た。得られた塗膜の性能試験結果を表2に示す。
Comparative Example 3 As shown in Table 1, zinc oxide, carbon fiber,
Without adding dispersant, defoamer and antibacterial agent, fungicide 4
A coating material composition was obtained in the same manner as in Example 1 using only parts by weight. Table 2 shows the performance test results of the obtained coating films.

【0042】[0042]

【表1】 [Table 1]

【0043】[0043]

【表2】 [Table 2]

【0044】[0044]

【発明の効果】本発明によれば、抗菌剤または/および
防黴剤を用いることにより、表面硬度や耐摩耗性等の機
械的物性を維持しつつ、導電性を損なうことなく抗菌性
能および又は防黴性能を付与可能にすることができる。
また、特定の分散剤と特定の消泡剤を用いることによ
り、塗膜外観および作業性を改善することができる。
According to the present invention, by using an antibacterial agent and / or an antifungal agent, the antibacterial performance and / or the antimicrobial performance can be maintained without impairing the conductivity while maintaining mechanical properties such as surface hardness and abrasion resistance. The antifungal property can be imparted.
Further, by using a specific dispersant and a specific antifoaming agent, the appearance and workability of the coating film can be improved.

【0045】さらに、本発明によれば、上述の効果に加
えて、特定の導電性フィラーを2種類混合することによ
って、それぞれ単独では充分な抵抗値が得られなかった
配合量で導電性が確保できると共に、炭素繊維のみでは
不可能とされていた着色を可能とすることができる。
Further, according to the present invention, in addition to the above-described effects, by mixing two kinds of specific conductive fillers, the conductivity can be ensured at a compounding amount at which a sufficient resistance value could not be obtained by itself. In addition to this, it is possible to achieve coloring that has been impossible with only carbon fibers.

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 エポキシ樹脂、導電性酸化亜鉛、抗菌剤
または/および防黴剤を必須成分とする導電性床用塗材
組成物。
1. A conductive floor coating composition comprising an epoxy resin, conductive zinc oxide, an antibacterial agent and / or an antifungal agent as essential components.
【請求項2】 エポキシ樹脂100重量部に対して、導
電性酸化亜鉛50〜150部、抗菌剤0.01〜0.1
重量部、または/および防黴剤1〜10重量部、分散剤
0.1〜5重量部、消泡剤0.1〜5重量部を含有する
ことを特徴とする請求項1に記載の導電性床用塗材組成
物。
2. 50 to 150 parts of conductive zinc oxide, 0.01 to 0.1 parts of antibacterial agent per 100 parts by weight of epoxy resin.
2. The conductive material according to claim 1, further comprising 1 to 10 parts by weight of a fungicide, 0.1 to 5 parts by weight of a dispersant, and 0.1 to 5 parts by weight of a defoamer. Floor coating composition.
【請求項3】 エポキシ樹脂100重量部に対して、粒
子径2〜20μmの導電性酸化亜鉛50〜150重量
部、平均直径が10〜20μmで平均長さが0.3〜3
mmの炭素繊維0.5〜6重量部、抗菌剤0.01〜
0.1重量部、または/および防黴剤1〜10重量部、
ポリエステル酸のアマイドアミン系分散剤0.1〜5重
量部、特殊変性ビニル系重合物の消泡剤0.1〜5重量
部、を含有することを特徴とする請求項1に記載の導電
性床用塗材組成物。
3. An electrically conductive zinc oxide having a particle diameter of 2 to 20 μm, an average diameter of 10 to 20 μm and an average length of 0.3 to 3 based on 100 parts by weight of the epoxy resin.
0.5 to 6 parts by weight of carbon fiber (mm), antimicrobial agent 0.01 to
0.1 part by weight, and / or 1 to 10 parts by weight of a fungicide,
2. The conductive material according to claim 1, comprising 0.1 to 5 parts by weight of an amide amine dispersant of a polyester acid and 0.1 to 5 parts by weight of an antifoaming agent of a specially modified vinyl polymer. 3. Floor coating material composition.
【請求項4】 請求項1、2または3記載の組成物を被
覆層の少なくとも一部に有することを特徴とする導電性
床材。
4. A conductive flooring material comprising the composition according to claim 1, 2 or 3 in at least a part of a coating layer.
JP23354697A 1997-08-29 1997-08-29 Electroconductive coating material composition for floor and electroconductive floor material Withdrawn JPH1171537A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP23354697A JPH1171537A (en) 1997-08-29 1997-08-29 Electroconductive coating material composition for floor and electroconductive floor material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP23354697A JPH1171537A (en) 1997-08-29 1997-08-29 Electroconductive coating material composition for floor and electroconductive floor material

Publications (1)

Publication Number Publication Date
JPH1171537A true JPH1171537A (en) 1999-03-16

Family

ID=16956761

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JPH1171537A (en)

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JP2007182356A (en) * 2006-01-10 2007-07-19 Nok Corp Method for forming carbon nanotube thin film
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