【０００１】[0001]
【発明の属する技術分野】本発明は、プラスチック基材
への密着性、透明性、導電性、耐溶剤性および耐水性に
優れた塗膜を形成する、水系で一液の帯電防止コーティ
ング用組成物に関する。このような塗膜は、電子材料包
装用のキャリアテープ、カバーテープ、およびトレイ、
ならびにワープロ、コンピュータ、テレビなどの各種デ
ィスプレイ、または偏光板などの光学部品の表面保護フ
ィルムなどに用いられる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based, one-part antistatic coating composition for forming a coating film having excellent adhesion to plastic substrates, transparency, conductivity, solvent resistance and water resistance. About things. Such coatings include carrier tapes, cover tapes, and trays for electronic material packaging,
In addition, it is used for various displays such as word processors, computers, and televisions, and surface protective films for optical components such as polarizing plates.
【０００２】[0002]
【従来の技術】プラスチックは軽くて成型しやすく、し
かも腐蝕し難いなどの利点があるために各種産業分野に
おいて数多く使用されている。しかしながら、プラスチ
ックは帯電しやすいために用途が制限されているのも事
実である。そこで、帯電防止のために、界面活性剤、カ
ーボンブラック、無機酸化物フィラー、金属粉、あるい
はπ共役系の導電性ポリマーなどをプラスチックに練り
込むか、これらの物質を用いてプラスチックの表面を加
工するなどの方法が試みられている。2. Description of the Related Art Plastics are widely used in various industrial fields because of their advantages such as being light, easy to mold, and resistant to corrosion. However, it is true that plastics are easily charged and their applications are limited. Therefore, in order to prevent static charge, surfactant, carbon black, inorganic oxide filler, metal powder, π-conjugated conductive polymer, etc. are kneaded into the plastic, or the plastic surface is processed using these substances. And other methods have been attempted.
【０００３】帯電防止のために用いられるπ共役系の導
電性ポリマーとしては、ポリアセチレン、ポリ（パラフ
ェニレン）、ポリアニリン、ポリピロール、ポリチオフ
ェンなどがある。これらは、そのほとんどが塗膜形成に
使用する溶媒に溶解しにくいため、容易には均一な塗膜
を形成できないのが実情である。そこで、これらのポリ
マーを化学修飾して溶解度を向上させる（特開平７−２
９２０８１号公報）、微粒子の分散液とする（時開平１
−３１３５２１号公報）などの方法で、均一な塗膜を形
成する工夫がなされている。[0003] Examples of the π-conjugated conductive polymer used for antistatic purposes include polyacetylene, poly (paraphenylene), polyaniline, polypyrrole, and polythiophene. Since most of them are hardly dissolved in a solvent used for forming a coating film, the fact is that a uniform coating film cannot be easily formed. Therefore, these polymers are chemically modified to improve solubility (Japanese Patent Laid-Open No. 7-2).
No. 92081), a dispersion of fine particles (Tokikaihei 1)
For example, a method of forming a uniform coating film has been devised by a method such as the method described in US Pat.
【０００４】また、ポリ（３,４−ジアルコキシチオフ
ェン）とポリ陰イオンとから成る導電性ポリマーは、
３，４−ジアルコキシチオフェンをポリ陰イオン存在下
で、酸化重合することによって得られるものである（特
開平１−３１３５２１号公報）が、高い導電性、高い化
学的安定性、および成膜した際の塗膜の高い透明性を有
していることで注目されている。A conductive polymer comprising poly (3,4-dialkoxythiophene) and a polyanion is:
It is obtained by oxidative polymerization of 3,4-dialkoxythiophene in the presence of a polyanion (JP-A-1-313521), but has high conductivity, high chemical stability, and film formation. Attention has been paid to the high transparency of the resulting coating film.
【０００５】しかしながら、このような導電性ポリマー
を含むコーティング液をプラスチック基材に塗布する場
合、基材に対する密着性、透明性、耐水性、耐溶剤性お
よび導電性のすべての性能を同時に満足する塗膜を得る
ことは非常に困難である。However, when a coating solution containing such a conductive polymer is applied to a plastic substrate, all the properties of adhesion to the substrate, transparency, water resistance, solvent resistance and conductivity are simultaneously satisfied. Obtaining a coating is very difficult.
【０００６】特に、 ポリ（３,４−ジアルコキシチオフ
ェン）とポリ陰イオンとから成る導電性ポリマーを含む
コーティング液は、その成分に親水性の高いポリ陰イオ
ンを含むため、バインダー樹脂を添加して基材に塗布し
た場合、得られる塗膜の耐水性は非常に悪い。In particular, a coating solution containing a conductive polymer composed of poly (3,4-dialkoxythiophene) and a polyanion contains a highly hydrophilic polyanion as a component thereof, and thus a binder resin is added. When applied to substrates, the resulting coating film has very poor water resistance.
【０００７】そこで、塗膜の耐水性を向上させるため
に、バインダー樹脂をメラミン系、ポリカルボジイミド
系、ポリオキサゾリジン系、ポリエポキシ系およびポリ
イソシアネート系の架橋剤で架橋する方法、バインダー
樹脂としてＵＶまたはＥＢ硬化樹脂を用いてＵＶまたは
ＥＢ照射して成膜する方法などが試みられている。Therefore, in order to improve the water resistance of the coating film, a method of crosslinking the binder resin with a melamine-based, polycarbodiimide-based, polyoxazolidine-based, polyepoxy-based, or polyisocyanate-based crosslinking agent; A method of forming a film by irradiating UV or EB using an EB cured resin has been attempted.
【０００８】しかしながら、ポリ（３,４−ジアルコキ
シチオフェン）とポリ陰イオンとから成る導電性ポリマ
ーを含むコーティング液に架橋剤を添加した場合、コー
ティング液の貯蔵安定性が悪くなる、ポットライフが短
くなるなどの問題点がある。また、成膜時の乾燥・硬化
の温度および時間が十分でないと、塗膜の耐水性は向上
しないという問題もある。However, when a cross-linking agent is added to a coating solution containing a conductive polymer composed of poly (3,4-dialkoxythiophene) and a polyanion, the storage stability of the coating solution is deteriorated and the pot life is reduced. There are problems such as shortening. Further, there is also a problem that the water resistance of the coating film is not improved unless the temperature and time for drying and curing during film formation are sufficient.
【０００９】さらに、ポリ（３,４−ジアルコキシチオ
フェン）とポリ陰イオンとから成る導電性ポリマーを含
むコーティング液にバインダー樹脂として、ＵＶ硬化性
樹脂あるいはＥＢ硬化性樹脂を添加した場合でも、架橋
剤を添加したときと同様に、コーティング液の貯蔵安定
性が悪くなる、ポットライフが短くなるなどの問題点が
ある。さらに、樹脂の硬化のためにＵＶまたはＥＢ照射
設備が必要となり、製造コストの増加につながり好まし
くない。Further, even when a UV-curable resin or an EB-curable resin is added as a binder resin to a coating solution containing a conductive polymer composed of poly (3,4-dialkoxythiophene) and a polyanion, cross-linking occurs. Similar to the case where the agent is added, there are problems such as the storage stability of the coating liquid being deteriorated and the pot life being shortened. Further, UV or EB irradiation equipment is required for curing the resin, which undesirably leads to an increase in manufacturing cost.
【００１０】特開平６−２９５０１６号公報には、ポリ
（３,４−ジアルコキシチオフェン）とポリ陰イオンと
から成る導電性ポリマーを用いた帯電防止コーティング
液組成物の上記問題点を改良するため、この組成物に架
橋剤を含む自己乳化型ポリエステル樹脂水分散体を含有
させ、ＰＥＴ基材に対して密着性がよく、基材の延伸後
も帯電防止に十分な表面抵抗率を示す帯電防止コーティ
ング液組成物が得られることが記載されている。しか
し、この自己乳化型ポリエステル樹脂のジカルボン酸成
分のうち、水分散性を高めるための５−スルホイソフタ
ル酸の含量は６〜１０モル％と高く、塗膜に耐水性を付
与することが期待できない。Japanese Unexamined Patent Publication No. 6-295016 discloses an antistatic coating liquid composition using a conductive polymer comprising poly (3,4-dialkoxythiophene) and a polyanion in order to improve the above problems. The composition contains an aqueous dispersion of a self-emulsifying polyester resin containing a cross-linking agent, has good adhesion to a PET substrate, and exhibits sufficient surface resistivity for preventing static electricity even after stretching the substrate. It is described that a coating liquid composition is obtained. However, among the dicarboxylic acid components of the self-emulsifying polyester resin, the content of 5-sulfoisophthalic acid for enhancing water dispersibility is as high as 6 to 10 mol%, and it is not expected to impart water resistance to the coating film. .
【００１１】また、特開平６−７３２７１号公報には、
ポリ（３,４−ジアルコキシチオフェン）とポリ陰イオ
ンとから成る導電性ポリマーの層と、これに隣接する層
との密着性を向上させる目的でエポキシ基を有するアル
コキシシラン化合物が用いられているが、塗膜の耐水性
を付与することは期待できない。Japanese Patent Application Laid-Open No. 6-73271 discloses that
An alkoxysilane compound having an epoxy group is used for the purpose of improving the adhesion between a conductive polymer layer composed of poly (3,4-dialkoxythiophene) and a polyanion and an adjacent layer. However, it cannot be expected to impart water resistance to the coating film.
【００１２】このように、コーティング液が一液で、比
較的低温で、短時間乾燥するだけで成膜でき、生じる塗
膜は基材、特にプラスチック基材に対して密着性、透明
性、導電性、耐溶剤性、および特に耐水性に優れた帯電
防止コーティング用組成物が望まれている。As described above, a single coating solution can be formed at a relatively low temperature at a relatively low temperature by simply drying it for a short time, and the resulting coating film has adhesion, transparency, and conductivity to a substrate, especially a plastic substrate. There is a need for a composition for an antistatic coating having excellent resistance, solvent resistance, and especially excellent water resistance.
【００１３】[0013]
【発明が解決しようとする課題】本発明は、上記課題を
解決しようとするものであり、その目的とするところ
は、基材、特にプラスチック基材に対して密着性が良
く、透明性、導電性、耐溶剤性、そして、特に耐水性に
優れた塗膜を形成する、一液で水系の帯電防止コーティ
ング用組成物を提供することにある。さらには、ロール
コーティング、スプレーコーティング、およびディッピ
ングなどの工業的なコーティングを可能にするために、
レベリング性が良好で、比較的低温・短時間の乾燥条件
で成膜可能な水系で一液の帯電防止コーティング用組成
物を提供することを目的とする。DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a substrate, particularly a plastic substrate, having good adhesion, transparency, and conductivity. An object of the present invention is to provide a one-part, water-based antistatic coating composition which forms a coating film having excellent properties, solvent resistance, and especially excellent water resistance. Furthermore, to enable industrial coatings such as roll coating, spray coating, and dipping,
An object of the present invention is to provide a one-part antistatic coating composition in an aqueous system which has good leveling properties and can be formed into a film under relatively low temperature and short time drying conditions.
【００１４】[0014]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するために種々検討した結果、基材、特にプラ
スチック基材に対して密着性が良く、透明性、導電性、
耐溶剤性および特に耐水性に優れた塗膜を形成し得る、
水系で一液の帯電防止コーティング用組成物を見出し
て、本発明を完成した。Means for Solving the Problems The present inventors have conducted various studies to solve the above-mentioned problems, and as a result, have good adhesion to a substrate, especially a plastic substrate, and have transparency, conductivity,
Can form a coating excellent in solvent resistance and especially water resistance,
The present invention was completed by finding a one-part aqueous antistatic coating composition.
【００１５】すなわち、本発明は、（ａ）以下の式
（Ｉ）：That is, the present invention provides (a) the following formula (I):
【００１６】[0016]
【化２】Embedded image
【００１７】（式中、Ｒ１およびＲ２は相互に独立して
水素またはＣ１−４のアルキル基を表すか、あるいは一
緒になって任意に置換されてもよいＣ１−４のアルキレ
ン基を表す）の反復構造単位からなる陽イオンの形態の
ポリチオフェンとポリ陰イオンとを含んで成る導電性ポ
リマーと、（ｂ）分子内にアミド結合あるいは水酸基を
有する室温では液体の水溶性化合物と、（ｃ）自己乳化
型ポリエステル樹脂水分散体と、を含有する水系の帯電
防止コーティング用組成物であって、該（ｂ）水溶性化
合物が、該（ａ）導電性ポリマー１００重量部に対し
て、４０から６０００重量部の範囲で含有され、該
（ｃ）自己乳化型ポリエステル樹脂水分散体が、芳香族
ジカルボン酸とジオールとから形成され、該芳香族ジカ
ルボン酸中、５−スルホイソフタル酸が４．０〜６．０
モル％含有されており、そして、該（ｃ）自己乳化型ポ
リエステル樹脂水分散体が、該（ａ）導電性ポリマー１
００重量部に対して固形分として２０から５０００重量
部の範囲で含有される、水系の帯電防止コーティング用
組成物に関する。(Wherein R1 and R2 each independently represent hydrogen or a C1-4 alkyl group, or together with a C1-4 alkylene group which may be optionally substituted) A) a conductive polymer comprising a polythiophene in the form of a cation comprising a repeating structural unit represented by formula (1) and a polyanion; (b) a water-soluble compound which has an amide bond or a hydroxyl group in a molecule and is liquid at room temperature; (C) a water-based antistatic coating composition containing a self-emulsifying polyester resin aqueous dispersion, wherein the (b) water-soluble compound is contained in 100 parts by weight of the (a) conductive polymer. Is contained in the range of 40 to 6000 parts by weight, and the (c) self-emulsifying aqueous polyester resin dispersion is formed from an aromatic dicarboxylic acid and a diol. 4.0-6.0 of isophthalic acid
Mol%, and (c) the aqueous dispersion of the self-emulsifying polyester resin is the (a) conductive polymer 1
The present invention relates to a water-based antistatic coating composition which is contained in a range of 20 to 5000 parts by weight as a solid content based on 00 parts by weight.
【００１８】より好ましい実施態様においては、本発明
の水系の帯電防止コーティング用組成物は、前記（ａ）
〜（ｃ）の成分に加え、さらに、（ｄ）エポキシ基を有
するアルコキシシラン化合物を、前記（ａ）導電性ポリ
マーの１００重量部に対して、２０〜３００重量部の範
囲で含有する。In a more preferred embodiment, the aqueous antistatic coating composition of the present invention comprises the above (a)
In addition to the components (a) to (c), (d) an alkoxysilane compound having an epoxy group is contained in the range of 20 to 300 parts by weight based on 100 parts by weight of the conductive polymer (a).
【００１９】[0019]
【発明の実施の形態】本発明の組成物には，下記式
（Ｉ）：DETAILED DESCRIPTION OF THE INVENTION The composition of the present invention has the following formula (I):
【００２０】[0020]
【化３】Embedded image
【００２１】で示される反復構造単位からなる陽イオン
の形態のポリチオフェン（以下、ポリ（３，４−ジ置換
チオフェン）ということがある）とポリ陰イオンを含ん
で成る（ａ）導電性ポリマーが含まれる。すなわち、こ
の導電性ポリマーは、ポリ（３，４−ジ置換チオフェ
ン）とポリ陰イオンとの複合化合物である。(A) a conductive polymer comprising a polythiophene in the form of a cation (hereinafter sometimes referred to as poly (3,4-disubstituted thiophene)) comprising a repeating structural unit represented by included. That is, this conductive polymer is a composite compound of poly (3,4-disubstituted thiophene) and polyanion.
【００２２】（ａ）の導電性ポリマーを構成するポリ
（３，４−ジ置換チオフェン）のＲ１およびＲ２は相互
に独立して水素またはＣ１−４のアルキル基を表すか、
あるいは一緒になって任意に置換されてもよいＣ１−４
のアルキレン基である。好適には、アルキル置換されて
いてもよいメチレン基、Ｃ１−１２のアルキル基もしく
はフェニル基で置換されていてもよい１，２−エチレン
基、１，３−プロピレン基が挙げられる。Ｒ１およびＲ
２が一緒になって形成される、置換基を有してもよいＣ
１−１２のアルキレン基の代表例は、１，２−アルキレ
ン基（例えば、１，２−シクロヘキシレンおよび２，３
−ブチレンなど）である。この１，２−アルキレン基
は、α−オレフィン類（例えば、エテン、プロペン、ヘ
キセン、オクテン、デセン、ドデセンおよびスチレン）
を臭素化して得られる１，２−ジブロモアルカン類から
誘導される。Ｒ１およびＲ２が一緒になって形成される
Ｃ１−１２のアルキレン基の好適な置換基は、メチレ
ン、１，２−エチレンおよび１，３−プロピレン基であ
り、１，２−エチレン基が特に好適である。R1 and R2 of the poly (3,4-disubstituted thiophene) constituting the conductive polymer (a) each independently represent hydrogen or a C1-4 alkyl group;
Alternatively, together with optionally substituted C1-4
Is an alkylene group. Preferable examples include a methylene group which may be substituted with an alkyl, a 1,2-ethylene group and a 1,3-propylene group which may be substituted with a C1-12 alkyl group or a phenyl group. R1 and R
2 together form an optionally substituted C
Representative examples of the alkylene group of1-12 include a 1,2-alkylene group (for example, 1,2-cyclohexylene and 2,3
-Butylene, etc.). The 1,2-alkylene group may be an α-olefin such as ethene, propene, hexene, octene, decene, dodecene and styrene.
Is derived from 1,2-dibromoalkanes obtained by bromination. Suitable substituents alkyleneC1-12 wherein R1 andR 2 are formed together is methylene, 1,2-ethylene and 1,3-propylene group, 1,2-ethylene Is particularly preferred.
【００２３】（ａ）導電性ポリマーを構成するポリ陰イ
オンとしては、ポリマー状カルボン酸類（例えば、ポリ
アクリル酸、ポリメタクリル酸、ポリマレイン酸な
ど）、ポリマー状スルホン酸（例えば、ポリスチレンス
ルホン酸、ポリビニルスルホン酸など）などが挙げられ
る。これらのカルボン酸およびスルホン酸類はまた、ビ
ニルカルボン酸およびビニルスルホン酸類と他の重合可
能なモノマー類、例えば、アクリレート類およびスチレ
ンなどとの共重合体であっても良い。ポリ陰イオンとし
ては、ポリスチレンスルホン酸が特に好適である。(A) The polyanions constituting the conductive polymer include polymeric carboxylic acids (eg, polyacrylic acid, polymethacrylic acid, polymaleic acid, etc.) and polymeric sulfonic acids (eg, polystyrene sulfonic acid, polyvinyl Sulfonic acid and the like). These carboxylic acids and sulfonic acids may also be copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as acrylates and styrene. Polystyrene sulfonic acid is particularly preferred as the polyanion.
【００２４】こららのポリ陰イオンの数平均分子量Ｍｎ
は、１，０００から２，０００，０００の範囲が好まし
く、より好ましくは２，０００から５００，０００の範
囲である。The number average molecular weight Mn of these polyanions
Is preferably in the range of 1,000 to 2,000,000, more preferably in the range of 2,000 to 500,000.
【００２５】本発明の組成物には、（ｂ）分子内にアミ
ド結合あるいは水酸基を有する室温では液体の水溶性化
合物が用いられる。In the composition of the present invention, (b) a water-soluble compound which has an amide bond or a hydroxyl group in a molecule and is liquid at room temperature is used.
【００２６】分子内にアミド結合を有する、室温では液
体の水溶性化合物（ｂ１）としては、ピロリドン系化合
物（例えば、Ｎ−メチル−２−ピロリドン、２−ピロリ
ドン、Ｎ−ビニル−２−ピロリドン）、アミド基含有化
合物（例えば、Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメ
チルホルムアミド、γ−ブチロラクトンなど）が挙げら
れる。Examples of the water-soluble compound (b1) having an amide bond in the molecule and being liquid at room temperature include pyrrolidone compounds (for example, N-methyl-2-pyrrolidone, 2-pyrrolidone, N-vinyl-2-pyrrolidone). And amide group-containing compounds (for example, N-methylformamide, N, N-dimethylformamide, γ-butyrolactone, etc.).
【００２７】これらの中でも、Ｎ−メチル−２−ピロリ
ドン、２−ピロリドン、Ｎ−ビニル−２−ピロリドン、
Ｎ−メチルホルムアミド、Ｎ，Ｎ−ジメチルホルムアミ
ドが好ましい。これらのアミド化合物は単独で用いても
よいし、２つ以上組合せて用いてもよい。Among these, N-methyl-2-pyrrolidone, 2-pyrrolidone, N-vinyl-2-pyrrolidone,
N-methylformamide and N, N-dimethylformamide are preferred. These amide compounds may be used alone or in combination of two or more.
【００２８】分子内に水酸基を有する、室温では液体の
水溶性化合物（ｂ２）としては、多価アルコールが好ま
しい例として挙げられる。例えば、グリセロール、１，
３−ブタンジオール、エチレングリコール、ジエチレン
グリコールモノエチルエーテルなどが挙げられる。これ
らは単独で用いてもよいし、２以上を組合せて用いても
よい。As the water-soluble compound (b2) having a hydroxyl group in the molecule and being liquid at room temperature, a polyhydric alcohol is a preferred example. For example, glycerol, 1,
Examples thereof include 3-butanediol, ethylene glycol, diethylene glycol monoethyl ether, and the like. These may be used alone or in combination of two or more.
【００２９】本発明においては、この（ｂ）の水溶性化
合物が、上記（ａ）の導電性ポリマー１００重量部に対
して、４０から６０００重量部の範囲で含有される。
（ｂ）の水溶性化合物が４０重量部に満たない場合、表
面抵抗率がほとんど低下しない。他方（ｂ）の水溶性化
合物が６０００重量部を超えると、いったん低下した表
面抵抗率が再び上昇するばかりでなく、ヘイズ値が急上
昇し、塗膜の曇りが激しくなり、透明性が低下する。In the present invention, the water-soluble compound (b) is contained in the range of 40 to 6000 parts by weight based on 100 parts by weight of the conductive polymer (a).
When the amount of the water-soluble compound (b) is less than 40 parts by weight, the surface resistivity hardly decreases. On the other hand, when the amount of the water-soluble compound (b) exceeds 6,000 parts by weight, not only does the once reduced surface resistivity increase again, but also the haze value sharply increases, the coating film becomes cloudy, and the transparency decreases.
【００３０】なお、「導電性ポリマー１００重量部に対
して」とは、「導電性ポリマーの固形分１００重量部に
対して」という意味である。The expression "per 100 parts by weight of the conductive polymer" means "per 100 parts by weight of the solid content of the conductive polymer".
【００３１】本発明の組成物には、（ｃ）自己乳化型ポ
リエステル樹脂水分散体が含有される。本発明に用いら
れる（ｃ）自己乳化型ポリエステル樹脂は、ジカルボン
酸とジオールとから形成されていることが好ましい。例
えば、５−スルホイソフタル酸アルカリ塩、芳香族ジカ
ルボン酸（例えば、テレフタル酸、イソフタル酸、フタ
ル酸など）と、ジオール（例えば、エチレングリコー
ル、プロピレングリコール、１，４−ブタンジオール、
１，６−へキサンジオール、ネオペンチルグリコール、
シクロヘキサンジメタノールなど）とを原料として、重
縮合反応を行うことによって製造される。The composition of the present invention contains (c) an aqueous dispersion of a self-emulsifying polyester resin. The (c) self-emulsifying polyester resin used in the present invention is preferably formed from a dicarboxylic acid and a diol. For example, 5-sulfoisophthalic acid alkali salt, aromatic dicarboxylic acid (eg, terephthalic acid, isophthalic acid, phthalic acid, etc.) and diol (eg, ethylene glycol, propylene glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol,
And cyclohexane dimethanol) as a raw material to carry out a polycondensation reaction.
【００３２】自己乳化型ポリエステル樹脂を形成するジ
カルボン酸は、１種類のジカルボン酸で構成されてもよ
く、２種以上のジカルボン酸を混合して用いてもよく、
３種以上組み合わせて用いてもよい。本発明ではテレフ
タル酸、イソフタル酸、および５−スルホイソフタル酸
からなることが最も好ましく、ジカルボン酸成分中、５
−スルホイソフタル酸が４．０〜６．０モル％含有され
ていることが特に好ましい。５−スルホイソフタル酸が
４．０〜６．０モル％含有されたコーティング組成物は
耐水性に優れる。５−スルホイソフタル酸が４．０モル
％未満であれば樹脂の水分散性が悪くなり、５−スルホ
イソフタル酸が６．０モル％を超えると塗膜の耐水性が
低下する。The dicarboxylic acid forming the self-emulsifying polyester resin may be composed of one kind of dicarboxylic acid, or may be used by mixing two or more kinds of dicarboxylic acids.
You may use it in combination of 3 or more types. In the present invention, it is most preferable to consist of terephthalic acid, isophthalic acid and 5-sulfoisophthalic acid.
It is particularly preferred that 4.0 to 6.0 mol% of sulfoisophthalic acid is contained. The coating composition containing 4.0 to 6.0 mol% of 5-sulfoisophthalic acid has excellent water resistance. If the content of 5-sulfoisophthalic acid is less than 4.0 mol%, the water dispersibility of the resin will be poor, and if the content of 5-sulfoisophthalic acid exceeds 6.0 mol%, the water resistance of the coating film will decrease.
【００３３】なお、ジカルボン酸成分として脂肪族ジカ
ルボン酸（例えば、アジピン酸、コハク酸、セバチン
酸、ドデカン二酸など）を用いた場合、塗膜の耐水性は
低下する傾向にある。When an aliphatic dicarboxylic acid (eg, adipic acid, succinic acid, sebacic acid, dodecane diacid, etc.) is used as the dicarboxylic acid component, the water resistance of the coating film tends to decrease.
【００３４】（ｃ）自己乳化型ポリエステル樹脂水分散
体は、例えば、特公昭４７−４０８３７号公報に記載さ
れた方法に従って製造され、使用に供される。市販品も
また、使用される。容易に入手できる好適材料として
は、帝国化学産業（株）の商品名ガブセンＥＳ−２１０
などがある。(C) The self-emulsifying type aqueous dispersion of polyester resin is produced, for example, according to the method described in JP-B-47-40837 and used. Commercial products are also used. Suitable materials that can be easily obtained include Gabsen ES-210 (trade name) of Teikoku Chemical Industry Co., Ltd.
and so on.
【００３５】（ｃ）自己乳化型ポリエステル樹脂水分散
体は、固形分として、（ａ）の導電性ポリマー１００重
量部に対して、２０〜５０００重量部の範囲の量で添加
される。好ましくは５０〜１５００重量部の範囲であ
る。（ｃ）自己乳化型ポリエステル樹脂水分散体の添加
量が２０重量部より少ないと、表面抵抗率は低く保てる
が、プラスチック基材への密着性が得られなくなる。他
方、５０００重量部を超えると、表面抵抗率は高くな
る。(C) The aqueous dispersion of the self-emulsifying polyester resin is added as a solid in an amount in the range of 20 to 5,000 parts by weight based on 100 parts by weight of the conductive polymer (a). Preferably it is in the range of 50 to 1500 parts by weight. (C) If the amount of the aqueous dispersion of the self-emulsifying polyester resin is less than 20 parts by weight, the surface resistivity can be kept low, but the adhesion to the plastic substrate cannot be obtained. On the other hand, if it exceeds 5000 parts by weight, the surface resistivity becomes high.
【００３６】また、本発明の帯電防止コーティング組成
物には、（ｄ）エポキシ基を有するアルコキシシラン化
合物を添加することが好ましい。すなわち、（ａ）の導
電性ポリマーと（ｂ）の水溶性化合物と（ｃ）の自己乳
化型ポリエステル樹脂水分散体との組成物に（ｄ）のエ
ポキシ基を有するアルコキシシラン化合物を添加するこ
とが好ましい。Further, it is preferable to add (d) an alkoxysilane compound having an epoxy group to the antistatic coating composition of the present invention. That is, an alkoxysilane compound having an epoxy group of (d) is added to a composition of the conductive polymer of (a), the water-soluble compound of (b), and the aqueous dispersion of the self-emulsifying polyester resin of (c). Is preferred.
【００３７】（ｄ）のエポキシ基を有するアルコキシシ
ラン化合物を添加することにより、形成された塗膜の耐
水性が向上する。従来、ガラス繊維などの接着剤として
用いられているエポキシ基を有するアルコキシシラン化
合物がプラスチックとの接着における耐水性を向上させ
ることが、初めて見い出された。The water resistance of the formed coating film is improved by adding the alkoxysilane compound having an epoxy group (d). Heretofore, it has been found for the first time that an alkoxysilane compound having an epoxy group, which is used as an adhesive for glass fiber or the like, improves the water resistance in bonding with plastic.
【００３８】（ｄ）のエポキシ基を有するアルコキシシ
ラン化合物としては、例えば、３−グリシドキシプロピ
ルトリメトキシシラン、３−グリシドキシプロピルメチ
ルジメトキシシラン、２−（３，４−エポキシシクロヘ
キシル）エチルトリメトキシシランなどが挙げられる。Examples of the alkoxysilane compound having an epoxy group (d) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane and the like.
【００３９】（ｄ）のエポキシ基を有するアルコキシシ
ラン化合物の添加量は、（ａ）の導電性ポリマー１００
重量部に対して、２０〜３００重量部の範囲が好まし
い。さらに好ましくは、４０〜１００重量部の範囲であ
る。添加量が２０重量部より少ないと耐水性は不十分と
なり、また、３００重量部を超えても塗膜の耐水性はか
えって低下する。The amount of the alkoxysilane compound having an epoxy group (d) is determined by the amount of the conductive polymer (a).
The range of 20 to 300 parts by weight with respect to parts by weight is preferable. More preferably, it is in the range of 40 to 100 parts by weight. If the added amount is less than 20 parts by weight, the water resistance becomes insufficient, and if it exceeds 300 parts by weight, the water resistance of the coating film is rather lowered.
【００４０】本発明の帯電防止コーティング用組成物
は、上記（ａ）の導電性ポリマー、（ｂ）の水溶性化合
物、（ｃ）の自己乳化型ポリエステル樹脂水分散体、お
よび必要に応じて、（ｄ）のエポキシ基を有するアルコ
キシシラン化合物とを混合して得られる。The antistatic coating composition of the present invention comprises the above-mentioned conductive polymer (a), a water-soluble compound (b), an aqueous dispersion of a self-emulsifying polyester resin (c), and if necessary, It is obtained by mixing (d) an alkoxysilane compound having an epoxy group.
【００４１】本発明の組成物により形成される塗膜は、
その厚みによっても表面抵抗率を調整できる。特に、薄
い塗膜を希望する時には固形分含量を少なくすればよ
く、そのためには、本発明の組成物を分散媒で希釈すれ
ば良い。使用される分散媒としては、水、メタノール、
エタノール、２−プロパノール、ｎ−プロピルアルコー
ル、イソブタノール、エチレングリコール、プロピレン
グリコール、アセトン、メチルエチルケトン、アセトニ
トリル、テトラヒドロフラン、およびジオキサン、なら
びにこれらの混合溶媒などが挙げられる。The coating film formed by the composition of the present invention comprises
The surface resistivity can also be adjusted by its thickness. In particular, when a thin coating film is desired, the solid content may be reduced, and for this purpose, the composition of the present invention may be diluted with a dispersion medium. As the dispersion medium used, water, methanol,
Examples thereof include ethanol, 2-propanol, n-propyl alcohol, isobutanol, ethylene glycol, propylene glycol, acetone, methyl ethyl ketone, acetonitrile, tetrahydrofuran, and dioxane, and a mixed solvent thereof.
【００４２】また、本発明のコーティング用組成物に
は、基材に対する濡れ性を向上させる目的で、少量の界
面活性剤を加えても良い。好ましい界面活性剤として
は、非イオン性界面活性剤（例えば、ポリオキシエチレ
ンアルキルフェニルエーテル、ポリオキシエチレンアル
キルエーテル、ソルビタン脂肪酸エステル、脂肪酸アル
キロールアミドなど）、およびフッ素系界面活性剤（例
えば、フルオロアルキルカルボン酸、パーフルオロアル
キルベンゼンスルホン酸、パープルオロアルキル４級ア
ンモニウム、パーフルオロアルキルポリオキシエチレン
エタノールなど）が挙げられる。Further, a small amount of a surfactant may be added to the coating composition of the present invention for the purpose of improving the wettability to a substrate. Preferred surfactants include nonionic surfactants (eg, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, fatty acid alkylolamide, etc.), and fluorine-based surfactants (eg, fluoro Alkyl carboxylic acid, perfluoroalkyl benzene sulfonic acid, perfluoroalkyl quaternary ammonium, perfluoroalkyl polyoxyethylene ethanol, etc.).
【００４３】本発明の帯電防止コーティング用組成物を
コーティングする基材としては、プラスチックのシー
ト、フィルム、および不織布が挙げられる。プラスチッ
クとしては、ポリエステル、ポリスチレン、ポリイミ
ド、ポリアミド、ポリスルホン、ポリカーボネート、ポ
リ塩化ビニル、ポリエチレン、ポリプロピレンおよびこ
れらのブレンドならびに共重合体、およびフェノール樹
脂、エポキシ樹脂、ＡＢＳ樹脂などが挙げられる。Substrates coated with the antistatic coating composition of the present invention include plastic sheets, films, and nonwoven fabrics. Examples of the plastic include polyester, polystyrene, polyimide, polyamide, polysulfone, polycarbonate, polyvinyl chloride, polyethylene, polypropylene and blends and copolymers thereof, and phenol resins, epoxy resins, ABS resins, and the like.
【００４４】適切なコーティング方法は、グラビアコー
ティング、ロールコーティング、バーコーティング、ス
プレーコーティング、およびディッビングなどである。Suitable coating methods include gravure coating, roll coating, bar coating, spray coating, and diving.
【００４５】塗膜の乾燥および硬化の条件は、それぞれ
のコーティング法に適した条件が選択される。ロールコ
ーティング法を用いる場合は、当業者が一般的に用い
る、６０〜１２０℃、５〜６０秒で行われることが好ま
しい。The conditions for drying and curing of the coating film are selected as appropriate for each coating method. When the roll coating method is used, it is preferably performed at 60 to 120 ° C. for 5 to 60 seconds, which is generally used by those skilled in the art.
【００４６】１２０℃を超えて乾燥および硬化しても、
成膜した塗膜の表面抵抗率、密着性、および耐水性は、
１２０℃以下で乾燥および硬化させたときとほとんど変
らないので、１２０℃を超えて乾燥・硬化しても塗膜の
性能面で有利にはならない。逆に１２０℃を超えて乾燥
・硬化すると、成膜コストが高くなる、高温加熱による
作業上の危険性が高くなるなどの問題がある。さらに
は、熱により変形する基材もある。When dried and cured above 120 ° C.,
The surface resistivity, adhesion, and water resistance of the formed coating film are
Since it is almost the same as when dried and cured at 120 ° C. or less, drying / curing at more than 120 ° C. is not advantageous in terms of coating film performance. Conversely, if the drying and curing are performed at a temperature exceeding 120 ° C., there are problems such as an increase in film formation cost and an increase in operational risk due to high-temperature heating. Further, there is a base material that is deformed by heat.
【００４７】乾燥および硬化時間が、５秒に満たない場
合は乾燥が不十分であり、６０秒を超えて乾燥および硬
化させても成膜した塗膜の表面抵抗率、密着性、および
耐水性は、６０秒以下で乾燥および硬化させたときとほ
とんど変らないので、６０秒を超えて乾燥・硬化しても
塗膜の性能面で有利にはならない。逆に６０秒を超えて
乾燥・硬化すると、成膜コストが高くなる。When the drying and curing time is less than 5 seconds, the drying is insufficient. Even when the drying and curing is performed for more than 60 seconds, the surface resistivity, adhesion and water resistance of the formed coating film are obtained. Is almost the same as when dried and cured in less than 60 seconds, so that drying and curing beyond 60 seconds is not advantageous in terms of the performance of the coating film. Conversely, if the drying and curing are performed for more than 60 seconds, the film formation cost will increase.
【００４８】このようにして得られた塗膜は、帯電防止
性にすぐれ、耐水性、および塗膜と基材との密着性が改
良される。特に、（ｄ）エポキシ基を有するアルコキシ
シラン化合物を配合した組成物で成膜された塗膜は、耐
水性に優れる。The coating thus obtained is excellent in antistatic properties, and has improved water resistance and adhesion between the coating and the substrate. In particular, a coating film formed of a composition containing (d) an alkoxysilane compound having an epoxy group is excellent in water resistance.
【００４９】[0049]
【実施例】以下に実施例を挙げて本発明を説明するが、
本発明はこの実施例に限定されない。 １．使用材料 本実施例においては、以下の材料を使用した。 （ａ）導電性ポリマー ポリ（３，４−エチレンジオキシチオフェン）０．５重
量％とポリスチレンスルホン酸（分子量Ｍｎ＝１５０，
０００）０.８重量％を含んで成るポリマーの水分散体
（ＢａｙｔｒｏｎＰ：バイエルＡＧ製）を使用した。 （ｂ）分子内にアミド結合を有する室温で液体の水溶性
化合物 Ｎ−メチルピロリドン （ｃ）自己乳化型ポリエステル樹脂水分散体 表１に示す（ｃ）−１〜（ｃ）−６の組成の分散体を調
製した。この自己乳化型ポリエステル樹脂水分散体は、
固形分含量２５％となるように調製して用いた。EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited to this embodiment. 1. Materials Used In this example, the following materials were used. (A) Conductive polymer Poly (3,4-ethylenedioxythiophene) 0.5% by weight and polystyrene sulfonic acid (molecular weight Mn = 150,
Aqueous dispersion of polymer (Baytron P, Bayer AG) comprising 0.8% by weight of 000) was used. (B) Room temperature liquid water-soluble compound having an amide bond in the molecule N-methylpyrrolidone (c) Self-emulsifying water dispersion of polyester resin The composition of (c) -1 to (c) -6 shown in Table 1 A dispersion was prepared. This self-emulsifying polyester resin aqueous dispersion is
It was prepared and used so as to have a solid content of 25%.
【００５０】[0050]
【表１】[Table 1]
【００５１】（ｄ）エポキシ基を有するアルコキシシラ
ン化合物 ３−グリシドキシプロピルトリメトキシシランを用い
た。 その他：界面活性剤として、プラスコートＲＹ−２（互
応化学：フッ素系界面活性剤）を用いた。(D) Alkoxysilane compound having epoxy group 3-glycidoxypropyltrimethoxysilane was used. Other: Pluscoat RY-2 (compatible chemical: fluorine-based surfactant) was used as the surfactant.
【００５２】２．塗布、乾燥方法 本発明の、あるいは比較例の組成物のプラスチック基材
への塗布、並びに乾燥は以下のように行った。すなわ
ち、プラスチック基材としてＰＥＴフィルム（ルミラー
Ｔタイプ：東レ）を用い、コーティング用組成物をワイ
ヤーバーでコーティングし、９０℃で１分間送風乾燥さ
せて、塗膜を得た。なお、実施例１〜３、６〜８および
比較例１、２、８〜１０は、Ｎｏ．４のワイヤーバー
（ｗｅｔ９．１４μｍ）でコーティングし、実施例４、
５および比較例３〜７は、Ｎｏ．５のワイヤーバー（Ｗ
ｅｔ１１．４３μｍ）でコーティングした。2. Coating and Drying Method The composition of the present invention or the comparative example was applied to a plastic substrate and dried, as follows. That is, using a PET film (Lumirror T type: Toray) as a plastic substrate, the coating composition was coated with a wire bar, and dried by blowing at 90 ° C. for 1 minute to obtain a coating film. Examples 1-3, 6-8 and Comparative Examples 1, 2, 8-10 are No. 4, coated with a wire bar (wet 9.14 μm),
No. 5 and Comparative Examples 3 to 7 are No. 5 wire bars (W
et 11.43 μm).
【００５３】３．塗膜の評価 3.1 表面抵抗率は、ＪＩＳ Ｋ６９１１に従い、三菱
化学（株）製ハイレスターＵＰ（ＭＣＰ−ＨＴ４５０）
を用いて測定した。3.2 耐水性は、クレシアハンドタ
オル（ソフトタイプ）に水を染み込ませ、塗膜を手拭き
で１０往復拭いた後、塗膜の外観を観察することにより
行なった。塗膜がほとんど取れてしまった場合は×、傷
が目立つ場合は△、僅かに傷が観察された場合は○、完
全に無傷であった場合は◎と判定した。3.3 耐溶剤性
は、水の代りにメタノールを用いて、耐水性と同様に試
験した。3.4 全光線透過率およびヘイズ値は、ＪＩＳ
Ｋ７１５０に従い、スガ試験機（株）製ヘイズコンピ
ュータＨＧＭ−２Ｂを用いて測定した。3.5 塗膜の基
材への密着性は、ＪＩＳ Ｋ５４００の碁盤目剥離試験
に従って行った。3. 3. Evaluation of coating film 3.1 The surface resistivity was measured according to JIS K6911 by Mitsubishi Chemical Corporation, Hiresta UP (MCP-HT450).
It measured using. 3.2 Water resistance was measured by impregnating water into a Crecia hand towel (soft type), wiping the coating film back and forth by hand 10 times, and then observing the appearance of the coating film. When the coating film was almost completely removed, it was evaluated as ×, when the scratches were conspicuous, as 僅 か when slight scratches were observed, and as ◎ when it was completely intact. 3.3 Solvent resistance was tested in the same way as water resistance, using methanol instead of water. 3.4 Total light transmittance and haze value are measured according to JIS.
According to K7150, it was measured using a haze computer HGM-2B manufactured by Suga Test Instruments Co., Ltd. 3.5 The adhesion of the coating film to the substrate was measured according to a cross-cut peeling test of JIS K5400.
【００５４】なお、実施例においては、（ａ）の導電性
ポリマーを（ａ）成分と、（ｂ）の水溶性化合物を
（ｂ）成分と、（ｃ）の自己乳化型ポリエステル水分散
体を（ｃ）成分と、（ｄ）のエポキシ基を有するアルコ
キシシラン化合物を（ｄ）成分ということがある。In the examples, the conductive polymer of (a) was used as the component (a), the water-soluble compound of (b) was used as the component (b), and the aqueous dispersion of the self-emulsifying polyester of (c) was used. The component (c) and the alkoxysilane compound having an epoxy group of (d) are sometimes referred to as component (d).
【００５５】実施例１〜８、比較例１〜１０の組成物の
組成を表２に示す。表２中（ａ）〜（ｄ）成分の数字は
ｇを表し、（ａ）成分の導電性ポリマーは固形分濃度で
１．３重量％の濃度のものを用いた。Table 2 shows the compositions of the compositions of Examples 1 to 8 and Comparative Examples 1 to 10. The numbers of the components (a) to (d) in Table 2 represent g, and the conductive polymer of the component (a) used had a solid content of 1.3% by weight.
【００５６】[0056]
【表２】[Table 2]
【００５７】（実施例１〜３および比較例１、２）表２
に記載の、実施例１〜３および比較例１、２のコーティ
ング用組成物を、上記方法でプラスチック膜に塗布し、
塗膜を評価した。結果を表３に示す。(Examples 1 to 3 and Comparative Examples 1 and 2) Table 2
The coating compositions of Examples 1 to 3 and Comparative Examples 1 and 2 are applied to a plastic film by the above method,
The coating was evaluated. Table 3 shows the results.
【００５８】[0058]
【表３】[Table 3]
【００５９】（ｂ）成分が（ａ）成分１００重量部に対
して約４４〜４４００重量部である実施例１〜３はヘイ
ズ値も低く、表面抵抗率も低下した。これに対して、比
較例１は（ｂ）成分を含まないので表面抵抗率が高い。
比較例２は（ｂ）成分が（ａ）成分１００重量部に対し
て６０００重量部を超えているため、ヘイズ値が高くな
り、透明性が低下している。In Examples 1 to 3 in which the component (b) was about 44 to 4400 parts by weight per 100 parts by weight of the component (a), the haze value was low and the surface resistivity was low. In contrast, Comparative Example 1 does not contain the component (b) and thus has a high surface resistivity.
In Comparative Example 2, since the component (b) exceeds 6000 parts by weight with respect to 100 parts by weight of the component (a), the haze value is high and the transparency is low.
【００６０】（実施例４、５および比較例３〜７）実施
例４、５および比較例３〜５は、（ｃ）成分の自己乳化
型ポリエステル樹脂のジカルボン酸の効果を検討したも
のである。実施例４および比較例６、７は（ｃ）成分の
添加量を検討したものである。表２に記載の組成物のう
ち、実施例４、５および比較例３〜７のコーティング用
組成物をプラスチック基材に塗布後、９０℃で１分間乾
燥した。結果を４に示す。Examples 4 and 5 and Comparative Examples 3 to 7 Examples 4 and 5 and Comparative Examples 3 to 5 examine the effect of the dicarboxylic acid of the self-emulsifying polyester resin as the component (c). . Example 4 and Comparative Examples 6 and 7 examine the amount of component (c) added. Among the compositions shown in Table 2, the coating compositions of Examples 4, 5 and Comparative Examples 3 to 7 were applied to a plastic substrate and then dried at 90 ° C for 1 minute. The results are shown in FIG.
【００６１】[0061]
【表４】[Table 4]
【００６２】実施例４および５は、（ｃ）自己乳化型ポ
リエステル樹脂のジカルボン酸成分が、ともにテレフタ
ル酸、イソフタル酸、および５−スルホイソフタル酸で
あり、そして、５−スルホイソフタル酸を５モル％含有
しているので、成膜した塗膜は耐水性に優れる。 実施
例５は、（ｃ）成分中のジオール成分がエチレングリコ
ール単独であったためか、耐溶剤性に優れていた。In Examples 4 and 5, (c) the dicarboxylic acid component of the self-emulsifying polyester resin was terephthalic acid, isophthalic acid, and 5-sulfoisophthalic acid, and 5-sulfoisophthalic acid was used in an amount of 5 mol. %, The formed coating film has excellent water resistance. Example 5 was excellent in solvent resistance probably because the diol component in the component (c) was ethylene glycol alone.
【００６３】これに対して、比較例３および４は、
（ｃ）自己乳化型ポリエステル樹脂のジカルボン酸成分
が、ともにテレフタル酸、イソフタル酸、および５−ス
ルホイソフタル酸であるが、５−スルホイソフタル酸を
６モル％を超えて含有しているので、成膜した塗膜の耐
水性、耐溶剤性が劣っている。さらに、比較例５は、ジ
カルボン酸成分として５−スルホイソフタル酸を５％含
んでいるが、ジカルボン酸成分として脂肪族ジカルボン
酸であるアジピン酸を含有しているので、成膜した塗膜
の耐水性、耐溶剤性が悪い。On the other hand, Comparative Examples 3 and 4
(C) The dicarboxylic acid component of the self-emulsifying polyester resin is terephthalic acid, isophthalic acid, and 5-sulfoisophthalic acid, but contains more than 6 mol% of 5-sulfoisophthalic acid. The water resistance and solvent resistance of the formed coating film are inferior. Further, Comparative Example 5 contained 5% of 5-sulfoisophthalic acid as a dicarboxylic acid component, but contained adipic acid, which is an aliphatic dicarboxylic acid, as a dicarboxylic acid component. Poor performance and solvent resistance.
【００６４】なお、表１の（ｃ）−６のポリエステル樹
脂分散体は、水分散安定性が悪かったので、コーティン
グ用組成物に供することができなかった。これは、ポリ
エステル樹脂のジカルボン酸成分中の５−スルホイソフ
タル酸成分が４モル％未満であったのが原因と考えられ
る。The polyester resin dispersion of (c) -6 in Table 1 was inferior in water dispersion stability and could not be used as a coating composition. This is considered to be because the 5-sulfoisophthalic acid component in the dicarboxylic acid component of the polyester resin was less than 4 mol%.
【００６５】また、実施例４のコーティング組成物は、
（ａ）成分の１００重量部に対して約９７０重量部の
（ｃ）成分を含んでいるので、得られた塗膜は、基材に
対して密着性がよく、低い表面抵抗率と優れた耐水性を
有していた。一方、比較例６のコーティング用組成物
は、（ａ）成分の１００重量部に対して約１４重量部の
（ｃ）成分しか含んでいないので、得られた塗膜は低い
表面抵抗率を有していたものの、基材に対する密着性が
悪く、耐水性および耐溶剤性も悪かった。他方、比較例
７のコーティング用組成物は、（ａ）成分の１００重量
部に対して約５０６０重量部もの（ｃ）成分を含んでい
るので、得られた塗膜は、基材に対する密着性が良く、
耐水性にも優れていたものの、表面抵抗率が大幅に高く
なった。これらの結果から、塗膜の基材に対する密着
性、低い表面抵抗率、高い耐水性を付与する観点から、
（ｃ）成分は、（ａ）成分１００重量部に対して２０〜
５０００重量部の範囲で含有するのが望ましいことが示
された。The coating composition of Example 4
Since about 970 parts by weight of the component (c) is contained with respect to 100 parts by weight of the component (a), the obtained coating film has good adhesion to the substrate, low surface resistivity and excellent. It had water resistance. On the other hand, since the coating composition of Comparative Example 6 contained only about 14 parts by weight of the component (c) with respect to 100 parts by weight of the component (a), the obtained coating film had a low surface resistivity. However, the adhesion to the substrate was poor, and the water resistance and solvent resistance were also poor. On the other hand, the coating composition of Comparative Example 7 contained about 5060 parts by weight of the component (c) per 100 parts by weight of the component (a). Is good,
Although excellent in water resistance, the surface resistivity was significantly increased. From these results, the adhesion of the coating film to the substrate, low surface resistivity, from the viewpoint of imparting high water resistance,
Component (c) is 20 to 100 parts by weight of component (a).
It has been shown that it is desirable to contain 5,000 parts by weight.
【００６６】（実施例６〜８、比較例８〜１０）この実
施例６〜８およ比較例８〜９は、（ｄ）成分のエポキシ
基を有するアルコキシシランの添加効果を検討したもの
である。比較例１０は、（ｄ）成分を添加して（ｃ）成
分を除いたコーティング用組成物の、成膜した塗膜の耐
水性および耐溶剤性を検討したものである。表２に記載
の組成物のうち、実施例６〜８および比較例８〜１０の
コーティング用組成物をプラスチック基材に塗布後、９
０℃で１分間乾燥した。結果を５に示す。Examples 6 to 8 and Comparative Examples 8 to 10 Examples 6 to 8 and Comparative Examples 8 to 9 examine the effect of adding an alkoxysilane having an epoxy group as the component (d). is there. Comparative Example 10 examined the water resistance and solvent resistance of the formed coating film of the coating composition to which the component (d) was added and the component (c) was removed. After applying the coating compositions of Examples 6 to 8 and Comparative Examples 8 to 10 to the plastic base material among the compositions shown in Table 2, 9
Dry at 0 ° C. for 1 minute. The results are shown in FIG.
【００６７】[0067]
【表５】[Table 5]
【００６８】表５の結果は、（ｄ）成分を添加していく
と塗膜の耐水性および耐溶剤性が向上するが、添加量が
一定量を超えると塗膜の耐水性および耐溶剤性が低下す
ることが示された。（ｄ）成分は、（ａ）成分の１００
重量部に対して、約６０重量部前後添加することが、耐
水性および耐溶剤性を付与する点から好ましいことが示
された。The results in Table 5 show that the water resistance and the solvent resistance of the coating film improve as the component (d) is added, but the water resistance and the solvent resistance of the coating film increase when the added amount exceeds a certain amount. Was shown to decrease. The component (d) is 100% of the component (a).
It was shown that it is preferable to add about 60 parts by weight to the parts by weight from the viewpoint of imparting water resistance and solvent resistance.
【００６９】また、比較例１０の結果から、（ｄ）成分
を添加しても（ｃ）成分を添加しなければ、成膜した塗
膜の、基材に対する密着性は得られるものの、耐水性お
よび耐溶剤性は得られないことが示された。Also, from the results of Comparative Example 10, if the component (d) was added and the component (c) was not added, the adhesion of the formed coating film to the substrate was obtained, but the water resistance was high. And no solvent resistance was obtained.
【００７０】なお、塗膜の基材への密着性は、比較例６
以外の実施例および比較例において１００／１００（碁
盤目剥離試験）で良好であった。The adhesion of the coating film to the substrate was determined in Comparative Example 6
In Examples and Comparative Examples other than the above, 100/100 (cross cut test) was good.
【００７１】[0071]
【発明の効果】本発明により、プラスチック基材に対し
て密着性がよく、透明性、導電性、耐溶剤性、および特
に耐水性にも優れた塗膜を形成する、水系で一液タイプ
の帯電防止コーティング用組成物が提供される。本発明
のコーティング用組成物は、特定の反復構造単位からな
る陽イオンの形態のポリチオフェンとポリ陰イオンを含
んで成る（ａ）導電性ポリマーと、（ｂ）分子内にアミ
ド結合あるいは水酸基を有する室温では液体の水溶性化
合物と、（ｃ）自己乳化型ポリエステル樹脂水分散体と
を特定の割合で配合することにより、密着性がよく、透
明性、導電性、耐溶剤性、および特に耐水性にも優れた
塗膜を形成する。（ｄ）エポキシ基を有するアルコキシ
シランを配合させることにより、得られる塗膜の耐水性
と耐溶剤性がさらに向上する。According to the present invention, a water-based, one-pack type coating film having good adhesion to a plastic substrate, and having excellent transparency, conductivity, solvent resistance, and especially excellent water resistance is formed. A composition for an antistatic coating is provided. The coating composition of the present invention comprises (a) a conductive polymer comprising a polythiophene in the form of a cation comprising a specific repeating structural unit and a polyanion, and (b) an amide bond or a hydroxyl group in the molecule. By mixing a water-soluble compound that is liquid at room temperature and (c) an aqueous dispersion of a self-emulsifying polyester resin in a specific ratio, the adhesion is good, and the transparency, conductivity, solvent resistance, and especially water resistance are obtained. Also forms an excellent coating film. By blending (d) an alkoxysilane having an epoxy group, the water resistance and solvent resistance of the resulting coating film are further improved.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） // Ｂ６５Ｄ 85/86 Ｈ０１Ｂ 1/12 Ｆ Ｈ０１Ｂ 1/12 Ｂ６５Ｄ 85/38 Ｓ (72)発明者 甲斐 大介 兵庫県伊丹市千僧５丁目41番地 帝国化学 産業株式会社伊丹工場内 Ｆターム(参考） 3E096 BA08 EA02X FA07 GA01 4J038 CC091 CG031 CG071 DD061 DD101 DK001 GA02 GA13 JA20 JA21 JA26 JA70 JB13 JB27 JC34 KA03 MA08 MA10 MA14 NA01 NA04 NA12 NA20 PB08 PB09──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl.7 Identification symbol FI Theme coat ゛ (Reference) // B65D 85/86 H01B 1/12 F H01B 1/12 B65D 85/38 S (72) Inventor Daisuke Kai 5-41 Senmon, Itami-shi, Hyogo F-term in the Imperial Chemical Industry Co., Ltd. Itami Plant (reference) 3E096 BA08 EA02X FA07 GA01 4J038 CC091 CG031 CG071 DD061 DD101 DK001 GA02 GA13 JA20 JA21 JA26 JA70 JB13 JB27 JC34 NA10 NA20 PB08 PB09
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000253289AJP4004214B2 (en) | 2000-08-24 | 2000-08-24 | Antistatic coating composition |
| TW090120602ATW555842B (en) | 2000-08-24 | 2001-08-22 | Antistatic coating composition |
| KR1020010050927AKR100737182B1 (en) | 2000-08-24 | 2001-08-23 | Antistatic coating composition |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000253289AJP4004214B2 (en) | 2000-08-24 | 2000-08-24 | Antistatic coating composition |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005140605ADivisionJP4621950B2 (en) | 2005-05-13 | 2005-05-13 | Antistatic coating composition |
| Publication Number | Publication Date |
|---|---|
| JP2002060736Atrue JP2002060736A (en) | 2002-02-26 |
| JP4004214B2 JP4004214B2 (en) | 2007-11-07 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000253289AExpired - LifetimeJP4004214B2 (en) | 2000-08-24 | 2000-08-24 | Antistatic coating composition |
| Country | Link |
|---|---|
| JP (1) | JP4004214B2 (en) |
| KR (1) | KR100737182B1 (en) |
| TW (1) | TW555842B (en) |
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