JPH10237362A - Electrodeposition coating material and electrodeposition coating - Google Patents
Electrodeposition coating material and electrodeposition coatingInfo
- Publication number
- JPH10237362A JPH10237362A JP9058479A JP5847997A JPH10237362A JP H10237362 A JPH10237362 A JP H10237362A JP 9058479 A JP9058479 A JP 9058479A JP 5847997 A JP5847997 A JP 5847997A JP H10237362 A JPH10237362 A JP H10237362A
- Authority
- JP
- Japan
- Prior art keywords
- electrodeposition coating
- solution
- antibacterial
- inorganic oxide
- aqueous
- 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.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は電着塗料および電着
塗装方法に関し、さらに詳しくは、抗菌性無機酸化物水
性コロイド溶液を含むアニオン型電着塗料および該塗料
を用いて被塗装物表面に抗菌性金属成分を含有する無機
酸化物コロイド粒子を含む塗膜を形成する電着塗装方法
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrodeposition paint and an electrodeposition coating method, and more particularly, to an anion-type electrodeposition paint containing an aqueous colloidal solution of an antibacterial inorganic oxide, and to the surface of an object to be coated using the paint. The present invention relates to an electrodeposition coating method for forming a coating film containing inorganic oxide colloid particles containing an antibacterial metal component.
【０００２】[0002]
【従来の技術】近年、高温多湿の我国に於いては、細菌
による食中毒などが多発しており、また、マンションな
どの乱立による居住環境の変化に伴い細菌、黴、悪臭な
どの生活環境の悪化が社会問題となりつつあることか
ら、これらの環境の清浄化が強く求められている。そし
て、このような生活環境を清浄化するため、人の皮膚が
接触する日用雑貨品、建材具、内装材料などの塗装面に
抗菌性を付与することが種々提案されている。2. Description of the Related Art In recent years, food poisoning due to bacteria has occurred frequently in Japan, which is hot and humid, and the living environment such as bacteria, mold, and odors has deteriorated due to changes in the living environment due to the confusion of apartment buildings and the like. Is becoming a social problem, and there is a strong demand for purification of these environments. In order to purify such a living environment, various proposals have been made to impart antibacterial properties to painted surfaces of daily goods, building materials, interior materials and the like, which come into contact with human skin.
【０００３】従来、塗装面に抗菌性を付与する方法とし
ては、塗料中に抗菌剤を添加し、これをはけ塗り塗装
や、吹き付け塗装する方法が実用化されているが、電着
塗装法においては実用化に至っていない。電着塗装法
は、（１）つきまわり性がよく被塗装物に均一に膜厚を
付け易い、内面や合わせ目にもよく塗装できる、（２）
通電する電気量を調整することによって定量的に膜厚を
管理できる、（３）塗料の損失が極めて少ない、（４）
塗膜にたれやわきが発生しにくい、（５）火災の危険が
ない、などの優れた長所を有する。しかし、これまでは
電着塗料中に抗菌剤を添加して電着塗装を行うと、電着
塗装時に抗菌剤が不純物として作用し、良好な外観が得
られず、また、密着性に優れた電着塗装被膜が得られな
いという問題点があった。Conventionally, as a method of imparting antibacterial properties to a painted surface, a method of adding an antibacterial agent to a paint and brushing or spraying the paint has been put to practical use. Has not been put to practical use. The electrodeposition coating method (1) has good throwing power and is easy to apply a uniform film thickness to an object to be coated, and can be coated well on inner surfaces and seams. (2)
The film thickness can be quantitatively controlled by adjusting the amount of electricity supplied. (3) Paint loss is extremely small. (4)
It has excellent advantages such that the coating film is hardly sagged or set aside, and (5) there is no danger of fire. However, hitherto, when an electrodeposition coating is performed by adding an antibacterial agent to the electrodeposition paint, the antibacterial agent acts as an impurity at the time of the electrodeposition coating, a good appearance is not obtained, and the adhesion is excellent. There was a problem that an electrodeposition coating film could not be obtained.
【０００４】特開平８−１２０４９６号公報には抗菌剤
を含有する電着塗装被膜の形成方法が開示されており、
同法はリン酸カルシウムと金属銀の焼結混合したセラミ
ックス微粒子よりなる抗菌剤を電着塗装溶液中に均一に
分散させ、該溶液中にて被塗装物と極板間に電圧を印加
して直流通電を行うことにより、被塗装物表面に抗菌剤
が共析した被膜を得ることを特徴とするものである。Japanese Patent Application Laid-Open No. 8-120496 discloses a method for forming an electrodeposition coating film containing an antibacterial agent.
In this method, an antibacterial agent composed of ceramic fine particles obtained by sintering and mixing calcium phosphate and metallic silver is uniformly dispersed in an electrodeposition coating solution, and a voltage is applied between the object to be coated and an electrode plate in the solution to apply a direct current. Is performed to obtain a film in which the antibacterial agent is codeposited on the surface of the object to be coated.
【０００５】しかし、この方法では、材料となる抗菌剤
を１０００℃以上の高温で焼結させるためコストが高く
なること、抗菌剤は粒子径が大きいため電着塗装溶液中
で沈降し易く均一に分散させることが困難であること、
また、抗菌剤粒子は電荷を有していないため電圧を印加
しても電気的な力によって移動するのではなく、塗料微
粒子の移動に伴って不純物として一緒に移動すること、
などから抗菌剤が被塗装物表面に均一に付着しにくいな
どの問題があり、さらに、塗膜の外観、密着性の点でも
改善が望まれていた。However, according to this method, the antibacterial agent as a material is sintered at a high temperature of 1000 ° C. or higher, which increases the cost. Further, the antibacterial agent easily sediments in an electrodeposition coating solution because of its large particle size, and is uniform. Difficult to disperse,
Also, since the antibacterial agent particles do not have a charge, they do not move by an electric force even when a voltage is applied, but move together as impurities with the movement of the paint particles,
For example, there is a problem that the antibacterial agent is difficult to uniformly adhere to the surface of the object to be coated, and further improvement in appearance and adhesion of the coating film has been desired.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、種々
の導体物品の塗装面に長時間にわたって優れた抗菌性を
付与し、良好な外観、密着性の優れた塗膜が得られる電
着塗料および電着塗装方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a coated surface of various conductive articles with excellent antibacterial properties over a long period of time, and to obtain a coating film having good appearance and excellent adhesion. A paint and an electrodeposition coating method are provided.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、特定の抗
菌性無機酸化物水性コロイド溶液を特定の電着塗料に添
加することにより、前述の問題点を解決し得ることを見
いだし、本発明を完成するに至った。The present inventors have found that the aforementioned problems can be solved by adding a specific antibacterial inorganic oxide aqueous colloid solution to a specific electrodeposition paint. The invention has been completed.
【０００８】本発明に係る電着塗料は、抗菌性金属成分
を含有する無機酸化物コロイド粒子が分散した水性コロ
イド溶液と、アニオン型電着塗料とを含む電着塗料であ
って、前記コロイド粒子のζ−電位が水性コロイド溶液
のｐＨ７．０〜９．０の範囲において−２ｍＶ以下であ
ることを特徴とするものである。The electrodeposition paint according to the present invention is an electrodeposition paint comprising an aqueous colloid solution in which inorganic oxide colloid particles containing an antibacterial metal component are dispersed, and an anionic electrodeposition paint. Has a コ ロ イ ド -potential of −2 mV or less in the range of pH 7.0 to 9.0 of the aqueous colloid solution.
【０００９】本発明に係る電着塗装方法は、前記電着塗
料中にて陽極の導体被塗装物とこれと反対電極との間に
直流を通電して、被塗装物表面に抗菌性金属成分を含有
する無機酸化物コロイド粒子を含む塗膜を形成すること
を特徴とするものである。The electrodeposition coating method according to the present invention is characterized in that a direct current is applied between the anode conductor coating object and the opposite electrode in the electrodeposition coating material, and the antibacterial metal component is applied to the surface of the coating object. A coating film containing inorganic oxide colloid particles containing
【００１０】[0010]
【発明の実施の形態】以下、本発明の好適な実施形態に
ついて詳細に説明する。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail.
【００１１】本発明において、水性コロイド溶液（ゾ
ル）は、抗菌性金属成分を含有する無機酸化物コロイド
粒子が分散した水性コロイド溶液（抗菌性無機酸化物水
性コロイド溶液）であって、該コロイド粒子のζ−電位
（界面動電位）が水性コロイド溶液のｐＨ７．０〜９．
０の範囲において−２ｍＶ以下、好ましくは−３ｍＶ〜
−２００ｍＶ、更に好ましくは−５ｍＶ〜−１００ｍＶ
の範囲であることが望ましい。該コロイド粒子のζ−電
位がアニオン型電着塗料のｐＨ範囲であるｐＨ７．０〜
９．０の範囲において−２ｍＶよりも高い場合には、該
コロイド粒子は電気的な力によって引き付けられる力が
弱く、陽極の導体被塗装物表面に均一に凝集析出しない
ことがある。また、水性コロイド溶液が不安定となるの
で好ましくない。In the present invention, the aqueous colloid solution (sol) is an aqueous colloid solution in which inorganic oxide colloid particles containing an antibacterial metal component are dispersed (an antibacterial inorganic oxide aqueous colloid solution). Ζ-potential (electrokinetic potential) of the aqueous colloid solution is pH 7.0 to 9.
-2 mV or less in the range of 0, preferably -3 mV to
-200 mV, more preferably -5 mV to -100 mV
Is desirably within the range. The colloid particles have a ζ-potential of pH 7.0 to pH which is the pH range of the anionic electrodeposition coating composition.
If the value is higher than -2 mV in the range of 9.0, the colloidal particles are weakly attracted by an electric force, and may not uniformly coagulate and precipitate on the surface of the anode to be coated with a conductor. Further, the aqueous colloid solution becomes unstable, which is not preferable.
【００１２】前述のコロイド粒子のζ−電位は、一般に
ゼータ電位計で測定されるが、自動的にｐＨを変化させ
てζ−電位の連続測定が可能な超音波方式ゼータ電位分
析システム装置（例えば、Matec Applied Sciences, In
c.製、ＥＳＡ８０００）を用いると簡便である。The ζ-potential of the above-mentioned colloidal particles is generally measured by a zeta potentiometer, but an ultrasonic zeta potential analysis system device (for example, an automatic zeta potential analyzer capable of continuously measuring the ζ-potential by automatically changing the pH). , Matec Applied Sciences, In
c., ESA8000).
【００１３】前記コロイド粒子に含有される抗菌性金属
成分としては、通常知られているものを用いることがで
き、例えば、銀、銅、亜鉛、錫、鉛、ビスマス、カドミ
ウム、クロムなどが例示される。特に、銀、銅、亜鉛か
ら選択される１種以上の抗菌性金属成分は、抗菌作用、
変色及び人体に対する安全性などの観点から好ましい。As the antibacterial metal component contained in the colloidal particles, generally known ones can be used, and examples thereof include silver, copper, zinc, tin, lead, bismuth, cadmium, and chromium. You. In particular, one or more antibacterial metal components selected from silver, copper, and zinc have an antibacterial action,
It is preferable from the viewpoint of discoloration and safety to the human body.
【００１４】また、抗菌性金属成分を含有する無機酸化
物コロイド粒子の無機酸化物としては、一般に知られて
いるコロイド溶液を構成する無機酸化物を挙げることが
でき、無機酸化物コロイド粒子としては、単一または複
合酸化物コロイド粒子、あるいはこれらの混合物を用い
ることが可能である。Examples of the inorganic oxide of the inorganic oxide colloid particles containing an antibacterial metal component include generally known inorganic oxides constituting a colloid solution. It is possible to use single or composite oxide colloid particles, or mixtures thereof.
【００１５】単一の無機酸化物としては、ＳｉＯ2 、Ａ
ｌ2 Ｏ3 、ＴｉＯ2 、ＺｒＯ2 、Ｆｅ2 Ｏ3 、Ｓｂ2 Ｏ
5 、ＷＯ3 、ＣｅＯ2 などが例示され、複合酸化物とし
ては、ＳｉＯ2 ・Ａｌ2 Ｏ3 、ＳｉＯ2 ・ＴｉＯ2 、Ｓ
ｉＯ2 ・ＺｒＯ2 、ＳｉＯ2・Ｆｅ2 Ｏ3 、Ａｌ2 Ｏ3
・ＴｉＯ2 、ＣｅＯ2 ・ＴｉＯ2 、Ａｌ2 Ｏ3 ・ＴｉＯ
2 ・Ｆｅ2 Ｏ3 、ＳｉＯ2 ・ＴｉＯ2 ・ＺｒＯ2 、Ｓｉ
Ｏ2 ・Ａｌ2 Ｏ3 ・ＴｉＯ2 などを挙げることができ
る。As a single inorganic oxide, SiO 2 , A
l 2 O 3 , TiO 2 , ZrO 2 , Fe 2 O 3 , Sb 2 O
5 , WO 3 , CeO 2 and the like. Examples of the composite oxide include SiO 2 .Al 2 O 3 , SiO 2 .TiO 2 , and S
iO 2 · ZrO 2 , SiO 2 · Fe 2 O 3 , Al 2 O 3
・ TiO 2 , CeO 2・ TiO 2 , Al 2 O 3・ TiO
2 · Fe 2 O 3, SiO 2 · TiO 2 · ZrO 2, Si
O 2 · Al 2 O 3 · TiO 2 and the like can be mentioned.
【００１６】抗菌性金属成分を含有する無機酸化物コロ
イド粒子の平均粒子径は、５００ｎｍ以下であることが
望ましい。コロイド粒子の平均粒子径が大きくなるにつ
れて、得られる塗膜の外観、密着性などが悪くなる傾向
にある。該コロイド粒子の好ましい平均粒子径の範囲は
３００ｎｍ以下、更に好ましい範囲は３ｎｍ〜２５０ｎ
ｍである。The average particle size of the inorganic oxide colloid particles containing the antibacterial metal component is desirably 500 nm or less. As the average particle size of the colloidal particles increases, the appearance and adhesion of the resulting coating film tend to deteriorate. The average particle diameter of the colloid particles is preferably 300 nm or less, more preferably 3 nm to 250 n.
m.
【００１７】抗菌性金属成分を含有する無機酸化物コロ
イド粒子における抗菌性金属成分の含有量は、酸化物換
算で０．０５〜２５重量％の範囲内であることが望まし
い。含有量が０．０５重量％に満たない場合は、抗菌作
用が十分に発現しないことがあり、また、２５重量％よ
りも多くしても、２５重量％の場合と比較して抗菌作用
に大差がない。より好ましい抗菌性金属成分の含有量
は、酸化物換算で０．１〜１５重量％である。The content of the antibacterial metal component in the inorganic oxide colloid particles containing the antibacterial metal component is desirably in the range of 0.05 to 25% by weight in terms of oxide. If the content is less than 0.05% by weight, the antibacterial effect may not be sufficiently exhibited. Even if the content is more than 25% by weight, the antibacterial effect is significantly different from that of 25% by weight. There is no. A more preferable content of the antibacterial metal component is 0.1 to 15% by weight in terms of oxide.
【００１８】本発明の抗菌性無機酸化物水性コロイド溶
液としては、例えば、本発明者らの先願に係る特開平７
−３３６１６号公報に記載の抗菌剤であって、抗菌性金
属成分と該抗菌性金属成分以外の無機酸化物から構成さ
れるコロイド粒子のζ−電位が水性コロイド溶液のｐＨ
７．０〜９．０の範囲において−２ｍＶ以下のものが好
ましい。この抗菌剤は抗菌性金属成分と該抗菌性金属成
分以外の無機酸化物から構成されるコロイド粒子が分散
してなる抗菌性無機酸化物コロイド溶液であって、当該
コロイド溶液中の抗菌性金属成分の重量をＡ、該コロイ
ド溶液を超遠心分離処理して遊離した抗菌性金属成分の
重量をＢとしたとき、Ｂ／Ａで表される抗菌性金属成分
の結合力指数（Ｉ）の値が１．０×１０-3以下であるこ
とを特徴とするものである。Examples of the aqueous colloidal solution of the antibacterial inorganic oxide of the present invention include, for example, Japanese Patent Application Laid-Open No.
No. 33616, wherein the ζ-potential of colloidal particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component is adjusted to the pH of the aqueous colloid solution.
Those having a value of -2 mV or less in the range of 7.0 to 9.0 are preferable. This antibacterial agent is an antibacterial inorganic oxide colloid solution in which colloid particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are dispersed, and the antibacterial metal component in the colloid solution When the weight of the antimicrobial metal component expressed by B / A is B, the weight of the antimicrobial metal component expressed by B / A is B It is characterized by being not more than 1.0 × 10 −3 .
【００１９】また、特開平６−８０５２７号公報に記載
の抗菌剤、即ち、負の電荷を有する無機酸化物コロイド
粒子に抗菌性金属成分を付着せしめた抗菌性無機酸化物
コロイド溶液からなる抗菌剤であって、抗菌性金属成分
を付着せしめた無機酸化物コロイド粒子のζ−電位が水
性コロイド溶液のｐＨ７．０〜９．０の範囲において−
２ｍＶ以下のものも好適に使用される。Also, an antibacterial agent described in JP-A-6-80527, that is, an antibacterial agent comprising an antibacterial inorganic oxide colloid solution obtained by adhering an antibacterial metal component to negatively charged inorganic oxide colloid particles. Wherein the ζ-potential of the inorganic oxide colloid particles to which the antibacterial metal component is attached is in the range of pH 7.0 to 9.0 of the aqueous colloid solution.
Those having a voltage of 2 mV or less are also preferably used.
【００２０】本発明においてアニオン型電着塗料として
は、通常のアニオン型電着塗料が使用可能である。アニ
オン型電着塗料では、水中に溶解した樹脂分子は負に荷
電していて、電場内では陽極に向かって移行する性質を
有しており、このような性質を有する種々の樹脂がアニ
オン型電着塗料として使用される。例えば、カルボン酸
樹脂、アクリル酸樹脂、エポキシ樹脂などの末端基（カ
ルボキシル基、水酸基など）をアンモニアまたはアミン
などの塩基化合物で少なくとも一部を中和して水分散可
能な形としたもの、マレイン化油、マレイン化脂肪酸エ
ステル、マレイン化ポリブタジエン、アクリル酸などの
酸モノマーとヒドロキシルエチルアクリレートのような
水酸基モノマーとの共重合体などが分散した水分散液ま
たは溶解した水溶液などが例示される。また、必要に応
じてこの液に、顔料およびその他の塗料用添加剤などを
配合することもできる。In the present invention, as the anion-type electrodeposition paint, a usual anion-type electrodeposition paint can be used. In anionic electrodeposition paints, resin molecules dissolved in water are negatively charged and have the property of migrating toward the anode in an electric field. Used as a coating. For example, a terminal group (carboxyl group, hydroxyl group, etc.) of a carboxylic acid resin, an acrylic acid resin, an epoxy resin or the like is at least partially neutralized with a basic compound such as ammonia or an amine to form a water-dispersible form, Examples thereof include aqueous dispersions or aqueous solutions in which a copolymer of an acid monomer such as a hydrogenated oil, a maleated fatty acid ester, a maleated polybutadiene, or acrylic acid and a hydroxyl group monomer such as hydroxylethyl acrylate is dispersed. If necessary, a pigment and other paint additives can be added to this liquid.
【００２１】本発明では、前述の抗菌性無機酸化物水性
コロイド溶液をアニオン型電着塗料中に０．１〜２０重
量％、好ましくは０．５〜１０重量％の範囲で含有する
ことが望ましい。アニオン型電着塗料中に含まれる抗菌
性無機酸化物水性コロイド溶液の量が０．１重量％より
も少ない場合には所望の抗菌効果が得られにくい。ま
た、該コロイド溶液の量を２０重量％よりも多くしても
得られる塗膜の抗菌効果には差がなく経済的でない。In the present invention, it is desirable that the above-mentioned aqueous colloidal solution of the antibacterial inorganic oxide is contained in the anionic electrodeposition paint in the range of 0.1 to 20% by weight, preferably 0.5 to 10% by weight. . If the amount of the antibacterial inorganic oxide aqueous colloid solution contained in the anionic electrodeposition paint is less than 0.1% by weight, it is difficult to obtain a desired antibacterial effect. Further, even if the amount of the colloid solution is more than 20% by weight, there is no difference in the antibacterial effect of the coating film obtained and it is not economical.
【００２２】次に、本発明の電着塗装方法について説明
する。本発明の電着塗装方法では、前述のアニオン型電
着塗料を満たした電着槽の中に陽極の導体被塗装物を浸
漬し、これと反対極となる槽内電極との間に直流を通電
することにより、浴中に分散している塗料微粒子と共に
抗菌性金属成分を含有する無機酸化物コロイド粒子が電
気的な力によって被塗装物に引き付けられて凝集析出し
て抗菌性を有する塗膜を形成する。Next, the electrodeposition coating method of the present invention will be described. In the electrodeposition coating method of the present invention, the conductor coated object of the anode is immersed in an electrodeposition tank filled with the above-described anionic electrodeposition coating, and a direct current is applied between the object and an electrode in the tank which is the opposite electrode. When an electric current is applied, the inorganic oxide colloid particles containing the antibacterial metal component together with the paint particles dispersed in the bath are attracted to the object to be coated by an electric force and are coagulated and precipitated to have antibacterial properties. To form
【００２３】本発明の電着塗装方法は、前述の電着塗料
を使用すること以外は特に制限されるものではなく、通
常のアニオン型電着塗装方法を採用することができ、例
えば、〔表１〕に示すような条件が例示される。また、
本発明方法において、塗膜の硬化は各塗料自体の樹脂組
成などに基づいて任意に選択でき、なんら制限されるも
のではない。The electrodeposition coating method of the present invention is not particularly limited except that the above-mentioned electrodeposition coating is used, and a general anion-type electrodeposition coating method can be employed. The conditions as shown in [1] are exemplified. Also,
In the method of the present invention, the curing of the coating film can be arbitrarily selected based on the resin composition of each paint itself, and is not limited at all.
【００２４】[0024]
【表１】 塗料の樹脂固形分濃度：３〜５０重量％ 塗料のｐＨ ：７〜９ 塗料の温度 ：２０〜４０℃ 電圧 ：１００〜４００Ｖ 通電時間 ：３０秒〜１０分[Table 1] Resin solid content concentration of paint: 3 to 50% by weight pH of paint: 7 to 9 Temperature of paint: 20 to 40 ° C Voltage: 100 to 400 V Conduction time: 30 seconds to 10 minutes
【００２５】本発明の電着塗装方法に使用される導体の
被塗装物としては、導電性を有するものであればよく、
形状、大きさ、材質等に限定されない。例えば、鉄、
銅、アルミニウム、マグネシウム、チタン等、あるいは
これらの合金、更には表面に金属メッキ層、その他導電
層を形成したプラスチック等が挙げられる。The object to be coated with the conductor used in the electrodeposition coating method of the present invention may be any one having conductivity.
The shape, size, material, etc. are not limited. For example, iron,
Examples thereof include copper, aluminum, magnesium, titanium, and the like, and alloys thereof, and a plastic having a metal plating layer or other conductive layer formed on the surface.
【００２６】以上、アニオン型電着塗料の好適な実施形
態について説明したが、本発明の抗菌性無機酸化物水性
コロイド溶液は、適当な電着条件を選定することによっ
てカチオン型電着塗料についても適用可能である。しか
し、アニオン型電着塗料と比べると、均一な無機酸化物
コロイド粒子を含む塗膜を形成することが難しい。Although the preferred embodiment of the anionic electrodeposition paint has been described above, the antibacterial inorganic oxide aqueous colloid solution of the present invention can be used for the cationic electrodeposition paint by selecting appropriate electrodeposition conditions. Applicable. However, it is more difficult to form a coating film containing uniform inorganic oxide colloid particles as compared with an anionic electrodeposition paint.
【００２７】[0027]
【実施例】以下に実施例を示し、本発明を更に具体的に
説明する。The present invention will be described more specifically with reference to the following examples.
【００２８】参考例１ 市販の２０重量％シリカ・アルミナゾル（触媒化成工業
（株）製：ファインカタロイド−ＵＳＢ）を水で希釈し
てシリカ・アルミナ濃度１．０重量％のゾル（コロイド
溶液）２０００ｇとした。一方、試薬の硝酸銀を６．３
ｇ採取し、水６２３．７ｇを加えて希釈し、銀酸化物と
しての濃度が１．０重量％の硝酸銀水溶液を調製した。
前記コロイド溶液を６０℃に加温し、撹拌しながらこれ
に該硝酸銀水溶液を２０ｃｃ／ｍｉｎの速度で添加し
た。 REFERENCE EXAMPLE 1 A commercially available 20 wt% silica-alumina sol (Fine Cataroid-USB manufactured by Catalyst Chemical Industry Co., Ltd.) was diluted with water to obtain a sol (colloidal solution) having a silica-alumina concentration of 1.0 wt%. 2000 g. On the other hand, the reagent silver nitrate was added to 6.3.
g of water was collected and diluted with 623.7 g of water to prepare a silver nitrate aqueous solution having a concentration of 1.0% by weight as silver oxide.
The colloid solution was heated to 60 ° C., and the silver nitrate aqueous solution was added thereto at a rate of 20 cc / min with stirring.
【００２９】次いで、このコロイド溶液を限外濾過装置
を用いて１０リットルの純水で洗浄し、その後、さらに
９０℃で１時間加熱熟成を行って、抗菌性銀成分を酸化
物として４重量％含有するシリカ・アルミナコロイド粒
子が分散した抗菌性無機酸化物水性コロイド溶液（Ａ）
を調製した。該コロイド溶液の固形分濃度は１重量％
で、コロイド溶液として安定であった。Next, this colloid solution was washed with 10 liters of pure water using an ultrafiltration apparatus, and then heated and aged at 90 ° C. for 1 hour to obtain an antibacterial silver component as an oxide of 4% by weight. Aqueous antibacterial inorganic oxide colloid solution containing dispersed silica-alumina colloid particles (A)
Was prepared. The solid content concentration of the colloid solution is 1% by weight.
Was stable as a colloid solution.
【００３０】抗菌性無機酸化物水性コロイド溶液（Ａ）
のコロイド粒子のζ−電位を超音波方式ゼータ電位分析
システム装置（Matec Applied Sciences, Inc.製、ＥＳ
Ａ８０００）を用いて測定した。測定方法は、試料２０
ｃｃを採取し、ｐＨ調整は１Ｎ−ＨＣｌおよび０．５Ｎ
−ＮａＯＨを用いて行った。ｐＨを変化させた場合の、
該シリカ・アルミナコロイド粒子のζ−電位変化を図１
に示す。Antibacterial inorganic oxide aqueous colloid solution (A)
The zeta potential of the colloidal particles of the zeta potential analysis system by ultrasonic method (Matec Applied Sciences, Inc., ES
A8000). The measurement method is as follows:
cc, and the pH was adjusted with 1N HCl and 0.5N
Performed using -NaOH. When the pH is changed,
Fig. 1 shows the ζ-potential change of the silica-alumina colloid particles.
Shown in
【００３１】参考例２ 硫酸チタンを純水に溶解して、ＴｉＯ2 として１．０重
量％の水溶液を調製した。この水溶液に、撹拌しながら
１５重量％アンモニア水を徐々に添加して白色のスラリ
ーを得た。このスラリーを濾過、洗浄して得た含水チタ
ン酸３１．４ｇに純水を加えてＴｉＯ2 濃度１．０重量
％に希釈し、更に濃度３３重量％の過酸化水素２１９．
３ｇを加えた後、８０℃で１４時間加熱して、過酸化水
素を分解しＴｉＯ2 として１．０重量％の水溶液３１３
６ｇを得た。このチタン酸溶液は黄褐色の透明液でｐＨ
８．２であった。この溶液に、ＴｉＯ2 に対して２５重
量％になるように２０重量％シリカゾル３９．２ｇを加
えた後、１５０℃で４８時間加熱した。 Reference Example 2 Titanium sulfate was dissolved in pure water to prepare a 1.0% by weight aqueous solution as TiO 2 . To this aqueous solution, 15% by weight of aqueous ammonia was gradually added with stirring to obtain a white slurry. Pure water was added to 31.4 g of hydrous titanic acid obtained by filtering and washing the slurry to dilute it to a TiO 2 concentration of 1.0% by weight.
After adding 3 g, the mixture was heated at 80 ° C. for 14 hours to decompose hydrogen peroxide to obtain a 1.0 wt% aqueous solution 313 as TiO 2.
6 g were obtained. This titanic acid solution is a tan transparent liquid and has a pH
8.2. 39.2 g of a 20% by weight silica sol was added to this solution so as to be 25% by weight with respect to TiO 2 and then heated at 150 ° C. for 48 hours.
【００３２】次に、この溶液を６０℃に保持し、酸化銀
として濃度１重量％の硝酸銀溶液２４９ｇを２０ｃｃ／
ｍｉｎの速度で添加した。次いで、このコロイド溶液を
限外濾過装置を用いて１０リットルの純水で洗浄し、そ
の後、さらに９０℃で１時間加熱熟成を行って、抗菌性
銀成分を酸化物として４重量％含有するチタニア粒子が
分散した抗菌性無機酸化物水性コロイド溶液（Ｂ）を調
製した。該コロイド溶液の固形分濃度は１重量％で、コ
ロイド溶液として安定であった。抗菌性無機酸化物水性
コロイド溶液（Ｂ）のコロイド粒子のζ−電位を参考例
１と同様にして測定したグラフを図２に示す。Next, this solution was kept at 60 ° C., and 249 g of a silver nitrate solution having a concentration of 1% by weight as silver oxide was added at 20 cc / cm 2.
Added at a rate of min. Next, this colloid solution was washed with 10 liters of pure water using an ultrafiltration apparatus, and then heat-aged at 90 ° C. for 1 hour to obtain titania containing 4% by weight of an antibacterial silver component as an oxide. An aqueous antibacterial inorganic oxide colloid solution (B) in which particles were dispersed was prepared. The colloid solution had a solid content of 1% by weight, and was stable as a colloid solution. FIG. 2 shows a graph in which the ζ-potential of the colloidal particles of the aqueous colloidal solution of antibacterial inorganic oxide (B) was measured in the same manner as in Reference Example 1.
【００３３】参考例３ 市販の銀成分を担持したリン酸カルシウムのセラミック
微粒子からなる抗菌剤（（株）サンギ製、アパサイダー
ＡＷ）を純水に懸濁して、固形分濃度１重量％の懸濁水
溶液（Ｃ）を調製した。この懸濁水溶液（Ｃ）のセラミ
ック微粒子のζ−電位を参考例１と同様にして測定した
グラフを図３に示す。 Reference Example 3 A commercially available antibacterial agent (Apacider AW, manufactured by Sanghi Co., Ltd.) composed of ceramic fine particles of calcium phosphate carrying a silver component was suspended in pure water to give a suspended aqueous solution having a solid content of 1% by weight ( C) was prepared. FIG. 3 is a graph showing the ζ-potential of the ceramic fine particles of the aqueous suspension (C) measured in the same manner as in Reference Example 1.
【００３４】実施例１ 市販の樹脂固形分濃度８重量％のアクリル−メラミン系
アニオン型電着塗料（ハニー化成（株）製、ハニーブラ
イト）に、前記コロイド溶液（Ａ）とコロイド溶液
（Ｂ）をそれぞれ１重量％になるように添加混合して、
抗菌性無機酸化物水性コロイド溶液を含むアニオン型電
着塗料（Ａ）および（Ｂ）を調製した。 Example 1 The above colloid solution (A) and colloid solution (B) were added to a commercially available acrylic-melamine-based anionic electrodeposition paint (Honey Bright, manufactured by Honey Chemical Co., Ltd.) having a resin solid content of 8% by weight. Are added and mixed so that each becomes 1% by weight,
Anionic electrodeposition coating compositions (A) and (B) containing an aqueous antimicrobial inorganic oxide colloid solution were prepared.
【００３５】比較例１ 実施例１と同様に、市販の樹脂固形分濃度８重量％のア
クリル−メラミン系アニオン型電着塗料（ハニー化成
（株）製、ハニーブライト）に、参考例３の懸濁水溶液
（Ｃ）を１重量％になるように添加混合して、抗菌剤懸
濁水溶液を含むアニオン型電着塗料（Ｃ）を調製した。[0035] Similarly to Comparative Example 1 Example 1, a commercially available resin solids concentration of 8 wt% of acrylic - melamine anionic electrocoating paint (Honey Kasei Co., Ltd., honey Bright), the suspension of Reference Example 3 The turbid aqueous solution (C) was added and mixed so as to be 1% by weight to prepare an anionic electrodeposition paint (C) containing an aqueous antimicrobial agent suspension.
【００３６】実施例２ 上記アニオン型電着塗料（Ａ）、（Ｂ）および（Ｃ）を
用いてアルミニウム板に電着塗装を行った。 Example 2 An aluminum plate was electrodeposited using the above-mentioned anionic electrodeposition coatings (A), (B) and (C).
【００３７】先ず、良く脱脂洗浄したアルミニウム板片
を常温で陽極酸化してアルマイト化し、酸化被膜を形成
した。このアルミニウム板片を陽極として、液温３０℃
の各アニオン型電着塗料中に浸漬し、陰極としてステン
レス板片を同様に浸漬して、両極間に直流電圧２００Ｖ
で２分間通電してアルミニウム板片表面に樹脂とコロイ
ド粒子を凝集析出させた。次いで、アルミニウム板片を
電着塗料から引き上げ、洗浄した後、１８０℃で３０分
間乾燥して各アルミニウム板片試料の表面に塗膜
（Ａ）、（Ｂ）および（Ｃ）を形成した。First, an aluminum plate piece that had been well degreased and washed was anodized at room temperature to be anodized to form an oxide film. Using this aluminum plate piece as the anode, a liquid temperature of 30 ° C.
Immersed in each of the anionic electrodeposition paints described above, a stainless plate piece was similarly immersed as a cathode, and a DC voltage of 200 V was applied between both electrodes.
For 2 minutes to coagulate and precipitate the resin and colloid particles on the surface of the aluminum plate piece. Next, the aluminum plate piece was pulled up from the electrodeposition paint, washed, and dried at 180 ° C. for 30 minutes to form coating films (A), (B) and (C) on the surface of each aluminum plate piece sample.
【００３８】実施例３ 上記各塗膜付きアルミニウム板片試料について、次の抗
菌力試験を行った。 Example 3 The following antibacterial test was carried out on the above-mentioned coated aluminum plate samples.
【００３９】大腸菌および黄色葡萄状球菌を生理食塩水
中に懸濁させ、その３０μｌを３ｃｍ×３ｃｍの上記各
試料面に滴下し、２８℃で２４時間放置後、生菌数を測
定して〔数１〕により死滅率を求めた。結果を表２に示
す。Escherichia coli and Staphylococcus aureus were suspended in physiological saline, and 30 μl of the suspension was dropped on each of the sample surfaces of 3 cm × 3 cm, left at 28 ° C. for 24 hours, and the viable cell count was measured. The death rate was determined according to 1). Table 2 shows the results.
【００４０】[0040]
【数１】死滅率（％）＝１００×（初期生菌数−２４時
間後の生菌数）／初期生菌数[Equation 1] Death rate (%) = 100 × (initial viable cell count−viable cell count after 24 hours) / initial viable cell count
【００４１】また、塗膜の性状についても、耐候性と外
観から評価した結果を表２に示す。耐候性は、デジタル
変角光沢度計（スガ試験機（株）製）を用い、サンシャ
インウェザーメータで２５０時間暴露の光沢保持率を示
した。Table 2 shows the results of the evaluation of the properties of the coating film in terms of weather resistance and appearance. The weather resistance was measured by using a digital gonio-gloss meter (manufactured by Suga Test Instruments Co., Ltd.) and the gloss retention after exposure for 250 hours with a sunshine weather meter.
【００４２】塗膜の外観は次の３段階で評価した。 ○・・・異常なく仕上がり良好。 △・・・肌あれ、クレーターの発生が認められた。 ×・・・電着塗膜に異常が発生した。The appearance of the coating film was evaluated on the following three levels.・ ・ ・: Good finish without any abnormality. Δ: rough skin and craters were observed. X: An abnormality occurred in the electrodeposition coating film.
【００４３】[0043]
【表２】 [Table 2]
【００４４】[0044]
【発明の効果】本発明に係る電着塗料と電着塗装方法に
よれば、被塗装物表面は長時間にわたって優れた抗菌性
を有し、良好な外観、密着性の優れた塗膜が得られる。
また、はけ塗り塗装や、吹き付け塗装では処理できなか
った複雑な形状の物品に対しても容易に塗膜を形成する
ことができる。According to the electrodeposition paint and the electrodeposition coating method of the present invention, the surface of the object to be coated has excellent antibacterial properties over a long period of time, and a coating film having good appearance and excellent adhesion can be obtained. Can be
Further, a coating film can be easily formed even on an article having a complicated shape which could not be processed by brush coating or spray coating.
【図１】参考例１における、抗菌性無機酸化物水性コロ
イド溶液（Ａ）のコロイド粒子のζ−電位を示すグラフ
である。FIG. 1 is a graph showing the ζ-potential of colloidal particles of an aqueous colloidal solution of an antibacterial inorganic oxide (A) in Reference Example 1.
【図２】参考例２における、抗菌性無機酸化物水性コロ
イド溶液（Ｂ）のコロイド粒子のζ−電位を示すグラフ
である。FIG. 2 is a graph showing the ζ-potential of colloidal particles in an aqueous colloidal solution of an antibacterial inorganic oxide (B) in Reference Example 2.
【図３】参考例３における、抗菌剤懸濁水溶液（Ｃ）の
セラミック微粒子のζ−電位を示すグラフである。FIG. 3 is a graph showing the ζ-potential of ceramic fine particles in an antimicrobial agent suspension aqueous solution (C) in Reference Example 3.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ２５Ｄ 13/10 Ｃ２５Ｄ 13/10 Ａ ──────────────────────────────────────────────────続 き Continued on front page (51) Int.Cl. 6 Identification code FI C25D 13/10 C25D 13/10 A
Claims (2)
ロイド粒子が分散した水性コロイド溶液と、アニオン型
電着塗料とを含む電着塗料であって、前記コロイド粒子
のζ−電位が水性コロイド溶液のｐＨ７．０〜９．０の
範囲において−２ｍＶ以下であることを特徴とする電着
塗料。1. An electrodeposition paint comprising an aqueous colloid solution in which inorganic oxide colloid particles containing an antibacterial metal component are dispersed, and an anion type electrodeposition paint, wherein the ζ-potential of the colloid particles is an aqueous colloid. An electrodeposition coating material having a solution pH of -2 mV or less in a pH range of 7.0 to 9.0.
体被塗装物とこれと反対電極との間に直流を通電して、
被塗装物表面に抗菌性金属成分を含有する無機酸化物コ
ロイド粒子を含む塗膜を形成することを特徴とする電着
塗装方法。2. A direct current is applied between a conductor coated object of an anode and an opposite electrode in the electrodeposition coating material according to claim 1,
An electrodeposition coating method comprising forming a coating film containing inorganic oxide colloid particles containing an antibacterial metal component on the surface of an object to be coated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9058479A JPH10237362A (en) | 1997-02-26 | 1997-02-26 | Electrodeposition coating material and electrodeposition coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9058479A JPH10237362A (en) | 1997-02-26 | 1997-02-26 | Electrodeposition coating material and electrodeposition coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10237362A true JPH10237362A (en) | 1998-09-08 |
Family
ID=13085577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9058479A Pending JPH10237362A (en) | 1997-02-26 | 1997-02-26 | Electrodeposition coating material and electrodeposition coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10237362A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001040287A (en) * | 1999-07-28 | 2001-02-13 | Catalysts & Chem Ind Co Ltd | Antimicrobial coating film and substrate with the same |
| JP2002138253A (en) * | 2000-08-25 | 2002-05-14 | Sakura Color Prod Corp | Aqueous metal oxide dispersion composition for electrodeposition coating |
| WO2003045845A1 (en) * | 2001-11-26 | 2003-06-05 | Hiroshi Ishikawa | Fired composition and electrodeposition coating |
| JP2005519201A (en) * | 2001-11-30 | 2005-06-30 | ザ ユニバーシティ オブ ノース カロライナ アット チャペル ヒル | Deposition methods for nanostructured materials |
| KR100661738B1 (en) | 2005-04-25 | 2006-12-27 | 정정철 | The manufacture method of bio-ceramic product having functions |
| JP2007536070A (en) * | 2004-03-03 | 2007-12-13 | アソシアシオン プール レ トランスフェル ドゥ テクノロジー ドュ マン | Method for reducing surface contamination by microorganisms |
| JP2008274099A (en) * | 2007-04-27 | 2008-11-13 | Kobe Steel Ltd | Coating, and coated titanium or titanium alloy |
| US7455757B2 (en) | 2001-11-30 | 2008-11-25 | The University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
| WO2010036543A3 (en) * | 2008-09-29 | 2010-07-01 | Carrier Corporation | Catalytic substrates and methods for creating catalytic coatings for indoor air quality applications |
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| JPH07150075A (en) * | 1993-11-29 | 1995-06-13 | Catalysts & Chem Ind Co Ltd | Antimicrobial coating composition and coating film |
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| JPH08134697A (en) * | 1994-11-11 | 1996-05-28 | Nisshin Steel Co Ltd | Method for coating antifungal and mildew-proofing zeolite by utilizing electrophoresis |
| JPH08302498A (en) * | 1995-05-10 | 1996-11-19 | Ykk Kk | Antibacterial and mildewproof building material |
| JPH08333139A (en) * | 1995-06-02 | 1996-12-17 | Wako Kagaku Kogyo Kk | Glass vessel subjected to antibacterial treatment |
| JPH09157550A (en) * | 1995-12-08 | 1997-06-17 | Honny Chem Ind Co Ltd | Antibacterial resin composition |
| JPH09164529A (en) * | 1995-12-18 | 1997-06-24 | Catalysts & Chem Ind Co Ltd | Production of antibacterial resin molded product |
| JPH1017406A (en) * | 1996-07-05 | 1998-01-20 | Catalysts & Chem Ind Co Ltd | Antibacterial agent |
| JPH10121294A (en) * | 1996-10-11 | 1998-05-12 | Toagosei Co Ltd | Electrodeposition coating method |
| JP2001501990A (en) * | 1996-09-14 | 2001-02-13 | ビーエーエスエフ コーティングス アクチェンゲゼルシャフト | Aqueous electrodeposition coatings, their use in coating conductive substrates and the use of silver ions and / or elemental silver in aqueous electrodeposition coatings |
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| JPH0680527A (en) * | 1992-08-31 | 1994-03-22 | Catalysts & Chem Ind Co Ltd | Antimicrobial agent |
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| JPH07150075A (en) * | 1993-11-29 | 1995-06-13 | Catalysts & Chem Ind Co Ltd | Antimicrobial coating composition and coating film |
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| JPH08104605A (en) * | 1994-10-05 | 1996-04-23 | Catalysts & Chem Ind Co Ltd | Antibacterial agent |
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|---|---|---|---|---|
| JP2001040287A (en) * | 1999-07-28 | 2001-02-13 | Catalysts & Chem Ind Co Ltd | Antimicrobial coating film and substrate with the same |
| JP2002138253A (en) * | 2000-08-25 | 2002-05-14 | Sakura Color Prod Corp | Aqueous metal oxide dispersion composition for electrodeposition coating |
| WO2003045845A1 (en) * | 2001-11-26 | 2003-06-05 | Hiroshi Ishikawa | Fired composition and electrodeposition coating |
| JP2005519201A (en) * | 2001-11-30 | 2005-06-30 | ザ ユニバーシティ オブ ノース カロライナ アット チャペル ヒル | Deposition methods for nanostructured materials |
| US7455757B2 (en) | 2001-11-30 | 2008-11-25 | The University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
| US7887689B2 (en) | 2001-11-30 | 2011-02-15 | The University Of North Carolina At Chapel Hill | Method and apparatus for attaching nanostructure-containing material onto a sharp tip of an object and related articles |
| US8002958B2 (en) | 2001-11-30 | 2011-08-23 | University Of North Carolina At Chapel Hill | Deposition method for nanostructure materials |
| JP2007536070A (en) * | 2004-03-03 | 2007-12-13 | アソシアシオン プール レ トランスフェル ドゥ テクノロジー ドュ マン | Method for reducing surface contamination by microorganisms |
| KR100661738B1 (en) | 2005-04-25 | 2006-12-27 | 정정철 | The manufacture method of bio-ceramic product having functions |
| JP2008274099A (en) * | 2007-04-27 | 2008-11-13 | Kobe Steel Ltd | Coating, and coated titanium or titanium alloy |
| WO2010036543A3 (en) * | 2008-09-29 | 2010-07-01 | Carrier Corporation | Catalytic substrates and methods for creating catalytic coatings for indoor air quality applications |
| US9095636B2 (en) | 2008-09-29 | 2015-08-04 | Carrier Corporation | Catalytic substrates and methods for creating catalytic coatings for indoor air quality applications |
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