JPH07150075A - Antimicrobial coating composition and coating film - Google Patents
Antimicrobial coating composition and coating filmInfo
- Publication number
- JPH07150075A JPH07150075A JP5320834A JP32083493A JPH07150075A JP H07150075 A JPH07150075 A JP H07150075A JP 5320834 A JP5320834 A JP 5320834A JP 32083493 A JP32083493 A JP 32083493A JP H07150075 A JPH07150075 A JP H07150075A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- metal component
- inorganic oxide
- fine particles
- weight
- 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.)
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Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は抗菌性、防カビ性、防臭
性、防藻性等に優れた塗膜を形成する抗菌性塗料組成物
に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial coating composition which forms a coating film having excellent antibacterial properties, antifungal properties, deodorizing properties, antialgal properties and the like.
【０００２】[0002]
【従来技術およびその問題点】従来、ゼオライトやシリ
カゲル、酸化チタン等の粉末に抗菌性を有する金属成分
をイオン交換や含浸などの方法により担持した抗菌剤を
含有する抗菌性塗料組成物が知られている。2. Description of the Related Art Conventionally, antibacterial coating compositions containing an antibacterial agent in which a powder of zeolite, silica gel, titanium oxide or the like is loaded with a metal component having antibacterial properties by a method such as ion exchange or impregnation are known. ing.
【０００３】例えば、特開昭６３−２２１１７５号公報
には、殺菌作用を有する金属イオンを保持している陽イ
オン交換体を含有してなる防カビおよび抗菌性を有する
塗壁材料または吹付け材料が開示されており、また、特
開平２−２５１５８５号公報には、特定の金属アルコキ
シドの加水分解物と、抗菌性金属イオンを含む含水アル
ミノケイ酸塩とからなるコーティング用組成物が記載さ
れている。[0003] For example, JP-A-63-221175 discloses a coating wall material or spraying material having antifungal and antibacterial properties, which contains a cation exchanger retaining metal ions having a bactericidal action. JP-A-2-251585 describes a coating composition comprising a hydrolyzate of a specific metal alkoxide and a hydrous aluminosilicate containing an antibacterial metal ion. .
【０００４】しかし、上記従来の抗菌剤は粉末状で、そ
の粒子径が大きいため塗料組成物中への分散性が悪く、
また、形成された塗膜の密着性が低下する要因となる。
更に、抗菌性成分を粉末に担持しているため利用効率が
低く、抗菌性が効果的に発現しにくくて、所望の抗菌活
性を得るためには多量の抗菌剤を添加する必要がある。
この場合、金属成分の含有量も多くなるので、銀などの
抗菌性金属成分を用いた抗菌剤を使用した塗料組成物で
は形成された塗膜が変色を起こすといった問題点があっ
た。However, the above-mentioned conventional antibacterial agents are powdery and have a large particle size, so that their dispersibility in a coating composition is poor,
In addition, it causes a decrease in the adhesion of the formed coating film.
Further, since the antibacterial component is supported on the powder, the utilization efficiency is low, and the antibacterial property is difficult to be effectively exhibited. Therefore, it is necessary to add a large amount of the antibacterial agent to obtain a desired antibacterial activity.
In this case, since the content of the metal component increases, there is a problem that the coating film formed by the coating composition using the antibacterial agent using the antibacterial metal component such as silver causes discoloration.
【０００５】また、特開平４−２５５７６７号公報に
は、（ａ）合成樹脂エマルジョン、（ｂ）コロイド状も
しくは微粒子状の金属酸化物、シリカゲルおよび／また
はゼオライト、（ｃ）抗菌性金属の錯イオン、および
（ｄ）水、を主成分とするコーティング用組成物が開示
されているが、この組成物はそもそも繊維材料に被膜を
形成するためのコーティング用組成物であり、また、抗
菌効果の持続性の点が隘路となっている。Further, JP-A-4-255767 discloses that (a) a synthetic resin emulsion, (b) a colloidal or particulate metal oxide, silica gel and / or zeolite, and (c) a complex ion of an antibacterial metal. , And (d) water as a main component are disclosed, but this composition is a coating composition for forming a film on a fiber material in the first place, and also has a sustained antibacterial effect. The point of sex is a bottleneck.
【０００６】さらに、特開平４−３２１６２８号公報に
は、抗菌性の高い銀コロイド粒子からなる抗菌剤が提案
されているが、該コロイド溶液は灰褐色に着色してお
り、透明性に欠け、また、銀成分そのものがコロイド粒
子であるため、凝集し易く安定性に欠けるという問題点
を有している。Further, JP-A-4-321628 proposes an antibacterial agent composed of silver colloid particles having high antibacterial properties, but the colloidal solution is colored grayish brown and lacks transparency. Further, since the silver component itself is colloidal particles, there is a problem in that it easily aggregates and lacks stability.
【０００７】[0007]
【発明の目的】本発明は、優れた抗菌活性、防カビ性、
消臭性、防藻性等を有し、平均粒子径が５００ｎｍ以下
の微粒子を使用することで、前述したような粉末状の抗
菌剤を使用することによる問題点を解決し、長期間にわ
たって優れた抗菌効果を維持することができ、しかも、
変色することがない塗膜を形成し得る抗菌性塗料組成
物、およびその塗膜を提供することを目的とするもので
ある。OBJECT OF THE INVENTION The present invention has excellent antibacterial activity, antifungal properties,
By using fine particles having an average particle size of 500 nm or less, which have deodorant properties, anti-algal properties, etc., the problems due to the use of the powdered antibacterial agent as described above are solved, and it is excellent for a long period of time. The antibacterial effect can be maintained, and
It is an object of the present invention to provide an antibacterial coating composition capable of forming a coating film that does not discolor, and the coating film.
【０００８】[0008]
【発明の概要】本発明に係る抗菌性塗料組成物は、抗菌
性金属成分と該抗菌性金属成分以外の無機酸化物とから
構成される平均粒子径が５００ｎｍ以下の微粒子を含有
することを特徴とする。また、本発明に係る抗菌性塗料
組成物は、抗菌性金属成分と該抗菌性金属成分以外の無
機酸化物とから構成される平均粒子径が５００ｎｍ以下
の微粒子が分散してなる抗菌性無機酸化物コロイド溶液
と、塗膜形成剤と、溶剤とからなることを特徴とする。SUMMARY OF THE INVENTION The antibacterial coating composition according to the present invention is characterized by containing fine particles having an average particle size of 500 nm or less, which are composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component. And Further, the antibacterial coating composition according to the present invention is an antibacterial inorganic oxide formed by dispersing fine particles having an average particle size of 500 nm or less composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component. It is characterized by comprising a colloidal solution of a substance, a film forming agent and a solvent.
【０００９】[0009]
【発明の具体的な説明】本発明において、抗菌性金属成
分と該抗菌性金属成分以外の無機酸化物とから構成され
る微粒子は、抗菌性金属成分が無機酸化物と混合物また
は化合物の形で微粒子を形成するか、あるいは、該抗菌
性金属成分が無機酸化物微粒子の表面に結合している。
特に、該微粒子が抗菌性金属成分と無機酸化物との混合
物または化合物の形、即ち、複合酸化物を形成している
ことが、長期間にわたり抗菌効果を持続して有する上で
好ましい。DETAILED DESCRIPTION OF THE INVENTION In the present invention, fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are fine particles of the antibacterial metal component in the form of a mixture or compound with the inorganic oxide. Fine particles are formed or the antibacterial metal component is bonded to the surface of the inorganic oxide fine particles.
In particular, it is preferable that the fine particles form a mixture or compound of an antibacterial metal component and an inorganic oxide, that is, form a composite oxide, in order to maintain the antibacterial effect for a long period of time.
【００１０】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, those generally known can be used, for example, silver, copper, zinc,
Examples are tin and lead. In particular, one or more antibacterial metal components selected from silver, copper, and zinc are preferable from the viewpoints of antibacterial action, discoloration, and safety to the human body.
【００１１】抗菌性成分としての銅イオンは青色を呈す
るが、銀イオンはそもそも無色である。しかし、銀イオ
ンは光化学反応や酸化作用により金属銀の凝集体あるい
は酸化物となり、褐色または黒色に変色する。特に紫外
線の光化学反応による銀成分の変色を防止するために
は、チタン、ジルコニウム、セリウム、亜鉛などを銀成
分と組合わせて使用することが望ましい。これは、チタ
ン、ジルコニウム、セリウムおよび亜鉛成分が紫外線吸
収剤として作用して、銀成分の変色を防止する効果を有
しているからである。Copper ion as an antibacterial component exhibits a blue color, while silver ion is originally colorless. However, silver ions become agglomerates or oxides of metallic silver due to photochemical reaction or oxidation, and turn brown or black. Particularly, in order to prevent the discoloration of the silver component due to the photochemical reaction of ultraviolet rays, it is desirable to use titanium, zirconium, cerium, zinc or the like in combination with the silver component. This is because the titanium, zirconium, cerium and zinc components act as an ultraviolet absorber and have the effect of preventing discoloration of the silver component.
【００１２】一方、本発明において、抗菌性金属成分以
外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。On the other hand, in the present invention, examples of the inorganic oxides other than the antibacterial metal component include inorganic oxides that form a generally known colloidal solution, and the inorganic oxide colloidal particles include single particles. Alternatively, it is possible to use composite oxide colloidal particles, or a mixture thereof.
【００１３】単一の酸化物コロイド粒子としては、Ｓｉ
Ｏ2 、ＴｉＯ2 、ＺｒＯ2 、Ｆｅ2Ｏ3 、Ｓｂ2 Ｏ5 、
ＷＯ3 、Ａｌ2 Ｏ3 、等が例示され、複合酸化物コロイ
ド粒子としては、前記各酸化物と他の無機酸化物の複合
酸化物コロイド粒子、例えば、ＳｉＯ2 ・Ａｌ2 Ｏ3 、
ＳｉＯ2 ・Ｂ2 Ｏ3 、ＳｉＯ2 ・Ｐ2 Ｏ5 、ＴｉＯ2・
ＣｅＯ2 、ＴｉＯ2 ・ＺｒＯ2 、ＳｉＯ2 ・ＺｒＯ2 、
ＳｎＯ2 ・Ｓｂ2 Ｏ5、ＳｉＯ2 ・Ａｌ2 Ｏ3 ・ＴｉＯ
2 、ＳｉＯ2 ・ＴｉＯ2 ・ＣｅＯ2 、ＴｉＯ2・ＳｉＯ
2 ・ＺｒＯ2 、ＳｉＯ2 ・Ａｌ2 Ｏ3 ・ＭｇＯ、ＳｉＯ
2 ・Ａｌ2 Ｏ3・ＣａＯ、ＳｉＯ2 ・ＴｉＯ2 ・Ｆｅ2
Ｏ3 などを挙げることができる。The single oxide colloidal particles include Si
O 2 , TiO 2 , ZrO 2 , Fe 2 O 3 , Sb 2 O 5 ,
WO 3 , Al 2 O 3 and the like are exemplified, and examples of the composite oxide colloidal particles include composite oxide colloidal particles of the above oxides and other inorganic oxides, for example, SiO 2 · Al 2 O 3 .
SiO 2 · B 2 O 3 , SiO 2 · P 2 O 5 , TiO 2 ·
CeO 2 , TiO 2 · ZrO 2 , SiO 2 · ZrO 2 ,
SnO 2 · Sb 2 O 5 , SiO 2 · Al 2 O 3 · TiO
2 , SiO 2 · TiO 2 · CeO 2 , TiO 2 · SiO
2・ ZrO 2 , SiO 2・ Al 2 O 3・ MgO, SiO
2・ Al 2 O 3・ CaO, SiO 2・ TiO 2・ Fe 2
O 3 and the like can be mentioned.
【００１４】本発明において抗菌性金属成分の量は、微
粒子中に酸化物換算で０．１〜２５重量％の範囲内であ
ることが望ましい。抗菌性金属成分が０．１重量％より
も少ない場合は、多量の微粒子を用いないと抗菌作用が
十分に発現しない。また、抗菌性金属成分を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
用に大差がなく、また、銀成分などでは、結合量が多く
なると変色しやすい。好ましい抗菌性金属成分の量は、
酸化物換算で０．１〜１５重量％、更に好ましくは、
０．５〜１０重量％の範囲である。In the present invention, the amount of the antibacterial metal component is preferably in the range of 0.1 to 25% by weight in terms of oxide in the fine particles. When the antibacterial metal component is less than 0.1% by weight, the antibacterial action is not sufficiently exhibited unless a large amount of fine particles are used. In addition, 25% by weight of antibacterial metal component
Even if the amount is more than 25% by weight, the antibacterial action is not so different from that in the case of 25% by weight, and in the case of a silver component or the like, discoloration is likely to occur when the amount of binding is large. The preferred amount of antibacterial metal component is
0.1 to 15% by weight in terms of oxide, more preferably,
It is in the range of 0.5 to 10% by weight.
【００１５】本発明において、抗菌性金属成分と該抗菌
性金属成分以外の無機酸化物とから構成される微粒子
は、コロイド粒子の次元の大きさのもので、その平均粒
子径は５００ｎｍ以下である。平均粒子径が５００ｎｍ
よりも大きくなると、可視光の散乱が多くなるため、該
微粒子を含有する塗料組成物および形成される塗膜の透
明性が損なわれたり、塗料組成物が有色である場合に
は、変色を起こす原因ともなる。また、形成される塗膜
との密着性が低下する要因となったり、塗膜における該
微粒子の分散性が悪くなるので、優れた抗菌効果を維持
することができない。該微粒子の平均粒子径は、好まし
くは、３００ｎｍ以下、更に好ましくは、３〜２５０ｎ
ｍの範囲であることが望ましい。In the present invention, the fine particles composed of the antibacterial metal component and the inorganic oxide other than the antibacterial metal component have a dimension of colloidal particles and an average particle size of 500 nm or less. . Average particle size is 500 nm
If it is larger than the above range, the scattering of visible light increases, so that the transparency of the coating composition containing the fine particles and the coating film formed is impaired, or when the coating composition is colored, discoloration occurs. It can be a cause. In addition, it is difficult to maintain an excellent antibacterial effect because it causes a decrease in the adhesion to the formed coating film or the dispersibility of the fine particles in the coating film deteriorates. The average particle size of the fine particles is preferably 300 nm or less, more preferably 3 to 250 n.
The range of m is desirable.
【００１６】前述の平均粒子径が５００ｎｍ以下の微粒
子は、コロイド溶液として提供されることが望ましく、
そのような抗菌性の無機酸化物コロイド溶液としては、
本出願人が先に提案した特願平５−１９８８９４号に記
載の抗菌剤が好適である。The fine particles having an average particle size of 500 nm or less are desirably provided as a colloidal solution,
As such an antibacterial inorganic oxide colloidal solution,
The antibacterial agent described in Japanese Patent Application No. 5-198894 previously proposed by the applicant is suitable.
【００１７】すなわち、該抗菌剤は、抗菌性金属成分と
該抗菌性金属成分以外の無機酸化物とから構成される微
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。That is, the antibacterial agent is an antibacterial inorganic oxide colloidal solution in which fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are dispersed. Where A is the weight of the antibacterial metal component and B is the weight of the antibacterial metal component liberated by subjecting the colloidal solution to ultracentrifugation, the binding strength index of the antibacterial metal component represented by B / A The value of (I) is 1.0 × 10 -3
It is characterized by the following.
【００１８】前記結合力指数（Ｉ）は、次の方法により
求める。すなわち、抗菌性無機酸化物コロイド溶液中の
抗菌性金属成分の重量をプラズマ発光分光分析装置によ
り、金属原子を定量して求め、次いで、所定量の該抗菌
性無機酸化物コロイド溶液を回転数４５，０００ｒｐｍ
の超遠心分離機にて１時間処理して固形分と溶液に分離
し、この分離された溶液中に含まれる抗菌性金属成分の
金属原子をプラズマ発光分析装置で定量して、遊離した
抗菌性金属成分の重量とする。The binding strength index (I) is obtained by the following method. That is, the weight of the antibacterial metal component in the antibacterial inorganic oxide colloidal solution was determined by quantitatively determining metal atoms with a plasma emission spectrophotometer, and then a predetermined amount of the antibacterial inorganic oxide colloidal solution was rotated at a rotation speed of 45. 1,000 rpm
Treated with the ultracentrifuge for 1 hour to separate into solid content and solution, the metal atom of the antibacterial metal component contained in the separated solution is quantified by the plasma emission spectrometer, and the released antibacterial property It is the weight of the metal component.
【００１９】結合力指数（Ｉ）が１．０×１０-3より大
きい場合には、抗菌性金属成分の無機酸化物コロイド粒
子への結合力が弱いため、抗菌性無機酸化物コロイド溶
液の溶媒中に抗菌性金属成分が溶出しやすく、該微粒子
を塗料組成物中に含有させ、塗膜を形成せしめた際に抗
菌効果の持続性に劣り、また、抗菌性金属成分として銀
を用いた場合には変色の原因ともなるので好ましくな
い。抗菌性金属成分の結合力指数（Ｉ）は、好ましくは
５．０×１０-4以下、特に、１．０×１０-4以下である
ことが望ましい。抗菌性金属成分が２種以上の場合に
は、それぞれの抗菌性金属成分の結合力指数が１．０×
１０-3以下であることを要する。When the binding strength index (I) is larger than 1.0 × 10 −3 , the binding strength of the antibacterial metal component to the inorganic oxide colloidal particles is weak, so that the solvent of the antibacterial inorganic oxide colloidal solution is used. When the antibacterial metal component is easily eluted therein, the fine particles are contained in the coating composition and the antibacterial effect is inferior when a coating film is formed, and when silver is used as the antibacterial metal component. Is also not preferable because it may cause discoloration. The binding strength index (I) of the antibacterial metal component is preferably 5.0 × 10 −4 or less, and particularly preferably 1.0 × 10 −4 or less. When two or more antibacterial metal components are used, the cohesion index of each antibacterial metal component is 1.0 x
It must be 10 −3 or less.
【００２０】上記抗菌性無機酸化物コロイド溶液の中で
も、特に、微粒子が抗菌性金属成分と該抗菌性金属成分
以外の無機酸化物との複合酸化物から構成されるもの
は、上記結合力指数（Ｉ）の値が小さいので好適であ
る。該複合酸化物の微粒子が分散した抗菌性無機酸化物
コロイド溶液は、例えば、特開平５−１３２３０９号公
報に記載された複合酸化物コロイド溶液の製造方法に準
じて調製することができる。即ち、アルカリ金属、アン
モニウムまたは有機塩基の珪酸塩と、アルカリ可溶の無
機化合物と、抗菌性金属成分の水溶液とを、ｐＨ１０以
上のアルカリ水溶液中に同時に添加し、抗菌性金属成分
と複合酸化物を形成した無機酸化物コロイド粒子を生成
させる方法である。Among the above antibacterial inorganic oxide colloidal solutions, especially those in which the fine particles are composed of a composite oxide of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component, the above binding strength index ( It is preferable because the value of I) is small. The antibacterial inorganic oxide colloidal solution in which the fine particles of the complex oxide are dispersed can be prepared, for example, according to the method for producing a composite oxide colloidal solution described in JP-A-5-132309. That is, a silicate of an alkali metal, ammonium or an organic base, an alkali-soluble inorganic compound, and an aqueous solution of an antibacterial metal component are simultaneously added to an alkaline aqueous solution having a pH of 10 or more to obtain an antibacterial metal component and a composite oxide. It is a method of producing the inorganic oxide colloidal particles having formed.
【００２１】また、特開昭６３−２７０６２０号公報に
記載された製造方法に準じて調製することもできる。即
ち、含水チタン酸のゲルまたはゾルに過酸化水素を加え
て得られるチタン酸水溶液と抗菌性金属成分の水溶液と
を、必要に応じてケイ素化合物および／またはジルコニ
ウム化合物等の存在下で加熱処理して、抗菌性金属成分
と該抗菌性金属成分以外の無機酸化物とから構成される
複合無機酸化物微粒子が分散したコロイド溶液を調製す
る方法である。It can also be prepared according to the production method described in JP-A-63-270620. That is, a titanic acid aqueous solution obtained by adding hydrogen peroxide to a hydrous titanic acid gel or sol and an aqueous solution of an antibacterial metal component are heat treated in the presence of a silicon compound and / or a zirconium compound, etc., if necessary. And a method for preparing a colloidal solution in which composite inorganic oxide fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are dispersed.
【００２２】上記方法で得られた抗菌性無機酸化物コロ
イド溶液の分散媒である水は、通常の方法で、メチルア
ルコール、エチルアルコール、イソプロピルアルコー
ル、トルエン、メチルエチルケトンなどの有機溶媒と置
換して、有機溶媒を分散媒とする抗菌性無機酸化物コロ
イド溶液とすることもできる。Water, which is the dispersion medium of the antibacterial inorganic oxide colloidal solution obtained by the above method, is replaced with an organic solvent such as methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene and methyl ethyl ketone by a conventional method, An antibacterial inorganic oxide colloidal solution using an organic solvent as a dispersion medium can also be used.
【００２３】また、本発明において前記コロイド溶液の
濃度は、通常使用に適したコロイド溶液の濃度に調節可
能であるが、コロイド溶液の安定性から言えば、酸化物
として１〜３０重量％の範囲とすることが好ましい。該
コロイド溶液は、限外濾過膜などを用いる公知の方法に
より所望の濃度に調整される。In the present invention, the concentration of the colloidal solution can be adjusted to the concentration of the colloidal solution suitable for normal use, but from the standpoint of stability of the colloidal solution, it is in the range of 1 to 30% by weight as an oxide. It is preferable that The colloidal solution is adjusted to a desired concentration by a known method using an ultrafiltration membrane or the like.
【００２４】なお、本発明方法で使用される抗菌性無機
酸化物コロイド溶液は、５０％以上、好ましくは６０％
以上の高い光透過率を示すことが望ましい。抗菌性無機
酸化物コロイド溶液の光透過率が高い場合には、形成さ
れる塗膜も透明性に優れている。ここで、光透過率と
は、厚さ１ｃｍの水に於ける波長５００ｎｍの光の透過
率を１００％とした場合に於いて、厚さ１ｃｍの酸化物
としての濃度が１．０重量％の抗菌性無機酸化物コロイ
ド溶液に於ける同波長光の透過率の相対値をいう。The antibacterial inorganic oxide colloidal solution used in the method of the present invention is 50% or more, preferably 60%.
It is desirable to exhibit the above high light transmittance. When the light transmittance of the antibacterial inorganic oxide colloidal solution is high, the coating film formed is also excellent in transparency. Here, the light transmittance means that when the transmittance of light having a wavelength of 500 nm in water having a thickness of 1 cm is 100%, the concentration as an oxide having a thickness of 1 cm is 1.0% by weight. This is the relative value of the transmittance of the same wavelength light in the antibacterial inorganic oxide colloidal solution.
【００２５】本発明に係る抗菌性塗料としては、油性塗
料、酒精塗料、セルロース塗料、合成樹脂塗料、水性塗
料、ゴム系塗料などを挙げることができ、該塗料組成物
は、前記抗菌性無機酸化物コロイド溶液と、塗膜形成剤
と、溶剤とからなる。当該コロイド溶液は、これらの塗
膜形成剤や溶剤中に添加したり、その他塗料組成物の製
造工程、あるいは塗膜を形成する任意の工程で添加混合
して調製される。Examples of the antibacterial paint according to the present invention include oil-based paints, alcoholic paints, cellulose paints, synthetic resin paints, water-based paints, rubber-based paints, and the like. It is composed of a substance colloidal solution, a film forming agent and a solvent. The colloidal solution is prepared by adding it to these coating film forming agents and solvents, or by adding and mixing it in the other manufacturing process of the coating composition or in any process for forming a coating film.
【００２６】本発明で使用する塗膜形成剤（ビヒクル）
は、通常、塗料組成物に用いられる塗膜形成剤が使用さ
れ、ボイル油、油ワニス、ニトロセルロース、ビニル樹
脂、アルキド樹脂、アミノ樹脂、エポキシ樹脂、フェノ
ール樹脂、ポリエステル樹脂、ポリウレタン樹脂、アク
リル樹脂、フッ素樹脂、ケイ素樹脂、塩化ゴムなどが例
示される。塗膜形成剤には、反応により塗膜を形成する
化合物も含み、これらは１種を単独使用しても、または
２種以上の化合物を併用してもよい。Film-forming agent (vehicle) used in the present invention
Is usually a coating film forming agent used in coating compositions, boil oil, oil varnish, nitrocellulose, vinyl resin, alkyd resin, amino resin, epoxy resin, phenol resin, polyester resin, polyurethane resin, acrylic resin. , Fluororesin, silicon resin, chlorinated rubber and the like. The film forming agent also includes a compound that forms a film by reaction, and these may be used alone or in combination of two or more compounds.
【００２７】本発明で使用する溶剤としては、通常、塗
料組成物に用いられる有機溶媒や水が使用される。有機
溶媒としては、メチルアルコール、エチルアルコール、
プロピルアルコール、ブチルアルコール等のアルコール
類、アセトン、メチルエチルケトン等のケトン類、エー
テル類、脂肪族炭化水素、または、トルエン、ベンゼン
等の芳香族炭化水素が例示される。The solvent used in the present invention is usually an organic solvent or water used in coating compositions. As the organic solvent, methyl alcohol, ethyl alcohol,
Examples thereof include alcohols such as propyl alcohol and butyl alcohol, ketones such as acetone and methyl ethyl ketone, ethers, aliphatic hydrocarbons, and aromatic hydrocarbons such as toluene and benzene.
【００２８】本発明の抗菌性塗料組成物は、前記微粒子
と塗膜形成剤の合計量に対して、該微粒子を０．１〜２
５重量％、好ましくは０．１〜１５重量％の範囲で含有
することが望ましい。この含有量が０．１重量％より少
ない場合には所望の抗菌効果が得られず、また、２５重
量％よりも多い場合には、均一な塗工が困難となるなど
塗料としての特性を損なったり、また、変色を起こし易
くなるので好ましくない。The antibacterial coating composition of the present invention contains the fine particles in an amount of 0.1 to 2 based on the total amount of the fine particles and the coating film forming agent.
It is desirable that the content is 5% by weight, preferably 0.1 to 15% by weight. If the content is less than 0.1% by weight, the desired antibacterial effect cannot be obtained, and if it is more than 25% by weight, the uniform coating becomes difficult and the properties as a coating are impaired. In addition, it is not preferable because discoloration easily occurs.
【００２９】本発明において、塗膜形成剤と溶剤の割合
は、通常の塗料組成物と同様であり、塗膜形成剤の割合
として１〜９９重量％、好ましくは５〜６０重量％の範
囲内である。また、本発明の抗菌性塗料組成物は、必要
に応じて、各種界面活性剤、分散剤、湿潤剤、増粘剤、
消泡剤、香料、染料、顔料、乾燥剤など、従来公知の添
加剤を含有することができる。In the present invention, the ratio of the coating film forming agent to the solvent is the same as in a usual coating composition, and the ratio of the coating film forming agent is within the range of 1 to 99% by weight, preferably 5 to 60% by weight. Is. Further, the antibacterial coating composition of the present invention, if necessary, various surfactants, dispersants, wetting agents, thickeners,
Conventionally known additives such as defoaming agents, fragrances, dyes, pigments and desiccants can be contained.
【００３０】本発明の抗菌性塗料組成物は、公知の方
法、例えば、スプレー、刷毛、ロール、ディッピングな
どの塗装方法や、グラビア印刷などの印刷方法により無
機基材や有機基材の表面にコーティング、乾燥して、塗
膜が形成される。本発明により得られる塗膜は、長期間
にわたって抗菌性、防黴性、防臭性、防藻性などの効果
を保持し、また、前記微粒子の粒子径が小さいため塗膜
の透明性に優れ、基材との密着性が阻害されることがな
い。従って、該塗料組成物は農業用、漁業用、家庭用、
建築用、医療用、衣料用、工業用などの各種産業用機器
や資材などの用途に広範囲に使用することができる。The antibacterial coating composition of the present invention is coated on the surface of an inorganic substrate or an organic substrate by a known method, for example, a coating method such as spraying, brushing, rolling, dipping, or a printing method such as gravure printing. Then, it is dried to form a coating film. The coating film obtained by the present invention retains effects such as antibacterial property, antifungal property, deodorant property, and antialgal property over a long period of time, and is excellent in transparency of the coating film because the particle size of the fine particles is small, Adhesion with the base material is not hindered. Therefore, the coating composition is for agriculture, fishing, household,
It can be used for a wide range of purposes such as various industrial equipment and materials such as construction, medical, clothing, and industrial use.
【００３１】本発明の塗料組成物は、特に、床材、壁
材、階段の手摺のような建築材料、消毒布、包帯、肌
着、シーツ、布団カバー、カーテン、カーペット、絨毯
などの繊維材料、便座、台所流し台、テーブル、冷蔵
庫、クーラーなどの室内備品、工業用タンク類、バケ
ツ、洗面器、食器などの日用雑貨品、船舶、漁網などの
漁業用材料、物品包装用フィルムなどの包装材、ハンド
ル、シート等の自動車や車両の内装品、エレベーターの
内装品、ヘルメット、玩具製品、靴用敷物、ファン備品
や電気部品、パッキン類などの他、電車などの吊り革の
把持部、電話受話器、待合室の椅子やベンチ等、不特定
多数の手に触れることが多いこの種製品の表面に塗布さ
れる。The coating composition of the present invention is particularly suitable for flooring materials, wall materials, building materials such as handrails for stairs, disinfecting cloths, bandages, underwear, sheets, duvet covers, curtains, carpets, carpets, and other fibrous materials, Indoor fixtures such as toilet seats, kitchen sinks, tables, refrigerators, coolers, industrial tanks, daily sundries such as buckets, washbasins, tableware, fishing products such as ships and fishing nets, and packaging materials such as film for packaging goods. , Interior parts of automobiles and vehicles such as steering wheels and seats, interior parts of elevators, helmets, toy products, rugs for shoes, fan equipment and electric parts, packing, etc., grips for hanging leather such as trains, telephone handsets, It is applied to the surface of this type of product, which is often touched by unspecified large numbers of hands such as chairs and benches in the waiting room.
【００３２】[0032]
【実施例】以下に実施例を挙げ、本発明を更に具体的に
説明する。EXAMPLES The present invention will be described in more detail with reference to the following examples.
【００３３】製造例１ 〔抗菌性無機酸化物コロイド溶液の調製〕硫酸チタンを
純水に溶解し、ＴｉＯ2 として１．０重量％を含む水溶
液を得た。この水溶液を撹拌しながら、１５重量％アン
モニア水を徐々に添加し、白色のスラリーを得た。この
スラリーを濾過、洗浄し、含水チタン酸のケーキを得
た。このケーキ３１．４ｇに水溶液濃度が１．０重量％
になるように純水を加えて希釈し、更に３３重量％過酸
化水素２１９．８ｇを加えた後、８０℃で１４時間加熱
し、過酸化水素を加熱分解させ、ＴｉＯ2 として１．０
重量％の溶液３１３６ｇを得た。このチタン酸溶液は黄
褐色透明で、ＰＨは８．２であった。 Production Example 1 [Preparation of antibacterial inorganic oxide colloidal solution] Titanium sulfate was dissolved in pure water to obtain an aqueous solution containing 1.0% by weight of TiO 2 . While stirring this aqueous solution, 15% by weight aqueous ammonia was gradually added to obtain a white slurry. The slurry was filtered and washed to obtain a hydrous titanic acid cake. An aqueous solution concentration of 1.0% by weight in 31.4 g of this cake
Pure water was diluted by adding so that, after addition of further 33% by weight hydrogen peroxide 219.8G, and heated at 80 ° C. 14 h, the hydrogen peroxide was heated decompose, as TiO 2 1.0
3136 g of a weight% solution was obtained. The titanic acid solution was yellowish-brown and transparent, and had a PH of 8.2.
【００３４】次いで、酸化銀０．６８ｇを１５重量％ア
ンモニア水２１．３ｇ、純水６１８．１ｇ中で溶解し
て、銀のアンミン錯塩水溶液とし、この水溶液に炭酸ジ
ルコニウムアンモニウム１５．４ｇを純水１６９．９ｇ
に溶解したものを添加した。この混合水溶液を前記チタ
ン酸水溶液に加え、次に、２０重量％シリカゾル３８．
７ｇを加えた後、１５０℃で４８時間加熱した。この溶
液は、初期黄褐色液であったが、４８時間後に淡乳白色
透明なコロイド溶液となった。Then, 0.68 g of silver oxide was dissolved in 21.3 g of 15% by weight ammonia water and 618.1 g of pure water to prepare an aqueous solution of silver ammine complex salt, and 15.4 g of zirconium ammonium carbonate was added to this aqueous solution. 169.9g
What was melt | dissolved in was added. This mixed aqueous solution was added to the titanic acid aqueous solution, and then 20 wt% silica sol 38.
After adding 7g, it heated at 150 degreeC for 48 hours. This solution was an initial yellowish brown liquid, but after 48 hours, it became a pale milky white transparent colloidal solution.
【００３５】この銀成分を含む複合酸化物コロイド溶液
のＰＨは７．５で、固形分濃度は１．０重量％であり、
コロイド粒子の平均粒径は、５．０ｎｍであった。ま
た、このコロイド溶液の抗菌性金属成分の結合力指数
（Ｉ）の値は、０．６×１０-4であり、波長５００ｎｍ
の光透過率は７６．３％であった。このコロイド溶液を
限外濾過膜を用いて１２．０重量％の濃度に濃縮した。The pH of the complex oxide colloidal solution containing this silver component was 7.5 and the solid content concentration was 1.0% by weight.
The average particle size of the colloidal particles was 5.0 nm. Further, the value of the binding force index (I) of the antibacterial metal component of this colloidal solution is 0.6 × 10 −4 , and the wavelength is 500 nm.
Had a light transmittance of 76.3%. This colloidal solution was concentrated to a concentration of 12.0% by weight using an ultrafiltration membrane.
【００３６】製造例２ 〔抗菌性無機酸化物オルガノコロイド溶液の調製〕上記
濃縮したコロイド溶液２４９ｇとメタノール１７８８．
３ｇとを混合し、この混合溶液中にメチルトリメトキシ
シラン５．９６ｇを添加した。この混合溶液を還流器付
ガラス容器に入れ、６５℃で１８時間加熱処理した後、
これを限外濾過膜で約１０重量％まで濃縮した。次い
で、メタノールを添加しながら混合液中の水を連続的に
限外濾過膜装置で溶媒置換した。置換後のオルガノコロ
イド溶液中の残存水分量は、０．４重量％で、固形分濃
度は１１．５重量％であった。このオルガノコロイド溶
液の濃度１重量％における光透過率は８５．６％であっ
た。 Preparation Example 2 [ Preparation of Antibacterial Inorganic Oxide Organocolloid Solution] 249 g of the above concentrated colloid solution and 1788.methanol of methanol.
3 g was mixed, and 5.96 g of methyltrimethoxysilane was added to this mixed solution. This mixed solution was placed in a glass container with a reflux device, and heat-treated at 65 ° C. for 18 hours,
This was concentrated to about 10% by weight with an ultrafiltration membrane. Next, while adding methanol, water in the mixed solution was continuously solvent-replaced by an ultrafiltration membrane device. The residual water content in the organocolloid solution after substitution was 0.4% by weight, and the solid content concentration was 11.5% by weight. The light transmittance of this organocolloid solution at a concentration of 1% by weight was 85.6%.
【００３７】製造例３ 〔抗菌性無機酸化物コロイド溶液の調製〕ＳｉＯ2 濃度
２０重量％のコロイド溶液２０ｇと純水３８０ｇの混合
物を８０℃に加温した。この反応母液のｐＨは１０．７
であり、同母液にＳｉＯ2 として１．５重量％の珪酸ソ
ーダ水溶液１５００ｇとＡｌ2 Ｏ3 として０．５重量％
のアルミン酸ソーダ水溶液１５００ｇとを同時に添加し
て、ｐＨ１２．３のシリカ・アルミナ複合酸化物コロイ
ド溶液とした後、限外濾過膜で濃縮して固形分濃度２
２．２重量％のコロイド溶液を調製した。 Production Example 3 [Preparation of antibacterial inorganic oxide colloidal solution] A mixture of 20 g of a colloidal solution having a SiO 2 concentration of 20% by weight and 380 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor is 10.7
In the mother liquor, 1500 g of a 1.5 wt% sodium silicate aqueous solution as SiO 2 and 0.5 wt% as Al 2 O 3 are added.
1500 g of sodium aluminate aqueous solution of 1 is added at the same time to obtain a silica / alumina composite oxide colloidal solution of pH 12.3, which is then concentrated with an ultrafiltration membrane to obtain a solid content concentration of 2
A 2.2 wt% colloidal solution was prepared.
【００３８】一方、酸化銀０．５２ｇを約８０ｇの水に
懸濁し、次いで１５重量％のアンモニア水を酸化銀が溶
解するまで加え、銀の酸化物としての濃度が０．５重量
％となる様に水を加えて調整した。この銀アンミン錯塩
水溶液を前記コロイド溶液に添加して十分に撹拌し、銀
成分とシリカ・アルミナ複合酸化物コロイド粒子とから
なるコロイド溶液を調製した。このコロイド溶液を濃度
調整して、固形分濃度１．０重量％のシリカ・アルミナ
コロイド溶液を得た。On the other hand, 0.52 g of silver oxide was suspended in about 80 g of water, and then 15% by weight of aqueous ammonia was added until the silver oxide was dissolved to give a silver oxide concentration of 0.5% by weight. Similarly, water was added to adjust. This silver ammine complex salt aqueous solution was added to the above colloidal solution and sufficiently stirred to prepare a colloidal solution consisting of silver components and silica-alumina composite oxide colloidal particles. The concentration of this colloidal solution was adjusted to obtain a silica / alumina colloidal solution having a solid content concentration of 1.0% by weight.
【００３９】このコロイド溶液のコロイド粒子の平均粒
径は１０．７ｎｍであり、抗菌性金属成分の結合力指数
（Ｉ）の値は、４．８×１０-4で、波長５００ｎｍの光
透過率は７４．２％であった。このコロイド溶液を限外
濾過膜を用いて１２．０重量％の濃度に濃縮した。The colloidal particles of this colloidal solution had an average particle size of 10.7 nm, the binding index (I) of the antibacterial metal component was 4.8 × 10 -4 , and the light transmittance at a wavelength of 500 nm. Was 74.2%. This colloidal solution was concentrated to a concentration of 12.0% by weight using an ultrafiltration membrane.
【００４０】製造例４ 〔ゼオライト系抗菌剤の調製〕Ｎａ−Ｙ型ゼオライトを
水に懸濁して、濃度５重量％の懸濁スラリー４００ｇを
調製した。ついで、この懸濁スラリーを７０℃に加温
し、濃度５重量％のＡｇＮ０3 水溶液９．２ｇを添加
し、９０℃に加温して１時間放置することにより銀のイ
オン交換を行った。このスラリーを濾過し、６０℃の温
水で十分に洗浄後、１２０℃で乾燥し、更に５５０℃で
１時間焼成して粉末状の抗菌剤を調製した。この粉末粒
子の平均粒子径は１．０μｍであった。 Production Example 4 [Preparation of zeolite antibacterial agent] Na-Y type zeolite was suspended in water to prepare 400 g of a suspension slurry having a concentration of 5% by weight. Next, this suspension slurry was heated to 70 ° C., 9.2 g of a 5 wt% AgNO 3 aqueous solution was added, and the mixture was heated to 90 ° C. and left for 1 hour for ion exchange of silver. This slurry was filtered, thoroughly washed with warm water of 60 ° C., dried at 120 ° C., and further calcined at 550 ° C. for 1 hour to prepare a powdered antibacterial agent. The average particle size of the powder particles was 1.0 μm.
【００４１】実施例１ 製造例１で得た酸化物換算で１．０重量％の銀を含む１
２．０重量％無機酸化物コロイド溶液１００ｇを、塗膜
形成剤濃度４０重量％のアクリル樹脂系水溶性塗料（日
本純薬（株）製、ジュリマーＦＣ６５）２９５ｇに添加
し、高速ミキサーで混合した。この塗料を１０ｃｍ×１
０ｃｍ×３ｍｍのガラス板に３μｍのバーコーターによ
り塗布した後、９０℃で２分間乾燥した。 Example 1 1 containing 1.0% by weight of silver calculated as oxide obtained in Production Example 1
100 g of a 2.0 wt% inorganic oxide colloidal solution was added to 295 g of an acrylic resin-based water-soluble paint (Jurimer FC65 manufactured by Nippon Pure Chemical Co., Ltd.) having a film forming agent concentration of 40 wt% and mixed with a high-speed mixer. . This paint 10cm × 1
It was applied on a 0 cm × 3 mm glass plate with a 3 μm bar coater and then dried at 90 ° C. for 2 minutes.
【００４２】実施例２ 製造例１で得た酸化物換算で１．０重量％の銀を含む１
２．０重量％無機酸化物コロイド溶液１００ｇを、塗膜
形成剤濃度５０重量％の不飽和ポリエステル樹脂系水溶
性塗料（日本合成化学（株）製、ポリエスターＷＲ−９
３０）２１６ｇに添加し、高速ミキサーで混合した。こ
の塗料を１０ｃｍ×１０ｃｍ×３ｍｍのガラス板に３μ
ｍのバーコーターにより塗布した後、９０℃で２分間乾
燥した。 Example 2 1 containing 1.0% by weight of silver calculated as oxide obtained in Production Example 1
An unsaturated polyester resin-based water-soluble paint having a film-forming agent concentration of 50% by weight (Polyester WR-9 manufactured by Nippon Synthetic Chemical Industry Co., Ltd.)
30) 216 g and mixed with a high speed mixer. 3μ of this paint on a glass plate of 10cm × 10cm × 3mm
After coating with a m bar coater, it was dried at 90 ° C. for 2 minutes.
【００４３】実施例３ 製造例２で得た酸化物換算で１．０重量％の銀を含む１
１．５重量％オルガノコロイド溶液１００ｇを、塗膜形
成剤濃度５０重量％のメラミン樹脂系塗料（三井東圧
（株）製、ユーラミンＴ−３４）２０７ｇに添加し、高
速ミキサーで混合した。この塗料を１０ｃｍ×１０ｃｍ
×３ｍｍのガラス板に３μｍのバーコーターにより塗布
した後、９０℃で２分間乾燥した。 Example 3 1 containing 1.0% by weight of silver in terms of oxide obtained in Production Example 1
100 g of a 1.5% by weight organocolloid solution was added to 207 g of a melamine resin-based paint (Euramine T-34 manufactured by Mitsui Toatsu Co., Ltd.) having a film forming agent concentration of 50% by weight and mixed with a high-speed mixer. This paint is 10 cm x 10 cm
After coating with a 3 μm bar coater on a × 3 mm glass plate, it was dried at 90 ° C. for 2 minutes.
【００４４】実施例４ 製造例３で得た酸化物換算で１．５重量％の銀を含む１
２．０重量％無機酸化物コロイド溶液６７ｇを、塗膜形
成剤濃度４０重量％のアクリル樹脂系水溶性塗料（日本
純薬（株）製、ジュリマーＦＣ６５）２９５ｇに添加
し、高速ミキサーで混合した。この塗料を１０ｃｍ×１
０ｃｍ×３ｍｍのガラス板に３μｍのバーコーターによ
り塗布した後、９０℃で２分間乾燥した。 Example 4 1 containing 1.5% by weight of silver in terms of oxide obtained in Production Example 1
67 g of a 2.0 wt% inorganic oxide colloidal solution was added to 295 g of an acrylic resin-based water-soluble paint (Jurimer FC65 manufactured by Nippon Pure Chemical Industries, Ltd.) having a coating film forming agent concentration of 40 wt% and mixed with a high-speed mixer. . This paint 10cm × 1
It was applied on a 0 cm × 3 mm glass plate with a 3 μm bar coater and then dried at 90 ° C. for 2 minutes.
【００４５】比較例１ 製造例４で得た酸化物換算で１．５重量％の銀を含むゼ
オライト系抗菌剤８．０ｇを９２ｇの水に懸濁させたも
のを、塗膜形成剤濃度４０重量％のアクリル樹脂系水溶
性塗料（日本純薬（株）製、ジュリマーＦＣ６５）２９
５ｇに添加し、高速ミキサーで混合した。この塗料を１
０ｃｍ×１０ｃｍ×３ｍｍのガラス板に３μｍのバーコ
ーターにより塗布した後、９０℃で２分間乾燥した。 Comparative Example 1 A suspension of 8.0 g of a zeolite-based antibacterial agent containing 1.5% by weight of oxide, obtained in Production Example 4, in 92 g of water was used as a film-forming agent concentration of 40. % By weight of acrylic resin water-soluble paint (Nippon Pure Chemical Co., Ltd., Julimer FC65) 29
Added to 5 g and mixed with high speed mixer. This paint 1
It was applied on a 0 cm × 10 cm × 3 mm glass plate with a 3 μm bar coater, and then dried at 90 ° C. for 2 minutes.
【００４６】実施例５ 〔抗菌力試験〕実施例１〜４および比較例１で得た塗膜
付きガラス板について抗菌力試験を行った。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３０
μｌを３ｃｍ×３ｃｍに切断した上記各試料面に滴下
し、２８℃で２４時間放置後、生菌数を測定して式１に
より死滅率を求めた。結果を表１に示す。 Example 5 [Antibacterial activity test] The antibacterial activity test was carried out on the coated glass sheets obtained in Examples 1 to 4 and Comparative Example 1. E. coli and Staphylococcus aureus were suspended in physiological saline,
μl was dropped on each sample surface cut into 3 cm × 3 cm, left standing at 28 ° C. for 24 hours, the number of viable cells was measured, and the mortality was calculated by the formula 1. The results are shown in Table 1.
【００４７】[0047]
【式１】死滅率（％）＝１００×（初期生菌数−２４時
間後の生菌数）／初期生菌数[Formula 1] Death rate (%) = 100 × (initial viable cell count-24 viable cells after 24 hours) / initial viable cell count
【００４８】[0048]
【表１】 [Table 1]
【００４９】実施例６ 〔耐候性試験〕実施例１〜４および比較例１で得た塗膜
付きガラス板について、抗菌効果の持続性および変色を
観るために、耐候性試験と同試験後の抗菌力試験を行っ
た。耐候性試験は、各試料を耐候性試験装置、ウェザー
メータ（スガ試験機器（株）製）を用いて、温度６０℃
にて、１５分間は水を散布し、４５分間は水の散布を停
止した状態で晒し、この操作を１時間周期で１００時間
繰り返した。この耐候性試験後の試料の変色の有無を目
視により観察し、また、抗菌力試験を実施例５と同様に
して行った。結果を表２に示す。 Example 6 [Weather resistance test] With respect to the glass plates with a coating film obtained in Examples 1 to 4 and Comparative Example 1, in order to observe the persistence and discoloration of the antibacterial effect, a weather resistance test and a test after the same were conducted. An antibacterial test was conducted. For the weather resistance test, each sample was subjected to a weather resistance tester and a weather meter (manufactured by Suga Test Instruments Co., Ltd.) at a temperature of 60 ° C.
At 15 minutes, water was sprinkled for 15 minutes and exposed for 45 minutes while water sprinkling was stopped, and this operation was repeated for 100 hours in a 1-hour cycle. After the weather resistance test, the sample was visually observed for discoloration, and an antibacterial activity test was conducted in the same manner as in Example 5. The results are shown in Table 2.
【００５０】[0050]
【表２】 [Table 2]
【００５１】[0051]
【発明の効果】本発明の抗菌性塗料組成物によれば、長
期間にわたって抗菌性、防黴性、防臭性、防藻性に優
れ、且つ、変色することがない塗膜を得ることが可能と
なる。また、前記微粒子の粒子径が小さいので、形成さ
れる塗膜は透明性に優れ、しかも、基材との密着性が良
好であることから、前記したような各種の用途に有用で
ある。EFFECT OF THE INVENTION According to the antibacterial coating composition of the present invention, it is possible to obtain a coating film which is excellent in antibacterial property, antifungal property, deodorant property and antialgal property for a long period of time and which does not discolor. Becomes Further, since the fine particles have a small particle diameter, the coating film formed is excellent in transparency and has good adhesiveness to the substrate, which is useful for various applications as described above.
Claims (3)
の無機酸化物とから構成される平均粒子径が５００ｎｍ
以下の微粒子を含有することを特徴とする抗菌性塗料組
成物。1. An average particle diameter of 500 nm composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component.
An antibacterial coating composition containing the following fine particles.
の無機酸化物とから構成される平均粒子径が５００ｎｍ
以下の微粒子が分散してなる抗菌性無機酸化物コロイド
溶液と、塗膜形成剤と、溶剤とからなる抗菌性塗料組成
物。2. An average particle diameter composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component is 500 nm.
An antibacterial coating composition comprising an antibacterial inorganic oxide colloidal solution in which the following fine particles are dispersed, a film forming agent, and a solvent.
料組成物から形成された塗膜。3. A coating film formed from the antibacterial coating composition according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32083493A JP3183766B2 (en) | 1993-11-29 | 1993-11-29 | Antimicrobial coating composition and coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32083493A JP3183766B2 (en) | 1993-11-29 | 1993-11-29 | Antimicrobial coating composition and coating film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07150075A true JPH07150075A (en) | 1995-06-13 |
| JP3183766B2 JP3183766B2 (en) | 2001-07-09 |
Family
ID=18125762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32083493A Expired - Lifetime JP3183766B2 (en) | 1993-11-29 | 1993-11-29 | Antimicrobial coating composition and coating film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3183766B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
| JPH10259325A (en) * | 1997-03-19 | 1998-09-29 | Sk Kaken Co Ltd | Water-based coating composition |
| JPH1180617A (en) * | 1997-09-05 | 1999-03-26 | Catalysts & Chem Ind Co Ltd | Antimicrobial treatment method |
| JPH11323213A (en) * | 1998-05-13 | 1999-11-26 | Catalysts & Chem Ind Co Ltd | Seaweedproofing/seashellproofing composition and machine component for submarine use coated therewith |
| JP2001040287A (en) * | 1999-07-28 | 2001-02-13 | Catalysts & Chem Ind Co Ltd | Antimicrobial coating film and substrate with the same |
| DE10146050A1 (en) * | 2001-09-18 | 2003-04-10 | Bio Gate Bioinnovative Materia | Antimicrobial adhesive and coating material and method for producing the same |
| JP2013075974A (en) * | 2011-09-30 | 2013-04-25 | Sumitomo Osaka Cement Co Ltd | Coating liquid for forming antifouling thin film, antifouling product, method of producing the coating liquid, and method of producing the antifouling product |
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| CN114316307A (en) * | 2021-12-31 | 2022-04-12 | 广东粤港澳大湾区国家纳米科技创新研究院 | Modified hydrogel and preparation method and application thereof |
| CN115286948A (en) * | 2022-08-29 | 2022-11-04 | 广东安捷伦新材料科技有限公司 | Preparation method of interior antibacterial coating |
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| KR102113445B1 (en) * | 2020-03-30 | 2020-05-20 | 박채형 | Sink with excellent antibacterial retention properties using silver nano sol |
-
1993
- 1993-11-29 JP JP32083493A patent/JP3183766B2/en not_active Expired - Lifetime
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237362A (en) * | 1997-02-26 | 1998-09-08 | Catalysts & Chem Ind Co Ltd | Electrodeposition coating material and electrodeposition coating |
| JPH10259325A (en) * | 1997-03-19 | 1998-09-29 | Sk Kaken Co Ltd | Water-based coating composition |
| JPH1180617A (en) * | 1997-09-05 | 1999-03-26 | Catalysts & Chem Ind Co Ltd | Antimicrobial treatment method |
| JPH11323213A (en) * | 1998-05-13 | 1999-11-26 | Catalysts & Chem Ind Co Ltd | Seaweedproofing/seashellproofing composition and machine component for submarine use coated therewith |
| JP2001040287A (en) * | 1999-07-28 | 2001-02-13 | Catalysts & Chem Ind Co Ltd | Antimicrobial coating film and substrate with the same |
| DE10146050B4 (en) * | 2001-09-18 | 2007-11-29 | Bio-Gate Ag | Process for the preparation of an antimicrobial adhesive and coating material |
| DE10146050A1 (en) * | 2001-09-18 | 2003-04-10 | Bio Gate Bioinnovative Materia | Antimicrobial adhesive and coating material and method for producing the same |
| JP2013075974A (en) * | 2011-09-30 | 2013-04-25 | Sumitomo Osaka Cement Co Ltd | Coating liquid for forming antifouling thin film, antifouling product, method of producing the coating liquid, and method of producing the antifouling product |
| JP2015080887A (en) * | 2013-10-22 | 2015-04-27 | 株式会社トッパン・コスモ | Interior decorative sheet having antiviral properties |
| CN114316307A (en) * | 2021-12-31 | 2022-04-12 | 广东粤港澳大湾区国家纳米科技创新研究院 | Modified hydrogel and preparation method and application thereof |
| CN114316307B (en) * | 2021-12-31 | 2023-10-27 | 广东粤港澳大湾区国家纳米科技创新研究院 | Modified hydrogel and preparation method and application thereof |
| CN115286948A (en) * | 2022-08-29 | 2022-11-04 | 广东安捷伦新材料科技有限公司 | Preparation method of interior antibacterial coating |
| CN115286948B (en) * | 2022-08-29 | 2023-09-22 | 广东安捷伦新材料科技有限公司 | Preparation method of interior antibacterial coating |
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|---|---|
| JP3183766B2 (en) | 2001-07-09 |
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