JP2000202939A - Antibacterial laminate - Google Patents

Antibacterial laminate

Info

Publication number
JP2000202939A
JP2000202939A JP11007904A JP790499A JP2000202939A JP 2000202939 A JP2000202939 A JP 2000202939A JP 11007904 A JP11007904 A JP 11007904A JP 790499 A JP790499 A JP 790499A JP 2000202939 A JP2000202939 A JP 2000202939A
Authority
JP
Japan
Prior art keywords
antibacterial
layer
laminate
photocatalyst
base material
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.)
Granted
Application number
JP11007904A
Other languages
Japanese (ja)
Other versions
JP3465018B2 (en
Inventor
Toshihide Suzuki
利英 鈴木
Tomoyuki Tawara
知之 田原
Fusao Togashi
房夫 冨樫
Hiroshi Nagaishi
博 永石
Hideo Takamura
日出夫 高村
Koji Watanabe
浩司 渡辺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JFE Steel Corp
Kawasaki Steel Metal Products and Engineering Inc
Original Assignee
Kawasaki Steel Metal Products and Engineering Inc
Kawasaki Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kawasaki Steel Metal Products and Engineering Inc, Kawasaki Steel Corp filed Critical Kawasaki Steel Metal Products and Engineering Inc
Priority to JP00790499A priority Critical patent/JP3465018B2/en
Publication of JP2000202939A publication Critical patent/JP2000202939A/en
Application granted granted Critical
Publication of JP3465018B2 publication Critical patent/JP3465018B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Abstract

PROBLEM TO BE SOLVED: To develop sterilizing properties, antibacterial properties, antifungal properties and deodorizing properties over a long period of time. SOLUTION: A laminate 1 has a base material at least one surface of which has antibacterial properties and a photocatalyst layer 4 formed on at least one antibacterial surface and containing a substance developing photocatalytic function. In this case, the base material may be a laminate consisting of a substrate 2 and the antibacterial layer 3 formed on at least one surface of the substrate 2 and containing an antibacterial agent or a single-layered material containing an antibacterial agent. It is preferable that the substance having photocatalytic function is exposed to the outermost surface of the laminate.

Description

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

【０００１】[0001]

【発明の属する技術分野】本発明は、長期にわたって殺
菌性、抗菌性、防カビ性（以下、これらを抗菌性と総称
する）を発現する抗菌性積層体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial laminate which exhibits bactericidal, antibacterial and antifungal properties (hereinafter referred to collectively as "antibacterial") for a long period of time.

【０００２】[0002]

【従来の技術】従来より、殺菌、抗菌、防カビ作用（以
下、これらを抗菌作用と総称する）を示す抗菌剤とし
て、金属状態またはイオン状態の銀、銅、亜鉛などが知
られている。これら抗菌剤を成形体あるいは構造体（以
下単に構造体という）の表面に含有させる方法として、
たとえば陶磁器または琺瑯の表面にリン酸銀粉末を積層
し、焼成する陶磁器・琺瑯の抗菌防カビ処理方法が提案
されている（特開平６−２３４５８４号）。2. Description of the Related Art Conventionally, silver, copper, zinc, and the like in a metal state or an ionic state have been known as antibacterial agents having a bactericidal, antibacterial, and antifungal action (hereinafter, these are collectively referred to as an antibacterial action). As a method of including these antimicrobial agents on the surface of a molded article or a structure (hereinafter simply referred to as a structure),
For example, a method of antibacterial and antifungal treatment of ceramics and enamel has been proposed in which silver phosphate powder is laminated on the surface of ceramics or enamel and fired (Japanese Patent Application Laid-Open No. 6-234584).

【０００３】また酸化チタンなどの光触媒による抗菌作
用を利用する方法も知られている。たとえば特開平６−
２０９９８５号には、建造物の壁材表面に光触媒を担持
させ、壁材にあたる光により室内を抗菌処理する方法が
提案されている。[0003] A method utilizing the antibacterial action of a photocatalyst such as titanium oxide is also known. For example,
No. 209985 proposes a method in which a photocatalyst is carried on the surface of a wall material of a building, and the interior of the room is subjected to antibacterial treatment by light impinging on the wall material.

【０００４】上記のような金属、金属イオンなどの抗菌
剤は、暗所でも抗菌作用を発揮するという利点がある
が、表面が汚れたり、菌の死骸が堆積したりすると効果
が低減する欠点がある。また抗菌剤（金属イオン）は、
脱離、剥離などにより経時的に減少して活性低下するた
め、無機金属イオンを構造体表面に継続して供給するシ
ステムが要求される。一方、光触媒は、汚染物や死骸を
も光分解しうるので清浄な表面を保ち抗菌作用を持続し
うるが、充分な光量がなければその作用を発現しない。
このため両者を複合して互いの欠点を補う方法も種々提
案されている。The above-mentioned antibacterial agents such as metals and metal ions have the advantage of exhibiting an antibacterial action even in a dark place, but have the drawback that the effect is reduced when the surface is soiled or dead bacteria accumulate. is there. Antibacterial agents (metal ions)
Since the activity decreases with the lapse of time due to desorption, separation, etc., the system continuously supplies inorganic metal ions to the surface of the structure. On the other hand, the photocatalyst can photoly decompose contaminants and dead bodies, so that it can maintain a clean surface and maintain the antibacterial action, but does not exhibit the action unless there is a sufficient amount of light.
For this reason, various methods have been proposed for combining the two to compensate for the disadvantages of each other.

【０００５】抗菌剤と光触媒とを複合して用いた構造体
たとえば琺瑯体としては、琺瑯層中に、抗菌剤と光触媒
とを含ませたもの（図３）、予め抗菌剤を含ませた光触
媒コーティング剤を琺瑯表面に塗布することにより、琺
瑯層表面に光触媒を濃縮させたもの（図４）、あるいは
琺瑯層表面に光触媒層を設け、光触媒層の表面に抗菌剤
を担持または固定したもの（図５）などが知られてい
る。しかしながら上記いずれの技術も、抗菌作用が不充
分であったり、あるいは作用の持続性が不充分であるな
どして、抗菌作用とその持続性の両方の要求を満たすと
はいえない。As a structure using an antibacterial agent and a photocatalyst in combination, for example, an enamel body, an enamel layer containing an antibacterial agent and a photocatalyst (FIG. 3) and a photocatalyst containing an antibacterial agent in advance The photocatalyst is concentrated on the surface of the enamel layer by applying a coating agent on the surface of the enamel (FIG. 4), or the photocatalyst layer is provided on the surface of the enamel layer, and the antibacterial agent is carried or fixed on the surface of the photocatalyst layer ( FIG. 5) is known. However, none of the above techniques can satisfy the requirements for both the antibacterial action and its sustainability due to insufficient antibacterial action or insufficient sustained action.

【０００６】[0006]

【発明が解決しようとする課題】本発明者は、上記のよ
うな従来の抗菌性構造体の問題点を解決すべく、抗菌剤
としての銀イオン（銀塩）と光触媒としての酸化チタン
粒子を含む抗菌琺瑯鋼板を具体例として、特にその構造
について検討した。たとえば前記図３に示す構造体で
は、酸化チタン粒子（光触媒）は琺瑯層中に埋もれて充
分に働けないことがわかった。また図４あるいは図５に
示す構造体では、長期間使用すると、抗菌剤（銀イオ
ン）が減少して抗菌作用が低下することがわかった。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems of the conventional antibacterial structure, the present inventors have developed silver ions (silver salt) as an antibacterial agent and titanium oxide particles as a photocatalyst. In particular, the structure of the antibacterial enameled steel sheet was examined as a specific example. For example, in the structure shown in FIG. 3, it was found that the titanium oxide particles (photocatalyst) were buried in the enamel layer and could not work sufficiently. In addition, it was found that the antibacterial agent (silver ion) was reduced and the antibacterial action was reduced when the structure shown in FIG. 4 or 5 was used for a long period of time.

【０００７】[0007]

【課題を解決するための手段】本発明者はさらに検討し
たところ、琺瑯層中に抗菌剤および光触媒を含ませた場
合には、抗菌剤は長期にわたって少しずつ表面に滲出し
て抗菌作用を持続するのに対し、光触媒は、表面に露出
しているもの以外は全く抗菌作用を示さないことがわか
った。さらに抗菌剤は、図４または図５に示すように、
表面に濃縮しておくとすぐに脱離して、抗菌作用がなく
なるのに対し、琺瑯層中に分散させておくと脱離せずに
長期に抗菌作用を持続し、一方、光触媒は表面に高度に
濃縮しておいた方が抗菌作用が高く、表面に濃縮しても
固定化すれば長期にわたって脱離せず、抗菌作用を持続
することもわかった。Means for Solving the Problems The present inventors have further studied and found that when an antibacterial agent and a photocatalyst are contained in the enamel layer, the antibacterial agent gradually exudes to the surface over a long period of time to maintain the antibacterial action. On the other hand, it was found that the photocatalyst did not show any antibacterial action except for those exposed on the surface. Further, as shown in FIG. 4 or FIG.
When concentrated on the surface, it desorbs immediately and loses its antibacterial effect, whereas when dispersed in the enamel layer, it does not desorb and maintains the antibacterial effect for a long time, while the photocatalyst has a high degree of It was also found that the concentrated antibacterial agent had a higher antibacterial effect, and even if it was concentrated on the surface, if it was immobilized, it was not desorbed for a long time, and the antibacterial effect was maintained.

【０００８】したがって抗菌剤は琺瑯層に分散し、かつ
光触媒は表面に濃縮固定化させる構造体とすれば、両者
の複合効果を最も効率的に発現し得る。本発明はこのよ
うな知見に基づいてなされたものであって、このような
概念（構造）は、本発明者によって創作されたものであ
る。またこのような構造による効果は、琺瑯鋼板のみな
らず塗装鋼板さらには抗菌剤を含むステンレス鋼板など
にも応用可能であることも分かった。Accordingly, if the antibacterial agent is dispersed in the enamel layer, and the photocatalyst is concentrated and fixed on the surface, the combined effect of the two can be exhibited most efficiently. The present invention has been made based on such knowledge, and such a concept (structure) has been created by the present inventors. It was also found that the effect of such a structure can be applied to not only an enameled steel plate but also a coated steel plate and a stainless steel plate containing an antibacterial agent.

【０００９】すなわち本発明に係る抗菌性積層体は、少
なくともひとつの表面が抗菌性を有する基材と、該抗菌
性表面の少なくともひとつの表面上に形成された光触媒
機能を発現する物質を含有する光触媒層とを有すること
を特徴としている。このような抗菌性積層体は、長期に
わたって抗菌性を発現する。上記基材は、下地基材と、
該下地基材の少なくともひとつの表面に形成された抗菌
性金属および／または抗菌性金属イオンを含有する抗菌
層とからなる積層体であっても、抗菌性金属および／ま
たは抗菌性金属イオンを含む単層体であってもよい。本
発明では、光触媒機能を有する物質が積層体最外表面に
露出していることが好ましい。That is, the antibacterial laminate according to the present invention comprises a substrate having at least one surface having antibacterial properties and a substance exhibiting a photocatalytic function formed on at least one of the antibacterial surfaces. And a photocatalyst layer. Such an antibacterial laminate exhibits antibacterial properties over a long period of time. The base material is a base material,
Even a laminate comprising an antimicrobial metal and / or an antimicrobial layer containing an antimicrobial metal ion formed on at least one surface of the base material, contains the antimicrobial metal and / or antimicrobial metal ion. It may be a single-layer body. In the present invention, the substance having a photocatalytic function is preferably exposed on the outermost surface of the laminate.

【００１０】前記抗菌性金属は、銀、銅および亜鉛から
選ばれる少なくとも一種であり、前記抗菌性金属イオン
は、銀イオン、銅イオン、亜鉛イオンから選ばれる少な
くとも一種であることが好ましい。またアンモニウム塩
系、環状窒素イオウ化合物系などの有機系抗菌剤の使用
も可能である。前記光触媒機能を有する物質は酸化チタ
ンであることが好ましい。抗菌層は、通常バインダーを
含み、たとえば琺瑯、ガラスまたは樹脂を含んでいる。The antibacterial metal is at least one selected from silver, copper and zinc, and the antibacterial metal ion is preferably at least one selected from silver, copper and zinc ions. Organic antibacterial agents such as ammonium salts and cyclic nitrogen sulfur compounds can also be used. The substance having a photocatalytic function is preferably titanium oxide. The antimicrobial layer usually contains a binder, for example, enamel, glass or resin.

【００１１】[0011]

【発明の実施の形態】以下、本発明に係る抗菌性積層体
を具体的に説明する。本発明に係る抗菌性積層体は、少
なくともひとつの表面が抗菌性を有する基材と、該抗菌
性表面の少なくともひとつの表面上に形成された光触媒
機能を発現する物質を含有する光触媒層とを有する。上
記表面が抗菌性である基材は、下地基材の少なくともひ
とつの表面に抗菌性を有する層が形成された多層構造で
あってもよく、あるいは基材自体が抗菌性を有する単層
構造であってもよい。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, an antibacterial laminate according to the present invention will be specifically described. The antibacterial laminate according to the present invention comprises a substrate having at least one surface having antibacterial properties, and a photocatalyst layer formed on at least one surface of the antibacterial surfaces and containing a substance exhibiting a photocatalytic function. Have. The substrate whose surface is antibacterial may have a multilayer structure in which a layer having antibacterial properties is formed on at least one surface of the base substrate, or a single-layer structure in which the substrate itself has antibacterial properties. There may be.

【００１２】図１に、基材が多層構造であるときの態様
例として、抗菌性積層体の部分断面図を示す。抗菌性積
層体１は、下地基材２と、該下地基材２の少なくともひ
とつの表面に形成された抗菌層３と、該抗菌層３の表面
に形成された光触媒層４とを有している。FIG. 1 shows a partial cross-sectional view of an antibacterial laminate as an example of an embodiment when the substrate has a multilayer structure. The antibacterial laminate 1 includes a base material 2, an antibacterial layer 3 formed on at least one surface of the base material 2, and a photocatalytic layer 4 formed on the surface of the antibacterial layer 3. I have.

【００１３】下地基材２の材質は、抗菌性積層体の用
途、製造条件に応じて適宜選択されればよく、金属、各
種樹脂、セラミックス、陶磁器、ガラス、さらにはこれ
らの複合体（たとえば鋼、ステンレス、アルミニウムな
どの金属の表面を、各種樹脂、セラミック、ガラスなど
で被覆したもの）などであればよい。下地基材２は特に
限定されないが、抗菌性積層体の製造時には、通常、光
触媒層４の焼成工程が加えられるので、焼成温度に耐え
うる材質であることが望ましい。The material of the base substrate 2 may be appropriately selected depending on the use of the antibacterial laminate and the manufacturing conditions. Metals, various resins, ceramics, ceramics, glass, and composites thereof (for example, steel) , A metal such as stainless steel, aluminum, or the like coated with various resins, ceramics, glass, or the like). Although the base substrate 2 is not particularly limited, a baking step of the photocatalyst layer 4 is usually added at the time of manufacturing the antibacterial laminate, so that a material that can withstand the baking temperature is desirable.

【００１４】より具体的な例として、抗菌性積層体が琺
瑯板である場合には、下地基材２は、たとえば鉄板、鋼
板、アルミニウム板などの金属板、およびこれら金属板
に、亜鉛メッキ、アルミニウムメッキ、アルミニウム亜
鉛合金メッキ、鉄亜鉛合金メッキなどのメッキ処理、化
成処理、クロメート処理などの表面処理を施したものが
用いられる。このうちでもメッキなどの表面処理を施
し、耐食性、耐候性等を備えた金属板であることが好ま
しい。また抗菌性積層体がタイルである場合には、下地
基材としては陶磁器が用いられる。下地基材２は、主と
して板状体について説明するが、以下のような抗菌層３
および光触媒層４を形成できるものであればその形状は
問わない。As a more specific example, when the antibacterial laminate is an enamel plate, the base material 2 is made of a metal plate such as an iron plate, a steel plate, an aluminum plate, or the like. Plated materials such as aluminum plating, aluminum zinc alloy plating, iron zinc alloy plating, and the like, and surface treatments such as a chemical conversion treatment and a chromate treatment are used. Among them, it is preferable to use a metal plate which has been subjected to surface treatment such as plating and has corrosion resistance, weather resistance and the like. When the antibacterial laminate is a tile, ceramic is used as a base material. The base material 2 will be described mainly with respect to a plate-like body.
Any shape can be used as long as the photocatalyst layer 4 can be formed.

【００１５】抗菌層３は、下地基材２の少なくともひと
つの表面に形成されており、抗菌性金属および／または
抗菌性金属イオンを含有している。ここで抗菌性とは、
殺菌性、抗菌性、防カビ性などをすべて含む意味で用い
られる。すなわち、細菌やカビなどの増殖を防止した
り、細菌、カビなどを殺すことを意味する。抗菌性金属
または抗菌性金属イオンの抗菌作用のメカニズムは定か
ではないが、抗菌層３に含まれる抗菌性金属および／ま
たは抗菌性金属イオンとしては、抗菌性作用を示す金属
または金属イオンとして公知のものが特に限定すること
なく挙げられる。抗菌性金属または抗菌性金属イオンと
しては、通常、金属状態またはイオン状態の銀、銅、亜
鉛、チタン、タングステンなどが挙げられる。抗菌層３
は、２種以上の金属種を含んでいてもよく、金属および
イオン状態の金属をいずれも含んでいてもよい。これら
のうちでも、銀、銅、亜鉛、銀イオン、銅イオン、亜鉛
イオンが好ましい。The antibacterial layer 3 is formed on at least one surface of the base substrate 2 and contains an antibacterial metal and / or an antibacterial metal ion. Here, antibacterial
It is used to include all of the bactericidal, antibacterial, and antifungal properties. In other words, it means preventing the growth of bacteria and mold, and killing bacteria and mold. The mechanism of the antibacterial action of the antibacterial metal or the antibacterial metal ion is unknown, but the antibacterial metal and / or antibacterial metal ion contained in the antibacterial layer 3 is known as a metal or metal ion exhibiting an antibacterial action. Those are mentioned without particular limitation. Examples of the antibacterial metal or the antibacterial metal ion include silver, copper, zinc, titanium, and tungsten in a metal state or an ionic state. Antibacterial layer 3
May contain two or more metal species, and may contain both metal and ionic metal. Among these, silver, copper, zinc, silver ions, copper ions, and zinc ions are preferred.

【００１６】イオン状態の金属は抗菌層３に含ませるに
は、抗菌層３を形成する際に抗菌性金属イオンを含む物
質を用いればよい。この物質としては、たとえば硝酸イ
オン、硫酸イオン、ハロゲンイオンとくに塩素イオン、
酢酸イオン、乳酸イオン、イオウイオンなどを上記金属
イオンの対イオンとする塩、および上記金属イオンを担
持したゼオライト、アパタイト、シリカ、ガラス、チタ
ニア、リン酸ジルコニウム、リン酸アルミニウムなどが
挙げられる。以下、抗菌性金属および抗菌性金属イオン
を含む物質を抗菌剤と称することもある。また、塩化ベ
ンザルニコムなどのアンモニウム塩、脂肪酸エステル、
環状窒素イオウ化合物などの有機系抗菌剤を用いてもよ
い。これら有機系抗菌剤は、後述するバインダーとし
て、樹脂を用いた場合に好適である。In order for the metal in the ionic state to be contained in the antibacterial layer 3, a substance containing an antibacterial metal ion may be used when the antibacterial layer 3 is formed. This substance includes, for example, nitrate ions, sulfate ions, halogen ions, particularly chloride ions,
Examples thereof include salts having acetate ions, lactate ions, sulfur ions and the like as counter ions of the above-mentioned metal ions, and zeolites, apatite, silica, glass, titania, zirconium phosphate, aluminum phosphate, etc. carrying the above-mentioned metal ions. Hereinafter, a substance containing an antibacterial metal and an antibacterial metal ion may be referred to as an antibacterial agent. Also, ammonium salts such as benzalnicum chloride, fatty acid esters,
An organic antibacterial agent such as a cyclic nitrogen sulfur compound may be used. These organic antibacterial agents are suitable when a resin is used as a binder described later.

【００１７】抗菌層３は、通常、上記のような抗菌剤と
バインダーとから形成される。バインダーとしては、抗
菌剤を下地基材２に保持しうるものであればよく、光触
媒層４の焼成温度に耐えうるものであれば有機質であっ
ても無機質であってもよく、また熱可塑性であっても、
熱硬化性であってもよい。このようなバインダーとして
は、琺瑯釉薬、ガラス釉薬、シリコーン樹脂、アクリル
樹脂、エポキシ樹脂、フッ素樹脂、金属アルコキシ樹
脂、アルカリシリケート、セメント、モルタルなどが挙
げられる。また着色剤などを含んでいてもよく、たとえ
ば上記バインダーを含む塗料などを用いることもでき
る。The antibacterial layer 3 is usually formed from the above antibacterial agent and a binder. The binder may be any as long as it can hold the antibacterial agent on the base material 2, and may be organic or inorganic as long as it can withstand the sintering temperature of the photocatalyst layer 4. Even so,
It may be thermosetting. Examples of such a binder include an enamel glaze, a glass glaze, a silicone resin, an acrylic resin, an epoxy resin, a fluororesin, a metal alkoxy resin, an alkali silicate, cement, and mortar. Further, it may contain a coloring agent and the like, and for example, a paint containing the above-mentioned binder can be used.

【００１８】本発明では、バインダーとして琺瑯釉薬が
好ましく用いられる。琺瑯釉薬は、公知の釉薬を広く用
いることができるが、たとえばＴi Ｏ2 、Ｓi Ｏ2 、Ｚ
r Ｏ 2 などのＭＯ2 系化合物、Ｐ2 Ｏ5 、Ｖ2 Ｏ5 など
のＭ2 Ｏ5 系化合物、Ｓb2Ｏ 3 、Ａl2Ｏ3 、Ｂ2 Ｏ3 な
どのＭ2 Ｏ3 系化合物、Ｎa2Ｏ、Ｋ2 Ｏ、Ｌi2Ｏなどの
Ｍ2 Ｏ系化合物、Ｚn Ｏ、Ｂa Ｏ、Ｃa ＯなどのＭＯ系
化合物、ＺｒＦ4 、ＡｌＦ3 などのフッ化物系化合物な
どの鉱物原料から得られる釉薬を用いることができる。
このなかでもＭ2 Ｏ5 系釉薬、特にＰ2 Ｏ5 を釉薬中に
５０重量％以上含有する釉薬は焼成温度が低いので好ま
しい。釉薬は、鉱物原料に加えて必要に応じて他の成分
たとえば水などを含んでいてもよい。In the present invention, an enamel glaze is used as a binder.
It is preferably used. For enamel glaze, use widely known glaze
But for example TiOTwo, SiOTwo, Z
r O TwoMO such asTwoCompound, PTwoOFive, VTwoOFiveSuch
MTwoOFiveCompound, SbTwoO Three, AlTwoOThree, BTwoOThree What
Which MTwoOThreeCompound, NaTwoO, KTwoO, LiTwoSuch as O
MTwoMO compounds such as O compounds, ZnO, BaO, and CaO
Compound, ZrFFour, AlFThreeSuch as fluoride compounds
Glazes from any mineral source can be used.
Among them, MTwoOFiveGlaze, especially PTwoOFiveIn the glaze
Glazes containing 50% by weight or more are preferred because the firing temperature is low.
New Glaze, other ingredients as needed in addition to mineral raw materials
For example, it may contain water.

【００１９】抗菌剤とバインダーとの使用量は、最終的
に抗菌層３の抗菌剤含量が、０．１〜２０重量％好まし
くは０．５〜５重量％となるように用いることが望まし
い。抗菌層３を形成する際には、抗菌剤をバインダー中
によく分散することが望ましい。抗菌層３は、通常、抗
菌剤とバインダーとの混合物から、基材２の少なくとも
ひとつの表面上に膜を形成し、膜を乾燥あるいは焼成す
ることにより形成される。膜の形成は、塗布あるいは吹
きつけなどどのような方法で行ってもよい。また膜の乾
燥あるいは焼成は、バインダーの種類などによっても異
なるが、たとえばバインダーとして上記琺瑯質釉薬を用
いる場合には、通常５００〜８００℃程度で焼成され
る。本発明では、抗菌層３の厚みは、１０μｍ以上好ま
しくは１０〜１０００μｍ程度であることが望ましい。
抗菌層３は、下地基材の少なくともひとつの表面に形成
されていればよく、たとえば下地基材が板状体であると
き、片面または両面に形成されていてもよい。The amount of the antibacterial agent and the binder used is preferably such that the antibacterial agent content of the antibacterial layer 3 is finally 0.1 to 20% by weight, preferably 0.5 to 5% by weight. When forming the antibacterial layer 3, it is desirable that the antibacterial agent is well dispersed in the binder. The antibacterial layer 3 is usually formed by forming a film on at least one surface of the substrate 2 from a mixture of an antibacterial agent and a binder, and drying or firing the film. The film may be formed by any method such as coating or spraying. The drying or baking of the film varies depending on the type of the binder and the like. For example, when the above-mentioned enamel glaze is used as the binder, baking is usually performed at about 500 to 800 ° C. In the present invention, the thickness of the antibacterial layer 3 is desirably 10 μm or more, preferably about 10 to 1000 μm.
The antimicrobial layer 3 only needs to be formed on at least one surface of the base substrate. For example, when the base substrate is a plate-like body, it may be formed on one surface or both surfaces.

【００２０】光触媒層４は、光触媒機能を発現する物質
を含有する層であって、上記のような抗菌層３の表面に
形成されている。光触媒機能を発現する物質としては、
活性酸素を生成しうる程度の光活性を有する物質であれ
ばよい。具体的には光触媒として公知のものを広く用い
ることができ、たとえばＴｉＯ2 、ＺｎＯ、ＳｒＴｉＯ
3 、ＳｎＯ2 、ＧａＰ、ＣｄＳ、ＣｄＳｅ、ＭｏＳ、Ｆ
ｅ2 Ｏ3 、ＷＯ3 、Ｋ 4 ＮｂＯ17、ＫＴａＯ3 などを用
いることができる。以下これらの物質を光触媒と称す。The photocatalyst layer 4 is made of a material exhibiting a photocatalytic function.
And the surface of the antibacterial layer 3 as described above
Is formed. Substances that exhibit a photocatalytic function include:
Any substance that is photoactive enough to generate active oxygen
I just need. Specifically, widely known photocatalysts are widely used.
For example, TiOTwo, ZnO, SrTiO
Three, SnOTwo, GaP, CdS, CdSe, MoS, F
eTwoOThree, WOThree, K FourNbO17, KTaOThreeUse
Can be. Hereinafter, these substances are referred to as photocatalysts.

【００２１】たとえばＴｉＯ2 は、紫外線があたると表
面にスーパーオキサイドイオン（・Ｏ2 - ）、水酸基ラ
ジカル（・ＯＨ）などが生成する。この・Ｏ2 - 、・Ｏ
Ｈには抗菌作用および油などの有機物を分解する浄化作
用、防臭作用がある。本発明では、光触媒のうちでも、
ＴｉＯ2 （酸化チタン）が好ましく用いられる。ＴｉＯ
2 は、ルチル型よりもアナターゼ型が高い抗菌作用を示
すため好ましい。For example, when TiO 2 is irradiated with ultraviolet rays, superoxide ions (.O 2 − ) and hydroxyl radicals (.OH) are generated on the surface. This · O 2 -, · O
H has an antibacterial action, a purifying action for decomposing organic substances such as oil, and an odor preventing action. In the present invention, among the photocatalysts,
TiO 2 (titanium oxide) is preferably used. TiO
2 is preferable since the anatase type has a higher antibacterial action than the rutile type.

【００２２】光触媒は、一次粒子の径が１００ｎｍ以下
であると充分な抗菌作用を示すので好ましい。さらに好
ましくは１〜５０ｎｍである。光触媒層４は、光触媒に
加えてバインダーを含有していてもよい。バインダーと
しては、光とくに紫外線透過性のものが好ましく、たと
えばシリコーン、シリカ、フッ素樹脂などが挙げられ
る。The photocatalyst is preferable if the primary particles have a diameter of 100 nm or less, since they exhibit a sufficient antibacterial action. More preferably, it is 1 to 50 nm. The photocatalyst layer 4 may contain a binder in addition to the photocatalyst. The binder is preferably one that transmits light, particularly ultraviolet rays, and examples thereof include silicone, silica, and fluororesin.

【００２３】本発明では、光触媒は光を吸収しうる状態
で存在する必要があり、光触媒は光とくに紫外線透過性
のバインダーであればバインダー中に埋もれていてもよ
いが、積層体最外表面に露出していることが好ましい。
光触媒とバインダーを含むものとして市販品を用いるこ
ともでき、たとえば酸化チタンゾルおよび／または酸化
チタンパウダーと、バインダーとを混合した酸化チタン
ゾル液などを用いることができる。より具体的には、Ｃ
ＺＧ２２０（多木化学（株）製）などが挙げられる。In the present invention, the photocatalyst needs to be present in a state capable of absorbing light. The photocatalyst may be buried in the binder if it is a binder that transmits light, particularly ultraviolet rays. It is preferably exposed.
A commercially available product containing a photocatalyst and a binder can also be used, and for example, a titanium oxide sol and / or a titanium oxide sol solution obtained by mixing a titanium oxide powder and a binder can be used. More specifically, C
ZG220 (manufactured by Taki Kagaku Co., Ltd.) and the like.

【００２４】光触媒層４は、たとえば光触媒とバインダ
ーとの混合物を、抗菌層３の表面上に膜を形成し、膜を
乾燥あるいは焼成することにより形成される。膜の形成
は、塗布あるいは吹きつけなどどのような方法で行って
もよい。塗布温度は通常、常温〜１００℃で行うが、こ
れ以外の温度域で行うことも可能である。また膜の乾燥
あるいは焼成は、バインダーの種類などによっても異な
るが、酸化チタンの場合には、８００℃以上で焼成する
とルチル型になるので、８００℃よりも低い温度で行う
ことが好ましい。たとえば市販の酸化チタンゾル液を用
いた場合には、通常１５０〜６００℃程度で焼成され
る。また常温乾燥型の酸化チタンゾル液を用いることも
可能である。本発明では、光触媒層４の厚みは、０．０
１〜５μｍ好ましくは０．１〜１μｍ程度であることが
望ましい。The photocatalyst layer 4 is formed, for example, by forming a film of a mixture of a photocatalyst and a binder on the surface of the antibacterial layer 3 and drying or firing the film. The film may be formed by any method such as coating or spraying. The application temperature is usually from room temperature to 100 ° C., but it can be performed in a temperature range other than this. The drying or baking of the film varies depending on the kind of the binder and the like. However, in the case of titanium oxide, the baking at 800 ° C. or higher results in a rutile type, and thus it is preferable to perform the baking at a temperature lower than 800 ° C. For example, when a commercially available titanium oxide sol solution is used, it is usually fired at about 150 to 600 ° C. It is also possible to use a room temperature drying type titanium oxide sol solution. In the present invention, the thickness of the photocatalyst layer 4 is 0.0
It is desirable that the thickness is about 1 to 5 μm, preferably about 0.1 to 1 μm.

【００２５】図２に、本発明に係る抗菌性積層体の他の
態様例を示す。図２において、基材５は抗菌性金属およ
び／または抗菌性金属イオン（抗菌剤）を含む単層体で
あり、図１と同一符番は図１と同様のものを示し、ここ
ではその説明を省略する。基材５は、それ自体に上記し
た抗菌剤を含むものであり、たとえば合金成分として銀
や銅などを含む抗菌ステンレス、抗菌アルミニウムなど
が挙げられる。図２に示す態様において、たとえば基材
５が板状体である場合には、その両表面とも抗菌性を示
すが、光触媒層４は少なくともひとつの表面に形成され
ていればよい。また基材５は、板状体に限定するもので
なく、光触媒層４を形成できるものであればその形状は
問わない。基材５の表面には、上記図１の態様と同様に
して光触媒層４を形成することができる。本発明では、
抗菌性積層体として、抗菌琺瑯鋼板、抗菌塗装鋼板、抗
菌タイル、抗菌鋼板が好ましく例示される。FIG. 2 shows another embodiment of the antibacterial laminate according to the present invention. In FIG. 2, a base material 5 is a single layer containing an antibacterial metal and / or an antibacterial metal ion (antibacterial agent), and the same reference numerals as those in FIG. Is omitted. The base material 5 itself contains the antibacterial agent described above, and examples thereof include antibacterial stainless steel and antibacterial aluminum containing silver or copper as an alloy component. In the embodiment shown in FIG. 2, for example, when the substrate 5 is a plate-like body, both surfaces thereof show antibacterial properties, but the photocatalyst layer 4 only needs to be formed on at least one surface. The shape of the substrate 5 is not limited to a plate-like body, and any shape can be used as long as the photocatalyst layer 4 can be formed. The photocatalyst layer 4 can be formed on the surface of the substrate 5 in the same manner as in the embodiment of FIG. In the present invention,
Preferred examples of the antibacterial laminate include an antibacterial enameled steel sheet, an antibacterial painted steel sheet, an antibacterial tile, and an antibacterial steel sheet.

【００２６】[0026]

【実施例】次に本発明を実施例により具体的に説明する
が、本発明はこれら実施例に限定されるものではない。 （実施例１）図１に示す抗菌性積層体を製造した。琺瑯
用フリット（組成：Ｐ2 Ｏ5 ５０重量％、Ｓｂ2 Ｏ3 １
１重量％、Ａｌ2Ｏ3 ８重量％、Ｂ2 Ｏ3 ０．５重量％
を含む）に、銀系抗菌剤（組成：ケイ酸ジルコニウム銀
（東亜合成（株）製）を混合してスリップを調製し、鋼
板片面に施釉し、５００℃で焼成し、厚み１００μｍの
抗菌性琺瑯層を形成した。なお、抗菌性琺瑯層中の銀系
抗菌剤の含有量は２重量％である。次いで抗菌層表面に
酸化チタンゾル液（ＴＡＫ７０多木化学（株）製）を塗
布し、３００℃で焼成して厚み０．３μｍの光触媒層を
形成して、抗菌琺瑯鋼板を製造した。EXAMPLES Next, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. Example 1 An antibacterial laminate shown in FIG. 1 was manufactured. Enamel frit (composition: P 2 O 5 50 wt%, Sb 2 O 3 1
1 wt%, Al 2 O 3 8 wt%, B 2 O 3 0.5 wt%
), And a silver-based antibacterial agent (composition: silver zirconium silicate (manufactured by Toagosei Co., Ltd.)) to prepare a slip, glaze one side of the steel plate, bake at 500 ° C, and antibacterial property with a thickness of 100 µm The antibacterial enamel layer contained a silver-based antibacterial agent in an amount of 2% by weight, and a titanium oxide sol solution (TAK70, manufactured by Taki Chemical Co., Ltd.) was applied to the surface of the antibacterial enamel layer. A photocatalyst layer having a thickness of 0.3 μm was formed by firing at 300 ° C. to produce an antibacterial enameled steel sheet.

【００２７】＜抗菌試験＞上記で得られた抗菌琺瑯鋼板
を、通常の室内に、製造後３日放置した試験片と、３ケ
月放置した試験片とについて抗菌試験を実施した。抗菌
試験は試験片に所定の方法（銀等無機抗菌剤研究会の抗
菌力試験法Ｉフィルム密着法に準拠）で大腸菌液を塗布
し、暗所２４時間放置後またはブラックライトで０．２
ｍＷ／cm2 の光を４時間照射した後に試験片表面より回
収した菌液中の菌数を培養によって測定し、死滅した菌
の割合を求めた。結果を表１に示す。３ケ月後でも殺菌
率は暗所、光照射後ともに９９％以上であり、十分な抗
菌作用を示した。<Antibacterial Test> The antibacterial enameled steel sheet obtained above was subjected to an antibacterial test on a test piece left in a normal room for three days after production and a test piece left for three months. The antibacterial test was performed by applying Escherichia coli solution to the test piece by a predetermined method (according to the antibacterial activity test method I film adhesion method of the Society for Research on Inorganic Antibacterial Agents such as Silver) and leaving it in a dark place for 24 hours or 0.2% with black light.
After irradiation with light of mW / cm 2 for 4 hours, the number of bacteria in the bacterial solution collected from the surface of the test piece was measured by culturing, and the ratio of dead bacteria was determined. Table 1 shows the results. Even after 3 months, the bactericidal rate was 99% or more both in the dark and after light irradiation, indicating a sufficient antibacterial effect.

【００２８】（比較例１）図３に示す態様の抗菌性積層
体を製造した。実施例１と同じ琺瑯用フリットに、銀系
抗菌剤（実施例１と同じ）と、光触媒活性を有する酸化
チタン微粒子（７ｎｍ）を混合してスリップを調製し、
鋼板片面に施釉し、５００℃で焼成し、厚み１００μｍ
の抗菌層を形成し、抗菌琺瑯鋼板を製造した。なお琺瑯
層中の銀系抗菌剤の含有量は２重量％、酸化チタンの含
有量は１０重量％である。得られた抗菌琺瑯鋼板につい
て実施例１と同様の抗菌試験を実施した。結果を表１に
示す。初期の暗所放置後殺菌率は高いものの、３ケ月後
の殺菌率は暗所、光照射後ともに大きく低下していた。
光照射後の殺菌率は５０％以下であり、光触媒効果はほ
とんど見られなかった。Comparative Example 1 An antibacterial laminate of the embodiment shown in FIG. 3 was manufactured. A slip was prepared by mixing a silver-based antibacterial agent (same as in Example 1) and titanium oxide fine particles (7 nm) having photocatalytic activity in the same enamel frit as in Example 1.
Glazed on one side of steel plate, fired at 500 ° C, thickness 100μm
Was formed to produce an antibacterial enameled steel sheet. The content of the silver-based antibacterial agent in the enamel layer was 2% by weight, and the content of titanium oxide was 10% by weight. The same antibacterial test as in Example 1 was performed on the obtained antibacterial enameled steel sheet. Table 1 shows the results. Although the sterilization rate after leaving in the dark in the initial stage was high, the sterilization rate after 3 months was greatly reduced in both the dark place and after light irradiation.
The sterilization rate after light irradiation was 50% or less, and almost no photocatalytic effect was observed.

【００２９】（比較例２）図４に示す態様の抗菌性積層
体を製造した。実施例１と同じ琺瑯用フリット（抗菌剤
および光触媒を含有しない）のみからスリップを調製
し、鋼板片面に施釉し、５００℃で焼成し、厚み１００
μｍの琺瑯層を形成した。次いで、銀系抗菌剤（実施例
１と同じ）を酸化チタンゾル液（実施例１と同じ）に５
重量％の量で混合したものを、琺瑯層表面に塗布し、３
００℃焼成して厚み０．３μｍとした。得られた抗菌琺
瑯鋼板について実施例１と同様の抗菌試験を実施した。
結果を表１に示す。初期の殺菌率はやや低く、３ケ月後
の暗所放置後の殺菌率は大きく低下していた。Comparative Example 2 An antibacterial laminate of the embodiment shown in FIG. 4 was manufactured. A slip was prepared only from the same enamel frit (containing no antibacterial agent and photocatalyst) as in Example 1, glazed on one side of the steel plate, baked at 500 ° C., thickness 100
A μm enamel layer was formed. Next, a silver-based antibacterial agent (same as in Example 1) was added to titanium oxide sol solution (same as in Example 1).
The mixture in a weight% amount is applied to the surface of the enamel layer,
It was baked at 00 ° C. to a thickness of 0.3 μm. The same antibacterial test as in Example 1 was performed on the obtained antibacterial enameled steel sheet.
Table 1 shows the results. The initial sterilization rate was rather low, and after 3 months, the sterilization rate after being left in the dark was greatly reduced.

【００３０】（比較例３）図５に示す態様の抗菌性積層
体を製造した。実施例１と同じ琺瑯用フリット（抗菌剤
および光触媒を含有しない）のみからスリップを調製
し、鋼板片面に施釉し、５００℃で焼成し、厚み１００
μｍの琺瑯層を形成した。次いで酸化チタンゾル液（実
施例１と同じ）を０．３μｍの厚みとなるように塗布
し、さらに塗膜上に膜厚０．１μｍとなる量の銀系抗菌
剤（実施例１と同じ）をのせて焼成し、抗菌琺瑯鋼板を
製造した。得られた抗菌琺瑯鋼板について実施例１と同
様の抗菌試験を実施した。結果を表１に示す。初期の殺
菌率はやや低く、３ケ月後の暗所放置後の殺菌率は大き
く低下していた。Comparative Example 3 An antibacterial laminate of the embodiment shown in FIG. 5 was manufactured. A slip was prepared only from the same enamel frit (containing no antibacterial agent and photocatalyst) as in Example 1, glazed on one side of the steel plate, baked at 500 ° C., thickness 100
A μm enamel layer was formed. Then, a titanium oxide sol solution (same as in Example 1) is applied so as to have a thickness of 0.3 μm, and a silver-based antibacterial agent (same as in Example 1) having a thickness of 0.1 μm is further applied on the coating film. It was then fired to produce an antibacterial enameled steel plate. The same antibacterial test as in Example 1 was performed on the obtained antibacterial enameled steel sheet. Table 1 shows the results. The initial sterilization rate was rather low, and after 3 months, the sterilization rate after being left in the dark was greatly reduced.

【００３１】（実施例２）図１に示す態様の抗菌性積層
体を製造した。フッ素樹脂系塗料に、銀系抗菌剤（実施
例１と同じ）を混合して抗菌塗料を調製し、鋼板表面に
塗布、１５０℃で乾燥して、厚み１００μｍの抗菌性塗
膜層を形成した。なお、抗菌性塗膜層中の銀系抗菌剤の
含有量は３重量％である。次いで抗菌性塗膜層表面に、
実施例１と同様にして厚み０．３μｍの光触媒層を形成
して抗菌塗装鋼板を製造した。得られた抗菌塗装鋼板に
ついて、実施例１と同様の抗菌試験を実施した。結果を
表１に示す。３ケ月後でも殺菌率は暗所、光照射後とも
に９９％以上と十分な抗菌作用を示した。Example 2 An antibacterial laminate of the embodiment shown in FIG. 1 was manufactured. An antibacterial coating was prepared by mixing a silver-based antibacterial agent (same as in Example 1) with a fluororesin-based coating, applied to the surface of a steel sheet, and dried at 150 ° C. to form an antibacterial coating layer having a thickness of 100 μm. . The content of the silver-based antibacterial agent in the antibacterial coating layer was 3% by weight. Next, on the antibacterial coating layer surface,
A 0.3 μm-thick photocatalyst layer was formed in the same manner as in Example 1 to produce an antibacterial coated steel sheet. The same antibacterial test as in Example 1 was performed on the obtained antibacterial coated steel sheet. Table 1 shows the results. Even after 3 months, the bactericidal rate was 99% or more in both the dark place and after light irradiation, indicating a sufficient antibacterial effect.

【００３２】（実施例３）Ｃｕを２％含む抗菌ステンレ
ス板の表面に、実施例１と同様にして厚み０．３μｍの
光触媒層を形成して図２に示す様態の抗菌性積層体を製
造した。３ケ月後でも殺菌率は暗所、光照射後ともに９
９％以上であり、十分な抗菌作用を示した。Example 3 A photocatalytic layer having a thickness of 0.3 μm was formed on the surface of an antibacterial stainless steel plate containing 2% of Cu in the same manner as in Example 1 to produce an antibacterial laminate having the form shown in FIG. did. Even after 3 months, the sterilization rate was 9 in both the dark place and after light irradiation.
9% or more, indicating a sufficient antibacterial effect.

【００３３】 [0033]

【００３４】[0034]

【発明の効果】本発明に係る抗菌性積層体は、上記のよ
うに特定構造を有しており、長期にわたって抗菌性を発
現することができる。The antibacterial laminate according to the present invention has a specific structure as described above, and can exhibit antibacterial properties for a long period of time.

【図面の簡単な説明】[Brief description of the drawings]

【図１】 本発明に係る抗菌性積層体の基材が多層構造
であるときの部分断面図である。FIG. 1 is a partial cross-sectional view when a substrate of an antibacterial laminate according to the present invention has a multilayer structure.

【図２】 本発明に係る抗菌性積層体の基材が単層構造
であるときの部分断面図である。FIG. 2 is a partial cross-sectional view when the substrate of the antibacterial laminate according to the present invention has a single-layer structure.

【図３】 抗菌剤と光触媒を含有する琺瑯層を有する従
来の抗菌性積層体を模式的に示す部分断面図である。FIG. 3 is a partial cross-sectional view schematically showing a conventional antibacterial laminate having an enamel layer containing an antibacterial agent and a photocatalyst.

【図４】 琺瑯層表面に抗菌剤と光触媒を含有する層を
有する従来の抗菌性積層体を模式的に示す部分断面図で
ある。FIG. 4 is a partial cross-sectional view schematically showing a conventional antibacterial laminate having a layer containing an antibacterial agent and a photocatalyst on the surface of an enamel layer.

【図５】 琺瑯層表面に光触媒層を設け、その表面近傍
に抗菌剤を担持または固定した従来の抗菌性積層体を模
式的に示す部分断面図である。FIG. 5 is a partial cross-sectional view schematically showing a conventional antibacterial laminate in which a photocatalytic layer is provided on the surface of an enamel layer and an antibacterial agent is carried or fixed near the surface.

【符号の説明】[Explanation of symbols]

１ 抗菌性積層体 ２ 下地基材 ３ 抗菌層 ４ 光触媒層 ５ 基材（抗菌剤を含む） DESCRIPTION OF SYMBOLS 1 Antibacterial laminated body 2 Base material 3 Antibacterial layer 4 Photocatalytic layer 5 Base material (including antibacterial agent)

───────────────────────────────────────────────────── フロントページの続き (72)発明者 田原 知之 千葉県千葉市中央区川崎町１番地 川崎製 鉄株式会社技術研究所内 (72)発明者 冨樫 房夫 兵庫県神戸市東灘区魚崎南町３丁目６番24 号 川鉄建材株式会社技術研究所内 (72)発明者 永石 博 千葉県習志野市東習志野２丁目18番13号 川鉄建材株式会社技術研究所内 (72)発明者 高村 日出夫 千葉県習志野市東習志野２丁目18番13号 川鉄建材株式会社技術研究所内 (72)発明者 渡辺 浩司 千葉県習志野市東習志野２丁目18番13号 川鉄建材株式会社技術研究所内 Ｆターム(参考） 4F100 AA21A AB01B AB01H AB03C AB24B AB24H AD20B AR00A AR00B AT00C BA02 BA03 BA07 BA10A BA10C CA30B GB08 GB09 JC00 JC00B JC00H JL08A JM01A  ──────────────────────────────────────────────────続 き Continuing on the front page (72) Tomoyuki Tahara 1st Kawasaki-cho, Chuo-ku, Chiba City, Chiba Prefecture Inside the Technical Research Institute of Kawasaki Steel Co., Ltd. No. 6-24 Inside Kawasaki Steel Construction Materials Co., Ltd. (72) Inventor Hiroshi Nagaishi 18-18-13 Higashi Narashino, Narashino City, Chiba Prefecture Inside Kawasaki Steel Construction Materials Co., Ltd. (72) Hideo Takamura 2-chome Higashi Narashino, Narashino City, Chiba Prefecture No. 18-13 Kawatetsu Construction Materials Co., Ltd.Technical Research Laboratories (72) Inventor Koji Watanabe 2-18-18 Higashi Narashino, Narashino City, Chiba Pref. AR00B AT00C BA02 BA03 BA07 BA10A BA10C CA30B GB08 GB09 JC00 JC00B JC00H JL08A JM01A

Claims (4)

【特許請求の範囲】[Claims] 【請求項１】少なくともひとつの表面が抗菌性を有する
基材と、該抗菌性表面の少なくともひとつの表面上に形
成された光触媒機能を発現する物質を含有する光触媒層
とを有する抗菌性積層体。An antimicrobial laminate comprising a substrate having at least one antimicrobial surface and a photocatalyst layer formed on at least one of the antimicrobial surfaces and containing a substance exhibiting a photocatalytic function. . 【請求項２】前記基材が、下地基材と、該下地基材の少
なくともひとつの表面に形成された抗菌性金属および／
または抗菌性金属イオンを含有する抗菌層とからなる積
層体である請求項１に記載の抗菌性積層体。2. The method according to claim 1, wherein the base material comprises: a base material; and an antibacterial metal formed on at least one surface of the base material.
The antibacterial laminate according to claim 1, which is a laminate comprising an antibacterial layer containing an antibacterial metal ion. 【請求項３】前記基材が、抗菌性金属および／または抗
菌性金属イオンを含む単層体である請求項１に記載の抗
菌性積層体。3. The antibacterial laminate according to claim 1, wherein the substrate is a monolayer containing an antibacterial metal and / or an antibacterial metal ion. 【請求項４】前記光触媒機能を有する物質が積層体最外
表面に露出していることを特徴とする請求項１〜３のい
ずれかに記載の抗菌性積層体。4. The antibacterial laminate according to claim 1, wherein the substance having a photocatalytic function is exposed on the outermost surface of the laminate.
JP00790499A 1999-01-14 1999-01-14 Antibacterial laminate Expired - Lifetime JP3465018B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP00790499A JP3465018B2 (en) 1999-01-14 1999-01-14 Antibacterial laminate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP00790499A JP3465018B2 (en) 1999-01-14 1999-01-14 Antibacterial laminate

Publications (2)

Publication Number Publication Date
JP2000202939A true JP2000202939A (en) 2000-07-25
JP3465018B2 JP3465018B2 (en) 2003-11-10

Family

ID=11678562

Family Applications (1)

Application Number Title Priority Date Filing Date
JP00790499A Expired - Lifetime JP3465018B2 (en) 1999-01-14 1999-01-14 Antibacterial laminate

Country Status (1)

Country Link
JP (1) JP3465018B2 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001232215A (en) * 2000-02-25 2001-08-28 Nippon Soda Co Ltd Photocatalyst carrying structure having antibacterial and antifungal effect
JP2002200696A (en) * 2000-12-28 2002-07-16 Mitsubishi Plastics Ind Ltd Decorative metallic plate
JP6200571B1 (en) * 2016-11-25 2017-09-20 大木 彬 Surface treatment agent and surface treatment method
WO2024034607A1 (en) * 2022-08-08 2024-02-15 日本製鉄株式会社 Coated metal sheet

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05253544A (en) * 1992-03-13 1993-10-05 Toto Ltd Production of plate-shape member having deodorizing function
JPH06278241A (en) * 1992-09-22 1994-10-04 Takenaka Komuten Co Ltd Building material
JPH0860302A (en) * 1994-08-11 1996-03-05 Nisshin Steel Co Ltd Austenitic stainless steel having antibacterial characteristic and its production
JPH0860303A (en) * 1994-08-11 1996-03-05 Nisshin Steel Co Ltd Ferritic stainless steel having antibacterial characteristic and its production
JPH10237597A (en) * 1997-02-24 1998-09-08 Nisshin Steel Co Ltd High strength and high ductility dual-phase stainless steel excellent in antibacterial property and its production
JP2000119955A (en) * 1998-10-07 2000-04-25 Toray Ind Inc Antibacterial and antifungus fiber structure

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05253544A (en) * 1992-03-13 1993-10-05 Toto Ltd Production of plate-shape member having deodorizing function
JPH06278241A (en) * 1992-09-22 1994-10-04 Takenaka Komuten Co Ltd Building material
JPH0860302A (en) * 1994-08-11 1996-03-05 Nisshin Steel Co Ltd Austenitic stainless steel having antibacterial characteristic and its production
JPH0860303A (en) * 1994-08-11 1996-03-05 Nisshin Steel Co Ltd Ferritic stainless steel having antibacterial characteristic and its production
JPH10237597A (en) * 1997-02-24 1998-09-08 Nisshin Steel Co Ltd High strength and high ductility dual-phase stainless steel excellent in antibacterial property and its production
JP2000119955A (en) * 1998-10-07 2000-04-25 Toray Ind Inc Antibacterial and antifungus fiber structure

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001232215A (en) * 2000-02-25 2001-08-28 Nippon Soda Co Ltd Photocatalyst carrying structure having antibacterial and antifungal effect
JP4549477B2 (en) * 2000-02-25 2010-09-22 日本曹達株式会社 Photocatalyst carrying structure having antibacterial and antifungal effects
JP2002200696A (en) * 2000-12-28 2002-07-16 Mitsubishi Plastics Ind Ltd Decorative metallic plate
JP6200571B1 (en) * 2016-11-25 2017-09-20 大木 彬 Surface treatment agent and surface treatment method
JP2018083179A (en) * 2016-11-25 2018-05-31 大木 彬 Surface treatment agent and surface treatment method
WO2024034607A1 (en) * 2022-08-08 2024-02-15 日本製鉄株式会社 Coated metal sheet

Also Published As

Publication number Publication date
JP3465018B2 (en) 2003-11-10

Similar Documents

Publication Publication Date Title
KR100327997B1 (en) Photocatalytic Complex and Method for Manufacturing the Same
JP3309591B2 (en) Multifunctional material with photocatalytic function
JP3559892B2 (en) Photocatalytic film and method for forming the same
CZ20002151A3 (en) Preparation exhibiting photocatalytic activity and process for preparing thereof
JP2006021994A (en) Method of manufacturing multifunctional material having photocatalytic function
JP6283922B1 (en) Photocatalyst material and photocatalyst coating composition
JP3136918B2 (en) Multifunctional material having antibacterial properties and method for producing the same
JP2001303276A (en) Enamel material
EP2726557B1 (en) Surface treatment agent with high photocatalytic and sanitary effects
JP2000202939A (en) Antibacterial laminate
JP3027739B2 (en) Photocatalyst and method for producing the same
JP3246235B2 (en) Multifunctional material having photocatalytic function and method for producing the same
JP2000237597A (en) Photocatalyst composite material
JP3267880B2 (en) Antibacterial aluminum or aluminum alloy material and method for producing the same
JP3486588B2 (en) Laminate, method for manufacturing the same, and equipment for manufacturing the same
JPH11278969A (en) Ceramic material having antibacterial mildewproofing property and its production
JPH11188272A (en) Photocatalytic body and its production
JP3267884B2 (en) Antibacterial and antifouling aluminum or aluminum alloy material and method for producing the same
JP2004154779A (en) Substrate coated with photocatalytic film and method for forming photocatalytic film thereon
JPH11131261A (en) Glazed article having photocatalysis function and its production
JP2000197827A (en) Material for atmospheric air cleaning
JP2000334309A (en) Photocatalyst
JPH11188271A (en) Photocatalytic body and its production
JP3326071B2 (en) Aluminum or aluminum alloy material coated with photocatalytic film and method for producing the same
JP3736995B2 (en) Antibacterial and antifungal glaze

Legal Events

Date Code Title Description
A01 Written decision to grant a patent or to grant a registration (utility model)

Free format text: JAPANESE INTERMEDIATE CODE: A01

Effective date: 20030617

S111 Request for change of ownership or part of ownership

Free format text: JAPANESE INTERMEDIATE CODE: R313117

S531 Written request for registration of change of domicile

Free format text: JAPANESE INTERMEDIATE CODE: R313531

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20080829

Year of fee payment: 5

R350 Written notification of registration of transfer

Free format text: JAPANESE INTERMEDIATE CODE: R350

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20090829

Year of fee payment: 6

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100829

Year of fee payment: 7

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20100829

Year of fee payment: 7

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20110829

Year of fee payment: 8

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120829

Year of fee payment: 9

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20120829

Year of fee payment: 9

FPAY Renewal fee payment (event date is renewal date of database)

Free format text: PAYMENT UNTIL: 20130829

Year of fee payment: 10

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

R250 Receipt of annual fees

Free format text: JAPANESE INTERMEDIATE CODE: R250

EXPY Cancellation because of completion of term