JPH09613A - Article with silica film containing powder of functional substance - Google Patents
Article with silica film containing powder of functional substanceInfo
- Publication number
- JPH09613A JPH09613A JP7172966A JP17296695A JPH09613A JP H09613 A JPH09613 A JP H09613A JP 7172966 A JP7172966 A JP 7172966A JP 17296695 A JP17296695 A JP 17296695A JP H09613 A JPH09613 A JP H09613A
- Authority
- JP
- Japan
- Prior art keywords
- silica film
- substrate
- functional substance
- resin layer
- article
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
- Laminated Bodies (AREA)
- Silicon Compounds (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は日常生活において発生す
る各種悪臭ガスや有害ガス、水中の有害化合物等の分
解、除去及び殺菌等に有用な物品に関し、具体的には紫
外線照射によって、各種有機物及び無機物の分解効果を
示す二酸化チタン、酸化亜鉛などの光触媒活性物質、及
び二酸化チタン、酸化鉄、酸化亜鉛等を含有する脱臭剤
などを含むシリカ膜を、樹脂層及び樹脂層上に固定され
たシリカ膜を介して基体上に形成した物品に関する。得
られた物品表面のシリカ膜は、加工性及び耐候性に優れ
ているという特徴を有する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an article useful for decomposing, removing and sterilizing various malodorous gases and harmful gases generated in daily life, harmful compounds in water, etc. And a silica film containing a photocatalytically active substance such as titanium dioxide and zinc oxide, which exhibits an effect of decomposing inorganic substances, and a deodorant containing titanium dioxide, iron oxide, zinc oxide, and the like, fixed on the resin layer and the resin layer. The present invention relates to an article formed on a substrate via a silica film. The silica film on the surface of the obtained article is characterized by excellent workability and weather resistance.
【0002】[0002]
【従来の技術】二酸化チタンなどの光触媒は紫外線を照
射すると、光励起により価電子帯から伝導帯に電子が移
行して、n型半導体となり、各種化合物の分解及び殺菌
効果を示すことは広く知られており、水中有機物の分解
(『用水と廃水』、vol.30 No.10(198
8)p943−948)、有機物分解や脱臭、殺菌
(『表面』vol.25 No.8(1987)p47
7−495、『セラミックス』21(1986)No.
4,p326−333)などに使用できることが報告さ
れている。しかし、実際にその光触媒活性を、排気ガス
中の有害ガスやタバコ、トイレ等の悪臭ガス、農薬など
の有害物質、環境汚染物質の分解除去及び殺菌等の目的
で使用する場合、その使用勝手から、何らかの基体上に
担持、固定することが必要である。その他、近年、開発
されている脱臭剤などの各種機能性物質粉末について
も、粉末の形態で使用されるものは僅かである。2. Description of the Related Art It is widely known that photocatalysts such as titanium dioxide, when irradiated with ultraviolet rays, transfer electrons from the valence band to the conduction band by photoexcitation to become n-type semiconductors, exhibiting decomposition and sterilizing effects of various compounds. Decomposition of organic matter in water (“Water and Wastewater”, vol. 30 No. 10 (198
8) p943-948), organic substance decomposition, deodorization, and sterilization ("Surface" vol. 25 No. 8 (1987) p47.
7-495, "Ceramics" 21 (1986) No.
4, p326-333) and the like. However, when actually using its photocatalytic activity for the purpose of decomposing and removing harmful gas in exhaust gas, bad smell gas such as cigarettes and toilets, harmful substances such as pesticides, environmental pollutants, sterilization, etc. It is necessary to carry and fix it on some kind of substrate. In addition, powders of various functional substances, such as deodorants, which have been recently developed, are rarely used in the form of powder.
【0003】機能性物質粉末の例として、光触媒用二酸
化チタンを基体に担持させる方法が例えば以下に提案さ
れている。 (1)ニトロセルロース、ガラス、ポリ塩化ビニル、ナ
イロン、メタクリル樹脂、ポリプロピレン等の光透過性
物質材料からなるフィルム状、ビーズ状、ボード状、繊
維状等の形状の基体に酸化チタン微粉末を付着させる方
法(特開昭62−66861) (2)多孔性ガラス支持体にチタン(IV)テトラブト
キシオキサイドのアルコール溶液を含浸し、加熱して、
アナターゼ型の酸化チタンにすることによって多孔性ガ
ラス支持体に保持・固定する方法(特開平2−5015
4) (3)色素又は金属錯体などの光増感剤を側鎖として持
つ多孔性高分子膜(例えばポリフッ化エチレン樹脂)中
に圧入、含浸、付着等の方法により、半導体触媒粉末を
保持・固定する方法(特開昭58−125602) (4)ポリプロピレン繊維あるいはセラミックスからな
る濾過フィルターに酸化チタンを担持する方法(特開平
2−68190) (5)石英、ガラス、プラスチックの繊維のからみの中
に酸化チタン粉末を保持・固定しその両面を光透過性の
ガラスでおさえつける方法(アメリカ特許488810
1) (6)アルミナ基板に白金をスパッタリング法により固
着させ、その上にアナターゼ型の酸化チタン粉末とメチ
ルメタクリレートの有機溶媒溶液との混合分散液をスピ
ンコーティング法により塗着し、しかるのちに結着剤と
してのメチルメタクリレートを加熱分解するとともに、
アナターゼ型の酸化チタンをルチル型の酸化チタンにす
る方法(Robert E.Hetric,Appli
ed PhysicsCommunications,
5,(3),177−187(1985)) (7)ポリエステル布の表面に酸化チタンを低温溶射方
法で溶射担持する方法(桜田司、表面技術41巻、10
号、P60(1990))As an example of the functional substance powder, a method of supporting titanium dioxide for photocatalyst on a substrate has been proposed, for example. (1) Titanium oxide fine powder is adhered to a film-like, bead-like, board-like, fiber-like substrate made of a light-transmitting substance material such as nitrocellulose, glass, polyvinyl chloride, nylon, methacrylic resin, and polypropylene. Method (JP-A-62-66861) (2) A porous glass support is impregnated with an alcohol solution of titanium (IV) tetrabutoxyoxide and heated to
Method of holding and fixing to a porous glass support by using anatase type titanium oxide (Japanese Patent Laid-Open No. 2-5015)
4) (3) Hold the semiconductor catalyst powder by a method such as press-fitting, impregnation, or adhesion in a porous polymer film (for example, polyfluoroethylene resin) having a photosensitizer such as a dye or a metal complex as a side chain. Method of fixing (JP-A-58-125602) (4) Method of supporting titanium oxide on a filtration filter made of polypropylene fiber or ceramics (JP-A-2-68190) (5) In the entanglement of quartz, glass and plastic fibers A method of holding and fixing titanium oxide powder on the both sides and holding both surfaces thereof with light-transmitting glass (US Pat. No. 4,888,810).
1) (6) Platinum is adhered to an alumina substrate by a sputtering method, a mixed dispersion liquid of anatase type titanium oxide powder and an organic solvent solution of methylmethacrylate is applied thereon by a spin coating method, and then bonded. While thermally decomposing methyl methacrylate as a binder,
Method for converting anatase-type titanium oxide into rutile-type titanium oxide (Robert E. Hetric, Appli
ed Physics Communications,
5, (3), 177-187 (1985)) (7) A method of thermally spraying titanium oxide on the surface of a polyester cloth by a low temperature thermal spraying method (Saji Sakurada, Surface Technology Vol. 41, 10
No., P60 (1990))
【0004】上記の公知の光触媒二酸化チタンの基体へ
の担持方法には、それぞれ以下の欠点があった。
(1),(3),(4),(5)などの有機物をバイン
ダ−とする固定では、二酸化チタンの光触媒作用で大部
分の有機物が分解されるので、長期使用時の固定は信頼
性が無い。(2)の方法は、高価な有機チタン化合物を
原料とする上に、破損し易いガラスに直接担持させてい
るため、強度の信頼性が無い。また(6),(7)の方
法は固定の際に非常に高温になり、二酸化チタンの高い
光触媒活性が失われるので好ましくない。その他、よく
使用される方法として、単に無機多孔質体、繊維にスラ
リ状の二酸化チタンを含浸、担持させる方法、及びシリ
カ系、アルミナ系等のアルカリ塩を加水分解や加熱溶融
させたバインダ−を使用する方法等があるが、前者では
二酸化チタン粒子が固定されていないために、振動、衝
撃で容易に脱落するし、後者では触媒を固定するための
バインダ−によって、触媒表面が被覆されて活性が大部
分失われるという問題があった。更にこれらの方法では
耐熱性等が必要とされるため、使用できる基体の種類も
制限され、広い面への固定や加工が困難なために、コス
トがかさむ一方、光エネルギ−を充分に利用できないと
いう問題があった。この問題は二酸化チタン以外の光触
媒や、更に吸着剤、殺菌剤等の高活性物質全てに共通の
ものである。これら高活性物質を実用化するに際して、
活性を低下させること無く、強度に優れ、安価で、取り
扱いが容易な固定方法が望まれていた。The above-mentioned known methods for supporting photocatalytic titanium dioxide on a substrate have the following drawbacks.
Fixing with organic substances such as (1), (3), (4), and (5) as a binder causes most of the organic substances to be decomposed by the photocatalytic action of titanium dioxide, so fixing during long-term use is reliable. There is no. In the method (2), since the expensive organic titanium compound is used as the raw material and the glass is directly supported on the glass which is easily broken, the strength is not reliable. Further, the methods (6) and (7) are not preferable because the temperature becomes extremely high during fixing and the high photocatalytic activity of titanium dioxide is lost. In addition, as a method often used, an inorganic porous material, a method of impregnating and supporting a slurry of titanium dioxide on fibers, and a binder obtained by hydrolyzing or melting an alkali salt such as silica-based or alumina-based are used. There is a method to use, but in the former, the titanium dioxide particles are not fixed, so they easily fall off due to vibration and shock, and in the latter, the catalyst surface is coated with a binder for fixing the catalyst and activated. Was lost. Furthermore, since heat resistance and the like are required in these methods, the types of substrates that can be used are also limited, and it is difficult to fix and process them on a wide surface, resulting in high cost, but insufficient utilization of light energy. There was a problem. This problem is common to all photocatalysts other than titanium dioxide, and also to highly active substances such as adsorbents and germicides. When putting these highly active substances into practical use,
A fixing method that is excellent in strength, inexpensive, and easy to handle without decreasing activity has been desired.
【0005】[0005]
【発明が解決すべき課題】本発明は上記の問題を解決す
ることを目的とし、脱臭剤の脱臭効果、抗菌剤の殺菌効
果、二酸化チタンなどの光触媒活性による、アセトアル
デヒド、メルカプタン等の悪臭ガス、NOX 等の有害ガ
ス、農薬等の有害物質、環境汚染物質の分解除去及び殺
菌効果に優れた、加工性及び耐候性に優れた物品を提供
することにある。DISCLOSURE OF THE INVENTION The present invention is intended to solve the above problems, and has a deodorizing effect of a deodorizing agent, an antibacterial effect of an antibacterial agent, and a malodorous gas such as acetaldehyde and mercaptan due to photocatalytic activity of titanium dioxide, harmful gas such as NO X, harmful substances such as agricultural chemicals, excellent decomposition removal and sterilization effects of environmental pollutants, is to provide a superior article in processability and weather resistance.
【0006】[0006]
【問題を解決するための手段】本発明者らは上記の目的
を達成するために鋭意研究を行った結果、基体の表面に
作製した樹脂層上に、ケイ酸エステル、水及び任意の有
機溶剤の混合液を塗布してシリカ膜を作製し、前記シリ
カ膜上にケイ酸エステル、水及び任意の有機溶剤とを混
合した中に機能性物質粉末を分散させた塗料を塗布して
形成した、基体、基体表面に作製された樹脂層、樹脂層
上に固定されたシリカ膜及び機能性物質粉末を含有する
シリカ膜からなる物品は、機能性物質の特徴を失わず、
脱臭剤の脱臭効果、抗菌剤の殺菌効果、紫外線の照射に
よるアルデヒド、メルカプタン等の悪臭ガス、NOX 等
の有害ガス、農薬等の有害物質、環境汚染物質の分解除
去及び殺菌などの光触媒効果を示すこと、及びアルミ板
や樹脂等の耐熱性の無い基体に適用した場合にも、付着
性、加工性及び耐候性に優れていることを見い出して本
発明を完成した。Means for Solving the Problems As a result of intensive studies for achieving the above object, the present inventors have found that a silicate ester, water and an arbitrary organic solvent are formed on a resin layer formed on the surface of a substrate. To form a silica film by applying a mixed solution of, a silicate ester on the silica film, water and any organic solvent was mixed to form a functional material powder was formed by applying a coating material, An article comprising a substrate, a resin layer formed on the surface of the substrate, a silica film fixed on the resin layer and a silica film containing a functional substance powder does not lose the characteristics of the functional substance,
Deodorizing effect of deodorant, bactericidal effect of the antimicrobial agents, aldehydes by irradiation with ultraviolet rays, malodorous gases mercaptan, harmful gases such as NO X, harmful substances such as agricultural chemicals, the photocatalytic effects such as decomposition and removal and sterilization of environmental pollutants The present invention has been completed by finding out that it has excellent adhesiveness, workability and weather resistance even when applied to a substrate having no heat resistance such as an aluminum plate and a resin.
【0007】すなわち、本発明は、基体、基体表面に作
製された樹脂層、樹脂層に固定されたシリカ膜及び前記
シリカ膜上に固定された、機能性物質粉末を含有するシ
リカ膜を有する物品に関する。基体は、その表面に樹脂
層を形成させる事ができるものであればどのようなもの
でも良いが、好ましくは、アルミニウム、鉄、ニッケル
及び銅から成る群より選ばれる少なくとも1種を主成分
とする金属材料、ガラス、セラミックス、樹脂、布、繊
維、またはこれらの組み合わせから選択される。基体表
面に作られる樹脂層の種類は、基体への付着性及びケイ
酸エステル、水および任意の有機溶剤の混合液またはケ
イ酸エステルの加水分解で生じるアルコールへの溶解性
があれば、エポキシ、アクリル、ウレタン、シリコン樹
脂等、通常の塗料用樹脂等、何でも使用し得る。中でも
アクリル及びエポキシ樹脂が好ましく、エポキシ樹脂が
多種の基体に対する接着性が強いので特に好ましい。エ
ポキシ樹脂としては、ビスフェノールAタイプ、ノボラ
ックタイプ、脂肪族タイプの樹脂のいずれも使用でき
る。エポキシ樹脂のタイプ、及び硬化剤の種類は使用す
る基体の種類および要求性能に応じて適宜選択できる。
また樹脂に顔料をいれて着色させたり、紫外線吸収剤を
添加して耐光性を向上させることも可能である。樹脂層
の厚みは1μm以上あれば十分である。That is, the present invention provides an article having a substrate, a resin layer formed on the surface of the substrate, a silica film fixed to the resin layer, and a silica film containing a functional substance powder fixed on the silica film. Regarding The substrate may be any substrate as long as it can form a resin layer on its surface, but preferably contains at least one selected from the group consisting of aluminum, iron, nickel and copper as a main component. It is selected from metallic materials, glass, ceramics, resins, cloth, fibers, or combinations thereof. The type of the resin layer formed on the surface of the substrate is epoxy, as long as it has adhesion to the substrate and solubility in a mixture of silicate ester, water and any organic solvent or alcohol generated by hydrolysis of silicate ester, Any material such as ordinary paint resins such as acrylic, urethane, and silicone resin can be used. Of these, acrylic and epoxy resins are preferable, and epoxy resins are particularly preferable because they have strong adhesion to various substrates. As the epoxy resin, any of bisphenol A type, novolac type and aliphatic type resins can be used. The type of epoxy resin and the type of curing agent can be appropriately selected according to the type of substrate used and required performance.
It is also possible to add a pigment to the resin for coloring, or to add an ultraviolet absorber to improve the light resistance. It is sufficient that the thickness of the resin layer is 1 μm or more.
【0008】本発明のシリカ膜の製造において使用され
る機能性物質粉末とは、光触媒、脱臭および抗菌等の機
能を有する粉末をいい、光触媒機能を有するものとして
は二酸化チタン、および酸化鉄、脱臭機能を有するもの
としては二酸化チタン、酸化鉄および酸化亜鉛、抗菌機
能を有するものとしては銀、銅、亜鉛等の化合物が挙げ
られる。また、これらを担持させた多孔質体や薬剤を包
含したマイクロカプセル等も含まれる。これらは高活性
を有するものの、固定化の際に、表面が被覆されたり、
加熱などで活性を失い易く、更に樹脂などで塗料化して
固定した場合には、その活性のために樹脂が劣化される
など問題の多いものである。本発明のシリカ膜による固
定は、比較的低温で、これら高活性物質を均一にシリカ
膜中に固定し、更にシリカ膜を介して基体表面に作製さ
れた樹脂層上に固定することで、樹脂層を劣化させる恐
れなく、樹脂層を強力な結合材として基体への固定を可
能にするものである。機能性物質粉末の粒子径は塗膜強
度のためには5μm以下が好ましく、さらに好ましくは
0.5μm以下であり、最も好ましくは0.1μm以下
である。機能性物質粉末の例として、光触媒用二酸化チ
タンはアナタ−ゼ型が好ましく、比表面積は20m2 /
g以上が好ましく、50m2 /g以上がさらに好まし
い。また二酸化チタンには、W、Sn、Mo、V、M
n、Pt、Ni、Ag、Cu及びZn等の触媒活性を向
上させる金属酸化物を含有させることも好ましい。また
シリカ膜にはこれら機能性物質粉末以外にも顔料などの
添加も可能である。The functional substance powder used in the production of the silica film of the present invention means a powder having a function of photocatalyst, deodorizing and antibacterial, and titanium dioxide, iron oxide and deodorizing are those having a photocatalytic function. Compounds having a function include titanium dioxide, iron oxide and zinc oxide, and compounds having an antibacterial function include compounds such as silver, copper and zinc. Further, it also includes a porous body supporting these and a microcapsule containing a drug. Although these have high activity, when immobilized, the surface is covered,
There are many problems such that the activity is easily lost by heating or the like, and when the resin is made into a paint and fixed, the resin is deteriorated due to the activity. The fixing by the silica film of the present invention is carried out by fixing these highly active substances uniformly in the silica film at a relatively low temperature, and further by fixing them on the resin layer formed on the substrate surface through the silica film. The resin layer can be fixed to the substrate by using the resin layer as a strong binder without fear of degrading the layer. The particle size of the functional substance powder is preferably 5 μm or less, more preferably 0.5 μm or less, and most preferably 0.1 μm or less for the strength of the coating film. As an example of the functional substance powder, titanium dioxide for photocatalyst is preferably anatase type and has a specific surface area of 20 m 2 /
It is preferably at least g, more preferably at least 50 m 2 / g. Also, for titanium dioxide, W, Sn, Mo, V, M
It is also preferable to contain a metal oxide such as n, Pt, Ni, Ag, Cu and Zn that improves the catalytic activity. In addition to the functional substance powder, a pigment or the like can be added to the silica film.
【0009】本発明の物品において、機能性物質粉末を
含有したシリカ膜は樹脂層上に固定されたシリカ膜を介
して基体に固定されている為、機能性物質粉末による樹
脂の劣化は無い。特に光触媒用二酸化チタン及び二酸化
チタンを含有する脱臭剤においては、紫外線照射により
樹脂を分解する傾向が強いが、本発明のシリカ膜では樹
脂層は長時間の紫外線に対しても劣化しにくいという特
徴がある。また樹脂層上に固定された両シリカ膜は互い
の接着面で一体化しており、ケイ酸エステルの加水分解
で生じるシリカゾルの脱水、溶剤の蒸発による体積の収
縮で、数μmから数十μm以上のブロックに分かれるた
め、例えば両シリカ膜を固定した金属板を曲げて加工し
たり、両シリカ膜を固定した布を畳む等の変形をさせて
も、その変形を吸収できるので、剥離が起こりにくいと
いう長所も合わせ持つ。両シリカ膜の厚さが大きくなる
と強度が下がる傾向にあるので、膜厚はそれぞれ100
μm以下であることが好ましい。樹脂層上に固定された
シリカ膜上に固定される、機能性物質粉末を含有したシ
リカ膜中の機能性物質粉末の割合は、10〜90重量%
が好ましく、より好ましくは20〜85重量%、最も好
ましくは40〜80重量%である。なお、基体表面に樹
脂層を設ける方法、樹脂層上にシリカ膜を設ける方法及
び前記シリカ膜上に機能性物質粉末を含有したシリカ膜
を設ける方法としては公知の方法が使用できるが、基体
の形状に応じて、塗布、吹き付け、浸漬等の適当な塗装
方法を選択できる。In the article of the present invention, since the silica film containing the functional substance powder is fixed to the substrate via the silica film fixed on the resin layer, the functional substance powder does not deteriorate the resin. Particularly in the case of titanium dioxide for photocatalyst and a deodorant containing titanium dioxide, the resin tends to be decomposed by irradiation of ultraviolet rays, but the silica film of the present invention is characterized in that the resin layer is not easily deteriorated even by long-time ultraviolet rays. There is. Further, both silica films fixed on the resin layer are integrated with each other on their adhesive surfaces, and the silica sol is dehydrated by the hydrolysis of the silicate ester, and the volume is contracted due to the evaporation of the solvent. Since it is divided into blocks, even if it is deformed such as bending and processing a metal plate with both silica films fixed, or folding the cloth with both silica films fixed, the deformation can be absorbed, so peeling is unlikely to occur It also has the advantage of. Since the strength tends to decrease as the thickness of both silica films increases, the film thickness is 100
It is preferably μm or less. The ratio of the functional substance powder in the silica film containing the functional substance powder, which is fixed on the silica film fixed on the resin layer, is 10 to 90% by weight.
Is more preferable, 20 to 85% by weight is more preferable, and 40 to 80% by weight is most preferable. Known methods can be used as a method for providing a resin layer on the surface of the substrate, a method for providing a silica film on the resin layer, and a method for providing a silica film containing a functional substance powder on the silica film, but Depending on the shape, an appropriate coating method such as coating, spraying or dipping can be selected.
【0010】本発明は更に、上記物品の製造方法であっ
て、ケイ酸エステル、水及び任意の有機溶剤の混合液を
基体表面に作製された樹脂層上に成膜し、さらにその上
にケイ酸エステル、水及び任意の有機溶剤に、機能性物
質粉末を分散させた塗料を成膜後、400℃以下で加熱
処理する製造方法を提供する。ケイ酸エステルとしては
公知のいずれのものも使用できるが、ケイ酸メチル、ケ
イ酸エチル、ケイ酸ブチルが好ましく、ケイ酸エチルが
最も好ましい。樹脂層上に成膜させるシリカ膜の原料と
なる混合液においては、有機溶剤はケイ酸エステル及び
その分解生成物であるアルコ−ルと混和して、シリカ膜
を基体に良好に接着させるために樹脂層を溶解できるこ
とが必要である。また、機能性物質粉末を分散させた塗
料においては、有機溶剤は、ケイ酸エステルの加水分解
で生成するシリカゾルと親和して、機能性物質粉末粒子
の分散性を高め、塗布を容易にすることが必要である。
なお、ケイ酸エステルの加水分解で生じるアルコールが
樹脂層を溶解できる性質を有し、かつその量が充分であ
る場合には溶剤は加える必要はない。The present invention further provides a method for producing the above article, which comprises forming a mixed solution of a silicate ester, water and an arbitrary organic solvent on a resin layer formed on the surface of a substrate, and further forming a film on the resin layer. Provided is a manufacturing method in which a coating material in which a functional substance powder is dispersed in an acid ester, water and an arbitrary organic solvent is formed into a film and then heat-treated at 400 ° C. or lower. Any known silicate ester can be used, but methyl silicate, ethyl silicate, and butyl silicate are preferred, and ethyl silicate is most preferred. In the mixed liquid which is a raw material of the silica film to be formed on the resin layer, the organic solvent is mixed with the silicate ester and its decomposition product, alcohol, in order to adhere the silica film to the substrate well. It is necessary to be able to dissolve the resin layer. Further, in the coating material in which the functional substance powder is dispersed, the organic solvent has an affinity for the silica sol generated by the hydrolysis of the silicate ester to enhance the dispersibility of the functional substance powder particles and facilitate the application. is necessary.
If the alcohol produced by the hydrolysis of the silicate has the property of dissolving the resin layer and the amount thereof is sufficient, it is not necessary to add a solvent.
【0011】溶剤の種類は使用する樹脂層の種類に応じ
て、適当な溶解性を有するものを適宜選択できるが、代
表的なものとしては、セロソルブ類、カルビト−ル類、
アルコール類が挙げられる。セロソルブ類ではアルキル
基を有するものが好ましく、特にブチル基を有するブチ
ルセロソルブが好ましい。カルビトール類では、カルビ
トールおよび酢酸カルビトールが好ましい。アルコール
類ではエタノール、ブタノールが好ましい。The type of solvent can be appropriately selected according to the type of resin layer used, and typical ones are cellosolves, carbitols,
Examples include alcohols. Among the cellosolves, those having an alkyl group are preferable, and butyl cellosolve having a butyl group is particularly preferable. Among carbitols, carbitol and carbitol acetate are preferred. Among alcohols, ethanol and butanol are preferable.
【0012】塗料に添加する水はケイ酸エステルの加水
分解に使用されるものであるが、塗料中での機能性物質
粉末の分散性、塗膜強度を上げるためには塗料pHは酸
性が好ましく、pH4以下がより好ましく、pH2以下
が特に好ましい。塗料pHを低下させる方法としては、
水に少量の酸を添加して塗料pHを調整することが好ま
しい。また機能性物質粉末を含まないシリカ膜原料とな
る混合液においてもpHは酸性が好ましい。水に添加す
る酸は塩酸、硫酸、硝酸等いずれも使用できる。The water added to the paint is used for the hydrolysis of the silicate ester, but the paint pH is preferably acidic in order to improve the dispersibility of the functional substance powder in the paint and the coating strength. , PH 4 or lower is more preferable, and pH 2 or lower is particularly preferable. As a method of lowering the paint pH,
It is preferable to adjust the coating pH by adding a small amount of acid to water. In addition, the pH is preferably acidic even in the mixed liquid which does not contain the functional substance powder and serves as the silica film raw material. As the acid to be added to water, any of hydrochloric acid, sulfuric acid, nitric acid and the like can be used.
【0013】まず樹脂層上に固定させるシリカ膜の原料
となる混合液の配合割合はケイ酸エステル100重量部
に対して水は25〜100重量部、好ましくは50〜1
00重量部であり、有機溶剤は0〜2000重量部、好
ましくは0〜500重量部である。次に前記シリカ膜上
に固定させる機能性物質粉末を含有したシリカ膜を作製
するための塗料の配合割合は、機能性物質粉末100重
量部に対し、ケイ酸エステルとしてケイ酸エチルを使用
した場合、ケイ酸エチルは30〜3200重量部、好ま
しくは60〜1400重量部、更に好ましくは80〜5
20重量部であり、ケイ酸エステルとしてケイ酸メチ
ル、ケイ酸ブチルを使用した場合、好ましい量はそれぞ
れの分子量の比に対応した係数、0.73、1.54を
ケイ酸エチルでの数値に乗じた値となる。溶剤は0〜1
000重量部、好ましくは0〜500重量部、また水は
10〜1100重量部、好ましくは20〜500重量
部、更に好ましくは30〜200重量部である。上記の
配合割合において、機能性物質粉末が該配合割合より少
なくなると、膜としての光触媒活性が低くなり、該配合
割合より多くなるとシリカ膜の付着性、強度が劣るので
好ましくない。First, the mixing ratio of the mixed liquid as the raw material of the silica film to be fixed on the resin layer is 25 to 100 parts by weight of water, preferably 50 to 1 part by weight with respect to 100 parts by weight of silicate ester.
The amount of the organic solvent is 0 to 2000 parts by weight, preferably 0 to 500 parts by weight. Next, the mixing ratio of the coating material for producing the silica film containing the functional substance powder to be fixed on the silica film is such that ethyl silicate is used as the silicate ester based on 100 parts by weight of the functional substance powder. , Ethyl silicate is 30 to 3200 parts by weight, preferably 60 to 1400 parts by weight, more preferably 80 to 5 parts by weight.
20 parts by weight, and when methyl silicate and butyl silicate are used as the silicate ester, the preferable amount is a coefficient corresponding to the ratio of the respective molecular weights, and 0.73 and 1.54 are converted into numerical values in ethyl silicate. Multiplied value. Solvent 0-1
000 parts by weight, preferably 0 to 500 parts by weight, and water 10 to 1100 parts by weight, preferably 20 to 500 parts by weight, more preferably 30 to 200 parts by weight. When the amount of the functional substance powder is less than the above-mentioned mixing ratio in the above mixing ratio, the photocatalytic activity as a film becomes low, and when it exceeds the mixing ratio, the adhesion and strength of the silica film are deteriorated, which is not preferable.
【0014】ケイ酸エステル、水及び任意の有機溶剤の
混合液を作成後、長時間経過した後に樹脂層上に塗布し
て得られるシリカ膜は剥離し易く、特に混合液の酸濃
度、液温が高い場合にはその傾向が強いので、該混合液
は90℃以下、好ましくは1週間以内に塗布するのがよ
い。ケイ酸エステル、水及び任意の有機溶剤の混合液を
塗布した直後に、機能性物質粉末を含有するシリカ膜を
作成するための塗料を塗布した場合は、両者が完全に混
ざり合って機能性物質粉末の割合の少ないシリカ膜を塗
布したのと同じことになり、機能性物質粉末と樹脂との
接触が生じるので好ましくない。樹脂層上に固定される
シリカ膜と前記シリカ膜上に固定される機能性物質粉末
を含有したシリカ膜を接着面で一体化させるためには、
ケイ酸エステル、水及び任意の有機溶剤の混合液を基体
上に作成された樹脂層上に塗布後、90℃以下、好まし
くは60℃以下で1週間以内、好ましくは3日以内、特
に好ましくは1日以内に機能性物質粉末を含有した塗料
を塗布するのがよい。後者を塗布した後の加熱処理は樹
脂層及び基体の酸化、変質及び変形が生じない温度範囲
で行うことが好ましい。一般的には400℃以下が好ま
しいが、100℃以下ではシリカゾルのゲル化に長時間
を要し、膜強度を得にくいため、100〜400℃が更
に好ましい。本発明の機能性物質粉末を含有したシリカ
膜は、ケイ酸エステルの加水分解で生じたアルコ−ルの
蒸発、シリカゾルの脱水、溶剤の蒸発によって多孔質と
なり、機能性物質粉末と雰囲気との接触を容易にする
が、よりシリカ膜を多孔質にするため、機能性物質粉末
を分散させた塗料にホウ酸などの可溶性物質を添加して
おき、シリカ膜を固化させた後、塗膜を温水で洗浄して
可溶性物質を除去することも可能である。また塗料に可
溶性物質を添加しない場合でも、塗膜を洗浄すること
で、遊離シリカ、付着物等が除去されるので、膜中の機
能性物質粉末の活性が向上する。更に機能性物質粉末が
光触媒活性を有するものの場合には、紫外線を照射して
機能性物質粉末粒子表面の有機物を分解することで、活
性が一段と強くなる。The silica film obtained by coating the resin layer after a long time has passed after preparing a mixed solution of silicate ester, water and any organic solvent is easily peeled off. Particularly, the acid concentration and the liquid temperature of the mixed solution are high. Since the tendency is strong when the value is high, the mixed solution is preferably applied at 90 ° C. or lower, preferably within one week. When the coating material for forming the silica film containing the functional substance powder is applied immediately after the mixed liquid of silicate ester, water and any organic solvent is applied, both are completely mixed and the functional substance is mixed. This is the same as applying a silica film containing a small amount of powder, and it is not preferable because the functional substance powder comes into contact with the resin. In order to integrate the silica film fixed on the resin layer and the silica film containing the functional substance powder fixed on the silica film on the adhesive surface,
After coating a mixture of a silicate ester, water and any organic solvent on a resin layer formed on a substrate, the temperature is 90 ° C. or lower, preferably 60 ° C. or lower within 1 week, preferably within 3 days, particularly preferably. It is preferable to apply the coating material containing the functional substance powder within one day. The heat treatment after applying the latter is preferably carried out within a temperature range where oxidation, alteration and deformation of the resin layer and the substrate do not occur. Generally, the temperature is preferably 400 ° C. or lower, but if the temperature is 100 ° C. or lower, it takes a long time to gel the silica sol, and it is difficult to obtain the film strength. The silica film containing the functional substance powder of the present invention becomes porous by evaporation of alcohol generated by hydrolysis of silicate ester, dehydration of silica sol, evaporation of solvent, and contact between the functional substance powder and the atmosphere. However, in order to make the silica film more porous, a soluble substance such as boric acid has been added to the coating material in which the functional substance powder is dispersed, and the silica film is solidified, and then the coating film is heated with warm water. It is also possible to remove soluble substances by washing with. Even if no soluble substance is added to the paint, washing the coating film removes free silica, deposits, etc., so that the activity of the functional substance powder in the film is improved. Further, when the functional substance powder has a photocatalytic activity, the activity is further enhanced by irradiating with ultraviolet rays to decompose the organic substance on the surface of the functional substance powder particles.
【0015】機能性物質粉末は、効率を上げる為に微粒
子を薄く広げて固定するのが好ましいため、塗料として
基体上に塗布し、塗膜として固定するのがよい。本発明
にかかる製造方法においては、ケイ酸エステルと水の混
合液に有機溶剤を加えることで、混合液としての安定
性、粘度、分散性、乾燥速度が改善されるばかりでな
く、基体表面に作製された樹脂層表面に塗布することで
樹脂を溶解させ、シリカと樹脂が混ざりあった層を作
り、さらにその上に機能性物質粉末を含有した塗料を塗
布し、両シリカ層を互いに接着面で一体化させると同時
に樹脂層上に強固に固定させることに成功した。しか
も、機能性物質粉末自体はシリカ膜中に固定され、樹脂
層上に固定されたシリカ膜を介しているので、樹脂と直
接接触せず樹脂を劣化させない効果が得られる。更に樹
脂が紫外線に弱いものであっても、樹脂層上に固定され
たシリカ膜及び機能性物質が紫外線を遮蔽するため、樹
脂の劣化を防ぐ長所も合わせ持つ。なお、最初のシリカ
膜を形成させるのに際し、前記混合液にあらかじめ樹脂
を溶解させたものを、樹脂層が作製されていない基板上
に塗布して、樹脂による固定を行うことも考えられる
が、この方法によると機能性物質と樹脂が接触し、樹脂
の劣化が生じ、好ましくない。Since it is preferable that the functional substance powder is spread and fixed as fine particles in order to improve efficiency, it is preferably applied as a paint on a substrate and fixed as a coating film. In the production method according to the present invention, by adding an organic solvent to the mixed solution of silicic acid ester and water, not only the stability as a mixed solution, viscosity, dispersibility, drying rate is improved, but also on the substrate surface. The resin is dissolved by applying it to the surface of the prepared resin layer to form a layer in which silica and resin are mixed, and then a coating material containing functional substance powder is applied on top of it, and both silica layers are bonded to each other. We succeeded in fixing it firmly on the resin layer at the same time as it was integrated with. Moreover, since the functional substance powder itself is fixed in the silica film and passes through the silica film fixed on the resin layer, the effect of not directly contacting the resin and deteriorating the resin can be obtained. Further, even if the resin is weak to ultraviolet rays, the silica film and the functional substance fixed on the resin layer block ultraviolet rays, so that it also has an advantage of preventing deterioration of the resin. Incidentally, in forming the first silica film, it is possible to apply a solution prepared by dissolving a resin in the mixed solution in advance onto a substrate on which a resin layer is not prepared, and fix the resin by the resin. According to this method, the functional substance comes into contact with the resin and the resin is deteriorated, which is not preferable.
【0016】本発明の物品におけるシリカ膜は、ケイ酸
エステルの加水分解で生成したシリカゾルからの脱水や
アルコールの蒸発、及び有機溶剤の蒸発で多孔質とな
り、包含された機能性物質粉末粒子が雰囲気のガスや
水、細菌等の表面吸着物質と接触し易いため、これらと
効率よく反応することができる。本発明にかかる物品は
脱臭剤として好適に使用される。すなわち、本発明はそ
の一態様として、基体、基体表面に作製された樹脂層、
樹脂層上に固定されたシリカ膜、及び前記シリカ膜上に
固定された、脱臭剤や光触媒活性を有する二酸化チタン
などの機能性物質粉末を含有するシリカ膜を有する脱臭
剤を提供する。なお、機能性物質のうち、光触媒活性を
有する二酸化チタンなどについては、アルデヒド、メル
カプタンなどの脱臭効果以外にも、NOX 、アンモニ
ア、硫化水素等の無機ガスや農薬等の有害物質、環境汚
染物質の分解除去及び菌類、藻類に対する殺菌、除去な
どが、光触媒効果として公知であり、脱臭効果が得られ
る場合には、光触媒効果として知られているその他の効
果も同時に得られることは明かである。以下に実施例を
挙げて、本発明の内容をより詳細に説明するが、これら
実施例はあくまでも例示であり、本発明の範囲はこれに
限定されるものではない。The silica film in the article of the present invention becomes porous by dehydration from the silica sol formed by hydrolysis of silicate ester, evaporation of alcohol, and evaporation of organic solvent, and the functional substance powder particles contained therein become the atmosphere. Since it is easy to come into contact with the gas, water, surface adsorbing substances such as bacteria, it can react efficiently with these. The article according to the present invention is preferably used as a deodorant. That is, the present invention, as one aspect thereof, a substrate, a resin layer formed on the substrate surface,
Provided is a deodorant having a silica film fixed on a resin layer and a silica film fixed on the silica film and containing a powder of a functional substance such as deodorant or titanium dioxide having photocatalytic activity. Among the functional substances, for such as titanium dioxide having photocatalytic activity, aldehyde, in addition to deodorization effects such as mercaptans, NO X, ammonia, harmful substances inorganic gases and pesticides such as hydrogen sulfide, environmental pollutants It is obvious that the decomposition and removal of lactic acid and the sterilization and removal of fungi and algae are known as photocatalytic effects, and when the deodorizing effect is obtained, other effects known as the photocatalytic effect can be obtained at the same time. Hereinafter, the contents of the present invention will be described in more detail with reference to Examples, but these Examples are merely examples, and the scope of the present invention is not limited thereto.
【0017】実施例1 特公平3−33022号公報記載の方法により、以下の
手順で二酸化チタンと酸化亜鉛の緊密結合体からなる脱
臭剤を製造した。5リットルビーカーに純水1リットル
を分取し、攪拌しながら温度60℃に加熱保持した。次
いで別途用意したTiO2 として144g、およびZn
Oとして16gを含む硫酸チタン−硫酸亜鉛混成水溶液
2リットルとアンモニア水溶液とをこれらの合体液のp
Hが7.5を維持するように注意しながら30分間かけ
て前記純水中に同時滴下した。生成物を濾過・洗浄後2
00℃で3時間乾燥し、二酸化チタンと酸化亜鉛の緊密
結合体粒子からなる脱臭剤(比表面積410m2 /g、
平均粒子径0.4μm)を製造した。上記脱臭剤6g、
ケイ酸エチル9g、塩酸0.5モルを添加した水3g、
ホウ酸0.12g及びブチルセロソルブ6gを、3mm
のガラスビーズ90gとともに120mlのマヨネーズ
瓶に仕込み、レッドデビル社製のペイントコンディショ
ナーで10分間分散、混合して、脱臭剤を含有する塗料
とした。またケイ酸エチル6g、および塩酸0.05モ
ルを添加した水2gを、120mlのマヨネーズ瓶に仕
込み、レッドデビル社製のペイントコンディショナーで
1分間分散して、混合液を作製した。スカイアルミニウ
ム(株)製スカイコ−トのエポキシ系樹脂塗布面(60
mm×150mm×0.5mm)に上記のシリカゾルを
2ミルのドクターブレードで塗布して30分後、上記の
塗料を2ミルのドクターブレードで塗布した。一昼夜風
乾後、150℃で1時間焼き付けしてシリカ膜を作製し
た後、60℃の温水で洗浄して、ホウ酸を除去した後、
紫外線を照射して脱臭剤粒子表面に付着した有機物を分
解、除去した。走査型電子顕微鏡観察より、基体表面
に、脱臭剤粒子を包含するシリカ膜が、脱臭剤を包含し
ないシリカ膜上に形成され、これらの膜は樹脂によって
基体上に固定されていることが確認された。シリカ膜の
厚さはともに約20μmで、シリカ膜重量は約1.5m
g/cm2 であった。この膜は、 JIS−K5400の
方法により塗膜の付着性、硬さを調べたところ、付着性
は評価点10で、鉛筆硬度3H以上であった。塗膜面を
5cm×1cm切り出して120mlのガラス製瓶に入
れ、アセトアルデヒドを瓶内のガス濃度が1000pp
mになる量まで注入し、室温で1時間静置した後、瓶内
の空気を柳本製作所製ガスクロマトグラフG3800
(検出器FID)で測定したところ、アセトアルデヒド
濃度は0ppmであった。同様の試験により、酢酸10
0ppm、トリメチルアミン1000ppm、エチルメ
ルカプタン1000ppm、およびジメチルスルフィド
50ppmのいずれの場合においても、1時間後に、0
ppmとなった。また、使用した脱臭剤粉末10mg
(5cm×1cmの塗膜面に含まれるのとほぼ同量)に
ついて、同様にしてアセトアルデヒドの脱臭試験を行っ
たところ、濃度の減少速度はほぼ同等で、今回の塗膜化
による活性の低下は余り無いと考えられる。表6に、ア
セトアルデヒド、エチルメルカプタンについて、今回の
脱臭デ−タを示す。更にこの塗膜をスガ試験機(株)製
デューパネル光コントロールウェザーメーターを使用し
て、3.0mW/cm2 ×500時間の紫外線照射を行
ったが、塗膜の変色、強度劣化は生じなかった。Example 1 According to the method described in Japanese Examined Patent Publication No. 3-33022, a deodorant consisting of a tightly bound body of titanium dioxide and zinc oxide was produced by the following procedure. 1 liter of pure water was dispensed into a 5 liter beaker and heated and maintained at a temperature of 60 ° C. with stirring. Next, 144 g of TiO 2 separately prepared and Zn
2 liters of a titanium sulfate-zinc sulfate mixed aqueous solution containing 16 g as O and an aqueous ammonia solution were mixed with p of the combined solution.
While being careful to maintain H at 7.5, the solution was simultaneously dropped into the pure water over 30 minutes. After filtering and washing the product 2
After drying at 00 ° C. for 3 hours, a deodorizing agent (specific surface area 410 m 2 / g, composed of particles of a tightly bound body of titanium dioxide and zinc oxide,
An average particle size of 0.4 μm) was produced. 6 g of the above deodorant,
9 g of ethyl silicate, 3 g of water added with 0.5 mol of hydrochloric acid,
Boric acid 0.12g and butyl cellosolve 6g 3mm
90 g of glass beads of No. 1 was charged into a 120 ml mayonnaise bottle, and the mixture was dispersed and mixed for 10 minutes with a paint conditioner manufactured by Red Devil Co. to obtain a deodorant-containing paint. Further, 6 g of ethyl silicate and 2 g of water to which 0.05 mol of hydrochloric acid was added were charged into a 120 ml mayonnaise bottle and dispersed for 1 minute with a paint conditioner manufactured by Red Devil Co. to prepare a mixed solution. Sky Aluminum Co., Ltd. Skycoat epoxy resin coated surface (60
(mm × 150 mm × 0.5 mm), the above silica sol was applied with a 2 mil doctor blade, and after 30 minutes, the above coating material was applied with a 2 mil doctor blade. After air-drying for 24 hours, baking at 150 ° C. for 1 hour to produce a silica film, washing with warm water at 60 ° C. to remove boric acid,
The organic substances attached to the surface of the deodorant particles were decomposed and removed by irradiation with ultraviolet rays. From scanning electron microscope observation, it was confirmed that a silica film containing deodorant particles was formed on the surface of the substrate on a silica film not containing deodorant, and these films were fixed on the substrate by a resin. It was The thickness of the silica film is about 20 μm, and the weight of the silica film is about 1.5 m.
It was g / cm 2 . When the adhesiveness and hardness of the coating film of this film were examined by the method of JIS-K5400, the adhesiveness was 10 at the evaluation point and the pencil hardness was 3H or more. Cut the coating surface 5 cm x 1 cm into a 120 ml glass bottle and add acetaldehyde at a gas concentration of 1000 pp in the bottle.
After injecting to an amount of m, and leaving it at room temperature for 1 hour, the air in the bottle is filled with gas chromatograph G3800 manufactured by Yanagimoto Seisakusho.
When measured by (detector FID), the acetaldehyde concentration was 0 ppm. Acetate 10
In each case of 0 ppm, trimethylamine 1000 ppm, ethyl mercaptan 1000 ppm, and dimethyl sulfide 50 ppm, after 1 hour,
ppm. In addition, 10 mg of the deodorant powder used
When a deodorizing test of acetaldehyde was carried out in the same manner (about the same amount as contained in the coating surface of 5 cm x 1 cm), the rate of decrease in concentration was almost the same, and the activity due to the coating film did not decrease. It seems that there are not many. Table 6 shows the deodorizing data of this time for acetaldehyde and ethyl mercaptan. Further, this coating film was irradiated with ultraviolet rays of 3.0 mW / cm 2 × 500 hours using a Sue Tester Co., Ltd. Dew Panel Light Control Weather Meter, but no discoloration or strength deterioration of the coating film occurred. It was
【0018】実施例2 二酸化チタン(アナタ−ゼ型、比表面積60m2 /g、
平均粒子径0.1μm)6g、ケイ酸エチル9g、塩酸
0.5モルを添加した水3g、ホウ酸0.12g及びブ
チルセロソルブ6gを、3mmのガラスビーズ90gと
ともに120mlのマヨネーズ瓶に仕込み、レッドデビ
ル社製のペイントコンディショナーで10分間分散、混
合して、二酸化チタンを含有する塗料とした。またケイ
酸エチル6g、塩酸0.05モルを添加した水2gおよ
びブチルセロソルブ4gを、120mlのマヨネーズ瓶
に仕込み、レッドデビル社製のペイントコンディショナ
ーで1分間分散して、混合液を作製した。スカイアルミ
ニウム(株)製スカイコ−トのエポキシ系樹脂塗布面
(60mm×150mm×0.5mm)に上記の混合液
を2ミルのドクターブレードで塗布して30分後、上記
の塗料を2ミルのドクターブレードで塗布した。一昼夜
風乾後、150℃で1時間焼き付けしてシリカ膜を作製
した後、90℃の温水で洗浄して、ホウ酸を除去した
後、紫外線を照射して触媒に付着した有機物を分解、除
去した。走査型電子顕微鏡観察より、基体表面に、二酸
化チタンを包含するシリカ膜が二酸化チタンを包含しな
いシリカ膜上に形成され、これらの膜は樹脂によって基
体上に固定されていることが確認された。シリカ膜の厚
さはともに約20μmで、シリカ膜の重量は約1.5m
g/cm2 であった。この膜は、 JIS−K5400の
方法により塗膜の付着性、硬さを調べたところ、付着性
は評価点10で、鉛筆硬度3H以上であった。5cm×
1cmに切り出した塗膜を120mlのガラス製瓶に入
れ、アセトアルデヒドを瓶内のガス濃度が1000pp
mになる量注入し、瓶の外から波長350nmの紫外線
を4.0−4.4mW/cm2 で1時間照射した後、瓶
内の空気を柳本製作所製ガスクロマトグラフG3800
(検出器FID)で測定したところ、アセトアルデヒド
濃度は0ppmであった。同様にして、酢酸50pp
m、トリメチルアミン1000ppm、およびジメチル
スルフィド50ppmでは、1時間の紫外線照射で0p
pmとなった。また、エチルメルカプタン1000pp
mでは、1時間の紫外線照射で60ppmとなった。ま
た、上記で使用した触媒用二酸化チタン粉末を10mg
(5cm×1cmの塗膜面に含まれるのとほぼ同量)に
ついて、同様にしてアセトアルデヒドの分解試験を行っ
たところ、濃度の減少速度はほぼ同等で、今回の塗膜化
による触媒活性の低下は余り無いと考えられる。表7
に、アセトアルデヒド、およびエチルメルカプタンにつ
いて、今回の紫外線照射による除去デ−タを示す。ガラ
ス製試験管に、5cm×1cmに切り出した塗膜と水2
0mlを入れて、室外に一週間放置したところ、塗膜を
入れないものには藻の発生が見られたが、塗膜を入れた
ものには変化は無かった。更にこの塗膜をスガ試験機
(株)製デューパネル光コントロールウェザーメーター
を使用して、300mW/cm2 ×500時間の紫外線
照射を行ったが、塗膜の変色、強度劣化は生じなかっ
た。Example 2 Titanium dioxide (anatase type, specific surface area 60 m 2 / g,
6 g of average particle diameter 0.1 μm), 9 g of ethyl silicate, 3 g of water added with 0.5 mol of hydrochloric acid, 0.12 g of boric acid and 6 g of butyl cellosolve were put in a 120 ml mayonnaise bottle together with 90 g of 3 mm glass beads, and red devil was added. A paint conditioner manufactured by the company was used to disperse and mix for 10 minutes to obtain a paint containing titanium dioxide. Further, 6 g of ethyl silicate, 2 g of water to which 0.05 mol of hydrochloric acid was added, and 4 g of butyl cellosolve were placed in a 120 ml mayonnaise bottle and dispersed for 1 minute with a paint conditioner manufactured by Red Devil to prepare a mixed solution. The above mixture was applied to the epoxy resin coated surface (60 mm × 150 mm × 0.5 mm) of Sky Aluminum Co., Ltd. (60 mm × 150 mm × 0.5 mm) with a doctor blade of 2 mil, and after 30 minutes, the coating composition of 2 mil was coated. It was applied with a doctor blade. After air-drying for a whole day and night, it was baked at 150 ° C. for 1 hour to form a silica film, washed with warm water at 90 ° C. to remove boric acid, and then irradiated with ultraviolet rays to decompose and remove organic substances attached to the catalyst. . It was confirmed by scanning electron microscope observation that a silica film containing titanium dioxide was formed on the surface of the substrate on a silica film not containing titanium dioxide, and these films were fixed on the substrate by a resin. The thickness of the silica film is about 20 μm, and the weight of the silica film is about 1.5 m.
It was g / cm 2 . When the adhesiveness and hardness of the coating film of this film were examined by the method of JIS-K5400, the adhesiveness was 10 at the evaluation point and the pencil hardness was 3H or more. 5 cm x
The coating film cut out to 1 cm is put in a 120 ml glass bottle, and acetaldehyde is added to the bottle at a gas concentration of 1000 pp.
After injecting an amount of m to reach 350 m, and irradiating ultraviolet rays having a wavelength of 350 nm at 4.0 to 4.4 mW / cm 2 for 1 hour from outside the bottle, the air in the bottle is gas chromatograph G3800 manufactured by Yanagimoto Seisakusho
When measured by (detector FID), the acetaldehyde concentration was 0 ppm. Similarly, acetic acid 50pp
m, trimethylamine 1000ppm, and dimethyl sulfide 50ppm, 0p after 1 hour of UV irradiation.
pm. Also, ethyl mercaptan 1000pp
In m, it became 60 ppm after 1 hour of ultraviolet irradiation. In addition, 10 mg of the titanium dioxide powder for catalyst used above was used.
When a decomposition test of acetaldehyde was carried out in the same manner (about the same amount as contained in the coated surface of 5 cm x 1 cm), the rate of decrease in concentration was almost the same, and the catalytic activity decreased due to the coating film this time. Is thought to be scarce. Table 7
Shows the removal data of acetaldehyde and ethyl mercaptan by ultraviolet irradiation this time. 5cm x 1cm coating film and water 2 in a glass test tube
When 0 ml was added and the mixture was allowed to stand outdoors for one week, algae were found to be generated in the film without coating, but there was no change in the film with coating. Furthermore, this coating film was irradiated with ultraviolet rays of 300 mW / cm 2 × 500 hours using a Dewpanel light control weather meter manufactured by Suga Test Instruments Co., Ltd. However, discoloration and strength deterioration of the coating film did not occur.
【0019】実施例3 実施例1において、塗料が、酸化鉄(板状ヘマタイト、
比表面積40m2 /g、長軸/短軸比5)6g、ケイ酸
エチル9g、硝酸0.5モルを添加した水3g、ホウ酸
0.12g及びブチルセロソルブ6gを、3mmのガラ
スビーズ90gとともに120mlのマヨネーズ瓶に仕
込み、レッドデビル社製のペイントコンディショナーで
10分間分散、混合して作製されたものであること以外
は同様にして、酸化鉄を包含するシリカ膜と酸化鉄を包
含しないシリカ膜とを基体上に作製した。Example 3 In Example 1, the coating material was iron oxide (plate-like hematite,
Specific surface area 40 m 2 / g, major axis / minor axis ratio 5) 6 g, ethyl silicate 9 g, water 3 g added with 0.5 mol of nitric acid, boric acid 0.12 g and butyl cellosolve 6 g 120 ml together with 3 mm glass beads 90 g In the same manner, except that the silica film containing iron oxide and the silica film containing no iron oxide were prepared in the same manner except that they were prepared by dispersing and mixing for 10 minutes with a paint conditioner manufactured by Red Devil Co., Ltd. Was prepared on a substrate.
【0020】実施例4 実施例1において、塗料が、酸化亜鉛(比表面積10m
2 /g)6g、ケイ酸エチル9g、硝酸0.5モルを添
加した水3g、及びブチルセロソルブ6gを、3mmの
ガラスビーズ90gとともに120mlのマヨネーズ瓶
に仕込み、レッドデビル社製のペイントコンディショナ
ーで10分間分散、混合して作製されたものであること
以外は同様にして、酸化亜鉛を包含するシリカ膜と酸化
亜鉛を包含しないシリカ膜とを基体上に作製した。Example 4 In Example 1, the coating material was zinc oxide (specific surface area 10 m
2 / g) 6 g, ethyl silicate 9 g, water 3 g to which 0.5 mol of nitric acid was added, and butyl cellosolve 6 g were charged together with 90 mm of 3 mm glass beads in a 120 ml mayonnaise bottle, and a red Devil paint conditioner for 10 minutes. A silica film containing zinc oxide and a silica film not containing zinc oxide were prepared on a substrate in the same manner except that they were prepared by dispersion and mixing.
【0021】実施例5−7 実施例2において、基体をスカイアルミニウム(株)製
スカイコ−トのポリエステル、アクリル及びフッ素系樹
脂塗布面(60mm×150mm×0.5mm)とした
以外は同様にして、二酸化チタンを包含するシリカ膜と
二酸化チタンを包含しないシリカ膜とを基体上に作製し
た。これらを表1および表2に示す。Example 5-7 The same procedure as in Example 2 was carried out except that the substrate was Skycoat Co., Ltd. Skycoat polyester, acrylic and fluorine resin coated surface (60 mm × 150 mm × 0.5 mm). , A silica film containing titanium dioxide and a silica film not containing titanium dioxide were prepared on a substrate. These are shown in Table 1 and Table 2.
【0022】実施例8−21 実施例2において、二酸化チタン粒子を含まないシリカ
ゾル及び二酸化チタン粒子を分散させた塗料の配合と、
基体に塗布する樹脂の種類、塗布方法等を変えた膜を作
製した。これらを表1および表2に示す。また、実施例
8−21について実施例2と同様に、紫外線照射による
アセトアルデヒド、およびエチルメルカプタン除去デ−
タを表7に示す。Example 8-21 Formulation of a coating composition prepared by dispersing silica sol containing no titanium dioxide particles and titanium dioxide particles in Example 2,
A film was prepared by changing the type of resin applied to the substrate and the coating method. These are shown in Table 1 and Table 2. Further, in the same manner as in Example 2 with respect to Example 8-21, acetaldehyde and ethyl mercaptan removal data by ultraviolet irradiation were used.
Table 7 shows the data.
【0023】実施例22,23 基体をポリプロピレン布、繊維とした以外は、実施例2
1と同様にして膜を作製した。これらは100回以上の
曲げ及び洗濯機での洗濯を行っても、シリカ膜の剥離に
よる重量減少は認められなかった。Examples 22 and 23 Example 2 was repeated except that the substrate was polypropylene cloth or fiber.
A film was prepared in the same manner as in 1. Even if they were bent 100 times or more and washed in a washing machine, no weight reduction due to peeling of the silica film was observed.
【0024】比較例1 実施例1において、二酸化チタンを含有する塗料を直接
アルミニウム板に塗布し、150℃×1時間焼き付けた
塗膜面は、手で触れただけで粉が剥落した。 比較例2 アルミニウム板に、表5の塗料組成で二酸化チタンをア
クリル樹脂に分散させた塗料を塗布した。スガ試験機
(株)製デューパネル光コントロールウェザーメーター
を使用した500時間の紫外線照射により、アクリル樹
脂膜は剥離した。 比較例3 アルミニウム板に、表5の塗料組成で二酸化チタンをウ
レタン樹脂に分散させた塗料を塗布した。スガ試験機
(株)製デューパネル光コントロールウェザーメーター
を使用した200時間の紫外線照射により、ウレタン樹
脂膜は剥離した。 比較例4 アルミニウム板に二酸化チタンをメラミン、アルキド樹
脂に分散させた塗料を塗布したものはアルデヒドの分解
効果はなかった。COMPARATIVE EXAMPLE 1 In Example 1, the coating containing titanium dioxide was directly applied to an aluminum plate and baked at 150 ° C. for 1 hour. Comparative Example 2 A paint prepared by dispersing titanium dioxide in an acrylic resin with the paint composition shown in Table 5 was applied to an aluminum plate. The acrylic resin film was peeled off by irradiation with ultraviolet rays for 500 hours using a Suga Test Instruments Co., Ltd. Dew Panel Light Control Weather Meter. Comparative Example 3 A paint prepared by dispersing titanium dioxide in a urethane resin with the paint composition shown in Table 5 was applied to an aluminum plate. The urethane resin film was peeled off by UV irradiation for 200 hours using a Suga Tester Co., Ltd. Dew Panel Light Control Weather Meter. Comparative Example 4 An aluminum plate coated with a coating in which titanium dioxide was dispersed in melamine and an alkyd resin had no aldehyde decomposition effect.
【0025】[0025]
【表1】 [Table 1]
【0026】[0026]
【表2】 [Table 2]
【0027】[0027]
【表3】 [Table 3]
【0028】[0028]
【表4】 [Table 4]
【0029】[0029]
【表5】 [Table 5]
【0030】[0030]
【表6】 [Table 6]
【0031】[0031]
【表7】 [Table 7]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C09D 5/14 PQM C09D 5/14 PQM 7/12 PSK 7/12 PSK 201/00 PDC 201/00 PDC (72)発明者 斎藤辰夫 山口県宇部市大字小串1978番地の25 チタ ン工業株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C09D 5/14 PQM C09D 5/14 PQM 7/12 PSK 7/12 PSK 201/00 PDC 201/00 PDC (72) Inventor Tatsuo Saito 25 Titan Industry Co., Ltd., 1978, Kogushi, Ube, Ube City, Yamaguchi Prefecture
Claims (7)
脂層上に固定されたシリカ膜、及び前記シリカ膜上に固
定された機能性物質粉末を含有するシリカ膜を有する物
品。1. An article having a substrate, a resin layer formed on the surface of the substrate, a silica film fixed on the resin layer, and a silica film containing the functional substance powder fixed on the silica film.
銅から成る群より選ばれる少なくとも1種を主成分とす
る金属材料、ガラス、セラミックス、樹脂、布、繊維、
またはこれらの組み合わせから選択される請求項1記載
の物品。2. A metal material whose main component is at least one selected from the group consisting of aluminum, iron, nickel and copper, glass, ceramics, resin, cloth, fiber,
Or the article of claim 1 selected from a combination thereof.
亜鉛および酸化鉄、またはこれらの組み合わせから選択
される請求項1の物品。3. The article of claim 1, wherein the functional material powder is selected from titanium dioxide, zinc oxide and iron oxide, or combinations thereof.
溶剤の混合液を基体表面に作製された樹脂層表面に被覆
してシリカ膜を作製し、さらにケイ酸エステル、水およ
び/または有機溶剤に機能性物質粉末を分散させた塗料
を前記シリカ膜上に被覆後、400℃以下で加熱処理す
る、請求項1の物品の製造方法。4. A silica film is produced by coating the surface of a resin layer formed on the surface of a substrate with a mixed solution of a silicate ester, water and / or an organic solvent, and further adding a silicate ester, water and / or an organic solvent. The method for producing an article according to claim 1, wherein after coating the silica film with a coating material in which the functional substance powder is dispersed, heat treatment is performed at 400 ° C or lower.
部に対して水25〜100重量部、有機溶剤0〜200
0重量部である請求項4記載の製造方法。5. The mixed solution comprises 25 to 100 parts by weight of water and 0 to 200 parts of an organic solvent based on 100 parts by weight of silicate ester.
The manufacturing method according to claim 4, wherein the amount is 0 part by weight.
に対して、ケイ酸エステル20〜5000重量部、水1
0〜1100重量部及び有機溶剤0〜1000重量部の
割合で混合、分散させた塗料である、請求項4記載の製
造方法。6. The coating composition comprises 20 to 5000 parts by weight of silicate ester and 1 part of water based on 100 parts by weight of the functional substance powder.
The manufacturing method according to claim 4, wherein the coating material is a coating material prepared by mixing and dispersing at a ratio of 0 to 1100 parts by weight and an organic solvent of 0 to 1000 parts by weight.
脂層上に固定されたシリカ膜及び前記シリカ膜上に固定
された、機能性物質粉末を含有するシリカ膜を有する脱
臭剤。7. A deodorant having a substrate, a resin layer formed on the substrate surface, a silica film fixed on the resin layer, and a silica film fixed on the silica film and containing a functional substance powder.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7172966A JPH09613A (en) | 1995-06-16 | 1995-06-16 | Article with silica film containing powder of functional substance |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7172966A JPH09613A (en) | 1995-06-16 | 1995-06-16 | Article with silica film containing powder of functional substance |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH09613A true JPH09613A (en) | 1997-01-07 |
Family
ID=15951666
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7172966A Pending JPH09613A (en) | 1995-06-16 | 1995-06-16 | Article with silica film containing powder of functional substance |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH09613A (en) |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10237794A (en) * | 1997-02-20 | 1998-09-08 | Titan Kogyo Kk | Paper and its production |
JPH10249210A (en) * | 1997-03-14 | 1998-09-22 | Titan Kogyo Kk | Photocatalyst, its manufacture and applications |
JPH10251558A (en) * | 1997-03-13 | 1998-09-22 | Dainippon Toryo Co Ltd | Formation of optically active coating layer |
JPH10264299A (en) * | 1997-03-26 | 1998-10-06 | Nisshin Steel Co Ltd | Coated metal plate with excellent stain resistance and its manufacture |
JPH1110782A (en) * | 1997-06-26 | 1999-01-19 | Nisshin Steel Co Ltd | Highly pollution-resistant metal panel |
JPH11115093A (en) * | 1997-10-20 | 1999-04-27 | Nippon Decor Kk | Decorative sheet with organic substance decomposing function and manufacture thereof |
JP2002526603A (en) * | 1998-10-08 | 2002-08-20 | ソーストーン ビジネス マネジメント リミティド | Adhesion promotion |
JP2008195609A (en) * | 1999-01-07 | 2008-08-28 | Canon Inc | Mesostructured material and silica mesostructured material |
JP2008212829A (en) * | 2007-03-05 | 2008-09-18 | Furukawa Sky Kk | Aluminum coating material excellent in weather resistance |
JP2011172539A (en) * | 2010-02-25 | 2011-09-08 | Chugoku Electric Power Co Inc:The | Cultivation device |
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EP0633064A1 (en) * | 1993-06-28 | 1995-01-11 | Ishihara Sangyo Kaisha, Ltd. | Photocatalyst composite and process for producing the same |
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1995
- 1995-06-16 JP JP7172966A patent/JPH09613A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0633064A1 (en) * | 1993-06-28 | 1995-01-11 | Ishihara Sangyo Kaisha, Ltd. | Photocatalyst composite and process for producing the same |
JPH07171408A (en) * | 1993-06-28 | 1995-07-11 | Ishihara Sangyo Kaisha Ltd | Photocatalytic body and its production |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH10237794A (en) * | 1997-02-20 | 1998-09-08 | Titan Kogyo Kk | Paper and its production |
JPH10251558A (en) * | 1997-03-13 | 1998-09-22 | Dainippon Toryo Co Ltd | Formation of optically active coating layer |
JPH10249210A (en) * | 1997-03-14 | 1998-09-22 | Titan Kogyo Kk | Photocatalyst, its manufacture and applications |
JPH10264299A (en) * | 1997-03-26 | 1998-10-06 | Nisshin Steel Co Ltd | Coated metal plate with excellent stain resistance and its manufacture |
JPH1110782A (en) * | 1997-06-26 | 1999-01-19 | Nisshin Steel Co Ltd | Highly pollution-resistant metal panel |
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