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JPH1033988A - Inorganic oxide composite and its producing process - Google Patents

Inorganic oxide composite and its producing process

Info

Publication number
JPH1033988A
JPH1033988A JP8194282A JP19428296A JPH1033988A JP H1033988 A JPH1033988 A JP H1033988A JP 8194282 A JP8194282 A JP 8194282A JP 19428296 A JP19428296 A JP 19428296A JP H1033988 A JPH1033988 A JP H1033988A
Authority
JP
Japan
Prior art keywords
inorganic oxide
titanium oxide
sio2
photocatalytic
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP8194282A
Other languages
Japanese (ja)
Inventor
Koji Hori
公二 堀
Masato Kakumoto
正人 角元
Masayoshi Maeda
正義 前田
Yasuji Miki
保二 三木
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.)
Miki Riken Kogyo KK
Original Assignee
Miki Riken Kogyo KK
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 Miki Riken Kogyo KK filed Critical Miki Riken Kogyo KK
Priority to JP8194282A priority Critical patent/JPH1033988A/en
Publication of JPH1033988A publication Critical patent/JPH1033988A/en
Pending legal-status Critical Current

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  • Paints Or Removers (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Catalysts (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain an inorganic oxide composite used for odor removal, catalyst action and bacterium removal without the deterioration of performance of a fixing agent by coating an inorganic oxide with a photocatalytic action such as titanium oxide with alkylsilicate of a specific structure. SOLUTION: An inorganic oxide with photocatalytic action such as titanium oxide is coated with alkylsilicate expressed by formula (1) [n = an integer of 0 or more; R=1-4C straight-chain or branched saturated alkyl group]. In addition, the inorganic oxide with photocatalytic action is titanium oxide and this titanium oxide is of such a nature that the weight ratio of TiO2 :SiO2 is 95:5-50:50 and the SiO2 content is high. If these requirements are met, the inorganic oxide composite with photooxidization catalytic properties obtained can be used without the definition of a fixing agent for applications such as an odor remover of odors generated by garbage and a toilet at home or cigarette odor, and catalytic action and bacterium removal, under oxidative decomposition reaction with solar rays and fluorescent lamps.

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、光触媒作用を有す
る無機酸化物複合材料及びその製造方法に関する。詳し
くは酸化チタンに代表される日光、蛍光灯等、紫外線照
射下に起こる酸化分解反応の触媒として使用しうる無機
酸化物複合体及びその製造方法に関するものであり、生
活臭やたばこ臭の消臭剤や化学分解触媒、除菌などの目
的に使用されるものである。
The present invention relates to a photocatalytic inorganic oxide composite material and a method for producing the same. More specifically, the present invention relates to an inorganic oxide complex that can be used as a catalyst for an oxidative decomposition reaction that occurs under ultraviolet irradiation such as sunlight or fluorescent light represented by titanium oxide, and a method for producing the same. It is used for purposes such as chemicals, chemical decomposition catalysts, and sterilization.

【0002】[0002]

【従来の技術】近年、消臭や化学分解反応の触媒等の用
途で光触媒能を有する酸化チタンが使用されている。酸
化チタンの光酸化触媒性は強く従来酸化チタンの表面処
理は酸化チタンの光酸化性に由来する劣化を少なくする
ために行われてきた。この処理はもっぱら酸化アルミニ
ウム、珪酸、酸化亜鉛等無機酸化物皮膜をチタン表面に
形成させることで行われており光酸化性がほとんどない
状態となっており、このため他の基材との接触において
基材を劣化させることはほとんどない。しかしこの光酸
化性を積極的に利用した光酸化触媒として使用される酸
化チタンにおいては基材との密着により基材を劣化させ
特に有機物の分解性が高いため光触媒体微粒子と基材と
を密着させる接着剤、バインダーの変色、劣化が激し
く、酸化チタンの固着剤にフッ素系樹脂やシリコーン系
樹脂等難分解性結着剤を用いたり(特開平7−1714
08)、(特開平7−265714)、酸化チタン微粒
子を多孔質体に坦持させる等の方法(特公平3−157
125)、(特開平7−213913)が取られている
が、従来から用いられている安価なアクリルやウレタン
樹脂を用い従来の顔料と同様に取り扱いができるものは
得られていない。
2. Description of the Related Art In recent years, titanium oxide having photocatalytic activity has been used for applications such as deodorization and catalysts for chemical decomposition reactions. Titanium oxide has a strong photooxidation catalytic property, and surface treatment of titanium oxide has been conventionally performed to reduce deterioration due to photooxidation of titanium oxide. This treatment is performed exclusively by forming an inorganic oxide film such as aluminum oxide, silicic acid, and zinc oxide on the titanium surface, and has almost no photo-oxidation property. It hardly degrades the substrate. However, titanium oxide, which is used as a photo-oxidation catalyst that positively utilizes this photo-oxidation property, degrades the base material due to close contact with the base material. The adhesive and binder to be discolored and deteriorated drastically, and a hardly decomposable binder such as a fluorine-based resin or a silicone-based resin was used as a fixing agent for titanium oxide (Japanese Patent Laid-Open No. 7-1714).
08), (JP-A-7-265714), a method of supporting titanium oxide fine particles on a porous body (Japanese Patent Publication No. 3-157).
125) and (Japanese Patent Application Laid-Open No. 7-21913), but there is no product which can be handled in the same manner as a conventional pigment using a conventionally used inexpensive acrylic or urethane resin.

【0003】[0003]

【発明が解決しようとする課題】近年、光触媒体を用い
た悪臭の分解消臭や有害物質の除去、浄化、抗菌性を利
用した衛生加工品等、光触媒性を有効利用する試み(特
開平7−148434)、(特開平6−63178)が
見られるようになり、これに伴い十分な光触媒性を有
し、且つ、基材を劣化させない光触媒体の出現が望まれ
ている。従来の方法では有機物基材たとえばバインダー
等にフッ素系樹脂を用いる等光酸化分解性が低い難分解
性の固着剤を併用する等使用するにあたって著しい制限
が存在する。また悪臭の消臭剤として従来行われている
方法は吸着、中和といったある量を消臭すると効果が飽
和に達するものがほとんどであり、触媒的に消臭を行う
ものであってもその効果は満足の行くものではなく、基
材劣化の無い光触媒体の開発が望まれる課題となってい
る。本発明は上記した従来の問題を解決するため、一般
に固着剤として使用されるアクリル樹脂やウレタン樹脂
を劣化させず、十分な光酸化触媒性を有する従来の無機
酸化物顔料と同様の取り扱いが出来る新規な光酸化触媒
性を有する無機酸化物複合体を提供することにある。
In recent years, attempts have been made to effectively utilize photocatalytic properties, such as sanitary products utilizing photocatalysts to eliminate malodors and remove and purify odors and harmful substances, and to utilize antibacterial properties (Japanese Patent Application Laid-Open No. 148434) and (Japanese Patent Application Laid-Open No. 6-63178), and accordingly, the appearance of a photocatalyst which has sufficient photocatalytic properties and does not deteriorate the base material has been desired. In the conventional method, there is a remarkable limitation in using an insoluble fixing agent having low photo-oxidative decomposability such as using a fluorine-based resin as an organic base material such as a binder. In addition, most of the conventional methods used as deodorants for odors reach their saturation when deodorizing a certain amount, such as adsorption and neutralization, and even if they are catalytically deodorized, the effect can be reduced. Is not satisfactory, and development of a photocatalyst without deterioration of the base material has been desired. The present invention solves the above-mentioned conventional problems without deteriorating an acrylic resin or a urethane resin generally used as a fixing agent, and can be handled in the same manner as a conventional inorganic oxide pigment having a sufficient photooxidation catalytic property. It is an object of the present invention to provide a novel inorganic oxide composite having photooxidation catalytic properties.

【0004】[0004]

【課題を解決するための手段】本発明の光触媒作用を有
する無機酸化物複合体は、前記の課題を達成するために
次の構成を有する。すなわち、光酸化触媒性を有する無
機酸化物を一般式(1)に示されるアルキルシリケート
でコーティングされることを特徴とする請求項1記載の
無機酸化物複合体と、請求項2記載の製造方法である。
The photocatalytic inorganic oxide composite of the present invention has the following structure to achieve the above object. That is, an inorganic oxide having photooxidation catalytic properties is coated with an alkyl silicate represented by the general formula (1), and the inorganic oxide composite according to claim 1, and the production method according to claim 2. It is.

【0005】[0005]

【化7】 n=0以上の整数、R=炭素数1〜4の直鎖または分岐
のある飽和アルキル基
Embedded image n is an integer of 0 or more, and R is a linear or branched saturated alkyl group having 1 to 4 carbon atoms.

【0006】また光酸化触媒性を有する無機酸化物が酸
化チタンであることを特徴とする請求項1記載の無機酸
化物複合体、および請求項2記載の無機酸化物複合体の
製造方法である。さらには光触媒作用を有する無機酸化
物が酸化チタンであり、かつTiO2:SiO2の重量比
が95:5〜50:50となっているSiO2の含有率
が高い請求項1記載の無機酸化物複合体、および請求項
2記載の製造方法が主となる。
[0008] The inorganic oxide composite according to claim 1, wherein the inorganic oxide having photooxidation catalytic activity is titanium oxide, and the method for producing an inorganic oxide composite according to claim 2, wherein . 2. The inorganic oxide composite according to claim 1, wherein the inorganic oxide having a photocatalytic action is titanium oxide, and the weight ratio of TiO2: SiO2 is 95: 5 to 50:50, and the content of SiO2 is high. , And the manufacturing method described in claim 2.

【0007】[0007]

【発明の実施の形態】以下、本発明の内容について詳述
する。本発明に用いられる光酸化性を有する無機物とし
ては酸化チタンがあり、酸化チタンは硫酸チタニルを加
水分解する硫酸法や四塩化チタンを気相酸化する塩素法
等、公知の方法で得られるアナタース型酸化チタン、ル
チル型酸化チタン、無定形酸化チタン、メタチタン酸、
オルソチタン酸、水和酸化チタン等やこれらの混合物が
例示される。本発明においては光触媒性が十分であれば
いずれでも良いが、光触媒性の強いアナタース型酸化チ
タンが良い。また光触媒性を強めるために他の無機物を
含有するものも望ましい。無機化合物の粒径は100μ
m以下であれば良く、好ましくは10μm以下であり更
に好ましくは1μm以下である。粒径が100μmより
大きい場合、加工処理された基材のざらつき感が大きく
なり繊維等の表面の風合いを重視する用途では価値が低
下する。また酸化チタンの光触媒活性は粒径が小さいほ
ど活性に富む傾向があり、より微粒子を用いる方が光触
媒活性の高い触媒体とすることが容易となり、希釈状態
での安定性も良く粒径の小さいものほど望ましい形とい
える。
DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the contents of the present invention will be described in detail. Titanium oxide is an inorganic substance having photo-oxidizing property used in the present invention. Titanium oxide is an anatase type obtained by a known method such as a sulfuric acid method for hydrolyzing titanyl sulfate and a chlorine method for vapor-phase oxidation of titanium tetrachloride. Titanium oxide, rutile-type titanium oxide, amorphous titanium oxide, metatitanic acid,
Examples thereof include orthotitanic acid, hydrated titanium oxide and the like, and mixtures thereof. In the present invention, any photocatalytic property may be used, but anatase-type titanium oxide having strong photocatalytic property is preferable. Further, those containing other inorganic substances for enhancing photocatalytic properties are also desirable. Particle size of inorganic compound is 100μ
m or less, preferably 10 μm or less, and more preferably 1 μm or less. When the particle size is larger than 100 μm, the roughness of the processed base material becomes large, and the value is reduced in applications where the texture of the surface of fibers or the like is emphasized. Also, the photocatalytic activity of titanium oxide tends to be richer as the particle size is smaller, and it is easier to use fine particles to make a catalyst body having a higher photocatalytic activity, the stability in a diluted state is good, and the particle size is small. Things are more desirable.

【0008】本発明に用いられるアルキルシリケートは
前記の一般式(1)に示されるものであり、アルキル基
はメチル、エチル、プロピル、イソプロピル等、直鎖ま
たは分岐のある飽和アルキル基である。これらアルキル
シリケートは1種または2種以上の混合物であっても良
いが、低温での反応性を考慮すればメチルまたはエチル
基のアルキルシリケートが好ましい。これらの化合物は
水分の存在下で容易に脱アルコール反応を起こし、シラ
ノール基を経てポリシロキサンとなる。アルキルシリケ
ートは通常2〜6量体のオリゴマーとなっており、単量
体のテトラアルキルシランの含有率は低いものが良く、
これらアルキルシリケートはアルコールを放出しながら
ポリシロキサンとなるため、ポリシロキサンの皮膜形成
時にはピンホールを生じることが知られている。さらに
利点として反応後に珪酸ナトリウムのようにナトリウム
塩の残留が無く、乾燥するだけで好ましい形とすること
ができ、シランカップリング剤等によりさらなる表面改
質も容易に行うことができる。
The alkyl silicate used in the present invention is represented by the general formula (1), and the alkyl group is a linear or branched saturated alkyl group such as methyl, ethyl, propyl and isopropyl. These alkyl silicates may be one kind or a mixture of two or more kinds, but in view of the reactivity at a low temperature, a methyl or ethyl group alkyl silicate is preferable. These compounds easily undergo a dealcoholization reaction in the presence of moisture and become polysiloxane via a silanol group. Alkyl silicates are usually oligomers of 2 to 6 mer, and the content of monomeric tetraalkylsilane is preferably low,
Since these alkyl silicates become polysiloxanes while releasing alcohol, it is known that pinholes occur when a polysiloxane film is formed. As an additional advantage, there is no residual sodium salt like sodium silicate after the reaction, and it can be formed into a preferable form only by drying, and further surface modification can be easily performed by a silane coupling agent or the like.

【0009】アルキルシリケートは一般に市販されてい
るもので単量体であるテトラアルコキシシランが微量含
まれているもので良く、エチルシリケート40(コルコ
ート社製)、エチルシリケート40(多摩化学工業
(株)製)、MKCシリケートMS−51(三菱化学
(株)製)、MKCシリケートMS−56(三菱化学
(株)製)等が例示される。これらアルキルシリケート
は室温で無機酸化物と水中で混合することにより、無機
酸化物に多孔質の皮膜を形成する。この水中での反応は
酸性、アルカリ性のいずれでも進行するが、酸性での反
応がマイルドな反応となり反応後の塩類の残留も無く望
ましい。この時使用される酸としては塩酸が好ましい
が、硫酸、硝酸、りん酸等無機酸やその塩類、蟻酸、酢
酸、乳酸、シュウ酸、酒石酸等の有機酸またはその塩類
も使用出来る。
The alkyl silicate is generally commercially available and may contain a small amount of a monomer, tetraalkoxysilane. Ethyl silicate 40 (manufactured by Colcoat) and ethyl silicate 40 (manufactured by Tama Chemical Industry Co., Ltd.) MKC silicate MS-51 (manufactured by Mitsubishi Chemical Corporation), MKC silicate MS-56 (manufactured by Mitsubishi Chemical Corporation), and the like. These alkyl silicates form a porous film on the inorganic oxide by being mixed with the inorganic oxide at room temperature in water. The reaction in water proceeds under both acidic and alkaline conditions, but the acidic reaction is a mild reaction and desirably has no residual salts after the reaction. The acid used at this time is preferably hydrochloric acid, but inorganic acids such as sulfuric acid, nitric acid and phosphoric acid and salts thereof, and organic acids such as formic acid, acetic acid, lactic acid, oxalic acid and tartaric acid or salts thereof can also be used.

【0010】アルキルシリケートの使用量は無機酸化物
の重量に対し5〜50%のシリカが付着する量であり、
好ましくは5〜20%、より好ましくは7〜15%であ
る。付着するシリカ分がこれより少ないと併用される固
着剤等の分解変色を低減することが出来ず、これより多
くなると光触媒活性の低下が著しくなる。アルキルシリ
ケートは無機酸化物に直接添加しても良いが、いったん
水中でアルキルシリケートを部分加水分解をさせ添加す
る方法が好ましい。また経験的ではあるが、加水分解の
温度は室温で2時間程度が良く、40℃以上で過剰に加
水分解を進めるとバインダーの変色がやや大きくなる傾
向にある。加水分解時にはアルキルシリケートの水への
溶解性を高めるため、メチルアルコールやイソプロピル
アルコールのような低級アルコールを添加しておくこと
が望ましい。これらの反応は加熱の必要もなく室温で進
行し、2時間程度で性能的に十分な無機酸化物複合体を
形成する。生成した無機酸化物複合体は溶媒を除去して
も柔らかく容易に解砕出来るものであり、従来の無機顔
料の分散方法で分散出来るものである。
The amount of the alkyl silicate used is such that 5 to 50% of silica adheres to the weight of the inorganic oxide,
Preferably it is 5 to 20%, more preferably 7 to 15%. If the amount of silica adhered is smaller than this, the decomposition and discoloration of the fixing agent used in combination cannot be reduced, and if it is larger than this, the photocatalytic activity will be significantly reduced. The alkyl silicate may be added directly to the inorganic oxide, but a method in which the alkyl silicate is partially hydrolyzed once in water and then added is preferred. Although it is empirical, the hydrolysis temperature is preferably about 2 hours at room temperature, and if the hydrolysis proceeds excessively at 40 ° C. or more, the discoloration of the binder tends to be slightly larger. At the time of hydrolysis, it is desirable to add a lower alcohol such as methyl alcohol or isopropyl alcohol in order to increase the solubility of the alkyl silicate in water. These reactions proceed at room temperature without the need for heating, and form an inorganic oxide composite having sufficient performance in about 2 hours. The resulting inorganic oxide composite is soft and easily crushed even after the solvent is removed, and can be dispersed by a conventional inorganic pigment dispersion method.

【0011】この無機酸化物複合体は一般のアクリル樹
脂、ウレタン樹脂等のバインダーにより基材に固着する
ことができる。バインダーの種類は特に限定されないが
耐熱性、耐候性、耐NOx性の良いものが望ましいこと
は言うまでもなく、バインダーの使用量が多過ぎると分
解させる成分と無機酸化物複合体の接触が妨げられ、光
触媒性が発揮されないため必要最低量とすることが望ま
しい。基材へ付着させる方法としては、バインダーと無
機酸化物複合体を溶液の状態とし塗布することができ、
浸漬し乾燥する方法や、コーティング法等でフィルム、
繊維等に連続加工することも出来る。
The inorganic oxide composite can be fixed to the substrate by a general binder such as acrylic resin and urethane resin. The type of the binder is not particularly limited, but it is needless to say that heat resistance, weather resistance, and good NOx resistance are desirable.If the amount of the binder is too large, contact between the component to be decomposed and the inorganic oxide composite is hindered, Since the photocatalytic property is not exhibited, it is desirable to set the minimum amount. As a method of attaching to the substrate, the binder and the inorganic oxide composite can be applied in a solution state,
Dipping and drying methods, coating methods, etc.
It can be continuously processed into fibers and the like.

【0012】[0012]

【実施例】以下、本発明を実施例により更に詳細に説明
する。 (実施例1)メチルシリケートMS−51(三菱化学
(株)製)4.5重量部、メタノール7.5重量部、精
製水57.7重量部に0.5N塩酸0.15部を加えて
攪拌しておき、酸化チタン(AMT−600テイカ
(株)製)30重量部を徐々に加え室温で4時間攪拌し
分散液1を得た。
The present invention will be described in more detail with reference to the following examples. (Example 1) 0.15 part of 0.5N hydrochloric acid was added to 4.5 parts by weight of methyl silicate MS-51 (manufactured by Mitsubishi Chemical Corporation), 7.5 parts by weight of methanol, and 57.7 parts by weight of purified water. After stirring, 30 parts by weight of titanium oxide (manufactured by AMT-600 Teika Co., Ltd.) was gradually added, and the mixture was stirred at room temperature for 4 hours to obtain Dispersion 1.

【0013】(実施例2)メチルシリケートMS−51
(三菱化学(株)製)15重量部、メタノール25重量
部、精製水9重量部に0.5N塩酸0.5部を加え1時
間室温で攪拌した。この液をA−1液とする。上記A−
1液15重量部、精製水55部、を攪拌しておき酸化チ
タン(AMT−600テイカ(株)製)30重量部を徐
々に加え室温で2時間攪拌し分散液2を得た。
(Example 2) Methyl silicate MS-51
0.5 part of 0.5N hydrochloric acid was added to 15 parts by weight (manufactured by Mitsubishi Chemical Corporation), 25 parts by weight of methanol and 9 parts by weight of purified water, and the mixture was stirred at room temperature for 1 hour. This solution is referred to as A-1 solution. A-
15 parts by weight of one liquid and 55 parts by weight of purified water were stirred, and 30 parts by weight of titanium oxide (manufactured by AMT-600 Teika Co., Ltd.) was gradually added, followed by stirring at room temperature for 2 hours to obtain a dispersion 2.

【0014】(実施例3)メチルシリケートMS−51
(三菱化学(株)製)15重量部、メタノール25重量
部、精製水9重量部に0.5N塩酸0.5部を加え50
℃で2時間攪拌した。この溶液をA−2液とする。上記
A−2液15重量部、精製水55部、を攪拌しておき酸
化チタン(AMT−600テイカ(株)製)30重量部
を徐々に加え2時間室温で攪拌し分散液3を得た。
Example 3 Methyl silicate MS-51
0.5 part of 0.5N hydrochloric acid was added to 15 parts by weight (manufactured by Mitsubishi Chemical Corporation), 25 parts by weight of methanol, and 9 parts by weight of purified water to obtain 50 parts by weight.
Stirred at C for 2 hours. This solution is designated as solution A-2. 15 parts by weight of the above A-2 solution and 55 parts by weight of purified water were stirred, 30 parts by weight of titanium oxide (manufactured by AMT-600 Teica Co., Ltd.) was gradually added, and the mixture was stirred at room temperature for 2 hours to obtain a dispersion 3. .

【0015】(実施例4)上記A−1液30重量部、精
製水40部を攪拌しておき酸化チタン(AMT−600
テイカ(株)製)30重量部を徐々に加え室温で2時間
攪拌し分散液4を得た。
Example 4 Titanium oxide (AMT-600) was stirred with 30 parts by weight of the above-mentioned A-1 solution and 40 parts of purified water.
30 parts by weight (manufactured by Teika Co., Ltd.) were gradually added, and the mixture was stirred at room temperature for 2 hours to obtain a dispersion 4.

【0016】(実施例5)上記A−1液60重量部、精
製水10部を攪拌しておき酸化チタン(AMT−600
テイカ(株)製)30重量部を徐々に加え室温で2時間
攪拌し分散液5を得た。
(Example 5) Titanium oxide (AMT-600) was stirred with 60 parts by weight of the above A-1 solution and 10 parts of purified water.
30 parts by weight (manufactured by Teica Co., Ltd.) were gradually added, and the mixture was stirred at room temperature for 2 hours to obtain a dispersion liquid 5.

【0017】(実施例6)上記A−1液120重量部を
攪拌しておき酸化チタン(AMT−600テイカ(株)
製)30重量部を徐々に加え、室温で2時間攪拌し得ら
れた分散液を120℃で乾燥させ乳鉢で粉末とした。こ
の粉末48重量部を精製水52重量部に攪拌しながら添
加し分散液6を得た。
(Example 6) Titanium oxide (AMT-600 Teika Co., Ltd.)
30 parts by weight) was gradually added, and the mixture was stirred at room temperature for 2 hours, and the obtained dispersion was dried at 120 ° C. to obtain a powder in a mortar. 48 parts by weight of this powder was added to 52 parts by weight of purified water with stirring to obtain a dispersion 6.

【0018】(実施例7)上記(実施例2)で得られた
分散液2を120℃で乾燥させ乳鉢で粉末とした。この
粉末32重量部を水70重量部に攪拌しながら添加し分
散液6を得た。
(Example 7) The dispersion liquid 2 obtained in the above (Example 2) was dried at 120 ° C and made into a powder in a mortar. 32 parts by weight of this powder was added to 70 parts by weight of water with stirring to obtain a dispersion 6.

【0019】(実施例8)エチルシリケート40(多摩
化学工業(株)製)5.6重量部、メタノール7.5重
量部、精製水56.6重量部に0.5N塩酸0.15を
加え40℃で2時間攪拌しておき酸化チタン(AMT−
600テイカ(株)製)30重量部を徐々に加え4時間
室温で攪拌し分散液8を得た。
Example 8 0.5N hydrochloric acid 0.15 was added to 5.6 parts by weight of ethyl silicate 40 (manufactured by Tama Chemical Industry Co., Ltd.), 7.5 parts by weight of methanol and 56.6 parts by weight of purified water. After stirring at 40 ° C. for 2 hours, titanium oxide (AMT-
30 parts by weight (600 Teika Co., Ltd.) were gradually added, and the mixture was stirred at room temperature for 4 hours to obtain a dispersion liquid 8.

【0020】[0020]

【比較例1】酸化チタン(AMT−600テイカ(株)
製)を30重量部を攪拌しながら精製水70重量部に添
加し分散液9を得た。
Comparative Example 1 Titanium oxide (AMT-600 Teica Co., Ltd.)
Was added to 70 parts by weight of purified water while stirring 30 parts by weight to obtain a dispersion liquid 9.

【0021】[0021]

【比較例2】酸化チタン(TTO−55A石原産業
(株)製)を30重量部を攪拌しながら精製水70重量
部に添加し分散液10を得た。
Comparative Example 2 Titanium oxide (TTO-55A, manufactured by Ishihara Sangyo Co., Ltd.) was added to 70 parts by weight of purified water while stirring 30 parts by weight to obtain a dispersion 10.

【0022】(紫外線照射下でのバインダーの変色性テ
スト)上記分散液1〜10を50重量部、各バインダー
を50重量部を増粘剤1重量部を用い混合増粘し、ガラ
ス板の上にアプリケーターを用いて塗布し、120℃熱
風乾燥機を用いて乾燥させた。この塗膜の張ったガラス
板を紫外線照射強度(10mW/cm2)になるように
紫外線照射機に入れ30分間暴露試験を行った。紫外線
照射強度測定はUM−1(ミノルタ(株)製)を用い行
った。 評価 ○:バインダーの変色と同等 ×:バインダー以
上に変色が認められる。この結果を下記の表1に示す。
表中のウレタンはリケンレヂンR−95−74(三木理
研工業(株)製)、アクリルはリケンゾールA−263
(三木理研工業(株)製)を示す。
(Discoloration test of binder under ultraviolet irradiation) 50 parts by weight of the above dispersions 1 to 10 and 50 parts by weight of each binder were mixed and thickened using 1 part by weight of a thickener, and the mixture was thickened on a glass plate. Was applied using an applicator and dried using a 120 ° C. hot air dryer. The coated glass plate was placed in an ultraviolet irradiator so as to have an ultraviolet irradiation intensity (10 mW / cm 2) and subjected to an exposure test for 30 minutes. The UV irradiation intensity measurement was performed using UM-1 (manufactured by Minolta Co., Ltd.). Evaluation :: Same as discoloration of binder ×: Discoloration is recognized more than binder. The results are shown in Table 1 below.
In the table, urethane is Riken Resin R-95-74 (manufactured by Miki Riken Kogyo KK), and acrylic is Rikensol A-263.
(Miki Riken Kogyo Co., Ltd.).

【0023】[0023]

【表1】 [Table 1]

【0024】(タバコ消臭性テスト)上記分散液1〜1
0を7重量部、精製水93重量部を混合した溶液を調液
しておき綿金巾布をその溶液に浸漬し、余分な液をマン
グルを用い絞り除去しピンテンターを用い熱風乾燥(1
00℃2分)し加工布を得た。500mlのガラス製三
角フラスコを入口を下にして入口の直下に発煙している
紙巻タバコを5秒間置いた後、素早く三角フラスコを横
にして試料3gを投入しガラス栓で密封した。1時間放
置後ガラス栓を開け残臭を嗅いで評価した。 評価 ○:残臭がほとんどない。△:やや残臭がある。
×:残臭が大きい。この結果を下記の表2に示す。
(Tobacco deodorizing test) Dispersions 1 to 1
A solution prepared by mixing 7 parts by weight of 0 with 93 parts by weight of purified water was prepared, a cotton cloth was immersed in the solution, excess liquid was squeezed out using a mangle, and dried with hot air using a pin tenter (1).
(00 ° C. for 2 minutes) to obtain a work cloth. A 500 ml glass Erlenmeyer flask was placed with the inlet facing down, and a smoking cigarette was placed immediately below the inlet for 5 seconds. Then, the Erlenmeyer flask was quickly laid down and 3 g of a sample was charged and sealed with a glass stopper. After leaving for 1 hour, the glass stopper was opened and the residual odor was smelled for evaluation. Evaluation :: Almost no residual odor. Δ: Slight residual odor.
X: The residual odor is large. The results are shown in Table 2 below.

【0025】[0025]

【表2】 [Table 2]

【0026】(タバコ消臭性テスト2)バインダーを添
加した加工布のタバコ消臭性を調べるため表3の配合1
の溶液を調整し、各溶液を綿金巾布に浸漬し、余分な液
をマングルを用いて絞り除去し、ピンテンターを用い熱
風乾燥(100℃2分)し加工布を得た。500mlの
ガラス製三角フラスコの入口を下にして入口の直下に発
煙している紙巻タバコを5秒間置いた後、素早く三角フ
ラスコを横にして試料3gを投入しガラス栓で密封し
た。1時間放置後ガラス栓を開け残臭を嗅いで評価し
た。
(Tobacco deodorant test 2) Formulation 1 shown in Table 3 to examine the tobacco deodorant properties of the processed cloth to which the binder was added
Was prepared, and each solution was immersed in a cotton cloth, excess liquid was removed by squeezing using a mangle, and dried with hot air (100 ° C. for 2 minutes) using a pin tenter to obtain a processed cloth. A 500-ml glass Erlenmeyer flask was placed with the inlet facing downward, and a smoking cigarette was placed immediately below the inlet for 5 seconds. Then, the Erlenmeyer flask was quickly laid down and 3 g of a sample was charged and sealed with a glass stopper. After leaving for 1 hour, the glass stopper was opened and the residual odor was smelled for evaluation.

【0027】[0027]

【表3】 [Table 3]

【0028】評価 ○:残臭がほとんどない。△:やや
残臭がある。×:残臭が大きい。この結果を表4に示
す。
Evaluation :: Almost no residual odor. Δ: Slight residual odor. X: The residual odor is large. Table 4 shows the results.

【0029】[0029]

【表4】 [Table 4]

【0030】(アンモニア、メチルメルカプタンの消臭
テスト)前記分散液2を7重量部、精製水93重量部を
混合した溶液を調液しておき、綿金巾布をその液に浸漬
し、余分な液をマングルを用いて絞り除去し、ピンテン
ターを用い熱風乾燥(100℃2分)を行い、その後ベ
ーキング(170℃30秒)を行い加工布を得た。2l
のデシケーターに各種ガスを入れて初期濃度を計り、試
料を投入し経時でのガス濃度を測定した。表中の単位は
ppmであり測定は検知管によりおこなった。この結果
を表5、表6に示す。
(Deodorizing test of ammonia and methyl mercaptan) A solution prepared by mixing 7 parts by weight of the dispersion 2 and 93 parts by weight of purified water was prepared, and a cotton cloth was immersed in the liquid. The solution was squeezed and removed using a mangle, dried with hot air (100 ° C. for 2 minutes) using a pin tenter, and then baked (170 ° C. for 30 seconds) to obtain a work cloth. 2l
Of various gases were put into a desiccator, and the initial concentration was measured. Then, a sample was put into the desiccator, and the gas concentration over time was measured. The unit in the table is ppm, and the measurement was performed using a detector tube. The results are shown in Tables 5 and 6.

【0031】[0031]

【表5】 [Table 5]

【表6】 [Table 6]

【0032】[0032]

【発明の効果】本発明によれば固着方法、固着剤等を限
定することなく従来の固着方法で使用出来る光酸化触媒
性を持つ無機酸化物複合体とすることができ、日光、蛍
光灯等、紫外線照射下に起こる酸化分解反応の触媒とし
て生活臭やたばこ臭の消臭剤や化学分解触媒、除菌など
の目的に使用することができる。
According to the present invention, it is possible to obtain an inorganic oxide composite having photooxidation catalytic properties which can be used in the conventional fixing method without limiting the fixing method, fixing agent, etc. It can be used as a catalyst for an oxidative decomposition reaction that occurs under irradiation with ultraviolet light, for a deodorant for living odor or tobacco odor, for a chemical decomposition catalyst, for disinfection, and the like.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 三木 保二 和歌山県和歌山市栄谷13−1 三木理研工 業株式会社研究所内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Yoji Miki 13-1 Sakaeya, Wakayama-shi, Wakayama Pref.

Claims (10)

【特許請求の範囲】[Claims] 【請求項1】 光触媒作用を有する無機酸化物の一般式
(1)に示されるアルキルシリケートでコーティングし
てなる無機酸化物複合体。 【化1】 n=0以上の整数、R=炭素数1〜4の直鎖または分岐
のある飽和アルキル基
1. An inorganic oxide composite obtained by coating a photocatalytic inorganic oxide with an alkyl silicate represented by the general formula (1). Embedded image n is an integer of 0 or more, and R is a linear or branched saturated alkyl group having 1 to 4 carbon atoms.
【請求項2】 光触媒作用を有する無機酸化物の一般式
(1)に示されるアルキルシリケートでコーティングし
てなる無機酸化物複合体の製造方法。 【化2】 n=0以上の整数、R=炭素数1〜4の直鎖または分岐
のある飽和アルキル基
2. A method for producing an inorganic oxide composite in which a photocatalytic inorganic oxide is coated with an alkyl silicate represented by the general formula (1). Embedded image n is an integer of 0 or more, and R is a linear or branched saturated alkyl group having 1 to 4 carbon atoms.
【請求項3】 光触媒作用を有する無機酸化物が酸化チ
タンである請求項1記載の無機酸化物複合体。
3. The inorganic oxide composite according to claim 1, wherein the inorganic oxide having a photocatalytic action is titanium oxide.
【請求項4】 光触媒作用を有する無機酸化物が酸化チ
タンである請求項2記載の無機酸化物複合体の製造方
法。
4. The method for producing an inorganic oxide composite according to claim 2, wherein the inorganic oxide having a photocatalytic action is titanium oxide.
【請求項5】 光触媒作用を有する無機酸化物が酸化チ
タンでありかつTiO2:SiO2の重量比が95:5〜
50:50となっているSiO2の付着率が高い請求項
1記載の無機酸化物複合体。
5. An inorganic oxide having a photocatalytic action is titanium oxide, and a weight ratio of TiO2: SiO2 is 95: 5-5.
2. The inorganic oxide composite according to claim 1, wherein the adhesion ratio of SiO2, which is 50:50, is high.
【請求項6】 光触媒作用を有する無機酸化物が酸化チ
タンでありかつTiO2:SiO2の重量比が95:5〜
50:50となっているSiO2の付着率が高い請求項
1記載の無機酸化物複合体の製造方法。
6. An inorganic oxide having a photocatalytic action is titanium oxide, and the weight ratio of TiO2: SiO2 is 95: 5-5.
The method for producing an inorganic oxide composite according to claim 1, wherein the adhesion ratio of SiO2 of 50:50 is high.
【請求項7】 光触媒作用を有する無機酸化物が酸化チ
タンであり、かつ一般式(1)のアルキルシリケートが
n=0のテトラアルコキシシランの含有量が1%未満の
アルキルシリケートでありかつTiO2:SiO2の重量
比が95:5〜50:50となっているSiO2の付着
率が高い請求項1記載の無機酸化物複合体。 【化3】 n=0以上の整数、R=炭素数1〜4の直鎖または分岐
のある飽和アルキル基
7. The photocatalytic inorganic oxide is titanium oxide, the alkyl silicate of the general formula (1) is an alkyl silicate having a content of n = 0 of tetraalkoxysilane of less than 1%, and TiO 2: 2. The inorganic oxide composite according to claim 1, wherein the weight ratio of SiO2 is 95: 5 to 50:50, and the adhesion ratio of SiO2 is high. Embedded image n is an integer of 0 or more, and R is a linear or branched saturated alkyl group having 1 to 4 carbon atoms.
【請求項8】 光触媒作用を有する無機酸化物が酸化チ
タンであり、かつ一般式(1)のアルキルシリケートが
n=0のテトラアルコキシシランの含有量が1%未満の
アルキルシリケートでありかつTiO2:SiO2の重量
比が95:5〜50:50となっているSiO2の付着
率が高い請求項1記載の無機酸化物複合体の製造方法。 【化4】 n=0以上の整数、R=炭素数1〜4の直鎖または分岐
のある飽和アルキル基
8. The photocatalytic inorganic oxide is titanium oxide, the alkyl silicate of the general formula (1) is an alkyl silicate having a content of n = 0 of a tetraalkoxysilane of less than 1%, and TiO 2: The method for producing an inorganic oxide composite according to claim 1, wherein the adhesion ratio of SiO2 having a weight ratio of SiO2 of 95: 5 to 50:50 is high. Embedded image n is an integer of 0 or more, and R is a linear or branched saturated alkyl group having 1 to 4 carbon atoms.
【請求項9】 光触媒作用を有する無機酸化物が酸化チ
タンであり、かつ一般式(1)のアルキルシリケートの
アルキル基がメチルまたはエチル基であってn=0の当
該テトラアルコキシシランの含有量が1%未満のアルキ
ルシリケートでありかつTiO2:SiO2の重量比が9
5:5〜50:50となっているSiO2の付着率が高
い請求項1記載の無機酸化物複合体。 【化5】 n=0以上の整数、R=炭素数1〜4の直鎖または分岐
のある飽和アルキル基
9. The inorganic oxide having a photocatalytic action is titanium oxide, and the content of the tetraalkoxysilane in which the alkyl group of the alkyl silicate of the general formula (1) is a methyl or ethyl group and n = 0. Less than 1% alkyl silicate and a weight ratio of TiO2: SiO2 of 9
The inorganic oxide composite according to claim 1, wherein the SiO2 adhesion ratio of 5: 5 to 50:50 is high. Embedded image n is an integer of 0 or more, and R is a linear or branched saturated alkyl group having 1 to 4 carbon atoms.
【請求項10】 光触媒作用を有する無機酸化物が酸化
チタンであり、かつ一般式(1)のアルキルシリケート
のアルキル基がメチルまたはエチル基であってn=0の
当該テトラアルコキシシランの含有量が1%未満のアル
キルシリケートでありかつTiO2:SiO2の重量比が
95:5〜50:50となっているSiO2の付着率が
高い請求項1記載の無機酸化物複合体の製造方法。 【化6】 n=0以上の整数、R=炭素数1〜4の直鎖または分岐
のある飽和アルキル基
10. The inorganic oxide having a photocatalytic action is titanium oxide, and the content of the tetraalkoxysilane in which the alkyl group of the alkyl silicate of the general formula (1) is a methyl or ethyl group and n = 0. The method for producing an inorganic oxide composite according to claim 1, wherein the adhesion ratio of SiO2, which is an alkyl silicate of less than 1% and the weight ratio of TiO2: SiO2 is 95: 5 to 50:50, is high. Embedded image n is an integer of 0 or more, and R is a linear or branched saturated alkyl group having 1 to 4 carbon atoms.
JP8194282A 1996-07-24 1996-07-24 Inorganic oxide composite and its producing process Pending JPH1033988A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8194282A JPH1033988A (en) 1996-07-24 1996-07-24 Inorganic oxide composite and its producing process

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8194282A JPH1033988A (en) 1996-07-24 1996-07-24 Inorganic oxide composite and its producing process

Publications (1)

Publication Number Publication Date
JPH1033988A true JPH1033988A (en) 1998-02-10

Family

ID=16322017

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JPH1033988A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6274399B1 (en) * 1998-06-05 2001-08-14 Lumileds Lighting, U.S. Llc Method of strain engineering and impurity control in III-V nitride semiconductor films and optoelectronic devices
JP2007016111A (en) * 2005-07-07 2007-01-25 Tayca Corp Silica-covered particulate titanium oxide or silica-covered particulate zinc oxide, manufacturing method thereof, water dispersion thereof, and cosmetics blended therewith
JP2011256367A (en) * 2010-05-10 2011-12-22 Natoko Kk Oligomer coated metal oxide fine particle
US11313700B2 (en) 2018-03-01 2022-04-26 Allegro Microsystems, Llc Magnetic field influence during rotation movement of magnetic target

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6274399B1 (en) * 1998-06-05 2001-08-14 Lumileds Lighting, U.S. Llc Method of strain engineering and impurity control in III-V nitride semiconductor films and optoelectronic devices
JP2007016111A (en) * 2005-07-07 2007-01-25 Tayca Corp Silica-covered particulate titanium oxide or silica-covered particulate zinc oxide, manufacturing method thereof, water dispersion thereof, and cosmetics blended therewith
JP2011256367A (en) * 2010-05-10 2011-12-22 Natoko Kk Oligomer coated metal oxide fine particle
US11313700B2 (en) 2018-03-01 2022-04-26 Allegro Microsystems, Llc Magnetic field influence during rotation movement of magnetic target

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