JP4520175B2 - Photocatalyst - Google Patents
Photocatalyst Download PDFInfo
- Publication number
- JP4520175B2 JP4520175B2 JP2004035634A JP2004035634A JP4520175B2 JP 4520175 B2 JP4520175 B2 JP 4520175B2 JP 2004035634 A JP2004035634 A JP 2004035634A JP 2004035634 A JP2004035634 A JP 2004035634A JP 4520175 B2 JP4520175 B2 JP 4520175B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- photocatalyst
- groups
- photocatalytic
- compound
- 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.)
- Expired - Fee Related
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- 125000003277 amino group Chemical group 0.000 claims description 8
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- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 5
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- 235000014113 dietary fatty acids Nutrition 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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Landscapes
- Catalysts (AREA)
Description
本発明は、悪臭や空気中の有害物質除去あるいは廃水処理や浄水処理などを行うための環境浄化材料として好適に用いられる多孔質光触媒体及びその前駆体である光触媒体に関するものである。 The present invention relates to a porous photocatalyst that is suitably used as an environmental purification material for removing bad odors and harmful substances in the air, wastewater treatment or water purification, and a photocatalyst that is a precursor thereof.
近年、居住空間や作業空間での悪臭や自動車の排気ガスなどの有害物質による汚染が深刻な問題となっている。また、生活排水や産業廃水などによる水質汚染、特に、現在行われている活性汚泥法などの水処理法では処理が難しい有機塩素系の溶剤やゴルフ場の農薬などによる水源の汚染なども広範囲に進んでおり、環境の汚染が重大な社会問題となっている。
従来、空気中の有害物質の除去法として、酸やアルカリなどの吸収液や、吸着剤、土壌などに吸収あるいは吸着させる方法がよく行われているが、この方法は廃液や使用済みの吸着剤や土壌の処理が問題で、二次公害を起こす恐れがある。また、芳香剤を使用して悪臭を隠ぺいする方法や、活性汚泥やオゾンで分解する方法もあるが、芳香剤の場合には芳香剤自体の臭いによる汚染の問題があり、活性汚泥の場合には処理能力が低く、かつ汚泥臭の発散が避けられず、オゾンの場合には有毒でコストがかかるという欠点を持っている
In recent years, foul odors in living spaces and work spaces and contamination by harmful substances such as automobile exhaust gas have become serious problems. In addition, water pollution due to domestic wastewater and industrial wastewater, especially water source contamination due to organic chlorine solvents and golf course pesticides that are difficult to treat with the current water treatment methods such as the activated sludge method, are widespread. Advanced and environmental pollution is a serious social problem.
Conventionally, as a method for removing harmful substances in the air, an absorbing solution such as acid or alkali, an adsorbent, or a method of absorbing or adsorbing to soil, etc., is often used, but this method is a waste liquid or a used adsorbent. There is a risk of secondary pollution due to the treatment of soil and soil. There are also methods of concealing bad odors using fragrances and methods of decomposing with activated sludge and ozone, but in the case of fragrances, there is a problem of contamination due to the odor of the fragrance itself, and in the case of activated sludge Has the disadvantages of low processing capacity, the inevitable emission of sludge odor, and the toxicity and cost of ozone.
これらの課題に対して、光触媒を利用した環境浄化が注目されている。これは、酸化チタン等の光触媒性物質が、特定波長の光照射により酸化作用が活性化され、悪臭や有害物質(水中に溶解している有機溶剤や農薬、界面活性剤などの環境汚染物質や空気中の有害化学物質など)を速やかに分解することを利用するものであり、生活環境の様々な場面における浄化が可能となる。この方法は光触媒と光を利用するだけであり、微生物を用いる生物処理などの方法に比べて、温度、pH、ガス雰囲気、毒性などの反応条件の制約が少なく、しかも生物処理法では処理しにくい有機ハロゲン化合物や有機リン化合物のようなものでも容易に分解・除去できるという長所を持っている。しかし、これまで行われてきた光触媒による有機物の分解除去の研究では、光触媒として粉末が用いられていたが、解決すべき課題があった。即ち、光触媒粉末の粒径が大きいと表面積が小さくなり分解の効率が非常に悪く光触媒粉末の粒径を小さくして表面積を大きくすると取扱いや使用が難しいという課題である。特に、水処理の場合、光触媒粉末を回収するため、処理した水を濾過しなければならないが、光触媒が微粉末であると目詰まりを起こしたりして、濾過が容易でなく、処理物と光触媒との分離や回収が困難で、連続的に水処理できないなどの問題があった。 For these problems, environmental purification using a photocatalyst has attracted attention. This is because photocatalytic substances such as titanium oxide are activated by the irradiation of light of a specific wavelength, and bad odors and harmful substances (organic pollutants dissolved in water, agricultural chemicals, surfactants and other environmental pollutants) It uses rapid decomposition of harmful chemical substances in the air, etc., and can be purified in various scenes of the living environment. This method only uses a photocatalyst and light, and there are fewer restrictions on reaction conditions such as temperature, pH, gas atmosphere, toxicity, etc. compared to methods such as biological treatment using microorganisms, and it is difficult to treat with biological treatment methods. It has the advantage that it can be easily decomposed and removed even with organic halogen compounds and organophosphorus compounds. However, in the research on the decomposition and removal of organic substances by the photocatalyst so far, powder was used as the photocatalyst, but there was a problem to be solved. That is, when the particle size of the photocatalyst powder is large, the surface area becomes small and the efficiency of decomposition is very poor. When the particle size of the photocatalyst powder is reduced and the surface area is increased, handling and use are difficult. In particular, in the case of water treatment, the treated water must be filtered in order to recover the photocatalyst powder. However, if the photocatalyst is a fine powder, clogging may occur, and filtration is not easy. It was difficult to separate and recover from water, and it was impossible to continuously treat water.
これらの課題に対し、例えば特開平6−298520号公報には、シリカゲル表面に酸化チタン光触媒をコーティングする方法、即ち酸化チタン超微粒子をシリカコロイドに分散した後、コロイドをゲル化し、次いで焼成することで酸化チタン超微粒子を分散状態で含むシリカゲルを製造する方法を用いることで、量子閉じ込め効果を有する透明性良好な酸化チタン超微粒子分散シリカゲルを、容易に入手可能な原料を用いて簡単な操作で効率良く得られることが記載されている。
しかし、この方法に置いては、光触媒ゾル中へのディップコーティング等によりシリカゲル表面を直接光触媒コーティングする場合、急激な水分吸収によるシリカゲルの膨張と吸着による発熱とが発生し、割れが生じて粉砕された状態となり、生産効率良く目的物を得ることが困難であるという課題があった。
In response to these problems, for example, JP-A-6-298520 discloses a method of coating a silica gel surface with a titanium oxide photocatalyst, that is, after dispersing ultrafine titanium oxide particles in a silica colloid, the colloid is gelled and then fired. By using a method for producing silica gel containing titanium oxide ultrafine particles in a dispersed state, titanium oxide ultrafine particle dispersed silica gel having a quantum confinement effect and good transparency can be easily obtained using readily available raw materials. It is described that it can be obtained efficiently.
However, in this method, when the silica gel surface is directly photocatalyzed by dip coating or the like in the photocatalyst sol, the silica gel expands due to rapid moisture absorption and heat is generated due to adsorption. There was a problem that it was difficult to obtain the target product with high production efficiency.
また、特開平8−103631号公報では、環境浄化に有用な光触媒材料として、チタンのアルコキシドとアルコールアミン類などから調製されたチタニアゾルあるいはそれにポリエチレングリコールまたはポリエチレンオキサイドを添加したものをコーティングした後、室温から徐々に600℃から700℃の最終温度にまで加熱昇温して焼成することにより製造される、表面が孔径の揃った細孔を有するアナターゼの酸化チタン膜で覆われたガラスフィルターを提案している。
しかし、この方法では製造方法が煩雑な上、耐熱性の良好な部材にしか多孔質の酸化チタンを固定化できないという欠点があった。
However, this method has a drawback that the manufacturing method is complicated and porous titanium oxide can be fixed only to a member having good heat resistance.
本発明の課題は、悪臭や空気中の有害物質除去あるいは廃水処理や浄水処理などを連続的に行うことができ、環境浄化材料として環境汚染物質の分解除去効果とその持続性に優れ、しかも適用する部材の選択範囲が広く、経済性、安全性、耐候性、安定性という面からも優れた特性を有する多孔質光触媒体及びその前駆体である光触媒体の提供することである。 The object of the present invention is to be able to continuously remove bad odors and harmful substances in the air, waste water treatment or water purification treatment, etc., and is excellent in the effect of decomposition and removal of environmental pollutants and its sustainability as an environmental purification material. The object of the present invention is to provide a porous photocatalyst having a wide selection range of members and having excellent characteristics in terms of economy, safety, weather resistance, and stability, and a photocatalyst that is a precursor thereof.
本発明者らは鋭意検討した結果、本発明をなすに至った。すなわち、本発明は以下の通りである。
発明の第1は、光触媒(a)と該光触媒への親和力が強く、光触媒作用によって分解される光触媒親和性有機成分(B)と光触媒作用により容易に分解しない難分解成分(C)とが結合した複合化合物(BC)を含有する光触媒体であって、該複合化合物(BC)が式(3)及び/または式(4)で表される光触媒親和性有機基(Q)を有するSi−H基含有化合物であることを特徴とする環境浄化材料用光触媒体である。
H−(R2SiO)m−SiR2−Q (3)
(式中、Rは各々独立して直鎖状または分岐状の炭素数が1〜30個のアルキル基、炭素数5〜20のシクロアルキル基、直鎖状または分岐状の炭素数が1〜30個のフルオロアルキル基、炭素数2〜30のアルケニル基、フェニル基、炭素数1〜20のアルコキシ基、水酸基から選ばれた1種以上からなる基を表す。
また、式中Qは下記(あ)〜(い)からなる群より選ばれる少なくとも1つの光触媒親和性有機基を含有する基である。
(あ)カルボキシル基あるいはその塩、リン酸基あるいはその塩、スルホン酸基あるいはその塩、アミノ基あるいはその塩、ポリオキシアルキレン基からなる群から選ばれた少なくとも1つの親水性基。
(い)エポキシ基、アクリロイル基、メタアクリロイル基、(環状)酸無水物基、ケト基、カルボキシル基、ヒドラジン残基、イソシアネート基、イソチオシアネート基、水酸基、アミノ基、環状カーボネート基、チオール基、エステル基からなる群から選ばれた少なくとも1つの反応性基。
mは整数であり、0≦m≦1000である。)
(RHSiO)p(R2SiO)q(RQSiO)r(R3SiO1/2)s (4)
(式中、RおよびQは式(3)で定義した通りである。
pは1以上の整数であり、q及びrは0又は1以上の整数であり、(p+q+r)≦10000であり、そしてsは0又は2である。但し、(p+q+r)が2以上の整数であり且つs=0の場合、該Hシリコーン化合物は環状シリコーン化合物であり、s=2の場合、該Hシリコーン化合物は鎖状シリコーン化合物である。)
As a result of intensive studies, the present inventors have made the present invention. That is, the present invention is as follows.
In the first aspect of the invention, the photocatalyst (a) has a strong affinity for the photocatalyst, and the photocatalytic affinity organic component (B) decomposed by the photocatalytic action is combined with the hardly decomposable component (C) that is not easily decomposed by the photocatalytic action. A photocatalyst containing the composite compound (BC), wherein the composite compound (BC) has a photocatalytic affinity organic group (Q) represented by formula (3) and / or formula (4) A photocatalyst for an environmental purification material , which is a group-containing compound.
H- (R 2 SiO) m- SiR 2 -Q (3)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon number of 1 to 1. It represents a group consisting of at least one selected from 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.
In the formula, Q is a group containing at least one photocatalytic affinity organic group selected from the group consisting of the following (a) to (ii).
(A) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an amino group or a salt thereof, and a polyoxyalkylene group.
(Ii) Epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups;
m is an integer, and 0 ≦ m ≦ 1000. )
(RHSiO) p (R 2 SiO ) q (RQSiO) r (R 3 SiO 1/2) s (4)
(Wherein R and Q are as defined in formula (3)).
p is an integer of 1 or more, q and r are 0 or an integer of 1 or more, (p + q + r) ≦ 10000, and s is 0 or 2. However, when (p + q + r) is an integer of 2 or more and s = 0, the H silicone compound is a cyclic silicone compound, and when s = 2, the H silicone compound is a chain silicone compound. )
発明の第2は、光触媒(a)のバンドギャップエネルギーよりも高いエネルギーの光を照射することによりBET表面積が10m2/g以上増加することを特徴とする第1の光触媒体である。
発明の第3は、発明の第1又は2の光触媒体が固定化されてなる環境浄化材料用光触媒部材である。
A second aspect of the invention is a first photocatalyst characterized in that the BET surface area is increased by 10 m 2 / g or more by irradiating light having energy higher than the band gap energy of the photocatalyst (a).
A third aspect of the invention is a photocatalyst member for an environmental purification material in which the first or second photocatalyst of the invention is fixed.
発明の第4は、発明の第1〜第3のいずれかの光触媒体に、含有する光触媒(a)のバンドギャップエネルギーよりも高いエネルギーの光を照射することにより生成する環境浄化材料用多孔質光触媒体である。
発明の第5は、発明の第4の多孔質光触媒体が固定化されてなる環境浄化材料用多孔質光触媒部材である。
A fourth aspect of the invention is a porous material for an environmental purification material produced by irradiating light of energy higher than the band gap energy of the photocatalyst (a) contained in any one of the first to third photocatalysts of the invention. It is a photocatalyst.
5th of this invention is the porous photocatalyst member for environmental purification materials by which the 4th porous photocatalyst body of this invention is fix | immobilized.
本発明の光触媒体からは、光照射という簡単な操作で、環境浄化材料として優れた性能を有する多孔質光触媒体を得ることができる。 From the photocatalyst of the present invention, a porous photocatalyst having excellent performance as an environmental purification material can be obtained by a simple operation of light irradiation.
以下、本発明について詳述する。
本発明の光触媒体は、該光触媒体に含まれる光触媒のバンドギャップエネルギーよりも高いエネルギーの光を照射することによりBET表面積が10m2/g以上増加することを特徴とする。本発明の光触媒体からは、上記光照射により、好適には環境浄化機能に優れた多孔質光触媒体が形成される。
本発明の光触媒体は、好ましくは光触媒(a)と該光触媒への親和力が強く、光触媒作用によって分解される光触媒親和性有機成分(B)、及び光触媒作用により容易に分解しない難分解成分(C)とを含有する。この様な光触媒体は、光触媒のバンドギャップエネルギーよりも高いエネルギーの光照射により、光触媒に近接する光触媒親和性有機成分(B)が効率的、かつ選択的に分解され、難分解成分(C)の存在によって光触媒体がバラバラに分解することを防止するため、外観の構造変化がほとんど無くBET表面積が増加することができる。
Hereinafter, the present invention will be described in detail.
The photocatalyst of the present invention is characterized in that the BET surface area is increased by 10 m 2 / g or more by irradiating light having energy higher than the band gap energy of the photocatalyst contained in the photocatalyst. From the photocatalyst of the present invention, a porous photocatalyst having an excellent environmental purification function is preferably formed by the light irradiation.
The photocatalyst of the present invention preferably has a photocatalyst (a) and a photocatalytic affinity organic component (B) which has a strong affinity for the photocatalyst and is decomposed by the photocatalytic action, and a hardly decomposable component (C ) And. In such a photocatalyst, the photocatalytic affinity organic component (B) adjacent to the photocatalyst is efficiently and selectively decomposed by light irradiation with energy higher than the band gap energy of the photocatalyst, and the hardly decomposable component (C) In order to prevent the photocatalyst from being decomposed apart due to the presence of, there is almost no change in the structure of the appearance, and the BET surface area can be increased.
本発明の光触媒体において、光触媒(a)と、光触媒親和性有機成分(B)と難分解成分(C)が結合した複合化合物(BC)とを含有するものは、上記光照射によるBET表面積の増加が大きく、生成する空孔の均一性にも優れるため好ましい。
また、本発明の光触媒体において、上記複合化合物(BC)で光触媒(a)が変性処理された変性光触媒(A)を含有するものは、上記光照射によるBET表面積の増加が非常に大きく、生成する空孔の均一性にも優れ、また、後述する種々の部材への固定化が容易であるため最も好ましい。
ここで、上記変性処理とは、上記複合化合物(BC)を、光触媒(a)の表面に固定化することを意味する。複合化合物(BC)の光触媒粒子の表面への固定化は、ファン・デル・ワールス力(物理吸着)、クーロン力または化学結合によるものである。特に、化学結合を利用した変性は、複合化合物(BC)と光触媒との相互作用が強く、複合化合物(BC)が光触媒粒子の表面に強固に固定化されるので好ましい。
In the photocatalyst body of the present invention, the one containing the photocatalyst (a), the composite compound (BC) in which the photocatalytic affinity organic component (B) and the hardly decomposable component (C) are bonded, It is preferable because the increase is large and the uniformity of generated holes is excellent.
Further, in the photocatalyst of the present invention, the composite compound (BC) containing the modified photocatalyst (A) obtained by modifying the photocatalyst (a) has a very large increase in BET surface area due to the light irradiation. It is most preferable because it is excellent in uniformity of pores to be formed and is easy to fix to various members described later.
Here, the modification treatment means immobilizing the composite compound (BC) on the surface of the photocatalyst (a). Immobilization of the composite compound (BC) on the surface of the photocatalyst particles is due to van der Waals force (physical adsorption), Coulomb force or chemical bonding. In particular, modification using a chemical bond is preferable because the interaction between the composite compound (BC) and the photocatalyst is strong and the composite compound (BC) is firmly immobilized on the surface of the photocatalyst particles.
本発明において上記光触媒(a)とは、光照射によって酸化、還元反応を起こす物質のことを言う。すなわち伝導帯と価電子帯との間のエネルギーギャップよりも大きなエネルギー(すなわち短い波長)の光(励起光)を照射したときに、価電子帯中の電子の励起(光励起)が生じて、伝導電子と正孔を生成しうる物質であり、このとき、伝導帯に生成した電子の還元力および/または価電子帯に生成した正孔の酸化力を利用して、種々の化学反応を行うことができる。例えば、種々の有機物の酸化分解反応を挙げることができる。 In the present invention, the photocatalyst (a) refers to a substance that undergoes an oxidation or reduction reaction upon irradiation with light. That is, when light (excitation light) with an energy larger than the energy gap between the conduction band and the valence band (ie, a short wavelength) is irradiated, excitation (photoexcitation) of electrons in the valence band occurs, resulting in conduction. It is a substance that can generate electrons and holes. At this time, various chemical reactions are performed using the reducing power of electrons generated in the conduction band and / or the oxidizing power of holes generated in the valence band. Can do. For example, oxidative decomposition reaction of various organic substances can be mentioned.
光触媒(a)としては、例えば、TiO2、ZnO、SrTiO3、CdS、GaP、InP、GaAs、BaTiO3、BaTiO4、BaTi4O9、K2NbO3、Nb2O5、Fe2O3、Ta2O5、K3Ta3Si2O3、WO3、SnO2、Bi2O3、BiVO4、NiO、Cu2O、SiC、MoS2、InPb、RuO2、CeO2、Ta3N5等、さらにはTi、Nb、Ta、Vから選ばれた少なくとも1種の元素を有する層状酸化物(例えば特開昭62−74452号公報、特開平2−172535号公報、特開平7−24329号公報、特開平8−89799号公報、特開平8−89800号公報、特開平8−89804号公報、特開平8−198061号公報、特開平9−248465号公報、特開平10−99694号公報、特開平10−244165号公報等参照)を挙げることができる。 Examples of the photocatalyst (a) include TiO 2 , ZnO, SrTiO 3 , CdS, GaP, InP, GaAs, BaTiO 3 , BaTiO 4 , BaTi 4 O 9 , K 2 NbO 3 , Nb 2 O 5 , Fe 2 O 3. , Ta 2 O 5 , K 3 Ta 3 Si 2 O 3 , WO 3 , SnO 2 , Bi 2 O 3 , BiVO 4 , NiO, Cu 2 O, SiC, MoS 2 , InPb, RuO 2 , CeO 2 , Ta 3 N 5, etc., further Ti, Nb, Ta, layered oxide containing at least one element selected from V (for example, JP 62-74452, JP-a No. 2-172535, JP-a No. 7- No. 24329, JP-A-8-89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, JP-A No. -248465, JP-A No. 10-99694 and JP-reference Publication No. Hei 10-244165) can be mentioned.
これらの光触媒(a)の中でTiO2(酸化チタン)は無害であり、化学的安定性にも優れるため好ましい。酸化チタンとしては、アナターゼ、ルチル、ブルッカイトのいずれも使用できる。
また、本発明に使用する光触媒(a)として、可視光(例えば約400〜800nmの波長)の照射により光触媒活性及び/又は親水性を発現することが出来る可視光応答型光触媒を選択すると、本発明の防汚被覆用組成物で処理された防汚性部材は、室内等の紫外線が十分に照射されない場所等においても防汚効果を十分に発現することが出来るため好ましい。
Of these photocatalysts (a), TiO 2 (titanium oxide) is preferable because it is harmless and has excellent chemical stability. Any of anatase, rutile, and brookite can be used as titanium oxide.
When a visible light responsive photocatalyst capable of expressing photocatalytic activity and / or hydrophilicity by irradiation with visible light (for example, a wavelength of about 400 to 800 nm) is selected as the photocatalyst (a) used in the present invention, The antifouling member treated with the antifouling coating composition of the invention is preferable because it can sufficiently exhibit the antifouling effect even in places such as indoors where ultraviolet rays are not sufficiently irradiated.
上記可視光応答型光触媒は、可視光で光触媒活性及び/又は親水性を発現するものであれば全て使用することが出来るが、例えばTaON、LaTiO2N、CaNbO2N、LaTaON2、CaTaO2N等のオキシナイトライド化合物(例えば特開2002−66333号公報参照)やSm2Ti2S2O7等のオキシサルファイド化合物(例えば特開2002−233770号公報参照)、Ta3N5等の窒化化合物、CaIn2O4、SrIn2O4、ZnGa2O4、Na2Sb2O6等のd10電子状態の金属イオンを含む酸化物(例えば特開2002−59008号公報参照)、アンモニアや尿素等の窒素含有化合物存在下でチタン酸化物前駆体(オキシ硫酸チタン、塩化チタン、アルコキシチタン等)や高表面酸化チタンを焼成して得られる窒素ドープ酸化チタン(例えば特開2002−29750号公報、特開2002−87818号公報、特開2002−154823号公報、特開2001−207082号公報参照)、チオ尿素等の硫黄化合物存在下にチタン酸化物前駆体(オキシ硫酸チタン、塩化チタン、アルコキシチタン等)を焼成して得られる硫黄ドープ酸化チタン、酸化チタンを水素プラズマ処理したり真空下で加熱処理したりすることによって得られる酸素欠陥型の酸化チタン(例えば特開2001−98219号公報参照)、さらには光触媒粒子をハロゲン化白金化合物で処理したり(例えば特開2002−239353号公報参照)、タングステンアルコキシドで処理(特開2001−286755号公報参照)することによって得られる表面処理光触媒等を好適に挙げることができる。 Any visible light responsive photocatalyst can be used as long as it exhibits photocatalytic activity and / or hydrophilicity with visible light. For example, TaON, LaTiO 2 N, CaNbO 2 N, LaTaON 2 , and CaTaO 2 N can be used. Oxynitride compounds such as JP-A-2002-66333, oxysulfide compounds such as Sm 2 Ti 2 S 2 O 7 (see JP-A-2002-233770, for example), and nitriding such as Ta 3 N 5 Compounds, oxides containing metal ions in the d10 electronic state such as CaIn 2 O 4 , SrIn 2 O 4 , ZnGa 2 O 4 , and Na 2 Sb 2 O 6 (see, for example, JP 2002-59008 A), ammonia and urea In the presence of nitrogen-containing compounds such as titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxytita Etc.) or nitrogen-doped titanium oxide obtained by firing high surface titanium oxide (for example, JP 2002-29750 A, JP 2002-87818 A, JP 2002-154823 A, JP 2001-207082 A). See), sulfur-doped titanium oxide obtained by firing titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxytitanium, etc.) in the presence of sulfur compounds such as thiourea, hydrogen plasma treatment or under vacuum Or oxygen-deficient titanium oxide obtained by heat treatment (for example, see JP-A-2001-98219), and further, photocatalyst particles are treated with a halogenated platinum compound (for example, JP-A-2002-239353). And treatment with tungsten alkoxide (see JP 2001-286755 A). The surface-treated photocatalyst obtained by this can be mentioned suitably.
上記可視光応答型光触媒の中でオキシナイトライド化合物、オキシサルファイド化合物は可視光による光触媒活性が大きく、特に好適に使用することができる。
本発明において特に好適に使用できるオキシナイトライド化合物は、遷移金属を含むオキシナイトライドであり、光触媒活性が大きいものとして、好ましくは遷移金属がTa、Nb、Ti、Zr、Wからなる群から選択される少なくとも1つであることを特徴とするオキシナイトライドであり、より好ましくは、アルカリ、アルカリ土類及びIIIB族の金属からなる群から選択される少なくとも1つの元素を更に含むことを特徴とするオキシナイトライドであり、更に好ましくはCa、Sr、Ba、Rb、La、Ndからなる群から選ばれる少なくとも1つの金属元素を更に含むことを特徴とするオキシナイトライドである。
Among the visible light responsive photocatalysts, oxynitride compounds and oxysulfide compounds have a large photocatalytic activity by visible light and can be used particularly preferably.
The oxynitride compound that can be particularly preferably used in the present invention is an oxynitride containing a transition metal, and preferably has a high photocatalytic activity, and the transition metal is preferably selected from the group consisting of Ta, Nb, Ti, Zr, and W. The oxynitride is characterized in that it further comprises at least one element selected from the group consisting of alkali, alkaline earth and group IIIB metals. The oxynitride further includes at least one metal element selected from the group consisting of Ca, Sr, Ba, Rb, La, and Nd.
上記遷移金属を含むオキシナイトライドの例としては、LaTiO2N、LavCawTiO2N(v+w=3)、LavCawTaO2N(v+w=3)、LaTaON2、CaTaO2N、SrTaO2N、BaTaO2N、CaNbO2N、CaWO2N、SrWO2N等の一般式AMOxNy(A=アルカリ金属、アルカリ土類金属、IIIB族金属;M=Ta、Nb、Ti、Zr、W;x+y=3)で表される化合物やTaON、NbON、WON、Li2LaTa2O6N等を挙げることができる。これらの中で、LaTiO2N、LavCawTiO2N(v+w=3)、LavCawTaO2N(v+w=3)、TaONが可視光での光触媒活性が非常に大きいため好ましい。 Examples of oxynitride containing the transition metal, LaTiO 2 N, La v Ca w TiO 2 N (v + w = 3), La v Ca w TaO 2 N (v + w = 3), LaTaON 2, CaTaO 2 N, General formula AMO x N y such as SrTaO 2 N, BaTaO 2 N, CaNbO 2 N, CaWO 2 N, SrWO 2 N (A = alkali metal, alkaline earth metal, group IIIB metal; M = Ta, Nb, Ti, Zr, W; x + y = 3), TaON, NbON, WON, Li 2 LaTa 2 O 6 N and the like. Among these, LaTiO 2 N, La v Ca w TiO 2 N (v + w = 3), La v Ca w TaO 2 N (v + w = 3), and TaON are preferable because the photocatalytic activity in visible light is very large.
本発明において特に好適に使用できるオキシサルファイド化合物は、遷移金属を含むオキシサルファイドであり、光触媒活性が大きいものとして、好ましくは遷移金属がTa、Nb、Ti、Zr、Wからなる群から選択される少なくとも1つであることを特徴とするオキシサルファイドであり、より好ましくは、アルカリ、アルカリ土類及びIIIB族の金属からなる群から選択される少なくとも1つの元素を更に含むことを特徴とするオキシサルファイドであり、更に好ましくは希土類元素を更に含むことを特徴とするオキシサルファイドである。
上記遷移金属を含むオキシサルファイドの例としては、Sm2Ti2S2O5、Nd2Ti2S2O5、La6Ti2S8O5、Pr2Ti2S2O5、Sm3NbS3O4等を挙げることができる。これらの中で、Sm2Ti2S2O5、Nd2Ti2S2O5が可視光での光触媒活性が非常に大きいため非常に好ましい。
The oxysulfide compound that can be used particularly preferably in the present invention is an oxysulfide containing a transition metal, and has a high photocatalytic activity, and the transition metal is preferably selected from the group consisting of Ta, Nb, Ti, Zr, and W. Oxysulfide, characterized in that it is at least one, more preferably at least one element selected from the group consisting of alkali, alkaline earth and Group IIIB metals More preferably, the oxysulfide is characterized by further containing a rare earth element.
Examples of the oxysulfide containing the transition metal include Sm 2 Ti 2 S 2 O 5 , Nd 2 Ti 2 S 2 O 5 , La 6 Ti 2 S 8 O 5 , Pr 2 Ti 2 S 2 O 5 , and Sm 3. NbS 3 O 4 and the like can be mentioned. Among these, Sm 2 Ti 2 S 2 O 5 and Nd 2 Ti 2 S 2 O 5 are very preferable because of their very high photocatalytic activity under visible light.
また、本発明における光触媒(a)として、アパタイト結晶中の金属イオンの一部を、光触媒作用を有する金属酸化物の金属イオン(例えばチタンイオン等)とイオン交換してなる金属修飾アパタイト(特開2000−327315号広報参照)も、菌やウィルス、汚れ等に対する吸着特性が優れるため好適に使用できる。
更に、上述した光触媒(a)は、好適にPt、Rh、Ru、Nb、Cu、Sn、Ni、Feなどの金属及び/又はこれらの酸化物を添加あるいは固定化したり、多孔質リン酸カルシウム等で被覆したり光触媒(例えば特開平10−244166号公報参照)して使用することもできる。
Further, as a photocatalyst (a) in the present invention, a metal-modified apatite obtained by ion-exchange of a part of metal ions in an apatite crystal with a metal ion of a metal oxide having a photocatalytic action (for example, titanium ion) 2000-327315 public information) can also be suitably used because of its excellent adsorption characteristics against bacteria, viruses, dirt and the like.
Furthermore, the above-described photocatalyst (a) is preferably added or fixed with a metal such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe and / or an oxide thereof, or coated with porous calcium phosphate or the like. It can also be used as a photocatalyst (see, for example, JP-A-10-244166).
上記光触媒(a)の結晶粒子径(1次粒子径)は1〜400nmであることが好ましく、より好ましくは1〜50nmの光触媒が好適に選択される。
本発明における上記光触媒親和性有機成分(B)としては、例えば光触媒粒子表面に存在する水酸基や物理吸着水と親和力を有する親水性化合物(B’)やエポキシ基、アクリロイル基、メタアクリロイル基、(環状)酸無水物基、ケト基、カルボキシル基、ヒドラジン残基、イソシアネート基、イソチオシアネート基、水酸基、アミノ基、環状カーボネート基、チオール基、エステル基等の反応性有機化合物(B’’)等を挙げることができる。
上記親水性化合物(B’)としては、下記構造単位(1)及び/又は(2)を有する数平均分子量100〜1000000の化合物を挙げることができる。
The crystal particle size (primary particle size) of the photocatalyst (a) is preferably 1 to 400 nm, and more preferably a photocatalyst of 1 to 50 nm is suitably selected.
Examples of the photocatalytic affinity organic component (B) in the present invention include, for example, a hydrophilic compound (B ′) having an affinity for the surface of the photocatalyst particles and physical adsorption water, an epoxy group, an acryloyl group, a methacryloyl group, Cyclic) acid anhydride groups, keto groups, carboxyl groups, hydrazine residues, isocyanate groups, isothiocyanate groups, hydroxyl groups, amino groups, cyclic carbonate groups, thiol groups, ester groups, and other reactive organic compounds (B ″), etc. Can be mentioned.
As said hydrophilic compound (B '), the compound of the number average molecular weights 100-1 million which has the following structural unit (1) and / or (2) can be mentioned.
−CH2CHR4O− (2)
(式中、R1、R2、R3、R4はそれぞれ独立に、水素原子あるいは置換基を有しても有さなくても良い炭素数が1〜20個の炭化水素基を表す。
Yは、ヒドロキシル基、アミノ基、アミド基、カルボキシル基あるいはその塩、リン酸基あるいはその塩、スルホン酸基あるいはその塩、ポリオキシアルキレン基からなる群から選ばれた少なくとも1つの親水性基、あるいは該親水性基を有する1価の有機基を表す。)
—CH 2 CHR 4 O— (2)
(In the formula, R 1 , R 2 , R 3 and R 4 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may or may not have a substituent.
Y is at least one hydrophilic group selected from the group consisting of hydroxyl group, amino group, amide group, carboxyl group or salt thereof, phosphoric acid group or salt thereof, sulfonic acid group or salt thereof, and polyoxyalkylene group; Alternatively, it represents a monovalent organic group having the hydrophilic group. )
上記親水性化合物の例としては、例えばポリビニルアルコール、変性ポリビニルアルコール、部分鹸化ポリ酢酸ビニル、アクリル酸重合体(共重合物を含む)、メタクリル酸重合体(共重合物を含む)、アクリルアミド重合体(共重合物を含む)、スチレンスルホン酸重合体(共重合物を含む)、ビニルピロリドン重合体(共重合物を含む)、ポリアリルアミン、ポリエチレングリコール類、ポリエチレングリコール−ポリテトラメチレングリコール共重合体、カルボキシルメチル化セルロース、カルボキシルメチル化ニトロセルロース等を挙げることができる。
これらの中で、式(2)等で表されるポリオキシアルキレン基を有する化合物が、一般に光触媒に対する親和力に優れ、光触媒作用により容易に分解することができるため好ましい。
Examples of the hydrophilic compound include, for example, polyvinyl alcohol, modified polyvinyl alcohol, partially saponified polyvinyl acetate, acrylic acid polymer (including copolymer), methacrylic acid polymer (including copolymer), and acrylamide polymer. (Including copolymer), styrenesulfonic acid polymer (including copolymer), vinylpyrrolidone polymer (including copolymer), polyallylamine, polyethylene glycols, polyethylene glycol-polytetramethylene glycol copolymer Carboxymethylated cellulose, carboxymethylated nitrocellulose and the like.
Among these, a compound having a polyoxyalkylene group represented by the formula (2) or the like is preferable because it generally has an excellent affinity for a photocatalyst and can be easily decomposed by a photocatalytic action.
本発明の光触媒体において、上述した光触媒(a)と光触媒親和性有機成分(B)は質量比(A)/(B)=0.001〜1000の割合で含む系が好ましい。
本発明における上記難分解成分(C)としては、好ましくは光触媒体表面の紫外線強度を7mW/cm2になるようにブラックライトの光を5時間照射した時の質量減少が5%以下であるもの等を挙げることができる。
上記難分解性成分(C)の具体例としては、例えば水ガラス等の無機系化合物やシリコーン系樹脂及びフッ素系樹脂等を挙げることができる。
In the photocatalyst of the present invention, a system containing the above-mentioned photocatalyst (a) and the photocatalytic affinity organic component (B) at a mass ratio (A) / (B) = 0.001 to 1000 is preferable.
In the present invention, the hardly decomposable component (C) preferably has a mass loss of 5% or less when irradiated with black light for 5 hours so that the ultraviolet intensity of the photocatalyst surface is 7 mW / cm 2. Etc.
Specific examples of the hardly decomposable component (C) include inorganic compounds such as water glass, silicone resins, and fluorine resins.
本発明において、上記シリコーン系樹脂を例示すると、例えばジメチルポリシロキサン、メチルフェニルポリシロキサン、メチルハイドロジェンポリシロキサン、アルコキシ基含有シリコーンオイル、シラノール基含有シリコーンオイル、ビニル基含有シリコーンオイル、オクタメチルシクロテトラシロキサン、デカメチルシクロペンタシロキサン等のシリコーンオイル類、ポリエーテル変性シリコーン、ポリグリセリン変性シリコーン、アミノ変性シリコーン、エポキシ変性シリコーン、メルカプト変性シリコーン、メタクリル変性シリコーン、カルボン酸変性シリコーン、脂肪酸エステル変性シリコーン、アルコール変性シリコーン、アルキル変性シリコーン、フロロアルキル変性シリコーン等の変性シリコーン類、テトラエトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン等の(アルキル)アルコキシシランのモノマー、オリゴマー、及び重合体、ビニルトリクロルシラン、ビニルトリメトキシシラン、γ-アミノプロピルトリメトキシシラン等のシランカップリング剤及びその反応生成物、シリコーン界面活性剤等である。これらのシリコーンは単独でも、2種以上を同時に用いることもできる。 In the present invention, examples of the silicone resin include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, alkoxy group-containing silicone oil, silanol group-containing silicone oil, vinyl group-containing silicone oil, octamethylcyclotetra Silicone oils such as siloxane and decamethylcyclopentasiloxane, polyether modified silicone, polyglycerin modified silicone, amino modified silicone, epoxy modified silicone, mercapto modified silicone, methacryl modified silicone, carboxylic acid modified silicone, fatty acid ester modified silicone, alcohol Modified silicones such as modified silicones, alkyl-modified silicones, fluoroalkyl-modified silicones, tetraethoxysila Silane coupling agents such as monomers, oligomers and polymers of (alkyl) alkoxysilanes such as methyltriethoxysilane and dimethyldiethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane and γ-aminopropyltrimethoxysilane and the like Reaction products, silicone surfactants, and the like. These silicones can be used alone or in combination of two or more.
本発明において、上記フッ素系樹脂としては、例えば2−パーフルオロオクチルエチルトリメトキシシラン、2−パーフルオロオクチルエチルトリエトキシシラン、2−パーフルオロオクチルエチルメチルジメトキシシラン、トリフルオロメチルエチルトリメトキシシラン、トリフルオロメチルエチルトリエトキシシラン等のフルオロアルキルシラン類やその重縮合体、PTFEやポリフッ化ビニリデン、さらにはナフィオン樹脂、クロロトリフルオロエチレンやテトラフルオロエチレン等のフルオロオレフィン類とモノマー類(ビニルエーテル、ビニルエステル、アリル化合物等)との共重合体等を挙げることができる。これらのフッ素系樹脂は、単独でも、2種以上を同時に用いることもできる。 In the present invention, examples of the fluororesin include 2-perfluorooctylethyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethylmethyldimethoxysilane, trifluoromethylethyltrimethoxysilane, Fluoroalkylsilanes such as trifluoromethylethyltriethoxysilane and their polycondensates, PTFE and polyvinylidene fluoride, and also fluoroolefins and monomers such as Nafion resin, chlorotrifluoroethylene and tetrafluoroethylene (vinyl ether, vinyl) And copolymers with esters and allyl compounds). These fluororesins can be used alone or in combination of two or more.
本発明の光触媒体において、上述した光触媒(a)と難分解性成分(C)は質量比(A)/(C)=0.001〜1000の割合で含む系が好ましい。
また、本発明において上記複合化合物(BC)は、例えば上述した光触媒親水性有機成分(B)を官能基として有する上記難分解成分(C)や、光触媒親水性有機成分(B)と難分解成分(C)のグラフト重合体、ブロック重合体、ランダム重合体等を例示することができる。
本発明において、光触媒(a)を変性処理するのに有用な上記複合化合物(BC)は、例えばSi−H基、加水分解性シリル基(アルコキシシリル基、ヒドロキシシリル基、ハロゲン化シリル基、アセトキシシリル基、アミノキシシリル基等)、エポキシ基、アセトアセチル基、チオール基、酸無水物基等の光触媒粒子(a)と反応性を有するものが好適に例示できる。
In the photocatalyst of the present invention, a system containing the above-mentioned photocatalyst (a) and the hardly decomposable component (C) in a ratio of mass ratio (A) / (C) = 0.001 to 1000 is preferable.
Further, in the present invention, the composite compound (BC) is, for example, the above-mentioned hardly decomposed component (C) having the above-described photocatalytic hydrophilic organic component (B) as a functional group, or the photocatalytic hydrophilic organic component (B) and the hardly decomposed component. Examples of the graft polymer (C), block polymer, and random polymer of (C) can be given.
In the present invention, the composite compound (BC) useful for modifying the photocatalyst (a) includes, for example, a Si—H group, a hydrolyzable silyl group (alkoxysilyl group, hydroxysilyl group, halogenated silyl group, acetoxy group). Suitable examples include those having reactivity with the photocatalyst particles (a) such as silyl group, aminoxysilyl group, etc.), epoxy group, acetoacetyl group, thiol group, acid anhydride group and the like.
本発明において、光触媒(a)の複合化合物(BC)による変性処理は、水及び/又は有機溶媒の存在、あるいは非存在下において、光触媒(a)と該複合化合物(BC)を好ましくは質量比(a)/(BC)=1/99〜99.9/0.1、より好ましくは(a)/(BC)=10/90〜99/1の割合で好ましくは0〜200℃にて混合することにより実施できる。
本発明において、光触媒(a)の変性に使用される複合化合物(BC)としてSi−H基を含有するものを用いると、非常に効率よく光触媒(a)の粒子表面を変性することができるため好ましい。
In the present invention, the modification treatment of the photocatalyst (a) with the composite compound (BC) is preferably performed by mass ratio of the photocatalyst (a) and the composite compound (BC) in the presence or absence of water and / or an organic solvent. (A) / (BC) = 1/99 to 99.9 / 0.1, more preferably (a) / (BC) = 10/90 to 99/1, preferably at 0 to 200 ° C. Can be implemented.
In the present invention, when a compound containing a Si—H group is used as the composite compound (BC) used for modification of the photocatalyst (a), the particle surface of the photocatalyst (a) can be modified very efficiently. preferable.
上記Si−H基を有する複合化合物(BC)の好ましい例として、例えば式(3)及び/または式(4)で表される光触媒親和性有機基(Q)を有するSi−H基含有化合物を例示することができる。
H−(R2SiO)m−SiR2−Q (3)
(式中、Rは各々独立して直鎖状または分岐状の炭素数が1〜30個のアルキル基、炭素数5〜20のシクロアルキル基、直鎖状または分岐状の炭素数が1〜30個のフルオロアルキル基、炭素数2〜30のアルケニル基、フェニル基、炭素数1〜20のアルコキシ基、水酸基から選ばれた1種以上からなる基を表す。
As a preferable example of the composite compound (BC) having the Si—H group, for example, an Si—H group-containing compound having a photocatalytic affinity organic group (Q) represented by the formula (3) and / or the formula (4) is used. It can be illustrated.
H- (R 2 SiO) m -SiR 2 -Q (3)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon number of 1 to 1. It represents a group consisting of at least one selected from 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.
また、式中Qは下記(あ)〜(う)からなる群より選ばれる少なくとも1つの光触媒親和性有機基を含有する基である。
(あ)カルボキシル基あるいはその塩、リン酸基あるいはその塩、スルホン酸基あるいはその塩、アミノ基あるいはその塩、ポリオキシアルキレン基からなる群から選ばれた少なくとも1つの親水性基。
(い)エポキシ基、アクリロイル基、メタアクリロイル基、(環状)酸無水物基、ケト基、カルボキシル基、ヒドラジン残基、イソシアネート基、イソチオシアネート基、水酸基、アミノ基、環状カーボネート基、チオール基、エステル基からなる群から選ばれた少なくとも1つの反応性基。
mは整数であり、0≦m≦1000である。)
(RHSiO)p(R2SiO)q(RQSiO)r(R3SiO1/2)s (4)
(式中、RおよびQは式(3)で定義した通りである。
pは1以上の整数であり、q及びrは0又は1以上の整数であり、(p+q+r)≦10000であり、そしてsは0又は2である。但し、(p+q+r)が2以上の整数であり且つs=0の場合、該Hシリコーン化合物は環状シリコーン化合物であり、s=2の場合、該Hシリコーン化合物は鎖状シリコーン化合物である。)
In the formula, Q is a group containing at least one photocatalytic affinity organic group selected from the group consisting of the following (a) to (u).
(A) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an amino group or a salt thereof, and a polyoxyalkylene group.
(Ii) Epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups;
m is an integer, and 0 ≦ m ≦ 1000. )
(RHSiO) p (R 2 SiO) q (RQSiO) r (R 3 SiO 1/2 ) s (4)
(Wherein R and Q are as defined in formula (3)).
p is an integer of 1 or more, q and r are 0 or an integer of 1 or more, (p + q + r) ≦ 10000, and s is 0 or 2. However, when (p + q + r) is an integer of 2 or more and s = 0, the H silicone compound is a cyclic silicone compound, and when s = 2, the H silicone compound is a chain silicone compound. )
また、本発明の光触媒体は、必要により通常、塗料や成型用樹脂に添加配合される成分、例えば、顔料、硬化触媒、架橋剤、充填剤、分散剤、光安定剤、湿潤剤、増粘剤、レオロジーコントロール剤、消泡剤、可塑剤、成膜助剤、防錆剤、染料、防腐剤等がそれぞれの目的に応じて選択、組み合わせて含有することができる。
本発明の光触媒体の形態には特に制限はないが、粒子、粉体、皮膜、成形体等を好ましく例示することができる。
Further, the photocatalyst of the present invention is usually added to a paint or a molding resin as necessary, for example, a pigment, a curing catalyst, a crosslinking agent, a filler, a dispersant, a light stabilizer, a wetting agent, a thickening agent. An agent, a rheology control agent, an antifoaming agent, a plasticizer, a film forming aid, a rust preventive agent, a dye, a preservative, and the like can be selected and combined in accordance with each purpose.
Although there is no restriction | limiting in particular in the form of the photocatalyst body of this invention, A particle | grain, powder, a membrane | film | coat, a molded object etc. can be illustrated preferably.
本発明の光触媒体は、それを構成する成分からなるペレット等を成形したり、それを構成する成分に溶剤等を含有させた光触媒体組成物(D)から形成することができる。本発明の光触媒体の形態が皮膜や粉体であったり、また後述する部材に固定化する場合は、上記光触媒体組成物(D)を用いて光触媒体を形成する方法が好ましい。
上記光触媒体組成物(D)に好適に用いることができる溶剤としては、例えば水、エチレングリコール、ブチルセロソルブ、n−プロパノール、イソプロパノール、n−ブタノール、エタノール、メタノール等のアルコール類、トルエンやキシレン等の芳香族炭化水素類、ヘキサン、シクロヘキサン、ヘプタン等の脂肪族炭化水素類、酢酸エチル、酢酸n−ブチル等のエステル類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、テトラヒドロフラン、ジオキサン等のエーテル類、ジメチルアセトアミド、ジメチルホルムアミド等のアミド類、クロロホルム、塩化メチレン、四塩化炭素等のハロゲン化合物類、ジメチルスルホキシド、ニトロベンゼン等、さらにはこれらの2種以上の混合物が挙げられる。
The photocatalyst of the present invention can be formed from a photocatalyst composition (D) in which pellets or the like composed of the components constituting the photocatalyst are formed or a solvent or the like is contained in the components constituting the photocatalyst. When the form of the photocatalyst of the present invention is a film or powder, or when it is immobilized on a member to be described later, a method of forming a photocatalyst using the photocatalyst composition (D) is preferred.
Examples of the solvent that can be suitably used for the photocatalyst composition (D) include water, alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol, and methanol, and toluene and xylene. Aromatic hydrocarbons, aliphatic hydrocarbons such as hexane, cyclohexane and heptane, esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane Amides such as dimethylacetamide and dimethylformamide, halogen compounds such as chloroform, methylene chloride and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more of these.
本発明の別の態様においては、光触媒体を部材上に有する光触媒部材が提供される。
本発明における光触媒体を皮膜状とする場合は、例えば上記光触媒体組成物(D)を部材に塗布し、乾燥した後、所望により好ましくは20℃〜500℃、より好ましくは40℃〜250℃の熱処理や紫外線照射等を行い、部材上に皮膜を形成することにより得ることができる。上記塗布方法としては、例えばスプレー吹き付け法、フローコーティング法、ロールコート法、刷毛塗り法、ディップコーティング法、スピンコーティング法、スクリーン印刷法、キャスティング法、グラビア印刷法、フレキソ印刷法等が挙げられる。
この際、本発明の光触媒体組成物(D)から形成される皮膜の膜厚は、好ましくは0.1〜200μm、より好ましくは0.5〜20μm、さらに好ましくは1.5〜10μmである。
In another aspect of the present invention, a photocatalytic member having a photocatalyst body on the member is provided.
When making the photocatalyst body in this invention into a film form, after apply | coating the said photocatalyst body composition (D) to a member and drying, for example, Preferably it is 20 to 500 degreeC, More preferably, it is 40 to 250 degreeC. The film can be obtained by forming a film on the member by performing heat treatment, ultraviolet irradiation or the like. Examples of the coating method include spray spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, flexographic printing, and the like.
Under the present circumstances, the film thickness of the film | membrane formed from the photocatalyst body composition (D) of this invention becomes like this. Preferably it is 0.1-200 micrometers, More preferably, it is 0.5-20 micrometers, More preferably, it is 1.5-10 micrometers. .
なお、本明細書では、皮膜という表現を使用しているが、必ずしも連続膜である必要はなく、不連続膜、島状分散膜等の態様であっても構わない。
本発明の光触媒部材を得るのに用いられる材質としては、特に限定はされなく、例えば本発明で開示した用途に使用される基材は全て用いることができる。
本発明の光触媒部材を得るのに用いられる材質としては、例えば合成樹脂、天然樹脂等の有機基材や、金属、セラミックス、ガラス、石、セメント、コンクリート等の無機基材や、それらの組み合わせや複合体、さらにはそれらが樹脂塗装もしくは金属メッキされた表面等を挙げることができる。
In the present specification, the expression “film” is used. However, the film is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.
The material used for obtaining the photocatalyst member of the present invention is not particularly limited, and for example, any base material used for the application disclosed in the present invention can be used.
Examples of materials used to obtain the photocatalytic member of the present invention include organic base materials such as synthetic resins and natural resins, inorganic base materials such as metals, ceramics, glass, stone, cement, and concrete, combinations thereof, Examples of the composite include a surface on which they are resin-coated or metal-plated.
本発明の光触媒部材においては、光触媒で分解する有機基材を用いた場合でも、耐久性は非常に優れたものとなる。
本発明の光触媒部材の製造方法は、部材上に本発明の光触媒体を形成する場合に限定されない。部材と本発明の光触媒組成物を同時に成形、たとえば、一体成形してもよい。また、本発明の光触媒体を成形後、部材の成形を行ってもよい。また、本発明の光触媒体と部材を個別に成形後、接着、融着等により光触媒体としてもよい。上記方法で、本来の部材と接しない状態で成形する場合は別の部材を用いても良い。この場合の部材は固体に限定されず、本発明の効果を損なわない範囲で、液体、気体でも良い。
In the photocatalyst member of the present invention, even when an organic base material that decomposes with a photocatalyst is used, the durability is very excellent.
The manufacturing method of the photocatalyst member of the present invention is not limited to the case where the photocatalyst body of the present invention is formed on the member. The member and the photocatalyst composition of the present invention may be simultaneously molded, for example, integrally molded. Moreover, you may shape | mold a member after shape | molding the photocatalyst body of this invention. Further, the photocatalyst body and the member of the present invention may be individually molded and then formed into a photocatalyst body by adhesion, fusion, or the like. In the above method, another member may be used when molding in a state where it does not contact the original member. The member in this case is not limited to a solid, and may be liquid or gas as long as the effects of the present invention are not impaired.
本発明の成形体または光触媒部材は、必要により、樹脂成形に用いる方法により、フィルム、シート、ブロック、ペレットさらに複雑な形状の成形体とすることができる。成形にあたり、本発明の効果を損なわない範囲で、他の樹脂と併用する事も可能である。
上記成形や上記併用のための混合を、本発明の成形体または光触媒部材や他の樹脂を粉体あるいは予めペレットとして行うことができる。一部に液状成分を含んでも良い。また、混合後の樹脂を下記方法でペレットに成形し、さらに成形に供する方法も可能である。ペレットは本発明の成形体または光触媒部材を他の樹脂中に高濃度に含有した所謂マスターバッチとすることもできる。
If necessary, the molded article or photocatalyst member of the present invention can be formed into a molded article having a film, a sheet, a block, a pellet, or a complicated shape by a method used for resin molding. In molding, it can be used in combination with other resins as long as the effects of the present invention are not impaired.
Mixing for the above-mentioned molding and the above-mentioned combination can be performed as a powder or a pellet in advance with the molded body or photocatalyst member of the present invention or other resin. Some of them may contain a liquid component. Moreover, the method of shape | molding resin after mixing into a pellet with the following method, and also using for shaping | molding is also possible. The pellet may be a so-called master batch in which the molded article or photocatalyst member of the present invention is contained in a high concentration in another resin.
本発明のための成形方法は、押出し成形法、射出成形法、プレス成形法等が可能である。また、熱可塑性樹脂を併用する等、樹脂の選定によってはカレンダー成形法も可能である。また、天然繊維を含む有機繊維、ガラス等の無機繊維(及びこれらの織物を含む)などを補強材に用いて本発明の成形体または光触媒部材、及びこれらと他の樹脂混合物を含浸し、積層成形する事も可能である。
本発明の成形体または光触媒部材は繊維状とすることもできる。繊維状に加工するにためには、本発明の効果を阻害しない範囲で通常の紡糸方法が使用できる。当該紡糸方法としては溶融紡糸、溶液紡糸が用いられる。紡糸に当って、前述の他の樹脂とともに用いて繊維状に加工する事もできる。例えば、通常の樹脂(熱可塑性樹脂が成形上は好ましい)、たとえばポリエステル、ナイロン等に本発明の成形体または光触媒部材をブレンドしたり、あるいは本発明の成形体または光触媒部材とこれら樹脂を複合紡糸(鞘芯、サイドバイサイド型等)してもよい。
The molding method for the present invention can be an extrusion molding method, an injection molding method, a press molding method, or the like. Further, depending on the selection of the resin, such as using a thermoplastic resin in combination, a calendar molding method is also possible. Further, organic fibers including natural fibers, inorganic fibers such as glass (and including these woven fabrics), and the like are used as a reinforcing material to impregnate the molded body or photocatalyst member of the present invention, and these and other resin mixtures, and laminated. Molding is also possible.
The molded body or photocatalyst member of the present invention may be in the form of a fiber. In order to process into a fiber form, a normal spinning method can be used as long as the effects of the present invention are not impaired. As the spinning method, melt spinning and solution spinning are used. In spinning, it can also be processed into a fibrous form together with the other resins described above. For example, an ordinary resin (thermoplastic resin is preferable for molding), for example, polyester, nylon or the like is blended with the molded article or photocatalyst member of the present invention, or the molded article or photocatalyst member of the present invention and these resins are composite-spun. (Sheath core, side-by-side type, etc.) may be used.
繊維は、長繊維でも短繊維でもよく、長さ方向に均一なものや太細のあるものでもよく、断面形状においても丸型、三角、L型、T型、Y型、W型、八葉型、偏平、ドッグボーン型等の多角形型、多葉型、中空型や不定形なものでもよい。
繊維状とした本発明の成形体または、繊維に光触媒体を固定化させた光触媒部材は織物や不織布(短繊維又は長繊維)として用いる事もできる。また、織物や不織布(短繊維又は長繊維)に光触媒体を固定化させて光触媒部材を形成することもできる。
The fibers may be long fibers or short fibers, and may be uniform or thick in the length direction, and the cross-sectional shape is round, triangular, L-shaped, T-shaped, Y-shaped, W-shaped, Yaba It may be a polygonal shape such as a shape, flatness, or dogbone shape, a multi-leaf shape, a hollow shape, or an irregular shape.
The molded article of the present invention in the form of a fiber or a photocatalyst member in which a photocatalyst is fixed to a fiber can be used as a woven fabric or a nonwoven fabric (short fiber or long fiber). Moreover, a photocatalyst member can also be formed by fixing a photocatalyst body to a woven fabric or a non-woven fabric (short fiber or long fiber).
また、使用できる繊維の形態は、糸条、糸条の集合体であるチーズ状、織物、編物、不織布等が挙げられ、他の樹脂の繊維と混用されていても良い。糸条の形態としては、原糸、仮撚糸(延伸仮撚糸を含む)、先撚仮撚糸、空気噴射加工糸、リング紡績糸、オープンエンド紡績糸等の紡績糸、マルチフィラメント原糸(極細糸を含む)、混繊糸等が挙げられる。又、混用する繊維としては、ポリエステル系繊維、ポリアミド系繊維、ポリアクリル系繊維、ポリビニル系繊維、ポリプロピレン系繊維、ポリウレタン系等の弾性繊維(酸化マグネシウム、酸化亜鉛に代表される金属酸化物、金属水酸化物等の塩素水劣化防止剤を添加したものを含む)等の合成繊維や、綿、麻、ウール、絹等の天然繊維やキュプラ、レーヨン、ポリノジック等のセルロース系繊維やアセテート系繊維がある。 Moreover, the form of the fiber which can be used includes a cheese, a woven fabric, a knitted fabric, a non-woven fabric, etc., which are aggregates of yarns and yarns, and may be mixed with fibers of other resins. As for the form of the yarn, raw yarn, false twisted yarn (including stretched false twisted yarn), pre-twisted false twisted yarn, air-jet processed yarn, ring spun yarn, open-end spun yarn, etc., multifilament raw yarn (extra fine yarn) ), Mixed fiber and the like. The mixed fibers include polyester fibers, polyamide fibers, polyacrylic fibers, polyvinyl fibers, polypropylene fibers, polyurethane fibers, etc. (metal oxides such as magnesium oxide and zinc oxide, metals) Synthetic fibers such as those added with chlorinated water deterioration inhibitors such as hydroxide), natural fibers such as cotton, hemp, wool and silk, and cellulose fibers and acetate fibers such as cupra, rayon and polynosic is there.
本発明の光触媒体は、含有する光触媒(a)のバンドギャップエネルギーよりも高いエネルギーの光を照射することによりBET表面積が、好ましくは10m2/g以上、より好ましくは20m2/g以上、更に好ましくは50m2/g以上増加する。この様にして好適に得られた多孔質光触媒体は、環境浄化機能に非常に優れるものとなる。また、光触媒体が固定化された光触媒部材からは、上記光照射により多孔質光触媒体が固定化された多孔質光触媒部材が得られる。この際、多孔質光触媒体は部材に強固に固定化されたまま(該部材が有機基材の場合には、基材保護性を有した状態で)、優れた防汚性能や汚れ分解性能等の環境浄化機能を発現するため非常に有用となる。 The photocatalyst of the present invention has a BET surface area of preferably 10 m 2 / g or more, more preferably 20 m 2 / g or more, by irradiating light with energy higher than the band gap energy of the photocatalyst (a) contained. Preferably, it increases by 50 m 2 / g or more. The porous photocatalyst body suitably obtained in this manner is very excellent in the environmental purification function. Moreover, the porous photocatalyst member in which the porous photocatalyst body is fixed by the light irradiation is obtained from the photocatalyst member in which the photocatalyst body is fixed. At this time, the porous photocatalyst is firmly fixed to the member (when the member is an organic substrate, the substrate has a protective property), and has excellent antifouling performance and dirt decomposition performance. It is very useful because of its environmental purification function.
ここで、光触媒(a)のバンドギャップエネルギーよりも高いエネルギーの光の光源としては、例えば太陽光や室内照明灯等の一般住宅環境下で得られる光の他、ブラックライト、キセノンランプ、水銀灯、LED等の光が利用できる。
本発明によって提供される上記多孔質光触媒体又は多孔質光触媒部材は、抗菌、防汚、防臭、NOx分解等の様々な機能を発現し、大気、水等の環境浄化等の用途に使用することができる。また、抗菌、防汚、防臭、有毒ガス分解、汚れ分解を目的として衣料用、ガス、液体のフィルター用に用いることができる。
Here, as a light source of light having an energy higher than the band gap energy of the photocatalyst (a), for example, light obtained in a general residential environment such as sunlight or indoor lighting, black light, xenon lamp, mercury lamp, Light such as LED can be used.
The porous photocatalyst body or porous photocatalyst member provided by the present invention expresses various functions such as antibacterial, antifouling, deodorant, and NOx decomposition, and is used for environmental purification such as air and water. Can do. It can also be used for clothing, gas and liquid filters for antibacterial, antifouling, deodorant, toxic gas decomposition and dirt decomposition.
本発明の多孔質光触媒体で汚れ分解処理及び/または汚れ防止処理をする部材としては、例えば繊維製品の場合、繊維の種類、織り方、繊維布の用途は限定されず、例えば寝具用シ−ツ、タオル、靴下、パンティ−ストッキング、下着、上着、カ−テン、テ−ブルクロス、スリッパ、帽子、マットレス、カ−ペット等や不織布、テント、帆、幌、ロ−プ、壁紙等に適用することができる。 As a member that performs soil decomposition treatment and / or soil prevention treatment with the porous photocatalyst of the present invention, for example, in the case of a textile product, the type of fiber, the weaving method, and the use of the fiber cloth are not limited. Applicable to fabrics, towels, socks, pantyhose, underwear, outerwear, curtains, tablecloths, slippers, hats, mattresses, carpets and non-woven fabrics, tents, sails, hoods, ropes, wallpaper, etc. can do.
また、本発明の多孔質光触媒体は家具、電化製品、壁などといった物に関しても同様に、その種類、材質、用途によっては限定されず適用でき、例えば、タンス、クロ−ゼット、食器棚、テ−ブル、いす、ソファ−等の家具や冷蔵庫、エアコンのフィルター、掃除機の吹き出し口等の電化製品、住居の内外壁、ブラインド、浴室、トイレ、キッチン周り、自動車、鉄道車輌、飛行機、船舶等の内装等に適用することができる。
本発明によって提供される多孔質光触媒体又は多孔質光触媒部材であって、光照射により20℃における水との接触角が60゜以下(好ましくは10゜以下)となった親水性のもの(親水性膜、及び該親水性膜で被覆された基材等)は、鏡やガラスの曇りを防止する防曇技術、さらには建築外装等に対する防汚技術や帯電防止技術等への応用が可能である。
Similarly, the porous photocatalyst of the present invention can be applied to items such as furniture, electrical appliances, walls, etc. without being limited by the type, material, and use. -Furniture such as bulls, chairs, sofas, etc., electrical appliances such as refrigerators, air conditioner filters, vacuum cleaner outlets, residential interior and exterior walls, blinds, bathrooms, toilets, kitchen areas, cars, railway vehicles, airplanes, ships, etc. It can be applied to interior decorations.
A porous photocatalyst or a porous photocatalyst member provided by the present invention, wherein the contact angle with water at 20 ° C. is 60 ° or less (preferably 10 ° or less) by light irradiation (hydrophilic) The film can be applied to anti-fogging technology to prevent fogging of mirrors and glass, and to antifouling technology and antistatic technology for building exteriors, etc. is there.
本発明の多孔質光触媒体又は多孔質光触媒部材の防汚技術分野への応用例としては、例えば建材、建物外装、建物内装、窓枠、窓ガラス、構造部材、住宅等建築設備、特に便器、浴槽、洗面台、照明器具、照明カバー、台所用品、食器、食器洗浄器、食器乾燥器、流し、調理レンジ、キッチンフード、換気扇等、また、乗物の外装および塗装、用途によってはその内装にも使用でき、車両用照明灯のカバー、窓ガラス、計器、表示盤等透明性が要求される部材での使用に効果があり、また、機械装置や物品の外装、防塵カバーおよび塗装、表示機器、そのカバー、交通標識、各種表示装置、広告塔等の表示物、道路用、鉄道用等の遮音壁、橋梁、ガードレールの外装および塗装、トンネル内装および塗装、碍子、太陽電池カバー、太陽熱温水器集熱カバー等外部で使用される電子、電気機器の外装部、特に透明部材、ビニールハウス、温室等の外装、特に透明部材、また、室内にあっても汚染のおそれのある環境、たとえば医療用や体育用の施設、装置等の用途を挙げることができる。 Examples of the application of the porous photocatalyst body or porous photocatalyst member of the present invention to the antifouling technology field include, for example, building materials, building exteriors, building interiors, window frames, window glass, structural members, building equipment such as houses, particularly toilets, Bathtub, wash basin, lighting fixture, lighting cover, kitchenware, tableware, dishwasher, tableware dryer, sink, cooking range, kitchen hood, exhaust fan, etc. It can be used, and is effective for use in parts that require transparency such as covers for vehicle lighting, window glass, instruments, display panels, etc. Covers, traffic signs, display devices, display items such as advertising towers, sound insulation walls for roads, railways, etc., bridges, exterior and painting of guardrails, interior and painting of tunnels, insulators, solar cell covers, solar hot water Exterior parts of electronic and electrical equipment used outside such as heat collecting covers, especially transparent members, exteriors of greenhouses, greenhouses, especially transparent members, and environments that may be contaminated even indoors, such as medical use And use of facilities and equipment for physical education.
本発明の多孔質光触媒体又は多孔質光触媒部材の防曇技術分野への応用例としては、例えば鏡(車両用後方確認ミラー、浴室用鏡、洗面所用鏡、歯科用鏡、道路鏡等)、レンズ(眼鏡レンズ、光学レンズ、照明用レンズ、半導体用レンズ、複写機用レンズ、車両用後方確認カメラレンズ等)、プリズム、建物や環視塔の窓ガラス、乗物の窓ガラス(自動車、鉄道車両、航空機、船舶、潜水艇、雪上車、ロープウェイのゴンドラ、遊園地のゴンドラ、宇宙船等)、乗物の風防ガラス(自動車、オートバイ、鉄道車両、航空機、船舶、潜水艇、雪上車、スノーモービル、ロープウェイのゴンドラ、遊園地のゴンドラ、宇宙船等)、防護用ゴーグル、スポーツ用ゴーグル、防護用マスクのシールド、スポーツ用マスクのシールド、ヘルメットのシールド、冷凍食品陳列ケースのガラス、保温食品の陳列ケースのガラス、計測機器のカバー、車両用後方確認カメラレンズのカバー、レーザー歯科治療器等の集束レンズ、車間距離センサー等のレーザー光検知用センサーのカバー、赤外線センサーのカバー、カメラ用フィルター等の用途を挙げることができる。 Examples of the application of the porous photocatalyst body or porous photocatalyst member of the present invention to the anti-fogging technology field include, for example, mirrors (vehicle rear-view mirrors, bathroom mirrors, toilet mirrors, dental mirrors, road mirrors, etc.) Lenses (glass lenses, optical lenses, illumination lenses, semiconductor lenses, photocopier lenses, vehicle rear-view camera lenses, etc.), prisms, window glass of buildings and viewing towers, vehicle window glasses (automobiles, railway vehicles, Aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola, spacecraft, etc.), windshields of vehicles (automobiles, motorcycles, rail vehicles, aircraft, ships, submersibles, snow vehicles, snowmobiles, ropeways) Gondola, amusement park gondola, spacecraft, etc.), protective goggles, sports goggles, protective mask shield, sports mask shield, helmet seat Glass for frozen food display cases, glass for insulated food display cases, covers for measuring devices, covers for vehicle rear-view camera lenses, focusing lenses for laser dental treatment devices, sensors for detecting laser light such as distance sensors between vehicles Applications, infrared sensor covers, camera filters, and the like.
本発明の多孔質光触媒体又は多孔質光触媒部材の帯電防止技術分野への応用例としては、例えばブラウン管、磁気記録メディア、光記録メディア、光磁気記録メディア、オーディオテープ、ビデオテープ、アナログレコード、家庭用電気製品のハウジングや部品や外装および塗装、OA機器製品のハウジングや部品や外装および塗装、建材、建物外装、建物内装、窓枠、窓ガラス、構造部材、乗物の外装および塗装、機械装置や物品の外装、防塵カバーおよび塗装等の用途を挙げることができる。 Examples of the application of the porous photocatalyst body or porous photocatalyst member of the present invention to the antistatic technical field include, for example, cathode ray tubes, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, households Housing, parts and exterior and coating for electrical products, housing and parts and exterior and coating for OA equipment products, building materials, building exteriors, building interiors, window frames, window glass, structural members, exterior and painting of vehicles, machinery and equipment Applications such as exteriors of articles, dustproof covers, and painting can be given.
本発明によって提供される多孔質光触媒体又は多孔質光触媒部材であって、光照射により20℃における水との接触角が70゜以上(好ましくは90゜以上)となった疎水性のもの(疎水性の成形体や疎水性膜、及び該疎水性膜で被覆された基材等)は、防滴性や水切れ性の付与、水系汚れの付着防止や流水洗浄性を利用した防汚技術、さらには着氷雪防止技術等への応用が可能であり、窓ガラス、風防ガラス、鏡、レンズ、ゴーグル、カバー、碍子、建材、建物外装、建物内装、構造部材、乗物の外装及び塗装、機械装置や物品の外装、各種表示装置、照明装置、住宅設備、食器、台所用品、家庭用電気製品、屋根材、アンテナ、送電線、氷雪滑走具等の用途に使用することができる。 A porous photocatalyst or a porous photocatalyst member provided by the present invention, wherein the contact angle with water at 20 ° C. is 70 ° or more (preferably 90 ° or more) by light irradiation (hydrophobic) A molded article, a hydrophobic film, and a substrate coated with the hydrophobic film) are provided with a drip-proof property and a water drainage property, an antifouling technique using water-based dirt adhesion prevention and running water detergency, Can be applied to icing and snow prevention technology, such as window glass, windshield glass, mirrors, lenses, goggles, covers, insulators, building materials, building exteriors, building interiors, structural members, exterior and painting of vehicles, machinery and equipment It can be used for applications such as exteriors of articles, various display devices, lighting devices, housing equipment, tableware, kitchen utensils, household electrical appliances, roofing materials, antennas, power transmission lines, ice and snow slides.
本発明によって提供される多孔質光触媒体又は多孔質光触媒部材であって光電変換機能を有するものは、太陽エネルギーの電力変換等の機能を発現することが可能であり、(湿式)太陽電池等に用いる光半導体電極等の用途に使用することができる。 The porous photocatalyst body or the porous photocatalyst member provided by the present invention, which has a photoelectric conversion function, can express functions such as power conversion of solar energy, and can be used in (wet) solar cells, etc. It can be used for applications such as an optical semiconductor electrode to be used.
以下の実施例、参考例及び比較例により本発明を具体的に説明するが、これらは本発明の範囲を限定するものではない。実施例、参考例及び比較例中において、各種の物性は下記の方法で測定した。
1.粒径分布及び数平均粒子径
試料中の光触媒含有量が1〜20質量%となるよう適宜溶媒を加えて希釈し、湿式粒度分析計(日機装製マイクロトラックUPA−9230)を用いて測定した。
The following examples, reference examples and comparative examples will specifically explain the present invention, but these do not limit the scope of the present invention. In Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods.
1. Particle size distribution and number average particle size A solvent was appropriately added to dilute the photocatalyst content in the sample to 1 to 20% by mass, and measurement was performed using a wet particle size analyzer (Nikkiso Microtrac UPA-9230).
2.重量平均分子量
ポリスチレン標品を用いて作成した検量線を用い、ゲルパーミエーションクロマトグラフィー(GPC)によって求めた。
GPCの条件は以下の通りである。
・装置:東ソー製HLC−8020 LC−3A型クロマトグラフ
・カラム:TSKgel G1000HXL、TSKgel G2000HXLおよびTSKgel G4000HXL(いずれも東ソー製)を直列に接続して用いた。
・データ処理装置:島津製作所製CR−4A型データ処理装置
・移動相:
テトラヒドロフラン(フェニル基含有シリコーンの分析に使用)
クロロホルム(フェニル基を含有しないシリコーンの分析に使用)
・流速:1.0ml/min.
・サンプル調製法
移動相に使用する溶媒で希釈(濃度は0.5〜2重量%の範囲で適宜調節した)して分析に供した。
2. Weight average molecular weight It calculated | required by the gel permeation chromatography (GPC) using the analytical curve created using the polystyrene sample.
The conditions for GPC are as follows.
Apparatus: Tosoh HLC-8020 LC-3A type chromatograph column: TSKgel G1000H XL , TSKgel G2000H XL, and TSKgel G4000H XL (all manufactured by Tosoh) were used in series.
-Data processing device: CR-4A type data processing device manufactured by Shimadzu Corporation-Mobile phase:
Tetrahydrofuran (used for analysis of phenyl group-containing silicone)
Chloroform (used for analysis of silicones that do not contain phenyl groups)
-Flow rate: 1.0 ml / min.
-Sample preparation method It diluted with the solvent used for a mobile phase (concentration was adjusted suitably in the range of 0.5-2 weight%), and used for the analysis.
3.赤外線吸収スペクトル
日本分光製FT/IR−5300型赤外分光計を用いて測定した。
4.光触媒活性
試料表面にメチレンブルーの5質量%エタノール溶液を塗布した後、東芝ライテック製FL20S BLB型ブラックライトの光を24時間照射後、光触媒の作用によるメチレンブルーの分解の程度(皮膜表面の退色の程度に基づき、目視で評価)に基づき、光触媒の活性を以下の3段階で評価した。
なおこのとき、トプコン製UVR−2型紫外線強度計{受光部として、トプコン製UD−36型受光部(波長310〜400nmの光に対応)を使用}を用いて測定した紫外線強度が1mW/cm2となるよう調整した。
◎:メチレンブルーが完全に分解。
△:メチレンブルーの青色がわずかに残る。
×:メチレンブルーの分解はほとんど観測されず。
3. Infrared absorption spectrum The infrared absorption spectrum was measured using an FT / IR-5300 type infrared spectrometer manufactured by JASCO Corporation.
4). Photocatalytic activity After applying a 5% ethanol solution of methylene blue to the sample surface, the light of FL20S BLB type black light manufactured by Toshiba Lighting & Technology was irradiated for 24 hours, and then the degree of decomposition of methylene blue by the action of the photocatalyst (to the degree of fading of the film surface) Based on visual evaluation), the activity of the photocatalyst was evaluated in the following three stages.
At this time, the UV intensity measured using a Topcon UVR-2 type UV intensity meter {using a TOPCON UD-36 type light receiving part (corresponding to light with a wavelength of 310 to 400 nm) as the light receiving part} is 1 mW / cm. It was adjusted to be 2 .
A: Methylene blue is completely decomposed.
Δ: Slightly methylene blue blue remains.
X: Methylene blue was hardly decomposed.
[参考例1]
変性光触媒ヒドロゾル(A−1)の合成。
[Reference Example 1]
Synthesis of modified photocatalytic hydrosol (A-1).
還流冷却器、温度計および撹拌装置を有する反応器に、LS−8600[1,3,5,7−テトラメチルシクロテトラシロキサンの商品名(信越化学工業製)]474g、LS−8620[オクタメチルシクロテトラシロキサンの商品名(信越化学工業製)]76.4g、LS−8490[1,3,5−トリメチル−1,3,5−トリフェニルシクロトリシロキサンの商品名(信越化学工業製)408g、LS−7130[ヘキサメチルジシロキサンの商品名(信越化学工業製)40.5g、及び硫酸化ジルコニア20gを仕込み、50℃で3時間攪拌した後、さらに80℃に加熱したまま5時間攪拌した。硫酸化ジルコニアをろ過したのち、130℃、真空下で低沸分を除去し、重量平均分子量6600、Si−H基含量7.93mmol/gのメチルハイドロジェンシロキサン−メチルフェニルシロキサン−ジメチルシロキサンコポリマー(合成シリコーン化合物)780gを得た。 In a reactor having a reflux condenser, a thermometer and a stirrer, LS-8600 [trade name of 1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)] 474 g, LS-8620 [Octamethyl] Trade name of cyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)] 76.4 g, product name of LS-8490 [1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) 408 g LS-7130 [trade name of hexamethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.), 40.5 g, and 20 g of sulfated zirconia were stirred, stirred at 50 ° C. for 3 hours, and further stirred at 80 ° C. for 5 hours. . After filtering the sulfated zirconia, the low boiling point content was removed under vacuum at 130 ° C., and a methylhydrogensiloxane-methylphenylsiloxane-dimethylsiloxane copolymer (weight average molecular weight 6600, Si—H group content 7.93 mmol / g) ( 780 g of a synthetic silicone compound) was obtained.
還流冷却器、温度計および撹拌装置を取りつけた反応器に、脱水したジオキサン100gと、上記合成シリコーン化合物100gを入れ、撹拌下90℃に昇温した。これにユニオックスPKA−5118[ポリオキシエチレンアリルメチルエーテルの商品名(日本油脂社製)、重量平均分子量800]80gと脱水したジオキサン75g、およびジクロロ−ジシクロペンタジエニル−白金(II)の0.25質量%ジオキサン溶液4.9gを混合した溶液を90℃にて攪拌下約1時間かけて添加し、さらに90℃にて5時間攪拌を続けた後室温にまで冷却することにより、Si−H基含有化合物溶液(1)を得た。
得られたSi−H基含有化合物溶液(1)4gに水100gを加えると、わずかに白濁した分散液となった。
In a reactor equipped with a reflux condenser, a thermometer, and a stirring device, 100 g of dehydrated dioxane and 100 g of the synthetic silicone compound were added, and the temperature was raised to 90 ° C. with stirring. To this, UNIOX PKA-5118 [trade name of polyoxyethylene allyl methyl ether (manufactured by NOF Corporation), weight average molecular weight 800] 80 g and dehydrated dioxane 75 g, and dichloro-dicyclopentadienyl-platinum (II) A solution obtained by mixing 4.9 g of a 0.25% by mass dioxane solution was added at 90 ° C. over about 1 hour with stirring, and further stirred at 90 ° C. for 5 hours, and then cooled to room temperature, thereby cooling Si. A —H group-containing compound solution (1) was obtained.
When 100 g of water was added to 4 g of the obtained Si—H group-containing compound solution (1), a slightly cloudy dispersion was obtained.
また、得られたSi−H基含有化合物溶液(1)0.88gにブチルセロソルブ8gを添加・混合した後、1N水酸化ナトリウム水溶液8mlを添加すると、水素ガスが発生し、その体積は21℃において41.0mlであった。この水素ガス生成量から求めた、Si−H基含有化合物溶液(1)1g当りのSi−H基含量は1.89mmol/g(合成シリコーン化合物1g当たりに換算したSi−H基含量は約6.81mmol/g)であった。 Further, 8 g of butyl cellosolve was added to and mixed with 0.88 g of the obtained Si—H group-containing compound solution (1), and 8 ml of 1N sodium hydroxide aqueous solution was added to generate hydrogen gas. 41.0 ml. The Si—H group content per 1 g of the Si—H group-containing compound solution (1) determined from this hydrogen gas production amount was 1.89 mmol / g (the Si—H group content calculated per 1 g of the synthetic silicone compound was about 6 0.8 mmol / g).
還流冷却器、温度計および撹拌装置を取りつけた反応器に、TKS−203[酸化チタンヒドロゾルの商品名(テイカ製)、中性、TiO2濃度19.2質量%、平均結晶子径6nm(カタログ値)のもの]117.2gと水107.8gを入れた後、これに合成したSi−H基含有化合物溶液(1)40.5gを30℃にて攪拌下約30分かけて添加し、さらに30℃にて12時間撹拌を続けることにより、非常に分散性の良好な変性光触媒ヒドロゾル(A−1)を得た。この時、Si−H基含有化合物溶液(1)の反応に伴い生成した水素ガス量は20℃において940mlであった。また、得られた変性光触媒ヒドロゾルをKBr板上にコーティングしIRスペクトルを測定したところ、Ti−OH基の吸収(3630〜3640cm−1)の消失が観測された。 To a reactor equipped with a reflux condenser, a thermometer and a stirrer, TKS-203 [trade name of titanium oxide hydrosol (manufactured by Teika), neutral, TiO 2 concentration 19.2 mass%, average crystallite diameter 6 nm ( Catalog value)] After 117.2 g and 107.8 g of water were added, 40.5 g of the synthesized Si—H group-containing compound solution (1) was added thereto at 30 ° C. with stirring for about 30 minutes. Further, by continuing stirring at 30 ° C. for 12 hours, a modified photocatalyst hydrosol (A-1) having very good dispersibility was obtained. At this time, the amount of hydrogen gas produced by the reaction of the Si—H group-containing compound solution (1) was 940 ml at 20 ° C. Moreover, when the obtained modified photocatalyst hydrosol was coated on a KBr plate and IR spectrum was measured, the disappearance of Ti—OH group absorption (3630 to 3640 cm −1 ) was observed.
また、得られた変性光触媒ヒドロゾル(A−1)の粒径分布は単一分散(数平均粒子径は24nm)であり、さらに変性処理前のTKS203の単一分散(数平均粒子径は12nm)の粒径分布が大きな粒径側に平行移動していることが確認できた。 Moreover, the particle size distribution of the obtained modified photocatalyst hydrosol (A-1) is a single dispersion (number average particle diameter is 24 nm), and further, the single dispersion of TKS203 before the modification treatment (number average particle diameter is 12 nm). It was confirmed that the particle size distribution of the particles moved parallel to the larger particle size side.
[実施例1]
変性光触媒ヒドロゾル(A−1)から溶媒を除去することにより、粉末状の光触媒体を得た。得られた光触媒体のBET表面積は12m2/gであった。この光触媒体に東芝ライテック製FL20S BLB型ブラックライトの光[トプコン製UVR−2型紫外線強度計{受光部として、トプコン製UD−36型受光部(波長310〜400nmの光に対応)を使用}を用いて測定した紫外線強度が2mW/cm2となるよう調整]を1日間照射すると、BET表面積は45m2/gに増加し多孔質光触媒体を得た。
[Example 1]
By removing the solvent from the modified photocatalyst hydrosol (A-1), a powdery photocatalyst was obtained. The obtained photocatalyst had a BET surface area of 12 m 2 / g. Light of FL20S BLB type black light manufactured by Toshiba Lighting & Technology [Topcon UVR-2 type UV intensity meter {using TOPCON UD-36 type light receiving unit (corresponding to light of wavelength 310 to 400 nm) as the light receiving unit}) UV intensity was measured using the is irradiated one day so Reconciliation as a 2mW / cm 2, BET surface area to obtain a porous photocatalyst increased to 45 m 2 / g.
[実施例2]
参考例1で得られた変性光触媒ヒドロゾル(A−1)を水で2質量%に希釈した水分散体に10cm×10cmの和紙を浸漬させた後、室温で12時間乾燥させることにより光触媒部材を作成した。
得られた光触媒部材に東芝ライテック製FL20SBLB型ブラックライトの光[トプコン製UVR−2型紫外線強度計(受光部:トプコン製UD−36型受光部)を用いて測定した紫外線強度が2mW/cm2となるよう調整]を1日間照射することにより多孔質光触媒部材を得た。
得られた多孔質光触媒部材をメチレンブルーの0.1質量%エタノール溶液に浸漬させた後、室温で2時間乾燥することにより着色させた。これに東芝ライテック製FL20SBLB型ブラックライトの光[上記と同じ強度に調整]を2日間照射すると、メチレンブルーは分解し、着色が消えた。更に、上記光を3ヶ月間照射したが、多孔質光触媒部材の外観は全く変化がなかった。
[Example 2]
A 10 cm × 10 cm Japanese paper was immersed in an aqueous dispersion obtained by diluting the modified photocatalyst hydrosol (A-1) obtained in Reference Example 1 with water to 2% by mass, and then dried at room temperature for 12 hours to obtain a photocatalyst member. Created.
The light intensity of the photocatalyst member obtained by using a light of a FL20SBLB type black light manufactured by Toshiba Lighting & Technology [Topcon UVR-2 type UV intensity meter (light receiving part: UD-36 type light receiving part made by Topcon)] is 2 mW / cm 2. Was adjusted for 1 day to obtain a porous photocatalyst member.
The obtained porous photocatalyst member was dipped in a 0.1% by mass ethanol solution of methylene blue and then colored by drying at room temperature for 2 hours. When this was irradiated with light of a FL20SBLB type black light manufactured by Toshiba Lighting & Technology (adjusted to the same intensity as above) for 2 days, the methylene blue decomposed and the color disappeared. Furthermore, although the said light was irradiated for 3 months, the external appearance of the porous photocatalyst member did not change at all.
[比較例1]
TKS203(参考例1と同じ)を水で2質量%に希釈した水分散体に10cm×10cmの和紙を浸漬させた後、室温で12時間乾燥させることにより光触媒部材(比較)を作成した。
得られた光触媒部材(比較)に東芝ライテック製FL20SBLB型ブラックライトの光[トプコン製UVR−2型紫外線強度計(受光部:トプコン製UD−36型受光部)を用いて測定した紫外線強度が2mW/cm2となるよう調整]を1日間照射した後、メチレンブルーの0.1質量%エタノール溶液に浸漬させ、室温で2時間乾燥することにより着色させた。これに東芝ライテック製FL20SBLB型ブラックライトの光[上記と同じ強度に調整]を2日間照射すると、メチレンブルーは分解し、着色が消えたが、更に光照射を続けると1週間の光照射で和紙の部分的な分解が観察され、1ヶ月の光照射で和紙は原形を留めなくなった。
[Comparative Example 1]
A 10 cm × 10 cm Japanese paper was immersed in an aqueous dispersion obtained by diluting TKS203 (same as Reference Example 1) with water to 2% by mass, and then dried at room temperature for 12 hours to prepare a photocatalytic member (comparison).
The light intensity of the photocatalyst member (comparison) measured using a light of a FL20SBLB type black light manufactured by Toshiba Lighting & Technology [Topcon UVR-2 type UV intensity meter (light receiving part: UD-36 type light receiving part made by Topcon)] is 2 mW. Was adjusted to be / cm 2 ] for 1 day, and then immersed in a 0.1% by mass ethanol solution of methylene blue and colored by drying at room temperature for 2 hours. When irradiated with the light of the FL20SBLB type black light manufactured by Toshiba Lighting & Technology (adjusted to the same intensity as above) for 2 days, the methylene blue decomposed and the color disappeared. Partial decomposition was observed, and the Japanese paper did not retain its original shape after one month of light irradiation.
[比較例2]
実施例2と同様の方法で、未処理の和紙をメチレンブルーで着色し、光照射を実施したが、着色は消えなかった。
[Comparative Example 2]
In the same manner as in Example 2, untreated Japanese paper was colored with methylene blue and irradiated with light, but the coloring did not disappear.
本発明の多孔質光触媒体は、悪臭や空気中の有害物質除去あるいは廃水処理や浄水処理などを行うための環境浄化材料として好適に用いられると共に、衣類等の繊維製品に付着した汚れ(汗、調味料、油等)や壁等に付着したタバコのヤニ等の分解、換気扇等の油汚れの分解、便器・タイル等の微生物等による汚れ防止など、生活空間の環境浄化にも広く利用できる。 The porous photocatalyst of the present invention is suitably used as an environmental purification material for removing bad odors and harmful substances in the air or performing wastewater treatment or water purification treatment, as well as dirt (sweat, (Condiments, oils, etc.) and cigarette dust attached to walls, etc., oil stains of ventilation fans, etc., and prevention of soiling by microorganisms such as toilets, tiles, etc.
Claims (5)
H−(R2SiO)m−SiR2−Q (3)
(式中、Rは各々独立して直鎖状または分岐状の炭素数が1〜30個のアルキル基、炭素数5〜20のシクロアルキル基、直鎖状または分岐状の炭素数が1〜30個のフルオロアルキル基、炭素数2〜30のアルケニル基、フェニル基、炭素数1〜20のアルコキシ基、水酸基から選ばれた1種以上からなる基を表す。
また、式中Qは下記(あ)〜(い)からなる群より選ばれる少なくとも1つの光触媒親和性有機基を含有する基である。
(あ)カルボキシル基あるいはその塩、リン酸基あるいはその塩、スルホン酸基あるいはその塩、アミノ基あるいはその塩、ポリオキシアルキレン基からなる群から選ばれた少なくとも1つの親水性基。
(い)エポキシ基、アクリロイル基、メタアクリロイル基、(環状)酸無水物基、ケト基、カルボキシル基、ヒドラジン残基、イソシアネート基、イソチオシアネート基、水酸基、アミノ基、環状カーボネート基、チオール基、エステル基からなる群から選ばれた少なくとも1つの反応性基。
mは整数であり、0≦m≦1000である。)
(RHSiO)p(R2SiO)q(RQSiO)r(R3SiO1/2)s (4)
(式中、RおよびQは式(3)で定義した通りである。
pは1以上の整数であり、q及びrは0又は1以上の整数であり、(p+q+r)≦10000であり、そしてsは0又は2である。但し、(p+q+r)が2以上の整数であり且つs=0の場合、該Hシリコーン化合物は環状シリコーン化合物であり、s=2の場合、該Hシリコーン化合物は鎖状シリコーン化合物である。) A composite compound (BC) in which a photocatalyst (a) has a strong affinity for the photocatalyst, and a photocatalytic affinity organic component (B) that is decomposed by photocatalysis and a hardly decomposable component (C) that is not easily decomposed by photocatalysis Wherein the composite compound (BC) is a Si—H group-containing compound having a photocatalytic affinity organic group (Q) represented by the formula (3) and / or the formula (4). A photocatalyst for an environmental purification material characterized by
H- (R 2 SiO) m- SiR 2 -Q (3)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon number of 1 to 1. It represents a group consisting of at least one selected from 30 fluoroalkyl groups, alkenyl groups having 2 to 30 carbon atoms, phenyl groups, alkoxy groups having 1 to 20 carbon atoms, and hydroxyl groups.
In the formula, Q is a group containing at least one photocatalytic affinity organic group selected from the group consisting of the following (a) to (ii).
(A) At least one hydrophilic group selected from the group consisting of a carboxyl group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, an amino group or a salt thereof, and a polyoxyalkylene group.
(Ii) Epoxy group, acryloyl group, methacryloyl group, (cyclic) acid anhydride group, keto group, carboxyl group, hydrazine residue, isocyanate group, isothiocyanate group, hydroxyl group, amino group, cyclic carbonate group, thiol group, At least one reactive group selected from the group consisting of ester groups;
m is an integer, and 0 ≦ m ≦ 1000. )
(RHSiO) p (R 2 SiO) q (RQSiO) r (R 3 SiO 1/2 ) s (4)
(Wherein R and Q are as defined in formula (3)).
p is an integer of 1 or more, q and r are 0 or an integer of 1 or more, (p + q + r) ≦ 10000, and s is 0 or 2. However, when (p + q + r) is an integer of 2 or more and s = 0, the H silicone compound is a cyclic silicone compound, and when s = 2, the H silicone compound is a chain silicone compound. )
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JPH06298520A (en) * | 1993-04-13 | 1994-10-25 | Agency Of Ind Science & Technol | Production of silica gel containing dispersed ultrafine titanium oxide particle |
JPH08103631A (en) * | 1993-12-09 | 1996-04-23 | Agency Of Ind Science & Technol | Photocatalytic filter and its production |
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JPH11226422A (en) * | 1998-02-16 | 1999-08-24 | Titan Kogyo Kk | Powdery photocatalyst body, composition for photocatalyst, photocatalyst body and its use |
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