JP2003064606A - Sintered block - Google Patents
Sintered blockInfo
- Publication number
- JP2003064606A JP2003064606A JP2001256179A JP2001256179A JP2003064606A JP 2003064606 A JP2003064606 A JP 2003064606A JP 2001256179 A JP2001256179 A JP 2001256179A JP 2001256179 A JP2001256179 A JP 2001256179A JP 2003064606 A JP2003064606 A JP 2003064606A
- Authority
- JP
- Japan
- Prior art keywords
- titanium dioxide
- sintered block
- apatite
- coated titanium
- sintered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 108
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 56
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims abstract description 56
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 47
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000035699 permeability Effects 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 239000002344 surface layer Substances 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000012790 adhesive layer Substances 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 230000001603 reducing effect Effects 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000002270 dispersing agent Substances 0.000 abstract description 2
- 239000003973 paint Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 239000003381 stabilizer Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 238000000746 purification Methods 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 230000009471 action Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 239000012890 simulated body fluid Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 102100032566 Carbonic anhydrase-related protein 10 Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 101000867836 Homo sapiens Carbonic anhydrase-related protein 10 Proteins 0.000 description 1
- 101000892360 Homo sapiens Protein AF-17 Proteins 0.000 description 1
- 102100040638 Protein AF-17 Human genes 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011990 functional testing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Finishing Walls (AREA)
- Catalysts (AREA)
- Road Paving Structures (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、光触媒作用による
ＮＯｘ低減性能を付与した燒結ブロックおよびその製造
方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sintered block having NOx reduction performance by photocatalysis and a method for producing the same.
【０００２】[0002]
【従来の技術】近年、酸化チタンの光触媒作用により大
気中のＮＯｘ成分を低減できる作用が知られている。こ
のＮＯｘ低減性を応用したものとして、たとえば舗装用
ブロックに酸化チタンの光触媒を付与すれば、それを用
いた舗装道路の近辺の住居等へ侵入するＮＯｘを低減す
ることが大いに期待される。2. Description of the Related Art In recent years, it has been known that the photocatalytic action of titanium oxide can reduce NOx components in the atmosphere. As an application of this NOx reduction property, for example, if a titanium oxide photocatalyst is applied to a paving block, it is expected that NOx entering a house or the like near a paved road using the photocatalyst will be reduced.
【０００３】しかしながら、このようなブロックは、屋
外の道路等に設置されるのが通常であるから、紫外線が
照射される昼間において有効であるが、紫外線が得られ
ない夜間には、ＮＯｘ低減の浄化作用が得られないとい
う欠点があり、効率上問題があった。However, since such a block is usually installed on an outdoor road or the like, it is effective in the daytime when ultraviolet rays are radiated, but it is effective in reducing NOx at night when ultraviolet rays are not obtained. There is a drawback in that a purifying action cannot be obtained, and there is a problem in efficiency.
【０００４】[0004]
【発明が解決しようとする課題】本発明はこのような問
題点を解決するためになされたものであり、耐久性に優
れ、紫外線が得られる昼間の他、紫外線が得られない夜
間でも、実質的に空気中のＮＯx を除去し得る舗装など
に供される燒結ブロックおよびその製造方法を提供す
る。SUMMARY OF THE INVENTION The present invention has been made to solve such problems, and it is excellent in durability and can be used substantially during the daytime when ultraviolet rays can be obtained and at night when ultraviolet rays cannot be obtained. to provide sintered block and a manufacturing method thereof are provided, such as the pavement can remove NO x in the air.
【０００５】[0005]
【課題を解決するための手段】本発明は、アパタイトが
ＮＯｘ ガスを吸着するという知見に基づいてなされた
もので、上記の問題は、透水係数が１×１０-2cm/sec以
上であり、少なくとも一面を形成する表層部分がアパタ
イト被覆二酸化チタンを主成分とする被膜で覆われてい
ることを特徴とする本発明の燒結ブロックによって、解
決することができる。また、本発明は、前記燒結ブロッ
クの表層部分を構成する骨材粒子の表面積の３０％以上
がアパタイト被覆二酸化チタンを含む前記被膜で覆われ
ている形態の前記の燒結ブロックに好ましく具体化され
る。According to the present invention, the apatite is NOx. It was made based on the finding that it adsorbs gas. The above problem is that the water permeability is 1 × 10 -2 cm / sec or more, and the surface layer portion forming at least one surface is composed mainly of apatite-coated titanium dioxide. It can be solved by the sintered block of the present invention, which is characterized in that it is covered with a coating. Further, the present invention is preferably embodied in the above-mentioned sintered block in a form in which 30% or more of the surface area of aggregate particles constituting the surface layer portion of the above-mentioned sintered block is covered with the above-mentioned coating containing apatite-coated titanium dioxide. .
【０００６】また、上記の問題は次のそれぞれの焼結ブ
ロックの製造方法によっても解決される。それは、焼結
ブロックの少なくとも一面にアパタイト被覆二酸化チタ
ン分散水性スラリーを塗布した後、２５０〜８５０℃の
範囲の温度で熱処理し、焼結ブロックの表層部分にアパ
タイト被覆二酸化チタンを主成分とする被膜を形成する
ことを特徴とする、第１の焼結ブロックの製造方法であ
り、また、焼結ブロックの少なくとも一面にアパタイト
被覆二酸化チタンと有機質バインダを含む塗料を塗布し
た後、乾燥し、焼結ブロックの表層部分にアパタイト被
覆二酸化チタンを主成分とする被膜を形成することを特
徴とする、第２の焼結ブロックの製造方法であり、さら
に、焼結ブロックの少なくとも一面に接着層を塗布し、
その上にアパタイト被覆二酸化チタン分散水性スラリー
を塗布した後、乾燥し、焼結ブロックの表層部分にアパ
タイト被覆二酸化チタンを主成分とする被膜を形成する
ことを特徴とする、第３の焼結ブロックの製造方法であ
る。The above problems can also be solved by the following respective manufacturing methods of sintered blocks. It is a coating containing an apatite-coated titanium dioxide-dispersed aqueous slurry on at least one surface of a sintered block and then heat-treated at a temperature in the range of 250 to 850 ° C. A method for producing a first sintered block, comprising: applying a coating containing apatite-coated titanium dioxide and an organic binder to at least one surface of the sintered block, followed by drying and sintering. A second method for producing a sintered block, characterized in that a coating film containing apatite-coated titanium dioxide as a main component is formed on a surface layer portion of the block, and an adhesive layer is applied to at least one surface of the sintered block. ,
A third sintered block, characterized in that an apatite-coated titanium dioxide-dispersed aqueous slurry is applied thereon and dried to form a coating film containing apatite-coated titanium dioxide as a main component on the surface layer portion of the sintered block. Is a manufacturing method.
【０００７】本発明の燒結ブロックは、昼間には、焼結
ブロックの表層部分に形成された二酸化チタン成分が空
気中のＮＯｘ濃度を低減するのは勿論であるが、夜間に
おいても以下の作用を有する。すなわち、本発明は、ア
パタイトが有するＮＯｘ ガスの吸着性を利用したもの
で、燒結ブロックの表層部分を被覆するよう形成された
アパタイト被覆二酸化チタンのアパタイト部分が、夜間
においてＮＯｘガスを吸着し、空気中のＮＯｘ濃度を低
減できる。さらに、その吸着されたＮＯｘは、昼間にお
いて、紫外線の存在下二酸化チタンにより分解されるの
で、実質的に２４時間にわたって、ＮＯｘ浄化作用を発
揮できることになる。In the sintered block of the present invention, the titanium dioxide component formed in the surface layer portion of the sintered block reduces the NOx concentration in the air during the day, but it also has the following effects at night. Have. That is, the present invention is based on NOx contained in apatite. The apatite portion of the apatite-coated titanium dioxide formed so as to cover the surface layer portion of the sintered block adsorbs NOx gas at night and can reduce the NOx concentration in the air by utilizing the adsorbability of gas. Further, the adsorbed NOx is decomposed by titanium dioxide in the presence of ultraviolet rays in the daytime, so that the NOx purification action can be exerted for substantially 24 hours.
【０００８】[0008]
【発明の実施の形態】本発明の焼結ブロックは、如上の
通り、透水係数が１×１０-2cm/sec以上である透水性の
ある燒結ブロックを基体とし、その燒結ブロックの外部
に露出する表面がアパタイト被覆二酸化チタンを主成分
とする被膜で覆われている点を特徴とするが、その実施
形態について、詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION As described above, the sintered block of the present invention uses a sintered block having a water permeability of 1 × 10 −2 cm / sec or more as a base, and is exposed to the outside of the sintered block. Its surface is covered with a film containing apatite-coated titanium dioxide as a main component, and its embodiment will be described in detail.
【０００９】（基体となる燒結ブロック本体について）
本発明の燒結ブロック本体は、少なくともその表層部分
が、主として吸水率１％以下の焼結セラミックスである
磁器質骨材からなることが好ましく、磁器質の骨材粒子
が釉薬質またはガラス質の焼結バインダによって結合さ
れているものが好ましい。(About the main body of the sintered block as a base)
In the sintered block body of the present invention, at least the surface layer portion is preferably made of a porcelain aggregate mainly made of sintered ceramics having a water absorption rate of 1% or less, and the porcelain aggregate particles are a glaze-like or glass-like calcinated substance. Those bound by a binding binder are preferable.
【００１０】本発明では、燒結ブロック本体の表層部分
を磁器質骨材で構成することにより、アパタイト被覆二
酸化チタンを含むスラリー、例えば、アパタイト被覆二
酸化チタンを分散させた水溶液を、燒結ブロックの表面
に塗布すれば、内部まで不要に浸透させることなく効率
よく塗布することができる。また、燒結ブロック自体の
耐圧強度を好ましい５Ｍｐａ以上に向上させることもで
きる。In the present invention, the surface layer portion of the sintered block body is made of porcelain aggregate so that a slurry containing apatite-coated titanium dioxide, for example, an aqueous solution in which the apatite-coated titanium dioxide is dispersed, is applied to the surface of the sintered block. If applied, it can be applied efficiently without unnecessarily penetrating the inside. Further, the pressure resistance of the sintered block itself can be improved to a preferable value of 5 MPa or more.
【００１１】また、本発明の燒結ブロックは、その多孔
性に基づく透水性を有しており、特に舗装用等における
燒結ブロックとして好ましく使用されるものである。そ
の透水性の尺度である透水係数は、インターロッキング
燒結ブロック協会が透水性インターロッキング燒結ブロ
ックの品質管理基準として定めている、１×１０-2（ｃ
ｍ／ｓｅｃ）以上であることが好ましい。また、この透
水係数を満足することにより、燒結ブロックに残留する
後記のＮＯｘ処理成分が雨水等により容易に洗い流され
るという利点がえられる。The sintered block of the present invention has water permeability based on its porosity, and is preferably used as a sintered block particularly for paving. The permeability coefficient, which is a measure of the water permeability, is set by the Interlocking Sintered Block Association as a quality control standard for the permeable interlocking sintered block, which is 1 × 10 -2 (c
m / sec) or more. Further, by satisfying this water permeability, there is an advantage that the NOx-treated component described below remaining in the sintered block is easily washed away by rainwater or the like.
【００１２】なお、この透水係数は、インターロッキン
グ燒結ブロック協会発行の「インターロッキング透水ブ
ロック舗装設計施工要領」（昭和６２年１０月印刷発
行）の第７６頁に記載されている「透水性試験」により
測定される値を用いる。This permeability is described in "Permeability test" on page 76 of "Interlocking permeable block pavement design and construction procedure" (printed in October 1987) issued by the Interlocking Sintered Block Association. The value measured by
【００１３】（アパタイト被覆二酸化チタン）本発明の
アパタイト被覆二酸化チタンは、二酸化チタン粒子をア
パタイトで被覆したものであり、基材となる二酸化チタ
ンは、平均粒径５０ｎｍ以下であることが好ましい。こ
の粒径は、Ｘ線回折法により、Ｄ＝Ｋλ／βｃｏｓθ
（Ｄ：粒径、λ：Ｘ線波長、２θ：散乱角、β：半価
幅、Ｋ＝０．９（シェラーの式））から計算で求められ
る。(Apatite-coated titanium dioxide) The apatite-coated titanium dioxide of the present invention is obtained by coating titanium dioxide particles with apatite, and the titanium dioxide serving as a base material preferably has an average particle size of 50 nm or less. This particle size is D = Kλ / β cos θ by the X-ray diffraction method.
(D: particle size, λ: X-ray wavelength, 2θ: scattering angle, β: half width, K = 0.9 (Scherrer's formula)).
【００１４】この平均粒径が、５０ｎｍを超えると、光
触媒としての活性が低下するので、ＮＯｘ低減効果が減
少する。また、二酸化チタンの結晶構造としては、光触
媒活性の高いアナターゼ型が望ましい。しかし、ルチル
型やブルッカイト、アモルファスの酸化チタンも使用可
能である。If the average particle size exceeds 50 nm, the activity as a photocatalyst decreases, and the NOx reduction effect decreases. Further, the crystal structure of titanium dioxide is preferably anatase type having high photocatalytic activity. However, rutile type, brookite, and amorphous titanium oxide can also be used.
【００１５】アパタイト被覆二酸化チタンは、次の方法
により作成することができる。酸化チタンからなる表面
を持つ基材を擬似体液に浸積することにより、この基材
の表面にアパタイト層が析出する。二酸化チタン膜表面
の大部分は露出していながら部分的にアパタイト層が覆
っている構造となる。このアパタイトの形状は、擬似体
液の組成や浸漬条件によって、形状や大きさ、密度、厚
さを変えることができる。擬似体液は、NaCl、NaHCO3、
KCl、 K2HPO4・3H2O、MgCl2・6H2O、CaCl2 とNa2SO4あ
るいはNaF などを、水に溶かすことで調製される。また
HCl や(CH2OH)3CNH2等によりｐＨを７〜８、特に７．４
に調整することが好ましい。The apatite-coated titanium dioxide can be prepared by the following method. By immersing the base material having the surface made of titanium oxide in the simulated body fluid, the apatite layer is deposited on the surface of the base material. Most of the surface of the titanium dioxide film is exposed, but the structure is partially covered by the apatite layer. The shape, size, density, and thickness of the apatite can be changed depending on the composition of the simulated body fluid and the immersion conditions. The simulated body fluid is NaCl, NaHCO 3 ,
It is prepared by dissolving KCl, K 2 HPO 4 , 3H 2 O, MgCl 2 , 6H 2 O, CaCl 2 and Na 2 SO 4 or NaF in water. Also
The pH is adjusted to 7-8, especially 7.4 with HCl or (CH 2 OH) 3 CNH 2.
It is preferable to adjust
【００１６】こうして得られたアパタイト被覆二酸化チ
タンは、表面がアパタイト膜によって被覆され、さらに
アパタイトは蛋白質やアミノ酸、細菌、ウイルスなどを
吸着するので、表面のアパタイト膜が水中や空気中の細
菌等を吸着することができる。そして、上記アパタイト
膜が表面に細孔を有し、この細孔の底に光触媒として活
性な酸化チタンが露出した状態となっているため、蛍光
灯、白熱灯、ブラックライト、ＵＶランプ、水銀灯、キ
セノンランプ、ハロゲンランプ、メタルハライドランプ
などからの人工光や太陽光などはこの露出部分に照射さ
れる。そして、光の照射によって酸化チタンに生成した
電子と正孔との酸化還元作用により、アパタイト膜が吸
着した蛋白質やアミノ酸、細菌、ウイルス、ＮＯｘなど
を迅速に、かつ連続的に分解除去することができるThe surface of the thus obtained apatite-coated titanium dioxide is coated with an apatite film, and since apatite adsorbs proteins, amino acids, bacteria, viruses, etc., the surface apatite film can prevent bacteria in water or air. Can be adsorbed. Since the apatite film has pores on the surface and titanium oxide active as a photocatalyst is exposed at the bottom of the pores, a fluorescent lamp, an incandescent lamp, a black light, a UV lamp, a mercury lamp, Artificial light such as xenon lamps, halogen lamps, metal halide lamps, and sunlight are applied to these exposed parts. Then, the redox action of electrons and holes generated in titanium oxide by light irradiation can rapidly and continuously decompose and remove proteins, amino acids, bacteria, viruses, NOx, etc. adsorbed on the apatite film. it can
【００１７】（被膜の形成）本発明の特徴的な被膜を有
する焼結ブロックは、以下に説明する本発明の焼結ブロ
ックの製造方法によって容易に得られる。先ず、前記し
た燒結ブロック本体の一表面、特に外部に露出する表面
に前記アパタイト被覆二酸化チタンを主成分とする被膜
を形成するのであるが、この被膜の形成手段としては、
例えばアパタイト被覆二酸化チタン分散水性スラリー
（濃度１〜２０％）を塗布した後、２５０〜８５０℃の
範囲の温度で熱処理すれば、適当なＮＯｘ浄化被膜が形
成される。(Formation of Coating) The sintered block having the characteristic coating of the present invention can be easily obtained by the method for producing a sintered block of the present invention described below. First, one surface of the above-mentioned sintered block body, in particular, a film having the apatite-coated titanium dioxide as a main component is formed on the surface exposed to the outside.
For example, when an apatite-coated titanium dioxide-dispersed aqueous slurry (concentration 1 to 20%) is applied and then heat-treated at a temperature in the range of 250 to 850 ° C., an appropriate NOx purification film is formed.
【００１８】また第２の方法として、アパタイト被覆二
酸化チタンを塗料化し、コーティングすることにより、
簡単に被膜を作ることもできる。例えば、アパタイト被
覆二酸化チタン分散スラリー（濃度１０％）２部に、フ
ッ素樹脂エマルジョンをバインダとして１部混合して得
られるアパタイト被覆二酸化チタンを含む塗料を塗布し
た後、乾燥し、焼結ブロックの表層部分にアパタイト被
覆二酸化チタンを主成分とするＮＯｘ浄化被膜を形成す
ることができる。なお、このフッ素樹脂に代えてシリコ
ン（アルコールタイプ）を用いても同様に有機質バイン
ダを含む塗料とすることができる。As a second method, the apatite-coated titanium dioxide is made into a paint and coated,
It is also possible to easily make a film. For example, a coating containing apatite-coated titanium dioxide obtained by mixing 1 part of a fluororesin emulsion as a binder is applied to 2 parts of an apatite-coated titanium dioxide dispersion slurry (concentration 10%), and then dried to form a surface layer of a sintered block. It is possible to form a NOx purification coating containing apatite-coated titanium dioxide as a main component on the portion. It should be noted that the silicone resin (alcohol type) may be used in place of the fluororesin to form a coating material containing an organic binder.
【００１９】また、第３の方法として、焼結ブロックの
ＮＯｘ浄化被膜の形成予定面に、予めアクリルエマルジ
ョン等を接着層として塗布し、さらに、その上から前記
アパタイト被覆二酸化チタン分散水性スラリーを塗布
し、乾燥させることによっても、前記と同様なＮＯｘ浄
化被膜が形成される。As a third method, an acrylic emulsion or the like is previously applied as an adhesive layer on the surface of the sintered block on which the NOx purification coating is to be formed, and then the apatite-coated titanium dioxide-dispersed aqueous slurry is applied thereon. The NOx purification film similar to the above is also formed by drying.
【００２０】このようなアパタイト被覆二酸化チタンの
コーティング方法には、通常の刷毛塗り、ローラ刷毛塗
り、スプレー方式、浸漬方式（ディッピング）などが適
宜に採用される。この場合、好ましい塗布量は１０〜２
００ｇ／ｍ2 （アパタイト被覆二酸化チタンとして）の
範囲であるが、好ましいＮＯｘ低減効果を得るために
は、形成される被膜は前記燒結ブロックの表面積の３０
％以上を覆うようにするのが望ましい。As a coating method for such apatite-coated titanium dioxide, ordinary brush coating, roller brush coating, spraying method, dipping method (dipping) and the like are appropriately adopted. In this case, the preferable coating amount is 10 to 2
Although it is in the range of 00 g / m 2 (as apatite-coated titanium dioxide), in order to obtain a preferable NOx reduction effect, the film formed is 30 times the surface area of the sintered block.
It is desirable to cover at least%.
【００２１】（本発明の作用）この本発明によれば、燒
結ブロック全体としては適当な透水性が維持されつつ、
その外気に接する表面側の表層部分に形成されたアパタ
イト被覆二酸化チタンを主成分とする被膜によって、Ｎ
Ｏｘを低減できる光触媒機能が付与される。この光触媒
機能により、光が照射された際、空気中のＮＯｘを分解
し、空気中のＮＯｘを積極的に低減することになる。ま
た分解処理された成分は該被膜部分に吸着あるいは残留
するが、それら残留成分は、雨水等によって、例えばＮ
Ｏ3 イオンなどとして洗い流される。(Operation of the present invention) According to the present invention, while the appropriate water permeability is maintained as the whole sintered block,
The apatite-coated titanium dioxide-based coating formed on the surface layer on the surface side that is in contact with the outside air causes N
A photocatalytic function capable of reducing Ox is imparted. With this photocatalytic function, when light is irradiated, NOx in the air is decomposed and NOx in the air is positively reduced. Further, the decomposed components are adsorbed or remain on the coating film portion, and the residual components are, for example, N 2 by rainwater or the like.
It is washed away as O 3 ions.
【００２２】さらに、紫外線が得られない夜間などに
は、空気中のＮＯｘ成分を、前記被膜中の主としてアパ
タイト部分が吸着する。そして、紫外線が得られる昼間
になれば、前記した光触媒機能により、吸着していたＮ
Ｏｘ成分を分解処理するよう機能する。Further, at night when ultraviolet rays are not obtained, NOx components in the air are adsorbed mainly by the apatite portion in the coating film. Then, in the daytime when ultraviolet rays are obtained, the adsorbed N is absorbed by the photocatalytic function.
It functions to decompose the Ox component.
【００２３】従って、本発明の燒結ブロックを路面の舗
装に使用すれば、昼夜を問わず大気中のＮＯｘが低減さ
れることになり、道路近辺の住居等に侵入するＮＯｘが
低減されるのである。また、燒結ブロックに残留したＮ
Ｏｘ処理成分は雨水等により適宜洗い流され、浄化効果
が永続する利点が得られる。Therefore, if the sintered block of the present invention is used for paving a road surface, NOx in the atmosphere will be reduced during the day and night, and NOx that will enter homes and the like near the road will be reduced. . In addition, N remaining in the sintered block
Ox-treated components are appropriately washed off with rainwater or the like, and the advantage that the purifying effect lasts is obtained.
【００２４】[0024]
【実施例】以下に、本発明を実施例に基づいて説明す
る。規定の燒結ブロックをサンプルサイズ１０×１０×
１ｃｍに切り出して基体サンプルとした。アパタイト被
覆二酸化チタン塗料としては、平均粒度２０ｎｍ、アナ
ターゼ型二酸化チタンに対しアパタイトを１０％被覆さ
せ、得た粉体を酸化チタン濃度１０重量％の水分散溶液
（安定剤として分散剤を含有）に調製したものである。
この溶液をアパタイト被覆二酸化チタン換算で１０ｇ／
ｍ2になるように前記サンプルの１表面に塗布し、その
後、乾燥し、被膜を形成し、試料１とした。EXAMPLES The present invention will be described below based on examples. Specified sintered block with sample size 10 × 10 ×
The substrate sample was cut into 1 cm. As the apatite-coated titanium dioxide coating, 10% of apatite is coated on anatase-type titanium dioxide having an average particle size of 20 nm, and the obtained powder is made into an aqueous dispersion solution (containing a dispersant as a stabilizer) having a titanium oxide concentration of 10% by weight. It was prepared.
10 g of this solution in terms of titanium dioxide coated with apatite /
It was applied to one surface of the sample so as to have m 2 and then dried to form a film, which was designated as sample 1.
【００２５】規定の燒結ブロックをサンプルサイズ１０
×１０×１ｃｍに切り出して基体サンプルとした。酸化
チタン濃度１０重量％になるように調整したアパタイト
被覆二酸化チタンスラリーをアパタイト被覆二酸化チタ
ン換算で１０ｇ／ｍ2になるように前記サンプルに１表
面に塗布し、その後、４００℃の温度で熱処理し、被膜
を形成し、試料２とした。A specified sintered block was used for sample size 10
The substrate sample was cut out to a size of x10x1 cm. Apatite-coated titanium dioxide slurry adjusted to have a titanium oxide concentration of 10% by weight was applied to one surface of the sample so as to have an apatite-coated titanium dioxide conversion of 10 g / m 2 , and then heat-treated at a temperature of 400 ° C. Then, a film was formed to obtain Sample 2.
【００２６】規定の燒結ブロックをサンプルサイズ１０
×１０×１ｃｍに切り出して基体サンプルとした。酸化
チタン濃度１０重量％になるように調整した二酸化チタ
ンだけからなるスラリーを二酸化チタン換算で１０ｇ／
ｍ2になるように前記サンプルに１表面に塗布し、その
後、４００℃の温度で熱処理し、被膜を形成し、試料３
とした。A specified sintered block was used for sample size 10
The substrate sample was cut out to a size of x10x1 cm. Slurry consisting only of titanium dioxide adjusted to have a titanium oxide concentration of 10% by weight is converted into titanium dioxide at 10 g /
Sample 1 was coated on one surface so as to have a surface area of m 2 and then heat-treated at a temperature of 400 ° C. to form a film.
And
【００２７】次いで、得られた試料１、２、３について
次の試験を行った。試料を透明ガラス蓋２のガラス容器
内に入れ、ガラス蓋２上方に紫外線光源３を設けて１ｍ
Ｗ／ｃｍ2 の強度の紫外線を照射できるようにした。
（図１参照）また、ＮＯガスボンベと空気ボンベから、
それぞれＮＯガスと空気を供給し、ＮＯ濃度が１ｐｐｍ
となるように調整し、１．０リットル／分の速度でフロ
ーさせ、紫外線を照射しときと照射を中止したときの、
容器内のＮＯ濃度の低減効果をガスメーターで測定し
た。試料１、２、３の低減効果は殆ど同一であり、その
結果を図２に示す。Next, the following tests were conducted on the obtained samples 1, 2, and 3. The sample is placed in the glass container of the transparent glass lid 2, the ultraviolet light source 3 is provided above the glass lid 2 and the distance is 1 m.
Irradiation with ultraviolet rays having an intensity of W / cm 2 was made possible.
(See Fig. 1) Also, from the NO gas cylinder and the air cylinder,
Supplying NO gas and air respectively, NO concentration is 1ppm
And flow at a rate of 1.0 liter / minute, and when the ultraviolet light is irradiated and when the irradiation is stopped,
The effect of reducing the NO concentration in the container was measured with a gas meter. The reduction effects of Samples 1, 2, and 3 are almost the same, and the results are shown in FIG.
【００２８】図２に示す結果によれば、実施例の試料に
接した試験ガスは、紫外線非照射時（ａ領域）には、Ｎ
Ｏ濃度１ｐｐｍレベルを示したが、紫外線照射時（ｂ領
域）には、０．１ｐｐｍレベルに低減し、いずれの試料
でも優れたＮＯ低減効果が得られた。According to the results shown in FIG. 2, the test gas in contact with the sample of the example is N
Although the O concentration was at a level of 1 ppm, it was reduced to a level of 0.1 ppm at the time of ultraviolet irradiation (b region), and an excellent NO reduction effect was obtained for all the samples.
【００２９】さらに、夜間の状態を想定した試験とし
て、テドラーバック（５ｌ）内に前記試料を入れた密閉
袋内に約３０ｐｐｍのＮＯガスを入れ、試験開始後、４
５分の遮光状態の後、紫外線を照射し、遮光時と照射時
の変化を検知管にて測定した。その結果を図３に示す。Furthermore, as a test assuming a nighttime condition, about 30 ppm of NO gas was put in a sealed bag containing the sample in a Tedlar bag (5 l), and after the start of the test, 4
After the light was shielded for 5 minutes, it was irradiated with ultraviolet rays, and the change between the light shield and the light shield was measured by a detector tube. The result is shown in FIG.
【００３０】図３の比較から明らかなように、遮光時に
おいても、本発明の試料１、２の燒結ブロックの場合
（曲線ａ）は、アパタイトの吸着作用によりＮＯｘ低減
効果が発現し、そのＮＯ低減効果は紫外線を照射するこ
とによりさらに促進されることが分った。一方、試料３
の単純な二酸化チタンのみの場合（曲線ｂ）や、二酸化
チタンを付与しないブランクの場合（曲線ｃ）は、遮光
時においてＮＯｘ低減効果が発現しないことが理解され
る。As is clear from the comparison of FIG. 3, in the case of the sintered blocks of Samples 1 and 2 of the present invention (curve a) even when the light is shielded, the NOx reduction effect is exhibited by the apatite adsorption action, and the NO It was found that the reducing effect is further promoted by irradiation with ultraviolet rays. On the other hand, sample 3
It is understood that the NOx reduction effect does not appear when light is shielded in the case of only simple titanium dioxide (curve b) or the blank without titanium dioxide (curve c).
【００３１】以上に述べた本発明の燒結ブロックは、主
に道路構造物、たとえば歩道、車道、公園その他の広
場、駐車場などの舗装用のみならず、各種建造物（ビル
等）の外壁・外溝などに使用されるが、さらにこれらの
用途に限らず、縁石、車止め、プランター、花壇境界
石、プールサイド、墓石、石段、バルコニー、屋上、溝
蓋、校庭、ペデストリアンデッキ、護岸燒結ブロックな
どにも広く用いることができる。The above-mentioned sintered block of the present invention is mainly used not only for paving road structures, such as sidewalks, roadways, parks and other plazas, parking lots, but also for the outer walls of various structures (buildings, etc.). It is used for outer gutters, but is not limited to these applications, but also for curbstones, car stops, planters, flowerbed boundary stones, poolsides, tombstones, stone steps, balconies, rooftops, gutters, schoolyards, pedestrian decks, seawall sinter blocks, etc. It can also be used widely.
【００３２】[0032]
【発明の効果】本発明の燒結ブロックおよびその製造方
法は以上説明したように、透水性を有する多孔性の燒結
ブロックの表層部分にアパタイト被覆二酸化チタンを主
成分とする被膜を設けるので、この燒結ブロックは、舗
装用等として単に前記表層部分を外面として敷設すれ
ば、夜間のＮＯｘ吸着効果と、昼間のＮＯｘ浄化効果の
相乗効果により、実質的に２４時間空気中のＮＯｘ濃度
を低減できるものである。As described above, the sintered block and the method for producing the same of the present invention form a coating containing apatite-coated titanium dioxide as a main component on the surface layer portion of a porous sintered block having water permeability. The block can substantially reduce the NOx concentration in the air for 24 hours by laying the surface layer portion as an outer surface for paving, etc., by the synergistic effect of the NOx adsorption effect at night and the NOx purification effect at daytime. is there.
【００３３】また、本発明の燒結ブロックの表層部分に
吸着または残留したＮＯｘ処理成分は、燒結ブロックの
透水性に基づき雨水等により洗い流すことができ、ＮＯ
ｘ浄化効果を長期間、保持できるなど優れた効果があ
る。従って、本発明は従来の問題を解消した燒結ブロッ
クおよびその製造方法として、技術的価値が極めて大で
ある。Further, the NOx treatment component adsorbed on or remaining on the surface layer portion of the sintered block of the present invention can be washed off with rainwater or the like based on the water permeability of the sintered block, and NO
x It has an excellent effect that the purifying effect can be maintained for a long period of time. Therefore, the present invention has extremely great technical value as a sintered block and a method for manufacturing the same that solve the conventional problems.
【図面の簡単な説明】[Brief description of drawings]
【図１】本発明の燒結ブロックの機能試験に用いる装置
の断面略図。FIG. 1 is a schematic cross-sectional view of an apparatus used for a functional test of a sintered block according to the present invention.
【図２】実施例のＮＯｘ浄化効果を示すグラフ。FIG. 2 is a graph showing the NOx purification effect of the example.
【図３】実施例のＮＯｘ浄化効果を他の観点から示すグ
ラフ。FIG. 3 is a graph showing the NOx purification effect of the embodiment from another viewpoint.
１ 試料、２ 透明ガラス蓋、３ 紫外線光源 1 sample, 2 transparent glass lid, 3 ultraviolet light source
───────────────────────────────────────────────────── フロントページの続き (72)発明者 中根 久志 茨城県北茨城市中郷町字ナメシ田1250番地 ジャニス工業株式会社茨城工場内 Ｆターム(参考） 2D051 AA02 AA05 AB03 AC05 AC08 AF07 AF11 AF17 AH02 AH03 DA01 DC09 2E110 AA64 AB04 AB22 AB46 BB04 GA05W GB01W GB26W 4G069 AA03 AA08 BA04A BA04B BA48A BB14A BB14B BC09A BC09B CA02 CA03 CA10 CA13 EE01 FB14 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Hisashi Nakane 1250 Nameshida, Nakago-cho, Kitaibaraki-shi, Ibaraki Janice Industry Co., Ltd. Ibaraki Factory F term (reference) 2D051 AA02 AA05 AB03 AC05 AC08 AF07 AF11 AF17 AH02 AH03 DA01 DC09 2E110 AA64 AB04 AB22 AB46 BB04 GA05W GB01W GB26W 4G069 AA03 AA08 BA04A BA04B BA48A BB14A BB14B BC09A BC09B CA02 CA03 CA10 CA13 EE01 FB14
Claims (7)
り、少なくとも一面を形成する表層部分がアパタイト被
覆二酸化チタンを主成分とする被膜で覆われていること
を特徴とする燒結ブロック。1. A sintered block having a water permeability of 1 × 10 −2 cm / sec or more and at least a surface layer forming one surface is covered with a film containing apatite-coated titanium dioxide as a main component. .
骨材粒子の表面積の３０％以上がアパタイト被覆二酸化
チタンを含む前記被膜で覆われている請求項１に記載の
燒結ブロック。2. The sintered block according to claim 1, wherein 30% or more of the surface area of aggregate particles constituting the surface layer portion of the sintered block is covered with the coating containing apatite-coated titanium dioxide.
ゼ型である請求項１または２に記載の燒結ブロック。3. The sintered block according to claim 1, wherein the main crystal structure of the titanium dioxide is anatase type.
結バインダによって結合されている請求項１から３まで
のいずれかに記載の燒結ブロック。4. The sintered block according to any one of claims 1 to 3, wherein aggregate particles forming the sintered block are bonded by a sintered binder.
ト被覆二酸化チタン分散水性スラリーを塗布した後、２
５０〜８５０℃の範囲の温度で熱処理し、焼結ブロック
の表層部分にアパタイト被覆二酸化チタンを主成分とす
る被膜を形成することを特徴とする焼結ブロックの製造
方法。5. An apatite-coated titanium dioxide-dispersed aqueous slurry is applied to at least one surface of a sintered block, and then 2
A method for producing a sintered block, comprising performing a heat treatment at a temperature in the range of 50 to 850 ° C. to form a coating film containing apatite-coated titanium dioxide as a main component on a surface layer portion of the sintered block.
ト被覆二酸化チタンと有機質バインダを含む塗料を塗布
した後、乾燥し、焼結ブロックの表層部分にアパタイト
被覆二酸化チタンを主成分とする被膜を形成することを
特徴とする焼結ブロックの製造方法。6. A coating containing apatite-coated titanium dioxide and an organic binder is applied to at least one surface of the sintered block and then dried to form a coating film containing apatite-coated titanium dioxide as a main component on the surface layer portion of the sintered block. A method of manufacturing a sintered block, comprising:
塗布し、その上にアパタイト被覆二酸化チタン分散水性
スラリーを塗布した後、乾燥し、焼結ブロックの表層部
分にアパタイト被覆二酸化チタンを主成分とする被膜を
形成することを特徴とする焼結ブロックの製造方法。7. An adhesive layer is applied to at least one surface of a sintered block, an apatite-coated titanium dioxide-dispersed aqueous slurry is applied thereto, and then dried, and the surface layer portion of the sintered block is mainly composed of apatite-coated titanium dioxide. A method of manufacturing a sintered block, comprising forming a coating film comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001256179A JP2003064606A (en) | 2001-08-27 | 2001-08-27 | Sintered block |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001256179A JP2003064606A (en) | 2001-08-27 | 2001-08-27 | Sintered block |
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| Publication Number | Publication Date |
|---|---|
| JP2003064606A true JP2003064606A (en) | 2003-03-05 |
Family
ID=19084029
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001256179A Pending JP2003064606A (en) | 2001-08-27 | 2001-08-27 | Sintered block |
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| Country | Link |
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| JP (1) | JP2003064606A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003089587A (en) * | 2001-09-14 | 2003-03-28 | National Institute Of Advanced Industrial & Technology | Humidity-controlled ceramics material |
| JP2006238717A (en) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | Culture medium container |
| KR101003010B1 (en) | 2009-12-07 | 2010-12-21 | 라이브텍(주) | Jig for boundary stone |
| KR101464316B1 (en) * | 2013-07-16 | 2014-11-25 | 이혜옥 | A hign-intense guide block and manufacturing method of the same for visually handicapped person |
| WO2016056184A1 (en) * | 2014-10-06 | 2016-04-14 | 株式会社デンソー | Nitrogen oxide storage catalyst |
| CN114423523A (en) * | 2019-09-05 | 2022-04-29 | 伊泰尔瑟股份公司 | Photocatalytic ceramic |
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| JPH0626002A (en) * | 1992-07-09 | 1994-02-01 | Atom Chem Paint Co Ltd | Elastic paving body and forming method therefor |
| JPH09249871A (en) * | 1996-03-14 | 1997-09-22 | Toli Corp Ltd | Stainproofing and deodorizing structure and interior material utilizing the same structure |
| JPH1133413A (en) * | 1997-07-18 | 1999-02-09 | Mitsubishi Materials Corp | Production of structure for air cleaning |
| JPH1150433A (en) * | 1997-08-01 | 1999-02-23 | Kawai Musical Instr Mfg Co Ltd | Photocatalytic wall material |
| JPH11253544A (en) * | 1997-10-31 | 1999-09-21 | Matsushita Electric Ind Co Ltd | Multi-functional member and sheet |
| JPH11268163A (en) * | 1998-03-25 | 1999-10-05 | Toto Ltd | Building material with sound absorbing, sound isolating and acoustic characteristics |
| JP2000045204A (en) * | 1998-07-27 | 2000-02-15 | Toray Ind Inc | Block and its manufacture |
| JP2000126611A (en) * | 1998-10-20 | 2000-05-09 | Rado Kikaku:Kk | Photocatalyst composition and its production |
| JP2001179112A (en) * | 1999-12-24 | 2001-07-03 | Tsuneo Sugito | Method of sticking/fixing titanium dioxide to three- dimensional and two-dimensional structures and contact method |
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2001
- 2001-08-27 JP JP2001256179A patent/JP2003064606A/en active Pending
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| JPH0626002A (en) * | 1992-07-09 | 1994-02-01 | Atom Chem Paint Co Ltd | Elastic paving body and forming method therefor |
| JPH09249871A (en) * | 1996-03-14 | 1997-09-22 | Toli Corp Ltd | Stainproofing and deodorizing structure and interior material utilizing the same structure |
| JPH1133413A (en) * | 1997-07-18 | 1999-02-09 | Mitsubishi Materials Corp | Production of structure for air cleaning |
| JPH1150433A (en) * | 1997-08-01 | 1999-02-23 | Kawai Musical Instr Mfg Co Ltd | Photocatalytic wall material |
| JPH11253544A (en) * | 1997-10-31 | 1999-09-21 | Matsushita Electric Ind Co Ltd | Multi-functional member and sheet |
| JPH11268163A (en) * | 1998-03-25 | 1999-10-05 | Toto Ltd | Building material with sound absorbing, sound isolating and acoustic characteristics |
| JP2000045204A (en) * | 1998-07-27 | 2000-02-15 | Toray Ind Inc | Block and its manufacture |
| JP2000126611A (en) * | 1998-10-20 | 2000-05-09 | Rado Kikaku:Kk | Photocatalyst composition and its production |
| JP2001179112A (en) * | 1999-12-24 | 2001-07-03 | Tsuneo Sugito | Method of sticking/fixing titanium dioxide to three- dimensional and two-dimensional structures and contact method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003089587A (en) * | 2001-09-14 | 2003-03-28 | National Institute Of Advanced Industrial & Technology | Humidity-controlled ceramics material |
| JP2006238717A (en) * | 2005-02-28 | 2006-09-14 | Central Res Inst Of Electric Power Ind | Culture medium container |
| KR101003010B1 (en) | 2009-12-07 | 2010-12-21 | 라이브텍(주) | Jig for boundary stone |
| KR101464316B1 (en) * | 2013-07-16 | 2014-11-25 | 이혜옥 | A hign-intense guide block and manufacturing method of the same for visually handicapped person |
| WO2016056184A1 (en) * | 2014-10-06 | 2016-04-14 | 株式会社デンソー | Nitrogen oxide storage catalyst |
| CN114423523A (en) * | 2019-09-05 | 2022-04-29 | 伊泰尔瑟股份公司 | Photocatalytic ceramic |
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