JPH10194780A - Glass having performance for cutting ultraviolet ray and heat ray and having antifouling performance and its production - Google Patents

Glass having performance for cutting ultraviolet ray and heat ray and having antifouling performance and its production

Info

Publication number
JPH10194780A
JPH10194780A JP34874096A JP34874096A JPH10194780A JP H10194780 A JPH10194780 A JP H10194780A JP 34874096 A JP34874096 A JP 34874096A JP 34874096 A JP34874096 A JP 34874096A JP H10194780 A JPH10194780 A JP H10194780A
Authority
JP
Japan
Prior art keywords
fine particles
glass
zno
ultraviolet
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP34874096A
Other languages
Japanese (ja)
Inventor
Takeshi Kondo
剛 近藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central Glass Co Ltd
Original Assignee
Central Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central Glass Co Ltd filed Critical Central Glass Co Ltd
Priority to JP34874096A priority Critical patent/JPH10194780A/en
Publication of JPH10194780A publication Critical patent/JPH10194780A/en
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials

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  • Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain glass having excellent performances for cutting UV rays and heat rays and an excellent stain-proofing performance by forming at least one coating layer comprising at least ZnO-Sb2 O3 particles and an inorganic binder on the surface of a glass substrate. SOLUTION: This glass is obtained by coating the surface of a glass substrate with a coating liquid comprising ZnO-Sb2 O3 particles having an average particle diameter of about <=100nm in an amount of 50-90wt.% (converted into oxides) based on the whole solid content of the coating liquid, an inorganic binder in an amount of 10-50wt.%, a diluting solvent and a dispersing agent, drying the coated surface at the ordinary temperature to 300 deg.C for 0.5-60min, and subsequently curing the dried coating layer at 300-700 deg.C for 0.1-30min to form at least one cured coating layer comprising at least the ZnO-Sb2 O3 particles and the inorganic binder. If necessary, a SiO2 thin coating film or a SiO2 -TiO2 or SiO2 -ZrO2 oxide thin coating film is formed as a primer layer on the surface of the glass substrate.

Description

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

【０００１】[0001]

【発明の属する技術分野】本発明は、紫外線遮蔽性能お
よび熱線反射性能、ならびに付着有機物を光分解する作
用による防汚・脱臭・抗菌の性能を少なくとも有し、建
築用窓ガラス等各種窓ガラスに使用できる有用な紫外線
と熱線遮蔽性能及び防汚性能を有するガラス及びその製
法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to various window glasses such as architectural window glasses, which have at least an ultraviolet ray shielding performance, a heat ray reflection performance, and an antifouling, deodorizing and antibacterial performance due to the action of decomposing organic substances adhered thereto. The present invention relates to a glass having useful ultraviolet and heat ray shielding performance and antifouling performance, and a method for producing the same.

【０００２】[0002]

【従来の技術】近年、各種基板、特に建築用や車輌用の
ガラスにおいて、人や物材等に対する日焼けなどを防止
し、生活空間における快適さを高め、ガラス基板の色調
や透明感を損なうことなく、可視光を選択的に透過し、
また電波透過性を損なうことがない等、人的および物的
さらに環境に優しくかつ安全性が高くしかも居住性に優
れるガラスが求められ、紫外線吸収膜、紫外線および熱
線吸収膜、あるいは防汚性膜のそれぞれを用いたものが
知られている。2. Description of the Related Art In recent years, various types of substrates, particularly architectural and vehicular glass, have been proposed to prevent sunburn, etc. against people and materials, enhance comfort in living spaces, and impair the color tone and transparency of glass substrates. Without selectively transmitting visible light,
In addition, there is a need for glass that is environmentally friendly, has high safety, and is excellent in habitability, as it does not impair the radio wave transmission properties, and is required to have an ultraviolet absorbing film, an ultraviolet and heat ray absorbing film, or an antifouling film. The use of each of these is known.

【０００３】例えば、特開平6-135746号公報にはゾルゲ
ル溶液を用いた紫外線吸収膜として酸化セリウムと酸化
チタンを含んだ膜が開示されている。また、特開昭63-1
00042 号公報には、微量のPt、RhないしPdを添加した二
酸化チタニウム薄膜が表面に形成された汚れ難いガラス
物品が開示されている。For example, JP-A-6-135746 discloses a film containing cerium oxide and titanium oxide as an ultraviolet absorbing film using a sol-gel solution. Also, JP-A-63-1
No. 00042 discloses a hardly soiled glass article in which a titanium dioxide thin film to which a trace amount of Pt, Rh or Pd is added is formed on the surface.

【０００４】また、特開昭63-5301 号公報には、反射鏡
の鏡面上の最上層に、透明な光触媒層が形成され、光触
媒層がTiO2、Fe2O3 、In2O3 およびWO3 からなる群より
選ばれた少なくとも１つでなり、また光触媒層に、Pt、
Pd、RhおよびIrよりなる群から選ばれた少なくとも１つ
の金属が担持されていることが開示されている。In Japanese Patent Application Laid-Open No. 63-5301, a transparent photocatalyst layer is formed on the uppermost layer on a mirror surface of a reflecting mirror, and the photocatalyst layer is made of TiO 2 , Fe 2 O 3 , In 2 O 3 and at least one in it selected from the group consisting of WO 3, also the photocatalytic layer, Pt,
It is disclosed that at least one metal selected from the group consisting of Pd, Rh and Ir is supported.

【０００５】また、特開平2-75683 号公報には、紫外線
及び赤外線吸収剤及びその処理方法が記載され、0.01μ
m 〜１μm の白色または淡色系の金属酸化物微粒子を高
分子材料含有溶液中に分散せしめたガラス用紫外線及び
赤外線吸収剤が開示され、金属酸化物微粒子がZnO およ
びTiO2の１種または２種の単体、またはこれらを含む化
合物、例えばZn2SiO4 からなる紫外線吸収剤と、金属酸
化物微粒子がTiO2、SiO2、CeO2、ZrO2、Al2O3 、MgO 、
La2O3 、Nd2O3 、Y2O3の中から選ばれた少なくとも１種
以上の単体、またはこれらを含む化合物からなる赤外線
吸収剤とであることが記載されている。Japanese Patent Application Laid-Open No. 2-75683 describes an ultraviolet and infrared absorbing agent and a method for treating the same.
Disclosed are ultraviolet and infrared absorbers for glass in which fine particles of white or light-colored metal oxides having a particle size of m to 1 μm are dispersed in a solution containing a polymer material, wherein the metal oxide fine particles are one or two of ZnO and TiO 2. Alone, or a compound containing these, for example, an ultraviolet absorber made of Zn 2 SiO 4 and metal oxide fine particles TiO 2 , SiO 2 , CeO 2 , ZrO 2 , Al 2 O 3 , MgO,
It describes that it is at least one or more simple substances selected from La 2 O 3 , Nd 2 O 3 , and Y 2 O 3 or an infrared absorbent composed of a compound containing these.

【０００６】また、特開平4-182327号公報には、基体上
にZnO を含有した膜厚0.5 μm 以上の紫外線吸収膜が設
けられた表面処理ガラス、ならびに焼成によりZnO にな
りうる原料を含む液体をガラス基板上に塗布し、これを
焼成すると同時に該ガラス基板に強化かつ／又は曲げ加
工を施す表面処理ガラスの製造方法が開示され、基体が
Na+ を含有するガラス、紫外線吸収膜のアンダ−コ−ト
やオ−バ−コ−ト膜として金属酸化物膜を形成するこ
と、前記表面処理ガラスを用いた自動車用窓ガラス、あ
るいはコ−ト膜の組成としてはZnO の超微粒子をシリコ
−ン系の無機バインダ−で保持した膜が厚膜組成として
用いられること等が開示されている。JP-A-4-182327 discloses a surface-treated glass having a substrate on which an ultraviolet absorbing film containing ZnO and having a thickness of 0.5 μm or more is provided, and a liquid containing a raw material which can be turned into ZnO by firing. Is coated on a glass substrate, and is baked and, at the same time, the glass substrate is strengthened and / or bent.
Glass containing Na + , forming a metal oxide film as an undercoat or overcoat film of an ultraviolet absorbing film, an automotive window glass using the surface-treated glass, It is disclosed that as a composition of a thin film, a film in which ZnO ultrafine particles are held by a silicon-based inorganic binder is used as a thick film composition.

【０００７】また、特開平4-307066号公報には、脱臭パ
ネル機構及び脱臭疑似窓機構が記載され、パネルの裏面
あるいは透光パネルの室内側面に光触媒を付設し、この
光触媒への波長410nm 以下の紫外線を含む光線を照射す
る短波長光ランプを設置し、光線を照射するようにした
ものが開示され、光触媒はTiO2単独またはTiO2に波長調
整のためにSnO2、WO3 、Y2O3等の添加物を添加したもの
であり、パネルはガラス板等であることが記載されてい
る。Japanese Patent Application Laid-Open No. 4-307066 describes a deodorizing panel mechanism and a deodorizing pseudo window mechanism. A photocatalyst is provided on the back surface of the panel or on the indoor side surface of the translucent panel, and the wavelength of the photocatalyst is 410 nm or less. UV established a short wavelength light lamp for irradiating light including of those so as to irradiate a light beam is disclosed, SnO 2, WO 3 photocatalyst for wavelength tuning to the TiO 2 alone or TiO 2, Y 2 It describes that an additive such as O 3 is added, and that the panel is a glass plate or the like.

【０００８】また、特開平5-339033号公報には、紫外線
遮断ガラスの製造方法、自動車用窓ガラス及び建築用窓
ガラスが記載され、粒径が0.1 μm 以下の酸化亜鉛微粉
末を、オルガノポリシロキサン溶液にSiO2／ZnO=0.25〜
0.67( 重量比）の割合となるよう混合し、酸化亜鉛微粉
末を分散させて得られた液を板ガラスに乾燥時膜厚で0.
2 〜1.5 μm の厚さになるように塗布し、その後この板
ガラスを580 〜700 ℃で焼成することが開示されてい
る。JP-A-5-339033 describes a method for producing an ultraviolet-shielding glass, a window glass for automobiles and a window glass for buildings, wherein a fine zinc oxide powder having a particle size of 0.1 μm or less is treated with an organopolysiloxane. SiO 2 /ZnO=0.25~ to the siloxane solution
Mix at a ratio of 0.67 (weight ratio), and disperse the zinc oxide fine powder.
It is disclosed that the glass sheet is applied to a thickness of 2 to 1.5 μm, and then the sheet glass is fired at 580 to 700 ° C.

【０００９】さらに、本出願人が既に出願した発明に係
わる特開平5-147978号公報には、ガラス上に紫外線吸収
膜を設け、外部被覆として酸化物被膜を有する紫外線吸
収ガラスを開示し、紫外線吸収膜が少なくとも酸化亜鉛
を含むこと、また外部被覆が少なくともシリコン、ジル
コニウムまたはチタンの１種以上の酸化物よりなるもの
であることを記載した。Further, Japanese Patent Application Laid-Open No. HEI 5-47978, which is related to the invention already filed by the present applicant, discloses an ultraviolet absorbing glass having an ultraviolet absorbing film provided on glass and an oxide coating as an outer coating. It is stated that the absorbing film contains at least zinc oxide, and that the outer coating is made of at least one oxide of silicon, zirconium or titanium.

【００１０】また、特開平5-253544号公報には、脱臭機
能を備えた板状部材の製造方法が記載され、板状部材の
表面にバインダ層を形成し、このバインダ層の表面にア
ナタ−ゼ型TiO2を主体とする光触媒微粉末をその一部が
バインダ層から露出するように吹き付けて付着させ、次
いで300 〜850 ℃で加熱しバインダ層を溶融せしめた
後、冷却し固化せしめるようにしたことが開示されてい
る。Japanese Patent Application Laid-Open No. 5-253544 discloses a method for manufacturing a plate-like member having a deodorizing function. A binder layer is formed on the surface of the plate-like member, and an anater is provided on the surface of the binder layer. A photocatalyst fine powder mainly composed of zeolite TiO 2 is sprayed and adhered so that a part thereof is exposed from the binder layer, and then heated at 300 to 850 ° C. to melt the binder layer, and then cool and solidify. Is disclosed.

【００１１】また、特開平7-232080号公報には、光触媒
機能を有する多機能材及びその製造方法が記載され、基
材表面にバインダ−層を介して光触媒層が保持された光
触媒機能を有する多機能材において、光触媒層の上層部
は外気と接するようにバインダ−層から露出され、また
光触媒層の下層部はその一部がバインダ−層内に埋設さ
れていることが開示され、光触媒粒子は、TiO2、ZnO 、
SrTiO2、Fe2O3 、WO3、FeTiO2、Bi2O3 、SnO2等であ
り、バインダ−層の厚さは0.1 〜0.9 μm であることが
好ましく、光触媒粒子の間隙に充填される粒子は、Sn、
Ti、Ag、Cu、Zn、Fe、Pt、Co、Ni等の金属または酸化物
であること、防臭性、防汚性、抗菌性、抗カビ性等の機
能を付加すること等が記載されている。Japanese Patent Application Laid-Open No. 7-232080 describes a multifunctional material having a photocatalytic function and a method for producing the same, and has a photocatalytic function in which a photocatalytic layer is held on a base material surface via a binder layer. In the multifunctional material, it is disclosed that the upper layer of the photocatalyst layer is exposed from the binder layer so as to be in contact with the outside air, and the lower layer of the photocatalyst layer is partially embedded in the binder layer. Is TiO 2 , ZnO,
SrTiO 2 , Fe 2 O 3 , WO 3 , FeTiO 2 , Bi 2 O 3 , SnO 2, etc., and the thickness of the binder layer is preferably 0.1 to 0.9 μm, and is filled in the gap between the photocatalyst particles. The particles are Sn,
It is described that it is a metal or oxide such as Ti, Ag, Cu, Zn, Fe, Pt, Co, Ni, etc., and that it adds a function such as deodorant, antifouling, antibacterial, antifungal, etc. I have.

【００１２】また、特開平7-289913号公報には、光触媒
体及びその製造方法が記載され、基板表面に亜鉛の陽極
酸化によって形成された粒径0.2 μm 以下の酸化亜鉛微
粒子からなる酸化亜鉛被膜を有することが開示されてい
る。JP-A-7-289913 describes a photocatalyst and a method for producing the same, and discloses a zinc oxide coating comprising fine particles of zinc oxide having a particle size of 0.2 μm or less formed on a substrate surface by anodic oxidation of zinc. Is disclosed.

【００１３】さらに、特開平7-300344号公報には、紫外
線・赤外線または赤外線遮断膜とその形成材が記載さ
れ、溶媒中に、Si、Ti、V 、Cr、Mn、Fe、Co、Ga、Ge、
Zr、In、SnおよびHfよりなる群から選ばれた１種または
２種以上の金属を合計で、全金属量の0.1 〜25原子％の
割合で含有する酸化亜鉛粉末と、加水分解により皮膜を
形成する金属アルコキシドとを含有することが開示され
ている。Further, Japanese Patent Application Laid-Open No. 7-300344 describes an ultraviolet / infrared or infrared ray shielding film and a material for forming the same, and in a solvent, Si, Ti, V, Cr, Mn, Fe, Co, Ga, Ge,
A zinc oxide powder containing a total of one or two or more metals selected from the group consisting of Zr, In, Sn and Hf at a ratio of 0.1 to 25 atomic% of the total metal; It contains a metal alkoxide to be formed.

【００１４】[0014]

【発明が解決しようとする課題】前述したように、紫外
線吸収膜に係わるものとして、特開平6-135746号公報に
記載のTiO2とCeO2を含む紫外線吸収膜、特開平4-182327
号公報に記載のZnO を含有した膜厚0.5 μm 以上の紫外
線吸収膜、特開平5-339033号公報に記載のオルガノポリ
シロキサン溶液にSiO2／ZnO=0.25〜0.67（重量比）の割
合で粒径が0.1 μm 以下の酸化亜鉛微粒子を分散した液
により0.2 〜1.5 μm の厚さに成膜した紫外線遮断ガラ
ス、あるいは本出願人が既に出願した発明に係わる特開
平5-147978号公報に記載のZnO を少なくとも含む紫外線
吸収膜／SiO2、ZrO2、TiO2の１種以上の外部被覆でなる
紫外線吸収ガラス等がある。As described above, as an ultraviolet absorbing film, an ultraviolet absorbing film containing TiO 2 and CeO 2 described in JP-A-6-135746,
JP-A-5-339033 discloses an ultraviolet absorbing film containing ZnO and having a film thickness of 0.5 μm or more, and particles of an organopolysiloxane solution described in JP-A-5-339033 in a ratio of SiO 2 /ZnO=0.25 to 0.67 (weight ratio). An ultraviolet shielding glass formed to a thickness of 0.2 to 1.5 μm with a liquid in which zinc oxide fine particles having a diameter of 0.1 μm or less are dispersed, or described in Japanese Patent Application Laid-Open No. 5-147978, which relates to the invention already filed by the present applicant. UV absorbing film containing at least ZnO / UV absorbing glass having at least one outer coating of SiO 2 , ZrO 2 , and TiO 2 .

【００１５】また、紫外線と赤外線吸収膜に係わるもの
として、特開平2-75683 号公報に記載の粒径0.01〜1 μ
m のZnO とTiO2、Zn2SiO4 の紫外線吸収金属微粒子と、
TiO2、SiO2、CeO2、ZrO2、Al2O3 、MgO 、La2O3 、Nd2O
3 、Y2O3の赤外線吸収金属酸化物微粒子とからなる紫外
線及び赤外線吸収剤、あるいは特開平7-300344号公報に
記載の全金属量の0.1 〜25原子％の割合でSi、Ti、V 、
Cr、Mn、Fe、Co、Ga、Ge、Zr、In、SnおよびHfなどを含
有する酸化亜鉛粉末等からなる紫外線・赤外線遮断膜等
がある。Further, as a material relating to the ultraviolet and infrared absorbing film, a particle size of 0.01 to 1 μm described in JP-A-2-75683 is disclosed.
m ultraviolet light absorbing metal fine particles of ZnO and TiO 2 , Zn 2 SiO 4 ,
TiO 2, SiO 2, CeO 2 , ZrO 2, Al 2 O 3, MgO, La 2 O 3, Nd 2 O
3, Y 2 O 3 of consisting of infrared absorbing metal oxide fine particles ultraviolet and infrared absorbing agent, or Si in a proportion of 0.1 to 25 atomic% of the total amount of metal described in JP-A-7-300344, Ti, V ,
There is an ultraviolet / infrared shielding film made of a zinc oxide powder containing Cr, Mn, Fe, Co, Ga, Ge, Zr, In, Sn, Hf and the like.

【００１６】また、光触媒による防汚性膜に係わるもの
として、特開昭63-100042 号公報に記載のPt、Rh、Pd微
量添加のTiO2薄膜、特開昭63-5301 号公報に記載の光触
媒層がTiO2、Fe2O3 、In2O3 、WO3 、またはPt、Rh、P
d、Ir担持の該酸化物でなる面を有する反射鏡、特開平4
-307066号公報に記載のTiO2単独またはTiO2に波長調整
のためのSnO2、WO3 、Y2O3を添加した光触媒を付設した
ガラス板、特開平5-253544号公報に記載のアナタ−ゼ型
TiO2を主体とする光触媒微粉末をその一部がバインダ層
表面から露出するようにした板状部材、特開平7-232080
号公報に記載の光触媒粒子がTiO2、ZnO 、SrTiO2、Fe2O
3 、WO3 、FeTiO2、Bi2O3 、SnO2等であり、光触媒粒子
の間隙充填粒子がSn、Ti、Ag、Cu、Zn、Fe、Pt、Co、Ni
の金属または酸化物である光触媒機能を有する多機能
材、あるいは特開平7-289913号公報に記載の特定の粒径
0.2 μm 以下の酸化亜鉛微粒子からなる酸化亜鉛被膜の
光触媒体等がある。[0016] Further, as for the antifouling film using a photocatalyst, a TiO 2 thin film to which a small amount of Pt, Rh and Pd is added as described in JP-A-63-100042, and a TiO 2 thin film as described in JP-A-63-5301 are disclosed. 2 photocatalyst layer is TiO, Fe 2 O 3, In 2 O 3, WO 3 , or Pt, Rh, P,
d, a reflector having a surface made of the oxide carrying Ir,
-307066 A glass plate provided alone with TiO 2 or a photocatalyst obtained by adding SnO 2 , WO 3 , and Y 2 O 3 for wavelength adjustment to TiO 2 , -Z type
Plate member in which a part of the photocatalyst fine powder mainly composed of TiO 2 is exposed from the surface of the binder layer, JP-A-7-232080
The photocatalyst particles described in the publication are TiO 2 , ZnO, SrTiO 2 , Fe 2 O
3, a WO 3, FeTiO 2, Bi 2 O 3, SnO 2 or the like, gap-filling particles Sn photocatalyst particles, Ti, Ag, Cu, Zn , Fe, Pt, Co, Ni
Multifunctional material having a photocatalytic function that is a metal or oxide, or a specific particle size described in JP-A-7-289913
There is a photocatalyst with a zinc oxide coating made of zinc oxide fine particles of 0.2 μm or less.

【００１７】これらはいずれも、最近求められている紫
外線および熱線遮蔽性能ならびに防汚性能等を同時に付
与した膜ではなく、このためこれら多機能を備えた膜ま
たは積層膜を簡便で効率よく提供できるようにすること
が望まれている。All of these are not films which simultaneously provide ultraviolet and heat ray shielding performance and antifouling performance, etc., which have been required recently, and therefore, a film or multilayer film having these multi-functions can be provided simply and efficiently. It is desired to do so.

【００１８】[0018]

【課題を解決するための手段】本発明は、従来のこのよ
うな課題に鑑みてなしたものであり、少なくとも紫外線
遮蔽性と導電性を有するZnO-Sb2O3 微粒子を塗布溶液中
に分散性がよく混合せしめた塗布液を用いて簡便にかつ
効率よく成膜でき、ZnO-Sb2O3 微粒子を無機バインダ−
で担持する膜とすることにより、紫外線遮蔽性能と熱線
遮蔽性能とを付与できることに加え、防汚性能をも付与
することができることを見出した。さらに本発明は、透
明性が高く、耐光性、耐薬品性等に優れ耐久性を発揮で
き、建築用窓材はもちろん各種窓材にも適用でき、最近
のニーズに答え得る有用な紫外線と熱線遮蔽性能及び防
汚性能を有するガラス及びその製法を下記の手段により
提供する。DISCLOSURE OF THE INVENTION The present invention has been made in view of such a conventional problem, and disperses ZnO-Sb 2 O 3 fine particles having at least ultraviolet shielding property and conductivity in a coating solution. sex can be easily and efficiently formed by using a coating solution was allowed mixing well, an inorganic binder and ZnO-Sb 2 O 3 fine particles -
It has been found that, by making the film supported by the above, it is possible to impart not only ultraviolet shielding performance and heat ray shielding performance but also antifouling performance. Furthermore, the present invention has high transparency, excellent durability against light and chemicals, etc., and can be applied to various window materials as well as architectural window materials. A glass having a shielding performance and an antifouling performance and a method for producing the same are provided by the following means.

【００１９】すなわち、本発明は、ガラス基板の表面
に、少なくともZnO-Sb2O3 微粒子と無機バインダ−から
なる膜層を、少なくとも−層成膜して成ることを特徴と
する紫外線と熱線遮蔽性能及び防汚性能を有するガラ
ス。That is, the present invention is characterized in that at least a film layer composed of at least ZnO—Sb 2 O 3 fine particles and an inorganic binder is formed on the surface of a glass substrate, and the ultraviolet ray and the heat ray shielding are formed. Glass with performance and antifouling performance.

【００２０】さらに、前記ZnO-Sb2O3 微粒子と無機バイ
ンダ−からなる膜層の下地層が、SiO2薄膜あるいはSiO2
系複合酸化物薄膜で成るとよい。また、前記SiO2系複合
酸化物薄膜は、SiO2-TiO2 あるいはSiO2-ZrO2 の薄膜で
あるとよい。Furthermore, the ZnO-Sb 2 O 3 fine particles and inorganic binder - underlayer made of film layers, SiO 2 thin film or SiO 2
It is preferable to use a composite oxide thin film. Further, the SiO 2 -based composite oxide thin film is preferably a SiO 2 -TiO 2 or SiO 2 -ZrO 2 thin film.

【００２１】さらに、前記した少なくともZnO-Sb2O3 微
粒子と無機バインダ−からなる膜層が、該ZnO-Sb2O3 微
粒子と無機バインダ−に，CeO2微粒子、TiO2微粒子また
はATO 微粒子のうち、少なくとも１種以上を含有して成
るものでもよい。Further, a film layer comprising at least the above-mentioned ZnO-Sb 2 O 3 fine particles and an inorganic binder is provided on the ZnO-Sb 2 O 3 fine particles and the inorganic binder to form CeO 2 fine particles, TiO 2 fine particles or ATO fine particles. Among them, those containing at least one kind may be used.

【００２２】また、製法は、ガラス基板の表面に、ZnO-
Sb2O3 微粒子と無機バインダ−と希釈溶媒と分散剤から
少なくとも成る塗布液を塗布し、次いで乾燥、焼成し、
少なくともZnO-Sb2O3 微粒子と無機バインダ−からなる
膜層を、少なくとも−層成膜する。The manufacturing method is such that ZnO-
Sb 2 O 3 fine particles and inorganic binder - and applying at least comprising coating solution from the dilution solvent and a dispersant, then dried, calcined,
At least a film layer composed of at least ZnO—Sb 2 O 3 fine particles and an inorganic binder is formed.

【００２３】さらに、前記塗布液中において、全固形分
量に対し酸化物換算で、ZnO-Sb2O3微粒子を50乃至90重
量％と無機バインダ−を10乃至50重量％を少なくとも含
むものであるとよい。Further, the coating liquid preferably contains at least 50 to 90% by weight of ZnO-Sb 2 O 3 fine particles and 10 to 50% by weight of an inorganic binder in terms of oxide based on the total solid content. .

【００２４】さらに、前記塗布液中において、全固形分
量に対し酸化物換算で、酸化物微粒子の合計量が60乃至
90重量％であって、ZnO-Sb2O3 微粒子を40乃至89重量
％、CeO2微粒子、TiO2微粒子またはATO 微粒子のうち少
なくとも１種以上を 1乃至20重量％、および無機バイン
ダ−を10乃至40重量％を少なくとも含むものであるとよ
い。Further, in the above-mentioned coating solution, the total amount of oxide fine particles in terms of oxide is 60 to
90% by weight, 40 to 89% by weight of ZnO-Sb 2 O 3 fine particles, 1 to 20% by weight of at least one of CeO 2 fine particles, TiO 2 fine particles or ATO fine particles, and 10% by weight of inorganic binder. It is preferred that the composition contains at least 40% by weight.

【００２５】さらに、前記無機バインダ−が、金属アル
コキド類を主成分とするものであるとよい。さらにま
た、前記ガラス基板の表面に下地層を形成するには、シ
リコンアルコキシド類、あるいはシリコンアルコキシド
類とチタンアルコキシド類またはジルコニアアルコキシ
ド類でなる溶液を塗布し、SiO2薄膜あるいはSiO2-TiO2
系あるいはSiO2-ZrO2 系の複合酸化物薄膜を形成して成
ることを特徴とする。Further, it is preferable that the inorganic binder contains a metal alkoxide as a main component. Furthermore, in order to form an underlayer on the surface of the glass substrate, a solution containing silicon alkoxides, or silicon alkoxides and titanium alkoxides or zirconia alkoxides is applied, and a SiO 2 thin film or SiO 2 -TiO 2
Or a composite oxide thin film of SiO 2 -ZrO 2 type.

【００２６】[0026]

【発明の実施の形態】前記したように、ガラス基板の表
面に、少なくともZnO-Sb2O3 微粒子と無機バインダ−か
らなる膜層を、少なくとも−層成膜して成る紫外線と熱
線遮蔽性能及び防汚性能を有するガラスを製造するにあ
たっては次のようにする。DESCRIPTION OF THE PREFERRED EMBODIMENTS As described above, at least a film layer composed of at least ZnO-Sb 2 O 3 fine particles and an inorganic binder is formed on the surface of a glass substrate, and the ultraviolet ray and heat ray shielding performance and In producing glass having antifouling performance, the following is performed.

【００２７】ガラス基板としては、自動車用ならびに建
築用ガラス等に通常用いられているソーダライムシリケ
ートガラスからなる普通板ガラス、所謂フロート板ガラ
スなどであり、クリアをはじめグリ−ン、ブロンズ等各
種着色ガラスや各種機能性ガラス、強化ガラスやそれに
類するガラス、合せガラスのほか複層ガラス等、さらに
平板あるいは曲げ板等各種板ガラス製品として使用でき
ることは言うまでもない。また板厚としては例えば約1.
0mm 程度以上約12mm程度以下であり、建築用としては約
2.0mm 程度以上約10mm程度以下が好ましく、自動車用と
しては約1.5mm程度以上約6.0mm 程度以下が好ましく、
より好ましくは約2.0mm 程度以上約4.0mm 程度以下のガ
ラスである。Examples of the glass substrate include ordinary plate glass made of soda lime silicate glass and so-called float plate glass which are usually used for automotive and architectural glass, and various types of colored glass such as clear, green and bronze. Needless to say, it can be used as various functional glass, tempered glass or similar glass, laminated glass, multi-layer glass, and various flat glass products such as flat and bent plates. The plate thickness is, for example, about 1.
It is about 0mm or more and about 12mm or less.
About 2.0 mm or more and about 10 mm or less are preferable, and about 1.5 mm or more and about 6.0 mm or less are preferable for automobiles.
More preferably, the glass is about 2.0 mm or more and about 4.0 mm or less.

【００２８】また、ZnO-Sb2O3 微粒子としては、三酸化
アンチモン（Sb2O3 ）と酸化亜鉛（ZnO ）のモル比が、
ZnO ／Sb2O3=約0.8 〜1.2 程度であり、好ましくは等モ
ルでなる複合酸化物であって、該アンチモン酸亜鉛（Zn
O-Sb2O3 ）を粉末にしたものであり、屈折率が約1.8 程
度で平均粒径が約100nm 程度以下、好ましくは約50nm程
度以下であり、コスト的にも比較的得易いものであり、
該ZnO-Sb2O3 微粒子は分散性がよくかつ加水分解液など
に混合することができ、耐光性や耐熱性に優れ、紫外線
遮蔽効果を持ちかつ透明性が高い膜を得ることができる
ものである。また、ZnO-Sb2O3 微粒子分散溶液として
は、セルナックスCX-Z200M〔日産化学工業（株）製、酸
化物ゾル液、固形分約20wt％、粒子径約20〜30nm〕等が
挙げられる。As the ZnO-Sb 2 O 3 fine particles, the molar ratio of antimony trioxide (Sb 2 O 3 ) to zinc oxide (ZnO) is as follows:
ZnO / Sb 2 O 3 = approximately 0.8 to 1.2, preferably an equimolar complex oxide, wherein the zinc antimonate (Zn
O-Sb 2 O 3 ) is a powder having a refractive index of about 1.8 and an average particle size of about 100 nm or less, preferably about 50 nm or less, and is relatively easy to obtain in terms of cost. Yes,
The ZnO-Sb 2 O 3 fine particles have good dispersibility and can be mixed with a hydrolyzing solution or the like, and can provide a film having excellent light resistance and heat resistance, having an ultraviolet shielding effect and having high transparency. It is. As the ZnO-Sb 2 O 3 fine particle dispersed solution, Celnax CX-Z200M (manufactured by Nissan Chemical Industries, Ltd.), an oxide sol solution, about 20 wt% solids, particle size about 20~30nm] and the like .

【００２９】さらに、上記したZnO-Sb2O3 微粒子の他
に、CeO2微粒子、TiO2微粒子（例えば、アナタ−ゼ型Ti
O2微粒子）またはATO （Sb2O3 ド−プSnO2である）微粒
子のうち、少なくとも１種以上を含有せしめることによ
って、紫外線吸収性能と熱線吸収性能と防汚性能を、高
いレベルでバランスせしめたり、場合によってはこれら
性能のうち、少なくとも１種以上の性能に強弱をもたら
しめたりする等、適宜調整することができる。Further, in addition to the above-mentioned ZnO-Sb 2 O 3 fine particles, CeO 2 fine particles and TiO 2 fine particles (for example, anatase type Ti)
O 2 particles) or ATO (Sb 2 O 3 de - among flop SnO 2 in a) particles, by allowed to contain at least one or more ultraviolet absorbing performance and heat ray absorbing performance and antifouling performance, balanced at a high level It can be adjusted as appropriate, for example, or depending on the case, the strength of at least one or more of these performances can be brought about.

【００３０】また、無機バインダ−としては、Si、Al、
Ti、Sn、Zrの金属アルコキド類の加水分解物等のうちの
１種あるいは２種以上が挙げられ、特にZnO-Sb2O3 微粒
子を分散性よく分散しかつ膜として充分に担持するバイ
ンダ−機能性膜層を形成するものであり、なかでも耐摩
耗性や耐候性や耐薬品性等を高め耐久性をアップせしめ
るものとしてはSiやSi系のものがより好ましい。As the inorganic binder, Si, Al,
Ti, Sn, 1 kind or 2 or more of the hydrolysis products of Zr metal alkoxide such are mentioned, a binder especially sufficiently carrying ZnO-Sb 2 O 3 fine particles as a dispersion with good dispersing and film - Of those which form a functional film layer, among them, Si or Si-based ones are more preferable as those which increase abrasion resistance, weather resistance, chemical resistance and the like and improve durability.

【００３１】無機バインダ−の主な原料としては、前記
金属アルコキド類であるが、具体例としては、Siアルコ
キシド類が、テトラエトキシシラン、テトラメトキシシ
ラン、モノメチルトリエトキシシラン、モノメチルトリ
メトキシシラン、テトラアルコキシシラン、アルキルア
ルコキシシラン、ジメチルジメトキシシラン、ジメチル
ジエトキシシランなど、またTiアルコキシド類が、テト
ライソプロポキシチタン、テトラノルマルブトキシチタ
ン、トリイソプロポキシチタンモノアセチルアセトナ−
トなど、またZrアルコキシド類が、テトラノルマルブト
キシジルコニウム、テトラノルマルブトキシジルコニウ
ムモノアセチルアセトナ−トなどである。さらに二次的
なものとしては、コロイダルシリカ、アルミナゾルなど
が挙げられる。The main raw materials of the inorganic binder are the above-mentioned metal alkoxides. Specific examples include Si alkoxides such as tetraethoxysilane, tetramethoxysilane, monomethyltriethoxysilane, monomethyltrimethoxysilane and tetramethylsilane. Alkoxysilane, alkylalkoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, etc., and Ti alkoxides are tetraisopropoxytitanium, tetranormal butoxytitanium, triisopropoxytitanium monoacetylacetonate
And Zr alkoxides such as tetra-n-butoxyzirconium and tetra-n-butoxy-zirconium monoacetylacetonate. Further secondary materials include colloidal silica and alumina sol.

【００３２】なお、上記した各微粒子あるいは無機バイ
ンダ−の他に、例えば着色や各種機能を付与するため、
適宜各種金属、金属および酸化物の微粒子あるいは各種
金属酸化物等を添加し含有させることができる。In addition to the above-mentioned fine particles or the inorganic binder, for example, for imparting coloring or various functions,
Various metals, fine particles of metals and oxides, various metal oxides, and the like can be appropriately added and contained.

【００３３】また、前記ZnO-Sb2O3 微粒子と無機バイン
ダ−からなる膜層の下地層として、SiO2薄膜、あるいは
SiO2-TiO2 またはSiO2-ZrO2 の薄膜であるSiO2系複合酸
化物薄膜を設けることが好ましく、該下地層を設けたこ
とによってZnO-Sb2O3 微粒子と無機バインダ−からなる
膜層に対し、ガラス基板からNaイオンが侵入するのを防
止し、前記した防汚性能等の性能低下を防ぎ、また光の
干渉による透過・反射の光彩を低減することができる。Further, as a base layer of the film layer composed of the ZnO—Sb 2 O 3 fine particles and the inorganic binder, an SiO 2 thin film or
It is preferable to provide a SiO 2 -based composite oxide thin film which is a thin film of SiO 2 -TiO 2 or SiO 2 -ZrO 2, and a film made of ZnO-Sb 2 O 3 fine particles and an inorganic binder by providing the underlayer. It is possible to prevent Na ions from entering the layer from the glass substrate, prevent the performance such as the antifouling performance from deteriorating, and reduce the transmission and reflection of light due to light interference.

【００３４】また、ガラス基板の表面に、ZnO-Sb2O3 微
粒子と無機バインダ−と希釈溶媒と分散剤から少なくと
も成る塗布液を塗布し、次いで乾燥、焼成し、少なくと
もZnO-Sb2O3 微粒子と無機バインダ−からなる膜層を、
少なくとも−層成膜する紫外線熱線遮蔽防汚ガラスの製
法は次のようにする。Further, a coating solution comprising at least ZnO—Sb 2 O 3 fine particles, an inorganic binder, a diluting solvent and a dispersant is applied to the surface of the glass substrate, and then dried and fired to obtain at least ZnO—Sb 2 O 3 A film layer comprising fine particles and an inorganic binder
The manufacturing method of the ultraviolet ray shielding and antifouling glass for forming at least the-layer is as follows.

【００３５】また、希釈溶媒としては、アルコ−ル系溶
媒が好ましく、具体例としては、メタノ−ル、エタノ−
ル、エタノ−ルとノルマルブタノ−ルの混合溶媒、イソ
プロパノ−ル、ブタノ−ル、エチレングリコ−ル、ヘキ
シレングリコ−ルを主成分とする溶媒、あるいはポリエ
チレングリコ−ル（平均分子量200 ）、ポリプロピレン
グリコ−ル（平均分子量400 ）等が挙げられる。本来溶
液中に含まれるアルコ−ル系やセロソルブ系のもの単独
または混合物を、該溶液の蒸発速度や被膜粘度を勘案し
て選択すればよい。The diluting solvent is preferably an alcoholic solvent, and specific examples thereof include methanol, ethanol and the like.
, A mixed solvent of ethanol and normal butanol, a solvent containing isopropanol, butanol, ethylene glycol, hexylene glycol as a main component, or polyethylene glycol (average molecular weight 200), polypropylene And glycol (average molecular weight: 400). Alcohols or cellosolves which are originally contained in the solution may be selected alone or in a mixture in consideration of the evaporation rate of the solution and the film viscosity.

【００３６】また、分散剤としては、燐酸エステル系活
性剤（テスコ−ルA-200 ）、ポリビニルアルコ−ル樹脂
（ゴ−セランL-0301）、エチルセルロ−ス（エトセル7C
P ）、高分子系では、アジスパ−PB711 、PN411 、PA11
〔味の素（株）製〕、Dysperbyk-110 、161 、162 〔ビ
ックケミ−社製〕等が挙げられる。また添加量として
は、ZnO-Sb2O3 微粒子の全表面積が分散剤の単分子で覆
われるのに必要な量として決める。Examples of the dispersant include a phosphoric acid ester-based activator (Tescol A-200), a polyvinyl alcohol resin (Goselan L-0301), and ethylcellulose (Ethocel 7C).
P), for polymer systems, Azispar-PB711, PN411, PA11
[Manufactured by Ajinomoto Co., Ltd.] and Dysperbyk-110, 161, 162 [manufactured by Big Chemical Co., Ltd.]. The addition amount is determined as an amount necessary for covering the entire surface area of the ZnO—Sb 2 O 3 fine particles with a single molecule of the dispersant.

【００３７】さらに、前記塗布液中において、全固形分
量に対し酸化物換算で、ZnO-Sb2O3微粒子を50乃至90重
量％と無機バインダ−を10乃至50重量％を少なくとも含
むものであることとしたのは、ZnO-Sb2O3 微粒子が50重
量％未満かつZnO-Sb2O3 微粒子が90重量％を超えれば、
充分な紫外線熱線吸収性能や防汚性能が得られず、また
ZnO-Sb2O3 微粒子が90重量％を超えかつ無機バインダ−
が10重量％未満であれば、ZnO-Sb2O3 微粒子を充分担持
することができないし、可視光透過率が低下することと
なるからである。Further, the coating liquid should contain at least 50 to 90% by weight of ZnO—Sb 2 O 3 fine particles and 10 to 50% by weight of an inorganic binder in terms of oxide based on the total solid content. The reason is that if the ZnO-Sb 2 O 3 fine particles are less than 50% by weight and the ZnO-Sb 2 O 3 fine particles exceed 90% by weight,
Sufficient UV heat ray absorption performance and antifouling performance cannot be obtained.
ZnO-Sb 2 O 3 fine particles exceeding 90% by weight and inorganic binder
Is less than 10% by weight, ZnO-Sb 2 O 3 fine particles cannot be sufficiently supported, and the visible light transmittance is reduced.

【００３８】さらに、前記塗布液中において、全固形分
量に対し酸化物換算で、ZnO-Sb2O3微粒子を40乃至89重
量％、CeO2微粒子、TiO2微粒子またはATO 微粒子のうち
少なくとも１種以上を 1乃至20重量％、および無機バイ
ンダ−を10乃至40重量％を少なくとも含むものであるこ
ととしたのは、CeO2微粒子、TiO2微粒子またはATO 微粒
子のうち少なくとも１種以上を 1乃至20重量％程度とす
ることで、紫外線吸収性能と熱線吸収性能と防汚性能を
補うことができ、しかも高い性能レベルでバランスせし
めたり、場合によってはこれら性能のうち、少なくとも
１種以上の性能に強弱を違和感を生じない程度にもたら
しめたりする等、適宜調整することができるからであ
る。Further, in the coating solution, 40 to 89% by weight of ZnO-Sb 2 O 3 fine particles, and at least one of CeO 2 fine particles, TiO 2 fine particles or ATO fine particles, in terms of oxide, based on the total solid content. The content of at least one of CeO 2 fine particles, TiO 2 fine particles and ATO fine particles is 1 to 20% by weight and the inorganic binder is 10 to 40% by weight. By setting the degree, it is possible to supplement the ultraviolet absorption performance, the heat absorption performance and the antifouling performance, and at the same time balance at a high performance level, and in some cases, at least one or more of these performances may give a sense of incongruity. This can be adjusted appropriately, for example, to such an extent that does not occur.

【００３９】また、前記ガラス基板の表面に形成する少
なくともZnO-Sb2O3 微粒子と無機バインダ−からなる膜
層の下地層としては、シリコンアルコキシド類、あるい
はシリコンアルコキシド類とチタンアルコキシド類また
はジルコニアアルコキシド類でなる溶液を塗布し、SiO2
薄膜あるいはSiO2-TiO2 系あるいはSiO2-ZrO2 系の複合
酸化物薄膜を形成して成るものである。最も好ましい具
体例としては、SiO2薄膜を形成する、コルコ−ト6P〔太
陽物産（株）製〕、MS51SG1 〔三菱化学（株）製〕の
他、トスガ−ド510 〔東芝シリコ−ン（株）製〕、Siコ
−ト〔大八化学（株）製〕等が挙げられる。なお、下層
（第１層）を侵すような強酸や強アルカリ分を含んでい
てはならないことは言うまでもない。Further, at least ZnO-Sb 2 O 3 fine particles and inorganic binder is formed on the surface of the glass substrate - as the base layer of a film layer from silicon alkoxides, or silicon alkoxides and titanium alkoxides or zirconium alkoxides A solution consisting of SiO 2
It is formed by forming a thin film or an SiO 2 —TiO 2 or SiO 2 —ZrO 2 based composite oxide thin film. As the most preferred specific examples, in addition to Corcoat 6P (manufactured by Taiyo Bussan Co., Ltd.) and MS51SG1 (manufactured by Mitsubishi Chemical Corporation), which form an SiO 2 thin film, Tosgard 510 [Toshiba Silicone Co., Ltd. )) And Si coat (manufactured by Daihachi Chemical Co., Ltd.). Needless to say, it should not contain a strong acid or a strong alkali that would attack the lower layer (first layer).

【００４０】また、塗布法としては、特に限定されるも
のではないが、生産性などの面からは例えばスピンコー
ト法あるいはディップコ−ト法、またリバ−スコ−ト
法、フレキソ印刷法、ロールコート法であり、さらには
ノズルコ−ト法、スプレーコ−ト法、スクリーン印刷法
などが適宜採用し得るものである。これら塗布法で塗布
成膜する際の塗布液中の固形分濃度としては約５〜30％
程度で、粘度としては１〜100cP 程度である。The coating method is not particularly limited, but from the viewpoint of productivity and the like, for example, a spin coating method or a dip coating method, a reverse coating method, a flexographic printing method, a roll coating method, or the like. A nozzle coating method, a spray coating method, a screen printing method, and the like. The solid content concentration in the coating liquid when forming a film by these coating methods is about 5 to 30%.
And the viscosity is about 1 to 100 cP.

【００４１】またさらに、塗布後の乾燥処理としては、
乾燥温度が常温〜300 ℃程度で乾燥時間が0.5 〜60分間
程度行うことがよく、より好ましくは前記乾燥温度が50
〜300 ℃程度で乾燥時間が 1〜50分間程度行うことであ
る。Further, as a drying treatment after coating,
The drying temperature is usually from room temperature to 300 ° C. and the drying time is preferably from 0.5 to 60 minutes, more preferably the drying temperature is 50 to 50 minutes.
The drying time is about 1 to 50 minutes at about 300 ° C.

【００４２】また、乾燥後の焼成処理としては、温度が
300 〜700 ℃程度で時間が0.1 〜30分間程度行うことが
よく、さらに前記ガラスの熱強化または／および熱曲げ
加工時に同時に行うことがよく、前記ガラスの熱強化ま
たは／および熱曲げ加工は、温度が550 〜700 ℃程度で
時間が0.5 〜10分間程度行うことがより好ましい。In the firing treatment after drying, the temperature is
The heat treatment is preferably performed at a temperature of about 300 to 700 ° C. for a time of about 0.1 to 30 minutes, and the heat treatment is preferably performed simultaneously with the heat strengthening and / or hot bending of the glass. More preferably, the temperature is about 550 to 700 ° C. and the time is about 0.5 to 10 minutes.

【００４３】少なくともZnO-Sb2O3 微粒子と無機バイン
ダ−からなる膜層の膜厚としては、約500 〜2000nm程度
であり、500nm 未満であれば、充分な紫外線と熱線吸収
性能が得られず、2000nmを超えると紫外線と熱線吸収性
能もさほど改善もされず、可視光透過率が70％以下に低
下してしまうためである。好ましくは約800 〜1500nm程
度である。The thickness of at least the film layer composed of ZnO-Sb 2 O 3 fine particles and the inorganic binder is about 500-2000 nm, and if it is less than 500 nm, sufficient ultraviolet and heat ray absorbing performance cannot be obtained. If it exceeds 2000 nm, the ultraviolet ray and heat ray absorption performances are not so much improved, and the visible light transmittance is reduced to 70% or less. Preferably, it is about 800 to 1500 nm.

【００４４】下地層の膜厚は、約50〜200nm 程度であ
り、50nm未満であれば、ガラス基板からのNaイオンの影
響でZnO-Sb2O3 微粒子の熱線遮蔽性能が低下し、200nm
を超えると経済的にも無駄であり、クラックの発現の要
因となるためである。好ましくは約80〜160nm 程度であ
る。The thickness of the underlayer is about 50 to 200 nm. If the thickness is less than 50 nm, the heat ray shielding performance of the ZnO—Sb 2 O 3 fine particles is reduced due to the influence of Na ions from the glass substrate.
It is because it is economically useless if it exceeds the number, and it becomes a factor of the appearance of cracks. Preferably, it is about 80 to 160 nm.

【００４５】前述したように、少なくとも紫外線遮蔽性
と導電性を有するZnO-Sb2O3 微粒子を無機バインダ−で
担持する膜とすることにより、紫外線遮蔽性能と熱線遮
蔽性能とを付与することに加え、防汚性能をも同時に付
与することができ、さらに電波透過性能等の各種機能特
性をも有するものとでき、しかも着色の色調の制御およ
び透視性の確保や反射性とぎらつき感の防止をバランス
よくもたらしめ、かつ欠陥の発現もなく優れた品質を得
るようにでき、各種熱処理工程で焼成できる等簡便にか
つ効率よく、しかもガラスの大きさや形態に自由自在に
対応でき、高硬度で耐薬品性に優れる等耐久性を発揮で
きる等、建築用窓材はもちろん各種車両用窓材にも充分
適用でき、最近のニーズに充分満足し得るものとなる。As described above, by providing ZnO—Sb 2 O 3 fine particles having at least ultraviolet shielding properties and conductivity with an inorganic binder, it is possible to impart ultraviolet shielding properties and heat ray shielding properties. In addition, anti-fouling performance can be provided at the same time, and it can also have various functional characteristics such as radio wave transmission performance. In addition, control of coloring color tone, ensuring transparency, and preventing reflection and glare With a good balance and high quality without defects.It can be fired in various heat treatment processes easily and efficiently, and can freely respond to the size and shape of glass. Since it can exhibit durability such as excellent chemical resistance, it can be sufficiently applied to window materials for construction as well as various window materials for vehicles, and can sufficiently satisfy recent needs.

【００４６】[0046]

【実施例】以下、実施例により本発明を具体的に説明す
る。ただし本発明はこれらの実施例に限定されるもので
はない。The present invention will be described below in detail with reference to examples. However, the present invention is not limited to these examples.

【００４７】実施例１ 大きさ約100mm ×100mm で厚み約２mmのソ−ダライムシ
リカ系ガラス基板（フロ−トガラス基板）を約500rpmで
回転させながら、該基板の表面にコルコ−ト6P〔太陽物
産（株）〕を供給し被膜を形成した。被膜形成後約100
℃の乾燥炉で乾燥し、続いて約500 ℃のマッフル炉で焼
成し成膜することで、膜厚が約100nm のシリカ膜付きガ
ラス基板を得た。 EXAMPLE 1 A soda lime silica glass substrate (float glass substrate) having a size of about 100 mm.times.100 mm and a thickness of about 2 mm was rotated at about 500 rpm, and the surface of the soda lime silica glass substrate was corrugated 6P [Taiyo Bussan Co., Ltd. Co., Ltd.) was supplied to form a film. About 100 after film formation
The resultant was dried in a drying furnace at a temperature of about 500 ° C., and subsequently fired in a muffle furnace at about 500 ° C. to form a film.

【００４８】次に、マグネチックスタ−ラ−で攪拌して
いるアンチモン酸亜鉛微粒子（平均粒径約20nm）20重量
％含有分散メタノ−ル溶液〔セルナックスCX−Z200M 、
日産化学工業（株）製〕に、アルコキシシランの加水分
解溶液〔MTS-2 、大八化学（株）、固形分20wt％〕を滴
下ロ−トにより約１時間かけて滴下混合した溶液を得
た。さらに該溶液に分散剤として燐酸エステル系活性剤
（テスコ−ルA-200 ）１ｇを添加混合して塗布液とし
た。Next, a dispersed methanol solution containing 20% by weight of zinc antimonate fine particles (average particle size: about 20 nm) stirred with a magnetic stirrer (Celnax CX-Z200M,
Nissan Chemical Industry Co., Ltd.] to obtain a solution in which a hydrolysis solution of alkoxysilane (MTS-2, Daihachi Chemical Co., Ltd., solid content: 20 wt%) was dropped and mixed over about 1 hour using a dropping funnel. Was. Further, 1 g of a phosphoric acid ester-based activator (Tescol A-200) was added to the solution as a dispersant and mixed to obtain a coating solution.

【００４９】次いで、スピンコ−タ−に上記シリカ膜付
きガラス基板を載せ、約500rpmで回転させながら該シリ
カ膜付きガラス基板のシリカ膜面に該塗布液を供給し被
膜を形成した。Next, the glass substrate with a silica film was placed on a spin coater, and the coating solution was supplied to the silica film surface of the glass substrate with a silica film while rotating at about 500 rpm to form a film.

【００５０】続いて、被膜・シリカ膜付きガラス基板を
約100 ℃で約20分間乾燥した後、再度前記した塗布液を
用いて同一条件で被膜を形成し、乾燥した積層膜付きガ
ラス基板を雰囲気温度約500 ℃のマッフル炉に約20分間
程度入れ焼成し成膜し、上記SiO2膜表面上に膜厚が約1.
63μm のZnO-Sb2O3 微粒子含有シリカ膜を得た。Subsequently, after drying the glass substrate with the coating and the silica film at about 100 ° C. for about 20 minutes, a coating is formed again under the same conditions using the above-mentioned coating solution, and the dried glass substrate with the laminated film is placed in an atmosphere. formed by firing about 20 minutes put in a muffle furnace at a temperature of about 500 ° C., the film thickness on the SiO 2 film on the surface of about 1.
A 63 μm-thick silica film containing ZnO—Sb 2 O 3 fine particles was obtained.

【００５１】得られたガラス基板／SiO2薄膜（約100nm
）／ZnO-Sb2O3 微粒子含有シリカ膜（約1.63μm ）で
なる積層膜付きガラス基板について、下記のような各項
目を測定評価した。 〔光学特性〕：分光光度計（U 4000型、日立製作所製）
で波長340 〜1800nmの間の透過率を測定し、JIS Z 8722
及びJIS R 3106又はJIS Z 8701によって可視光透過率Tv
（％）(380〜780nm)、ISO 9050によって紫外線透過率Tu
v(％）(282.5〜377.5nm)、刺激純度（％）、色調等を求
めた。〔D65 光源による〕 〔防汚性〕： 20wt％ステアリン酸のエタノ−ル溶液を
約1000rpm で回転する積層膜表面（第２層表面：光触媒
膜面）にスピンコ−タ−で塗布し約50℃で乾燥して厚さ
約１μm のステアリン酸膜を成膜した。The obtained glass substrate / SiO 2 thin film (about 100 nm)
) / ZnO-Sb 2 O 3 fine particle-containing silica film (approximately 1.63 μm), a glass substrate with a laminated film was measured and evaluated for the following items. [Optical characteristics]: Spectrophotometer (U4000, manufactured by Hitachi, Ltd.)
Measure the transmittance between 340 and 1800 nm with JIS Z 8722
And visible light transmittance Tv according to JIS R 3106 or JIS Z 8701
(%) (380-780nm), UV transmittance Tu according to ISO 9050
v (%) (282.5 to 377.5 nm), stimulus purity (%), color tone, etc. were determined. [ D65 light source] [Anti-fouling property]: Ethanol solution of 20 wt% stearic acid is applied to the surface of the laminated film (second layer surface: photocatalytic film surface) rotating at about 1000 rpm with a spin coater to about 50%. The resultant was dried at ℃ to form a stearic acid film having a thickness of about 1 μm.

【００５２】これに2mW/cm2(360nm)になるように紫外線
ランプを取り付けて照射し、ステアリン酸膜の消滅時間
を調べた。該消滅時間が短いほど光触媒能は高く、高防
汚性である。 〔耐薬品性〕：耐酸性：１％塩酸に室温（約25℃）下で
24時間浸漬。This was irradiated with an ultraviolet lamp attached thereto at 2 mW / cm 2 (360 nm), and the disappearance time of the stearic acid film was examined. The shorter the disappearance time, the higher the photocatalytic activity and the higher the antifouling property. [Chemical resistance]: Acid resistance: 1% hydrochloric acid at room temperature (about 25 ° C)
Soak for 24 hours.

【００５３】耐アルカリ：１％苛性ソーダ水溶液に室温
（約25℃）下で24時間浸漬。光学特性ならびに外観目視
による評価、膜強度の変化を調べ異常がないものを合格
とした。Alkali resistance: Immersion in a 1% aqueous solution of caustic soda at room temperature (about 25 ° C.) for 24 hours. The optical characteristics and the appearance were evaluated by visual inspection, and the change in film strength was examined.

【００５４】その結果、可視光透過率Tvが約71％程度、
紫外線透過率Tuv が約 7％程度、日射透過率Tsが約52％
程度であり、反射によるギラツキもなく、熱線遮蔽性を
有しかつ高可視光透過率で、付着ステアリン酸が約３時
間で消滅しており、充分光触媒能を発揮し高防汚性能を
有するものであり、優れた防汚性と紫外線遮蔽性を有す
るものであった。As a result, the visible light transmittance Tv is about 71%,
UV transmittance Tuv is about 7%, solar transmittance Ts is about 52%
About 3 hours, no glare due to reflection, has heat ray shielding property, has high visible light transmittance, and stearic acid adhered disappears in about 3 hours, exhibits sufficient photocatalytic ability and has high antifouling performance And had excellent antifouling property and ultraviolet shielding property.

【００５５】さらに、耐酸性ならびに耐アルカリ性試験
後での外観、紫外線透過率等の光学特性における変化は
認められなかった。建築用窓ガラス等で充分採用できる
紫外線と熱線遮蔽性能及び防汚性能を有するガラスであ
った。Further, no change was observed in the optical properties such as appearance and ultraviolet transmittance after the acid resistance and alkali resistance tests. The glass had ultraviolet and heat ray shielding performance and antifouling performance that could be sufficiently employed in architectural window glass and the like.

【００５６】なお、他に耐候性（例、サンシヤインウエ
ザーメーターで約3000時間：可視光透過率がほぼ変化が
ないこと）等の種々の特性をも評価したところ、いずれ
も合格するものであった。また、鉛筆硬度は約５Ｈ程度
であった。In addition, when various properties such as weather resistance (eg, about 3000 hours with a sunshine weather meter: almost no change in visible light transmittance) were evaluated, all passed. there were. The pencil hardness was about 5H.

【００５７】実施例２ 実施例１と同様に、大きさ約100mm ×100mm で厚み約２
mmのソ−ダライムシリカ系ガラス基板（フロ−トガラス
基板）を約1000rpm で回転させながら、該表面にMS51SG
1 〔三菱化学（株）、固形分濃度10wt％〕を供給し被膜
を形成した。被膜形成後約100 ℃の乾燥炉で乾燥し、続
いて約500 ℃のマッフル炉で焼成し成膜することで、膜
厚が約150nm のシリカ膜付きガラス板を得た。 Example 2 As in Example 1, the size was about 100 mm × 100 mm and the thickness was about 2 mm.
mm soda lime silica glass substrate (float glass substrate) was rotated at about 1000 rpm while MS51SG
1 [Mitsubishi Chemical Corporation, solid content 10 wt%] was supplied to form a coating. After the film was formed, it was dried in a drying furnace at about 100 ° C., and then fired in a muffle furnace at about 500 ° C. to form a film, thereby obtaining a glass plate with a silica film having a thickness of about 150 nm.

【００５８】次に、10ｇノルマルブタノ−ルと39ｇのエ
タノ−ルの混合溶液にモノメチルトリメトキシシラン1
3.6ｇを溶かし、さらに0.1Nの塩酸7.2 ｇを約１時間か
けて滴下攪拌した。この溶液に、アンチモン酸亜鉛微粒
子（平均粒径約20nm）20重量％含有メタノ−ル溶液〔セ
ルチックスCX−Z200M 、日産化学工業（株）製〕50ｇ、
セリア微粒子分散液〔U-20、固形分20重量％、多木化学
（株）製〕20ｇ、ポリビニルアルコ−ル樹脂（ゴ−セラ
ンL-0301）0.5 ｇを加えてサンドミルで解膠しゾル溶液
でなる塗布液を得た。Next, monomethyltrimethoxysilane 1 was added to a mixed solution of 10 g of normal butanol and 39 g of ethanol.
3.6 g was dissolved, and 7.2 g of 0.1N hydrochloric acid was further dropped and stirred over about 1 hour. 50 g of a methanol solution (Celtics CX-Z200M, manufactured by Nissan Chemical Industries, Ltd.) containing 20% by weight of zinc antimonate fine particles (average particle size of about 20 nm) was added to this solution.
20 g of a ceria fine particle dispersion (U-20, solid content: 20% by weight, manufactured by Taki Kagaku Co., Ltd.) and 0.5 g of polyvinyl alcohol resin (Goselan L-0301) were added and pulverized by a sand mill to obtain a sol solution. Was obtained.

【００５９】次いで、スピンコ−タ−に上記シリカ膜付
きガラス基板を載せ、約500rpmで回転させながら該シリ
カ膜付きガラス基板のシリカ膜面に該塗布液を約10秒間
供給し被膜を形成した。Next, the above glass substrate with a silica film was placed on a spin coater, and the coating solution was supplied to the silica film surface of the glass substrate with a silica film for about 10 seconds while rotating at about 500 rpm to form a film.

【００６０】続いて、被膜・シリカ膜付きガラス基板を
約100 ℃で約20分間乾燥した後、雰囲気温度約500 ℃の
マッフル炉に約20分間程度入れ焼成し成膜し、上記SiO2
膜表面上に膜厚が約1.5 μm のZnO-Sb2O3,CeO2微粒子含
有シリカ膜を得た。[0060] Subsequently, after dried for about 20 minutes the glass substrate with coating silica film at about 100 ° C., is deposited and fired about 20 minutes put in a muffle furnace at ambient temperature to about 500 ° C., the SiO 2
A ZnO-Sb 2 O 3 and CeO 2 fine particle-containing silica film having a thickness of about 1.5 μm was obtained on the film surface.

【００６１】得られたガラス基板／SiO2薄膜（約150nm)
／ZnO-Sb2O3,CeO2微粒子含有シリカ膜（約1.5 μm ）で
なる積層膜付きガラス基板について、実施例１と同様に
して各項目を測定評価した。The obtained glass substrate / SiO 2 thin film (about 150 nm)
Each item was measured and evaluated in the same manner as in Example 1 for a glass substrate with a laminated film composed of a silica film (about 1.5 μm) containing / ZnO-Sb 2 O 3 and CeO 2 fine particles.

【００６２】その結果、可視光透過率Tvが約73％程度、
紫外線透過率Tuv が約 3％程度、日射透過率Tsが約55％
程度等であり、反射によるギラツキもなく、熱線遮蔽性
を有しかつ高可視光透過率で、付着ステアリン酸は約４
時間で消滅し、充分光触媒能を発揮し高防汚性能を有す
るものであり、優れた防汚性と紫外線遮蔽性を有するも
のであった。As a result, the visible light transmittance Tv is about 73%,
UV transmittance Tuv is about 3%, solar transmittance Ts is about 55%
Degree, etc., there is no glare due to reflection, it has a heat ray shielding property, has a high visible light transmittance, and adhering stearic acid is about 4%.
It disappeared with time, exhibited sufficient photocatalytic activity and had high antifouling performance, and had excellent antifouling properties and ultraviolet shielding properties.

【００６３】さらに、耐酸性ならびに耐アルカリ性試験
も実施例１と同様、紫外線透過率等の光学特性における
変化は認められなかった。前記実施例１と同様、建築用
窓ガラス等で充分採用できる紫外線と熱線遮蔽性能及び
防汚性能を有するガラスであった。なお、前記耐候性等
の種々の特性をも評価したところ、いずれも合格するも
のであった。また、鉛筆硬度は約６Ｈ程度であった。Further, in the acid resistance and alkali resistance tests, as in Example 1, no change in the optical characteristics such as the ultraviolet transmittance was observed. As in the case of Example 1, the glass had ultraviolet and heat ray shielding performance and antifouling performance that could be sufficiently employed for architectural window glass and the like. In addition, when various characteristics such as the above-mentioned weather resistance were also evaluated, all passed. The pencil hardness was about 6H.

【００６４】実施例３ 実施例１と同様にして、膜厚が約110nm のシリカ膜付き
ガラス板を得た。次に、30ｇのエタノ−ルにテトラエト
キシシラン20.8ｇを溶かし、0.1Nの塩酸8ｇを約１時間
かけて滴下攪拌した。この溶液にアンチモン酸亜鉛微粒
子（平均粒径約20nm）20重量％含有メタノ−ル溶液〔セ
ルチックスCX−Z200M 、日産化学工業（株）製〕75ｇ、
チタニア微粒子〔平均粒径約50nm、富士チタン（株）
製〕9ｇ、エチルセルロ−ス（エトセル7CP ）0.5 ｇを
加えて、0.4mm 径のジルコニアビ−ズを用いたボ−ルミ
ルで解膠しゾル溶液でなる塗布液を得た。 Example 3 A glass plate with a silica film having a thickness of about 110 nm was obtained in the same manner as in Example 1. Next, 20.8 g of tetraethoxysilane was dissolved in 30 g of ethanol, and 8 g of 0.1N hydrochloric acid was dropped and stirred over about 1 hour. 75 g of a methanol solution (Celtics CX-Z200M, manufactured by Nissan Chemical Industries, Ltd.) containing 20% by weight of zinc antimonate fine particles (average particle size: about 20 nm) was added to this solution.
Titania fine particles [average particle size of about 50 nm, Fuji Titanium Co., Ltd.
9 g) and 0.5 g of ethylcellulose (Ethocel 7CP) were added and pulverized with a ball mill using zirconia beads having a diameter of 0.4 mm to obtain a coating solution comprising a sol solution.

【００６５】次いで、スピンコ−タ−に上記シリカ膜付
きガラス基板を載せ、約1000rpm で回転させながら該シ
リカ膜付きガラス基板のシリカ膜面に該塗布液を約10秒
間供給し被膜を形成した。Next, the glass substrate with the silica film was placed on a spin coater, and the coating solution was supplied to the silica film surface of the glass substrate with the silica film for about 10 seconds while rotating at about 1000 rpm to form a film.

【００６６】続いて、被膜・シリカ膜付きガラス基板を
約100 ℃で約20分間乾燥した後、雰囲気温度約500 ℃の
マッフル炉に約20分間程度入れ焼成し成膜し、上記SiO2
膜表面上に膜厚が約1.2 μm のZnO-Sb2O3,TiO2微粒子含
有シリカ膜を得た。[0066] Subsequently, after dried for about 20 minutes the glass substrate with coating silica film at about 100 ° C., is deposited and fired about 20 minutes put in a muffle furnace at ambient temperature to about 500 ° C., the SiO 2
A ZnO-Sb 2 O 3 , TiO 2 fine particle-containing silica film having a thickness of about 1.2 μm was obtained on the film surface.

【００６７】得られたガラス基板／SiO2薄膜（約150nm)
／ZnO-Sb2O3,TiO2微粒子含有シリカ膜（約1.2 μm ）で
なる積層膜付きガラス基板について、実施例１と同様に
して各項目を測定評価した。The obtained glass substrate / SiO 2 thin film (about 150 nm)
Each item was measured and evaluated in the same manner as in Example 1 for a glass substrate with a laminated film composed of a silica film (about 1.2 μm) containing / ZnO—Sb 2 O 3 and TiO 2 fine particles.

【００６８】その結果、可視光透過率Tvが約72％程度、
紫外線透過率Tuv が約 9％程度、日射透過率Tsが約57％
程度等であり、反射によるギラツキもなく、熱線遮蔽性
を有しかつ高可視光透過率で、付着ステアリン酸は約２
時間で消滅し、充分光触媒能を発揮し高防汚性能を有す
るものであり、優れた紫外線遮蔽性と格段に優れた防汚
性とを有するものであった。As a result, the visible light transmittance Tv is about 72%,
UV transmittance Tuv is about 9%, solar transmittance Ts is about 57%
Degree, etc., there is no glare due to reflection, it has a heat ray shielding property, has a high visible light transmittance, and has a stearic acid adhesion of about 2
It disappeared over time, exhibited sufficient photocatalytic activity, and had high antifouling performance, and had excellent ultraviolet shielding properties and remarkably excellent antifouling properties.

【００６９】さらに、耐酸性ならびに耐アルカリ性試験
も実施例１と同様、紫外線透過率等の光学特性における
変化は認められなかった。前記実施例１と同様、建築用
窓ガラス等で充分採用できる紫外線と熱線遮蔽性能及び
防汚性能を有するガラスであった。なお、前記耐候性等
の種々の特性をも評価したところ、いずれも合格するも
のであった。また、鉛筆硬度は約４Ｈ程度であった。Further, in the acid resistance and alkali resistance tests, as in Example 1, no change in the optical properties such as the ultraviolet transmittance was observed. As in the case of Example 1, the glass had ultraviolet and heat ray shielding performance and antifouling performance that could be sufficiently employed for architectural window glass and the like. In addition, when various characteristics such as the above-mentioned weather resistance were also evaluated, all passed. The pencil hardness was about 4H.

【００７０】実施例４ 実施例１と同様にして、膜厚が約110nm のシリカ膜付き
ガラス板を得た。次に、30ｇのエタノ−ルにテトラエト
キシシラン20.8ｇを溶かし、0.1Nの塩酸8ｇを約１時間
かけて滴下攪拌した。この溶液にアンチモン酸亜鉛微粒
子（平均粒径約20nm）20重量％含有メタノ−ル溶液〔セ
ルチックスCX−Z200M 、日産化学工業（株）製〕75ｇ、
ATO 微粒子〔平均粒径約50nm、富士チタン（株）製〕 9
ｇ、エチルセルロ−ス（エトセル7CP ）0.5 ｇを加えて
サンドミルで解膠しゾル溶液でなる塗布液を得た。 Example 4 In the same manner as in Example 1, a glass plate with a silica film having a thickness of about 110 nm was obtained. Next, 20.8 g of tetraethoxysilane was dissolved in 30 g of ethanol, and 8 g of 0.1N hydrochloric acid was dropped and stirred over about 1 hour. 75 g of a methanol solution (Celtics CX-Z200M, manufactured by Nissan Chemical Industries, Ltd.) containing 20% by weight of zinc antimonate fine particles (average particle size: about 20 nm) was added to this solution.
ATO fine particles (average particle size about 50 nm, manufactured by Fuji Titanium Co., Ltd.) 9
g of ethylcellulose (Ethocel 7CP) and pulverized with a sand mill to obtain a coating solution composed of a sol solution.

【００７１】次いで、スピンコ−タ−に上記シリカ膜付
きガラス基板を載せ、約1000rpm で回転させながら該シ
リカ膜付きガラス基板のシリカ膜面に該塗布液を約10秒
間供給し被膜を形成した。Next, the glass substrate with a silica film was placed on a spin coater, and the coating solution was supplied to the silica film surface of the glass substrate with a silica film for about 10 seconds while rotating at about 1000 rpm to form a film.

【００７２】続いて、被膜・シリカ膜付きガラス基板を
約100 ℃で約20分間乾燥した後、雰囲気温度約500 ℃の
マッフル炉に約20分間程度入れ焼成し成膜し、上記SiO2
膜表面上に膜厚が約1.3 μm のZnO-Sb2O3,ATO 微粒子含
有シリカ膜を得た。[0072] Subsequently, after dried for about 20 minutes the glass substrate with coating silica film at about 100 ° C., is deposited and fired about 20 minutes put in a muffle furnace at ambient temperature to about 500 ° C., the SiO 2
A silica film containing ZnO-Sb 2 O 3 and ATO fine particles having a thickness of about 1.3 μm was obtained on the film surface.

【００７３】得られたガラス基板／SiO2薄膜（約150nm)
／ZnO-Sb2O3,ATO 微粒子含有シリカ膜（約1.3 μm ）で
なる積層膜付きガラス基板について、実施例１と同様に
して各項目を測定評価した。The obtained glass substrate / SiO 2 thin film (about 150 nm)
Each item was measured and evaluated in the same manner as in Example 1 for a glass substrate with a laminated film composed of a silica film (about 1.3 μm) containing / ZnO-Sb 2 O 3 and ATO fine particles.

【００７４】その結果、可視光透過率Tvが約70％程度、
紫外線透過率Tuv が約12％程度、日射透過率Tsが約45％
程度等であり、反射によるギラツキもなく、熱線遮蔽性
を有しかつ高可視光透過率で、付着ステアリン酸は約２
時間で消滅し、充分光触媒能を発揮し高防汚性能を有す
るものであり、優れた紫外線遮蔽性と格段に優れた防汚
性とを有するものであった。As a result, the visible light transmittance Tv is about 70%,
UV transmittance Tuv is about 12%, solar transmittance Ts is about 45%
Degree, etc., there is no glare due to reflection, it has a heat ray shielding property, has a high visible light transmittance, and has a stearic acid adhesion of about 2
It disappeared over time, exhibited sufficient photocatalytic activity, and had high antifouling performance, and had excellent ultraviolet shielding properties and remarkably excellent antifouling properties.

【００７５】さらに、耐酸性ならびに耐アルカリ性試験
も実施例１と同様、紫外線透過率等の光学特性における
変化は認められなかった。前記実施例１と同様、建築用
窓ガラス等で充分採用できる紫外線と熱線遮蔽性能及び
防汚性能を有するガラスであった。なお、前記耐候性等
の種々の特性をも評価したところ、いずれも合格するも
のであった。また、鉛筆硬度は約４Ｈ程度であった。Further, in the acid resistance and alkali resistance tests, as in Example 1, no change in the optical characteristics such as the ultraviolet transmittance was observed. As in the case of Example 1, the glass had ultraviolet and heat ray shielding performance and antifouling performance that could be sufficiently employed for architectural window glass and the like. In addition, when various characteristics such as the above-mentioned weather resistance were also evaluated, all passed. The pencil hardness was about 4H.

【００７６】比較例１ 実施例１と同様の膜厚が約100nm のシリカ膜付きガラス
基板のシリカ膜面に、酸化亜鉛微粒子含有分散シリカ溶
液〔住友大阪セメント（株）製〕でなる塗布液を塗布
し、実施例１と同様に乾燥、焼成し成膜した。上記SiO2
膜表面上に膜厚が約0.97μm のZnO 微粒子含有シリカ膜
を得た。COMPARATIVE EXAMPLE 1 A coating solution composed of a zinc oxide fine particle-dispersed silica solution (manufactured by Sumitomo Osaka Cement Co., Ltd.) was applied on the silica film surface of a glass substrate having a silica film having a thickness of about 100 nm as in Example 1. It was applied, dried and fired in the same manner as in Example 1 to form a film. The above SiO 2
A silica film containing ZnO fine particles having a thickness of about 0.97 μm was obtained on the film surface.

【００７７】得られたガラス基板／SiO2薄膜（約100nm)
／ZnO 微粒子含有シリカ膜（約0.97μm ）でなる積層膜
付きガラス基板について、実施例１と同様にして各項目
を測定評価した。The obtained glass substrate / SiO 2 thin film (about 100 nm)
Each item was measured and evaluated in the same manner as in Example 1 for a glass substrate with a laminated film composed of a / ZnO fine particle-containing silica film (about 0.97 μm).

【００７８】その結果、可視光透過率Tvが約88％程度、
紫外線透過率Tuv が約 2％程度、日射透過率Tsが約86％
程度等であり、付着ステアリン酸の量は10時間以上照射
しても変化はほとんどなく減量する気配は認められず、
到底光触媒能を有するものとは言えず、防汚性能を有し
ないものであり、優れた紫外線遮蔽性を有するものの熱
線遮蔽性もあるものとは言えず、かつ防汚性がないもの
であった。As a result, the visible light transmittance Tv is about 88%,
UV transmittance Tuv is about 2%, solar transmittance Ts is about 86%
The amount of stearic acid adhered was almost unchanged even after irradiation for 10 hours or more, and there was no sign of weight loss.
It can not be said that it has photocatalytic ability at all, it does not have antifouling performance, it has excellent ultraviolet shielding properties, but it can not be said that it also has heat ray shielding properties, and it has no antifouling properties .

【００７９】さらに、耐酸性ならびに耐アルカリ性試験
でもZnO 膜が消失し、紫外線透過率が約67％程度と変化
した。建築用窓ガラス等でも採用し難い紫外線遮蔽ガラ
スに過ぎないものであり、到底めざす紫外線と熱線遮蔽
性能及び防汚性能を有するガラスではなかった。また、
鉛筆硬度は約８Ｈ程度であった。Further, in the acid resistance and alkali resistance tests, the ZnO film disappeared and the ultraviolet transmittance changed to about 67%. It is only an ultraviolet shielding glass that is hardly adopted even in a window glass for a building and the like, and it is not a glass having an ultraviolet and heat ray shielding performance and an antifouling performance that is aimed at. Also,
The pencil hardness was about 8H.

【００８０】[0080]

【発明の効果】本発明によれば、ガラスに環境や人に優
しくなる格段の紫外線遮蔽性を付与し、かつ優れた熱線
遮蔽性と防汚性を同時に有するものとでき、優れた透視
性の確保と反射性のぎらつき感の防止等をバランスよく
もたらしめる。さらに、通常のフロ−トガラス並の電波
透過性能であり、またゴ−スト現象等の電波障害を低減
することができ、室内外での快適な環境を確保すること
ができる等、建築用窓材としてはもちろん、車両用や船
舶用など各種窓材等に適用できる有用な紫外線と熱線遮
蔽性能及び防汚性能を有するガラスを簡便かつ生産性よ
く提供することができる。According to the present invention, glass can be provided with a remarkable ultraviolet ray shielding property which is friendly to the environment and humans, and can have excellent heat ray shielding property and antifouling property at the same time. It is possible to achieve a good balance between securing and preventing reflection glare. Furthermore, it has the same radio wave transmission performance as that of ordinary float glass, can reduce radio interference such as ghost phenomenon, and can secure a comfortable environment both indoors and outdoors. As a matter of course, it is possible to provide a glass having useful ultraviolet ray and heat ray shielding performance and antifouling performance which can be applied to various window materials for vehicles and ships, etc. simply and with good productivity.

Claims (9)

【特許請求の範囲】[Claims] 【請求項１】 ガラス基板の表面に、少なくともZnO-Sb
2O3 微粒子と無機バインダ−からなる膜層を、少なくと
も−層成膜して成ることを特徴とする紫外線と熱線遮蔽
性能及び防汚性能を有するガラス。At least ZnO-Sb is provided on a surface of a glass substrate.
A glass having ultraviolet and heat ray shielding performance and antifouling performance, characterized by being formed by forming at least a film layer comprising 2 O 3 fine particles and an inorganic binder. 【請求項２】 ZnO-Sb2O3 微粒子と無機バインダ−から
なる膜層の下地層として、SiO2薄膜あるいはSiO2系複合
酸化物薄膜で成る層を有することを特徴とする請求項１
記載の紫外線と熱線遮蔽性能及び防汚性能を有するガラ
ス。2. The method according to claim 1, wherein the underlayer of the film layer composed of ZnO—Sb 2 O 3 fine particles and an inorganic binder has a layer composed of a SiO 2 thin film or a SiO 2 composite oxide thin film.
A glass having the above described ultraviolet and heat ray shielding performance and antifouling performance. 【請求項３】 SiO2系複合酸化物薄膜が、SiO2-TiO2 あ
るいはSiO2-ZrO2 の薄膜であることを特徴とする請求項
２記載の紫外線と熱線遮蔽性能及び防汚性能を有するガ
ラス。3. The ultraviolet and heat ray shielding performance and antifouling performance according to claim 2 , wherein the SiO 2 -based composite oxide thin film is a SiO 2 -TiO 2 or SiO 2 -ZrO 2 thin film. Glass. 【請求項４】 少なくともZnO-Sb2O3 微粒子と無機バイ
ンダ−からなる膜層が、ZnO-Sb2O3 微粒子と無機バイン
ダ−に、CeO2微粒子、TiO2微粒子またはATO微粒子のう
ち、少なくとも１種以上を含有して成ることを特徴とす
る請求項１乃至３記載の紫外線と熱線遮蔽性能及び防汚
性能を有するガラス。4. A film layer comprising at least ZnO-Sb 2 O 3 fine particles and an inorganic binder, wherein at least one of CeO 2 fine particles, TiO 2 fine particles and ATO fine particles is formed on the ZnO-Sb 2 O 3 fine particles and the inorganic binder. 4. The glass having ultraviolet and heat ray shielding performance and antifouling performance according to claim 1, comprising one or more kinds. 【請求項５】 ガラス基板の表面に、ZnO-Sb2O3 微粒子
と無機バインダ−と希釈溶媒と分散剤から少なくとも成
る塗布液を塗布し、次いで乾燥、焼成し、少なくともZn
O-Sb2O3 微粒子と無機バインダ−からなる膜層を、少な
くとも−層成膜することを特徴とする紫外線と熱線遮蔽
性能及び防汚性能を有するガラスの製法。5. A coating solution comprising at least ZnO—Sb 2 O 3 fine particles, an inorganic binder, a diluting solvent, and a dispersant is applied to the surface of a glass substrate, and then dried and baked.
The consists film layer, at least - - O-Sb 2 O 3 fine particles and inorganic binder layer forming process of the glass having an ultraviolet and heat ray-shielding performance and antifouling performance, characterized by. 【請求項６】 塗布液において、全固形分量に対し酸化
物換算で、ZnO-Sb2O 3 微粒子を50乃至90重量％と無機バ
インダ−を10乃至50重量％含むものであることを特徴と
する請求項５記載の紫外線と熱線遮蔽性能及び防汚性能
を有するガラスの製法。6. The coating solution is oxidized with respect to the total solid content.
In terms of material, ZnO-SbTwoO Three50-90% by weight of fine particles and inorganic
Characterized in that it contains 10 to 50% by weight of indder
6. The ultraviolet and heat ray shielding performance and the antifouling performance according to claim 5.
A method for producing a glass having: 【請求項７】 塗布液が、全固形分量に対し酸化物換算
で、酸化物微粒子の合計量が60乃至90重量％であって、
ZnO-Sb2O3 微粒子を40乃至89重量％、粒径80nm以下のCe
O2微粒子、TiO2微粒子またはATO 微粒子のうち少なくと
も１種以上を1乃至20重量％、および無機バインダ−を1
0乃至40重量％含むものであることを特徴とする請求項
５記載の紫外線と熱線遮蔽性能及び防汚性能を有するガ
ラスの製法。7. The coating liquid, wherein the total amount of the oxide fine particles is 60 to 90% by weight in terms of oxide based on the total solid content,
40 to 89% by weight of ZnO-Sb 2 O 3 fine particles, Ce having a particle size of 80 nm or less
1 to 20% by weight of at least one of O 2 fine particles, TiO 2 fine particles or ATO fine particles, and 1% of an inorganic binder.
6. The method for producing glass having ultraviolet and heat ray shielding performance and antifouling performance according to claim 5, wherein the glass content is 0 to 40% by weight. 【請求項８】 無機バインダ−が、金属アルコキド類を
主成分とするものであることを特徴とする請求項５乃至
７記載の紫外線と熱線遮蔽性能及び防汚性能を有するガ
ラスの製法。8. The method for producing glass having ultraviolet and heat ray shielding performance and antifouling performance according to claim 5, wherein the inorganic binder is mainly composed of metal alkoxides. 【請求項９】 ガラス基板の表面に下地層として、シリ
コンアルコキシド類、あるいはシリコンアルコキシド類
とチタンアルコキシド類またはジルコニアアルコキシド
類でなる溶液を塗布し、SiO2薄膜あるいはSiO2-TiO2 系
あるいはSiO2-ZrO2 系の複合酸化物薄膜を形成して成る
ことを特徴とする請求項５乃至８記載の紫外線と熱線遮
蔽性能及び防汚性能を有するガラスの製法。9. A solution comprising silicon alkoxides or a mixture of silicon alkoxides and titanium alkoxides or zirconia alkoxides as an underlayer on the surface of a glass substrate, and forms an SiO 2 thin film or an SiO 2 —TiO 2 or SiO 2 -ZrO 2 system preparation of glass having an ultraviolet and heat ray-shielding performance and antifouling performance of claims 5 to 8, wherein the obtained by forming a composite oxide thin film.
JP34874096A 1996-12-26 1996-12-26 Glass having performance for cutting ultraviolet ray and heat ray and having antifouling performance and its production Pending JPH10194780A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP34874096A JPH10194780A (en) 1996-12-26 1996-12-26 Glass having performance for cutting ultraviolet ray and heat ray and having antifouling performance and its production

Applications Claiming Priority (1)

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JP34874096A JPH10194780A (en) 1996-12-26 1996-12-26 Glass having performance for cutting ultraviolet ray and heat ray and having antifouling performance and its production

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JPH10194780A true JPH10194780A (en) 1998-07-28

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999041066A1 (en) * 1998-02-17 1999-08-19 Nippon Kayaku Kabushiki Kaisha Transparent sheet or film
JP2000143292A (en) * 1998-11-06 2000-05-23 Central Glass Co Ltd Porous photo-catalyst film coating glass and its coating method
JP2003531087A (en) * 2000-04-14 2003-10-21 インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク Support comprising a thick film of inorganic gel, glass, glass-ceramic or ceramic material, method for its production and its use
WO2008008190A1 (en) * 2006-07-14 2008-01-17 Guardian Industries Corp. Coated article with oxides and/or oxynitrides of antimony and/or zinc dielectric layer(s) and corresponding method
JP2011063703A (en) * 2009-09-17 2011-03-31 Kbl Eizen Center:Kk Photocatalytic coating shielding heat ray
JP2012140621A (en) * 2010-12-31 2012-07-26 Eternal Chemical Co Ltd Coating composition and uses thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999041066A1 (en) * 1998-02-17 1999-08-19 Nippon Kayaku Kabushiki Kaisha Transparent sheet or film
US6723423B1 (en) 1998-02-17 2004-04-20 Nippon Kayaku Kabushiki Kaisha Transparent sheet or film
JP2000143292A (en) * 1998-11-06 2000-05-23 Central Glass Co Ltd Porous photo-catalyst film coating glass and its coating method
JP2003531087A (en) * 2000-04-14 2003-10-21 インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク Support comprising a thick film of inorganic gel, glass, glass-ceramic or ceramic material, method for its production and its use
WO2008008190A1 (en) * 2006-07-14 2008-01-17 Guardian Industries Corp. Coated article with oxides and/or oxynitrides of antimony and/or zinc dielectric layer(s) and corresponding method
US7695785B2 (en) 2006-07-14 2010-04-13 Guardian Industries Corp. Coated article with oxides and/or oxynitrides of antimony and/or zinc dielectric layer(s) and corresponding method
JP2011063703A (en) * 2009-09-17 2011-03-31 Kbl Eizen Center:Kk Photocatalytic coating shielding heat ray
JP2012140621A (en) * 2010-12-31 2012-07-26 Eternal Chemical Co Ltd Coating composition and uses thereof

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