JPH10278165A - Manufacture of laminate - Google Patents
Manufacture of laminateInfo
- Publication number
- JPH10278165A JPH10278165A JP9089657A JP8965797A JPH10278165A JP H10278165 A JPH10278165 A JP H10278165A JP 9089657 A JP9089657 A JP 9089657A JP 8965797 A JP8965797 A JP 8965797A JP H10278165 A JPH10278165 A JP H10278165A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- film
- oxide film
- substrate
- ultraviolet
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 238000004544 sputter deposition Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 27
- 239000011521 glass Substances 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 8
- 230000004888 barrier function Effects 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 8
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract description 2
- 239000010936 titanium Substances 0.000 description 35
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 7
- 239000005357 flat glass Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000004071 soot Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005477 sputtering target Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
-
- 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
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
- C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
- C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
-
- 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
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Surface Treatment Of Glass (AREA)
- Catalysts (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は積層体の製造方法に
関する。[0001] The present invention relates to a method for producing a laminate.
【０００２】[0002]
【従来の技術】窓ガラスには様々な物質の汚れが付く。
汚れは窓ガラスの透過性を落とし、居住空間の快適性を
減ずる。汚れの除去には多大な労力と費用を必要とする
ばかりでなく、高層ビルの窓ガラスの場合などでは危険
を伴う。カーボン等の有機物は窓ガラスの汚れの代表的
な物質であり、室外側の有機物の汚れは工場等からの煤
煙、車等からの排気ガスに由来し、室内側の有機物の汚
れは、たばこの煙、空調排気口からの煤、厨房からの油
蒸気、人の皮膚の油などに由来する。また室内側におい
ては、冷房または暖房の使用により昼夜で乾燥、結露を
繰り返すことが多く、そのため、窓ガラス表面にかびが
発生することもある。2. Description of the Related Art Window glass is stained with various substances.
Dirt reduces the permeability of the window glass and reduces the comfort of the living space. Removal of dirt not only requires a great deal of labor and cost, but also involves dangers in the case of window glass of a high-rise building. Organic matter such as carbon is a representative substance of window glass dirt, organic dirt on the outdoor side is derived from soot from factories, exhaust gas from cars, etc., and organic dirt on the indoor side is tobacco. It is derived from smoke, soot from air-conditioning exhaust, oil vapor from kitchen, oil on human skin, etc. On the indoor side, drying and dew condensation are often repeated day and night due to the use of cooling or heating, so that mold may be generated on the surface of the window glass.
【０００３】近年、チタニア（ＴｉＯ2 ）等の金属酸化
物半導体の光触媒性を利用し、これらの有機物の汚れを
分解する、または、かびの発生を防ぐという研究が注目
を浴びてきている。例えば、特開平６−１９８１９６、
特開平６−２７８２４１にはＴｉＯ2 と光触媒活性を向
上させる貴金属等を混合した例が述べられている。ま
た、特開平８−２６７６４６には基材に光触媒活性層を
形成して、親水化し、防汚性を付与する例が述べられて
いる。[0003] In recent years, attention has been focused on the use of photocatalytic properties of metal oxide semiconductors such as titania (TiO 2 ) to decompose these organic contaminants or prevent the occurrence of mold. For example, JP-A-6-198196,
JP-A-6-278241 describes an example in which TiO 2 is mixed with a noble metal or the like for improving photocatalytic activity. Japanese Patent Application Laid-Open No. 8-267646 describes an example in which a photocatalytically active layer is formed on a substrate to make it hydrophilic and impart antifouling properties.
【０００４】従来の検討では光触媒活性を示すＴｉＯ2
膜の形成方法として、ＴｉＯ2 の微粒子を有機または無
機のバインダーにより固定したり、チタン有機金属溶液
からゾルゲル法で形成する等、ウェット法が主として検
討されてきた。この方法ではＴｉＯ2 の大きな光触媒活
性を引き出すことができるが、窓ガラスのような大面積
へのコートに対しては、膜厚の均一性を出すのが難し
く、また膜の耐擦傷性が不充分であった。また、原料で
あるコート液を一定の状態に保管するのに注意を必要と
した。[0004] Conventional studies have shown that TiO 2 exhibiting photocatalytic activity can be used.
As a method for forming a film, a wet method has been mainly studied, such as fixing fine particles of TiO 2 with an organic or inorganic binder, or forming a sol-gel method from a titanium organic metal solution. Although this method can bring out the large photocatalytic activity of TiO 2 , it is difficult to achieve uniform film thickness for a large area coating such as a window glass, and the film has poor scratch resistance. It was enough. In addition, care must be taken to store the coating solution as a raw material in a constant state.
【０００５】一方、従来より建築用、自動車用熱線反射
ガラスの製造で用いられているＤＣスパッタリング法は
大面積への均一なコーティングが容易で、かつ膜の基板
への密着性も優れている。また、スパッタリングターゲ
ットの保管には特別な注意を必要としない。しかしなが
ら、通常のスパッタリング法よるＴｉＯ2 膜は膜質がウ
ェット法による膜に比べて劣るため、充分な光触媒活性
は得られなかった。On the other hand, the DC sputtering method conventionally used in the production of heat-reflective glass for architectural use and automobiles allows easy uniform coating on a large area and excellent adhesion of the film to the substrate. Further, no special care is required for storing the sputtering target. However, since the film quality of the TiO 2 film formed by the ordinary sputtering method is inferior to that of the film formed by the wet method, sufficient photocatalytic activity cannot be obtained.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、耐擦傷性が
改善され、充分な光触媒活性を有する酸化物膜が形成さ
れた積層体の製造方法の提供を目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a laminate in which an oxide film having improved scratch resistance and sufficient photocatalytic activity is formed.
【０００７】[0007]
【課題を解決するための手段】本発明は、基体上に、Ｔ
ｉを主成分とする金属ターゲットから酸化性雰囲気で反
応性ＤＣスパッタリング法によりＴｉの酸化物を主成分
とする酸化物膜を成膜してなる積層体の製造方法におい
て、該Ｔｉの酸化物を主成分とする酸化物膜を、主とし
てアナターゼ型結晶の結晶粒を有し、かつ、大気中で測
定時の仕事関数が４．５〜６．０ｅＶの範囲であり、光
量１μＷで一定値以上のエネルギーの紫外線を当てたと
きに出てくる電子数の紫外線エネルギーに対する傾きが
８．５以下となるように形成することを特徴とする積層
体の製造方法を提供する。SUMMARY OF THE INVENTION The present invention provides a method for forming a substrate on a substrate.
In a method for manufacturing a laminated body formed by forming an oxide film mainly containing a Ti oxide by a reactive DC sputtering method in an oxidizing atmosphere from a metal target mainly containing i, The oxide film as a main component mainly has crystal grains of anatase type crystal, and has a work function in the range of 4.5 to 6.0 eV when measured in the atmosphere, and has a certain value or more at a light amount of 1 μW. Provided is a method for manufacturing a laminate, characterized in that the number of electrons emitted when ultraviolet light of energy is applied has a slope with respect to ultraviolet energy of 8.5 or less.
【０００８】Ｔｉを主成分とする酸化物膜（以下、単に
Ｔｉ酸化物膜という）をＴｉを主成分とする金属ターゲ
ットから基板無加熱で酸化性雰囲気で反応性ＤＣスパッ
タリング法で形成する技術は現在非常にポピュラーであ
り、熱線反射ガラス等の製造にすでに用いられている。
しかし、この方法によるＴｉＯ2 膜はＸ線的にはアモル
ファスであり、ほとんど光触媒活性を示さない。光触媒
活性を得るためには、まず膜に光触媒活性の大きいアナ
ターゼ型の結晶粒を成長させなければならない。また、
Ｔｉ酸化物膜の酸化度も重要な因子である。Ｔｉ酸化物
膜が還元気味であると、バンド中に金属Ｔｉ等の準位が
できてバンドギャップが不鮮明になり、光触媒性能が低
下する傾向にある。A technique for forming an oxide film containing Ti as a main component (hereinafter simply referred to as a Ti oxide film) from a metal target containing Ti as a main component by reactive DC sputtering in an oxidizing atmosphere without heating the substrate is known. It is now very popular and has already been used in the production of heat ray reflective glass and the like.
However, the TiO 2 film obtained by this method is amorphous in X-ray, and shows almost no photocatalytic activity. In order to obtain photocatalytic activity, first, anatase-type crystal grains having high photocatalytic activity must be grown on the film. Also,
The degree of oxidation of the Ti oxide film is also an important factor. If the Ti oxide film tends to be reduced, the level of metal Ti or the like is formed in the band, the band gap becomes unclear, and the photocatalytic performance tends to decrease.
【０００９】Ｔｉ酸化物膜の酸化度は表面分析装置（理
研計器製ＡＣ−１）により大気中で測定したときの、
１）仕事関数と、および２）一定値以上のエネルギーの
紫外線を当てたときに出てくる電子数とにより評価でき
る。図１に紫外線エネルギー（ｅＶ）と膜から出てくる
光量１μＷあたりの電子数（Ｙ）との関係の模式図を示
す。紫外線の単位エネルギーに対する傾き（Ｙ／ｅＶ）
を測定したデータの模式図を示す。膜の酸化度が高けれ
ば、出てくる電子量は少ないため、傾きは小さくなる。
本発明においては、仕事関数が４．５〜６．０ｅＶの範
囲であり、光量１μＷで一定値以上のエネルギーの紫外
線を当てたときに出てくる電子数の紫外線エネルギーに
対する傾きが８．５以下となるように形成することが重
要である。前記「一定値」はその測定条件にもよるが、
約５．８ｅＶである。また、光量が０．３５μＷの場合
に換算すると、傾きは３．０以下となるように形成す
る。The degree of oxidation of the Ti oxide film was measured by a surface analyzer (AC-1 manufactured by Riken Keiki) in the air.
It can be evaluated by 1) the work function and 2) the number of electrons emitted when ultraviolet light having energy equal to or higher than a certain value is applied. FIG. 1 is a schematic diagram showing the relationship between the ultraviolet energy (eV) and the number of electrons (Y) per 1 μW of light emitted from the film. Slope of UV against unit energy (Y / eV)
FIG. 1 shows a schematic diagram of data obtained by measuring the data. If the degree of oxidation of the film is high, the amount of emitted electrons is small, and the inclination becomes small.
In the present invention, the work function is in the range of 4.5 to 6.0 eV, and the slope of the number of electrons emitted when applying an ultraviolet ray having an energy of a certain value or more at a light amount of 1 μW to the ultraviolet energy is 8.5 or less. It is important to form such that The “constant value” depends on the measurement conditions,
It is about 5.8 eV. Further, when converted to a case where the light amount is 0.35 μW, the inclination is formed to be 3.0 or less.
【００１０】本発明者らは種々の方法を検討した結果、
特定の操作を行うことによりアナターゼ型の結晶粒を成
長させ、かつ、Ｔｉ酸化物膜の酸化度を充分なものとす
ることができることを見い出した。The present inventors have studied various methods, and as a result,
It has been found that by performing a specific operation, anatase-type crystal grains can be grown, and the degree of oxidation of the Ti oxide film can be made sufficient.
【００１１】本発明においては、Ｔｉ酸化物膜を成膜中
に、基体を、１００℃以上、基体の軟化温度以下の温度
に加熱し、かつ酸素分圧を４ｍＴｏｒｒ以上とすること
が好ましい。１００℃より温度が低いと、アナターゼ型
結晶粒が充分に成長しない。また、実用上、基体として
ガラス基板を用いることが好ましく、したがって、前記
加熱温度の上限は６５０℃とすることが好ましい。６５
０℃より高いと、ガラス基板が熱により軟化し、歪んで
しまう。特に、２００〜６５０℃が好ましい。In the present invention, it is preferable that the substrate is heated to a temperature of 100 ° C. or higher and lower than the softening temperature of the substrate during the formation of the Ti oxide film, and the oxygen partial pressure is set to 4 mTorr or higher. When the temperature is lower than 100 ° C., the anatase crystal grains do not grow sufficiently. Further, in practice, it is preferable to use a glass substrate as the base, and therefore, it is preferable that the upper limit of the heating temperature is 650 ° C. 65
If the temperature is higher than 0 ° C., the glass substrate is softened by heat and is distorted. Particularly, 200 to 650 ° C. is preferable.
【００１２】基体加熱はアナターゼ型結晶粒の成長の点
で重要な操作であるが、その条件次第では光触媒活性が
充分でないこともある。酸素分圧を４ｍＴｏｒｒ以上と
することで、Ｔｉ酸化物膜の酸化度を充分なものとする
ことができる。Heating the substrate is an important operation in growing anatase type crystal grains, but depending on the conditions, the photocatalytic activity may not be sufficient. By setting the oxygen partial pressure to 4 mTorr or more, the degree of oxidation of the Ti oxide film can be made sufficient.
【００１３】また、本発明においては、Ｔｉ酸化物膜を
成膜後、基体を、１００℃以上基体の軟化温度以下の温
度に加熱することも好ましい。該温度範囲が好ましい理
由は前記と同様の理由からであり、特に、２００〜６５
０℃が好ましい。成膜中に加熱し、さらに成膜後にも加
熱すれば、アナターゼ型結晶粒の成長はより完全なもの
となる。In the present invention, it is also preferable that after forming the Ti oxide film, the substrate is heated to a temperature not lower than 100 ° C. and not higher than the softening temperature of the substrate. The reason why the temperature range is preferable is the same as the reason described above, and in particular, 200 to 65.
0 ° C. is preferred. If heating is performed during the film formation and further after the film formation, the growth of the anatase crystal grains will be more complete.
【００１４】ガラスの上にＴｉ酸化物膜を成膜する場合
には、ガラス中のナトリウムのＴｉ酸化物膜への拡散を
防ぐため、ガラスとＴｉ酸化物膜の間にアルカリバリア
のアンダーコートが必要である。通常Ｓｉの酸化物を主
成分とする膜が用いられる。Ｓｉの酸化物を主成分とす
る膜はどのような方法で成膜してもよい。図２に、本発
明により得られる積層体の一例の断面図を示す。１は、
アルカリバリアー膜、２は、Ｔｉ酸化物膜、１１は、基
体を示す。When a Ti oxide film is formed on glass, an undercoat of an alkali barrier is formed between the glass and the Ti oxide film to prevent sodium in the glass from diffusing into the Ti oxide film. is necessary. Usually, a film mainly containing an oxide of Si is used. The film containing Si oxide as a main component may be formed by any method. FIG. 2 shows a cross-sectional view of an example of the laminate obtained by the present invention. 1 is
An alkali barrier film, 2 is a Ti oxide film, and 11 is a base.
【００１５】Ｓｉの酸化物を主成分とする膜の幾何学的
厚さは１〜１００ｎｍであることが好ましい。１ｎｍ未
満ではアルカリバリア性能が充分でなく、また１００ｎ
ｍ超としてもアルカリバリア性能に差はなく、効率が悪
い。また、Ｔｉの酸化物を主成分とする層の幾何学的厚
さは３〜５００ｎｍであることが好ましい。３ｎｍ未満
では光触媒活性が充分でなく、また５００ｎｍ超として
も光触媒活性に差はなく、効率が悪い。The geometric thickness of the film mainly composed of Si oxide is preferably 1 to 100 nm. If it is less than 1 nm, the alkali barrier performance is not sufficient, and
Even if it exceeds m, there is no difference in alkali barrier performance, and the efficiency is poor. The geometric thickness of the layer mainly composed of Ti oxide is preferably 3 to 500 nm. If it is less than 3 nm, the photocatalytic activity is not sufficient, and if it exceeds 500 nm, there is no difference in photocatalytic activity and the efficiency is poor.
【００１６】本発明においては、ガラスとＴｉ酸化物膜
の間に、金属酸化物、金属窒化物および金属炭化物から
なる群から選ばれる１種以上の機能性膜を形成すること
もできる。機能性膜はどのような方法で成膜してもよ
い。機能性膜がアルカリバリアの性質を有する場合には
アルカリバリアのアンダーコートは必要としない。In the present invention, one or more functional films selected from the group consisting of metal oxides, metal nitrides and metal carbides can be formed between the glass and the Ti oxide film. The functional film may be formed by any method. When the functional film has an alkali barrier property, an alkali barrier undercoat is not required.
【００１７】[0017]
【作用】本発明において、成膜中の基体加熱、または成
膜後の後加熱によりＴｉ酸化物膜中にアナターゼ型結晶
粒が成長する。成膜中に酸素分圧を上げることによりＴ
ｉ酸化物膜の酸化度は充分なものとなる。また、スパッ
タリング法を用いるため、膜の基体への密着性が強く、
膜の耐擦傷性が強い膜が得られる。According to the present invention, anatase crystal grains grow in the Ti oxide film by heating the substrate during film formation or post-heating after film formation. By increasing the oxygen partial pressure during film formation, T
The oxidation degree of the i-oxide film becomes sufficient. In addition, since the sputtering method is used, the adhesion of the film to the substrate is strong,
A film having strong scratch resistance is obtained.
【００１８】[0018]
【実施例】以下の例で例１〜５は本発明の実施例を、例
６〜１１は比較例を示す。実施例および比較例において
用いた膜の成膜条件は表１に示すとおりである。これら
の膜の光触媒活性は次のようにして評価した。大きさ
４．５ｃｍ×５．０ｃｍ×２ｍｍのサンプルを膜面を上
にしてのパイレックス製容器（容量３リットル）に入
れ、アセトアルデヒド蒸気を数百ｐｐｍ入れた。次に容
器の外側からサンプルの膜面に６Ｗのブラックライト４
本で紫外光を当てた。一定時間おきに容器の中のアセト
アルデヒド濃度をガス検知管により測定し、アセトアル
デヒド濃度の減少速度を測定した。これらの膜の耐擦傷
性はテーバー試験（摩耗輪ＣＳ−１０Ｆ、荷重５００
ｇ）によりテーバー１００回転前後のヘーズ値変化ΔＨ
によって評価した。ΔＨが５未満の場合を○、５以上の
場合を×とした。EXAMPLES In the following examples, Examples 1 to 5 show examples of the present invention, and Examples 6 to 11 show comparative examples. The film forming conditions used in the examples and comparative examples are as shown in Table 1. The photocatalytic activity of these films was evaluated as follows. A sample having a size of 4.5 cm × 5.0 cm × 2 mm was placed in a Pyrex container (capacity: 3 liters) with the membrane surface facing upward, and several hundred ppm of acetaldehyde vapor was introduced. Next, a 6 W black light 4 was applied to the sample from the outside of the container.
The book was exposed to ultraviolet light. The acetaldehyde concentration in the container was measured at regular intervals using a gas detector tube, and the rate of decrease in the acetaldehyde concentration was measured. The abrasion resistance of these films was evaluated by the Taber test (wear wheel CS-10F, load 500).
g), the haze value change ΔH before and after 100 rotations of Taber
Was evaluated by. The case where ΔH was less than 5 was evaluated as ○, and the case where ΔH was 5 or more was evaluated as ×.
【００１９】膜の酸化度は、表面分析装置（理研計器製
ＡＣ−１）により、仕事関数および電子数の紫外線エネ
ルギーに対する傾きを求めた。なお、傾きを求めたとき
の光量は０．３５μＷとした。結果は表２にまとめた。
表中の「濃度減少速度」は、アセトアルデヒド濃度減少
速度（ppm/時間）の意である。The degree of oxidation of the film was determined by using a surface analyzer (AC-1 manufactured by Riken Keiki) to determine the slope of the work function and the number of electrons with respect to the ultraviolet energy. The amount of light when the inclination was obtained was 0.35 μW. The results are summarized in Table 2.
"Concentration reduction rate" in the table means the acetaldehyde concentration reduction rate (ppm / hour).
【００２０】［例１］洗浄した厚さ２ｍｍのフロートガ
ラス板をスパッタリング装置内にセットし、１０-6Ｔｏ
ｒｒ台まで排気した。次に表１の条件で、ＳｉＯ2 膜
（幾何学的膜厚５０ｎｍ）／Ｔｉ酸化物膜−１（２００
ｎｍ）を成膜した。この膜は充分な光触媒活性を示し、
また実用上充分な耐擦傷性を示した。（ ）内の数字は
幾何学的膜厚であり、以下も同様である。表２における
（ ）内の数字は幾何学的膜厚（ｎｍ）である。また、
表２においては、Ｔｉ酸化物膜−１を単にＴｉＯ2 −１
と示し、以下も同様とする。Example 1 A washed float glass plate having a thickness of 2 mm was set in a sputtering apparatus, and 10 -6 To
The air was exhausted to the rr level. Next, under the conditions shown in Table 1, the SiO 2 film (geometric thickness: 50 nm) / Ti oxide film-1 (200
nm). This film shows sufficient photocatalytic activity,
In addition, practically sufficient scratch resistance was exhibited. The numbers in parentheses are geometric film thicknesses, and the same applies to the following. The numbers in parentheses in Table 2 are the geometric film thickness (nm). Also,
In Table 2, simply TiO 2 -1 the Ti oxide film -1
And the same applies to the following.
【００２１】［例２］例１と同様にして、ＳｉＯ2 膜
（５０ｎｍ）／Ｔｉ酸化物膜−２（２０ｎｍ）を成膜し
た。この膜は充分な光触媒活性を示し、また実用上充分
な耐擦傷性を示した。Example 2 A SiO 2 film (50 nm) / Ti oxide film-2 (20 nm) was formed in the same manner as in Example 1. This film exhibited sufficient photocatalytic activity and also exhibited practically sufficient scratch resistance.
【００２２】［例３］実施例１と同様にして、ＳｉＯ2
膜（５０ｎｍ）／Ｔｉ酸化物膜−３（２００ｎｍ）を成
膜した。成膜後この膜を空気中で６００℃、１時間熱処
理した。この膜は充分な光触媒活性を示し、また実用上
充分な耐擦傷性を示した。Example 3 In the same manner as in Example 1, SiO 2
Film (50 nm) / Ti oxide film-3 (200 nm) was formed. After the film formation, the film was heat-treated in air at 600 ° C. for 1 hour. This film exhibited sufficient photocatalytic activity and also exhibited practically sufficient scratch resistance.
【００２３】［例４］実施例１と同様にして、ＴｉＮx
膜（３０ｎｍ）／Ｔｉ酸化物膜−１（２００ｎｍ）を成
膜した。この膜は充分な光触媒活性を示し、また実用上
充分な耐擦傷性を示した。Example 4 In the same manner as in Example 1, TiN x
Film (30 nm) / Ti oxide film-1 (200 nm) was formed. This film exhibited sufficient photocatalytic activity and also exhibited practically sufficient scratch resistance.
【００２４】［例５］実施例１と同様にして、Ｔｉ酸化
物膜−３（５０ｎｍ）／ＴｉＮx （１０ｎｍ）／Ｔｉ酸
化物膜−３（２０ｎｍ）／Ｔｉ酸化物膜−１（２００ｎ
ｍ）を成膜した。この膜は充分な光触媒活性を示し、ま
た実用上充分な耐擦傷性を示した。[0024] [Example 5] In the same manner as in Example 1, Ti oxide film -3 (50nm) / TiN x ( 10nm) / Ti oxide film -3 (20nm) / Ti oxide film -1 (200n
m) was formed. This film exhibited sufficient photocatalytic activity and also exhibited practically sufficient scratch resistance.
【００２５】［例６］実施例１と同様にして、ＳｉＯ2
膜（５０ｎｍ）／Ｔｉ酸化物膜−２（２００ｎｍ）を成
膜した。この膜は実用上充分な耐擦傷性を示したが、光
触媒活性は例１より劣ることが確認された。Example 6 In the same manner as in Example 1, SiO 2
Film (50 nm) / Ti oxide film-2 (200 nm) was formed. Although this film showed practically sufficient scratch resistance, it was confirmed that the photocatalytic activity was inferior to that of Example 1.
【００２６】［例７］実施例１と同様にして、ＳｉＯ2
膜（５０ｎｍ）／Ｔｉ酸化物膜−３（２００ｎｍ）を成
膜した。この膜は実用上充分な耐擦傷性を示したが、光
触媒活性は例１より劣ることが確認された。Example 7 As in Example 1, SiO 2
Film (50 nm) / Ti oxide film-3 (200 nm) was formed. Although this film showed practically sufficient scratch resistance, it was confirmed that the photocatalytic activity was inferior to that of Example 1.
【００２７】［例８］実施例１と同様にして、ＳｉＯ2
膜（５０ｎｍ）／Ｔｉ酸化物膜−４（２００ｎｍ）を成
膜した。この膜は実用上充分な耐擦傷性を示したが、光
触媒活性は例１より劣ることが確認された。Example 8 In the same manner as in Example 1, SiO 2
Film (50 nm) / Ti oxide film-4 (200 nm) was formed. Although this film showed practically sufficient scratch resistance, it was confirmed that the photocatalytic activity was inferior to that of Example 1.
【００２８】［例９］ゾルゲル法により、ＳｉＯ2 膜
（５０ｎｍ）／Ｔｉ酸化物（２００ｎｍ）を成膜した。
この膜は充分な光触媒活性を示したが、耐擦傷性は例１
より劣ることを確認した。Example 9 A SiO 2 film (50 nm) / Ti oxide (200 nm) was formed by a sol-gel method.
Although this film exhibited sufficient photocatalytic activity, the scratch resistance was as shown in Example 1.
We confirmed that it was worse.
【００２９】［例１０］実施例１と同様にして、ＴｉＮ
x （３０ｎｍ）を成膜した。この膜は実用上充分な耐擦
傷性を示したが、光触媒活性は例１より劣ることが確認
された。Example 10 In the same manner as in Example 1, TiN
x (30 nm) was deposited. Although this film showed practically sufficient scratch resistance, it was confirmed that the photocatalytic activity was inferior to that of Example 1.
【００３０】［例１１］実施例１と同様にして、Ｔｉ酸
化物膜−３（５０ｎｍ）／ＴｉＮx （１０ｎｍ）／Ｔｉ
酸化物膜−３（２０ｎｍ）を成膜した。この膜は実用上
充分な耐擦傷性を示したが、光触媒活性は例１より劣る
ことが確認された。Example 11 In the same manner as in Example 1, Ti oxide film-3 (50 nm) / TiN x (10 nm) / Ti
An oxide film-3 (20 nm) was formed. Although this film showed practically sufficient scratch resistance, it was confirmed that the photocatalytic activity was inferior to that of Example 1.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【発明の効果】本発明によれば、ウェット法によるチタ
ン酸化物膜と同等の光触媒活性を持ちながら、耐擦傷性
に優れている積層体を得ることができる。したがって特
に耐擦傷性向上のための施策を講ずることもなく、その
ままビル用の窓ガラスに使用できる。According to the present invention, it is possible to obtain a laminate having excellent scratch resistance while having the same photocatalytic activity as a titanium oxide film formed by a wet method. Therefore, it can be used as it is for a building window glass without taking measures to improve the scratch resistance.
【図面の簡単な説明】[Brief description of the drawings]
【図１】紫外線エネルギーと膜から出てくる電子数との
関係の模式図FIG. 1 is a schematic diagram showing a relationship between ultraviolet energy and the number of electrons emitted from a film.
【図２】本発明により得られる積層体の一例の断面図FIG. 2 is a cross-sectional view of an example of a laminate obtained by the present invention.
１：アルカリバリアー膜 ２：Ｔｉ酸化物膜 １１：基体 1: Alkali barrier film 2: Ti oxide film 11: Base
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ２３Ｃ 14/34 Ｃ２３Ｃ 14/34 Ｍ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C23C 14/34 C23C 14/34 M
Claims (3)
ットから酸化性雰囲気で反応性ＤＣスパッタリング法に
よりＴｉの酸化物を主成分とする酸化物膜を成膜してな
る積層体の製造方法において、該Ｔｉの酸化物を主成分
とする酸化物膜を、主としてアナターゼ型結晶の結晶粒
を有し、かつ、大気中で測定時の仕事関数が４．５〜
６．０ｅＶの範囲であり、光量１μＷで一定値以上のエ
ネルギーの紫外線を当てたときに出てくる電子数の紫外
線エネルギーに対する傾きが８．５以下となるように形
成することを特徴とする積層体の製造方法。1. Production of a laminate comprising a metal target containing Ti as a main component and an oxide film containing Ti oxide as a main component formed by a reactive DC sputtering method in an oxidizing atmosphere from a metal target containing Ti as a main component. In the method, the oxide film mainly composed of the Ti oxide has a work function of 4.5 to 4.5 mainly having anatase type crystal grains and having a work function of 4.5 in the atmosphere.
A layer having a range of 6.0 eV and having a light quantity of 1 μW and a gradient of the number of electrons emitted when the ultraviolet ray having an energy of a predetermined value or more is applied to the ultraviolet energy is 8.5 or less. How to make the body.
膜中に、基体を、１００℃以上、基体の軟化温度以下の
温度に加熱し、かつ酸素分圧を４ｍＴｏｒｒ以上とする
請求項１記載の積層体の製造方法。2. The substrate is heated to a temperature of 100.degree. C. or higher and lower than the softening temperature of the substrate during the formation of the oxide film containing Ti oxide as a main component, and the oxygen partial pressure is set to 4 mTorr or higher. A method for manufacturing a laminate according to claim 1.
膜後、基体を、１００℃以上基体の軟化温度以下の温度
に加熱する請求項１または２記載の積層体の製造方法。3. The method for producing a laminate according to claim 1, wherein the substrate is heated to a temperature not lower than 100 ° C. and not higher than the softening temperature of the substrate after forming an oxide film containing a Ti oxide as a main component. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08965797A JP3518240B2 (en) | 1997-04-08 | 1997-04-08 | Manufacturing method of laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08965797A JP3518240B2 (en) | 1997-04-08 | 1997-04-08 | Manufacturing method of laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10278165A true JPH10278165A (en) | 1998-10-20 |
| JP3518240B2 JP3518240B2 (en) | 2004-04-12 |
Family
ID=13976836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08965797A Expired - Fee Related JP3518240B2 (en) | 1997-04-08 | 1997-04-08 | Manufacturing method of laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3518240B2 (en) |
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|---|---|---|---|---|
| EP1068899A1 (en) * | 1999-07-14 | 2001-01-17 | Nippon Sheet Glass Co., Ltd. | Multilayer structure and process for producing the same |
| FR2814094A1 (en) * | 2000-09-20 | 2002-03-22 | Saint Gobain | Deposition of a titanium oxide layer on a vitreous surface to provide an antireflective coating for e.g. glass roofs |
| US6777091B2 (en) | 2000-03-22 | 2004-08-17 | Nippon Sheet Glass Co., Ltd. | Substrate with photocatalytic film and method for producing the same |
| WO2004108283A1 (en) * | 2003-06-09 | 2004-12-16 | Nippon Sheet Glass Co., Ltd. | Photocatalyst member |
| JP2007319731A (en) * | 2006-05-30 | 2007-12-13 | Ｙｋｋ Ａｐ株式会社 | Photocatalytically active film-coated article |
| JP2008505841A (en) * | 2004-07-12 | 2008-02-28 | 日本板硝子株式会社 | Low maintenance coating |
| JP2008229419A (en) * | 2007-03-16 | 2008-10-02 | Bridgestone Corp | Photocatalytic nitrogen-doped titanium oxide thin film and its depositing method |
| US7612015B2 (en) | 2001-12-21 | 2009-11-03 | Nippon Sheet Glass Company, Limited | Member having photocatalytic function and method for manufacture thereof |
| JP2013503812A (en) * | 2009-09-08 | 2013-02-04 | サン−ゴバン グラス フランス | Material and glazing containing the material |
| JP2013505820A (en) * | 2009-09-25 | 2013-02-21 | エクス−マルセイユ ユニヴェルシテ | Superporous photocatalytic material, method for producing the same, and use thereof |
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1997
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1068899A1 (en) * | 1999-07-14 | 2001-01-17 | Nippon Sheet Glass Co., Ltd. | Multilayer structure and process for producing the same |
| US6777091B2 (en) | 2000-03-22 | 2004-08-17 | Nippon Sheet Glass Co., Ltd. | Substrate with photocatalytic film and method for producing the same |
| FR2814094A1 (en) * | 2000-09-20 | 2002-03-22 | Saint Gobain | Deposition of a titanium oxide layer on a vitreous surface to provide an antireflective coating for e.g. glass roofs |
| JP2004510051A (en) * | 2000-09-20 | 2004-04-02 | サン−ゴバン グラス フランス | Substrate with photocatalytic coating |
| US7612015B2 (en) | 2001-12-21 | 2009-11-03 | Nippon Sheet Glass Company, Limited | Member having photocatalytic function and method for manufacture thereof |
| WO2004108283A1 (en) * | 2003-06-09 | 2004-12-16 | Nippon Sheet Glass Co., Ltd. | Photocatalyst member |
| USRE44155E1 (en) | 2004-07-12 | 2013-04-16 | Cardinal Cg Company | Low-maintenance coatings |
| JP2008505841A (en) * | 2004-07-12 | 2008-02-28 | 日本板硝子株式会社 | Low maintenance coating |
| JP2008505842A (en) * | 2004-07-12 | 2008-02-28 | 日本板硝子株式会社 | Low maintenance coating |
| USRE43817E1 (en) | 2004-07-12 | 2012-11-20 | Cardinal Cg Company | Low-maintenance coatings |
| JP2007319731A (en) * | 2006-05-30 | 2007-12-13 | Ｙｋｋ Ａｐ株式会社 | Photocatalytically active film-coated article |
| US9738967B2 (en) | 2006-07-12 | 2017-08-22 | Cardinal Cg Company | Sputtering apparatus including target mounting and control |
| JP2008229419A (en) * | 2007-03-16 | 2008-10-02 | Bridgestone Corp | Photocatalytic nitrogen-doped titanium oxide thin film and its depositing method |
| US9102565B2 (en) | 2009-09-08 | 2015-08-11 | Saint-Gobain Glass France | Material and glazing comprising said material |
| JP2013503812A (en) * | 2009-09-08 | 2013-02-04 | サン−ゴバン グラス フランス | Material and glazing containing the material |
| JP2013505820A (en) * | 2009-09-25 | 2013-02-21 | エクス−マルセイユ ユニヴェルシテ | Superporous photocatalytic material, method for producing the same, and use thereof |
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| US11325859B2 (en) | 2016-11-17 | 2022-05-10 | Cardinal Cg Company | Static-dissipative coating technology |
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