JP4581650B2 - Method for producing synthetic resin molding - Google Patents
Method for producing synthetic resin molding Download PDFInfo
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- JP4581650B2 JP4581650B2 JP2004342089A JP2004342089A JP4581650B2 JP 4581650 B2 JP4581650 B2 JP 4581650B2 JP 2004342089 A JP2004342089 A JP 2004342089A JP 2004342089 A JP2004342089 A JP 2004342089A JP 4581650 B2 JP4581650 B2 JP 4581650B2
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- metal oxide
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- synthetic resin
- oxide film
- fluorine
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- 229920003002 synthetic resin Polymers 0.000 title claims description 48
- 239000000057 synthetic resin Substances 0.000 title claims description 48
- 238000000465 moulding Methods 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 91
- 150000004706 metal oxides Chemical class 0.000 claims description 91
- 229910052731 fluorine Inorganic materials 0.000 claims description 49
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 46
- 239000011737 fluorine Substances 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 41
- 239000000758 substrate Substances 0.000 claims description 38
- 238000004544 sputter deposition Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 4
- 239000010408 film Substances 0.000 description 132
- 239000010410 layer Substances 0.000 description 38
- 239000000203 mixture Substances 0.000 description 30
- 229920005989 resin Polymers 0.000 description 29
- 239000011347 resin Substances 0.000 description 29
- 229910052710 silicon Inorganic materials 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 229910052718 tin Inorganic materials 0.000 description 13
- 238000009792 diffusion process Methods 0.000 description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052814 silicon oxide Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 7
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- -1 perfluoro Chemical group 0.000 description 7
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
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- 229910052760 oxygen Inorganic materials 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
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- 229910052715 tantalum Inorganic materials 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
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- 229910052738 indium Inorganic materials 0.000 description 3
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- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
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- 238000002834 transmittance Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
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- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 229910008355 Si-Sn Inorganic materials 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- 229910006453 Si—Sn Inorganic materials 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
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- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
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- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
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- 229920000728 polyester Polymers 0.000 description 1
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- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 125000004805 propylene group Chemical class [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000005546 reactive sputtering Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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Landscapes
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
Description
本発明は含フッ素合成樹脂を主成分とする表面上に金属酸化物膜を形成して合成樹脂成形物を製造する方法に関する。 The present invention relates to a method for producing a synthetic resin molding by forming a metal oxide film on a surface containing a fluorine-containing synthetic resin as a main component.
従来、表面が疎水性を有する合成樹脂基体は、その疎水性に起因して不具合を生ずる場合があった。例えば、疎水性を有する合成樹脂基体の代表例である含フッ素樹脂フィルムは、透明性、耐久性、耐候性、防汚性等に優れており、その特性から塩化ビニル樹脂に代わって、農園芸ハウス用フィルムとしても使用され始めている。しかし、含フッ素樹脂フィルムを農園芸ハウス用に使用した場合、表面の親水性が低いために、フィルムの室内側表面に結露が生じ易い。このため作物の生育に必要な太陽光が遮断されたり、フィルムの室内側表面に付着した水滴が作物の上に落ち、農作物に悪影響を与えるといった問題が生じる。 Conventionally, a synthetic resin substrate having a hydrophobic surface sometimes causes problems due to its hydrophobicity. For example, a fluororesin film, which is a typical example of a synthetic resin substrate having hydrophobicity, is excellent in transparency, durability, weather resistance, antifouling properties, etc. It is also beginning to be used as a house film. However, when the fluorine-containing resin film is used for an agricultural or horticultural house, dew condensation is likely to occur on the indoor side surface of the film because the hydrophilicity of the surface is low. For this reason, there is a problem that sunlight necessary for the growth of the crop is blocked, or water droplets attached to the indoor surface of the film fall on the crop and adversely affect the crop.
かかる問題を解決する方法として、下記特許文献１には、疎水性を有する合成樹脂基体上に、Ｓｉ、Ｚｒ、Ｔｉ、Ｔａ、Ｈｆ、Ｍｏ、Ｗ、Ｎｂ、Ｓｎ、Ｉｎ、Ａｌ、ＣｒおよびＺｎからなる群から選ばれる一種以上の金属の酸化物からなる薄膜を、スパッタリング方等の乾式法により形成することで、基体の表面に親水性を付与する方法が記載されている。スパッタリング時のターゲットに対する電力密度は１〜２０Ｗ／ｃｍ２程度である。
しかしこの方法では、疎水成分の金属酸化物薄膜中への拡散が生じ、その結果、設計通りの金属酸化物薄膜を形成することが難しい。
As a method for solving such a problem, the following Patent Document 1 discloses Si, Zr, Ti, Ta, Hf, Mo, W, Nb, Sn, In, Al, Cr, and Zn on a hydrophobic synthetic resin substrate. There is described a method of imparting hydrophilicity to the surface of a substrate by forming a thin film made of one or more metal oxides selected from the group consisting of by a dry method such as sputtering. The power density with respect to the target at the time of sputtering is about 1 to 20 W / cm 2 .
However, in this method, diffusion of the hydrophobic component into the metal oxide thin film occurs, and as a result, it is difficult to form a metal oxide thin film as designed.
下記特許文献２では、フッ素樹脂フィルム上に機能性膜を形成する際に、フッ素成分が機能性膜に拡散するのを防止するために、該フッ素樹脂フィルムと機能性膜との間にＳｎ、Ｃｒ、ＩｒおよびＰｔからなる群から選ばれる１種以上の金属の酸化物を含有するフッ素拡散防止膜を形成する方法が提案されている。フッ素拡散防止膜を形成するためのスパッタリング時において、直径４インチ（１０．１６ｃｍ）のターゲットに対するスパッタ電力は３００Ｗであり、電力密度に換算すると約３．７Ｗ／ｃｍ２である。
上述のような、疎水性を有する合成樹脂基体の表面上に金属酸化物層を形成して親水性を付与する方法において、より高度な親水性を達成するためには、疎水成分の金属酸化物層中への拡散をより低く抑えて、設計通りの金属酸化物薄膜を形成できる技術が求められる。
本発明は、含フッ素合成樹脂を主成分とする表面上に金属酸化物膜を形成する際に、フッ素成分の金属酸化物膜中への拡散をより低く抑えることができる方法を提供する。
In the method of forming a metal oxide layer on the surface of a synthetic resin substrate having hydrophobicity as described above and imparting hydrophilicity, in order to achieve higher hydrophilicity, the metal oxide of the hydrophobic component is used. There is a need for a technique capable of forming a metal oxide thin film as designed while suppressing diffusion into the layer.
The present invention provides a method capable of suppressing diffusion of a fluorine component into a metal oxide film to a lower level when forming a metal oxide film on a surface containing a fluorine-containing synthetic resin as a main component.
前記課題を解決するために、本発明の合成樹脂成形物の製造方法は、含フッ素合成樹脂を主成分とする表面を有する基体の、前記表面に、プラズマを用いた乾式法により、１．０Ｗ／ｃｍ２未満の電力密度で第１の金属酸化物膜を形成する第１の工程、および前記第１の金属酸化物膜上に、プラズマを用いた乾式法により、１．０Ｗ／ｃｍ２以上の電力密度で第２の金属酸化物膜を形成する第２の工程を含むことを特徴とする。 In order to solve the above-mentioned problems, a method for producing a synthetic resin molded product according to the present invention is characterized in that a substrate having a surface containing a fluorine-containing synthetic resin as a main component has a surface of 1.0 W by a dry method using plasma on the surface. 1.0 W / cm 2 or more by a first step of forming a first metal oxide film with a power density of less than / cm 2 and a dry method using plasma on the first metal oxide film. And a second step of forming a second metal oxide film at a power density of.
前記第２の金属酸化物膜が、少なくともＳｉを含む金属酸化物からなる態様が好ましい。
前記第１の金属酸化物膜と、前記第２の金属酸化物膜とが、同じ金属の酸化物からなる態様が好ましい。
プラズマを用いた乾式法が、スパッタリング法である態様が好ましい。
第１の工程と第２の工程との間に、基体の雰囲気を排気する工程を有する態様が好ましい。
前記第１の金属酸化物膜の膜厚が０．３ｎｍ以上、かつ前記第２の金属酸化物膜の膜厚が１００ｎｍ以下である態様が好ましい。
It is preferable that the second metal oxide film is made of a metal oxide containing at least Si.
It is preferable that the first metal oxide film and the second metal oxide film are made of the same metal oxide.
An embodiment in which the dry method using plasma is a sputtering method is preferable.
An embodiment having a step of evacuating the atmosphere of the substrate between the first step and the second step is preferable.
It is preferable that the first metal oxide film has a thickness of 0.3 nm or more and the second metal oxide film has a thickness of 100 nm or less.
本発明によれば、含フッ素合成樹脂を主成分とする表面上に、フッ素成分の拡散がより低くて、組成が設計値により近い良好な金属酸化物膜を形成できる。 According to the present invention, it is possible to form a good metal oxide film having a lower diffusion of the fluorine component and a composition closer to the design value on the surface containing the fluorine-containing synthetic resin as a main component.
＜基体＞
本発明における基体は、含フッ素合成樹脂を主成分とする表面（以下、含フッ素樹脂表面という。）を有する。本発明において「含フッ素合成樹脂を主成分とする」とは、含フッ素合成樹脂の含有割合が５０質量％以上であることをいう。含フッ素合成樹脂が１００質量％であってもよい。
基体は、基体全体が含フッ素合成樹脂を主成分とする材質であってもよく、含フッ素合成樹脂を主成分とする材質と他の材質とが組み合わされている場合には、表面の一部または全部が含フッ素合成樹脂を主成分とする材質であればよい。
<Substrate>
The substrate in the present invention has a surface (hereinafter referred to as a fluorine-containing resin surface) containing a fluorine-containing synthetic resin as a main component. In the present invention, “having a fluorine-containing synthetic resin as a main component” means that the content ratio of the fluorine-containing synthetic resin is 50% by mass or more. The fluorine-containing synthetic resin may be 100% by mass.
The substrate may be made of a material mainly composed of a fluorine-containing synthetic resin as a whole, and if the material mainly composed of the fluorine-containing synthetic resin is combined with another material, a part of the surface of the substrate Alternatively, all may be a material mainly composed of a fluorine-containing synthetic resin.
含フッ素樹脂表面に用いられる含フッ素合成樹脂は、樹脂の分子構造式中にフッ素を含有する熱可塑性樹脂であれば特に限定されず、公知の各種のフッ素系樹脂が使用できる。例えば、テトラフルオロエチレン系樹脂、クロロトリフルオロエチレン系樹脂、フッ化ビニリデン系樹脂、フッ化ビニル系樹脂、またはこれら樹脂の複合物が挙げられる。特に、耐薬品性に優れるという点から、テトラフルオロエチレン系樹脂が好ましい。 The fluorine-containing synthetic resin used on the surface of the fluorine-containing resin is not particularly limited as long as it is a thermoplastic resin containing fluorine in the molecular structural formula of the resin, and various known fluorine resins can be used. For example, a tetrafluoroethylene resin, a chlorotrifluoroethylene resin, a vinylidene fluoride resin, a vinyl fluoride resin, or a composite of these resins can be given. In particular, a tetrafluoroethylene resin is preferable from the viewpoint of excellent chemical resistance.
テトラフルオロエチレン系樹脂としては、例えば、テトラフルオロエチレン樹脂（ＰＴＦＥ）、テトラフルオロエチレン・パーフルオロ（アルコキシエチレン）共重合体（ＰＦＡ）、テトラフルオロエチレン・ヘキサフルオロプロピレン・パーフルオロ（アルコキシエチレン）共重合体（ＥＰＥ）、テトラフルオロエチレン・ヘキサフルオロプロピレン共重合体（ＦＥＰ）、テトラフルオロエチレン・エチレン共重合体（ＥＴＦＥ）、エチレン・トリクロロフルオロエチレン共重合体（ＥＴＣＦＥ）が挙げられる。
これらのうち、ＰＦＡ、ＥＴＦＥ、ＦＥＰ、ＥＴＣＦＥが好ましく、特に、コスト、機械的強度、成膜性等の点からＥＴＦＥが好ましい。ＥＴＦＥは、エチレンおよびテトラフルオロエチレンを主体とするものであって、必要に応じ、少量のコモノマー成分を共重合させたものであってもよい。
Examples of tetrafluoroethylene resins include tetrafluoroethylene resin (PTFE), tetrafluoroethylene / perfluoro (alkoxyethylene) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene / perfluoro (alkoxyethylene) Examples thereof include a polymer (EPE), a tetrafluoroethylene / hexafluoropropylene copolymer (FEP), a tetrafluoroethylene / ethylene copolymer (ETFE), and an ethylene / trichlorofluoroethylene copolymer (ETFFE).
Of these, PFA, ETFE, FEP, and ETCFE are preferable, and ETFE is particularly preferable from the viewpoint of cost, mechanical strength, film formability, and the like. ETFE is mainly composed of ethylene and tetrafluoroethylene, and may be obtained by copolymerizing a small amount of a comonomer component as necessary.
前記コモノマー成分としては、テトラフルオロエチレンおよびエチレンと共重合可能なモノマー、例えば、ＣＦ２＝ＣＦＣｌ、ＣＦ２＝ＣＨ２等の含フッ素エチレン類；ＣＦ２＝ＣＦＣＦ３、ＣＦ２＝ＣＨＣＦ３等の含フッ素プロピレン類；ＣＨ２＝ＣＨＣ２Ｆ５、ＣＨ２＝ＣＨＣ４Ｆ９、ＣＨ２＝ＣＦＣ４Ｆ９、ＣＨ２＝ＣＦ（ＣＦ２）３Ｈ等のフルオロアルキル基の炭素数が２〜１０の含フッ素アルキルエチレン類；ＣＦ２＝ＣＦＯＲｆ（式中Ｒｆは炭素数１〜６のパーフルオロアルキル基を示す。）等のパーフルオロ（アルコキシエチレン）類；ＣＦ２＝ＣＦＯ（ＣＦ２ＣＦＸＯ）ｍＲｆ（式中Ｒｆは炭素数１〜６のパーフルオロアルキル基、Ｘはフッ素原子またはトリフルオロメチル基、ｍは１〜５の整数を示す。）等のパーフルオロ（アルキルビニルエーテル）類；ＣＦ２＝ＣＦＯＣＦ２ＣＦ２ＣＦ２ＣＯＯＣＨ３、ＣＦ２＝ＣＦＯＣＦ２ＣＦ（ＣＦ３）ＯＣＦ２ＣＦ２ＳＯ２Ｆ等の、容易にカルボン酸基またはスルホン酸基に変換可能な基を有するビニルエーテル類等の化合物が挙げられる。 Examples of the comonomer component include monomers copolymerizable with tetrafluoroethylene and ethylene, for example, fluorine-containing ethylenes such as CF 2 = CFCl and CF 2 = CH 2 ; CF 2 = CFCF 3 , CF 2 = CHCF 3 and the like. Fluorine-containing propylenes: CH 2 ═CHC 2 F 5 , CH 2 ═CHC 4 F 9 , CH 2 ═CFC 4 F 9 , CH 2 ═CF (CF 2 ) 3 H, etc. 10 fluorine-containing alkylethylenes; perfluoro (alkoxyethylene) s such as CF 2 ═CFOR f (wherein R f represents a C 1-6 perfluoroalkyl group); CF 2 ═CFO (CF 2 CFXO) m R f (formula in the R f perfluoroalkyl group having 1 to 6 carbon atoms, X is a fluorine atom or a trifluoromethyl group, m is 1 . An integer of 5) perfluoro (alkyl vinyl ether) such as; CF 2 = CFOCF 2 CF 2 CF 2 COOCH 3, CF 2 = CFOCF 2 CF (CF 3) , such as OCF 2 CF 2 SO 2 F, easily And compounds such as vinyl ethers having a group that can be converted into a carboxylic acid group or a sulfonic acid group.
ＥＴＦＥ中のエチレン／テトラフルオロエチレンのモル比は、４０／６０〜７０／３０であるのが好ましく、４０／６０〜６０／４０であるのがより好ましい。また、コモノマー成分の含有量は、全モノマーに対して０．３〜１０モル％であるのが好ましく、０．３〜５モル％であるのがより好ましい。 The molar ratio of ethylene / tetrafluoroethylene in ETFE is preferably 40/60 to 70/30, and more preferably 40/60 to 60/40. Moreover, it is preferable that it is 0.3-10 mol% with respect to all the monomers, and, as for content of a comonomer component, it is more preferable that it is 0.3-5 mol%.
前記クロロトリフルオロエチレン系樹脂としては、例えば、クロロトリフルオロエチレンホモポリマー（ＣＴＦＥ）、エチレン・クロロトリフルオロエチレン共重合体（ＥＣＴＦＥ）が挙げられる。 Examples of the chlorotrifluoroethylene-based resin include chlorotrifluoroethylene homopolymer (CTFE) and ethylene / chlorotrifluoroethylene copolymer (ECTFE).
また含フッ素樹脂表面をなす材料が、上記の含フッ素合成樹脂を主成分とし、他の熱可塑性樹脂を含有した混合系の樹脂であってもよい。
熱可塑性合成樹脂としては、例えば、アクリル樹脂、ポリカーボネート樹脂、ポリエステル樹脂、ポリアミド樹脂、塩化ビニル樹脂、オレフィン系樹脂、ポリアセタール樹脂、ポリエーテルイミド樹脂、ポリエーテルスルホン樹脂、ポリエーテルケトン樹脂、ポリフェニレンスルフィド樹脂、ポリスルホン樹脂、ポリアリレート樹脂、ポリエチレンナフタレート樹脂、ポリメチルペンテン樹脂、ＡＢＳ樹脂、酢酸ビニル樹脂、またはポリスチレン樹脂等が挙げられる。
The material forming the surface of the fluorine-containing resin may be a mixed resin containing the above-mentioned fluorine-containing synthetic resin as a main component and other thermoplastic resin.
Examples of the thermoplastic synthetic resin include acrylic resin, polycarbonate resin, polyester resin, polyamide resin, vinyl chloride resin, olefin resin, polyacetal resin, polyetherimide resin, polyethersulfone resin, polyetherketone resin, polyphenylene sulfide resin. , Polysulfone resin, polyarylate resin, polyethylene naphthalate resin, polymethylpentene resin, ABS resin, vinyl acetate resin, or polystyrene resin.
また含フッ素樹脂表面には、顔料、紫外線吸収剤、カーボンブラック、カーボンファイバ、炭化ケイ素、ガラスファイバ、マイカ、または架橋剤等の添加剤および充填物のいずれか１種以上が含まれていてもよい。 Further, the surface of the fluorine-containing resin may contain any one or more of additives and fillers such as pigments, ultraviolet absorbers, carbon black, carbon fibers, silicon carbide, glass fibers, mica, or crosslinking agents. Good.
基体の形状は、特に限定されない。例えばフィルム状、シート状または板状が好ましく挙げられる。基体の厚さは、特に制限されない。例えば光透過性の点では薄くする方が好ましく、強度の点からは厚くする方が好ましい。用途に応じて設定される。例えば１０〜３００μｍ、特に３０〜２００μｍの厚みとすることが好ましい。 The shape of the substrate is not particularly limited. For example, a film shape, a sheet shape or a plate shape is preferable. The thickness of the substrate is not particularly limited. For example, it is preferable to reduce the thickness in terms of light transmittance, and it is preferable to increase the thickness in terms of strength. It is set according to the application. For example, the thickness is preferably 10 to 300 μm, particularly 30 to 200 μm.
＜金属酸化物膜＞
本発明における第１の金属酸化物材料および第２の金属酸化物膜の材料としては、Ｓｉ、Ｚｒ、Ｔｉ、Ｔａ、Ｈｆ、Ｍｏ、Ｗ、Ｎｂ，Ｓｎ、Ｉｎ、Ａｌ、ＣｒおよびＺｎからなる群から選ばれる一種または二種以上が好ましい。
第１の金属酸化物材料と第２の金属酸化物膜とは、組成が同じでもよく、異なっていてもよい。第１の金属酸化物膜と第２の金属酸化物膜とが同じ金属の酸化物からなる膜であると、両方の膜を成膜するのに同種のダーゲットを用いることができるので、簡単な装置で、容易に、生産性良く成膜できる。
<Metal oxide film>
The material of the first metal oxide material and the second metal oxide film in the present invention is made of Si, Zr, Ti, Ta, Hf, Mo, W, Nb, Sn, In, Al, Cr and Zn. One or more selected from the group is preferred.
The first metal oxide material and the second metal oxide film may have the same composition or different compositions. If the first metal oxide film and the second metal oxide film are films made of the same metal oxide, the same kind of darget can be used to form both films. With this apparatus, it is possible to easily form a film with high productivity.
第２の金属酸化物膜として、少なくともＳｉを含む金属の酸化物からなる膜を用いると、より高い親水性が得られることから好ましい。これは、第２の金属酸化物膜表面に存在するＳｉと大気中に存在する水分とが結合し、親水性の高いＳｉＯＨの状態が生じるためと考えられる。
第１の金属酸化物膜と第２の金属酸化物膜の両方が、少なくともＳｉを含む金属の酸化物からなる膜であることがより好ましい。
It is preferable to use a film made of a metal oxide containing at least Si as the second metal oxide film because higher hydrophilicity can be obtained. This is presumably because Si present on the surface of the second metal oxide film and moisture present in the atmosphere combine to produce a highly hydrophilic SiOH state.
More preferably, both the first metal oxide film and the second metal oxide film are films made of a metal oxide containing at least Si.
前記少なくともＳｉを含む金属の酸化物の具体例としては、ＳｉＯ2、ＳｉとＺｒとの酸化物、ＳｉとＴｉとの酸化物、ＳｉとＴａとの酸化物、ＳｉとＮｂとの酸化物、ＳｉとＳｎとの酸化物、ＳｉとＺｎとの酸化物またはＳｉとＳｎとＴｉとの酸化物、を主成分とする酸化物等が挙げられる。
なお、初期の親水性、親水性の長期持続性、材料コスト等の観点から、ＳｉＯ2を主成分とする金属酸化物膜が好ましい。
また、初期の親水性、親水性の長期持続性、基体との密着性、および生産性の観点から、ＳｉとＳｎとの酸化物、ＳｉとＺｒとの酸化物、ＳｉとＴｉとの酸化物、を主成分とする酸化物が好ましく、特に、ＳｉとＳｎとの酸化物を主成分とする酸化物が好ましい。
また、親水性の長期持続性を妨げる要因のひとつと考えられる汚れの付着に対して、太陽光照射により分解、付着抑制作用を発現させる光触媒機能を有する点から、ＳｉとＳｎとの酸化物、ＳｉとＴｉとの酸化物、ＳｉとＳｎとＴｉとの酸化物、を主成分とする酸化物が好ましい。
Specific examples of the metal oxide containing at least Si include SiO 2 , Si and Zr oxide, Si and Ti oxide, Si and Ta oxide, Si and Nb oxide, Examples thereof include oxides of Si and Sn, oxides of Si and Zn, and oxides of Si, Sn, and Ti as main components.
A metal oxide film containing SiO 2 as a main component is preferable from the viewpoint of initial hydrophilicity, long-term hydrophilicity, material cost, and the like.
In addition, from the viewpoint of initial hydrophilicity, long-lasting hydrophilicity, adhesion to a substrate, and productivity, an oxide of Si and Sn, an oxide of Si and Zr, an oxide of Si and Ti Is preferable, and an oxide mainly containing an oxide of Si and Sn is particularly preferable.
In addition, it has a photocatalytic function of decomposing and adhering to the adhesion of dirt, which is considered to be one of the factors hindering the long-term sustainability of hydrophilicity, from the point that it has a photocatalytic function that expresses an adhesion suppression action, An oxide mainly composed of an oxide of Si and Ti and an oxide of Si, Sn, and Ti is preferable.
前記少なくともＳｉを含む金属酸化物膜におけるＳｉの含有割合は、全金属に対してＳｉが２０〜８０原子％であることが好ましく、特に、３０〜７０原子％であることが好ましい。
Ｓｉの含有割合を前記の範囲内とすることで、１）金属酸化物膜に含まれるＳｉの作用により、金属酸化物膜の屈折率が適当に小さくでき、所望の色調を有する合成樹脂成形物が得られる、２）また、Ｓｉ以外の金属成分の作用により、酸化物膜を薄くしても前記した親水性をはじめとする各種性能が発現される、３）成膜法として直流スパッタリング法を用いる場合に、得ようとする金属酸化物膜と同様の前記組成範囲の合金ターゲットを用いることができ、これによりアーキングが防止される、４）Ｓｉ以外の金属として、Ｔｉおよび／またはＳｎを用いる場合、該金属の酸化物の光触媒機能の強さを適度にできる。
金属酸化物膜の水に対する接触角（以下、水接触角という。）は、成膜直後から時間が経るにつれ増大する傾向にあるが、Ｓｉの含有割合が大きい（例えばＳｉが５０原子％以上）ほど前記水接触角の経時変化量は小さい。
一方、合金ターゲットを用いる場合に、Ｓｉの含有割合が大きくなると、成膜速度が低下する傾向にあるため、生産性の観点からは、Ｓｉは７０原子％以下であることが好ましい。
The content ratio of Si in the metal oxide film containing at least Si is preferably 20 to 80 atom%, particularly preferably 30 to 70 atom%, based on the total metal.
By making the content ratio of Si within the above range, 1) a synthetic resin molded article having a desired color tone, the refractive index of the metal oxide film can be appropriately reduced by the action of Si contained in the metal oxide film. 2) In addition, due to the action of metal components other than Si, various properties including the above-described hydrophilicity can be exhibited even if the oxide film is thinned. 3) The direct current sputtering method is used as a film forming method. When used, an alloy target having the same composition range as the metal oxide film to be obtained can be used, thereby preventing arcing. 4) Ti and / or Sn is used as a metal other than Si. In this case, the strength of the photocatalytic function of the metal oxide can be moderated.
The contact angle (hereinafter referred to as the water contact angle) of the metal oxide film with water tends to increase as time passes immediately after the film formation, but the content ratio of Si is large (for example, Si is 50 atomic% or more). The amount of change with time of the water contact angle is small.
On the other hand, when an alloy target is used, if the Si content ratio increases, the deposition rate tends to decrease. Therefore, from the viewpoint of productivity, Si is preferably 70 atomic% or less.
第１の金属酸化物膜の膜厚は、０．３ｎｍ以上が好ましく、０．３〜５ｎｍがより好ましく、０．５〜３ｎｍがさらに好ましい。
第２の金属酸化物膜の膜厚は、１００ｎｍ以下が好ましく、２．７〜９５ｎｍがより好ましく、３．５〜２７ｎｍがさらに好ましい。
第１の金属酸化物膜と第２の金属酸化物膜の合計の膜厚は、３〜１００ｎｍが好ましく、４〜３０ｎｍがより好ましい。
第１の金属酸化物膜の膜厚が上記範囲の下限値以上であると含フッ素合成基体からのフッ素成分の拡散を充分抑制でき、上記範囲の上限値以下であると成膜時間を短くできるため生産性に優れる。
第２の金属酸化物膜の膜厚が上記範囲の下限値以上であると充分な親水性、流滴性が得られ、上記範囲の上限値以下であると成膜時間を短くできるため生産性に優れる。
第１の金属酸化物膜と第２の金属酸化物膜の合計の膜厚が上記範囲の下限値以上であると充分な親水性、流滴性が得られ、上記範囲の上限値以下であると可視光透過性が良好であり、合成樹脂成形物の可撓性が充分であり、基体と金属酸化物膜との密着性に優れる。
The thickness of the first metal oxide film is preferably 0.3 nm or more, more preferably 0.3 to 5 nm, and further preferably 0.5 to 3 nm.
The thickness of the second metal oxide film is preferably 100 nm or less, more preferably 2.7 to 95 nm, and further preferably 3.5 to 27 nm.
3-100 nm is preferable and, as for the total film thickness of a 1st metal oxide film and a 2nd metal oxide film, 4-30 nm is more preferable.
When the thickness of the first metal oxide film is not less than the lower limit of the above range, the diffusion of the fluorine component from the fluorine-containing synthetic substrate can be sufficiently suppressed, and when it is not more than the upper limit of the above range, the film formation time can be shortened. Therefore, it is excellent in productivity.
If the thickness of the second metal oxide film is equal to or greater than the lower limit of the above range, sufficient hydrophilicity and dropability can be obtained, and if it is equal to or less than the upper limit of the above range, the film formation time can be shortened, so that productivity is achieved. Excellent.
When the total film thickness of the first metal oxide film and the second metal oxide film is equal to or greater than the lower limit of the above range, sufficient hydrophilicity and flowability can be obtained, and is equal to or less than the upper limit of the above range. Visible light transmittance is good, the flexibility of the synthetic resin molding is sufficient, and the adhesion between the substrate and the metal oxide film is excellent.
＜製造方法＞
本発明における、第１の金属酸化物膜および第２の金属酸化物膜を製造する方法は、プラズマを用いた乾式法であれば特に限定されない。乾式法は、湿式法に比べ、膜が均一にでき、成膜された膜は基体との密着性が高い点で好ましい。
プラズマを用いた乾式法としては、例えば、スパッタリング法、イオンプレーティング法等の物理的蒸着法（ＰＶＤ）；プラズマＣＶＤ法等の化学的蒸着法（ＣＶＤ）が挙げられる。特にスパッタリング法は、生産性に優れ、工業的に幅広く使われているとともに、該方法により、非常に緻密で、かつ、基体との密着性が高い膜が均一な膜厚で得られるため好ましい。
スパッタリング法としては、直流スパッタリング法、高周波スパッタリング法のいずれでも使用できる。
イオンプレーティング法は、例えば、直流放電方式、高周波放電方式、マイクロ波放電方式、電子サイクロトロン共鳴放電方式、バイアスプローブ方式、熱電子活性化方式、多負極方式、アノード・アーク放電方式、カソード・アーク放電方式、ホローカソード放電方式、圧力勾配型プラズマガン方式が挙げられる。
プラズマＣＶＤ法は、ＤＣ（直流）グロー放電、高周波グロー放電、マイクロ波放電等の方式が挙げられる。
特に、大面積への均一な成膜が可能であること、生産性が高いこと、膜厚の精密なコントロールが比較的容易であること等の利点を有することから、スパッタリング法が好ましい。
<Manufacturing method>
The method for producing the first metal oxide film and the second metal oxide film in the present invention is not particularly limited as long as it is a dry method using plasma. The dry method is preferable in that the film can be made more uniform than the wet method, and the formed film has high adhesion to the substrate.
Examples of the dry method using plasma include physical vapor deposition (PVD) such as sputtering and ion plating; and chemical vapor deposition (CVD) such as plasma CVD. In particular, the sputtering method is preferable because it is excellent in productivity and widely used industrially, and by this method, a very dense film with high adhesion to the substrate can be obtained with a uniform film thickness.
As the sputtering method, either a direct current sputtering method or a high frequency sputtering method can be used.
The ion plating method includes, for example, a direct current discharge method, a high frequency discharge method, a microwave discharge method, an electron cyclotron resonance discharge method, a bias probe method, a thermionic activation method, a multiple negative electrode method, an anode arc discharge method, a cathode arc. Examples of the discharge method include a hollow cathode discharge method and a pressure gradient plasma gun method.
Examples of the plasma CVD method include DC (direct current) glow discharge, high-frequency glow discharge, and microwave discharge.
In particular, the sputtering method is preferable because it has advantages such as uniform film formation over a large area, high productivity, and relatively easy control of the film thickness.
第１の金属酸化物膜および／または第２の金属酸化物膜が、ＳｉＯ2からなる膜である場合は、例えばＳｉターゲットを用い、酸素含有雰囲気中での高周波スパッタリング法により成膜できる。また、ＳｉＯ2ターゲットを用い、無酸素雰囲気中での高周波スパッタリング法により成膜することもできる。
なお、高周波スパッタリング法に代えて、間欠的な負の直流電圧をターゲットに印加する直流スパッタリング法によっても得られる。
When the first metal oxide film and / or the second metal oxide film is a film made of SiO 2 , it can be formed by, for example, a high frequency sputtering method in an oxygen-containing atmosphere using an Si target. Alternatively, a film can be formed by a high-frequency sputtering method in an oxygen-free atmosphere using a SiO 2 target.
In addition, it replaces with a high frequency sputtering method, and it can obtain also by the direct current | flow sputtering method which applies an intermittent negative direct current voltage to a target.
第１の金属酸化物膜および／または第２の金属酸化物膜が、ＳｉとＳｎとの酸化物からなる膜である場合は、ＳｉとＳｎとの混合物ターゲットを用い、酸素含有雰囲気中での反応性スパッタリング法により成膜できる。
ＳｉとＳｎの混合物ターゲットを用いた場合、前記のＳｉターゲットとは異なり、ターゲットの導電性の向上等の理由から通常の直流スパッタリング法の使用が可能となる。
その他の、Ｚｒ、Ｔｉ、Ｔａ、Ｈｆ、Ｍｏ、Ｗ、Ｎｂ、Ｉｎ、Ａｌ、ＣｒおよびＺｎからなる群から選ばれる一種以上の金属とＳｉとからなるターゲットを用いた場合でも同様の効果が得られるが、特にＳｉ−Ｓｎ系の金属ターゲットを用いた場合は、成膜速度が大きく、生産性に優れる点で好ましい。
前記ＳｉとＳｎとからなるターゲットは、混合物の状態のものでも、合金の状態のものでも用いることができる。例えば、ＳｉとＳｎと混合物ターゲットは、ＳｉとＳｎとの混合物をＣＩＰ法（冷間等方プレス法）または温間プレス（Ｓｎの融点直下の温度で金型成形プレス）で成形して得ることができる。
When the first metal oxide film and / or the second metal oxide film is a film made of an oxide of Si and Sn, a mixture target of Si and Sn is used in an oxygen-containing atmosphere. A film can be formed by a reactive sputtering method.
When a mixture target of Si and Sn is used, it is possible to use a normal DC sputtering method for reasons such as improving the conductivity of the target, unlike the Si target.
The same effect can be obtained even when a target composed of one or more metals selected from the group consisting of Zr, Ti, Ta, Hf, Mo, W, Nb, In, Al, Cr and Zn and Si is used. However, in particular, when a Si—Sn metal target is used, the film formation rate is high, which is preferable in terms of excellent productivity.
The target composed of Si and Sn can be used in a mixture state or an alloy state. For example, the Si, Sn and mixture target can be obtained by molding a mixture of Si and Sn by the CIP method (cold isotropic press method) or warm press (molding press at a temperature just below the melting point of Sn). Can do.
プラズマを用いた乾式法により第１の金属酸化物膜を形成する第１の工程における、電力密度は１．０Ｗ／ｃｍ２未満である。
本発明における電力密度は、スパッタリング法、イオンプレーティング法等、金属の蒸発源となるターゲットを使用する場合は「ターゲットの単位面積当たりの電力密度の値」を意味する。またプラズマＣＶＤ法等、ターゲットを使用しない場合は電極の単位面積あたりの電力密度の値を意味する。
第１の工程における前記電力密度の下限値は第１の金属酸化物膜を成膜できればよく、特に限定されないが、生産性を考慮すると０．１Ｗ／ｃｍ２以上が好ましい。より好ましい範囲は０．２Ｗ／ｃｍ２以上、１Ｗ／ｃｍ２未満である。
第１の工程における電力密度を上記範囲とすることにより、金属酸化物膜中へのフッ素成分の拡散を効果的に抑え、良好な組成の金属酸化物膜が得られる。
The power density in the first step of forming the first metal oxide film by a dry method using plasma is less than 1.0 W / cm 2 .
The power density in the present invention means “a value of power density per unit area of the target” when using a target as a metal evaporation source such as a sputtering method or an ion plating method. Moreover, when a target is not used, such as a plasma CVD method, it means a power density value per unit area of the electrode.
The lower limit of the power density in the first step is not particularly limited as long as the first metal oxide film can be formed, but is preferably 0.1 W / cm 2 or more in consideration of productivity. A more preferable range is 0.2 W / cm 2 or more and less than 1 W / cm 2 .
By setting the power density in the first step within the above range, diffusion of the fluorine component into the metal oxide film can be effectively suppressed, and a metal oxide film having a favorable composition can be obtained.
プラズマを用いた乾式法により第２の金属酸化物膜を形成する第２の工程における、ターゲットに対する電力密度は１．０Ｗ／ｃｍ２以上である。
該電力密度の上限値は特に限定されないが、基体へのダメージ抑制の点から１０Ｗ／ｃｍ２以下程度が好ましい。より好ましい範囲は１〜４Ｗ／ｃｍ２である。
第２の工程における電力密度を上記範囲とすることにより基体への熱ダメージを抑制できる。
第１の工程および第２の工程における、基体雰囲気のガス圧は、特に限定されないが、０．１〜２Ｐａ程度が好ましく、０．２〜１Ｐａ程度がより好ましい
In the second step of forming the second metal oxide film by a dry method using plasma, the power density with respect to the target is 1.0 W / cm 2 or more.
The upper limit of the power density is not particularly limited, but is preferably about 10 W / cm 2 or less from the viewpoint of suppressing damage to the substrate. A more preferable range is 1 to 4 W / cm 2 .
By setting the power density in the second step within the above range, thermal damage to the substrate can be suppressed.
The gas pressure in the substrate atmosphere in the first step and the second step is not particularly limited, but is preferably about 0.1 to 2 Pa, more preferably about 0.2 to 1 Pa.
前記第１の工程と第２の工程との間に、基体の雰囲気を排気する工程を設けることが好ましい。該排気工程は、例えば、成膜装置の反応室内で第１の工程を行った後、該反応室を排気した後、同じ反応室内で第２の工程を行う方法で実施してもよい。
または、複数の反応室を備えた成膜装置を用い、第１の反応室内で第１の工程を行った後、基体を、別の第２の反応室へ移動させ、該第２の反応室内で第２の工程を行う方法で実施してもよい。この場合、第１の反応室から第２の反応室への移動は、真空中で行う。
前記排気工程を設けると、第１の工程で温度が上昇した基体が、一旦冷却されてから第２の工程に供されるため、基体の温度上昇が抑えられる。
また、第１の工程では、基体の含フッ素合成樹脂に由来するフッ素含有ガスが発生し易い。該フッ素含有ガスが存在する雰囲気中で、引き続き第２の工程を行うと、該フッ素含有ガスに由来するフッ素が第２の金属酸化物膜中に取り込まれ易い。これに対して、前記排気工程を行うと、該含フッ素ガスによる悪影響を防止できる。
It is preferable to provide a step of exhausting the atmosphere of the substrate between the first step and the second step. The evacuation step may be performed, for example, by a method in which the first step is performed in the reaction chamber of the film forming apparatus, the reaction chamber is evacuated, and then the second step is performed in the same reaction chamber.
Alternatively, after a first step is performed in the first reaction chamber using a film formation apparatus including a plurality of reaction chambers, the substrate is moved to another second reaction chamber, and the second reaction chamber is moved. In this case, the second step may be performed. In this case, the movement from the first reaction chamber to the second reaction chamber is performed in a vacuum.
When the evacuation step is provided, the substrate whose temperature has increased in the first step is once cooled and then used in the second step, so that an increase in the temperature of the substrate can be suppressed.
In the first step, a fluorine-containing gas derived from the fluorine-containing synthetic resin of the substrate is easily generated. When the second step is subsequently performed in an atmosphere containing the fluorine-containing gas, fluorine derived from the fluorine-containing gas is likely to be taken into the second metal oxide film. On the other hand, when the exhaust process is performed, adverse effects due to the fluorine-containing gas can be prevented.
本発明によれば、基体上に、第１の金属酸化物膜および第２の金属酸化物膜からなる金属酸化物層が形成された合成樹脂成形物が得られる。該２つの膜の界面が判別できなくてもよい。
本発明により得られる合成樹脂成形物にあっては、前記金属酸化物層中へのフッ素成分の拡散が抑えられ、より設計値に近い組成の金属酸化物層を形成できる。これにより、基体の含フッ素樹脂表面に、より高度な親水性を付与できる。
したがって、含フッ素合成樹脂の優れた透明性、耐久性、耐候性、防汚性等を備えるとともに、表面の親水性、流滴性に優れ、結露が生じ難い合成樹脂成形物が得られる。
According to the present invention, a synthetic resin molded article in which a metal oxide layer composed of a first metal oxide film and a second metal oxide film is formed on a substrate is obtained. The interface between the two films may not be discriminated.
In the synthetic resin molded article obtained by the present invention, diffusion of the fluorine component into the metal oxide layer is suppressed, and a metal oxide layer having a composition closer to the design value can be formed. Thereby, a higher degree of hydrophilicity can be imparted to the surface of the fluororesin of the substrate.
Therefore, a synthetic resin molded article having excellent transparency, durability, weather resistance, antifouling properties, etc. of the fluorine-containing synthetic resin, excellent surface hydrophilicity, and droplet resistance, and hardly causing condensation is obtained.
前記金属酸化物層へのフッ素成分の拡散の程度は、該金属酸化物層中におけるフッ素の存在割合によって評価できる。
また、例えば、前記金属酸化物層がＳｉを含有する場合、該金属酸化物層中へのフッ素の拡散が生じると、フッ素とＳｉとの反応よりＳｉとフッ素を含有するガス（ＳｉＦＸ）が発生し、これによって金属酸化物層中におけるＳｉの含有割合が設計値よりも低くなる。したがって、金属酸化物層における金属組成が設計値により近いほど、金属酸化物層中へのフッ素成分の拡散がより抑えられたことを意味する。
The degree of diffusion of the fluorine component into the metal oxide layer can be evaluated by the proportion of fluorine present in the metal oxide layer.
Further, for example, when the metal oxide layer contains Si, when fluorine diffuses into the metal oxide layer, a gas containing Si and fluorine (SiF x ) is generated by the reaction between fluorine and Si. As a result, the content ratio of Si in the metal oxide layer becomes lower than the design value. Therefore, the closer the metal composition in the metal oxide layer is to the design value, the more suppressed the diffusion of the fluorine component into the metal oxide layer.
本発明の製造方法で得られる合成樹脂成形物の用途は、特に限定されない。例えば、温室等に用いられる農業用フィルム、園芸用フィルム、食品用フィルム等が挙げられる。これらの用途の場合は、第１の金属酸化物膜および第２の金属酸化物膜が透明であることが好ましい。 The use of the synthetic resin molded product obtained by the production method of the present invention is not particularly limited. For example, an agricultural film, a horticultural film, a food film and the like used in a greenhouse or the like can be given. In these applications, the first metal oxide film and the second metal oxide film are preferably transparent.
以下に本発明を、実施例および比較例を挙げてさらに具体的に説明するが、この説明
が本発明を限定するものではない。
以下の実施例および比較例において、第１の金属酸化物膜を初期層といい、第２の金属酸化物膜を上層という。
［実施例１］
基体としてＥＴＦＥからなるフィルム（厚さ６０μｍ）を用意した。１０ｃｍ角のガラス板上に１０ｃｍ角の上記フィルム片を固定した基板を、スパッタリング装置の第１の反応室内の陽極側にセットし、ＳｉとＳｎとの混合物（原子比５０：５０）からなるターゲット（以下、ターゲットＡという）を陰極側にセットした。装置内を１０-４Ｐａ台まで真空排気した後、アルゴンと酸素を流量比（アルゴン：酸素）１：４で装置内に導入し、スパッタリングガス圧（基体雰囲気のガス圧）が０．６Ｐａになるように調節した。
直流電源を用い、電力密度０．６Ｗ／ｃｍ2で８秒間のスパッタリングを行うことによって、初期層として、ＳｉとＳｎとの酸化物を主成分とする膜（以下、ＳＴＯ膜という。）を成膜した。
その後、基板を、第１の反応室と同じ構成の第２の反応室内に移動させ、電力密度を１．６Ｗ／ｃｍ2に変更した他は、初期層と同様にして８秒間のスパッタリングを行い、前記初期層上に、上層としてのＳＴＯ膜を成膜して、合成樹脂成形物を得た。
The present invention will be described more specifically with reference to examples and comparative examples below, but this description does not limit the present invention.
In the following examples and comparative examples, the first metal oxide film is referred to as an initial layer, and the second metal oxide film is referred to as an upper layer.
[Example 1]
A film (thickness: 60 μm) made of ETFE was prepared as a substrate. A substrate on which a 10 cm square film piece is fixed on a 10 cm square glass plate is set on the anode side in the first reaction chamber of the sputtering apparatus, and is made of a mixture of Si and Sn (atomic ratio 50:50). (Hereinafter referred to as target A) was set on the cathode side. After the inside of the apparatus is evacuated to a level of 10 −4 Pa, argon and oxygen are introduced into the apparatus at a flow ratio (argon: oxygen) 1: 4, and the sputtering gas pressure (gas pressure in the substrate atmosphere) is 0.6 Pa. It adjusted so that it might become.
By performing sputtering for 8 seconds at a power density of 0.6 W / cm 2 using a direct current power source, a film containing Si and Sn as its main component (hereinafter referred to as STO film) is formed as an initial layer. Filmed.
Thereafter, the substrate is moved into a second reaction chamber having the same configuration as the first reaction chamber, and the power density is changed to 1.6 W / cm 2. A STO film as an upper layer was formed on the initial layer to obtain a synthetic resin molded product.
＜膜厚＞
得られた合成樹脂成形物における金属酸化物の膜厚を蛍光Ｘ線を用いて測定した結果を表１に示す。蛍光Ｘ線分析による膜厚測定は、ＲＩＧＡＫＵ社製、走査型蛍光Ｘ線分析装置（製品名；ＲＩＸ３０００）を用い、予めＴＥＭ（透過型電子顕微鏡）による観察と湿式分析により膜厚および組成を確認した試料に基づいて作成した検量線を用いた検量線法により、初期層と上層の合計の膜厚を求めた。このとき、膜厚はＳｎ強度よりＳｎ：Ｓｉ＝１：１のＳＴＯ膜厚として計算した値を採用した。そして、初期層と上層のそれぞれの膜厚は、スパッタリング時に印加した電力と成膜時間とを掛け合わせて得られる仕事量に比例した計算値を採用した。
<Film thickness>
Table 1 shows the result of measuring the film thickness of the metal oxide in the obtained synthetic resin molding using fluorescent X-rays. Film thickness measurement by fluorescent X-ray analysis is performed by using a scanning fluorescent X-ray analyzer (product name: RIX3000) manufactured by RIGAKU, and the film thickness and composition are confirmed in advance by TEM (transmission electron microscope) and wet analysis. The total film thickness of the initial layer and the upper layer was determined by a calibration curve method using a calibration curve created based on the prepared samples. At this time, the value calculated as the STO film thickness of Sn: Si = 1: 1 from the Sn intensity was adopted. For the film thicknesses of the initial layer and the upper layer, calculated values proportional to the work amount obtained by multiplying the power applied during sputtering and the film formation time were adopted.
＜初期水接触角＞
得られた合成樹脂成形物の表面層の親水性の良否をみるために、上層表面の水接触角（初期水接触角）を測定した。その結果を表１に示す。接触角の測定は、協和界面科学株式会社製 接触角計（ＣＡ−Ｘ型）を用い、大気圧下で２３℃に温度調整された部屋で純水４μｌを被測定面に滴下し、２０秒後の安定した接触角度を顕微鏡により読み取る方法で行った。水接触角が小さいほど、親水性が高いことを意味する。
<Initial water contact angle>
In order to check the hydrophilicity of the surface layer of the obtained synthetic resin molding, the water contact angle (initial water contact angle) of the upper layer surface was measured. The results are shown in Table 1. The contact angle is measured using a contact angle meter (CA-X type) manufactured by Kyowa Interface Science Co., Ltd., in a room whose temperature is adjusted to 23 ° C. under atmospheric pressure, 4 μl of pure water is dropped onto the surface to be measured, and 20 seconds. The subsequent stable contact angle was read by a microscope. A smaller water contact angle means higher hydrophilicity.
＜低温親水性＞
低温下での親水性試験（低温親水性）を行った。試験装置として、２０℃の恒温水槽の開口部を、測定しようとする合成樹脂成形物で覆って密閉した装置を用いた。このとき合成樹脂成形物の被測定面が水槽内側になるようにした。該装置の外気温を１０℃に制御して、３時間保持した後、被測定面における結露の発生状態を観察し、親水性の良否を評価した。目視判定で、結露がほとんど生じていないもの（評価；５）から多く結露しているもの（評価；１）まで５段階評価した。その結果を表１に示す。
<Low temperature hydrophilicity>
A hydrophilicity test at low temperature (low temperature hydrophilicity) was performed. As a test apparatus, an apparatus in which the opening of a constant temperature water bath at 20 ° C. was covered with a synthetic resin molding to be measured and sealed was used. At this time, the surface to be measured of the synthetic resin molded product was set inside the water tank. After controlling the external temperature of this apparatus to 10 degreeC and hold | maintaining for 3 hours, the generation | occurrence | production state of the dew condensation in the to-be-measured surface was observed, and the quality of hydrophilic property was evaluated. By visual judgment, the evaluation was made on a five-point scale from the one with almost no condensation (evaluation: 5) to the one with much condensation (evaluation: 1). The results are shown in Table 1.
＜Ｓｉ／Ｓｎ組成比＞
初期層および上層からなる膜全体におけるＳｉとＳｎとの組成比（Ｓｉ／Ｓｎ組成比）を蛍光Ｘ線分析を用いて求めた。その結果を表１に示す。該組成比は「Ｓｉ強度より算出したＳＴＯ換算膜厚」／「Ｓｎ強度より算出したＳＴＯ換算膜厚」として算出した。この値が１に近いほど、膜組成がターゲット組成に近くて良好であることを意味する。
該組成比が、１より小さくなる理由は必ずしも明らかではないが、金属酸化物膜形成時、該金属酸化物膜中のＳｉ原子が、該膜中に拡散したＦ成分中のＦ原子と反応し、ＳｉＦＸ（Ｘは１〜４の整数を示す。）のガスとなり揮散するためと考えられる。該組成比が小さくなるほどＦ成分の拡散が多いと考えられる。
<Si / Sn composition ratio>
The composition ratio of Si and Sn (Si / Sn composition ratio) in the entire film composed of the initial layer and the upper layer was determined by fluorescent X-ray analysis. The results are shown in Table 1. The composition ratio was calculated as “STO equivalent film thickness calculated from Si strength” / “STO equivalent film thickness calculated from Sn strength”. The closer this value is to 1, the better the film composition is close to the target composition.
The reason why the composition ratio is smaller than 1 is not always clear, but when the metal oxide film is formed, Si atoms in the metal oxide film react with F atoms in the F component diffused in the film. , SiF X (X represents an integer of 1 to 4) gas is considered to volatilize. It is considered that the diffusion of the F component increases as the composition ratio decreases.
＜Ｆ／Ｓｎ組成比＞
Ｘ線光電子分光装置（アルバック・ファイ社製、Ｑｕａｎｔｕｍ ２０００）を用いて、初期層および上層からなる膜全体におけるＦとＳｎとの組成比（Ｆ／Ｓｎ組成比）を測定した。その結果を表１に示す。
Ｘ線源としては単色化ＡｌＫα線を用い、光電子検出角度は２０°とした。中和銃を併用し光電子のＰａｓｓ Ｅｎｅｒｇｙを２３．５ｅＶとしてＤｅｐｔｈ Ｐｒｏｆｉｌｅ分析を行なった。検出元素はＦ、Ｏ、Ｓｎ、Ｃ、Ｓｉで、Ｆ１ｓスペクトルを６８８ｅＶ付近のＥＴＦＥ中のＣ−Ｆ結合成分（基体由来）と、６８５．５ｅＶ付近のＳＴＯ膜中Ｆ成分とにピーク分離により分離し、膜中におけるＦ成分とＳｎ成分のプロファイルを得た。このプロファイルを積分することにより、膜中に存在するＦ成分と膜中に存在するＳｎ成分の比を求め、この値をＦ／Ｓｎ組成比として採用した。この値が小さいほど膜中に拡散したＦ成分の量が少ないことを意味する。
<F / Sn composition ratio>
The composition ratio of F and Sn (F / Sn composition ratio) in the entire film composed of the initial layer and the upper layer was measured using an X-ray photoelectron spectrometer (manufactured by ULVAC-PHI, Quantum 2000). The results are shown in Table 1.
Monochromatic AlKα ray was used as the X-ray source, and the photoelectron detection angle was 20 °. Depth profile analysis was performed using a neutralization gun in combination with a photoelectron Pass Energy of 23.5 eV. The detection elements are F, O, Sn, C, and Si, and the F1s spectrum is separated by peak separation into the C—F bond component (derived from the substrate) in ETFE near 688 eV and the F component in the STO film near 685.5 eV. Thus, profiles of the F component and the Sn component in the film were obtained. By integrating this profile, the ratio of the F component present in the film to the Sn component present in the film was determined, and this value was adopted as the F / Sn composition ratio. The smaller this value, the smaller the amount of F component diffused in the film.
［実施例２］
トータル膜厚が実施例１と同じ６ｎｍとなるように、初期層および上層の成膜条件を変更した。
すなわち、実施例１における初期層成膜条件を電力密度０．５Ｗ／ｃｍ２、成膜時間１０秒に変え、上層成膜条件を電力密度１．３Ｗ／ｃｍ２、成膜時間１０秒に変えた他は実施例１と同様にして合成樹脂成形物を得た。得られた合成樹脂成形物について、実施例１と同様に測定した結果を表１に示す。
[Example 2]
The film formation conditions for the initial layer and the upper layer were changed so that the total film thickness was 6 nm, which was the same as in Example 1.
That is, the initial layer deposition conditions in Example 1 were changed to a power density of 0.5 W / cm 2 and a deposition time of 10 seconds, and the upper layer deposition conditions were changed to a power density of 1.3 W / cm 2 and a deposition time of 10 seconds. Otherwise, a synthetic resin molded product was obtained in the same manner as in Example 1. About the obtained synthetic resin molding, the result measured like Example 1 is shown in Table 1.
［比較例１］
初期層の成膜を行わず、基体上に膜厚６ｎｍのＳＴＯ膜を成膜した。
すなわち、基体上に成膜する条件を電力密度２．２Ｗ／ｃｍ2、成膜時間８秒間とした他は実施例１と同様にして、基体上に膜厚６ｎｍのＳＴＯ膜を成膜した。得られた合成樹脂成形物について、実施例１と同様に測定した結果を表１に示す。
[Comparative Example 1]
An STO film having a thickness of 6 nm was formed on the substrate without forming an initial layer.
That is, an STO film having a film thickness of 6 nm was formed on the substrate in the same manner as in Example 1 except that the film formation conditions on the substrate were a power density of 2.2 W / cm 2 and a film formation time of 8 seconds. About the obtained synthetic resin molding, the result measured like Example 1 is shown in Table 1.
表１に示されるように、電力密度を変えて２段階の成膜を行った実施例１，２は、１段階で成膜した比較例１に比べて、Ｓｉ／Ｓｎ組成比およびＦ／Ｓｎ組成比がいずれも改善された。また、初期接触角および低温親水性が向上した。 As shown in Table 1, Examples 1 and 2 in which the power density was changed and two stages of film formation were performed, compared with Comparative Example 1 in which the film was formed in one stage, the Si / Sn composition ratio and F / Sn. Both composition ratios were improved. Also, the initial contact angle and low temperature hydrophilicity were improved.
［実施例３］
実施例１における初期層成膜時の電力密度を０．２Ｗ／ｃｍ2に変更し、上層成膜時の電力密度を２．２Ｗ／ｃｍ2に変更した以外は実施例１と同様にして合成樹脂成形物を得た。得られた合成樹脂成形物について、表２に示す各評価項目を実施例１と同様に測定した。その結果を表２に示す。
[Example 3]
Synthesis was performed in the same manner as in Example 1 except that the power density at the initial layer formation in Example 1 was changed to 0.2 W / cm 2 and the power density at the upper layer formation was changed to 2.2 W / cm 2. A resin molded product was obtained. About the obtained synthetic resin molding, each evaluation item shown in Table 2 was measured similarly to Example 1. The results are shown in Table 2.
［実施例４］
実施例３における初期層成膜時の電力密度を０．６Ｗ／ｃｍ２に変えた以外は実施例３と同様に行った。得られた合成樹脂成形物について、実施例３と同様に測定した結果を表２に示す。
[Example 4]
The same operation as in Example 3 was performed except that the power density at the time of forming the initial layer in Example 3 was changed to 0.6 W / cm 2 . About the obtained synthetic resin molding, the result measured similarly to Example 3 is shown in Table 2.
［比較例２］
実施例３における初期層成膜時の電力密度を１．０Ｗ／ｃｍ２に変えた以外は実施例３と同様に行った。得られた合成樹脂成形物について、実施例３と同様に測定した結果を表２に示す。
[Comparative Example 2]
The same operation as in Example 3 was performed except that the power density at the time of forming the initial layer in Example 3 was changed to 1.0 W / cm 2 . About the obtained synthetic resin molding, the result measured similarly to Example 3 is shown in Table 2.
［比較例３］
実施例３における初期層成膜時の電力密度を２．２Ｗ／ｃｍ２に変えた以外は実施例３と同様に行った。得られた合成樹脂成形物について、実施例３と同様に測定した結果を表２に示す。
[Comparative Example 3]
The same operation as in Example 3 was performed except that the power density at the time of forming the initial layer in Example 3 was changed to 2.2 W / cm 2 . About the obtained synthetic resin molding, the result measured similarly to Example 3 is shown in Table 2.
表２に示されるように、実施例３、４はいずれも良好な親水性を有することが確認された。特に比較例２、３よりも低温親水性が向上した。
また、ＳｉとＳｎの組成比は、初期層のスパッタ電力密度を減ずるほど増加し、初期層の電力密度が１．０Ｗ／ｃｍ2未満の範囲でＳｉ／Ｓｎ組成比の改善効果が顕著であった。
As shown in Table 2, it was confirmed that Examples 3 and 4 all have good hydrophilicity. In particular, the low temperature hydrophilicity was improved as compared with Comparative Examples 2 and 3.
In addition, the composition ratio of Si and Sn increases as the sputtering power density of the initial layer is reduced, and the effect of improving the Si / Sn composition ratio is significant when the power density of the initial layer is less than 1.0 W / cm 2. It was.
Claims (6)
前記第１の金属酸化物膜上に、プラズマを用いた乾式法により、１．０Ｗ／ｃｍ２以上の電力密度で第２の金属酸化物膜を形成する第２の工程を含むことを特徴とする合成樹脂成形物の製造方法。 A first metal oxide film having a power density of less than 1.0 W / cm 2 is formed on the surface of a substrate having a surface mainly composed of a fluorine-containing synthetic resin by a dry method using plasma. And a second step of forming a second metal oxide film on the first metal oxide film with a power density of 1.0 W / cm 2 or more by a dry method using plasma. A method for producing a synthetic resin molded product.
The synthetic resin molding according to any one of claims 1 to 5, wherein the thickness of the first metal oxide film is 0.3 nm or more and the thickness of the second metal oxide film is 100 nm or less. Manufacturing method.
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| WO1996023910A1 (en) * | 1995-02-01 | 1996-08-08 | Asahi Glass Company Ltd. | Synthetic resin moldings and process for producing the same |
| JPH1044300A (en) * | 1996-07-31 | 1998-02-17 | Asahi Glass Co Ltd | Synthetic resin molding |
| JP2001205729A (en) * | 2000-01-28 | 2001-07-31 | Asahi Glass Co Ltd | Laminate and manufacturing method therefor |
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| WO1996023910A1 (en) * | 1995-02-01 | 1996-08-08 | Asahi Glass Company Ltd. | Synthetic resin moldings and process for producing the same |
| JPH1044300A (en) * | 1996-07-31 | 1998-02-17 | Asahi Glass Co Ltd | Synthetic resin molding |
| JP2001205729A (en) * | 2000-01-28 | 2001-07-31 | Asahi Glass Co Ltd | Laminate and manufacturing method therefor |
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