JP2004026558A - Glass member having fluorine coating film and its manufacturing process - Google Patents
Glass member having fluorine coating film and its manufacturing process Download PDFInfo
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- JP2004026558A JP2004026558A JP2002184542A JP2002184542A JP2004026558A JP 2004026558 A JP2004026558 A JP 2004026558A JP 2002184542 A JP2002184542 A JP 2002184542A JP 2002184542 A JP2002184542 A JP 2002184542A JP 2004026558 A JP2004026558 A JP 2004026558A
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- 239000011521 glass Substances 0.000 title claims abstract description 85
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 40
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000011737 fluorine Substances 0.000 title claims abstract description 38
- 239000011248 coating agent Substances 0.000 title claims abstract description 15
- 238000000576 coating method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 150000004819 silanols Chemical class 0.000 claims abstract description 23
- 229910000077 silane Inorganic materials 0.000 claims abstract description 21
- 238000010411 cooking Methods 0.000 claims abstract description 16
- -1 silane compound Chemical class 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000006121 base glass Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003610 charcoal Substances 0.000 claims description 5
- 238000003980 solgel method Methods 0.000 claims description 5
- 239000005387 chalcogenide glass Substances 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 239000006089 photosensitive glass Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- 238000007766 curtain coating Methods 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- 239000005383 fluoride glass Substances 0.000 claims description 3
- 239000005300 metallic glass Substances 0.000 claims description 3
- 239000013307 optical fiber Substances 0.000 claims description 3
- 239000000075 oxide glass Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 125000005372 silanol group Chemical group 0.000 abstract description 3
- 229910008051 Si-OH Inorganic materials 0.000 abstract description 2
- 229910006358 Si—OH Inorganic materials 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000012611 container material Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000005315 stained glass Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Landscapes
- Electric Ovens (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、調理器具等に使用されるフッ素皮膜を有するガラス部材及びその製造方法に関する。
【０００２】
【従来の技術】
近年、電磁調理器や調理用コンロ等で用いられているガラス部品について、耐衝撃性向上のために結晶化ガラスが用いられている。結晶化ガラスはキズがつきにくく、見た目にも美しいが、防汚性・焦付き防止性に問題がある。特に、電磁調理器や調理用コンロ等については、主にふきこぼれなどに由来する焦付き等が発生して、実用上の大きな問題となっている。
【０００３】
このため、フッ素樹脂コーティングなどにより撥水性・防汚性を付与する場合もあるが、塗膜の密着性が弱いため、耐摩耗性が少なく耐久性を持たせることは困難である。
【０００４】
【発明が解決しようとする課題】
本発明の主な目的は、撥水性・防汚性を付与し、電磁調理器、調理用コンロ等、各種調理器具等の使用に適したフッ素皮膜を有するガラス部材を提供することである。さらに、簡便な手法により低コストで製造でき、しかも複雑な形状部分にも容易に適用できるフッ素皮膜を有するガラス部材の製造方法を提供することにある。
【０００５】
【課題を解決するための手段】
本発明者は、上記のような従来技術の問題点に鑑みて鋭意研究を重ねた結果、ガラス基体上にシラン系化合物を用いてフッ素皮膜を形成する場合には、従来技術の問題点を大幅に低減あるいは解消することができ、上記目標を達成できることを見いだし、これに基づき本発明を完成するに至った。
【０００６】
即ち、本発明は、以下のガラス部材及びその製造方法を提供するものである。
【０００７】
項１． 基材ガラス表面に、シラン系化合物を含む溶液を用いて形成された皮膜を有するガラス部材。
【０００８】
項２． 前記皮膜が、シラン系化合物を含む溶液の塗布により形成された皮膜である項１に記載のガラス部材。
【０００９】
項３． 前記皮膜が、シラン系化合物を含む溶液を塗布した後、加熱処理により形成された皮膜である項１に記載のガラス部材。
【００１０】
項４． 前記皮膜が、シラン系化合物を含む溶液を用いてゾル−ゲル法により形成された皮膜である項１に記載のガラス部材。
【００１１】
項５． 前記シラン系化合物が含フッ素シラノール誘導体である項１〜４のいずれか１項に記載のガラス部材。
【００１２】
項６． 前記含フッ素シラノール誘導体が、一般式（Ｉ）：
ＲｆＳｉ（ＯＲ）３ （Ｉ）
（式中、Ｒｆはポリフルオロアルキル基、ＲはＨ又はアルキル基を表す）
で示される化合物である項５に記載のガラス部材。
【００１３】
項７． 前記含フッ素シラノール誘導体が、一般式（ＩＩ）：
（ＣｎＦ２ｎ＋１）（ＣＨ２）ｍＳｉ（ＯＲ１）３ （ＩＩ）
（式中、ｎは１〜２０の整数、ｍは１〜２０の整数、Ｒ１はＨ又は低級アルキル基を表す）
で示される化合物である項５に記載のガラス部材。
【００１４】
項８． 基材ガラスが、酸化物ガラス、フッ化物ガラス、カルコゲン化物ガラス、ハロゲン化ガラス、金属ガラス、高分子ガラス、ガラスカーボン、アモルファスカーボン、アモルファスシリコン、シリカゲル、感光ガラス、結晶化ガラス、電子伝導ガラス、フォトクロミックガラス、超イオンガラス、光ファイバー及び光ディスクメモリーからなる群から選ばれる少なくとも１種である項１〜７のいずれか１項に記載のガラス部材。
【００１５】
項９． 基材ガラスが、Ｌｉ、Ａｌ、Ｓｉからなる群から選ばれる少なくとも１種の金属を含むガラスである項１〜８のいずれか１項に記載のガラス部材。
【００１６】
項１０． ガラス部材が、電子レンジ、調理用コンロ、電磁調理器、及びストーブからなる群から選ばれる少なくとも一種の器具の部材である項１〜９のいずれか１項に記載のガラス部材。
【００１７】
項１１． ガラス部材が、電子レンジの棚板、電子レンジのターンテーブル、調理用コンロのトッププレート、電磁調理器のトッププレート、ハイテク製品用耐熱基板、電子部品焼成用カッター、電気炉内壁材料、及びストーブ前面窓用の部材からなる群から選ばれる少なくとも一種の部材である項１〜９のいずれか１項に記載のガラス部材。
【００１８】
項１２． 項１〜１１のいずれか１項に記載のガラス部材を備えた調理用器具。
【００１９】
項１３． 基材ガラス表面に、含フッ素シラノール誘導体を含む溶液で皮膜を形成することを特徴とするフッ素皮膜を有するガラス部材の製造方法。
【００２０】
項１４． 基材ガラス表面に含フッ素シラノール誘導体を含む溶液で皮膜を形成した後、該皮膜を加熱処理することを特徴とする項１３に記載の方法。
【００２１】
項１５． 前記皮膜の形成方法が、塗布、カーテンコート、ゾル−ゲル法、デッピング法、及びスプレー法からなる群から選ばれる１つである項１３又は１４に記載の方法。
【００２２】
項１６． 基材ガラス表面に、含フッ素シラノール誘導体を含む溶液で皮膜を形成した後、該皮膜を加熱処理することを特徴とするフッ素皮膜の形成方法。
【００２３】
【発明の実施の形態】
本発明のガラス部材は、基材となるガラス表面にシラン系化合物を用いて形成されるフッ素皮膜を有している。
【００２４】
本発明のガラス部材の基体となるガラスの種類は、特に制限されず、例えば、いわゆるガラス（酸化物ガラス）のほかに、フッ化物ガラス、カルコゲン化物ガラス、ハロゲン化ガラス、金属ガラス、高分子ガラス、ガラスカーボン、アモルファスカーボン、アモルファスシリコン、シリカゲル、感光ガラス、結晶化ガラス、電子伝導ガラス、フォトクロミックガラス、超イオン伝導ガラス、光ファイバー、光ディスクメモリー等の広義のガラス等が例示される。そのうち、結晶化ガラス、カルコゲン化物ガラス、感光ガラス等を好適に選択することができる。
【００２５】
フッ素皮膜は、基材ガラス表面にシラン系化合物を含む溶液を用いて形成される。
【００２６】
シラン系化合物とは、基材ガラス表面との高い親和性を有するケイ素原子を有する化合物をいう。例えば、分子内にシラノール基（Ｓｉ−ＯＨ基）を有するシラノール誘導体等が挙げられる。特に、撥水性、防汚性、耐焦げ付き性等の効果を奏するフッ素を含むシラノール誘導体が挙げられる。フッ素を含むシラノール誘導体とは、１分子内にフッ素を含む有機基とシラノール基（又はその誘導体）とを有する化合物をいう。
【００２７】
上記含フッ素シラノール誘導体の具体例としては、一般式（Ｉ）：
ＲｆＳｉ（ＯＲ）３ （Ｉ）
（式中、Ｒｆはポリフルオロアルキル基、ＲはＨ又はアルキル基を表す）
で示される化合物が挙げられる。
【００２８】
Ｒｆで示されるポリフルオロアルキル基としては、直鎖又は分岐鎖の炭素数１〜４０のパーフルオロアルキル基、又は少なくとも１つの水素がフッ素原子で置換された直鎖又は分岐鎖の炭素数１〜４０のアルキル基が挙げられる。
【００２９】
直鎖又は分岐鎖の炭素数１〜４０のパーフルオロアルキル基としては、例えば、ＣＦ３、Ｃ２Ｆ５、（ｎ−又はｉｓｏ−）Ｃ３Ｆ７、（ｎ−又はｉｓｏ−、ｓｅｃ−又はｔｅｒｔ−）Ｃ４Ｆ９、ＣＦ３（ＣＦ２）ｊ（ｊは４〜３９の整数）、（ＣＦ３）２ＣＦ（ＣＦ２）ｋ（ｋは２〜３７の整数）等を挙げることができる。
【００３０】
少なくとも１つの水素がフッ素原子で置換された直鎖又は分岐鎖の炭素数１〜４０のアルキル基としては、例えば、ＣＨＦ２（ＣＦ２）ｐ（ＣＨ２）ｑ（ｐは０〜１９の整数、ｑは０〜２０の整数）、ＣＨ２Ｆ（ＣＦ２）ｒ（ＣＨ２）ｓ（ｒは０〜１９の整数、ｓは０〜２０の整数）、ＣＦ３（ＣＦ２）ｔ（ＣＨ２）ｕ（ｔは０〜１９の整数、ｕは１〜２０の整数）、（ＣＦ３）２ＣＦ（ＣＦ２）ｖ（ＣＨ２）ｗ（ｖは０〜１７の整数、ｗは１〜２０の整数）等が挙げられる。
【００３１】
Ｒで示されるアルキル基としては、直鎖又は分岐鎖の炭素数１〜１０のアルキル基が挙げられる。
【００３２】
含フッ素シラノール誘導体のうち、好ましくは、一般式（ＩＩ）：
（ＣｎＦ２ｎ＋１）（ＣＨ２）ｍＳｉ（ＯＲ１）３ （ＩＩ）
（式中、ｎは１〜２０の整数、ｍは１〜２０の整数、Ｒ１はＨ又は低級アルキル基を表す）
で示される化合物が挙げられる。
【００３３】
ＣｎＦ２ｎ＋１で示される基は、直鎖又は分岐鎖のいずれであってもよい。特に、直鎖のものが好ましい。好ましいｎとしては、１〜１０の整数であり、好ましいｍとしては、１〜１５の整数である。
【００３４】
Ｒ１で示される低級アルキル基としては、直鎖又は分岐鎖の炭素数１〜６のアルキル基が挙げられる。好ましくは、メチル、エチル、ｎ−プロピル、ｉ−プロピル等の直鎖又は分岐鎖の炭素数１〜３のアルキル基が例示される。より好ましくは、メチルである。
【００３５】
上記の一般式（Ｉ）及び（ＩＩ）で示される含フッ素シラノール誘導体は、いずれも公知の方法により製造することができる。また、例えば、ＣＦ３（ＣＨ２）３Ｓｉ（ＯＣＨ３）３、Ｃ８Ｆ１７（ＣＨ２）２Ｓｉ（ＯＣＨ３）３等のシラン系化合物は、それぞれ信越化学工業（株）社製のＬＳ１０９０、ＬＳ４８７５等として容易に入手することができる。
【００３６】
シラン系化合物を含む溶液の溶剤としては、アルコール系溶剤、水、酢酸等、又はこれらの混合溶媒が例示される。アルコール系溶剤としては、メタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール等が例示される。特に、シラン系化合物と基材ガラスとの反応速度を好適に制御できるエタノールが好ましい。
【００３７】
シラン系化合物を含む溶液の濃度は、溶液の安定性及びガラス表面への単分子皮膜の形成のしやすさの点から、通常０．５〜５ｖｏｌ％程度であればよく、好ましくは１〜３ｖｏｌ％程度であればよい。
【００３８】
塗膜形成は、塗布若しくはカーテンコートのほか、遠心塗布など公知の方法を用いて行えばよい。また、ゾル−ゲル法、ディッピング法、スプレー法等の公知の方法を用いて皮膜を形成してもよい。
【００３９】
フッ素皮膜の厚さについては、基材ガラスの材質及び形状、基材ガラスが使用される環境等により異なるが、通常、１０〜５０００ｎｍ程度、好ましくは２０〜５００ｎｍとすればよい。フッ素皮膜は、単分子層を形成し、シラン系化合物のフッ素を含む基が表面に露出することが必要である。そのため、膜厚が厚すぎると皮膜中の分子配向が乱れ、フッ素の表面露出率が低くなってしまう。また、膜厚が薄すぎると、表面を均一に覆うだけのシラン系化合物が供給されず、ムラが生じてしまう。
【００４０】
塗膜形成後の熱処理としては、公知の方法に従って処理を行えばよく、室温から３００℃程度、好ましくは、１００〜１５０℃程度とすればよい。熱処理時間は、通常２０分〜１時間程度であればよい。熱処理を行うことにより、塗膜がより強固に形成され耐摩耗性、撥水性、平滑性が向上する。
【００４１】
本発明のガラス部材は、例えば、調理用器具及び耐熱部品に用いるガラス部材の材料として、有効に用いることができる。
【００４２】
本発明のガラス部材の好適な用途としては、電子レンジ、調理用コンロ、電磁調理器、ストーブ等の器具の部材が挙げられる。該部材としては、例えば、電子レンジの棚板、電子レンジのターンテーブル、調理用コンロのトッププレート、電磁調理器のトッププレート、ハイテク製品用耐熱基板、電子部品焼成用カッター、電気炉内壁材料、ストーブ前面窓用の部材等が挙げられる。
【００４３】
また、本発明のガラス部材は、ステンドグラスなどの装飾部材、花瓶、コップ、ビーカーなどの容器部材、家や車の窓材料、鍋やホットプレート等のふた材料、食器棚、本棚などの戸部材等の各種ガラス部材として使用できる。
【００４４】
更に、本発明の部材は、光通信材料、感光材料、遮音材料、断熱材料、容器材料、装飾材料その他種々の部材としても使用でき、利用価値の極めて高い部材である。
【００４５】
【発明の効果】
本発明のシラン系化合物を含む塗料を用いて形成される皮膜は、食品の焦付きなどの有機物付着や汚れの付着が生じ難く、お手入れ性にも優れるものである。
【００４６】
また、本発明で採用するガラス表面の処理方法によれば、基材の色彩や質感を損なうことなく皮膜処理が可能であり、しかも簡便な方法でかつ低コストで製造することができる。しかも、複雑な形状部分のガラス部材であっても、簡単に製造することができる。
【００４７】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明する。
【００４８】
実施例１
下記のようにして、基材ガラスに対しフッ素皮膜の形成を行った。
（１）含フッ素シラノール誘導体を含む溶液の調製
含フッ素シラノール誘導体（ＣＦ３（ＣＨ２）３Ｓｉ（ＯＣＨ３）３：信越化学工業（株）社製 ＬＳ１０９０）を、エタノール中に室温で撹拌しながらゆっくり添加し、１５〜３０分撹拌して、下記の組成を有する含フッ素シラノール誘導体を含む溶液を調整した。
【００４９】
ＣＦ３（ＣＨ２）３Ｓｉ（ＯＣＨ３）３ １ｖｏｌ．％
エタノール ９９ｖｏｌ．％
（２）基材ガラス
下記の結晶化ガラス試験片を基材ガラスとして用いた。この試験片をエタノールにて払拭した後、（３）の方法で処理を行った。
【００５０】
材質：ＬｉｘＡｌｘＳｉ１−ｘＯｙ（ｘは１／３、ｙは２）
寸法：５０ｍｍ×５０ｍｍ×３ｍｍ
（３）皮膜の形成
まず、上記（１）の組成の含フッ素シラノール誘導体を含む溶液を用いて、室温２５℃、湿度６０％の条件下で、上記（２）の基材ガラス表面にハケを用いて膜厚が１００ｎｍになるまで塗布した。そののち、２４時間室温で放置し、熱風乾燥炉を用いて１５０℃で２０分熱処理を行うことにより、本発明のガラス部材を得た。
比較例１
実施例１と同じ結晶化ガラス試験片を基材ガラスとして用い、下記のように、フッ素樹脂コートを行った。
【００５１】
試験片をエタノールにて払拭した後、ＰＴＦＥ微粉末を静電塗装し、３５０℃で３０分焼付け処理を行うことにより、比較例のガラス部材を得た。
実験例１
（１）接触角試験
ＦＡＣＥ接触角測定装置（協和界面科学（株）社製、ＣＡ−Ａ型）を用い、液滴法により試料（皮膜面）に対する水の接触角を測定した。なお、撥水性の良否は、接触角の大小で評価できる。結果を表１に示す。
（２）耐摩耗性試験
先端に羊毛フェルトを取付けた摺動試験器（大平理化工業（株）社製）を用いて、加重１０００ｇで皮膜面に押しつけながら、往復１０ｃｍの距離を摺動させ、１０００往復後の重量変化及び接触角の変化を調べた。結果を表１に示す。
【００５２】
【表１】
表１に示すように、接触角試験結果において、摩耗試験後の本発明のガラス部材は比較例よりも接触角が大きく、極めて良好な撥水性の持続性を有することが確認された。
【００５４】
更に、表に示すように、耐摩耗性試験において、本発明例は比較例に比べ重量変化が小さく、耐摩耗性に優れることが確認された。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a glass member having a fluorine film used for cooking utensils and the like and a method for producing the same.
[0002]
[Prior art]
In recent years, crystallized glass has been used for glass parts used in electromagnetic cookers, cooking stoves, and the like to improve impact resistance. Crystallized glass is not easily scratched and looks beautiful, but has problems in antifouling property and anti-stick property. Particularly, electromagnetic cookers, cooking stoves, and the like have a serious problem in practical use, mainly due to burning such as spills.
[0003]
For this reason, water repellency and antifouling properties may be imparted by a fluororesin coating or the like, but it is difficult to impart durability due to low abrasion resistance due to weak adhesion of the coating film.
[0004]
[Problems to be solved by the invention]
A main object of the present invention is to provide a glass member having a fluorine coating which imparts water repellency and antifouling property and is suitable for use in various cooking utensils such as an electromagnetic cooker and a cooking stove. It is still another object of the present invention to provide a method for manufacturing a glass member having a fluorine film, which can be manufactured at a low cost by a simple method and can be easily applied to a complicated shape portion.
[0005]
[Means for Solving the Problems]
The present inventor has conducted intensive studies in view of the problems of the prior art as described above, and as a result, when a fluorine film is formed on a glass substrate using a silane-based compound, the problems of the prior art are greatly reduced. It has been found that the above objective can be achieved, and the present invention has been completed based on this.
[0006]
That is, the present invention provides the following glass member and a method for manufacturing the same.
[0007]
Item 1. A glass member having a film formed on a surface of a base glass using a solution containing a silane compound.
[0008]
Item 2. Item 2. The glass member according to Item 1, wherein the film is a film formed by applying a solution containing a silane compound.
[0009]
Item 3. Item 2. The glass member according to Item 1, wherein the film is a film formed by applying a solution containing a silane-based compound and then performing a heat treatment.
[0010]
Item 4. Item 2. The glass member according to Item 1, wherein the film is a film formed by a sol-gel method using a solution containing a silane-based compound.
[0011]
Item 5. Item 5. The glass member according to any one of Items 1 to 4, wherein the silane compound is a fluorine-containing silanol derivative.
[0012]
Item 6. The fluorine-containing silanol derivative has a general formula (I):
RfSi (OR) 3 (I)
(Wherein, Rf represents a polyfluoroalkyl group, R represents H or an alkyl group)
Item 6. The glass member according to Item 5, which is a compound represented by the formula:
[0013]
Item 7. The fluorine-containing silanol derivative has a general formula (II):
(C n F 2n + 1) (CH 2) m Si (OR 1) 3 (II)
(In the formula, n is an integer of 1 to 20, m is an integer of 1 to 20, R 1 represents H or a lower alkyl group.)
Item 6. The glass member according to Item 5, which is a compound represented by the formula:
[0014]
Item 8. The base glass is oxide glass, fluoride glass, chalcogenide glass, halogenated glass, metallic glass, polymer glass, glass carbon, amorphous carbon, amorphous silicon, silica gel, photosensitive glass, crystallized glass, electron conductive glass, Item 8. The glass member according to any one of Items 1 to 7, which is at least one selected from the group consisting of photochromic glass, superionic glass, optical fiber, and optical disk memory.
[0015]
Item 9. Item 9. The glass member according to any one of Items 1 to 8, wherein the base glass is a glass containing at least one metal selected from the group consisting of Li, Al, and Si.
[0016]
Item 10. Item 10. The glass member according to any one of Items 1 to 9, wherein the glass member is a member of at least one utensil selected from the group consisting of a microwave oven, a cooking stove, an electromagnetic cooker, and a stove.
[0017]
Item 11. Glass member is microwave oven shelf, microwave oven turntable, cooking stove top plate, induction cooker top plate, heat-resistant substrate for high-tech products, electronic component firing cutter, electric furnace inner wall material, and stove front Item 10. The glass member according to any one of Items 1 to 9, which is at least one member selected from the group consisting of window members.
[0018]
Item 12. Item 12. A cooking appliance provided with the glass member according to any one of Items 1 to 11.
[0019]
Item 13. A method for producing a glass member having a fluorine film, comprising forming a film on a surface of a base glass with a solution containing a fluorine-containing silanol derivative.
[0020]
Item 14. Item 14. The method according to Item 13, wherein a film is formed on the surface of the base glass with a solution containing a fluorine-containing silanol derivative, and then the film is heated.
[0021]
Item 15. Item 15. The method according to item 13 or 14, wherein the method for forming the film is one selected from the group consisting of coating, curtain coating, a sol-gel method, a dipping method, and a spraying method.
[0022]
Item 16. A method for forming a fluorine film, comprising: forming a film on a surface of a base glass with a solution containing a fluorine-containing silanol derivative; and heating the film.
[0023]
BEST MODE FOR CARRYING OUT THE INVENTION
The glass member of the present invention has a fluorine film formed using a silane-based compound on the surface of glass as a base material.
[0024]
The type of glass used as the base of the glass member of the present invention is not particularly limited. For example, in addition to so-called glass (oxide glass), fluoride glass, chalcogenide glass, halogenated glass, metallic glass, and polymer glass Glass, amorphous carbon, amorphous silicon, silica gel, photosensitive glass, crystallized glass, electron conductive glass, photochromic glass, superionic conductive glass, optical fiber, optical disk memory, etc. in a broad sense. Among them, crystallized glass, chalcogenide glass, photosensitive glass and the like can be suitably selected.
[0025]
The fluorine film is formed on the surface of the base glass using a solution containing a silane compound.
[0026]
The silane compound refers to a compound having a silicon atom having a high affinity for the surface of the base glass. For example, a silanol derivative having a silanol group (Si-OH group) in the molecule may be used. In particular, a fluorine-containing silanol derivative having effects such as water repellency, antifouling property, and burning resistance is exemplified. The silanol derivative containing fluorine refers to a compound having an organic group containing fluorine and a silanol group (or a derivative thereof) in one molecule.
[0027]
Specific examples of the fluorine-containing silanol derivative include a compound represented by the general formula (I):
RfSi (OR) 3 (I)
(Wherein, Rf represents a polyfluoroalkyl group, R represents H or an alkyl group)
The compound shown by these is mentioned.
[0028]
As the polyfluoroalkyl group represented by Rf, a linear or branched perfluoroalkyl group having 1 to 40 carbon atoms, or a linear or branched chain having 1 to 40 carbon atoms substituted with a fluorine atom, having 1 to 40 carbon atoms. 40 alkyl groups.
[0029]
Examples of the linear or branched perfluoroalkyl group having 1 to 40 carbon atoms of, for example, CF 3, C 2 F 5 , (n- or iso-) C 3 F 7, ( n- or iso-, sec- or tert-) C 4 F 9, CF 3 (CF 2) j (j is an integer of 4~39), (CF 3) 2 CF (CF 2) k (k is the like of an integer), such as 2-37 Can be.
[0030]
Examples of the linear or branched alkyl group having 1 to 40 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom include, for example, CHF 2 (CF 2 ) p (CH 2 ) q (p is an integer of 0 to 19) , Q is an integer of 0 to 20), CH 2 F (CF 2 ) r (CH 2 ) s (r is an integer of 0 to 19, s is an integer of 0 to 20), CF 3 (CF 2 ) t (CH 2 ) u (t is an integer of 0 to 19, u is an integer of 1 to 20), (CF 3 ) 2 CF (CF 2 ) v (CH 2 ) w (v is an integer of 0 to 17, w is 1 to 20 integers) and the like.
[0031]
Examples of the alkyl group represented by R include a linear or branched alkyl group having 1 to 10 carbon atoms.
[0032]
Among the fluorine-containing silanol derivatives, preferably, the compound represented by the general formula (II):
(C n F 2n + 1) (CH 2) m Si (OR 1) 3 (II)
(In the formula, n is an integer of 1 to 20, m is an integer of 1 to 20, R 1 represents H or a lower alkyl group.)
The compound shown by these is mentioned.
[0033]
The group represented by C n F 2n + 1 may be linear or branched. In particular, a linear one is preferred. Preferred n is an integer of 1 to 10, and preferred m is an integer of 1 to 15.
[0034]
Examples of the lower alkyl group represented by R 1 include a linear or branched alkyl group having 1 to 6 carbon atoms. Preferably, a linear or branched alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl and i-propyl is exemplified. More preferably, it is methyl.
[0035]
Each of the fluorine-containing silanol derivatives represented by the above general formulas (I) and (II) can be produced by a known method. Further, for example, silane compounds such as CF 3 (CH 2 ) 3 Si (OCH 3 ) 3 and C 8 F 17 (CH 2 ) 2 Si (OCH 3 ) 3 are manufactured by Shin-Etsu Chemical Co., Ltd. It can be easily obtained as LS1090, LS4875, or the like.
[0036]
Examples of the solvent of the solution containing the silane compound include an alcohol solvent, water, acetic acid, and the like, or a mixed solvent thereof. Examples of the alcohol solvent include methanol, ethanol, n-propanol, i-propanol and the like. In particular, ethanol capable of suitably controlling the reaction rate between the silane compound and the base glass is preferable.
[0037]
The concentration of the solution containing the silane compound is usually about 0.5 to 5 vol%, preferably 1 to 3 vol%, from the viewpoint of the stability of the solution and the ease of forming a monomolecular film on the glass surface. %.
[0038]
The coating film may be formed by a known method such as centrifugal coating, in addition to coating or curtain coating. Moreover, you may form a film using well-known methods, such as a sol-gel method, a dipping method, and a spray method.
[0039]
The thickness of the fluorine film varies depending on the material and shape of the base glass, the environment in which the base glass is used, and the like, but is usually about 10 to 5000 nm, preferably 20 to 500 nm. The fluorine film needs to form a monomolecular layer, and the fluorine-containing group of the silane compound needs to be exposed on the surface. Therefore, if the film thickness is too large, the molecular orientation in the film is disturbed, and the surface exposure rate of fluorine is reduced. On the other hand, if the film thickness is too small, the silane compound enough to uniformly cover the surface is not supplied, resulting in unevenness.
[0040]
The heat treatment after forming the coating film may be performed according to a known method, and may be performed at a temperature from room temperature to about 300 ° C, preferably about 100 to 150 ° C. The heat treatment time may be generally about 20 minutes to 1 hour. The heat treatment improves the abrasion resistance, water repellency, and smoothness of the coating film formed more firmly.
[0041]
The glass member of the present invention can be effectively used, for example, as a material of a glass member used for cooking utensils and heat-resistant parts.
[0042]
Suitable uses of the glass member of the present invention include members of appliances such as microwave ovens, cooking stoves, electromagnetic cookers, and stoves. As the member, for example, a shelf plate of a microwave oven, a turntable of a microwave oven, a top plate of a cooking stove, a top plate of an electromagnetic cooker, a heat-resistant substrate for high-tech products, a cutter for firing electronic components, an electric furnace inner wall material, And a member for a stove front window.
[0043]
Further, the glass member of the present invention includes decorative members such as stained glass, container members such as vases, cups and beakers, window materials for homes and cars, lid materials such as pots and hot plates, cupboards and door members such as bookcases. It can be used as various glass members.
[0044]
Further, the member of the present invention can be used as an optical communication material, a photosensitive material, a sound insulation material, a heat insulating material, a container material, a decoration material and various other members, and is a member having extremely high utility value.
[0045]
【The invention's effect】
The film formed by using the coating material containing the silane compound of the present invention hardly causes adhesion of organic substances such as scorching of food and adhesion of dirt, and is excellent in careability.
[0046]
Further, according to the method for treating a glass surface employed in the present invention, it is possible to carry out a film treatment without impairing the color and texture of the substrate, and it is possible to produce the substrate in a simple manner and at low cost. Moreover, even a glass member having a complicated shape can be easily manufactured.
[0047]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples.
[0048]
Example 1
A fluorine film was formed on the base glass as described below.
(1) Preparation of Solution Containing Fluorine-Containing Silanol Derivative Fluorine-containing silanol derivative (CF 3 (CH 2 ) 3 Si (OCH 3 ) 3 : LS1090 manufactured by Shin-Etsu Chemical Co., Ltd.) is stirred in ethanol at room temperature. While stirring for 15 to 30 minutes to prepare a solution containing a fluorinated silanol derivative having the following composition.
[0049]
CF 3 (CH 2 ) 3 Si (OCH 3 ) 3 1 vol. %
Ethanol 99 vol. %
(2) Base glass The following crystallized glass test piece was used as the base glass. After wiping the test piece with ethanol, the test piece was treated by the method (3).
[0050]
Material: LixAlxSi1-xOy (x is 1/3, y is 2)
Dimensions: 50mm x 50mm x 3mm
(3) Formation of film First, using a solution containing the fluorine-containing silanol derivative having the composition of the above (1), at a room temperature of 25 ° C. and a humidity of 60%, a brush is applied to the surface of the base glass of the above (2). It was applied until the film thickness reached 100 nm. After that, the glass member of the present invention was obtained by leaving it to stand at room temperature for 24 hours and performing heat treatment at 150 ° C. for 20 minutes using a hot air drying oven.
Comparative Example 1
The same crystallized glass test piece as in Example 1 was used as a base glass, and a fluororesin coating was performed as described below.
[0051]
After wiping the test piece with ethanol, PTFE fine powder was electrostatically coated and baked at 350 ° C. for 30 minutes to obtain a glass member of a comparative example.
Experimental example 1
(1) Contact Angle Test Using a FACE contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., CA-A type), the contact angle of water to the sample (film surface) was measured by a droplet method. In addition, the quality of water repellency can be evaluated by the magnitude of the contact angle. Table 1 shows the results.
(2) Abrasion resistance test Using a sliding tester (manufactured by Ohira Rika Kogyo Co., Ltd.) with a wool felt attached to the tip, while pressing against the film surface with a load of 1000 g, slide a distance of 10 cm back and forth, Changes in weight and changes in contact angle after 1000 reciprocations were examined. Table 1 shows the results.
[0052]
[Table 1]
As shown in Table 1, in the contact angle test results, it was confirmed that the glass member of the present invention after the abrasion test had a larger contact angle than the comparative example and had extremely good durability of water repellency.
[0054]
Furthermore, as shown in the table, in the abrasion resistance test, it was confirmed that the present invention example had a smaller weight change than the comparative example and was excellent in abrasion resistance.
Claims (16)
ＲｆＳｉ（ＯＲ）３ （Ｉ）
（式中、Ｒｆはポリフルオロアルキル基、ＲはＨ又はアルキル基を表す）
で示される化合物である請求項５に記載のガラス部材。The fluorine-containing silanol derivative has a general formula (I):
RfSi (OR) 3 (I)
(Wherein, Rf represents a polyfluoroalkyl group, R represents H or an alkyl group)
The glass member according to claim 5, which is a compound represented by the formula:
（ＣｎＦ２ｎ＋１）（ＣＨ２）ｍＳｉ（ＯＲ１）３ （ＩＩ）
（式中、ｎは１〜２０の整数、ｍは１〜２０の整数、Ｒ１はＨ又は低級アルキル基を表す）
で示される化合物である請求項５に記載のガラス部材。The fluorine-containing silanol derivative has a general formula (II):
(C n F 2n + 1) (CH 2) m Si (OR 1) 3 (II)
(In the formula, n is an integer of 1 to 20, m is an integer of 1 to 20, R 1 represents H or a lower alkyl group.)
The glass member according to claim 5, which is a compound represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002184542A JP2004026558A (en) | 2002-06-25 | 2002-06-25 | Glass member having fluorine coating film and its manufacturing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002184542A JP2004026558A (en) | 2002-06-25 | 2002-06-25 | Glass member having fluorine coating film and its manufacturing process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004026558A true JP2004026558A (en) | 2004-01-29 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002184542A Pending JP2004026558A (en) | 2002-06-25 | 2002-06-25 | Glass member having fluorine coating film and its manufacturing process |
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| Country | Link |
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| JP (1) | JP2004026558A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008508173A (en) * | 2004-07-30 | 2008-03-21 | ユーロケラ ソシエテ オン ノーム コレクティフ | Plate made of glass material for fireplace inserts or stove-type equipment |
| ES2660430A1 (en) * | 2016-07-21 | 2018-03-22 | Bsh Electrodomésticos España, S.A. | Plate of cooking field and cooking field with said plate (Machine-translation by Google Translate, not legally binding) |
-
2002
- 2002-06-25 JP JP2002184542A patent/JP2004026558A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008508173A (en) * | 2004-07-30 | 2008-03-21 | ユーロケラ ソシエテ オン ノーム コレクティフ | Plate made of glass material for fireplace inserts or stove-type equipment |
| ES2660430A1 (en) * | 2016-07-21 | 2018-03-22 | Bsh Electrodomésticos España, S.A. | Plate of cooking field and cooking field with said plate (Machine-translation by Google Translate, not legally binding) |
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