JPH10151421A - Stainproofing agent and stainproofing method - Google Patents
Stainproofing agent and stainproofing methodInfo
- Publication number
- JPH10151421A JPH10151421A JP31457496A JP31457496A JPH10151421A JP H10151421 A JPH10151421 A JP H10151421A JP 31457496 A JP31457496 A JP 31457496A JP 31457496 A JP31457496 A JP 31457496A JP H10151421 A JPH10151421 A JP H10151421A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- water
- antifouling
- agent
- ethanol
- 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
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Cleaning By Liquid Or Steam (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、家庭において簡易
に食器等を撥水・防汚処理できる防汚処理剤および防汚
処理方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antifouling agent and an antifouling method for easily repelling and repelling tableware at home.
【０００２】[0002]
【従来の技術】従来、物質に対して撥水・防汚処理する
方法として、フルオロカーボン系のシランカップリング
剤の溶液に基材を浸漬した後取り出し、加熱処理を行っ
て基材とシランカップリング剤との結合を促進させる方
法が知られている（例えば井手文雄著、「界面制御と複
合材料の設計」）。この方法では、反応を促進させるた
めに、２００℃に加熱したり（例えば好野則夫、材料技
術、１３巻、ｐ５５、１９９５年）、あるいは２００℃
以下の温度で処理するために塩酸を触媒として添加する
方法（例えば湯浅章、セラミックス、２９巻、ｐ５３
３、１９９４年）が提案されている。2. Description of the Related Art Conventionally, as a method of water repellent / antifouling treatment for a substance, a substrate is immersed in a solution of a fluorocarbon silane coupling agent, taken out, and then subjected to a heat treatment to perform silane coupling with the substrate. A method for promoting the binding with an agent is known (for example, Fumio Ide, "Interface Control and Design of Composite Material"). In this method, in order to promote the reaction, heating to 200 ° C. (for example, Norio Yoshino, Materials Technology, Vol. 13, p. 55, 1995) or 200 ° C.
A method in which hydrochloric acid is added as a catalyst for treatment at the following temperature (for example, Akira Yuasa, Ceramics, Vol. 29, p53
3, 1994).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
ような従来の方法で撥水・防汚処理を行った場合、いく
つかの課題が存在する。However, when the water repellent / antifouling treatment is performed by the above-mentioned conventional method, there are some problems.
【０００４】まず第１に、撥水・防汚処理工程の１つと
して上記したように２００℃に加熱する工程が必要とな
るわけであるが、２００℃に加熱するといった工程は家
庭内では困難である。このような温度雰囲気を容易には
作り出せなく、仮につくれるような設備があったとして
も、家庭内で使用する場合には、火傷等の危険がともな
う。First, as described above, a step of heating to 200 ° C. is required as one of the water-repellent and antifouling treatment steps, but the step of heating to 200 ° C. is difficult in homes. It is. Even if there is equipment that cannot easily create such a temperature atmosphere and can be created, there is a danger of burns and the like when used at home.
【０００５】次に第２に、触媒として塩酸を含有する処
理液は、塩酸が劇薬であるため、食器等に使用するには
衛生上および安全上、人体にとっては好ましくないとい
う課題が存在する。Second, the treatment solution containing hydrochloric acid as a catalyst has a problem that it is not preferable for use on tableware and the like in terms of hygiene and safety and for the human body because hydrochloric acid is a powerful drug.
【０００６】そこで本発明は、家庭において、簡易的に
食器を撥水・防汚処理することの可能な、塩酸のような
劇薬を使用することなく、５０〜６０℃程度の低い温度
で処理できる防汚処理方法およびこれらの処理を施す防
汚処理剤を提供することを目的とする。Therefore, the present invention can be used at home at a temperature as low as about 50 to 60 ° C. without using a powerful agent such as hydrochloric acid, which can easily perform water-repellent and antifouling treatment on tableware. An object of the present invention is to provide an antifouling treatment method and an antifouling treatment agent for performing these treatments.
【０００７】[0007]
【課題を解決するための手段】従来、シランカップリン
グ剤のアルコキシシリル基をシラノール基に変えるため
には、上記の文献に記述されているように、塩酸のよう
な強酸が必要だと考えられていた。Conventionally, in order to convert an alkoxysilyl group of a silane coupling agent into a silanol group, a strong acid such as hydrochloric acid is considered to be necessary as described in the above literature. I was
【０００８】しかしながら、本発明者らはアルコキシシ
リル基をシラノール基に変える反応が酸による加水分解
反応なので、弱酸でも進むと考えて、各種の有機酸を検
討した。その結果、酒石酸のような食用有機酸でも加水
分解が進むことを見いだした。However, the present inventors have studied various organic acids on the assumption that the reaction for converting an alkoxysilyl group into a silanol group is a hydrolysis reaction with an acid. As a result, they found that hydrolysis progressed even for edible organic acids such as tartaric acid.
【０００９】そこで、本発明の防汚処理剤はフッ化アル
キルアルコキシシランと食用有機酸と水とエタノールと
を有する構成となっている。この構成により、用いてい
る酸が食用の酸であるため、防汚処理を食器などにも応
用することが可能となる。なおここで、防汚処理剤に用
いる食用酸としては、酒石酸、クエン酸、りんご酸、コ
ハク酸および乳酸のいずれかを含むとが望ましい。Therefore, the antifouling agent of the present invention has a structure comprising a fluoroalkylalkoxysilane, an edible organic acid, water and ethanol. With this configuration, since the acid used is an edible acid, the antifouling treatment can be applied to tableware and the like. The edible acid used in the antifouling agent preferably contains tartaric acid, citric acid, malic acid, succinic acid, or lactic acid.
【００１０】また、家庭で簡易的に撥水・防汚処理する
方法として、基材表面に、フッ化アルキルアルコキシシ
ランと食用有機酸と水とエタノールとを有する防汚処理
剤を塗布した後、４０℃以上の温度雰囲気に暴露する防
汚処理方法により容易に防汚処理することが可能とな
る。[0010] As a method for easily performing water-repellent and antifouling treatment at home, an antifouling treatment agent containing a fluoroalkylalkoxysilane, an edible organic acid, water and ethanol is applied to the surface of a substrate. Antifouling treatment can be easily performed by an antifouling treatment method of exposing to an atmosphere at a temperature of 40 ° C. or higher.
【００１１】[0011]
【発明の実施の形態】以下に本発明の実施の形態におけ
る防汚処理剤及び防汚処理方法について説明する。DESCRIPTION OF THE PREFERRED EMBODIMENTS An antifouling agent and an antifouling method according to an embodiment of the present invention will be described below.
【００１２】本発明の防汚処理剤は、フッ化アルキルア
ルコキシシランと食用有機酸と水とエタノールとを有す
る構成となっている。なお上記のフッ化アルキルアルコ
キシシランとしては、例えば、ＣＦ3（ＣＦ2）7ＣＨ2Ｃ
Ｈ2Ｓｉ（ＯＣＨ3）3、ＣＦ3（ＣＦ2）7ＣＨ2ＣＨ2Ｓｉ
（ＯＣ2Ｈ5）3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＯＣ
Ｈ3）3、ＣＦ3（ＣＦ2）5ＣＨ2ＣＨ2Ｓｉ（ＯＣ
2Ｈ5）3、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2Ｓｉ（ＯＣ
Ｈ3）3、ＣＦ3（ＣＦ2）3ＣＨ2ＣＨ2Ｓｉ（ＯＣ2Ｈ5）3
などが挙げることができる。[0012] The antifouling agent of the present invention has a structure comprising fluorinated alkylalkoxysilane, edible organic acid, water and ethanol. The above-mentioned fluorinated alkylalkoxysilane is, for example, CF 3 (CF 2 ) 7 CH 2 C
H 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 7 CH 2 CH 2 Si
(OC 2 H 5 ) 3 , CF 3 (CF 2 ) 5 CH 2 CH 2 Si (OC
H 3) 3, CF 3 ( CF 2) 5 CH 2 CH 2 Si (OC
2 H 5) 3, CF 3 (CF 2) 3 CH 2 CH 2 Si (OC
H 3 ) 3 , CF 3 (CF 2 ) 3 CH 2 CH 2 Si (OC 2 H 5 ) 3
And the like.
【００１３】また、食用有機酸としては、例えば酒石
酸、クエン酸、りんご酸、コハク酸および乳酸が例とし
て挙げられる。Examples of edible organic acids include, for example, tartaric acid, citric acid, malic acid, succinic acid and lactic acid.
【００１４】フッ化アルキルアルコキシシランの濃度
は、０．０１ｗｔ％〜３０ｗｔ％が望ましく、さらに好
ましくは０．１ｗｔ％〜１０ｗｔ％である。０．０１ｗ
ｔ％以下では、撥水・防汚処理剤としての効果が小さく
なり、一方、３０ｗｔ％以上では、防汚処理剤中のフッ
化アルキルアルコキシシランが重合して、白い沈澱がで
き防汚処理剤として使用できなくなる。[0014] The concentration of the fluorinated alkylalkoxysilane is preferably 0.01 wt% to 30 wt%, more preferably 0.1 wt% to 10 wt%. 0.01w
When the amount is less than t%, the effect as a water repellent / antifouling agent is reduced. On the other hand, when the amount is more than 30% by weight, the fluorinated alkylalkoxysilane in the antifouling agent is polymerized to form a white precipitate and the antifouling agent. Can no longer be used.
【００１５】食用有機酸の濃度は、フッ化アルキルアル
コキシシランに対してモル比で１．５倍〜５倍が望まし
い。１．５倍以下では、フッ化アルキルアルコキシシラ
ンの一部の分子が下記に示すようなシラノール化反応を
起こさないため、撥水・防汚効果が低下する。The concentration of the edible organic acid is preferably 1.5 to 5 times the molar ratio of the fluorinated alkylalkoxysilane. When the ratio is 1.5 times or less, some molecules of the fluorinated alkylalkoxysilane do not cause a silanolation reaction as described below, and thus the water repellent and antifouling effects are reduced.
【００１６】[0016]
【化１】 Embedded image
【００１７】また、５倍以上では、食器等に防汚処理剤
を塗布した場合、食用有機酸が白い沈澱となって析出
し、撥水・防汚性を低下させる。On the other hand, when the antifouling treatment agent is applied to tableware or the like at a factor of 5 or more, the edible organic acid precipitates as a white precipitate, which lowers water repellency and antifouling properties.
【００１８】水の量は、モル比で少なくともフッ化アル
キルアルコキシシランの３倍量が必要で、エタノールに
対して、容積比で０．２倍以下が望ましい。水の量が
０．２倍以上になると、フッ化アルキルアルコキシシラ
ンは水に溶けないため、水／エタノールの混合溶媒に溶
けずに、二層に分離してしまって防汚処理剤としての機
能を発揮しなくなるからである。The amount of water must be at least three times the molar amount of the fluorinated alkylalkoxysilane, and is preferably not more than 0.2 times the volume ratio of ethanol. When the amount of water becomes 0.2 times or more, the fluorinated alkylalkoxysilane does not dissolve in water, so it does not dissolve in the mixed solvent of water / ethanol and separates into two layers to function as an antifouling agent. This is because it is no longer possible.
【００１９】次に、本発明の防汚処理方法について説明
する。 本発明の防汚処理方法は、基材表面に、フッ化ア
ルキルアルコキシシランと有機酸と水とエタノールとを
有する防汚処理剤を塗布した後、４０℃〜８０℃の温度
雰囲気に少なくとも１０分間暴露する。Next, the antifouling treatment method of the present invention will be described.
I do. In the antifouling treatment method of the present invention, a fluoride
Alkyl alkoxysilane, organic acid, water and ethanol
After applying an antifouling agent having a temperature of 40 ° C. to 80 ° C.
Expose to atmosphere for at least 10 minutes.
【００２０】本発明の防汚処理方法で、撥水・防汚処理
できる基材は、ガラス、セラミックおよび金属である。
また塗布法としては、スプレーコーティング法、ロール
コーティング法、スピンコーティング法、ブラシコーテ
ィング法、ディッピング法などを例として挙げることが
できる。Substrates which can be subjected to the water-repellent / anti-fouling treatment by the anti-fouling treatment method of the present invention are glass, ceramic and metal.
Examples of the coating method include a spray coating method, a roll coating method, a spin coating method, a brush coating method, and a dipping method.
【００２１】本発明の防汚処理方法で、加熱処理する温
度は４０℃〜８０℃が望ましい。市販の食器乾燥器の吹
き出し熱風温度が７０℃程度であるので、この温度雰囲
気は家庭で容易に得られる。４０℃以下では、シラノー
ル化したフッ化アルキルアルコキシシランと基材との反
応が進ににくく、処理面がすぐれた撥水・防汚性を示さ
ないことがある。８０℃以上にあげても、処理品の撥水
・防汚特性は変わらないため、あげる必要がない。但
し、８０℃以上の温度で熱処理を行ってもよいことは言
うまでもない。In the antifouling treatment method of the present invention, the temperature for the heat treatment is preferably from 40 ° C. to 80 ° C. Since the temperature of hot air blown out from a commercially available tableware dryer is about 70 ° C., this temperature atmosphere can be easily obtained at home. At a temperature of 40 ° C. or lower, the reaction between the silanolated fluoroalkylalkoxysilane and the base material is difficult to proceed, and the treated surface may not exhibit excellent water-repellent and antifouling properties. Even if the temperature is raised to 80 ° C. or higher, there is no need to raise the water repellency and antifouling properties of the treated product because they do not change. However, it goes without saying that the heat treatment may be performed at a temperature of 80 ° C. or higher.
【００２２】４０℃〜８０℃の温度雰囲気に暴露する時
間は、少なくとも１０分は必要であるが、１０分以上で
は、処理品の撥水・防汚特性は一定となる。At least 10 minutes are required for exposure to an atmosphere at a temperature of 40 ° C. to 80 ° C., but if it is 10 minutes or more, the water repellency and antifouling properties of the treated product become constant.
【００２３】次に、本発明の防汚処理剤および防汚処理
方法の具体的な実施例について説明する。Next, specific examples of the antifouling agent and the antifouling method of the present invention will be described.
【００２４】（実施例１）５００ｍｌのビーカーにエタ
ノール２７０ｍｌ、純水３０ｍｌ、ヘプタデカフルオロ
デシルトリメトキシシラン３ｇ、Ｌ−（＋）−酒石酸
２．３９ｇを入れ、マグネットスターラーで１０分攪拌
する。このようにして、作製した防汚処理剤をＡ剤とす
る。(Example 1) 270 ml of ethanol, 30 ml of pure water, 3 g of heptadecafluorodecyltrimethoxysilane, and 2.39 g of L-(+)-tartaric acid are placed in a 500 ml beaker and stirred with a magnetic stirrer for 10 minutes. The antifouling agent thus prepared is referred to as agent A.
【００２５】（実施例２）実施例１においてヘプタデカ
フルオロデシルトリメトキシシラン３ｇをヘプタデカフ
ルオロデシルトリエトキシシシラン３ｇに変えて防汚処
理剤を同じように作製した。この防汚処理剤をＢ剤とす
る。Example 2 An antifouling agent was prepared in the same manner as in Example 1 except that 3 g of heptadecafluorodecyltrimethoxysilane was changed to 3 g of heptadecafluorodecyltriethoxysilane. This antifouling agent is referred to as agent B.
【００２６】（実施例３）実施例１においてＬ−（＋）
−酒石酸２．３９ｇをクエン酸３．３２ｇに変えて防汚
処理剤を同じように作製した。この防汚処理剤をＣ剤と
する。(Embodiment 3) In the embodiment 1, L-(+)
-An antifouling agent was prepared in the same manner by changing tartaric acid (2.39 g) to citric acid (3.32 g). This antifouling agent is referred to as agent C.
【００２７】（実施例４）実施例１においてＬ−（＋）
−酒石酸２．３９ｇをリンゴ酸２．１４ｇに変えて防汚
処理剤を同じように作製した。この防汚処理剤をＤ剤と
する。(Embodiment 4) In the first embodiment, L-(+)
-An antifouling agent was prepared in the same manner by changing 2.39 g of tartaric acid to 2.14 g of malic acid. This antifouling agent is referred to as agent D.
【００２８】（実施例５）実施例１においてＬ−（＋）
−酒石酸２．３９ｇをこはく酸１．８８ｇに変えて防汚
処理剤を同じように作製した。この防汚処理剤をＥ剤と
する。(Embodiment 5) In the first embodiment, L-(+)
-An antifouling agent was prepared in the same manner by changing 2.39 g of tartaric acid to 1.88 g of succinic acid. This antifouling agent is referred to as agent E.
【００２９】（実施例６）実施例１においてＬ−（＋）
−酒石酸２．３９ｇを乳酸１．４３ｇに変えて防汚処理
剤を同じように作製した。この防汚処理剤をＦ剤とす
る。(Embodiment 6) In the embodiment 1, L-(+)
-An antifouling agent was prepared in the same manner by changing tartaric acid (2.39 g) to lactic acid (1.43 g). This antifouling agent is referred to as agent F.
【００３０】（実施例７）セラミック製の茶碗、皿およ
びスライドガラスを各６枚用意し、上記の防汚処理剤Ａ
〜Ｆをスプレーコーティングした。つぎに、コーティン
グした試料を市販の食器乾燥器セットし、１０分間加熱
した。Example 7 Six ceramic bowls, dishes and slide glasses were prepared, and the above antifouling agent A was prepared.
~ F was spray coated. Next, the coated sample was set in a commercially available dish dryer and heated for 10 minutes.
【００３１】加熱終了後、試料を取り出し、茶碗には炊
きたてのご飯粒を、皿には半熟卵の黄身を付着させて一
昼夜放置し、未処理の茶碗および皿と汚れの落ちる程度
を比較した。また、スライドガラスの水に対する接触角
を自動接触角計で測定した。After the heating was completed, the sample was taken out, freshly cooked rice grains were adhered to the bowl, and the yolk of the soft-boiled egg was adhered to the dish, and allowed to stand for 24 hours. The degree of dirt removal was compared with that of the untreated bowl and dish. Further, the contact angle of the slide glass with water was measured by an automatic contact angle meter.
【００３２】その結果を下記の表にまとめた。The results are summarized in the following table.
【００３３】[0033]
【表１】 [Table 1]
【００３４】上記の表より明らかなとおり、本発明の防
汚処理剤で処理した茶碗、皿は食物汚れがこびりつか
ず、またスライドガラスの水に対する接触角は１１０度
以上と高く、優れた撥水・防汚性を示すことがわかる。As is clear from the above table, the bowls and dishes treated with the antifouling agent of the present invention do not stick to food stains, and the contact angle of the slide glass to water is as high as 110 ° or more, and the water repellency is excellent. -It shows that it shows antifouling property.
【００３５】[0035]
【発明の効果】以上の通り本発明の防汚処理剤で処理す
ることにより、食器等に対しても優れた撥水・防汚性を
付与できる。本発明の防汚処理法は簡易であるため、家
庭においても容易にできるとともに、人体に影響のない
食用酸を用いているため、容易に食器などに用いること
ができる。As described above, by treating with the antifouling agent of the present invention, excellent water repellency and antifouling properties can be imparted to dishes and the like. Since the antifouling treatment method of the present invention is simple, it can be easily used at home, and because it uses edible acid that does not affect the human body, it can be easily used for tableware and the like.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 森 國人 大阪府門真市大字門真1006番地 松下電器 産業株式会社内 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kunito Mori 1006 Kadoma Kadoma, Osaka Prefecture Matsushita Electric Industrial Co., Ltd.
Claims (3)
機酸、水及びエタノールを有する防汚処理剤。An antifouling agent comprising a fluorinated alkylalkoxysilane, an edible organic acid, water and ethanol.
酸、コハク酸および乳酸のいずれかを含むことを特徴と
する請求項１記載の防汚処理剤。2. The antifouling agent according to claim 1, wherein the edible organic acid contains tartaric acid, citric acid, malic acid, succinic acid or lactic acid.
ランと有機酸と水とエタノールとを有する防汚処理剤を
塗布した後、４０℃以上の温度雰囲気に暴露することを
特徴とする防汚処理方法。3. An antifouling method comprising applying an antifouling treatment agent having a fluoroalkylalkoxysilane, an organic acid, water and ethanol to a surface of a substrate, and exposing it to an atmosphere at a temperature of 40 ° C. or higher. Processing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31457496A JP3787928B2 (en) | 1996-11-26 | 1996-11-26 | Antifouling treatment agent and antifouling treatment method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31457496A JP3787928B2 (en) | 1996-11-26 | 1996-11-26 | Antifouling treatment agent and antifouling treatment method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10151421A true JPH10151421A (en) | 1998-06-09 |
| JP3787928B2 JP3787928B2 (en) | 2006-06-21 |
Family
ID=18054933
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31457496A Expired - Fee Related JP3787928B2 (en) | 1996-11-26 | 1996-11-26 | Antifouling treatment agent and antifouling treatment method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3787928B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6395331B1 (en) * | 1997-10-28 | 2002-05-28 | Yazaki Corporation | Transparent substrate bearing an anti-stain, hydrophobic coating, and process for making it |
| JP2008138109A (en) * | 2006-12-04 | 2008-06-19 | Kazufumi Ogawa | Water-repelling, oil-repelling and stainproofing liquid and method for producing the same, and water-repelling, oil-repelling and stainproofing method using the same |
| KR20110074462A (en) | 2009-12-24 | 2011-06-30 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Surface treatment method for solid material |
-
1996
- 1996-11-26 JP JP31457496A patent/JP3787928B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6395331B1 (en) * | 1997-10-28 | 2002-05-28 | Yazaki Corporation | Transparent substrate bearing an anti-stain, hydrophobic coating, and process for making it |
| JP2008138109A (en) * | 2006-12-04 | 2008-06-19 | Kazufumi Ogawa | Water-repelling, oil-repelling and stainproofing liquid and method for producing the same, and water-repelling, oil-repelling and stainproofing method using the same |
| KR20110074462A (en) | 2009-12-24 | 2011-06-30 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Surface treatment method for solid material |
| EP2341108A1 (en) | 2009-12-24 | 2011-07-06 | Shin-Etsu Chemical Co., Ltd. | Surface treatment method for solid material |
| US8541631B2 (en) | 2009-12-24 | 2013-09-24 | Shin-Etsu Chemical Co., Ltd. | Surface treatment method for solid material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3787928B2 (en) | 2006-06-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5587209A (en) | Fluorocarbon-based polymer lamination coating film and method of manufacturing the same | |
| JP2004130785A (en) | Easily cleanable apparatus which can be easily cleaned and provided with heat resistant surface coating | |
| TW383335B (en) | A method for manufacturing a chemically adsorbed film and a chemical adsorbent solution for the method | |
| KR950011183B1 (en) | Fluorocarbon-based coating film and method of manufacturing the same | |
| KR950004153B1 (en) | Chemically adsorbed monomolecular lamination film and method of manufacturing the same | |
| JP2670724B2 (en) | Compositions and treatment methods for imparting non-stick and water repellency to articles | |
| JP2000239283A (en) | Fluoro-organic functional silane and/or siloxane-bearing composition, its production, its use and surface-modified supporter therewith | |
| JP2981040B2 (en) | Chemisorbed monomolecular cumulative film and method for producing the same | |
| JP2003145042A (en) | Production method of coating film | |
| US6509101B2 (en) | Silane coating for cooking utensils | |
| JPH10151421A (en) | Stainproofing agent and stainproofing method | |
| JPH11513359A (en) | A system that imparts tack-free and non-wetting properties to the surface | |
| CN105592702B (en) | Antibiosis additive, antibacterial processing method and sanitary ware part | |
| JPH10292057A (en) | Chemisorbent film, its production and chemisorbent solution used therefor | |
| JPH05161844A (en) | Preparation of chemisorption film | |
| JP2981043B2 (en) | Antifouling adsorption film and method for producing the same | |
| JPH0531441A (en) | Fluorocarbon coating film and its production | |
| JPH04240171A (en) | Stainproof ceramic product and production thereof | |
| JP2018075800A (en) | Hydrophilic article and manufacturing method therefor | |
| JP2528228B2 (en) | Fluorine-based resin laminated film and method for producing the same | |
| JPH04256710A (en) | Cooking utensil and its manufacture | |
| FR2768947A1 (en) | Treatment of surface of substrate | |
| JP2891103B2 (en) | Chemisorption membrane glass, method for producing the same, and cooker having chemisorption membrane glass | |
| JPH04244518A (en) | Heating cooking device | |
| JPH0616455A (en) | Water-repellent oxide film and its formation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Effective date: 20050401 Free format text: JAPANESE INTERMEDIATE CODE: A971007 |
|
| RD01 | Notification of change of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7421 Effective date: 20050623 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20051108 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20051214 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20060307 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20060320 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100407 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 5 Free format text: PAYMENT UNTIL: 20110407 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120407 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130407 Year of fee payment: 7 |
|
| LAPS | Cancellation because of no payment of annual fees |