JP5114355B2 - Water- and oil-repellent coated articles and their manufacture - Google Patents
Water- and oil-repellent coated articles and their manufacture Download PDFInfo
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- JP5114355B2 JP5114355B2 JP2008261484A JP2008261484A JP5114355B2 JP 5114355 B2 JP5114355 B2 JP 5114355B2 JP 2008261484 A JP2008261484 A JP 2008261484A JP 2008261484 A JP2008261484 A JP 2008261484A JP 5114355 B2 JP5114355 B2 JP 5114355B2
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- 239000005871 repellent Substances 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 75
- 239000008199 coating composition Substances 0.000 claims description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 27
- 239000011248 coating agent Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000010419 fine particle Substances 0.000 claims description 17
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 230000002940 repellent Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 230000001737 promoting effect Effects 0.000 claims description 8
- -1 perfluoroalkyl silanes Chemical class 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims 1
- 239000002352 surface water Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 description 59
- 239000011521 glass Substances 0.000 description 12
- 238000007654 immersion Methods 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 238000007598 dipping method Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PMQIWLWDLURJOE-UHFFFAOYSA-N triethoxy(1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F PMQIWLWDLURJOE-UHFFFAOYSA-N 0.000 description 2
- KKYDYRWEUFJLER-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)CCC(F)(F)F KKYDYRWEUFJLER-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 240000008415 Lactuca sativa Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 208000037998 chronic venous disease Diseases 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 235000012045 salad Nutrition 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Paints Or Removers (AREA)
Description
本発明は、表面に高い撥水性及び撥油性を持たせたコーティング物品、および該コーティング物品の製造方法に関する。 The present invention relates to a coated article having a surface having high water repellency and oil repellency, and a method for producing the coated article.
ガラス、プラスチックス、紙、繊維製品、金属などの固体表面に対して撥水性を付与することは多く行なわれているが、撥油性の付与はあまり行なわれていない。
しかし、これらの固体表面に、油汚れなどに対してより高い防汚効果を求める場合には、水のみでなく、油を代表とする低表面張力物質に対しても高い接触角と低い転落角とを有することが望まれる。つまり、撥水性と撥油性との両方を兼ね備えたコーティング膜の形成が求められ、さらに、高い撥水性・撥油性、すなわち超撥水性と超撥油性を兼ね備えたコーティング膜が望まれている。
Although water repellency is often imparted to solid surfaces such as glass, plastics, paper, textiles, and metals, oil repellency is not often imparted.
However, when a higher antifouling effect against oil stains is required on these solid surfaces, not only water but also low surface tension materials represented by oil have high contact angles and low sliding angles. It is desirable to have That is, it is required to form a coating film having both water repellency and oil repellency, and further, a coating film having high water repellency / oil repellency, that is, super water repellency and super oil repellency is desired.
特許文献１には、建築材料用のコーティング組成物で、撥水性と撥油性とを同時に付与しようとする組成物が記載されている。具体的には、加水分解性パーフルオロアルキルシラン、ポリオルガノシロキサン、及び加水分解反応を促進する触媒成分を含む組成物であるが、その撥水性接触角は１００〜１１０度程度、撥油性接触角が９０〜１００度程度にしか過ぎないので、さらに高い接触角が要求される。
また、特許文献２には、防汚性ガラスとして、無機顔料などで表面粗さＲｙが０．０５μｍ以上０．４μｍ以下である表面を形成し、その上にパーフルオロアルキルシランで膜形成させたものが記載されている。油焼付け汚れも拭き取り易いことが記載されてはいるが、これも水に対する接触角は、１００〜１１０度程度である。
さらに特許文献３では、油の接触角が１５０度を超える超撥油状態を作製するための方法として、表面粗さを６００ｎｍ以上に調整し、フルオロアルキルシランなどの表面エネルギーを低下させる材料で撥油層を形成する方法が開示されている。具体的には、ベーマイトのエマルジョンを準備し、ガラス表面にスピンコートし焼成するサイクルを１２回繰り返した後、パーフルオロアルキルシランをＣＶＤ処理する方法が開示されているが、この方法では、工程数も多く複雑である。
Patent Document 1 describes a coating composition for building materials which is intended to impart water repellency and oil repellency at the same time. Specifically, it is a composition containing a hydrolyzable perfluoroalkylsilane, a polyorganosiloxane, and a catalyst component that accelerates the hydrolysis reaction, and its water-repellent contact angle is about 100 to 110 degrees, and the oil-repellent contact angle. Is only about 90 to 100 degrees, so a higher contact angle is required.
In Patent Document 2, as antifouling glass, a surface having a surface roughness Ry of 0.05 μm or more and 0.4 μm or less is formed with an inorganic pigment or the like, and a film is formed on the surface with perfluoroalkylsilane. Things are listed. Although it is described that oil-baked stains can be easily wiped off, the contact angle with respect to water is about 100 to 110 degrees.
Furthermore, in Patent Document 3, as a method for producing a super oil-repellent state in which the contact angle of oil exceeds 150 degrees, the surface roughness is adjusted to 600 nm or more, and a material that reduces surface energy such as fluoroalkylsilane is used. A method of forming an oil layer is disclosed. Specifically, a method of preparing a boehmite emulsion, spin-coating the glass surface and firing it 12 times and then performing CVD treatment of perfluoroalkylsilane is disclosed. There are many complicated.
さらにまた、特許文献４記載の発明では、皮膜表面における二乗平均粗さ（ＲＭＳ）値を５〜６０ｎｍの範囲にすることにより、水に対する接触角が１４０度以上、ドデカンに対する接触角が１００度以上である撥水撥油性皮膜を得たというが、実際得られている皮膜は、最高で水に対する接触角が１４９度／１４８度（前進接触角／後退接触角）、ドデカンに対する接触角が１１７度／１０４度（前進接触角／後退接触角）というものであり、水に対する接触角が１５０度以上であって且つ油に対する接触角が１３０度以上という超撥水且つ高撥油性の皮膜は得られていない。しかも、特許文献４には、得られた皮膜の転落角は記載されておらず、本発明者らの追試によると、９０度にしても水滴は転落しなかった。
また、特許文献５には、撥水性および撥油性を有する物品であって、撥水性および撥油性を有する層は、下層が疎水性を有するポリマーからなる凹凸構造を有する撥水性層であり、上層がフッ素含有シランカップリング剤からなる撥油性層であるものが記載されている。この表面は、撥水性が水に対する接触角が１５０度以上、撥油性がサラダ油に対する接触角が１００度以上であるというが、下層の凹凸構造を有するポリマー層を形成するために電解酸化（還元）重合を行い、その上に撥油性層を設けるという複雑な工程を必要としている。
このような従来技術の中で、簡便な方法で、より高い撥水性と撥油性とを同時に有し、且つ転落角の低い表面を得ることが望まれている。
Furthermore, in the invention described in Patent Document 4, when the root mean square (RMS) value on the surface of the film is in the range of 5 to 60 nm, the contact angle with water is 140 degrees or more, and the contact angle with dodecane is 100 degrees or more. The water / oil-repellent coating was obtained, but the actually obtained coating had a maximum contact angle with water of 149 degrees / 148 degrees (advanced contact angle / retracted contact angle) and a contact angle with dodecane of 117 degrees. / 104 degrees (advancing contact angle / retreating contact angle), a super-water-repellent and highly oil-repellent film having a contact angle with water of 150 degrees or more and a contact angle with oil of 130 degrees or more is obtained. Not. Moreover, Patent Document 4 does not describe the falling angle of the obtained film, and according to the follow-up test by the present inventors, water drops did not fall even at 90 degrees.
Patent Document 5 discloses an article having water repellency and oil repellency, wherein the layer having water repellency and oil repellency is a water repellency layer having a concavo-convex structure made of a polymer having a hydrophobic lower layer, and an upper layer. Is an oil-repellent layer made of a fluorine-containing silane coupling agent. This surface is said to have a water repellency with a water contact angle of 150 ° or more, and an oil repellency with a salad oil contact angle of 100 ° or more. In order to form a polymer layer having an underlying concavo-convex structure, electrolytic oxidation (reduction) It requires a complicated process of polymerizing and providing an oil repellent layer thereon.
Among such conventional techniques, it is desired to obtain a surface having a higher water repellency and oil repellency at the same time and having a low falling angle by a simple method.
本発明の課題は、上記の従来技術の問題点を解決することであって、高い撥水性と高い撥油性を同時に有し且つ転落角の低い物品表面を、簡単な方法で得る手段を提供することにある。より具体的には、そのような撥水・撥油性を有するコーティング物品を提供すること、及びその製造方法を提供することにある。 An object of the present invention is to solve the above-mentioned problems of the prior art, and provides a means for obtaining an article surface having a high water repellency and a high oil repellency at the same time and having a low falling angle by a simple method. There is. More specifically, an object of the present invention is to provide a coated article having such water / oil repellency and a method for producing the same.
本発明者らは、超撥水性表面を得るためのコーティングに際して、ゾルゲル法によるコーティング組成物に疎水性シリカ微粒子を配合する方法を開発して特許出願した（特開２００６−２３２８７０号公報：特許第４０６０３３３号公報）。本発明者らは、該ゾルゲル法を高い撥水性・撥油性を同時に有し転落角の低いコーティング物品の製造のために応用することを考え、鋭意研究した。
その結果、本発明者らは、高い撥水性・撥油性を有し転落角の低いコーティング物品のためには、コーティング物品の表面粗さ（二乗平均粗さ（ＲＭＳ）値）が特定の値以上である必要があることを見出した。具体的には、本発明者らは、二乗平均粗さ（ＲＭＳ）が１００ｎｍ以上であれば、水に対する接触角が１５０度以上、油に対する接触角が１３０度以上の超撥水・高撥油性が得られ、さらに、二乗平均粗さ（ＲＭＳ）が１５０ｎｍ以上であれば、水に対する接触角も油に対する接触角も１４０度以上の超撥水・超撥油性が得られることを見出した。
また、本発明者らは、そのような、二乗平均粗さ（ＲＭＳ）値が特定値以上のコーティング物品をゾルゲル法で得るために、コーティング組成物中の触媒を塩基性物質にする、及び／またはコーティング組成物への浸漬・乾燥を例えば3回あるいは５回以上という多数回繰り返せば良いことを見出した。
さらにまた、意外なことに被コーティング物品とコーティング組成物の組成や調製法、コーティング方法を組み合せて調整することで、接触角が１５０度以上という高い撥水性および撥油性を有すると共に水滴および油滴に対する転落角も１０度以下という低いコーティング物品表面が得られることも見出した。
The present inventors have developed a method for blending hydrophobic silica fine particles into a coating composition by a sol-gel method for coating to obtain a super water-repellent surface (Japanese Patent Laid-Open No. 2006-232870: Patent No. 1). No. 40603333). The inventors of the present invention have intensively studied in consideration of applying the sol-gel method to the production of a coated article having high water repellency and oil repellency at the same time and having a low sliding angle.
As a result, the present inventors have found that a coated article having a high water repellency / oil repellency and a low rolling angle has a surface roughness (root mean square roughness (RMS) value) of a specific value or more. I found that it was necessary. Specifically, the present inventors have a super water repellency / high oil repellency having a contact angle with water of 150 degrees or more and a contact angle with oil of 130 degrees or more when the root mean square roughness (RMS) is 100 nm or more. Furthermore, it has been found that when the root mean square roughness (RMS) is 150 nm or more, the water contact angle and the oil contact angle are both 140 ° C. or more, and super water repellency / super oil repellency can be obtained.
In addition, the present inventors have made the catalyst in the coating composition a basic substance in order to obtain a coated article having a root mean square roughness (RMS) value of a specific value or more by a sol-gel method, and / or Alternatively, it has been found that immersion and drying in the coating composition may be repeated many times, for example, 3 times or 5 times or more.
Furthermore, surprisingly, by adjusting the composition, preparation method, and coating method of the article to be coated, the coating composition, and the coating method, it has high water repellency and oil repellency with a contact angle of 150 degrees or more, and water droplets and oil droplets. It has also been found that a coated article surface having a falling angle of 10 degrees or less can be obtained.
すなわち、本発明は、以下の発明に関する。
（１）アルコール、アルコキシシラン、パーフルオロアルキルシラン、シリカ微粒子、アルコキシシランの加水分解反応を促進する触媒、および水を含むコーティング組成物をコーティングして得られるコーティング物品であって、その物品表面における二乗平均粗さ（ＲＭＳ）値が１００ｎｍ以上であることを特徴とする撥水・撥油性コーティング物品。
（２）物品表面における二乗平均粗さ（ＲＭＳ）値が１５０ｎｍ以上である上記（１）に記載の撥水・撥油性コーティング物品。
（３）物品がガラス製品あるいは繊維製品である上記（１）または（２）に記載の撥水・撥油性コーティング物品。
（４）水に対する接触角が１５０度以上の表面を有する上記（１）〜（３）のいずれかに記載の撥水・撥油性コーティング物品。
（５）油に対する接触角が１３０度以上の表面を有する上記（４）に記載の撥水・撥油性コーティング物品。
（６）転落角が１０度以下の表面を有する上記（１）〜（５）のいずれかに記載の撥水・撥油性コーティング物品。
（７）水に対する接触角が１５０度以上、油に対する接触角が１５０度以上、転落角が１０度以下の表面を有する撥水・撥油性コーティング物品。
（８）アルコール、アルコキシシラン、パーフルオロアルキルシラン、シリカ微粒子、テトラアルコキシシランの加水分解反応を促進する触媒としての塩基、および水を含むコーティング組成物に被コーティング物品を浸漬した後、引き上げ、乾燥することを特徴とする上記（１）〜（７）のいずれかに記載の撥水・撥油性コーティング物品の製造方法。
（９）アルコール、アルコキシシラン、パーフルオロアルキルシラン、シリカ微粒子、アルコキシシランの加水分解反応を促進する触媒、および水を含むコーティング組成物に被コーティング物品を浸漬した後、引き上げ、乾燥する工程を複数回繰り返すことを特徴とする上記（１）〜（７）のいずれかに記載の撥水・撥油性コーティング物品の製造方法。
（１０）アルコール、アルコキシシラン、パーフルオロアルキルシラン、シリカ微粒子、テトラアルコキシシランの加水分解反応を促進する触媒としての塩基、および水を含むコーティング組成物に被コーティング物品を浸漬した後、引き上げ、乾燥する工程を３回以上繰り返すことを特徴とする上記（１）〜（７）のいずれかに記載の撥水・撥油性コーティング物品の製造方法。
That is, the present invention relates to the following inventions.
(1) A coated article obtained by coating a coating composition containing alcohol, alkoxysilane, perfluoroalkylsilane, silica fine particles, a catalyst for promoting hydrolysis reaction of alkoxysilane, and water, on the surface of the article A water / oil repellent coating article having a root mean square roughness (RMS) value of 100 nm or more.
(2) The water / oil repellent coated article according to the above (1), which has a root mean square (RMS) value of 150 nm or more on the article surface.
(3) The water / oil repellent coated article according to the above (1) or (2), wherein the article is a glass product or a fiber product.
(4) The water / oil repellent coated article according to any one of the above (1) to (3), which has a surface having a contact angle with water of 150 ° or more.
(5) The water / oil repellent coated article according to the above (4) having a surface having a contact angle to oil of 130 ° or more.
(6) The water / oil repellent coated article according to any one of the above (1) to (5), which has a surface having a falling angle of 10 degrees or less.
(7) A water / oil repellent coated article having a surface with a contact angle with water of 150 ° or more, a contact angle with oil of 150 ° or more, and a falling angle of 10 ° or less.
(8) The article to be coated is immersed in a coating composition containing alcohol, alkoxysilane, perfluoroalkylsilane, silica fine particles, a base as a catalyst for promoting the hydrolysis reaction of tetraalkoxysilane, and water, and then pulled up and dried. The method for producing a water- and oil-repellent coated article according to any one of (1) to (7) above.
(9) A plurality of steps in which an article to be coated is dipped in a coating composition containing alcohol, alkoxysilane, perfluoroalkylsilane, silica fine particles, a catalyst for promoting hydrolysis reaction of alkoxysilane, and water, and then pulled up and dried. The method for producing a water- and oil-repellent coated article according to any one of (1) to (7), wherein the method is repeated once.
(10) The article to be coated is immersed in a coating composition containing alcohol, alkoxysilane, perfluoroalkylsilane, silica fine particles, a base as a catalyst for promoting the hydrolysis reaction of tetraalkoxysilane, and water, and then pulled up and dried. The method for producing a water- and oil-repellent coated article according to any one of the above (1) to (7), wherein the step of performing is repeated 3 times or more.
本発明によれば、接触角が高く転落角の低い撥水・撥油性コーティング物品が簡便に得られた。
すなわち、本発明のコーティング物品の製造方法は、コーティング組成物に物品を浸漬、引き上げ、乾燥するという、特殊な装置を必要としない簡単な方法で、表面に所望の表面粗さ（二乗平均粗さ（ＲＭＳ）値）を形成でき、物品に撥水性と撥油性とを同時に付与できるという利点を有する。
また、乾燥を室温でも行なうことができるので、本発明は、熱に弱い物品に対しても適用することができる。
According to the present invention, a water- and oil-repellent coated article having a high contact angle and a low sliding angle was easily obtained.
That is, the method for producing a coated article according to the present invention is a simple method that does not require a special apparatus such as dipping, pulling up, and drying the article in the coating composition, and a desired surface roughness (root mean square roughness) on the surface. (RMS value) can be formed, and it has the advantage that water repellency and oil repellency can be simultaneously imparted to the article.
In addition, since the drying can be performed at room temperature, the present invention can be applied to an article that is vulnerable to heat.
以下に、本発明を具体的に説明するが、本発明はそれに限定されるものではない。
本発明のコーティング組成物は、固体物品の表面を撥水・撥油処理するのに用いられる。固体物品は、金属、セラミック、ガラス、プラスチックなどの硬い素材でも、紙、繊維などの柔らかい素材でもいずれでも適用できるが、ガラス製品、繊維製品に特に有用に適用できる。本発明のコーティングはフレキシビリティーが高く、紙、繊維などに適用しても柔軟性を保つことができる。
Hereinafter, the present invention will be specifically described, but the present invention is not limited thereto.
The coating composition of the present invention is used for water / oil repellent treatment of the surface of a solid article. The solid article can be applied to either a hard material such as metal, ceramic, glass, or plastic, or a soft material such as paper or fiber, but can be particularly usefully applied to glass products and fiber products. The coating of the present invention has high flexibility and can maintain flexibility even when applied to paper, fiber, and the like.
本発明のコーティング組成物に用いるアルコールとしては、メタノール、エタノール、プロピルアルコールなどが挙げられるが、安全性を考慮するとエタノールが好ましい。 Examples of the alcohol used in the coating composition of the present invention include methanol, ethanol, propyl alcohol and the like, and ethanol is preferable in consideration of safety.
本発明のコーティング組成物に用いるアルコキシシランは、一般式（ＲＯ）ｎＳｉＲ４−ｎ（ｎは、４以下の整数；Ｒはアルキル基）で表されるアルコキシ置換のシランであればよく、一般式（ＲＯ）ｎＳｉＲ４−ｎにおけるアルキル基（Ｒ）の炭素数は１〜８程度が好ましいが、１あるいは２がより好ましい。また、ｎは４または３が好ましく、テトラエトキシシラン、メチルトリエトキシシランがより好ましい。
コーティング組成物中のテトラアルコキシシラン濃度は、１〜２０重量％程度が好ましい。
The alkoxysilane used in the coating composition of the present invention may be an alkoxy-substituted silane represented by the general formula (RO) n SiR 4-n (n is an integer of 4 or less; R is an alkyl group). The number of carbon atoms of the alkyl group (R) in the formula (RO) n SiR 4-n is preferably about 1 to 8, but more preferably 1 or 2. Further, n is preferably 4 or 3, more preferably tetraethoxysilane or methyltriethoxysilane.
The tetraalkoxysilane concentration in the coating composition is preferably about 1 to 20% by weight.
本発明のコーティング組成物に用いるパーフルオロアルキルシランは、アルキルシランのアルキル基のいくつかがフッ化炭素基（パーフルオロ基）に置換されたものであり、例えば、ＣＦ３（ＣＨ２）２Ｓｉ（ＯＣＨ３）３、ＣＦ３（ＣＦ２）５（ＣＨ２）２Ｓｉ（ＯＣＨ３）３、ＣＦ３（ＣＦ２）７（ＣＨ２）２Ｓｉ（ＯＣＨ３）３、ＣＦ３（ＣＦ２）７（ＣＨ２）２ＳｉＣＨ３（ＯＣＨ３）２、ＣＦ３（ＣＦ２）３（ＣＨ２）２Ｓｉ（ＯＣＨ３）３、ＣＦ３（ＣＦ２）７（ＣＨ２）２ＳｉＣｌ３が挙げられるが、ＣＦ３（ＣＦ２）７（ＣＦ２）２Ｓｉ（ＯＣＨ３）３で表されるヘプタデカフルオロデシルトリメトキシシランが好ましい。コーティング組成物中のパーフルオロアルキルシラン濃度は、１０重量％以下が好ましい。 The perfluoroalkylsilane used in the coating composition of the present invention is one in which some of the alkyl groups of the alkylsilane are substituted with fluorocarbon groups (perfluoro groups). For example, CF 3 (CH 2 ) 2 Si ( OCH 3 ) 3 , CF 3 (CF 2 ) 5 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 7 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCH 3 (OCH 3 ) 2 , CF 3 (CF 2 ) 3 (CH 2 ) 2 Si (OCH 3 ) 3 , CF 3 (CF 2 ) 7 (CH 2 ) 2 SiCl 3 Heptadecafluorodecyltrimethoxysilane represented by CF 3 (CF 2 ) 7 (CF 2 ) 2 Si (OCH 3 ) 3 is preferable. The perfluoroalkylsilane concentration in the coating composition is preferably 10% by weight or less.
本発明のコーティング組成物で用いるシリカ微粒子としては、日本アエロジル株式会社製、アエロジル200、300、380、90G、OX50、R 972、972V、R972CF、R974、R812、R805、RX200、RX300、RY200などが挙げられる。
撥水性のみでなく、撥油性を奏させるために、シリカ微粒子の平均一次粒径は、２０〜４０ｎｍが好ましい。この一次粒径範囲であれば、コーティング物品表面に撥水性・撥油性に望ましい凹凸を付与することができる。
Examples of silica fine particles used in the coating composition of the present invention include Aerosil 200, 300, 380, 90G, OX50, R 972, 972V, R972CF, R974, R812, R805, RX200, RX300, RY200, manufactured by Nippon Aerosil Co., Ltd. Can be mentioned.
In order to achieve not only water repellency but also oil repellency, the average primary particle size of the silica fine particles is preferably 20 to 40 nm. If it is this primary particle size range, the unevenness | corrugation desirable for water repellency and oil repellency can be provided to the coated article surface.
コーティング組成物中のシリカ微粒子の濃度は、２重量％以上が好ましく、平均一次粒径１５ｎｍ以下については２〜５重量％が、１５ｎｍ以上については２〜１０重量％がより好ましい。２重量％未満の場合は、物品表面をシリカ微粒子が十分被覆しないので表面に凹凸が得られない。一方、１５ｎｍ以下については５重量％を、１５ｎｍ以上については１０重量％を超えると、シリカ微粒子による被覆にクラックが入る恐れがあるので好ましくない。 The concentration of the silica fine particles in the coating composition is preferably 2% by weight or more, more preferably 2 to 5% by weight for an average primary particle size of 15 nm or less, and more preferably 2 to 10% by weight for 15 nm or more. When the amount is less than 2% by weight, the surface of the article is not sufficiently covered with silica fine particles, so that unevenness cannot be obtained on the surface. On the other hand, if it exceeds 5% by weight for 15 nm or less and exceeds 10% by weight for 15 nm or more, there is a risk of cracks in the coating with silica fine particles, such being undesirable.
コーティング組成物の作製はいかなる方法によって行っても良いが、アルコール中にシリカ微粒子を加えて混合攪拌し、次にテトラアルコキシシランおよびパーフルオロアルキルシランを加えてさらに混合攪拌し、水およびテトラアルコキシシランの加水分解反応を促進させる触媒としての酸又は塩基を加えてｐＨを２〜３に調整して攪拌する工程を含む方法によって作製するのが好ましい。触媒として酸を用いるとき塩酸、塩基を用いるとき水酸化ナトリウムが好ましい。水は純水が好ましい。
好ましいコーティング組成物は、モル比で、アルコール：テトラアルコキシシラン：パーフルオロアルキルシラン：水が１００〜３００：１：０〜０．８：［テトラアルコキシシラン＋パーフルオロアルキルシラン］×４〜２０程度である。
The coating composition may be prepared by any method, but silica fine particles are added to alcohol and mixed and stirred, then tetraalkoxysilane and perfluoroalkylsilane are added and further mixed and stirred, and water and tetraalkoxysilane are mixed. It is preferable to prepare by a method including a step of adding acid or base as a catalyst for promoting the hydrolysis reaction and adjusting the pH to 2-3 and stirring. Hydrochloric acid is preferred when an acid is used as the catalyst, and sodium hydroxide is preferred when a base is used. The water is preferably pure water.
A preferable coating composition has a molar ratio of alcohol: tetraalkoxysilane: perfluoroalkylsilane: water of 100 to 300: 1: 0 to 0.8: [tetraalkoxysilane + perfluoroalkylsilane] × about 4 to 20 It is.
コーティング組成物の作製にあたっての撹拌は、アルコールとシリカ微粒子との混合を１０〜３０分程度、テトラアルコキシシランおよびパーフルオロアルキルシランを加えてさらに１０分程度、水と触媒を加えてから２．５〜３時間程度が好ましい。 Stirring in the preparation of the coating composition involves mixing the alcohol and silica fine particles for about 10 to 30 minutes, adding tetraalkoxysilane and perfluoroalkylsilane for about 10 minutes, adding water and a catalyst, and then adding 2.5 minutes. About 3 hours is preferable.
上記のようにして作製したコーティング組成物溶液に、被コーティング物品であるガラス基板、紙・布などの繊維物品を浸漬した後、物品を引き上げ、乾燥することによってコーティング物品が得られる。
浸漬速度は、０．２〜２０ｍｍ／ｓｅｃが好ましく、１０ｍｍ／ｓｅｃが最も好ましい。引き上げ速度は、０．２〜２０ｍｍ／ｓｅｃが好ましく、０．３ｍｍ／ｓｅｃが最も好ましい。引き上げ速度が遅いと、コーティングが付着しにくく、引き上げ速度が速いと均一に付着しない。
乾燥は室温〜１０５℃程度で行なう。加熱するほうが早く乾燥できるが、室温でも十分乾燥できる。
A coated article is obtained by immersing a fiber article such as a glass substrate or paper / cloth, which is the article to be coated, in the coating composition solution produced as described above, and then pulling the article up and drying it.
The immersion speed is preferably 0.2 to 20 mm / sec, and most preferably 10 mm / sec. The pulling speed is preferably 0.2 to 20 mm / sec, and most preferably 0.3 mm / sec. When the pulling speed is slow, the coating is difficult to adhere, and when the pulling speed is high, the coating does not adhere uniformly.
Drying is performed at room temperature to about 105 ° C. Heating can dry faster, but it can also be sufficiently dried at room temperature.
上記のコーティング物品の製造方法において、触媒である酸あるいは塩基の添加量によりｐＨを調整することによって、コーティング物品表面のＲＭＳ値を変化させることができることを本発明者らは見出した（実施例１参照）。
その結果、コーティング組成物のｐＨは、触媒として塩基を加えることによって、１１〜１３．５に調整するのが好ましく、ｐＨ１２程度が最適であることが分かった。
In the above-described method for producing a coated article, the present inventors have found that the RMS value on the surface of the coated article can be changed by adjusting the pH according to the amount of acid or base that is a catalyst (Example 1). reference).
As a result, it was found that the pH of the coating composition was preferably adjusted to 11 to 13.5 by adding a base as a catalyst, and a pH of about 12 was optimal.
また、上記の浸漬、引き上げ、乾燥の工程（以下、単に浸漬工程という）は、複数回繰り返すのが好ましい。本発明者らは、この浸漬工程を３回以上繰り返すことによって、より好ましいＲＭＳ値および撥水・撥油性が得られることを見出した（実施例２参照）。 Moreover, it is preferable to repeat the above-mentioned immersion, pulling-up, and drying steps (hereinafter simply referred to as an immersion step) a plurality of times. The present inventors have found that more preferable RMS value and water / oil repellency can be obtained by repeating this dipping step three times or more (see Example 2).
さらに、コーティング組成物の組成、コーティング方法を調整することによって、水・油に対する接触角が１５０度以上と高く、且つ、水滴・油滴に対する転落角も１０度以下という低い製品が得られることが分かった（実施例３〜５）。 Furthermore, by adjusting the composition of the coating composition and the coating method, it is possible to obtain a product having a high contact angle with respect to water / oil of 150 ° or more and a low drop angle of 10 ° or less with respect to water / oil. Okay (Examples 3-5).
コーティングの膜厚を可視光の波長である４８０ｎｍ以下にすることで、コーティングの透明性を確保できる。 By setting the film thickness of the coating to 480 nm or less which is the wavelength of visible light, the transparency of the coating can be ensured.
以下には、本発明の実施例を詳述するが、本発明はこれに限られるものではない。
実施例において、接触角および転落角は、接触角計（協和界面科学製: CA-DT）で測定した。測定は、接触角計に１０μｌの水または油を滴下して行なった。
また、ＲＭＳ値は、原子間力顕微鏡（ＡＦＭ；Ｄｉｇｉｔａｌ Ｉｎｓｔｒｕｍｅｎｔ社製）を用いて測定した。ＡＦＭ像から得た表面ピーク高Ｚを基に次の式により、ＲＭＳ値を算出した（「（株）東陽テクニカ ＮａｎｏＳｃｏｐｅIII Ｏｆｆ−ｌｉｎｅ機能」参照）。
ＲＭＳ ＝ √Σ（Ｚｉ−Ｚａｖｅ）２／Ｎ
Ｎ：データポイント数
Ｚｉ：各データポイントのＺの値
Ｚａｖｅ：全Ｚ値の平均
Examples of the present invention will be described in detail below, but the present invention is not limited thereto.
In the examples, the contact angle and the sliding angle were measured with a contact angle meter (manufactured by Kyowa Interface Science: CA-DT). The measurement was performed by dropping 10 μl of water or oil into a contact angle meter.
The RMS value was measured using an atomic force microscope (AFM; manufactured by Digital Instrument). Based on the surface peak height Z obtained from the AFM image, the RMS value was calculated by the following formula (see “Toyo Technica NanoScope III Off-line Function”).
RMS = √Σ (Zi-Zave) 2 / N
N: Number of data points Zi: Z value of each data point Zave: Average of all Z values
＜コーティング組成物のｐＨとＲＭＳ値・接触角との関係＞
１）コーティング組成物の作製
エタノール１６．４ｇ、シリカ微粒子３．０ｇ、テトラエトキシシラン０．４１ｇ、ヘプタデカフルオロデシルトリエトキシシラン０．２２ｇを混合し、酸およびアルカリを加えて、液のｐＨを制御した。酸は塩酸、アルカリは水酸化ナトリウム水溶液を用いた。以上の操作によりコーティング組成物を得た。
２）ガラス基板へのコーティング方法
このコーティング組成物を用い、ガラス基板に浸漬速度１０ｍｍ／ｓｅｃ、引き上げ速度０．３ｍｍ／ｓｅｃで浸漬し、１０分室温で乾燥する工程を５回繰り返し、最後に１０５℃で３０分乾燥して、ガラス物品とした。
<Relationship between pH of coating composition and RMS value / contact angle>
1) Preparation of coating composition Ethanol 16.4g, silica fine particles 3.0g, tetraethoxysilane 0.41g, heptadecafluorodecyltriethoxysilane 0.22g are mixed, acid and alkali are added, and the pH of the liquid is adjusted. Controlled. Hydrochloric acid was used as the acid and sodium hydroxide aqueous solution was used as the alkali. The coating composition was obtained by the above operation.
2) Coating method on glass substrate Using this coating composition, a step of immersing in a glass substrate at an immersion speed of 10 mm / sec and a pulling speed of 0.3 mm / sec and drying at room temperature for 10 minutes was repeated five times. The glass article was dried at 30 ° C. for 30 minutes.
結果を図1および図2に示した。図1において、横軸は、触媒として添加する酸あるいは塩基の添加量を、縦軸は、接触角およびＲＭＳである。図２には、同じデータを横軸をｐＨに換算して示した。油滴に対する接触角の測定には、オレイン酸を用いた。オレイン酸の表面張力は３２．７ｍＮ／ｍであり、撥油性を試験するために標準的に用いられるものである。
この図1および図２の結果から、水滴および油滴の接触角はＲＭＳと良い相関を有すること、ＲＭＳが１００ｎｍ以上であるとき、水滴の接触角は１５０度を超え、油滴の接触角も１３０度を超えていることが分かる。さらに、ＲＭＳが１５０ｎｍ以上であればさらに水滴および油滴の接触角は高くなることが分かる。
また、水滴および油滴に対する高い接触角を得るためには、塩基の添加により、ｐＨを上昇させることが有効で、ｐＨ１１〜１３．５で高い撥水・撥油性が得られ、さらにｐＨ１２程度で最高のＲＭＳが得られることが分かる。
The results are shown in FIG. 1 and FIG. In FIG. 1, the horizontal axis represents the amount of acid or base added as a catalyst, and the vertical axis represents the contact angle and RMS. FIG. 2 shows the same data with the horizontal axis converted to pH. Oleic acid was used to measure the contact angle with respect to the oil droplets. The surface tension of oleic acid is 32.7 mN / m, which is normally used for testing oil repellency.
From the results of FIG. 1 and FIG. 2, the contact angle of water droplets and oil droplets has a good correlation with RMS. When RMS is 100 nm or more, the contact angle of water droplets exceeds 150 degrees, and the contact angle of oil droplets is also It can be seen that it exceeds 130 degrees. Furthermore, it can be seen that when RMS is 150 nm or more, the contact angle of water droplets and oil droplets is further increased.
Moreover, in order to obtain a high contact angle with respect to water droplets and oil droplets, it is effective to increase the pH by adding a base, and high water and oil repellency can be obtained at pH 11 to 13.5. It can be seen that the best RMS is obtained.
＜浸漬回数とＲＭＳ値との関係＞
浸漬、引き上げ、乾燥という浸漬工程の繰り返し回数（浸漬回数）と得られるコーティング物品の接触角およびＲＭＳとの関係を調べた。
コーティング組成物は、実施例１と同様に作製した。ただし、水酸化ナトリウムを0.3140ｇ添加した。ガラス基板へのコーティング方法も浸漬回数以外は実施例１と同じである。
結果を図３に示した。
図３の結果から、浸漬回数が3回以上になると、接触角１５０度以上の撥水性、１４０度以上の撥油性、ＲＭＳが１００ｎｍを超え、5回以上になるとＲＭＳは１５０ｎｍを超えることが分かる。さらに浸漬回数を増やすことで接触角およびＲＭＳがさらに高くなることが分かる。
<Relationship between number of immersions and RMS value>
The relationship between the number of repetitions of the dipping process of dipping, pulling up, and drying (number of dippings) and the contact angle and RMS of the resulting coated article was examined.
The coating composition was prepared in the same manner as in Example 1. However, 0.3140 g of sodium hydroxide was added. The coating method on the glass substrate is the same as that of Example 1 except for the number of immersions.
The results are shown in FIG.
From the results shown in FIG. 3, it can be seen that when the number of immersions is 3 times or more, the water repellency with a contact angle of 150 degrees or more, the oil repellency with 140 degrees or more, and the RMS exceeds 100 nm, and when the number of immersions is 5 or more, the RMS exceeds 150 nm. . It can also be seen that the contact angle and RMS are further increased by increasing the number of immersions.
＜転落角＞
以下の実施例では、転落角の測定も示す。
エタノールを１３ｇ、テトラエトキシシランを０．３ｇ、ヘプタデカフルオロデシルトリエトキシシランを０．３g、粒径４０ｎｍのシリカ微粒子を１.０ｇ、水および加水分解のための触媒を１規定塩酸を０．０４ｇ加えて、コーティング組成物１を得た。
コーティング組成物１にスライドガラスを浸漬し、引上げ速度０．６ｍｍ／ｓで引上げた後、１０５℃で３０分乾燥させて超撥水高撥油コーティング表面１を得た。この表面１のＲＭＳは、２２８ｎｍであった。
<Tumble angle>
The following examples also show the measurement of the falling angle.
Ethanol (13 g), tetraethoxysilane (0.3 g), heptadecafluorodecyltriethoxysilane (0.3 g), silica fine particles having a particle size of 40 nm (1.0 g), water and a catalyst for hydrolysis (1N hydrochloric acid in 0.1 g). 04g was added and the coating composition 1 was obtained.
A slide glass was immersed in the coating composition 1, pulled up at a pulling rate of 0.6 mm / s, and then dried at 105 ° C. for 30 minutes to obtain a super water-repellent and highly oil-repellent coating surface 1. The RMS of this surface 1 was 228 nm.
綿９５／ナイロン５の布をコーティング組成物１に２回浸漬した。引上げ速度０．６ｍｍ／ｓで引上げた後、１０５℃で３０分乾燥させて超撥水高撥油コーティング表面２を得た。
表面の接触角および転落角は表２に示した。表面のＲＭＳは５６０ｎｍであった。
A cotton 95 / nylon 5 fabric was dipped in coating composition 1 twice. After pulling up at a pulling rate of 0.6 mm / s, it was dried at 105 ° C. for 30 minutes to obtain a super-water-repellent and highly oil-repellent coating surface 2.
The contact angle and sliding angle of the surface are shown in Table 2. The surface RMS was 560 nm.
綿９５／ナイロン５の布にコーティング組成物１をスプレーコーティングした。コーティング量は１平方センチメートル辺り０．０４ミリリットルにした。コーティングした後に、１０５℃で３０分乾燥させて超撥水超撥油コーティング表面３を得た。
表面の接触角および転落角は表２に示した。表２に示すとおり、この表面３は、水に対する接触角も油に対する接触角も１５０度以上であって、且つ、転落角が１０度以下という超撥水・超撥油性であった。なお、表面のＲＭＳは７６１ｎｍであった。この場合、被コーティング物品が布であるため、被コーティング物品自体が、ＲＭＳ２８８ｎｍという高いＲＭＳを有しており、それに本発明のコーティング処理を行なうことによって、水に対しても油に対しても転落角が１０度以下である極めて優れた撥水・撥油表面が得られることが分かった。
［比較例１］
Coating composition 1 was spray coated onto a cotton 95 / nylon 5 fabric. The coating amount was 0.04 milliliter per square centimeter. After coating, it was dried at 105 ° C. for 30 minutes to obtain a super-water-repellent super-oil-repellent coating surface 3.
The contact angle and sliding angle of the surface are shown in Table 2. As shown in Table 2, this surface 3 was super water- and oil-repellent such that the contact angle with water and the contact angle with oil were 150 degrees or more, and the falling angle was 10 degrees or less. The surface RMS was 761 nm. In this case, since the article to be coated is a cloth, the article to be coated itself has a high RMS of RMS 288 nm, and by performing the coating treatment of the present invention, it falls down against both water and oil. It was found that an extremely excellent water / oil repellent surface having an angle of 10 degrees or less can be obtained.
[Comparative Example 1]
布用撥水撥油剤「アサヒガードＡＧ−７１０５」（旭硝子株式会社製）３０ｇを水１Ｌに混合し、コーティング組成物２を得た。コーティング組成物２に綿９５／ナイロン５の布を浸漬し、余分な液を絞った後、１５０℃で乾燥させてコーティング表面４を得た。
表面の接触角および転落角を表２に示した。
30 g of water / oil repellent for fabric “Asahi Guard AG-7105” (manufactured by Asahi Glass Co., Ltd.) was mixed with 1 L of water to obtain a coating composition 2. A cloth of cotton 95 / nylon 5 was dipped in the coating composition 2 to squeeze excess liquid, and then dried at 150 ° C. to obtain a coating surface 4.
Table 2 shows the contact angle and sliding angle of the surface.
本発明によれば、接触角が高く転落角の低い撥水・撥油性コーティング物品が簡便に得られた。 According to the present invention, a water- and oil-repellent coated article having a high contact angle and a low sliding angle was easily obtained.
Claims (3)
A step of lifting and drying the article to be coated after immersing the article to be coated in a coating composition containing alcohol, alkoxysilane, perfluoroalkylsilane, silica fine particles, base as a catalyst for promoting hydrolysis reaction of tetraalkoxysilane, and water. It repeats 3 times or more, The manufacturing method of the water-repellent | oil-repellent coated article of Claim 1 characterized by the above-mentioned.
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| JP5242841B1 (en) * | 2012-10-13 | 2013-07-24 | 日本アエロジル株式会社 | Water- and oil-repellent coating films and articles containing the coating films |
| EP2942380B1 (en) * | 2013-01-07 | 2018-01-31 | Mitsubishi Electric Corporation | Coating composition, method for producing same, and coated article |
| JP5839134B2 (en) * | 2013-01-30 | 2016-01-06 | 旭硝子株式会社 | Transparent substrate with antifouling film |
| JP6326258B2 (en) * | 2013-05-08 | 2018-05-16 | 株式会社Kri | Modified metal oxide nanoparticles |
| JP6403069B2 (en) * | 2015-04-30 | 2018-10-10 | 石原ケミカル株式会社 | Coating composition |
| JP6498091B2 (en) * | 2015-09-25 | 2019-04-10 | Ｊｘ金属株式会社 | Surface-treated metal foil, laminate, printed wiring board, semiconductor package, electronic equipment |
| JP2017096685A (en) * | 2015-11-19 | 2017-06-01 | 国立大学法人 岡山大学 | Needle, and injection needle equipped with the same |
| CN109072008B (en) | 2016-04-13 | 2021-07-23 | 大金工业株式会社 | Super-liquid-repellent film and composition for forming super-liquid-repellent curable film |
| JP6937585B2 (en) * | 2017-02-14 | 2021-09-22 | 株式会社ハウステック | Coating film composition for water-related housing equipment |
| CN111225961A (en) | 2017-10-18 | 2020-06-02 | 大金工业株式会社 | Coating film |
| JP6980145B1 (en) * | 2021-03-31 | 2021-12-15 | ナガセケムテックス株式会社 | Dough coating composition |
| CN116133843A (en) * | 2020-08-04 | 2023-05-16 | 长濑化成株式会社 | Composition for coating laminate and grey cloth |
| JP7267343B2 (en) * | 2020-08-04 | 2023-05-01 | ナガセケムテックス株式会社 | laminate |
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| JPH0913018A (en) * | 1995-07-03 | 1997-01-14 | Nippon Sheet Glass Co Ltd | Composition for water-repellent coating film and water-repellent glass |
| JPH11286784A (en) * | 1999-02-18 | 1999-10-19 | Kansai Shingijutsu Kenkyusho:Kk | Method for modifying surface of glass |
| JP4231983B2 (en) * | 2000-12-22 | 2009-03-04 | 信越化学工業株式会社 | Water-soluble water and oil repellent treatment agent and method for producing the same |
| JP2003236977A (en) * | 2002-02-19 | 2003-08-26 | Matsushita Electric Works Ltd | Stainproof member |
| AU2003289311A1 (en) * | 2002-12-10 | 2004-06-30 | Nippon Sheet Glass Co., Ltd. | Article having coating film thereon, method for manufacture thereof, and applying material for forming coating film |
| JP2004256939A (en) * | 2003-02-25 | 2004-09-16 | Toray Ind Inc | Water-repellent fabric and clothes using the same |
| JP4384898B2 (en) * | 2003-11-28 | 2009-12-16 | 日油株式会社 | Method for producing water / oil repellent coating |
| JP2007144916A (en) * | 2005-11-30 | 2007-06-14 | Asahi Glass Co Ltd | Super-water repellent substrate |
| JP2008189705A (en) * | 2007-02-01 | 2008-08-21 | Hokkaido Univ | Article having water-repellent and oil-repellent surface and method for producing the same |
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