JPS63135435A - Water-repellent and oil-repellent plastic molding and its production - Google Patents
Water-repellent and oil-repellent plastic molding and its productionInfo
- Publication number
- JPS63135435A JPS63135435A JP28209686A JP28209686A JPS63135435A JP S63135435 A JPS63135435 A JP S63135435A JP 28209686 A JP28209686 A JP 28209686A JP 28209686 A JP28209686 A JP 28209686A JP S63135435 A JPS63135435 A JP S63135435A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- protective layer
- plastic molded
- organosilane compound
- molded article
- 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
- 238000010137 moulding (plastic) Methods 0.000 title claims abstract 4
- 239000005871 repellent Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- -1 organosilane compound Chemical class 0.000 claims abstract description 46
- 239000010410 layer Substances 0.000 claims abstract description 36
- 239000011241 protective layer Substances 0.000 claims abstract description 36
- 239000011247 coating layer Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010409 thin film Substances 0.000 claims abstract description 18
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000005370 alkoxysilyl group Chemical group 0.000 claims abstract 2
- 239000004033 plastic Substances 0.000 claims description 43
- 229920003023 plastic Polymers 0.000 claims description 43
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000008199 coating composition Substances 0.000 claims 1
- 125000003709 fluoroalkyl group Chemical group 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 239000004417 polycarbonate Substances 0.000 abstract description 21
- 229920000515 polycarbonate Polymers 0.000 abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 239000000203 mixture Substances 0.000 abstract description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 abstract description 6
- 239000004926 polymethyl methacrylate Substances 0.000 abstract description 6
- 125000000217 alkyl group Chemical group 0.000 abstract description 5
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 239000004793 Polystyrene Substances 0.000 abstract description 2
- 239000012780 transparent material Substances 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract 2
- 238000005336 cracking Methods 0.000 abstract 1
- 239000011521 glass Substances 0.000 abstract 1
- 238000000465 moulding Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 239000003921 oil Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- 229910000077 silane Inorganic materials 0.000 description 11
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 10
- 230000002940 repellent Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 125000005372 silanol group Chemical group 0.000 description 6
- 239000005046 Chlorosilane Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 238000006482 condensation reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000013005 condensation curing Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- ZVBWPVOCTORPLM-UHFFFAOYSA-N formylsilicon Chemical group [Si]C=O ZVBWPVOCTORPLM-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000006120 scratch resistant coating Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229920004142 LEXAN™ Polymers 0.000 description 1
- 239000004418 Lexan Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003302 alkenyloxy group Chemical group 0.000 description 1
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000003544 oxime group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical class CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、被覆層の形成されてなるプラスチック成形体
に関し、特に被覆剤の特性にもとづく優れた特性を有す
る撥水撥油性プラスチッり成形体およびその製造方法に
関するものである。Detailed Description of the Invention [Industrial Application Field] The present invention relates to a plastic molded article formed with a coating layer, and in particular to a water- and oil-repellent plastic molded article that has excellent properties based on the characteristics of the coating material. and its manufacturing method.
［従来の技術］
プラスチック成形体は、プラスチック自身の有する特性
を活かして各種分野に広く使用されている０例えば、プ
ラスチックの透明性を活かして各種窓ガラス代替品、Ｎ
根材、透明防音壁、屋外灯保護材、車輌用照明灯◆風防
などに使用されている。[Prior art] Plastic molded bodies are widely used in various fields by taking advantage of the properties of plastic itself.
Used for root materials, transparent soundproof walls, outdoor light protection materials, vehicle lighting, windshields, etc.
しかしながら、プラスチック成形体はその有用な特性を
有する一方で傷がつき易く、これによって透明性が低下
するという耐擦傷性に劣るという欠点を有している。さ
らに、吸湿性を有することから、空気中の湿分や雨滴な
どによって変質、劣化が進行し、光沢や透明性が低下す
るという耐湿性に劣るという欠点をも有していて用途面
が制約されることもある。However, while plastic molded articles have useful properties, they have the disadvantage of being easily scratched and having poor scratch resistance, which reduces transparency. Furthermore, because it has hygroscopic properties, it has the disadvantage of poor moisture resistance, such as deterioration and deterioration due to moisture in the air and raindrops, and a decrease in gloss and transparency, which limits its use. Sometimes.
上記のような欠点に対する手段として従来より、例えば
オルガノポリシロキサンを主成分とする被覆剤をプラス
チック成形体の表面に塗装して加熱硬化させることによ
って耐擦傷性被覆層を形成させる方法（米国特許第４２
１０８９９号、同第４２２４３７８号、同第４２３７２
０号）が知られている。また、耐湿性を向上せしめるた
めに、プラスチック表面に例えば、フッ素系、シリコン
系、ジルコニア系など種々の撥水撥油剤を処理して撥水
撥油性を有する被膜を形成させる方法が知られている。As a solution to the above-mentioned drawbacks, there has been a conventional method of forming a scratch-resistant coating layer by coating the surface of a plastic molded article with a coating material mainly composed of organopolysiloxane and curing it with heat (U.S. Patent No. 42
No. 10899, No. 4224378, No. 42372
No. 0) is known. Furthermore, in order to improve moisture resistance, a method is known in which a plastic surface is treated with various water and oil repellents such as fluorine-based, silicone-based, and zirconia-based agents to form a water- and oil-repellent film. .
かかる撥水撥油剤において、フッ素系によって形成され
る被膜は表面自由エネルギーが低いことから、撥水撥油
性に最も優れていて、しかも化学的に安定であり、耐薬
品にも優れている。In such water and oil repellents, the coating formed from fluorine-based agents has the best water and oil repellency due to its low surface free energy, and is also chemically stable and has excellent chemical resistance.
［発明の解決しようとする問題点］
前記の如きオルガノポリシロキサンを主成分とする耐擦
傷性被覆層は加熱硬化されて形成されるが、加熱硬化後
においても被覆層の表面には未反応のシラノール基が残
存していて、これが徐々に縮合反応を起こし、この進行
に伴いクラックが発生したり、また、シラノール基と結
合し得る水垢、埃などが付着し、それが汚染の原因とな
り、しかも結合が強固であって、汚染を除去し難くする
という問題がある。さらに、吸湿することによってシリ
カ成分の溶出、被覆層の付着性の低下を招き易いという
問題点を有している。[Problems to be Solved by the Invention] The scratch-resistant coating layer mainly composed of organopolysiloxane as described above is formed by heating and curing, but even after heating and curing, unreacted particles remain on the surface of the coating layer. Silanol groups remain, which gradually cause a condensation reaction, and as this progresses, cracks occur, and water scale, dust, etc. that can bond with the silanol groups adhere, which causes contamination. The problem is that the bond is strong, making it difficult to remove contamination. Furthermore, there is a problem that moisture absorption tends to cause elution of the silica component and a decrease in the adhesion of the coating layer.
一方、従来の撥水撥油剤による処理は、撥水撥油剤をプ
ラスチック成形体の表面に直接塗布あるいは撥水撥油剤
中にプラスチック成形体を浸漬することによって被膜を
形成させる方法よりなるが、一般に撥水撥油剤は表面自
由エネルギーが低いために、上記の如き処理方法では塗
布ムラや被膜の不均質化を生じ易い、また、プラスチッ
クに対する接着力が弱いために被膜の耐久性に難点があ
った。したがって、撥水撥油処理に際し、プラスチック
表面を例えばプラズマ処理する方法、プラスチックに含
まれる活性水素やプラスチック表面に存在する水分との
化学的反応を利用する方法（特開昭５７−１５１８２８
号公報）、プラスチック表面に予め塗布するシランカッ
プリング剤に含まれるシラノール基と撥水撥油剤に含ま
れるシラノール基との縮合反応を利用する方法（特開昭
８０−４０２５４号公報）が開示されている。しかるに
、上記のプラスチックに含まれる活性水素やプラスチッ
ク表面に存在する水分との化学的反応を利用する方法で
はプラスチック表面の活性点と処理剤の反応性に難点が
あり、初期特性や効果の持続性が予期されるほどのもの
ではない、また、シラノール基相互の縮合反応を利用す
る方法では、プラスチック表面に予め塗布するシランカ
ップリング剤の被膜を半硬化の状態に保って撥水撥油剤
を塗布し、加熱することによって縮合反応により硬化さ
せ被膜を形成させるために工程が煩雑となるという問題
点もある。On the other hand, conventional treatment with water and oil repellents consists of forming a film by directly applying the water and oil repellent to the surface of the plastic molded body or by immersing the plastic molded body in the water and oil repellent. Water and oil repellents have low surface free energy, so the above-mentioned treatment methods tend to cause uneven coating and non-uniform coatings, and the weak adhesion to plastics poses problems in the durability of the coating. . Therefore, when performing water and oil repellent treatment, there are methods such as plasma treatment of plastic surfaces, methods that utilize active hydrogen contained in plastics, and chemical reactions with water present on the plastic surfaces (Japanese Patent Laid-Open No. 57-151828).
JP-A No. 80-40254 discloses a method that utilizes a condensation reaction between silanol groups contained in a silane coupling agent and silanol groups contained in a water- and oil-repellent agent that are applied in advance to a plastic surface. ing. However, the method that utilizes the chemical reaction between the active hydrogen contained in plastics and the water present on the plastic surface has problems with the reactivity of the treatment agent with the active sites on the plastic surface, resulting in poor initial properties and durability of the effect. In addition, in the method that utilizes the condensation reaction between silanol groups, the silane coupling agent coating applied to the plastic surface is kept in a semi-cured state before the water and oil repellent is applied. However, there is also the problem that the process becomes complicated because it is cured by a condensation reaction by heating to form a film.
［問題点を解決するための手段］
本発明の目的は、前述の問題点を解消し、被覆層の形成
されてなるプラスチック成形体において、被覆剤の特性
にもとづく優れた性能を有する撥水撥油性プラスチック
成形体およびその製造方法を提供することにある。[Means for Solving the Problems] An object of the present invention is to solve the above-mentioned problems, and to provide a water-repellent product having excellent performance based on the characteristics of the coating material in a plastic molded article formed with a coating layer. An object of the present invention is to provide an oil-based plastic molded article and a method for producing the same.
即ち、本発明の一つは、表面に被覆層の形成されてなる
プラスチック成形体において、被覆層の最上層が保護層
の表面をポリフルオロアルキル基含有オルガノシラン化
合物を接触反応させて形成された薄膜層からなり、保護
層が加水分解性オルガノシラン化合物の加水分解物ある
いはシリカゾルに由来する微粒状シリカからなるかある
いはそれを含む層であることを特徴とする撥水撥油性プ
ラスチック成形体である。That is, one of the present inventions is a plastic molded article having a coating layer formed on its surface, in which the uppermost layer of the coating layer is formed by contacting the surface of the protective layer with an organosilane compound containing a polyfluoroalkyl group. A water- and oil-repellent plastic molded article consisting of a thin film layer, characterized in that the protective layer is a layer consisting of or containing fine particulate silica derived from a hydrolyzate of a hydrolyzable organosilane compound or silica sol. .
上記の本発明の撥水撥油性プラスチック成形体は下記の
製造方法によって製造することができる。The water- and oil-repellent plastic molded article of the present invention described above can be manufactured by the following manufacturing method.
即ち、本発明の他の一つは、プラスチック成形体表面に
加水分解性オルガノシラン化合物の加水分解物あるいは
シリカゾルに由来する微粒状シリカからなるかあるいは
それを含む保護層を形成し、次いで該保護層の表面に気
体状のポリフルオロアルキル基含有オルガノシラン化合
物を接触反応させることを特徴とする撥水撥油性プラス
チック成形体の製造方法である。That is, another aspect of the present invention is to form a protective layer made of or containing fine particulate silica derived from a hydrolyzate of a hydrolyzable organosilane compound or silica sol on the surface of a plastic molded article, and then to apply the protective layer to the surface of the plastic molded article. This is a method for producing a water- and oil-repellent plastic molded article, which is characterized in that a gaseous polyfluoroalkyl group-containing organosilane compound is brought into contact with the surface of the layer.
本発明におけるプラスチック成形体は、例えばポリカー
ボネート、ポリメチルメタクリレート、ポリスチレン、
ポリオールポリアリルカーボネートなどの透明性材料か
らなる成形体であるのが好適である。かかる成形体にお
いて、表面に例えば、アクリル系樹脂材料、その他の熱
可塑性樹脂系材料などによる硬化層の設けられた成形体
、あるいはその他の材料からなる成形体拳積層体など、
それらの表面に被覆層の下層である保護層が形成されう
る材料からなる成形体であれば特に限定されない。The plastic molded article in the present invention is made of, for example, polycarbonate, polymethyl methacrylate, polystyrene,
A molded body made of a transparent material such as polyol polyallyl carbonate is preferred. In such a molded product, a molded product whose surface is provided with a hardened layer made of, for example, an acrylic resin material or other thermoplastic resin material, or a molded product laminate made of other materials, etc.
There are no particular limitations on the molded product as long as it is made of a material on which a protective layer, which is a lower layer of the coating layer, can be formed on the surface of the molded product.
本発明における保護層は、加水分解性オルガノシラン化
合物の加水分解物あるいはシリカゾルに由来する微粒状
シリカを含有することが必要である。この保護層は表面
にシラノール基が存在すると考えられ、これによって後
述のポリフルオロアルキル基含有シラン化合物が保護表
面に接触した際シロキサン結合が生じてポリフルオロア
ルキル基含有シラン化合物の残基が保護層表面に結合す
るものと考えられる。保護層は加水分解性シラン化合物
やその部分加水分解物、またはそれらとバインダー成分
などの添加成分を含む組成物を塗布硬化することによっ
て形成される。さらに上記微粒状シリカとバインダー成
分を含む組成物を塗布硬化することによっても形成され
る。また、微粒状シリカは加水分解性シラン化合物やそ
の部分加水分解物と併用されてもよい、保護層形成用の
材料としては、従来ハードコート用塗料あるいは、シラ
ンカップリング剤と呼ばれているものが適当である。特
に、加熱縮合硬化型のオルガノシラン化合物あるいはそ
の部分解氷分解物の溶液、シランカップリング剤溶液、
加水分解性基含有シリル基を側鎖に有する重合体の溶液
などが好ましい。The protective layer in the present invention needs to contain fine particulate silica derived from a hydrolyzate of a hydrolyzable organosilane compound or silica sol. This protective layer is thought to have silanol groups on its surface, which causes siloxane bonds to occur when a polyfluoroalkyl group-containing silane compound (described later) comes into contact with the protective surface, and the residue of the polyfluoroalkyl group-containing silane compound is transferred to the protective layer. It is thought that it binds to the surface. The protective layer is formed by applying and curing a composition containing a hydrolyzable silane compound, a partially hydrolyzed product thereof, or an additive component such as a binder component and the like. Furthermore, it can also be formed by coating and curing a composition containing the above-mentioned fine particulate silica and a binder component. In addition, fine particulate silica may be used in combination with a hydrolyzable silane compound or its partially hydrolyzed product.As a material for forming a protective layer, conventional hard coat paints or silane coupling agents can be used. is appropriate. In particular, solutions of heat condensation curing organosilane compounds or their partially decomposed decomposed products, silane coupling agent solutions,
A solution of a polymer having a hydrolyzable group-containing silyl group in its side chain is preferred.
加水分解性オルガノシラン化合物は、ケイ素原子に結合
したアルコキシ基などの加水分解性基を少なくとも１個
有する化合物であり、好ましくは、さらにケイ素原子に
結合した炭素原子を含む有機基を少なくとも１個有する
化合物である。加水分解性オルガノシラン化合物は。The hydrolyzable organosilane compound is a compound having at least one hydrolyzable group such as an alkoxy group bonded to a silicon atom, and preferably further has at least one organic group containing a carbon atom bonded to a silicon atom. It is a compound. Hydrolyzable organosilane compounds.
一般に下記式で表わさる化合物である。Generally, it is a compound represented by the following formula.
Ａｌ−５ｉ−Ａ３
■
Ａ１−Ａ４の少なくとも２つは、アルコキシ基などの加
水分解可能な基である。また、好ましくは少なくとも１
つが上記有機基（重合体の残基を含む）である、最も好
ましくは、Ａ１−Ａ４の１つが上記有機基であり、他の
３つが加水分解可能な基である。有機基が少なくとも１
個の官能性基（エボキン基、アミ７基、α、β−不飽和
基、メルカプト基、インシアネート基、塩素原子、水酸
基など）を有するオルガノシラン化合物を本発明ではシ
ランカップリング剤と呼ぶ。Al-5i-A3 ■ At least two of A1-A4 are hydrolyzable groups such as alkoxy groups. Also, preferably at least 1
Most preferably, one of A1-A4 is the organic group described above and the other three are hydrolyzable groups. At least 1 organic group
In the present invention, an organosilane compound having several functional groups (evoquine group, ami7 group, α, β-unsaturated group, mercapto group, incyanate group, chlorine atom, hydroxyl group, etc.) is referred to as a silane coupling agent.
官°能性基を有しない有機基（アルキル基など）を有す
るかあるいは有しないオルガノシラン化合物を本発明で
は加熱縮合型のオルガノシラン化合物という、また、重
合体鎖を有するオルガノシラン化合物を加水分解性シリ
ル基含有重合体という、加水分解性基としては、アルコ
キシ基が最も好ましいが、これに限られずアルカノール
以外のアルコールからその水酸基の水素原子を除いた基
、種々のアシルオキシ基、アルケニルオキシ基、アミノ
オキシ基、オキシム基などであってもよい。アルコキシ
基としては炭素数８以下のアルコキシ基、特に炭素数４
以下の低級アルコキシ基が好ましく、メトキシ基が最も
好ましい、以下、代表的な加水分解性オルカッシラン化
合物についてさらに説明する。In the present invention, organosilane compounds with or without organic groups (such as alkyl groups) that do not have functional groups are referred to as heat-condensation type organosilane compounds, and organosilane compounds with polymer chains are also referred to as organosilane compounds having a polymer chain. The hydrolyzable group of the silyl group-containing polymer is most preferably an alkoxy group, but is not limited to this, but is not limited to groups obtained by removing the hydrogen atom of the hydroxyl group from an alcohol other than alkanol, various acyloxy groups, alkenyloxy groups, It may also be an aminooxy group, an oxime group, etc. As an alkoxy group, an alkoxy group having 8 or less carbon atoms, especially 4 carbon atoms.
The following lower alkoxy groups are preferred, and methoxy groups are most preferred. Representative hydrolyzable orcassilane compounds will be further explained below.
加熱縮合硬化型のすルガノボリシロキサン系被覆剤は一
般式
％式％）
（式中、Ｒ１は炭素数１〜８のアルキル基、炭素ｆｉ２
〜８のアルケニル基、フェニル基、アルコキシｇ；Ｒ２
は炭素数１〜８のアルキル基；ａはθ〜３の整数）
で表わされるアルコキシシラン化合物の部分加水分解縮
合物を主成分とする溶液が好ましく、これは一般的に容
易に入手しうるちのである。The heat condensation curing type surganobolisiloxane coating agent has the general formula % formula %) (wherein, R1 is an alkyl group having 1 to 8 carbon atoms, carbon fi2
~8 alkenyl group, phenyl group, alkoxyg; R2
is an alkyl group having 1 to 8 carbon atoms; a is an integer of θ to 3) A solution containing as a main component a partially hydrolyzed condensate of an alkoxysilane compound is preferred, and this solution is generally easily available. It is.
上記のオルガノポリシロキサン溶液には接着性、耐久性
などの特性を向とさせる目的で他の添加物、例えば、微
粒子状のシリカゾルなどを添加してもよい。Other additives, such as particulate silica sol, may be added to the above organopolysiloxane solution for the purpose of improving properties such as adhesion and durability.
次にシランカップリング剤としては、例えばＮＨ２（Ｃ
Ｈ２）２ ＮＨ（Ｃ）！？）２ Ｓｉ （ＯＣＨ３）３
、ＮＨ２（ＣＨ２ｈＳｉ（ＯＣＨ３）＋ 、 Ｃ
Ｈ２＊Ｃｔ（Ｓｉ（ＯＣＨａ）３ＧＨ２−ＣＨ５ｉ （
ＱＣ２Ｈ５）３ 、ＣＨ３−
ＣＴｏ−Ｃ−ＣＯＯ（ＣＨ２）３Ｓｉ（ＯＣＨ３）ｚ
、Ｈ５（ＣＨ２）３Ｓｉ（ＯＣＨ３ｈ 、 ０ＣＮ（
Ｃ）Ｉ？）：＋５ｉ（ＯＧＨｘｌ＋ＣＩ （ＣＨ２）３
Ｓ ｉ （ＱＣ：Ｈａ ）３などに代表されるトリメ
トキシシラン化合物が好ましい。かかるシランカップリ
ング剤は２種以Ｊ二を併用、あるいは、接着性、耐久性
などの特性を向上させる目的で他の添加剤を添加しても
よい。Next, as a silane coupling agent, for example, NH2 (C
H2)2NH(C)! ? )2 Si (OCH3)3
, NH2(CH2hSi(OCH3)+ , C
H2*Ct(Si(OCHa)3GH2-CH5i (
QC2H5)3, CH3-CTo-C-COO(CH2)3Si(OCH3)z
, H5(CH2)3Si(OCH3h, 0CN(
C) I? ):+5i(OGHxl+CI (CH2)3
Preferred are trimethoxysilane compounds such as S i (QC:Ha )3. Two or more types of such silane coupling agents may be used in combination, or other additives may be added for the purpose of improving properties such as adhesiveness and durability.
さらに、アルコキシシラン基を側鎖に有する重合体とし
ては、例えば。Further, as the polymer having an alkoxysilane group in its side chain, for example.
〒１１３
ＣＨ２＝Ｃ−Ｃ：００（ＣＨ２ｈＳｉ（ＱＣ）１３ｂ
などのα、β−不飽和基な有するシランカップリング
剤とそれと共重合しうるアルキルメタクリレートなどの
他のモノマーとを共重合させて得られる共重合体が好適
に使用しうる。ここで、アルキルメタクリレートとして
は、メチルメタクリレート、エチルメタクリレート、ｎ
−プロピルメタクリレート、ｎ−ブチルメタクリレート
などが好適であり、これらを２種以上併用して共重合さ
せたものでもよい、共重合体中に含まれるシランカップ
リング剤の量は １〜８０重量％であるのが望ましく、
量が少ないと、上層に形成されるポリフルオロアルキル
基含有シリル化合物の薄膜との密着性が低下し、一方、
多量にすぎると共重合体としてのガラス転位温度が低く
なり所要の硬度は得られず、上層にポリフルオロアルキ
ル基含有シリル化合物の薄膜の形成処理に際し、クラッ
クを生ずるという問題がある。〒113 CH2=C-C:00(CH2hSi(QC)13b
A copolymer obtained by copolymerizing a silane coupling agent having an α,β-unsaturated group such as silane coupling agent and other monomers such as alkyl methacrylate that can be copolymerized with the silane coupling agent can be suitably used. Here, as the alkyl methacrylate, methyl methacrylate, ethyl methacrylate, n
-Propyl methacrylate, n-butyl methacrylate, etc. are preferred, and a copolymer of two or more of these may also be used.The amount of silane coupling agent contained in the copolymer is 1 to 80% by weight. It is desirable to have
If the amount is small, the adhesion with the thin film of the polyfluoroalkyl group-containing silyl compound formed on the upper layer will decrease;
If the amount is too large, the glass transition temperature of the copolymer will be low, making it impossible to obtain the required hardness, and there will be problems in that cracks will occur during the process of forming a thin film of the polyfluoroalkyl group-containing silyl compound on the upper layer.
よって、シランカップリング剤の量は ５〜６０重量％
、特に好ましくは１０〜５０重量％である。Therefore, the amount of silane coupling agent is 5 to 60% by weight.
, particularly preferably 10 to 50% by weight.
上記の如き加水分解性オルガノシラン化合物あるいはそ
の部分加水分解物はプラスチック成形体の表面に直接、
あるいは予め形成されてなる硬化層上への処理において
、処理を容易とするために適当な溶剤によって希釈され
る。溶剤の量は、処理の難易性と形成される保護層とし
ての被覆層の厚さとの関係において適宜決定される。The above-mentioned hydrolyzable organosilane compound or its partially hydrolyzed product is directly applied to the surface of the plastic molded article.
Alternatively, in processing a previously formed cured layer, it is diluted with a suitable solvent to facilitate processing. The amount of solvent is appropriately determined in relation to the difficulty of processing and the thickness of the coating layer as a protective layer to be formed.
保護層の上に形成される最上層のポリフルオロアルキル
基含有シラン化合物薄膜層はポリフルオロアルキル基含
有ハロシラン化合物を処理することによって形成される
。かかるポリフルオロアルキル基含有ハロシラン化合物
としては、一般式
％式％
（式中、Ｒｆは炭素数４〜１６のポリフルオロアルキル
基、Ｘはハロゲン、炭素数１〜４のアルキル基であり、
Ｘの少なくとも１つはハロゲンである）
で表わされる化合物が好ましい、 Ｒｆとしては、特に
パーフルオロアルキル基が好ましい、上記式の化合物に
おいてＸで表わされるハロゲンとしてはＣ１であるのが
好適である。上記式に従ったポリフルオロアルキル基含
有ノ＼ロシラン化合物は２種以上を併用してもよい。The uppermost polyfluoroalkyl group-containing silane compound thin film layer formed on the protective layer is formed by treating a polyfluoroalkyl group-containing halosilane compound. Such a polyfluoroalkyl group-containing halosilane compound has the general formula % (wherein, Rf is a polyfluoroalkyl group having 4 to 16 carbon atoms, X is a halogen, and is an alkyl group having 1 to 4 carbon atoms,
At least one of X is a halogen) Rf is particularly preferably a perfluoroalkyl group. In the compound of the above formula, the halogen represented by X is preferably C1. Two or more types of polyfluoroalkyl group-containing silane compounds according to the above formula may be used in combination.
本発明の撥水撥油性プラスチック成形体の製造方法にお
いて、保護層の形成方法は加水分解性オルガノシラン化
合物あるいはその部分加水分解物またはその溶剤希釈液
をプラスチック成形体の表面に直接または、成形体に予
め形成されている硬化層上に通常行なわれる塗布方法、
例えば刷毛塗り、ロール塗り、吹付は及び浸漬法などに
よって塗布し、しかる後、室温で乾燥することによって
行なわれる。保護層の厚さは０．５鉢以上であるのが好
ましいが、必要以上に厚くする必要はなく、１０ｇ位ま
でであれば充分である。一方、極端に薄いと膜強度が維
持されず、特性の優れた保護層を得ることが困難となる
。In the method for producing a water- and oil-repellent plastic molded body of the present invention, the protective layer is formed by applying a hydrolyzable organosilane compound, a partial hydrolyzate thereof, or a diluted solution thereof in a solvent to the surface of the plastic molded body directly or A coating method that is usually carried out on a cured layer that has been formed in advance,
For example, the coating may be applied by brushing, rolling, spraying, dipping or the like, followed by drying at room temperature. The thickness of the protective layer is preferably 0.5 g or more, but there is no need to make it thicker than necessary, and a thickness of up to about 10 g is sufficient. On the other hand, if it is extremely thin, the film strength will not be maintained, making it difficult to obtain a protective layer with excellent properties.
最上層としてのポリフルオロアルキル基含有シラン化合
物の薄膜の形成方法は、保護層表面とポリフルオアルキ
ル基含有シラン化合物との固体気相反応によって行なわ
れる。固体気相応は具体的には、例えば保護層の形成さ
れた成形体を密閉容器に入れ、容器内温度を６０℃以上
、好ましくは８０℃以上に加温し、保護層の表面にポリ
フルオロアルキル基含有シラン化合物の蒸気を接触させ
る。この場合の接触状態に保持する時間、即ち、反応時
間は５分以上、好ましくは１０分以上である。而して、
反応温度と反応時間は用いられるポリフルオロアルキル
基含有シラン化合物の種類と形成される薄膜の所望厚さ
によって適宜決定される。薄膜層厚さは経済的評価との
関係で決定され必要以上に厚くなると耐擦傷性に優れた
保護層の特性を損なう傾向があり、また経済的にも不利
となる。実用上において最上層の薄膜層の厚さは０．１
ｗ以下であっても充分な撥水撥油性が得られる。The method for forming the thin film of the polyfluoroalkyl group-containing silane compound as the uppermost layer is carried out by a solid gas phase reaction between the surface of the protective layer and the polyfluoroalkyl group-containing silane compound. Specifically, the solid-gas phase reaction is carried out by, for example, placing a molded product with a protective layer in a sealed container, heating the container to a temperature of 60°C or higher, preferably 80°C or higher, and adding polyfluoroalkyl to the surface of the protective layer. Contact with vapor of a group-containing silane compound. In this case, the time for maintaining the contact state, that is, the reaction time, is 5 minutes or more, preferably 10 minutes or more. Then,
The reaction temperature and reaction time are appropriately determined depending on the type of polyfluoroalkyl group-containing silane compound used and the desired thickness of the thin film to be formed. The thickness of the thin film layer is determined in relation to economic evaluation, and if it becomes thicker than necessary, it tends to impair the characteristics of the protective layer, which has excellent scratch resistance, and is also economically disadvantageous. In practice, the thickness of the top thin film layer is 0.1
Sufficient water and oil repellency can be obtained even if it is less than w.
かくして、本発明の製造方法にしたがえば。Thus, according to the manufacturing method of the present invention.
撥水撥油性はもとより、耐擦傷性、摺動性、その他の特
性に優れたプラスチック成形体を得ることができる。It is possible to obtain a plastic molded article that has not only water and oil repellency but also excellent scratch resistance, sliding properties, and other properties.
［作用］
本発明の撥水撥油性プラスチック成形体において、撥水
撥油性、その他の特性が付与される作用機構は必ずしも
明確ではないが、保護層が耐擦傷性を有し、また最上層
の薄膜層がポリフルオロアルキル基含有シラン化合物よ
りなることにより撥水撥油性が付与され、特に特性の持
続性、耐久性などが良好なのは保護層の表面に存在する
活性部位としてのシラール基とその上に処理されるポリ
フルオロアルキル基含有シラン化合物とが化学的に反応
して結合することによるものと考えられる。[Function] The mechanism of action by which the water- and oil-repellent plastic molded article of the present invention is imparted with water- and oil-repellency and other properties is not necessarily clear, but the protective layer has scratch resistance and the top layer The thin film layer is made of a polyfluoroalkyl group-containing silane compound, which imparts water and oil repellency, and the reason why the properties are particularly long lasting and durable is because of the silal groups as active sites present on the surface of the protective layer and the silal groups on the surface of the protective layer. This is thought to be due to chemical reaction and bonding with the polyfluoroalkyl group-containing silane compound that is treated.
［実施例］
合成例１
ＲｆＣＨ＝ＣＨ２（但し、 Ｒｆは ＧｎＦｚｎ＋＋、
ｎは ６゜８、１０．１２の混合物で平均値９） ４
９．６ｇ （０，１モル） 、 ＨＳｉＣｈ １５．９
ｇ （０，１８モル） 、 Ｈ２ＰｔＣｌ６・６Ｈ２０
の５０％インプロパツール溶液０．２ｇを内容積２００
ｍＭのオートクレーブ中に入れ、撹拌しながら、８５℃
で２０時間反応させた０反応終了後、減圧蒸留によって
６０〜ｂ
反応生成物として得た。この反応生成物をガスクロマト
グラフィーで分析した結果Ｒｆ （Ｃ）（２）２ Ｓ
ｉＯｈであることが確認され、収率は９５％であった。[Example] Synthesis Example 1 RfCH=CH2 (However, Rf is GnFzn++,
n is a mixture of 6°8 and 10.12 with an average value of 9) 4
9.6g (0.1 mol), HSiCh 15.9
g (0.18 mol), H2PtCl6・6H20
0.2g of 50% Improper Tools solution in an internal volume of 200
Place in an autoclave at 85°C with stirring.
After the reaction was completed for 20 hours, the reaction product 60-b was obtained by distillation under reduced pressure. Analysis of this reaction product by gas chromatography revealed that Rf(C)(2)2S
It was confirmed to be iOh, and the yield was 95%.
合成例２〜３
合成例１におけるＨＳｉＣｈに代えてＨＳｉＣＨ３ＣＩ
２及びＨＳｉ（ＣＨ３）２ＣＩを用いた他は合成例１と
同様に反応させて１反応生成物としてＲｆ（ＣＨ２ｈＳ
ｉＣＨ：＋Ｃ１２及びＲｆ（ＣＨ２）２ｓｉ（ＣＨ３）
２Ｇｌを得た。Synthesis Examples 2-3 HSiCH3CI in place of HSiCh in Synthesis Example 1
The reaction was carried out in the same manner as in Synthesis Example 1 except that Rf(CH2hS
iCH: +C12 and Rf(CH2)2si(CH3)
Obtained 2Gl.
合成例４〜６
合成例１〜３におけるＲｆＣＨ＝ＣＴｏ （但し、Ｒｆ
はＣｎＦ２ｎ、１ 、 ｎは８．８．１０．１２の混合
物で平均値９）に代えてＣａ Ｆｇ ０Ｈ−ＣＨ２を用
いた他は合成例１〜３と同様に反応させて反応生成物と
して、Ｃ４Ｆｑ（Ｃ）Ｉ２）２ｓｉｃ１３． ＣｎＦｑ
（ＣＨ２）？５ｉｃＨ３ｃＩ２及びＣ４Ｆｑ （ＣＨ；
＋）ｚＳｉ（ＣＨ３）２Ｃ１を得た。Synthesis Examples 4 to 6 RfCH=CTo in Synthesis Examples 1 to 3 (However, Rf
is CnF2n, 1, n is a mixture of 8.8.10.12 with an average value of 9).The reaction was carried out in the same manner as in Synthesis Examples 1 to 3, except that CaFgOH-CH2 was used, and as a reaction product, C4Fq(C)I2)2sic13. CnFq
(CH2)? 5icH3cI2 and C4Fq (CH;
+)zSi(CH3)2C1 was obtained.
合成例１〜６において得られた生成物と収率をまとめて
第１表に示す。Table 1 summarizes the products and yields obtained in Synthesis Examples 1 to 6.
第１表
寥） Ｒｆ ： ＣｎＦ２ｎ４＋ 、 ｎは８．８．
１０．１２ （７）混合物で平均値９
実施例１
メチルメタクリレート２５部（重量部、以下同じ）とシ
ランカップリング剤として
チルケトンに４０重量％となるように加え、アゾビスイ
ソブチロニトリルを開始剤として７０℃にて８時間反応
させて、共重合物を得た。この共重合物３０部に５ｅｃ
−ブチルアルコール ７０部を加えて保護層用被覆剤を
調製した。1st table) Rf: CnF2n4+, n is 8.8.
10.12 (7) Average value for the mixture: 9 Example 1 Add 25 parts (parts by weight, same hereinafter) of methyl methacrylate to til ketone as a silane coupling agent to a concentration of 40% by weight, and start azobisisobutyronitrile. A copolymer was obtained by reacting as an agent at 70°C for 8 hours. 5ec for 30 parts of this copolymer
-70 parts of butyl alcohol was added to prepare a protective layer coating material.
別に、予め用意されたポリカーボネート板（°“レキサ
ン−９０３４”：旭硝子社製品）を上記の被覆剤に浸漬
した後引上げて １２０℃にて乾燥し、保護層を形成し
た。このようにして保護層の形成されたポリカーボネー
ト板を密閉容器に入れ、 １２０℃に加熱して、合成例
１で得たポリフルオロアルキル基を有するクロロシラン
化合物の蒸気に １２０分間接触させて、最上層の薄膜
層を形成させて、被覆層の設けられたポリカーボネート
板を得た。Separately, a previously prepared polycarbonate plate (Lexan-9034, manufactured by Asahi Glass Co., Ltd.) was dipped in the above-mentioned coating material, then pulled up and dried at 120°C to form a protective layer. The polycarbonate plate with the protective layer formed in this way was placed in a closed container, heated to 120°C, and brought into contact with the vapor of the chlorosilane compound having a polyfluoroalkyl group obtained in Synthesis Example 1 for 120 minutes to form the top layer. A thin film layer was formed to obtain a polycarbonate plate provided with a coating layer.
このポリカーボネート板について次のように特性の測定
を行なった。The properties of this polycarbonate plate were measured as follows.
■撥水撥油性：水及びｎ−ヘキサデカンの接触角の測定
。■Water and oil repellency: Measurement of contact angle of water and n-hexadecane.
■撥水撥油性の耐久性：
ａ） イオン交換水中で２時間煮沸後のｎ−ヘキサデカ
ンの接触角の測定。■Durability of water and oil repellency: a) Measurement of contact angle of n-hexadecane after boiling in ion-exchanged water for 2 hours.
ｂ）キシレン含浸脱脂綿を １ｋｇ荷重下に２００回の
ラビングを行なった後のｎ−ヘキサデカンの接触角の測
定。b) Measurement of the contact angle of n-hexadecane after rubbing xylene-impregnated absorbent cotton 200 times under a load of 1 kg.
■耐擦傷性： ＡＳＴＭ Ｃ５−１０における摩耗輪を
用いて５００ｇ荷重下に５００回のテーパー試験を行な
い、前後のヘーズ値を測定。■Scratch resistance: A taper test was performed 500 times under a load of 500g using a worn wheel according to ASTM C5-10, and the haze value before and after was measured.
■硬度： ＪＩＳ Ｋ−５４００に従い１０００ｇ荷重
下の鉛筆硬度を測定。■Hardness: Measure the pencil hardness under a load of 1000g according to JIS K-5400.
■汚れ性−カーポンブラック粉末の０．１％懸濁水を調
製し、試料にスプレーした後、８０℃で２０分間乾燥す
ることを２回繰返し、水道水でシャワーすることを１サ
イクルとして６サイクル後のヘーズ値を測定。■ Stainability - After preparing a 0.1% suspension of carbon black powder in water and spraying it on the sample, drying it at 80℃ for 20 minutes was repeated twice, and after 6 cycles, one cycle was showering with tap water. Measure the haze value of.
上記の特性測定結果を第２表に示す。The above characteristic measurement results are shown in Table 2.
実施例２
実施例１における最上層の薄膜層を合成例５で得たクロ
ロシラン化合物に代えて、その蒸気に８０℃にて１０分
間接触させた他は、実施例１と同様にして被覆層の形成
されたポリカーボネート板を得た。Example 2 The coating layer was formed in the same manner as in Example 1, except that the uppermost thin film layer in Example 1 was replaced with the chlorosilane compound obtained in Synthesis Example 5, and the mixture was brought into contact with its vapor at 80°C for 10 minutes. A formed polycarbonate plate was obtained.
このポリカーボネート板の特性を実施例１と同様に測定
した。その結果を第２表に示す。The properties of this polycarbonate plate were measured in the same manner as in Example 1. The results are shown in Table 2.
実施例３〜４
ポリカーボネート板（゛レキサン９０３４′′旭硝子社
製品）の表面に市販のアクリル系塗料（“ＰＨ９１”二
東芝シリコン社製品）をブライマーとして塗布ル、室温
にて乾燥してプライマ一層を形成した０次にこのブライ
マ一層上に市販の加水分解性オルガノシラン化合物を用
いた被覆剤（゛トスガード５１０”：東芝シリコン社製
品）を塗布して１２０℃に６０分間保持して硬化させ、
保護層を形成した。このようにして保護層の形成された
ポリカーボネート板を密閉容器に入れ、８０°Ｃに加温
して、合成例２または合成例５のクロロシラン化合物の
蒸気に１０分間接触させて最上層の薄膜層を形成し、被
覆層の設けられたポリカーボネート板を得た。Examples 3 to 4 A commercially available acrylic paint ("PH91", a product of Toshiba Silicon Co., Ltd.) was applied as a primer on the surface of a polycarbonate plate (Lexan 9034'', a product of Asahi Glass Co., Ltd.), and dried at room temperature to form a layer of primer. Next, a coating agent using a commercially available hydrolyzable organosilane compound (Tossguard 510'', a product of Toshiba Silicone Co., Ltd.) was applied onto the first layer of the brimer that had been formed, and was kept at 120°C for 60 minutes to cure.
A protective layer was formed. The polycarbonate plate with the protective layer formed thereon was placed in a sealed container, heated to 80°C, and brought into contact with the vapor of the chlorosilane compound of Synthesis Example 2 or Synthesis Example 5 for 10 minutes to form the top thin film layer. A polycarbonate plate provided with a coating layer was obtained.
このポリカーボネート板の特性を実施例１と同様に測定
した。その結果を第２表に示す。The properties of this polycarbonate plate were measured in the same manner as in Example 1. The results are shown in Table 2.
実施例５〜８
実施例３と同様にして下層膜の形成されたポリカーボネ
ート板を用いて、合成例３，４．５及び６のクロロシラ
ン化合物を用いて、第２表に示す処゛理条件にしたがっ
て最上層の薄膜層を形成させて、被覆層の設けられたポ
リカーボネート板を得た。Examples 5 to 8 Using a polycarbonate plate on which a lower layer film was formed in the same manner as in Example 3, using the chlorosilane compounds of Synthesis Examples 3, 4.5, and 6, the treatment conditions shown in Table 2 were applied. Therefore, a top thin film layer was formed to obtain a polycarbonate plate provided with a covering layer.
このポリカーボネート板の特性を実施例１と同様に測定
した。その結果を第２表に示す。The properties of this polycarbonate plate were measured in the same manner as in Example 1. The results are shown in Table 2.
実施例９〜１０
ポリメチルメタクリレート板の表面に市販の加水分解性
オルカッシラン化合物を用いた被覆剤（“°トスガード
５２０”東芝シリコン社製品）を塗布して、１２０℃に
８０分間保持して硬化させ保護層を形成した。このよう
にして保護層の形成されたポリメチルメタクリレート板
を実施例３または７と同様にしてクロロシラン蒸気に接
触させて最上層の薄膜層を形成し、被覆層の設けられた
ポリメチルメタクリレート板を得た。Examples 9 to 10 A coating agent using a commercially available hydrolyzable orcassilane compound ("Tosguard 520", a product of Toshiba Silicone Co., Ltd.) was applied to the surface of a polymethyl methacrylate plate and cured by holding it at 120 °C for 80 minutes. A protective layer was formed. The polymethyl methacrylate plate on which the protective layer was formed in this way was brought into contact with chlorosilane vapor in the same manner as in Example 3 or 7 to form the uppermost thin film layer, and the polymethyl methacrylate plate on which the coating layer was provided was Obtained.
このポリメチルメタクリレート板の特性を実施例１と同
様に測定した。その結果を第２表に示す。The properties of this polymethyl methacrylate plate were measured in the same manner as in Example 1. The results are shown in Table 2.
比較例１
ポリカーボネート板の表面を全く処理することなく、被
覆層の設けられていない状態における特性を実施例１と
同様に測定した。その結果を第２表に示す。Comparative Example 1 The properties of a polycarbonate plate without any coating layer were measured in the same manner as in Example 1, without any surface treatment. The results are shown in Table 2.
比較例２
ポリカーボネート板を密閉容器内に入れ、１２０℃に加
熱して合成例５のクロロシラン化合物の蒸気に１２０分
間接触させてポリカーボネート板の表面に直接薄膜層を
形成させた。Comparative Example 2 A polycarbonate plate was placed in a closed container, heated to 120° C., and brought into contact with the vapor of the chlorosilane compound of Synthesis Example 5 for 120 minutes to form a thin film layer directly on the surface of the polycarbonate plate.
このポリカーボネート板について特性を実施例１と同様
に測定した。その結果を第２表に示す。The properties of this polycarbonate plate were measured in the same manner as in Example 1. The results are shown in Table 2.
比較例３
ポリカーボネート板の表面に市販のアクリル系塗料（”
ＰＨ９１”：東芝シリコン社製品）をプライマーとして
塗布し、室温にて乾燥してプライマ一層を形成した０次
にこのプライマ一層上に市販の前記被覆剤（” ）スガ
ード５１０”：東芝シリコン社製品）を塗布して １２
０°Ｃに６０分間保持して被覆を形成した。Comparative Example 3 Commercially available acrylic paint ("
PH91'': Toshiba Silicon Co., Ltd. product) was applied as a primer and dried at room temperature to form a single layer of primer.Next, on this primer layer, the commercially available coating agent ('') Sugard 510'': Toshiba Silicon Co., Ltd. product) was applied. Apply 12
A coating was formed by holding at 0°C for 60 minutes.
このポリカーボネート板の特性を実施例１と同様に測定
した。その結果を第２表に示す。The properties of this polycarbonate plate were measured in the same manner as in Example 1. The results are shown in Table 2.
実施例１１．比較例４
実施例７及び比較例２で得られた被覆層の設けられたポ
リカーボネート板について、さらに次の特性を測定した
。Example 11. Comparative Example 4 Regarding the polycarbonate plates provided with the coating layer obtained in Example 7 and Comparative Example 2, the following characteristics were further measured.
くのすベリ性二表面のすべり性をＡＳＴＭ Ｄ−１８９
４の上面圧子を用いて、ワイパー紙（” Ｊ Ｋワイパ
ー″°：＋ キンパリ社製量）との間の動摩擦抵抗及び
静摩擦抵抗をＨＥＩＤＯＮ試験装置（新東科学社製）に
て５０ｇ荷重下で測定。ASTM D-189
Using the top indenter of 4, the dynamic frictional resistance and static frictional resistance between the wiper paper ("JK Wiper"°: + produced by Kinpari Co., Ltd.) were measured under a load of 50 g using a HEIDON test device (manufactured by Shinto Kagaku Co., Ltd.). measurement.
■耐湿性：温度５０°Ｃ１湿度９８％条件下におけるｎ
−ヘキサデカンの接触角の経時変化を測定。■Humidity resistance: under the conditions of temperature 50°C and humidity 98%
-Measure the change in contact angle of hexadecane over time.
それらの結果を第３表に示す。The results are shown in Table 3.
第３表
［発明の効果］
本発明の撥水撥油性プラスチック成形体は、特性として
の撥水撥油性に関して、水の接触角、ｎ−ヘキサデカン
の接触角の測定結果からも明らかなように極めて優れて
いる。したがって表面に汚れが付着し難く、一方付着し
た汚れは容易に除去することができる。しかも、撥水撥
油性は種々の過酷な条件を経た後においても劣化は全く
認められず、優れた耐久性を有している。Table 3 [Effects of the Invention] The water- and oil-repellent plastic molded article of the present invention has extremely high water- and oil-repellency characteristics, as is clear from the measurement results of the contact angle of water and the contact angle of n-hexadecane. Are better. Therefore, it is difficult for dirt to adhere to the surface, and on the other hand, the adhered dirt can be easily removed. Furthermore, the water and oil repellency shows no deterioration at all even after undergoing various harsh conditions, and has excellent durability.
特に、従来より撥水撥油性と他の特性、例えば耐擦傷性
、硬度、すべり性などを調和させて向上させることは困
難であるとされているが、本願発明の撥水撥油性プラス
チック成形体は、これら特性の向上をも達成される。さ
らに被覆層の形成された撥水撥油性プラスチック成形体
の製造方法として、薄膜層の形成には処理剤の蒸気を応
用することから、極めて均質な被覆層が形成されるとい
う特徴を有していて、工程も簡略化されるという効果も
認められる。In particular, it has been considered difficult to harmoniously improve water and oil repellency with other properties such as scratch resistance, hardness, and slipperiness, but the water and oil repellent plastic molded article of the present invention Improvements in these properties can also be achieved. Furthermore, as a manufacturing method for water- and oil-repellent plastic molded articles with a coating layer formed, the process uses vapor of a processing agent to form a thin film layer, which has the characteristic of forming an extremely homogeneous coating layer. It is also recognized that the process is simplified.
Claims (5)
体において、被覆層の最上層が保護層の表面をポリフル
オロアルキル基含有オルガノシラン化合物を接触反応さ
せて形成された薄膜層からなり、保護層が加水分解性オ
ルガノシラン化合物の加水分解物あるいはシリカゾルに
由来する微粒状シリカからなるかあるいはそれを含む層
であることを特徴とする撥水撥油性プラスチック成形体
。(1) In a plastic molded article with a coating layer formed on the surface, the top layer of the coating layer is a thin film layer formed by contacting and reacting the surface of the protective layer with an organosilane compound containing a polyfluoroalkyl group, and protects the plastic molded article. 1. A water- and oil-repellent plastic molded article, characterized in that the layer is made of or contains fine-grained silica derived from a hydrolyzate of a hydrolyzable organosilane compound or silica sol.
物がポリフルオロアルキル基を有するハロシランである
特許請求の範囲第１項記載のプラスチック成形体。(2) The plastic molded article according to claim 1, wherein the polyfluoroalkyl group-containing organosilane compound is a halosilane having a polyfluoroalkyl group.
リル基を有する化合物である特許請求の範囲第１項記載
のプラスチック成形体。(3) The plastic molded article according to claim 1, wherein the hydrolyzable organosilane compound is a compound having an alkoxysilyl group.
はその部分加水分解物を含む塗料組成物をプラスチック
成形体表面に塗布硬化して形成された層である特許請求
の範囲第１項記載のプラスチック成形体。(4) The plastic molding according to claim 1, wherein the protective layer is a layer formed by coating and curing a coating composition containing a hydrolyzable organosilane compound or a partially hydrolyzed product thereof on the surface of the plastic molded product. body.
ラン化合物の加水分解物あるいはシリカゾルに由来する
微粒状シリカからなるかあるいはそれを含む保護層を形
成し、次いで該保護層の表面に気体状のポリフルオロア
ルキル基含有オルガノシラン化合物を接触反応させるこ
とを特徴とする被覆層を有する撥水撥油性プラスチック
成形体の製造方法。(5) A protective layer consisting of or containing fine particulate silica derived from a hydrolyzate of a hydrolyzable organosilane compound or silica sol is formed on the surface of the plastic molded article, and then a gaseous polyester is formed on the surface of the protective layer. A method for producing a water- and oil-repellent plastic molded article having a coating layer, which comprises carrying out a catalytic reaction with a fluoroalkyl group-containing organosilane compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61282096A JPH0745586B2 (en) | 1986-11-28 | 1986-11-28 | Method for producing water- and oil-repellent plastic molding |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61282096A JPH0745586B2 (en) | 1986-11-28 | 1986-11-28 | Method for producing water- and oil-repellent plastic molding |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63135435A true JPS63135435A (en) | 1988-06-07 |
| JPH0745586B2 JPH0745586B2 (en) | 1995-05-17 |
Family
ID=17648069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61282096A Expired - Fee Related JPH0745586B2 (en) | 1986-11-28 | 1986-11-28 | Method for producing water- and oil-repellent plastic molding |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0745586B2 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02139726U (en) * | 1989-04-26 | 1990-11-21 | ||
| JPH04359031A (en) * | 1991-06-04 | 1992-12-11 | Matsushita Electric Ind Co Ltd | Water-and-oil repellent film |
| JPH0531441A (en) * | 1990-10-25 | 1993-02-09 | Matsushita Electric Ind Co Ltd | Fluorocarbon coating film and its production |
| EP1224983A2 (en) * | 1991-01-23 | 2002-07-24 | Matsushita Electric Industrial Co., Ltd. | Transparent substrate and method for preparing same |
| JP2011093964A (en) * | 2009-10-27 | 2011-05-12 | Shin-Etsu Chemical Co Ltd | Method for producing antifouling substrate and antifouling product |
| JP2011526536A (en) * | 2008-07-04 | 2011-10-13 | アーベーベー・リサーチ・リミテッド | Apparatus for electrostatically coating a workpiece and method for reducing its contamination |
| WO2013018518A1 (en) * | 2011-08-02 | 2013-02-07 | コニカミノルタアドバンストレイヤー株式会社 | Functional film |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09151357A (en) | 1995-11-28 | 1997-06-10 | Toray Dow Corning Silicone Co Ltd | Coating agent composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59115840A (en) * | 1982-12-24 | 1984-07-04 | 旭硝子株式会社 | Low reflectivity coating |
-
1986
- 1986-11-28 JP JP61282096A patent/JPH0745586B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59115840A (en) * | 1982-12-24 | 1984-07-04 | 旭硝子株式会社 | Low reflectivity coating |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02139726U (en) * | 1989-04-26 | 1990-11-21 | ||
| JPH0531441A (en) * | 1990-10-25 | 1993-02-09 | Matsushita Electric Ind Co Ltd | Fluorocarbon coating film and its production |
| EP1224983A2 (en) * | 1991-01-23 | 2002-07-24 | Matsushita Electric Industrial Co., Ltd. | Transparent substrate and method for preparing same |
| EP1224983A3 (en) * | 1991-01-23 | 2002-12-18 | Matsushita Electric Industrial Co., Ltd. | Transparent substrate and method for preparing same |
| JPH04359031A (en) * | 1991-06-04 | 1992-12-11 | Matsushita Electric Ind Co Ltd | Water-and-oil repellent film |
| JP2011526536A (en) * | 2008-07-04 | 2011-10-13 | アーベーベー・リサーチ・リミテッド | Apparatus for electrostatically coating a workpiece and method for reducing its contamination |
| JP2011093964A (en) * | 2009-10-27 | 2011-05-12 | Shin-Etsu Chemical Co Ltd | Method for producing antifouling substrate and antifouling product |
| WO2013018518A1 (en) * | 2011-08-02 | 2013-02-07 | コニカミノルタアドバンストレイヤー株式会社 | Functional film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0745586B2 (en) | 1995-05-17 |
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