TW201420695A - Coating agents for use in coating surface of vehicle - Google Patents
Coating agents for use in coating surface of vehicle Download PDFInfo
- Publication number
- TW201420695A TW201420695A TW102134435A TW102134435A TW201420695A TW 201420695 A TW201420695 A TW 201420695A TW 102134435 A TW102134435 A TW 102134435A TW 102134435 A TW102134435 A TW 102134435A TW 201420695 A TW201420695 A TW 201420695A
- Authority
- TW
- Taiwan
- Prior art keywords
- modified
- coating agent
- solvent
- fluorine
- group
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
Description
本發明係關於一種對汽車等之車輛，特別是對其車身等之車體，尤其是對其塗飾面的塗布劑。 The present invention relates to a vehicle for an automobile or the like, particularly a vehicle body such as a vehicle body thereof, particularly a coating agent for a coated surface thereof.
以往作為車體表面的塗布劑，常利用藉由將濕氣硬化性矽酮寡聚物作為主成分，並添加經有機官能基改性的矽酮油(silicone oil)而提升撥水性等種種特性的系統。 Conventionally, as a coating agent for the surface of a vehicle body, various properties such as water repellency are often utilized by using a moisture-curable fluorenone oligomer as a main component and adding an organic functional group-modified silicone oil. system.
又，已知有將作為車體表面的塗布劑之利用濕氣硬化反應的矽酮系的塗布劑、或利用使聚矽氮烷濕氣硬化的硬質膜、使用氟化合物的塗布劑形成於塗飾表面的方法。該等以往的塗布劑，根據顯示利用矽酮化合物的撥水性或利用氟化合物的撥油性、利用源自全氫聚矽氮烷的玻璃質被膜的親水性，可對處理面賦予光澤或防污性。 Further, an anthrone-based coating agent which is a moisture-curing reaction of a coating agent on the surface of a vehicle body, or a hard film which is obtained by moisture-curing polyazide or a coating agent using a fluorine compound is formed on the coating. Surface method. These conventional coating agents can impart gloss or antifouling to the treated surface by exhibiting the water repellency of the fluorenone compound or the oil repellency of the fluorine compound and the hydrophilicity of the vitreous film derived from the perhydropolyazane. Sex.
根據專利文獻1，提供一種作為表面處理劑為有用的全氟聚醚改性聚矽氮烷，其係為常溫硬化性且以無引體(primer)而於基材表面形成強固的被膜，該被膜經長時間可保持撥水撥油性、離型性等之良好的性能。 According to Patent Document 1, there is provided a perfluoropolyether-modified polyazide which is useful as a surface treatment agent, which is a room temperature hardenability and forms a strong film on a surface of a substrate without a primer. The film can maintain good performance such as water repellency and release property over a long period of time.
根據專利文獻2，揭示一種抗反射膜、以及在 支持基材上具有該抗反射膜的光學構件；為了提供具有耐污染性、易擦拭除去性、耐擦傷性、撥水性等之性能且包含長期持續該等性能之特定的含氟矽氮烷化合物之硬化物而成的抗反射膜，以及提供在支持基材上具有前述物並具有同樣性能的光學構件，其係為包含具有二氧化矽系無機層的單層結構或多層結構的抗反射層、與作為表面層所設置的抗污染層而成之抗反射膜，其特徵為：該抗污染層包含特定的含氟矽氮烷化合物的硬化物而成。 According to Patent Document 2, an antireflection film is disclosed, and Supporting an optical member having the antireflection film on a substrate; in order to provide a fluorine-containing sulfazene compound having properties such as stain resistance, easy wiping off, scratch resistance, water repellency, etc., and containing such properties for a long period of time An antireflection film made of a cured material, and an optical member having the foregoing properties and having the same properties on a support substrate, which is an antireflection layer comprising a single layer structure or a multilayer structure having a ceria-based inorganic layer. And an anti-reflection film formed as an anti-contamination layer provided as a surface layer, wherein the anti-contamination layer comprises a cured product of a specific fluorine-containing ceria compound.
根據專利文獻3，特定的含氟鈦矽氧烷化合物的撥水功效顯著優異，例如，可使水滴落下性極高的硬化皮膜在常溫輕易地形成。又，有揭示出該化合物容易溶解於一般的有機溶劑，可不使用氟系等之例外的溶劑而作為硬化被膜形成劑使用的優點。 According to Patent Document 3, the water-repellent effect of the specific fluorine-containing titanium oxyhalide compound is remarkably excellent, and for example, the hardened film having extremely high drop dripping property can be easily formed at normal temperature. In addition, it is revealed that the compound is easily dissolved in a general organic solvent, and it is possible to use it as a curing film forming agent without using a solvent other than a fluorine-based one.
又，最近也有人研究將特定的含氟矽氮烷化合物溶解於特定的溶劑，應用於車輛的塗飾表面，並使其發揮進一步的高撥水性或非常高的防污性能(專利文獻4)。 Further, recently, it has been studied to dissolve a specific fluorine-containing sulfazene compound in a specific solvent, and to apply it to a painted surface of a vehicle, and to exhibit further high water repellency or very high antifouling performance (Patent Document 4).
[專利文獻1]日本特開2010-43251號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-43251
[專利文獻2]日本特開2002-174702號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-174702
[專利文獻3]日本特開平6-271679號公報 [Patent Document 3] Japanese Patent Laid-Open No. Hei 6-271679
[專利文獻4]日本特願2012-050288 [Patent Document 4] Japan's Special Wish 2012-050288
該等車輛的塗飾表面用塗布劑，可活用各自的特徵，將各式各樣的性能賦予至車體表面，但僅組合矽酮系塗布劑在性能上有極限，需要與氟改性聚矽氮烷組合，而提供一種新穎的車輛之塗飾表面塗布劑。又，利用氟系化合物的塗布劑中，為了展現足夠的性能，需要氟烷基的長度，但，從PFOA(全氟辛酸)或PFOS(全氟辛烷磺酸鹽)問題的觀點而言，其使用被視為問題。 The coating agents for the finishing surfaces of these vehicles can utilize their respective characteristics and impart various properties to the surface of the vehicle body. However, only the combination of the anthrone-based coating agent has a limit in performance and needs to be modified with fluorine. The nitroxane combination provides a novel vehicle finish coating agent. Further, in the coating agent using a fluorine-based compound, the length of the fluoroalkyl group is required in order to exhibit sufficient performance, but it is used from the viewpoint of the problem of PFOA (perfluorooctanoic acid) or PFOS (perfluorooctane sulfonate). It is considered a problem.
本發明的課題，以如前述的事情為前提，係提供一種車輛之塗飾表面用塗布劑，藉由在將以往的矽酮烷氧寡聚物作為主成分的硬化被膜，添加氟改性聚矽氮烷，可賦予源自氟的高撥水性及撥油性。然後，由於該氟改性基為全氟聚醚基，所以不會有被PFOA或PFOS問題限制的情形。亦即，本發明為一種車輛之塗飾表面用塗布劑，其包含氟改性聚矽氮烷(a)、矽酮烷氧寡聚物(b)、硬化觸媒(c)、以及有機溶媒(d)。 In view of the above-mentioned problems, a coating agent for a coating surface of a vehicle is provided, and a fluorine-modified polyfluorene is added to a hardened film containing a conventional anthrone oxime alkoxy oligomer as a main component. The azane can impart high water repellency and oil repellency derived from fluorine. Then, since the fluorine-modified group is a perfluoropolyether group, there is no case where it is limited by the PFOA or PFOS problem. That is, the present invention relates to a coating agent for a finishing surface of a vehicle comprising a fluorine-modified polyazane (a), an anthrone alkoxysilane (b), a hardening catalyst (c), and an organic solvent ( d).
又，本發明的車輛之塗飾表面用塗布劑中，氟改性聚矽氮烷為下述通式表示的全氟聚醚改性聚矽氮烷，F(CxF2xO)mCyF2y-Q-Si(NH)1.5(式中，Q表示2價有機基，m為1以上的整數，x及y分別為1~3的整數)；在選自由六氟化間二甲苯(m-xylene hexafluoride)及氟系溶媒、二甲基聚矽氧烷、環狀矽氧烷、醇系溶媒、二醇系溶媒、丙酮、脂肪族烴、芳香族烴所組成的群組 中之1種或2種的溶媒中，以固體成分濃度計含有0.01~3質量份全氟聚醚改性聚矽氮烷為較佳。 Further, in the coating agent for a finishing surface of a vehicle of the present invention, the fluorine-modified polyazane is a perfluoropolyether-modified polyazane represented by the following formula, F(C x F 2x O) m C y F 2y -Q-Si(NH) 1.5 (wherein Q represents a divalent organic group, m is an integer of 1 or more, and x and y are each an integer of 1 to 3); and is selected from the group consisting of metaxylene hexafluoride ( 1 of a group consisting of a fluorine-based solvent, a dimethylpolysiloxane, a cyclic oxime, an alcohol solvent, a glycol solvent, acetone, an aliphatic hydrocarbon, and an aromatic hydrocarbon. Among the two types of solvents, it is preferred to contain 0.01 to 3 parts by mass of perfluoropolyether-modified polyoxazane as a solid concentration.
再者，本發明的車輛之塗飾表面用塗布劑中，可進一步包含有機改性矽酮油及/或矽烷偶合劑。 Further, the coating agent for a finishing surface of a vehicle of the present invention may further comprise an organic modified fluorenone oil and/or a decane coupling agent.
又，本發明的車輛之塗飾表面用塗布劑中，較理想為：該有機改性矽酮油在分子的末端具有甲醇基，該矽烷偶合劑具有異氰酸酯基或縮水甘油醚(glycidyl ether)基。 Further, in the coating agent for a finishing surface of a vehicle of the present invention, it is preferred that the organic modified fluorenone oil has a methanol group at a terminal of the molecule, and the decane coupling agent has an isocyanate group or a glycidyl ether group.
其次，本發明的車輛之塗飾表面用塗布劑中，可使該氟改性聚矽氮烷為1.0~50質量份，該矽酮烷氧寡聚物為3.0~15.0質量份，該觸媒為0.1~2.0質量份，該改性矽酮油為1.0~10.0質量份，該矽烷偶合劑為0.1~1.5質量份，其餘部分為該溶劑。 Next, in the coating agent for a finishing surface of a vehicle of the present invention, the fluorine-modified polyazide may be 1.0 to 50 parts by mass, and the anthrone oxyalkylene oligomer may be 3.0 to 15.0 parts by mass, and the catalyst is 0.1 to 2.0 parts by mass, the modified fluorenone oil is 1.0 to 10.0 parts by mass, and the decane coupling agent is 0.1 to 1.5 parts by mass, and the balance is the solvent.
又，本發明的車輛之塗飾表面用塗布劑中，該硬化觸媒為鋁系或鈦系，該溶劑為異烷烴系溶劑或是可在異烷烴系溶劑添加少量的矽酮系溶劑。 Further, in the coating agent for a finishing surface of a vehicle of the present invention, the curing catalyst is an aluminum-based or titanium-based solvent, and the solvent is an isoparaffin-based solvent or a small amount of an anthrone-based solvent may be added to the isoparaffin-based solvent.
關於本發明的車輛用塗布劑而言，實施例所示的塗布劑相較於比較例的塗布劑，顯示非常優異的撥水性、撥油性。又，藉由以本塗布劑保護車的車身表面，也可發揮非常優異的防污功效。不僅製品設計之幅度擴展，且對於車輛車體之塗飾表面的實際使用也非常有用。 In the coating agent for vehicles of the present invention, the coating agent shown in the examples showed very excellent water repellency and oil repellency as compared with the coating agent of the comparative example. Moreover, by protecting the body surface of the vehicle with the present coating agent, it is possible to exhibit an excellent antifouling effect. Not only is the range of product design extended, but it is also very useful for the practical use of the painted surface of the vehicle body.
本發明所使用的氟改性矽氮烷，已在市面上販售，尤能適用下述通式表示的全氟聚醚改性聚矽氮烷(以下為氟改性矽氮烷)。 The fluorine-modified decazane used in the present invention is commercially available, and a perfluoropolyether-modified polyazide (hereinafter referred to as a fluorine-modified decazane) represented by the following formula can be suitably used.
F(CxF2xO)mCyF2y-Q-Si(NH)1.5(式中，Q表示2價有機基，m為1以上的整數，x及y分別為1~3的整數。) F(C x F 2x O) m C y F 2y -Q-Si(NH) 1.5 (wherein Q represents a divalent organic group, m is an integer of 1 or more, and x and y are each an integer of 1-3. )
本發明所使用的全氟聚醚改性聚矽氮烷，已知係溶解於六氟化間二甲苯。本發明者發現：可溶解於包含選自由六氟化間二甲苯及氫氟醚、氟碳等之氟系溶媒、二甲基聚矽氧烷、環狀矽氧烷、乙醇、異丙醇等之醇系溶媒、二乙二醇二甲醚、丙二醇單甲醚乙酸酯等之二醇系溶媒、丙酮、脂肪族烴、芳香族烴所組成的群組中之1種或2種的溶媒而成之混合溶媒，而在塗布被膜上形成全氟聚醚改性被膜。 The perfluoropolyether-modified polyoxazane used in the present invention is known to be dissolved in meta-xylene hexafluoride. The present inventors have found that it is soluble in a fluorine-containing solvent selected from the group consisting of m-hexafluorobenzene, hydrofluoroether, fluorocarbon, dimethylpolysiloxane, cyclic oxirane, ethanol, isopropyl alcohol, and the like. One or two kinds of solvents of a group consisting of a glycol-based solvent such as an alcohol-based solvent, diethylene glycol dimethyl ether, and propylene glycol monomethyl ether acetate, and acetone, an aliphatic hydrocarbon, or an aromatic hydrocarbon. A mixed solvent is formed to form a perfluoropolyether modified film on the coated film.
作為本發明所使用的全氟聚醚改性聚矽氮烷的良溶媒，可舉出六氟化間二甲苯或氫氟醚、氟碳等之氟系溶媒；作為本發明所使用的全氟聚醚改性聚矽氮烷的不良溶媒，可舉出脂肪族或芳香族烴等之溶媒。 The good solvent of the perfluoropolyether-modified polyazane used in the present invention may, for example, be a fluorine-based solvent such as hexafluoride, hydrofluoroether or fluorocarbon; or a perfluorocarbon used in the present invention. The poor solvent of the polyether modified polyazane may be a solvent such as an aliphatic or aromatic hydrocarbon.
再者，已知有氟改性矽氮烷的六氟化間二甲苯稀釋溶液。 Further, a diluted solution of hexafluoride xylene in a fluorine-modified decazane is known.
使用：以六氟化間二甲苯將氟改性矽氮烷稀釋成其固體成分濃度成為3%而成的溶液。 Use: A solution obtained by diluting a fluorine-modified decazane with hexafluoro-m-xylene to a solid concentration of 3%.
又，作為本發明中可使用的矽酮烷氧寡聚物 ，係為分子末端為烷氧矽基的低分子矽酮樹脂，可舉出KC-89S(信越化學工業製)、KR-500(信越化學工業製)、BS-290(旭化成wacker silicone製)等。 Further, as an anthrone alkoxy oligopolymer which can be used in the present invention The low molecular weight fluorenone resin whose molecular terminal is an alkoxy fluorenyl group, such as KC-89S (made by Shin-Etsu Chemical Co., Ltd.), KR-500 (made by Shin-Etsu Chemical Co., Ltd.), BS-290 (made by Asahi Kasei Wacker silicone), etc. .
又，作為本發明中可使用的硬化觸媒，只要是可促進矽酮烷氧寡聚物的硬化反應者即可，可舉出酸類、胺類、金屬類，惟，特別是鋁系(DX-9740；信越化學工業製)或鈦系(D-25；信越化學工業製)的有機金屬化合物較佳。 Further, the curing catalyst which can be used in the present invention may be any one which can promote the curing reaction of the fluorenone alkoxy oligopolymer, and examples thereof include acids, amines, and metals, and particularly aluminum (DX). -9740; manufactured by Shin-Etsu Chemical Co., Ltd.) or an organometallic compound of a titanium system (D-25; manufactured by Shin-Etsu Chemical Co., Ltd.) is preferred.
作為本發明中可使用之具有甲醇改性基的矽酮油，分子的單側末端上具有甲醇基之下式所示之在常溫為液體狀者，可舉出在X-22-170BX(信越化學工業製)、X-22-170DX(信越化學工業製)等(下式)。 The fluorenone oil having a methanol-modified group which can be used in the present invention has a methanol group on one side of the molecule and is liquid at room temperature as shown in the following formula, and is exemplified in X-22-170BX (Shin-Etsu Chemical industry), X-22-170DX (manufactured by Shin-Etsu Chemical Co., Ltd.), etc. (the following formula).
又，可使用具有二甲醇改性基代替甲醇改性基的矽酮油，但作為如前述之具有二甲醇改性基的矽酮油，分子的單側末端上具有二甲醇基之下式所示之在常溫為液 體狀者，可舉出X-22-176DX(信越化學工業製)、X-22-176F等。 Further, an anthrone oil having a dimethanol-modified group instead of a methanol-modified group may be used, but as the above-described anthrone oil having a dimethanol-modified group, the molecule has a dimethanol group on one side of the terminal. Shown at room temperature for liquid Examples of the shape include X-22-176DX (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-176F, and the like.
通常矽烷偶合劑係由有機物與矽構成的化合物，且在分子中具有2種以上之不同的反應基，因此通常可發揮可將非常難鍵結的有機材料與無機材料鍵結之作為中介者的作用；惟，作為本發明中可使用的矽烷偶合劑，無論是何者均佳，但較佳使用具有末端異氰酸酯的偶合劑或具有末端縮水甘油醚基的偶合劑。 In general, a decane coupling agent is a compound composed of an organic substance and hydrazine, and has two or more kinds of reactive groups in a molecule, and therefore generally functions as an intermediary capable of bonding an organic material which is very difficult to bond with an inorganic material. However, as the decane coupling agent which can be used in the present invention, any one of them is preferable, but a coupling agent having a terminal isocyanate or a coupling agent having a terminal glycidyl ether group is preferably used.
又，作為本發明中可使用的溶劑，可舉出正烷烴或異烷烴系的石油系溶劑等。 In addition, examples of the solvent which can be used in the present invention include n-alkane or isoparaffin-based petroleum solvents.
尤其較佳使用在異烷烴系溶劑中添加少量的矽酮系溶劑者。 It is particularly preferable to use a small amount of an anthrone-based solvent added to an isoparaffin-based solvent.
以下表示具體例，但本發明並沒有限定於該等。 Specific examples are shown below, but the present invention is not limited to these.
得到包含下述而成的塗布劑：氟改性聚矽氮 烷液(固體成分濃度3%六氟化間二甲苯)50.0質量份、KR-400(鋁系觸媒DX-9740 10%摻合品；信越化學工業製)10.0質量份、IPsolvent1620(出光興產製)90.0質量份。 A coating agent comprising the following: a fluorine-modified polyfluorene nitrogen is obtained Alkaline liquid (solid content concentration 3% hexafluoride meta-xylene) 50.0 parts by mass, KR-400 (aluminum-based catalyst DX-9740 10% blended product; Shin-Etsu Chemical Co., Ltd.) 10.0 parts by mass, IPsolvent 1620 (Ishigaki Kogyo Co., Ltd.) System) 90.0 parts by mass.
得到包含下述而成的塗布劑：氟改性聚矽氮烷液1.0%、KR-500(信越化學工業製)5.0%、BS-290(旭化成wacker silicone製)5.0%、DX-9740(鋁系，信越化學工業製)1.0%、D-25(鈦系，信越化學工業製)0.5%、X-22-176DX(單末端二甲醇改性，信越化學工業製)2.0%、KBE-9007(3-異氰酸酯丙基三乙氧基矽烷(3-isocyanatopropyltriethoxysilane)，信越化學工業製)0.1%、KF-96L-1CS(信越化學工業製)5.0%、IPsolvent1620(出光興產製)81.4%。 A coating agent comprising the following: a fluorine-modified polyxazane solution 1.0%, KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, BS-290 (made by Asahi Kasei wacker silicone) 5.0%, and DX-9740 (aluminum) were obtained. Department, Shin-Etsu Chemical Co., Ltd.) 1.0%, D-25 (titanium system, Shin-Etsu Chemical Co., Ltd.) 0.5%, X-22-176DX (single-end dimethanol modification, Shin-Etsu Chemical Co., Ltd.) 2.0%, KBE-9007 ( 3-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.1%, KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, and IPsolvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.) 81.4%.
得到包含下述而成的塗布劑：氟改性聚矽氮烷液5.0%、KR-500(信越化學工業製)5.0%、BS-290(旭化成wacker silicone製)5.0%、DX-9740(鋁系，信越化學工業製)1.0%、D-25(鈦系，信越化學工業製)0.5%、X-22-176DX(單末端二甲醇改性，信越化學工業製)5.0%、KBE-9007(3-異氰酸酯丙基三乙氧基矽烷，信越化學工業製)0.5%、(F)KF-96L-1CS(信越化學工業製)5.0%、IPsolvent1620(出光興產製)78.0%。 A coating agent comprising the following: a fluorine-modified polyazoxide solution of 5.0%, KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, BS-290 (made by Asahi Kasei wacker silicone) of 5.0%, and DX-9740 (aluminum) were obtained. Department, Shin-Etsu Chemical Co., Ltd.) 1.0%, D-25 (titanium system, Shin-Etsu Chemical Co., Ltd.) 0.5%, X-22-176DX (single-end dimethanol modification, Shin-Etsu Chemical Co., Ltd.) 5.0%, KBE-9007 ( 3-isocyanate propyl triethoxy decane, manufactured by Shin-Etsu Chemical Co., Ltd., 0.5%, (F) KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, and IPsolvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.) 78.0%.
得到包含下述而成的塗布劑：氟改性聚矽氮烷液20.0%、BS-290(旭化成wacker silicone製)10.0%、 (C)DX-9740(鋁系，信越化學工業製)0.5%、D-25(鈦系，信越化學工業製)1.0%、(D)X-22-170BX(單末端甲醇改性，信越化學工業製)5.0%、(E)KBE-9007(3-異氰酸酯丙基三乙氧基矽烷，信越化學工業製)0.5%、(F)KF-96L-1CS(信越化學工業製)5.0%、IPsolvent1620(出光興產製)78.0%。 A coating agent comprising the following: a fluorine-modified polyazane liquid 20.0%, and a BS-290 (made by Asahi Kasei wacker silicone) 10.0% were obtained. (C) DX-9740 (aluminum system, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5%, D-25 (titanium system, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0%, (D) X-22-170BX (single-end methanol modification, Shin-Etsu Chemical Co., Ltd.) Industrially produced) 5.0%, (E) KBE-9007 (3-isocyanate propyl triethoxy decane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5%, (F) KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, IPsolvent 1620 (Idemitsu Kosan) 78.0%.
得到包含下述而成的塗布劑：氟改性聚矽氮烷液100.0%、KR-500(信越化學工業製)5.0%、BS-290(旭化成wacker silicone製)5.0%、(C)DX-9740(鋁系，信越化學工業製)1.0%、D-25(鈦系，信越化學工業製)0.5%、(D)X-22-160AS(雙末端甲醇改性，信越化學工業製)5.0%、(E)KBM-403(3-環氧丙氧基丙基三甲氧基矽烷，信越化學工業製)0.5%、(F)KF-96L-1CS(信越化學工業製)5.0%、IPsolvent1620(出光興產製)78.0%。 A coating agent comprising the following: a fluorine-modified polyxazane solution 100.0%, KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, BS-290 (made by Asahi Kasei wacker silicone) 5.0%, and (C) DX- were obtained. 9740 (aluminum system, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0%, D-25 (titanium system, Shin-Etsu Chemical Co., Ltd.) 0.5%, (D) X-22-160AS (double-end methanol modification, Shin-Etsu Chemical Co., Ltd.) 5.0% (E) KBM-403 (3-glycidoxypropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5%, (F) KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, IPsolvent 1620 (lighting) Production system) 78.0%.
(比較例1) (Comparative Example 1)
得到包含下述而成的塗布劑：(B)KR-400(鋁系觸媒DX-9740 10%摻合品；信越化學工業製)10.0%、(F)IPsolvent1620(出光興產製)90.0%。 A coating agent comprising the following was obtained: (B) KR-400 (aluminum-based catalyst DX-9740 10% blended product; manufactured by Shin-Etsu Chemical Co., Ltd.) 10.0%, (F) IPsolvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.) 90.0% .
(比較例2) (Comparative Example 2)
得到包含下述而成的塗布劑：(B)KR-400(鋁系觸媒DX-9740 10%摻合品；信越化學工業製)10.0%、(C)D-25(鈦系，信越化學工業製)0.5%、(D)X-22-176DX(單末端二甲醇改性，信越化學工業製)2.0%、(F)KF-96L-1CS(信越化學工業製)5.0%、IPsolvent1620(出光興產製)82.5%。 A coating agent comprising the following was obtained: (B) KR-400 (aluminum-based catalyst DX-9740 10% blended product; manufactured by Shin-Etsu Chemical Co., Ltd.) 10.0%, (C) D-25 (titanium system, Shin-Etsu Chemical Co., Ltd.) Industrial) 0.5%, (D) X-22-176DX (single-end dimethanol modification, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.0%, (F) KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, IPsolvent 1620 (lighting) Industrial production system) 82.5%.
(比較例3) (Comparative Example 3)
得到包含下述而成的塗布劑：(B)KR-500(信越化學工業製)10.0%、(C)DX-9740(鋁系，信越化學工業製)1.0%、D-25(鈦系，信越化學工業製)0.5%、(D)X-22-160AS(雙末端甲醇改性，信越化學工業製)2.0%、(F)KF-96L-1CS(信越化學工業製)5.0%(F)IPsolvent1620(出光興產製)81.5%。 A coating agent containing the following was obtained: (B) KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd.) 10.0%, (C) DX-9740 (aluminum-based, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0%, D-25 (titanium-based, Shin-Etsu Chemical Co., Ltd.) 0.5%, (D) X-22-160AS (double-end methanol modification, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.0%, (F) KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0% (F) IPsolvent1620 (Idemitsu Kosan) 81.5%.
※實施例及比較例1、2的DX-9740係表示KR-400所包含的量。 * The DX-9740 of the examples and the comparative examples 1 and 2 shows the quantity contained in the KR-400.
(A)氟改性聚矽氮烷液、(B)矽酮烷氧寡聚物、(C)觸媒、(D)改性矽酮、(E)矽烷偶合劑、(F)溶媒 (A) fluorine-modified polyazide liquid, (B) anthrone alkoxy oligomer, (C) catalyst, (D) modified anthrone, (E) decane coupling agent, (F) solvent
關於各塗布液，係以如下述所示的方法對基材處理；關於各評價項目，係以下述所示的方法與結果判定，歸納於表1。 Each of the coating liquids was treated with a substrate as described below, and each evaluation item was determined by the method and results described below, and is summarized in Table 1.
在以將包含丙烯酸三聚氰胺系樹脂而成的汽車用塗料作為底塗層(base coat)與表塗層(top coat)的積層形態焙燒並塗飾而製作的塗飾板表面，使用含浸各塗布液的布均勻地處理。處理後在常溫乾燥5分鐘，以新的布擦拭，使其無不均勻而收尾，進一步於常溫下乾燥1週。 A surface of a coated panel produced by baking and coating a coating material for an automobile containing a melamine-based acrylic resin as a base coat and a top coat, using a cloth impregnated with each coating liquid Process evenly. After the treatment, it was dried at room temperature for 5 minutes, wiped with a new cloth, and it was finished without unevenness, and further dried at normal temperature for 1 week.
(撥水性) (water repellent)
將塗布處理表面之斥水的狀態，使用接觸角計測量水的接觸角，並如下述進行評價。 The state of water repellent of the treated surface was measured, and the contact angle of water was measured using a contact angle meter and evaluated as follows.
◎：100°~ ◎: 100°~
○：95°~99° ○: 95°~99°
△：90°~94° △: 90°~94°
×：~89° ×:~89°
(撥油性) (oil oil)
將塗布處理表面之斥油的狀態，使用接觸角計測量油(正十二烷)的接觸角，並如下述進行評價。 The state of the oil-repellent surface of the treated surface was measured, and the contact angle of the oil (n-dodecane) was measured using a contact angle meter and evaluated as follows.
◎：30°~ ◎: 30°~
○：25°~29° ○: 25°~29°
△：20°~24° △: 20 ° ~ 24 °
×：~19° ×:~19°
(滑動性) (slidability)
藉由以市售的毛巾擦拭塗布處理表面，確認處理表面的滑動性，並如下述進行評價。 The surface of the treated surface was wiped by wiping with a commercially available towel, and the slidability of the treated surface was confirmed and evaluated as follows.
◎：表面光滑且很滑 ◎: The surface is smooth and very slippery
○：光滑感有些下降但還是滑 ○: The smoothness is somewhat reduced but still slippery
△：沒什麼光滑感且不易滑動 △: No smooth feeling and not easy to slide
×：滑動差且卡住 ×: Sliding is poor and stuck
(耐擦傷性) (scratch resistance)
藉由以市售的毛巾擦拭塗布處理表面，確認處理表面的耐擦傷性，並如下述進行評價。 The surface of the treated surface was wiped with a commercially available towel, and the scratch resistance of the treated surface was confirmed and evaluated as follows.
◎：傷痕幾乎不明顯 ◎: the scar is almost inconspicuous
○：有些許傷痕但不太明顯 ○: Some scars but not too obvious
△：傷痕明顯 △: the scar is obvious
×：有很多傷痕 ×: There are many scars
(耐久性評價) (durability evaluation)
參考「JIS K2396 9.12撥水持續性的評價」確認耐久性。清洗液係利用碳酸鈉與十二苯磺酸鈉製備(pH11)，將在500g的荷重繞設清潔布(micro cloth)，以清洗機試驗機來回清洗500次後的撥水性、撥油性之耐久性與初期性能評價同樣地進行確認。 Refer to "JIS K2396 9.12 Evaluation of Water Retention Sustainability" to confirm durability. The cleaning solution is prepared by using sodium carbonate and sodium dodecyl sulfonate (pH 11), and the water-repellent and oil-repellent durability of the cleaning machine is carried out after being washed 500 times with a cleaning machine at a load of 500 g. The performance was confirmed in the same manner as the initial performance evaluation.
(撥水耐久性) (water retention durability)
將塗布處理表面之斥水的狀態，使用接觸角計測量水的接觸角，並如下述進行評價。 The state of water repellent of the treated surface was measured, and the contact angle of water was measured using a contact angle meter and evaluated as follows.
◎：100°~ ◎: 100°~
○：95°~99° ○: 95°~99°
△：90°~94° △: 90°~94°
×：~89° ×:~89°
(撥油耐久性) (oil durability)
將塗布處理表面之斥油的狀態，使用接觸角計測量油(正十二烷)的接觸角，並如下述進行評價。 The state of the oil-repellent surface of the treated surface was measured, and the contact angle of the oil (n-dodecane) was measured using a contact angle meter and evaluated as follows.
◎：30°~ ◎: 30°~
○：25°~29° ○: 25°~29°
△：20°~24° △: 20 ° ~ 24 °
×：~19° ×:~19°
本發明的車輛之塗飾表面用塗布劑，係顯示非常優異的撥水性、撥油性與其功效之持續性，甚至也發揮非常優異的防污功效。又，不僅可活化售後服務，而且對車輛車體之塗飾本身帶來技術革新的可能性也高。 The coating agent for a finishing surface of a vehicle of the present invention exhibits excellent water repellency, oil repellency and durability of its efficacy, and even exhibits an excellent antifouling effect. Moreover, not only can the after-sales service be activated, but also the possibility of bringing technological innovation to the painting of the vehicle body itself is high.
Claims (6)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012211872A JP6074655B2 (en) | 2012-09-26 | 2012-09-26 | Coating agent for painted surfaces of vehicles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201420695A true TW201420695A (en) | 2014-06-01 |
| TWI577759B TWI577759B (en) | 2017-04-11 |
Family
ID=50305051
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102134435A TWI577759B (en) | 2012-09-26 | 2013-09-25 | Coating agents for use in coating surface of vehicle |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6074655B2 (en) |
| KR (1) | KR101801421B1 (en) |
| CN (1) | CN103666253A (en) |
| TW (1) | TWI577759B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852234A (en) * | 2018-10-09 | 2021-05-28 | 刘鹏 | Preparation method of waterproof weather-resistant bi-component exterior wall latex paint |
Families Citing this family (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5768805B2 (en) * | 2012-11-26 | 2015-08-26 | 信越化学工業株式会社 | Perfluoropolyether-modified polysilazane, method for producing the same, surface treatment agent, and article treated with the surface treatment agent |
| JP2015183014A (en) * | 2014-03-20 | 2015-10-22 | 株式会社ソフト９９コーポレーション | coating agent |
| CN104893571A (en) * | 2015-05-22 | 2015-09-09 | 上海伯瑟瑞新材料科技有限公司 | Inorganic flexible crystal plating material with strong water skiing property for automobile coating and using method of inorganic flexible crystal plating material |
| CN105385349B (en) * | 2015-12-10 | 2018-08-31 | 广州弘海化工科技有限公司 | Hydrophobic antifouling organopolysilazane coating of one kind and its preparation method and application |
| CN105542658B (en) * | 2015-12-10 | 2017-12-26 | 广州弘海化工科技有限公司 | A kind of antifouling anti-graffiti organopolysilazane coating and its preparation method and application |
| KR102492582B1 (en) * | 2016-12-30 | 2023-01-27 | 주식회사 동진쎄미켐 | Coating composition for antiglare and antiglare substrate comprising the same |
| CN107236454A (en) * | 2017-07-21 | 2017-10-10 | 南通天驰环保科技有限公司 | A kind of vehicle glass rainy day expelling water agent of long-acting wear resistant and its preparation method and application |
| EP3674375A4 (en) | 2017-08-22 | 2020-10-28 | Osaka Gas Chemicals Co., Ltd. | Curable composition and use of same |
| CN111465666A (en) * | 2017-12-26 | 2020-07-28 | 三键有限公司 | Coating film-forming composition |
| CN108329480B (en) * | 2018-02-27 | 2020-12-25 | 广州弘海化工科技有限公司 | Modified polysilazane prepolymer, modified polysilazane coating, and method of using same |
| JP6981532B2 (en) * | 2018-03-14 | 2021-12-15 | 信越化学工業株式会社 | Fluorine-containing coating agent compositions, surface treatment agents and articles |
| JP6930475B2 (en) * | 2018-03-30 | 2021-09-01 | 信越化学工業株式会社 | Polysilazane composition, as well as substrates and multilayers coated with it |
| CN108727979B (en) * | 2018-06-26 | 2021-05-07 | 广东美的厨房电器制造有限公司 | Coating composition and coating material and coating layer and silicon oxide coating layer and article having the coating layer and method for forming coating layer on substrate surface |
| CN109337544A (en) * | 2018-09-18 | 2019-02-15 | 深圳市派旗纳米技术有限公司 | PCBA board waterproof, moisture-proof, corrosion resistant nano coating, preparation method and its construction method |
| KR102216046B1 (en) * | 2019-04-04 | 2021-02-16 | 주식회사 기술과창조 | The coating method of anti-fouling hydrophobic coating solution |
| CN114341277A (en) * | 2019-09-10 | 2022-04-12 | 汉高股份有限及两合公司 | Coating composition |
| KR102348386B1 (en) | 2020-01-05 | 2022-01-06 | 황영민 | Coating Composition With Good Printabiity And Coating Film Using The Same |
| KR102348370B1 (en) | 2020-01-05 | 2022-01-06 | 황영민 | Coating Composition With Good Chemical Resistance And Coating Film Using The Same |
| KR102155987B1 (en) | 2020-03-02 | 2020-09-14 | 박시현 | Uv curing type polysilazane coating composition for vehicle and coating method using same |
| TWI730741B (en) * | 2020-04-29 | 2021-06-11 | 宗揚科技有限公司 | Car body coating method and coating structure |
| KR102414240B1 (en) * | 2020-04-29 | 2022-06-29 | 주식회사 디어스엠 | Mechanical glass film coating method |
| CN111607323A (en) * | 2020-07-01 | 2020-09-01 | 广州希森美克新材料科技股份有限公司 | Easy-to-clean anti-graffiti nano coating for automobile paint surface and construction process |
| CN115595064A (en) * | 2022-11-02 | 2023-01-13 | 郑州市超前涂料有限公司（Cn） | Natural self-cleaning antifouling paint and preparation method thereof |
| CN116606594A (en) * | 2023-06-06 | 2023-08-18 | 广东致格纳米科技有限公司 | Energy-saving ceramic coating slurry and preparation method thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05311121A (en) * | 1992-05-14 | 1993-11-22 | Shin Etsu Chem Co Ltd | Coating film forming agent composition |
| JPH11333987A (en) * | 1998-05-22 | 1999-12-07 | Asahi Glass Co Ltd | Transparent coated molding and manufacture thereof |
| TW555825B (en) * | 2001-01-31 | 2003-10-01 | Willson Co Ltd | Two-pack protective polishing agent for coating surface |
| MXPA05009578A (en) * | 2003-03-07 | 2005-11-17 | Henkel Corp | Curable coating compositions. |
| JP2006143970A (en) * | 2004-11-24 | 2006-06-08 | Soft99 Corporation | Colored coating composition |
| JP4698541B2 (en) * | 2006-09-22 | 2011-06-08 | 株式会社ソフト９９コーポレーション | Vehicle coating agent |
| JP4946400B2 (en) * | 2006-12-01 | 2012-06-06 | セイコーエプソン株式会社 | Ink for inkjet recording |
| DE102007013262A1 (en) * | 2007-03-15 | 2008-09-18 | Basf Coatings Ag | Coating compositions containing adducts with silane functionality and highly scratch-resistant coatings produced therefrom with improved crack resistance |
| JP2010013523A (en) * | 2008-07-02 | 2010-01-21 | Soft99 Corporation | Method and coating composition for recovering transparency of transparent resin member |
| JP2010043251A (en) * | 2008-07-17 | 2010-02-25 | Shin-Etsu Chemical Co Ltd | Perfluoropolyether-modified polysilazane and surface treatment agent using the same |
| JP5679540B2 (en) * | 2009-02-28 | 2015-03-04 | 神戸合成株式会社 | Surface water-repellent protective agent for exterior surfaces |
| JP2011052202A (en) * | 2009-08-07 | 2011-03-17 | Cci Corp | Coating composition, and method for producing the same |
| JP5567415B2 (en) * | 2010-07-07 | 2014-08-06 | 菊水化学工業株式会社 | Coating agent composition |
| KR101139571B1 (en) * | 2011-10-18 | 2012-04-27 | 김진수 | Coating agent for protecting a painting of vehicle |
-
2012
- 2012-09-26 JP JP2012211872A patent/JP6074655B2/en active Active
-
2013
- 2013-07-09 CN CN201310285590.2A patent/CN103666253A/en active Pending
- 2013-09-05 KR KR1020130106551A patent/KR101801421B1/en active IP Right Grant
- 2013-09-25 TW TW102134435A patent/TWI577759B/en active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112852234A (en) * | 2018-10-09 | 2021-05-28 | 刘鹏 | Preparation method of waterproof weather-resistant bi-component exterior wall latex paint |
| CN112852234B (en) * | 2018-10-09 | 2022-04-05 | 揭阳市鑫炜建材科技实业有限公司 | Preparation method of waterproof weather-resistant bi-component exterior wall latex paint |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20140040634A (en) | 2014-04-03 |
| JP2014065814A (en) | 2014-04-17 |
| JP6074655B2 (en) | 2017-02-08 |
| KR101801421B1 (en) | 2017-11-24 |
| TWI577759B (en) | 2017-04-11 |
| CN103666253A (en) | 2014-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI577759B (en) | Coating agents for use in coating surface of vehicle | |
| US6592659B1 (en) | Compositions for aqueous delivery of fluorinated silanes | |
| CN107109128B (en) | Water-and oil-repellent coating composition and transparent coating film | |
| JP6073353B2 (en) | Fluorinated coatings containing lubricating additives | |
| TWI558678B (en) | Oleophobic coatings | |
| TW201605992A (en) | Fluorochemical coating composition and article treated therewith | |
| CN108368379A (en) | Coating agent composition | |
| JP5631640B2 (en) | Anti-fogging agent composition | |
| TWI762582B (en) | Hybrid composition, coating and method for producing the same | |
| JP2009138063A (en) | Water-repellent surface protective agent for exterior surface | |
| JP2011207924A (en) | Antifouling coating and product coated therewith | |
| JP6928849B2 (en) | Curable composition | |
| JP6036132B2 (en) | Substrate with water repellent film and article for transportation equipment | |
| JP2002121286A (en) | Fluorine-containing organosilicon compound, water- repelling composition containing the same, and surface- treated base and method for producing the same | |
| TWI577757B (en) | Coating agents for use in coating surface of vehicle body | |
| JP6996898B2 (en) | Composition | |
| JP2013185038A (en) | Coating agent for coated surface of vehicle body | |
| CN114269869B (en) | Compositions comprising polyorganosiloxane and amino-functional silane and methods of use thereof | |
| CN114402048B (en) | Coating composition and article having coating | |
| JP2023079531A (en) | Fluoropolyether-containing polysilazane composition, and cured film thereof | |
| JP2023038975A (en) | Polysilazane composition and cured film thereof | |
| JP2024004092A (en) | Coating agent composition for scratch-resistant film formation, cured film, and scratch-resistant coating film | |
| WO2019087831A1 (en) | Production method for fluorinated ether compound, and production method for articles | |
| JP2017066205A (en) | Water-repellent coating composition |