JP2014065814A - Coating agent for coating surface of vehicle - Google Patents

Coating agent for coating surface of vehicle Download PDF

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JP2014065814A
JP2014065814A JP2012211872A JP2012211872A JP2014065814A JP 2014065814 A JP2014065814 A JP 2014065814A JP 2012211872 A JP2012211872 A JP 2012211872A JP 2012211872 A JP2012211872 A JP 2012211872A JP 2014065814 A JP2014065814 A JP 2014065814A
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coating agent
fluorine
modified
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JP6074655B2 (en
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Daiki Takashima
大樹 高島
Katsuhisa Takishita
勝久 滝下
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Ishihara Chemical Co Ltd
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Ishihara Chemical Co Ltd
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Priority to KR1020130106551A priority patent/KR101801421B1/en
Priority to TW102134435A priority patent/TWI577759B/en
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    • 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

Abstract

PROBLEM TO BE SOLVED: To provide a new coating agent for a coating surface of a vehicle by combining a silicone-based coating agent with fluorine-modified polysilazane.SOLUTION: The coating agent for a coating surface of a vehicle comprises: fluorine-modified polysilazane (A); a silicone alkoxy oligomer (B); a curing catalyst (C); and an organic solvent (D).

Description

自動車等の車両、特にそのボディ等の車体、中でもその塗装面へのコーティング剤に関するものである。   The present invention relates to a coating agent for a vehicle such as an automobile, particularly a vehicle body such as a body thereof, particularly a painted surface thereof.

従来、車体表面のコーティング剤として、湿気硬化性シリコーンオリゴマーを主成分とし、有機官能基で変性されたシリコーンオイルを加えることで、撥水性など種々の性能を向上させた系がよく利用されている。
また、車体表面のコーティング剤として、湿気硬化反応を利用したシリコーン系のコーティング剤や、ポリシラザンを湿気硬化させることによる硬質膜、フッ素化合物を用いたコーティング剤を塗装表面に形成させる方法が知られている。これら従来のコーティング剤は、シリコーン化合物による撥水性やフッ素化合物による撥油性、パーヒドロポリシラザンに由来するガラス質被膜による親水性を示すことにより、処理面に優れたツヤや防汚性を付与することが出来る。 Conventionally, as a coating agent for the surface of a vehicle body, a system in which various properties such as water repellency are improved by adding a silicone oil mainly composed of a moisture curable silicone oligomer and modified with an organic functional group is often used. .
In addition, as a coating agent on the surface of a vehicle body, a silicone-based coating agent utilizing a moisture curing reaction, a hard film obtained by moisture curing polysilazane, and a method of forming a coating agent using a fluorine compound on a painted surface are known. Yes. These conventional coating agents impart excellent gloss and antifouling properties to the treated surface by exhibiting water repellency with a silicone compound, oil repellency with a fluorine compound, and hydrophilicity with a glassy coating derived from perhydropolysilazane. I can do it.

特許文献１によれば、常温硬化性で、プライマーなしで基材表面に強固な被膜を形成し、該被膜は撥水撥油性、離型性等の良好な性能を長期間にわたって保持する表面処理剤として有用なパーフルオロポリエーテル変性ポリシラザンを提供されている。   According to Patent Document 1, a surface treatment that cures at room temperature and forms a strong film on a substrate surface without a primer, and the film retains good performance such as water and oil repellency and releasability over a long period of time. Perfluoropolyether-modified polysilazanes useful as agents are provided.

特許文献２によれば、耐汚染性、易拭取り除去性、耐擦傷性、撥水性などの性能を有し、これらの性能が長期に持続する特定の含フッ素シラザン化合物の硬化物からなる反射防止膜を提供すること、及びこれを支持基材上に有し、同様の性能を有する光学部材を提供するために、二酸化ケイ素系無機層を有する単層構造又は複層構造の反射防止層と、表面層として設けられた汚染防止層とからなる反射防止膜であって、前記汚染防止層が特定の含フッ素シラザン化合物の硬化物からなることを特徴とする反射防止膜、及びこの反射防止膜を支持基材上に有する光学部材が、開示されている。   According to Patent Document 2, a reflection made of a cured product of a specific fluorine-containing silazane compound having performances such as contamination resistance, easy wiping removal property, scratch resistance, and water repellency, and these performances last for a long time. In order to provide an antireflection film, and to provide an optical member having the same on a supporting substrate and having the same performance, an antireflection layer having a single-layer structure or a multi-layer structure having a silicon dioxide-based inorganic layer; An antireflection film comprising a contamination prevention layer provided as a surface layer, wherein the contamination prevention layer comprises a cured product of a specific fluorine-containing silazane compound, and the antireflection film An optical member having a substrate on a support substrate is disclosed.

特許文献３によれば、特定の含フッ素チタノシロキサン化合物の撥水効果が著しく優れ、例えば水滴の落下性が極めて高い硬化皮膜を、常温で容易に形成することが可能となる。またこの化合物は、通常の有機溶剤に容易に溶解し、フッ素系等の格別の溶剤を用いずに硬化被膜形成剤として使用することができる点が開示されている。
また、最近では、特定の含フッ素シラザン化合物を特定の溶剤に溶解して、車両の塗装表面に適用し、格段に高い撥水性や非常に高い防汚性能を発揮させることも研究されている（特許文献４）。 According to Patent Document 3, a specific fluorine-containing titanosiloxane compound has a water repellent effect that is remarkably excellent. For example, a cured film having extremely high water drop dropping properties can be easily formed at room temperature. Further, it is disclosed that this compound can be easily dissolved in a normal organic solvent and can be used as a cured film forming agent without using a special solvent such as fluorine.
In addition, recently, it has been studied that a specific fluorine-containing silazane compound is dissolved in a specific solvent and applied to the painted surface of a vehicle to exhibit extremely high water repellency and extremely high antifouling performance ( Patent Document 4).

特開２０１０−４３２５１号公報JP 2010-43251 A 特開２００２−１７４７０２号公報JP 2002-174702 A 特開平６−２７１６７９号公報JP-A-6-271679 特願２０１２−０５０２８８Japanese Patent Application No. 2012-050288

これら車両の塗装表面用コーティング剤は、それぞれの特徴を生かして様々な性能を車体表面に付与することが出来るが、シリコーン系コーティング剤の組み合わせのみでは性能に限界があり、フッ素変性ポリシラザンと組み合わせて新しい車両の塗装表面用コーティング剤を提供する。また、フッ素系化合物によるコーティング剤では、十分な性能を発現するためには、フルオロアルキル基の長さが必要であるが、PFOA（パーフルオロオクタン酸）やPFOS（パーフルオロオクタンスルホン酸塩）問題といった観点から、その使用が問題視されている。   These coating agents for painted surfaces of vehicles can give various performances to the body surface by taking advantage of their respective characteristics, but there are limits to the performance only with the combination of silicone coating agents, and in combination with fluorine-modified polysilazane. Providing coating materials for new vehicle paint surfaces. In addition, fluorocarbon coating agents require a fluoroalkyl group length to exhibit sufficient performance, but PFOA (perfluorooctanoic acid) and PFOS (perfluorooctanesulfonate) problems From such a viewpoint, its use is regarded as a problem.

本発明の課題は、このような事情の下、従来のシリコーンアルコキシオリゴマーを主成分とした硬化被膜に、フッ素変性ポリシラザンを加えることで、フッ素に由来した高い撥水性及び撥油性を付与することが出来る車両の塗装表面用コーティング剤を提供する。そして、このフッ素変性基がパーフルオロポリエーテル基であることから、PFOAやPFOS問題にも規制されることはない。すなわち、本発明は、フッ素変性ポリシラザン（イ）とシリコーンアルコキシオリゴマー（ロ）と硬化触媒（ハ）と有機溶媒（ニ）とを含む車両の塗装表面用コーティング剤である。
また、本発明の車両の塗装表面用コーティング剤においては、
フッ素変性ポリシラザンが一般式

Figure 2014065814
（式中、Ｑは２価の有機基、ｍは１以上の整数、ｘ及びｙはそれぞれ１〜３の整数である。）で表わされるパーフルオロポリエーテル変性ポリシラザンであり、m-キシレンヘキサフロライド及びフッ素系溶媒、ジメチルポリシロキサン、環状シロキサン、アルコール系溶媒、グリコール系溶媒、アセトン、脂肪族炭化水素、芳香族炭化水素からなる群れより選ばれる1種若しくは2種の溶媒に、パーフルオロポリエーテル変性ポリシラザンが固形分濃度として０．０１〜３質量％含むことが好ましい。
さらに、本発明の車両の塗装表面用コーティング剤においては、さらに、有機変性シリコーンオイルおよび/又はシランカップリング剤を含むことができる。
また、本発明の車両の塗装表面用コーティング剤においては、有機変性シリコーンオイルが分子の末端にカルビノール基を有し、シランカップリング剤がイソシアネート基もしくはグリシジルエーテル基を有することが望ましい。
さらに、本発明の車両の塗装表面用コーティング剤においては、フッ素変性ポリシラザン液１．０〜５０質量部、シリコーンアルコキシオリゴマー３．０〜１５．０質量部、触媒０．１〜２．０質量部、:変性シリコーンオイル、１．０〜１０．０質量部、シランカップリング剤０．１〜１．５質量部、残部が溶剤とすることができる。
また、本発明の車両の塗装表面用コーティング剤においては、硬化触媒がアルミ系若しくは、チタン系であり、溶剤がイソパラフィン系溶剤若しくはイソパラフィン系溶剤に少量のシリコーン系溶剤を添加することができる。 Under such circumstances, the object of the present invention is to add high water repellency and oil repellency derived from fluorine by adding fluorine-modified polysilazane to a cured film mainly composed of a conventional silicone alkoxy oligomer. Provide a coating agent for vehicle paint surfaces. Since this fluorine-modified group is a perfluoropolyether group, it is not restricted by PFOA and PFOS problems. That is, this invention is a coating agent for the coating surface of the vehicle containing fluorine-modified polysilazane (I), silicone alkoxy oligomer (B), curing catalyst (C), and organic solvent (D).
Moreover, in the coating agent for the painted surface of the vehicle of the present invention,
Fluorine-modified polysilazane is a general formula
Figure 2014065814
 (Wherein Q is a divalent organic group, m is an integer of 1 or more, x and y are each an integer of 1 to 3), and m-xylene hexafluoro Ride and fluorine-based solvents, dimethylpolysiloxane, cyclic siloxane, alcohol-based solvents, glycol-based solvents, acetone, aliphatic hydrocarbons, one or two solvents selected from the group consisting of aromatic hydrocarbons, The ether-modified polysilazane is preferably contained in an amount of 0.01 to 3% by mass as the solid content concentration.
Furthermore, the coating agent for a painted surface of a vehicle of the present invention can further contain an organically modified silicone oil and / or a silane coupling agent.
In the vehicle coating surface coating agent of the present invention, it is desirable that the organically modified silicone oil has a carbinol group at the end of the molecule and the silane coupling agent has an isocyanate group or a glycidyl ether group.
Furthermore, in the coating agent for the painted surface of the vehicle of the present invention, 1.0 to 50 parts by mass of the fluorine-modified polysilazane liquid, 3.0 to 15.0 parts by mass of the silicone alkoxy oligomer, and 0.1 to 2.0 parts by mass of the catalyst. : Modified silicone oil, 1.0 to 10.0 parts by mass, 0.1 to 1.5 parts by mass of silane coupling agent, and the balance can be used as a solvent.
In the vehicle coating surface coating agent of the present invention, the curing catalyst is aluminum or titanium, and the solvent can be an isoparaffin solvent or an isoparaffin solvent with a small amount of silicone solvent added.

本発明の車両用コーティング剤は実施例に示されたコーティング剤は比較例のそれに比べ、非常に優れた撥水性、撥油性、を示す。また、車のボディー表面を本コーティング剤で保護することで、非常に優れた防汚効果をも発揮できる。製品設計の幅が広がるばかりか、車両車体の塗装表面への実使用においても非常に有用である。 In the coating agent for vehicles of the present invention, the coating agent shown in the examples shows very excellent water repellency and oil repellency compared with those of the comparative example. In addition, by protecting the car body surface with this coating agent, a very excellent antifouling effect can be exhibited. In addition to widening the range of product design, it is also very useful in actual use on the painted surface of a vehicle body.

本発明で用いるフッ素変性シラザンは、すでに市販されており、とくに、一般式

Figure 2014065814
（式中、Ｑは２価の有機基、ｍは１以上の整数、ｘ及びｙはそれぞれ１〜３の整数である。）で表わされるパーフルオロポリエーテル変性ポリシラザン（以下、フッ素変性シラザン）が好適にもちいることができる。、
本発明で用いるパーフルオロポリエーテル変性ポリシラザンは、m-キシレンヘキサフロライドに溶解することが知られている。本発明者は、m-キシレンヘキサフロライド及びハイドロフルオローエテル、フルオロカーボン等のフッ素系溶媒、ジメチルポリシロキサン、環状シロキサン、エタノール、イソプロピルアルコール等のアルコール系溶媒、ジエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコール系溶媒、アセトン、脂肪族炭化水素、芳香族炭化水素から選ばれる群れより選ばれる1種若しくは2種の溶媒からなる混合溶媒に溶解して、塗装被膜上にパーフルオロポリエーテル変性被膜を形成させることができる。
本発明で用いるパーフルオロポリエーテル変性ポリシラザンの良溶媒としては、m-キシレンヘキサフロライドやハイドロフルオロエーテル、フルオロカーボンなどのフッ素系溶媒が挙げられ、本発明で用いるパーフルオロポリエーテル変性ポリシラザンの貧溶媒としては、脂肪族や芳香族炭化水素などの溶媒があげられる。
なお、フッ素変性シラザンのm-キシレンヘキサフロライド希釈溶液は、知られている。 The fluorine-modified silazane used in the present invention is already commercially available, and in particular, has the general formula
Figure 2014065814
 (Wherein Q is 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 a perfluoropolyether-modified polysilazane (hereinafter referred to as fluorine-modified silazane) represented by It can be used suitably. ,
It is known that the perfluoropolyether-modified polysilazane used in the present invention is soluble in m-xylene hexafluoride. The present inventor uses m-xylene hexafluoride, hydrofluoroether, fluorocarbon solvents such as fluorocarbon, dimethylpolysiloxane, cyclic siloxane, alcohol solvents such as ethanol, isopropyl alcohol, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, etc. A perfluoropolyether-modified coating is dissolved on the coating film by dissolving it in a mixed solvent consisting of one or two solvents selected from the group selected from the group consisting of glycol solvents, acetone, aliphatic hydrocarbons and aromatic hydrocarbons Can be formed.
Examples of the good solvent for the perfluoropolyether-modified polysilazane used in the present invention include fluorine-based solvents such as m-xylene hexafluoride, hydrofluoroether, and fluorocarbon, and the poor solvent for the perfluoropolyether-modified polysilazane used in the present invention. Examples thereof include solvents such as aliphatic and aromatic hydrocarbons.
A diluted solution of fluorine-modified silazane in m-xylene hexafluoride is known.

フッ素変性シラザンを固形分濃度が３％になるようにm-キシレンヘキサフロライドで希釈した溶液を用いた。 A solution obtained by diluting fluorine-modified silazane with m-xylene hexafluoride so as to have a solid content concentration of 3% was used.

また、本発明で用いる本発明で用いることが出来るシリコーンアルコキシオリゴマーとしては、分子の末端がアルコキシシリル基である低分子のシリコーンレジンであって、KC-89S（信越化学工業製）、KR-500（信越化学工業製）、BS-290（旭化成ワッカーシリコーン製）等を挙げることができる。
また、本発明で用いることが出来る硬化触媒としては、シリコーンアルコキシオリゴマーの硬化反応を促進するものであればよく、酸類、アミン類、金属類が挙げられるが、特にアルミ系（DX-9740；信越化学工業製）やチタン系（D-25；信越化学工業製）の有機金属化合物が好まれる。
本発明で用いることが出来るカルビノール変性基を有するシリコーンオイルとしては、分子の片側の末端にカルビノール基を有する、X-22-170BX（信越化学工業製）、X-22-170DX（信越化学工業製）等をあげることができる（下式）。

Figure 2014065814
（式中、ｎは0〜100の整数であり、R1はメチル基またはブチル基等の炭化水素基であり、R2はアルキレン基であり間に酸素原子をはさんだアルキレンオキシド基でもよい。）で表され常温で液体状のものである。
また、カルビノール変性基に代えてジカルビノール変性基を有するシリコーンオイルシリコーンオイルを用いることが出来るが、このようなジカルビノール変性基を有するシリコーンオイルシリコーンオイルとしては、分子の片側の末端にジカルビノール基を有する、X-22-176DX（信越化学工業製）、X-22-176F等をあげることができる。
Figure 2014065814
 （式中、ｎは0〜100の整数であり、R3はメチル基またはブチル基等の炭化水素基であり、R4はアルキレン基であり間に酸素原子をはさんだアルキレンオキシド基でもよい。R5およびR6はアルキレン基である。）で表され、常温で液体状のものである。 The silicone alkoxy oligomer that can be used in the present invention is a low molecular silicone resin having an alkoxysilyl group at the end of the molecule, such as KC-89S (manufactured by Shin-Etsu Chemical Co., Ltd.), KR-500. (Manufactured by Shin-Etsu Chemical), BS-290 (manufactured by Asahi Kasei Wacker Silicone) and the like.
The curing catalyst that can be used in the present invention may be any catalyst that accelerates the curing reaction of the silicone alkoxy oligomer, and examples thereof include acids, amines, and metals. Particularly, aluminum-based (DX-9740; Shin-Etsu Chemical metal) and titanium-based (D-25; Shin-Etsu Chemical) organometallic compounds are preferred.
Silicone oils having carbinol-modified groups that can be used in the present invention include X-22-170BX (Shin-Etsu Chemical Co., Ltd.), X-22-170DX (Shin-Etsu Chemical Co., Ltd.) having a carbinol group at one end of the molecule. (Made by industry) etc. can be raised (the following formula).
Figure 2014065814
 (In the formula, n is an integer of 0 to 100, R 1 is a hydrocarbon group such as a methyl group or a butyl group, R 2 is an alkylene group, and may be an alkylene oxide group with an oxygen atom between them. ) And is liquid at room temperature.
Further, a silicone oil silicone oil having a dicarbinol-modified group can be used in place of the carbinol-modified group, but the silicone oil silicone oil having such a dicarbinol-modified group has a dicarbinol group at one end of the molecule. X-22-176DX (manufactured by Shin-Etsu Chemical Co., Ltd.), X-22-176F, and the like.
Figure 2014065814
 (In the formula, n is an integer of 0 to 100, R 3 is a hydrocarbon group such as a methyl group or a butyl group, R 4 is an alkylene group, and may be an alkylene oxide group with an oxygen atom between them. R 5 and R 6 are alkylene groups.) And are liquid at room temperature.

通常、シランカップリング剤は、有機物とケイ素から構成される化合物で、分子中に2種以上の異なった反応基を持っているため、通常では非常に結びつきにくい有機材料と無機材料を結ぶ仲介役としての働きをするが、本発明で用いることが出来るシランカップリング剤としては、どのようなものでも良いが、末端イソシアネートを有するカップリング剤若しくは末端グリシジルエーテル基を有するカップリング剤が好ましく用いられる。

また、本発明で用いることが出来る溶剤としては、ノルマルパラフィンやイソパラフィン系の石油系溶剤等をあげることができる。
とくにイソパラフィン系ソルベントに少量のシリコーン系溶剤を添加したものが好ましく用いられる。
つぎに具体例を示すが、本発明はこれに拘束されるものではない。 Usually, a silane coupling agent is a compound composed of an organic substance and silicon, and has two or more different reactive groups in the molecule, so it usually serves as an intermediary between organic and inorganic materials that are very difficult to bond. As the silane coupling agent that can be used in the present invention, any silane coupling agent may be used, but a coupling agent having a terminal isocyanate or a coupling agent having a terminal glycidyl ether group is preferably used. .

Examples of the solvent that can be used in the present invention include normal paraffin and isoparaffin-based petroleum solvents.
In particular, those obtained by adding a small amount of a silicone solvent to an isoparaffin solvent are preferably used.
Next, although a specific example is shown, this invention is not restrained by this.

フッ素変性ポリシラザン液（固形分濃度３％m-キシレンヘキサフロライド）50.0質量%、KR-400（アルミ系触媒DX-9740 10％配合品；信越化学工業製）10.0質量%、IPsolvent1620（出光興産製）90.0質量%からなるコーティング剤を得た。 Fluorine-modified polysilazane solution (solid content concentration 3% m-xylene hexafluoride) 50.0% by mass, KR-400 (aluminum catalyst DX-9740 10% compounded product; Shin-Etsu Chemical Co., Ltd.) 10.0% by mass, IPsolvent 1620 (manufactured by Idemitsu Kosan) ) A coating agent consisting of 90.0% by mass was obtained.

フッ素変性ポリシラザン液1.0%、KR-500（信越化学工業製）5.0%、BS-290（旭化成ワッカーシリコーン製）5.0%、DX-9740（アルミ系、信越化学工業製）1.0%、D-25（チタン系、信越化学工業製）0.5%、X-22-176DX（片末端ジカルビノール変性、信越化学工業製）2.0%、KBE-9007（3-イソシアネートプロピルトリエトキシシラン、信越化学工業製）0.1%、KF-96L-1CS（信越化学工業製）5.0%、IPsolvent1620（出光興産製）81.4%からなるコーティング剤を得た。 Fluorine-modified polysilazane solution 1.0%, KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, BS-290 (manufactured by Asahi Kasei Wacker Silicone) 5.0%, DX-9740 (aluminum-based, manufactured by Shin-Etsu Chemical Co., Ltd.) 1.0%, D-25 ( Titanium, Shin-Etsu Chemical Co., Ltd.) 0.5%, X-22-176DX (one-end dicarbinol modified, Shin-Etsu Chemical Co., Ltd.) 2.0%, KBE-9007 (3-isocyanatopropyltriethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.1%, A coating agent comprising KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0% and IPsolvent 1620 (manufactured by Idemitsu Kosan) 81.4% was obtained.

フッ素変性ポリシラザン液5.0%、KR-500（信越化学工業製）5.0%、BS-290（旭化成ワッカーシリコーン製）5.0%、DX-9740（アルミ系、信越化学工業製）1.0%、D-25（チタン系、信越化学工業製）0.5%、X-22-176DX（片末端ジカルビノール変性、信越化学工業製）5.0%、KBE-9007（3-イソシアネートプロピルトリエトキシシラン、信越化学工業製）0.5%、（F）KF-96L-1CS（信越化学工業製）5.0%、IPsolvent1620（出光興産製）78.0%からなるコーティング剤を得た。 Fluorine-modified polysilazane solution 5.0%, KR-500 (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, BS-290 (manufactured by Asahi Kasei Wacker Silicone) 5.0%, DX-9740 (aluminum, Shin-Etsu Chemical Co., Ltd.) 1.0%, D-25 ( Titanium, Shin-Etsu Chemical Co., Ltd.) 0.5%, X-22-176DX (one-end dicarbinol modified, Shin-Etsu Chemical Co., Ltd.) 5.0%, KBE-9007 (3-isocyanatopropyltriethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.5%, (F) A coating agent comprising 5.0% KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) and 78.0% IPsolvent 1620 (manufactured by Idemitsu Kosan) was obtained.

フッ素変性ポリシラザン液20.0%、BS-290（旭化成ワッカーシリコーン製）10.0%、（C）DX-9740（アルミ系、信越化学工業製）0.5%、D-25（チタン系、信越化学工業製）1.0%、（D）X-22-170BX（片末端カルビノール変性、信越化学工業製）5.0%、（E）KBE-9007（3-イソシアネートプロピルトリエトキシシラン、信越化学工業製）0.5%、（F）KF-96L-1CS（信越化学工業製）5.0%、IPsolvent1620（出光興産製）78.0%からなるコーティング剤を得た。 Fluorine-modified polysilazane solution 20.0%, BS-290 (Asahi Kasei Wacker Silicone) 10.0%, (C) DX-9740 (Aluminum, Shin-Etsu Chemical) 0.5%, D-25 (Titanium, Shin-Etsu Chemical) 1.0 %, (D) X-22-170BX (one-end carbinol modified, Shin-Etsu Chemical Co., Ltd.) 5.0%, (E) KBE-9007 (3-isocyanatopropyltriethoxysilane, Shin-Etsu Chemical Co., Ltd.) 0.5%, (F ) A coating agent composed of KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0% and IPsolvent 1620 (manufactured by Idemitsu Kosan) 78.0% was obtained.

フッ素変性ポリシラザン液100.0%、KR-500（信越化学工業製）5.0%、BS-290（旭化成ワッカーシリコーン製）5.0%、（C）DX-9740（アルミ系、信越化学工業製）1.0%、D-25（チタン系、信越化学工業製）0.5%、（D）X-22-160AS（両末端カルビノール変性、信越化学工業製）5.0%、（E）KBM-403（3-グリキドキシプロピルトリメトキシシラン、信越化学工業製）0.5%、（F）KF-96L-1CS（信越化学工業製）5.0%、IPsolvent1620（出光興産製）78.0%からなるコーティング剤を得た。
Fluorine-modified polysilazane solution 100.0%, KR-500 (Shin-Etsu Chemical Co., Ltd.) 5.0%, BS-290 (Asahi Kasei Wacker Silicone Co., Ltd.) 5.0%, (C) DX-9740 (Aluminum, Shin-Etsu Chemical Co., Ltd.) 1.0%, D -25 (Titanium, Shin-Etsu Chemical Co., Ltd.) 0.5%, (D) X-22-160AS (both ends carbinol modified, Shin-Etsu Chemical Co., Ltd.) 5.0%, (E) KBM-403 (3-Glyoxydoxypropyl A coating agent comprising 0.5% trimethoxysilane (manufactured by Shin-Etsu Chemical), (F) KF-96L-1CS (manufactured by Shin-Etsu Chemical) 5.0%, and IPsolvent 1620 (manufactured by Idemitsu Kosan) 78.0% was obtained.

（比較例1）
（B）KR-400（アルミ系触媒DX-9740
10％配合品；信越化学工業製）10.0%、(F)IPsolvent1620（出光興産製）90.0%からなるコーティング剤を得た。 (Comparative Example 1)
(B) KR-400 (Aluminum catalyst DX-9740
A coating agent comprising 10% blended product; manufactured by Shin-Etsu Chemical Co., Ltd.) 10.0% and (F) IPsolvent 1620 (produced by Idemitsu Kosan Co., Ltd.) 90.0% was obtained.

（比較例2）
（B）KR-400（アルミ系触媒DX-9740
10％配合品；信越化学工業製）10.0%、（C）D-25（チタン系、信越化学工業製）0.5%、（D）X-22-176DX（片末端ジカルビノール変性、信越化学工業製）2.0%、（F）KF-96L-1CS（信越化学工業製）5.0%、IPsolvent1620（出光興産製）82.5%からなるコーティング剤を得た。 (Comparative Example 2)
(B) KR-400 (Aluminum catalyst DX-9740
10% blended product; Shin-Etsu Chemical Co., Ltd.) 10.0%, (C) D-25 (Titanium, Shin-Etsu Chemical Co., Ltd.) 0.5%, (D) X-22-176DX (One-end dicarbinol modified, Shin-Etsu Chemical Co., Ltd.) A coating agent comprising 2.0%, (F) KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, and IPsolvent 1620 (manufactured by Idemitsu Kosan) was obtained.

（比較例3）
（B）KR-500（信越化学工業製）10.0%、（C）DX-9740（アルミ系、信越化学工業製）1.0%、D-25（チタン系、信越化学工業製）0.5%、（D）X-22-160AS（両末端カルビノール変性、信越化学工業製）2.0%、（F）KF-96L-1CS（信越化学工業製）5.0%、IPsolvent1620（出光興産製）81.5%からなるコーティング剤を得た。 (Comparative Example 3)
(B) KR-500 (Shin-Etsu Chemical Co., Ltd.) 10.0%, (C) DX-9740 (Aluminum, Shin-Etsu Chemical Co., Ltd.) 1.0%, D-25 (Titanium, Shin-Etsu Chemical Co., Ltd.) 0.5%, (D ) X-22-160AS (both ends carbinol modified, manufactured by Shin-Etsu Chemical Co., Ltd.) 2.0%, (F) KF-96L-1CS (manufactured by Shin-Etsu Chemical Co., Ltd.) 5.0%, IPsolvent1620 (manufactured by Idemitsu Kosan Co., Ltd.) 81.5% Got.

Figure 2014065814
※実施例1および比較例1,2のDX-9740は、KR-400に含まれている量を示した。
（A）フッ素変性ポリシラザン液、（B）シリコーンアルコキシオリゴマー、（C）触媒、（D）変性シリコーン、（E）シランカップリング剤、（F）溶媒
各コーティング液については、以下に示すような方法で基材に処理し、各評価項目については、以下に示す方法と結果で判定し、表１にまとめた。
Figure 2014065814
 * DX-9740 of Example 1 and Comparative Examples 1 and 2 showed the amount contained in KR-400.
(A) Fluorine-modified polysilazane solution, (B) silicone alkoxy oligomer, (C) catalyst, (D) modified silicone, (E) silane coupling agent, (F) solvent Each coating solution is as shown below. Then, each evaluation item was determined by the following methods and results and summarized in Table 1.

アクリル−メラミン系樹脂からなる自動車用塗料をベースコートとトップコートの積層形態で焼付け塗装して作製した塗装板表面に、各コーティング液を含浸させたクロスを用いて均一に処理した。処理後5分間常温にて乾燥させ、新しいクロスにてムラがないように拭き取って仕上げ、さらに1週間常温下で乾燥させた。 The surface of the coated plate produced by baking and painting a paint for automobiles made of an acrylic-melamine resin in a laminated form of a base coat and a top coat was uniformly treated using a cloth impregnated with each coating solution. After the treatment, it was dried at room temperature for 5 minutes, wiped with a new cloth so that there was no unevenness, finished, and further dried at room temperature for 1 week.

（撥水性）
コーティング処理表面の水はじきの様子を、接触角計を用いて水の接触角を測定し、以下のように評価した。
◎：100°〜
○：95°〜99°
△：90°〜94°
×：〜89° (Water repellency)
The state of water repelling on the surface of the coating treatment was evaluated as follows by measuring the contact angle of water with a contact angle meter.
: 100 ° ~
○: 95 ° to 99 °
Δ: 90 ° to 94 °
×: ~ 89 °

（撥油性）
コーティング処理表面の油のはじく様子を、接触角計を用いて油(n-ドデカン)の接触角を測定し、以下のように評価した。
◎：30°〜
○：25°〜29°
△：20°〜24°
×：〜19° (Oil repellency)
The repelling behavior of the oil on the coating treated surface was evaluated by measuring the contact angle of the oil (n-dodecane) using a contact angle meter as follows.
: 30 ° ~
○: 25 ° to 29 °
Δ: 20 ° to 24 °
×: ~ 19 °

（滑り性）
市販のタオルでコーティング処理表面を擦ることで、処理表面の滑り性を確認し、以下のように評価した。
◎：表面がツルツルで良く滑る
○：僅かにツルツル感は落ちるが滑る
△：ツルツル感があまりなく滑りにくい
×：滑りが悪く引っかかる (Slippery)
By rubbing the coated surface with a commercially available towel, the slipperiness of the treated surface was confirmed and evaluated as follows.
◎: The surface slips well with a smooth surface ○: Slightly slippery but slightly slips △: There is not much slippery feeling and is difficult to slip ×: The slipping is bad and caught

（耐擦傷性）
市販のタオルでコーティング処理表面を擦ることで、処理表面の耐擦傷性を確認し、以下のように評価した。
◎：傷がほとんど目立たない
○：僅かに傷が入るがあまり目立たない
△：傷が目立つ
×：傷が多く入る (Abrasion resistance)
By rubbing the coated surface with a commercially available towel, the scratch resistance of the treated surface was confirmed and evaluated as follows.
◎: Scratches are hardly noticeable ○: Slightly scratched but not so noticeable △: Scratches are conspicuous ×: Many scratches are entered

（耐久性評価）
「JIS
K2396 9.12撥水持続性の評価」を参考に耐久性を確認した。洗浄液は炭酸ナトリウムとドデシルベンゼンスルホン酸ナトリウムより調製（pH11）し、500gの荷重にマイクロクロスを巻きつけ、洗浄機試験機にて500往復洗浄後の撥水性、撥油性の耐久性を、初期性能評価と同様に確認した。
（撥水耐久性）
コーティング処理表面の水はじきの様子を、接触角計を用いて水の接触角を測定し、以下のように評価した。
◎：100°〜
○：95°〜99°
△：90°〜94°
×：〜89°
（撥油耐久性）
コーティング処理表面の油のはじく様子を、接触角計を用いて油(n-ドデカン)の接触角を測定し、以下のように評価した。
◎：30°〜
○：25°〜29°
△：20°〜24°
×：〜19° (Durability evaluation)
"JIS
Durability was confirmed with reference to “K2396 9.12 Evaluation of water repellency durability”. The cleaning solution was prepared from sodium carbonate and sodium dodecylbenzenesulfonate (pH 11), wound with a micro cloth around a load of 500 g, and the initial performance of the water and oil repellency after 500 reciprocating cleanings in the machine washer. It confirmed similarly to evaluation.
(Water repellent durability)
The state of water repelling on the surface of the coating treatment was evaluated as follows by measuring the contact angle of water with a contact angle meter.
: 100 ° ~
○: 95 ° to 99 °
Δ: 90 ° to 94 °
×: ~ 89 °
(Oil repellent durability)
The repelling behavior of the oil on the coating treated surface was evaluated by measuring the contact angle of the oil (n-dodecane) using a contact angle meter as follows.
: 30 ° ~
○: 25 ° to 29 °
Δ: 20 ° to 24 °
×: ~ 19 °

Figure 2014065814
Figure 2014065814

本発明の車両の塗装表面用コーティング剤は非常に優れた撥水性、撥油性とその効果の持続性を示し、さらに、非常に優れた防汚効果をも発揮する。また、アフターマーケットの活性化のみならず、車両車体の塗装そのものに技術革新をもたらす可能性が高いものである。 The coating agent for a painted surface of a vehicle according to the present invention exhibits very excellent water repellency and oil repellency and the durability of the effect, and also exhibits a very excellent antifouling effect. In addition to the activation of the aftermarket, there is a high possibility of bringing about technological innovation in the painting of the vehicle body itself.

Claims (6)

フッ素変性ポリシラザン（イ）とシリコーンアルコキシオリゴマー（ロ）と硬化触媒（ハ）と有機溶媒（ニ）とを含む車両の塗装表面用コーティング剤。 A coating agent for a painted surface of a vehicle, comprising fluorine-modified polysilazane (I), a silicone alkoxy oligomer (B), a curing catalyst (C), and an organic solvent (D). フッ素変性ポリシラザンが一般式
Figure 2014065814
 （式中、Ｑは２価の有機基、ｍは１以上の整数、ｘ及びｙはそれぞれ１〜３の整数である。）で表わされるパーフルオロポリエーテル変性ポリシラザンであり、m-キシレンヘキサフロライド及びフッ素系溶媒、ジメチルポリシロキサン、環状シロキサン、アルコール系溶媒、グリコール系溶媒、アセトン、脂肪族炭化水素、芳香族炭化水素からなる群れより選ばれる1種若しくは2種の溶媒に、パーフルオロポリエーテル変性ポリシラザンが固形分濃度として、０．０１〜３質量％含まれている請求項１記載の車両の塗装表面用コーティング剤。 Fluorine-modified polysilazane is a general formula
Figure 2014065814
 (Wherein Q is a divalent organic group, m is an integer of 1 or more, x and y are each an integer of 1 to 3), and m-xylene hexafluoro Ride and fluorine-based solvents, dimethylpolysiloxane, cyclic siloxane, alcohol-based solvents, glycol-based solvents, acetone, aliphatic hydrocarbons, one or two solvents selected from the group consisting of aromatic hydrocarbons, The coating agent for the painted surface of a vehicle according to claim 1, wherein the ether-modified polysilazane is contained in an amount of 0.01 to 3% by mass as a solid content concentration. 有機変性シリコーンオイルおよび/又はシランカップリング剤を含む請求項１または請求項２に記載の車両の塗装表面用コーティング剤。 The coating agent for a painted surface of a vehicle according to claim 1 or 2, comprising an organically modified silicone oil and / or a silane coupling agent. 有機変性シリコーンオイルが分子の末端にカルビノール基を有し、シランカップリング剤がイソシアネート基もしくはグリシジルエーテル基を有している請求項３記載の車両の塗装表面用コーティング剤。 The coating agent for a painted surface of a vehicle according to claim 3, wherein the organically modified silicone oil has a carbinol group at a molecular end, and the silane coupling agent has an isocyanate group or a glycidyl ether group. フッ素変性ポリシラザン液１．０〜５０質量部、シリコーンアルコキシオリゴマー３．０〜１５．０質量部、触媒０．１〜２．０質量部、:変性シリコーンオイル、１．０〜１０．０質量部、シランカップリング剤０．１〜１．５質量部、残部が溶剤である請求項３又は請求項４に記載した塗装表面を保護する車両の塗装表面用コーティング剤。 Fluorine-modified polysilazane liquid 1.0-50 parts by mass, silicone alkoxy oligomer 3.0-15.0 parts by mass, catalyst 0.1-2.0 parts by mass: modified silicone oil, 1.0-10.0 parts by mass The coating agent for a painted surface of a vehicle for protecting a painted surface according to claim 3, wherein the silane coupling agent is 0.1 to 1.5 parts by mass and the balance is a solvent. 硬化触媒がアルミ系若しくは、チタン系であり、溶剤がイソパラフィン系溶剤若しくはイソパラフィン系溶剤に少量のシリコーン系溶剤を添加したことを特徴とする請求項１ないし請求項５のいずれかに記載の塗装表面を保護する車両の塗装表面用コーティング剤。
The coating surface according to any one of claims 1 to 5, wherein the curing catalyst is aluminum or titanium, and the solvent is an isoparaffin solvent or a small amount of silicone solvent added to the isoparaffin solvent. A coating agent for the painted surface of vehicles that protects.
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