JP2009221026A - Method for producing window glass for vehicle formed with sol-gel film - Google Patents
Method for producing window glass for vehicle formed with sol-gel film Download PDFInfo
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本発明は、アルコキシド化合物を加水分解及び重縮合する工程を有する方法を経て形成された膜、すなわちゾルゲル膜が形成された車両用窓ガラスの製造方法に関する。 The present invention relates to a method for manufacturing a window glass for a vehicle in which a film formed through a method having a step of hydrolyzing and polycondensing an alkoxide compound, that is, a sol-gel film is formed.
車両用窓ガラスは、大寸法のガラス板から所定の形状に切断して得られる。切断された直後のガラス板の端部には、端面に微細なクラック、凹凸が存在し、特に端面の角部が鋭利な状態となっている。そのため、ダイヤモンドホイール等を用いて端面を研磨し、特には形状を略半円状に加工する等して、鋭利な状態をなくしている。ただし、研磨処理された端面は、白濁化した外観を呈しており、とりわけ、ガラス板が緑色や濃緑色等の有色の場合、研磨処理された端面の白濁感は際立ったものとなる。こうした背景のもと、特許文献1は、端面の白濁がなく、良好な外観を有する車両用窓ガラスを得るために、ガラス板の端面にガラスフリットを含む焼成体からなる透明被覆層を形成することを開示している。
本出願人は、特許文献2で、ゾルゲル膜の一種である熱線遮蔽膜を開示している。ここで、ゾルゲル膜とは、アルコキシド化合物などを加水分解及び重縮合反応を進めオリゴマーを有する塗布液を形成し、これを基材に塗布、そして乾燥させる等の工程を経て形成された膜のことである。ゾルゲル膜は、光学的、電気的、化学的に機能を生じせしめることが可能な機能性材料を導入することが可能なので、様々な用途での使用、提案がなされている。特に、0.5μmを超える膜厚をもつゾルゲル膜は、光学的、化学的な機能を付与することを考えた場合、有用性が高い。 The present applicant discloses in Patent Document 2 a heat ray shielding film which is a kind of sol-gel film. Here, the sol-gel film is a film formed through processes such as hydrolysis and polycondensation reaction of an alkoxide compound and the like to form a coating liquid having an oligomer, which is coated on a substrate and dried. It is. Since the sol-gel film can introduce a functional material capable of causing optical, electrical, and chemical functions, it has been proposed and used in various applications. In particular, a sol-gel film having a film thickness exceeding 0.5 μm is highly useful in consideration of imparting optical and chemical functions.
特許文献2での熱線遮蔽膜を得るための塗布液は、塗布液を部材に保持させ、該部材をガラス板に接触させる手段、所謂手塗り塗布にてガラス板上に塗布できるものであり、少量の塗布液で効率良くガラス板に塗着させることができるものとなっている。 The coating liquid for obtaining a heat ray shielding film in Patent Document 2 is a means for holding a coating liquid on a member and applying the member on a glass plate by means of bringing the member into contact with the glass plate, so-called hand coating, It can be efficiently applied to a glass plate with a small amount of coating solution.
塗布液をガラス板の主面だけでなく、ガラス板の端部にも塗着させてゾルゲル膜を形成させると、ガラス板端部の白濁感が解消されるので、良好な外観を有する車両用窓ガラスを提供できる。 When the coating solution is applied not only to the main surface of the glass plate but also to the edge of the glass plate to form a sol-gel film, the cloudiness at the edge of the glass plate is eliminated, so that the vehicle has a good appearance. Can provide window glass.
手塗り塗布にて、ガラス板の主面だけでなく端面にも塗着させようと、主面に塗布液を塗り広げる塗布方式を、端面にも適用すると、前記主面とは反対側の主面に塗布液が廻り込み、外観品質の低下をもたらす。 If a coating method that spreads the coating liquid on the main surface is applied to the end surface in order to apply it to the end surface as well as the main surface of the glass plate by hand coating, the main surface on the side opposite to the main surface is applied. The coating solution goes around the surface, resulting in a decrease in appearance quality.
本発明は、良好な外観を有する車両用窓ガラスを提供することを目的とし、手塗りによる塗布液の塗布にて、端面が研磨されたガラス板の主面と端面とにゾルゲル膜を形成する方法を提供することを課題とする。 An object of the present invention is to provide a vehicle window glass having a good appearance, and a sol-gel film is formed on a main surface and an end surface of a glass plate whose end surfaces are polished by application of a coating solution by hand coating. It is an object to provide a method.
すなわち本発明の車両用窓ガラスの製造方法は、可視化可能な端面を有する車両用窓ガラスの製造方法であり、該方法は、
端面が研磨されたガラス板を準備する工程、
該ガラス板の主面及び研磨された端面の少なくとも可視化可能な端面にゾルゲル膜を形成する工程
を有し、ゾルゲル膜を形成する工程は、ゾルゲル膜を形成するための塗布液を保持した保持材をガラス板に接触させて塗布する工程を有し、保持材からの塗布液の吐出状態を、主面への塗布と端面への塗布とで異なったものとなるように調整することを特徴とする。
That is, the vehicle window glass manufacturing method of the present invention is a vehicle window glass manufacturing method having an end face that can be visualized.
A step of preparing a glass plate whose end face is polished;
A step of forming a sol-gel film on at least a visible end surface of the main surface and the polished end surface of the glass plate, and the step of forming the sol-gel film includes a holding material that holds a coating solution for forming the sol-gel film Characterized by adjusting the discharge state of the coating liquid from the holding material to be different between the application to the main surface and the application to the end surface. To do.
主面には塗布液を塗り広げることに適した塗布方式、端面には、前記主面とは反対側の主面に塗布液が塗り広がらない塗布方式を適用することで、前記主面とは反対側の主面に塗布液が廻り込み、外観品質の低下をもたらすことを防止せしめる。尚、前記の可視化可能な端面とは、車両用窓ガラスが車両に組み込まれたときに、窓ガラスの昇降作業や、開閉作業でガラス板の端面が露出され、人により観察可能な状態にさらされることのある端面部位を指す。このような状態を呈する窓ガラスとして、車両の側面に組み込まれる窓ガラスや、天井に組み込まれる窓ガラス等がある。 By applying a coating method suitable for spreading the coating liquid on the main surface, and by applying a coating method in which the coating liquid does not spread on the main surface opposite to the main surface, the end surface is the main surface. It prevents the coating liquid from getting into the opposite main surface and causing the appearance quality to deteriorate. The end face that can be visualized is exposed to a state in which the end face of the glass plate is exposed when the window glass for a vehicle is incorporated into a vehicle, and the end face of the glass plate is exposed during opening and closing operations. It refers to the end face part that may be damaged. As the window glass exhibiting such a state, there are a window glass incorporated in a side surface of a vehicle, a window glass incorporated in a ceiling, and the like.
主面には塗布液を塗り広げることに適した塗布方式、端面には、前記主面とは反対側の主面に塗布液が塗り広がらない塗布方式を適用する方法としては、主面に塗布する塗布液と、端面に塗布する塗布液とを異なったものとすることが好ましい。例えば、主面に塗布する塗布液は、レベリング性が高い方が好ましいため、その粘度は25℃で1mPa・s〜7mPa・sが好ましく、さらには2mPa・s〜6mPa・sが特に好ましい。一方、端面に塗布する塗布液は、前記主面とは反対側の主面に塗布液が塗り広がりにくいものが好ましいため、その粘度は25℃で3mPa・s〜30mPa・sが好ましく、さらには4mPa・s〜30mPa・sが特に好ましい。 As a method of applying a coating method suitable for spreading the coating liquid on the main surface and applying a coating method in which the coating liquid does not spread on the main surface opposite to the main surface, the end surface is coated on the main surface. It is preferable that the coating liquid to be applied is different from the coating liquid applied to the end face. For example, since the coating liquid applied to the main surface preferably has higher leveling properties, the viscosity is preferably 1 mPa · s to 7 mPa · s at 25 ° C., more preferably 2 mPa · s to 6 mPa · s. On the other hand, since it is preferable that the coating liquid applied to the end surface is difficult to spread the coating liquid on the main surface opposite to the main surface, the viscosity is preferably 3 mPa · s to 30 mPa · s at 25 ° C. 4 mPa · s to 30 mPa · s is particularly preferable.
また、主面には塗布液を塗り広げることに適した塗布方式、端面には前記主面とは反対側の主面に塗布液が塗り広がらない塗布方式を適用する他の方法としては、主面に接触させる保持材への塗布液の保持率と、端面に接触させる保持材への塗布液の保持率とを調整することで、保持材からの塗布液の吐出状態を主面への塗布と端面への塗布とで異なったものとすることが好ましい。特には、主面に接触させる保持材の塗布液の保持率を大きいものとすることが好ましく、この保持率は、例えば、端面に接触させる保持材への塗布液の保持率に対して1.5倍〜200倍、好ましくは2倍〜100倍となるように調整することが好ましい。 Other methods that apply a coating method suitable for spreading the coating solution on the main surface and applying a coating method in which the coating solution does not spread on the main surface opposite to the main surface are applied to the end surface. By adjusting the retention rate of the coating liquid to the holding material that is in contact with the surface and the retention rate of the coating liquid to the holding material that is in contact with the end surface, the discharge state of the coating liquid from the holding material is applied to the main surface. It is preferable that the coating is different from that applied to the end face. In particular, it is preferable that the holding rate of the coating liquid of the holding material brought into contact with the main surface is large. This holding rate is, for example, 1. It is preferable to adjust so as to be 5 to 200 times, preferably 2 to 100 times.
本発明において主面及び端面に形成されるゾルゲル膜は、好ましくは0.1μm〜5μmの膜厚を有する膜のことで、好ましくは酸化ケイ素オリゴマーを経て得られた酸化ケイ素化合物を有する膜のことで、該ケイ素化合物がシロキサン結合を介して基材と結合して形成された膜のことを言う。 The sol-gel film formed on the main surface and the end surface in the present invention is preferably a film having a film thickness of 0.1 μm to 5 μm, preferably a film having a silicon oxide compound obtained through a silicon oxide oligomer. The film is formed by bonding the silicon compound to a substrate through a siloxane bond.
このようなゾルゲル膜を形成する塗布液として、特に主面に塗布する塗布液としては、固形分と溶媒を有し、該固形分はアルコキシシランを酸性水溶液中で加水分解及び重縮合することで得られる酸化ケイ素オリゴマーを有し、該酸化ケイ素オリゴマーはポリスチレン換算の数平均分子量が500〜6000、好ましくは500〜4000であり、さらに前記塗布液に対する固形分の割合は8〜40重量%、好ましくは、8〜30重量%であり、さらに該固形分に対する酸化ケイ素オリゴマーに由来する固形分の割合は10重量%以上のものが好ましい。尚、ここでいう数平均分子量は、ゲルパーミエーションクロマトグラフィー(GPC)分析において、ポリスチレン換算で計算される数平均分子量を示す。 As a coating solution for forming such a sol-gel film, particularly a coating solution to be applied to the main surface, it has a solid content and a solvent, and the solid content is obtained by hydrolysis and polycondensation of alkoxysilane in an acidic aqueous solution. The resulting silicon oxide oligomer has a polystyrene-equivalent number average molecular weight of 500 to 6000, preferably 500 to 4000, and the solid content to the coating solution is preferably 8 to 40% by weight, preferably Is 8 to 30% by weight, and the ratio of the solid content derived from the silicon oxide oligomer to the solid content is preferably 10% by weight or more. In addition, the number average molecular weight here shows the number average molecular weight calculated in polystyrene conversion in a gel permeation chromatography (GPC) analysis.
酸化ケイ素オリゴマーが8重量%未満では、塗布液のハジキ欠陥が生じやすい。また、固形分が40重量%超では、得られるゾルゲル膜が厚くなってクラックが生じやすくなる。同様に、酸化ケイ素オリゴマーの数平均分子量が6000超になると、得られるゾルゲル膜が厚くなってクラックが生じやすくなる。また、アルコキシシランの加水分解反応が進行する条件では、同時に重縮合反応も進行するため、数平均分子量は500未満に制御することは難しい。本発明では、主面用塗布液と端面用塗布液は同じものを使っても良い。 If the silicon oxide oligomer is less than 8% by weight, repellency defects of the coating solution tend to occur. On the other hand, if the solid content exceeds 40% by weight, the resulting sol-gel film becomes thick and cracks are likely to occur. Similarly, when the number average molecular weight of the silicon oxide oligomer exceeds 6000, the resulting sol-gel film becomes thick and cracks are likely to occur. In addition, since the polycondensation reaction proceeds at the same time under the condition where the alkoxysilane hydrolysis reaction proceeds, it is difficult to control the number average molecular weight to less than 500. In the present invention, the main surface coating solution and the end surface coating solution may be the same.
ただし、本発明のように塗布液を保持した保持材をガラス板に接触させることによって塗布液を塗布する方法では、主面用塗布液に対してより高いレベリング性がある方が好ましい。そして、レベリング性に影響を与える要因しては、塗布液の溶媒の揮発速度、塗布液の粘度、塗布液中の固形分濃度などがあり、25℃における塗布液の粘度を7mPa・s以下とするとレベリング性が高くなるので好ましい。 However, in the method of applying the coating liquid by bringing the holding material holding the coating liquid into contact with the glass plate as in the present invention, it is preferable that the main surface coating liquid has higher leveling property. Factors affecting the leveling properties include the solvent volatilization rate of the coating solution, the viscosity of the coating solution, the solid content concentration in the coating solution, and the viscosity of the coating solution at 25 ° C. is 7 mPa · s or less. Then, since leveling property becomes high, it is preferable.
そのような塗布液としては、固形分と溶媒を有し、該固形分はアルコキシシランを酸性水溶液中で加水分解及び重縮合することで得られる酸化ケイ素オリゴマーを有し、溶媒は沸点が100℃以上、かつ25℃における粘度が3.5mPa・s以下、好ましくは2.5mPa・s以下の有機溶媒、さらには酸性水溶液を有するものとすることが好ましい。また、レベリング性の観点から、塗布液中の固形分の濃度を、30重量%以下、好ましくは20重量%以下とすることが好ましく、さらに酸化ケイ素オリゴマーの分子量を4000以下とすることが好ましい。 Such a coating liquid has a solid content and a solvent, and the solid content has a silicon oxide oligomer obtained by hydrolysis and polycondensation of alkoxysilane in an acidic aqueous solution, and the solvent has a boiling point of 100 ° C. It is preferable to have an organic solvent having a viscosity at 25 ° C. of 3.5 mPa · s or less, preferably 2.5 mPa · s or less, and further an acidic aqueous solution. Further, from the viewpoint of leveling properties, the solid content in the coating solution is preferably 30% by weight or less, preferably 20% by weight or less, and the molecular weight of the silicon oxide oligomer is preferably 4000 or less.
本発明の車両用窓ガラスの製造方法は、手塗りによる塗布液の塗布にて、ガラス板の主面と研磨された端面とにゾルゲル膜を効率良く、良好な外観を有する車両用窓ガラスを提供することに奏功する。 The method for manufacturing a window glass for a vehicle according to the present invention is a method for producing a vehicle window glass having a good appearance by efficiently applying a sol-gel film on a main surface and a polished end surface of a glass plate by applying a coating solution by hand coating. Succeeded in providing.
本発明の車両用窓ガラスの製造方法を詳細に説明する。本発明の車両用窓ガラスの製造方法は、可視化可能な端面を有する車両用窓ガラスの製造方法であり、該方法は、
端面が研磨されたガラス板を準備する工程、
該ガラス板の主面及び研磨された端面の少なくとも可視化可能な端面にゾルゲル膜を形成する工程
を有し、ゾルゲル膜を形成する工程は、ゾルゲル膜を形成するための塗布液を保持した保持材をガラス板に接触させて塗布する工程を有し、保持材からの塗布液の吐出状態を、主面への塗布と端面への塗布とで異なったものとなるように調整することを特徴とする。
The manufacturing method of the window glass for vehicles of this invention is demonstrated in detail. The vehicle window glass manufacturing method of the present invention is a vehicle window glass manufacturing method having an end face that can be visualized.
A step of preparing a glass plate whose end face is polished;
A step of forming a sol-gel film on at least a visible end surface of the main surface and the polished end surface of the glass plate, and the step of forming the sol-gel film includes a holding material that holds a coating solution for forming the sol-gel film Characterized by adjusting the discharge state of the coating liquid from the holding material to be different between the application to the main surface and the application to the end surface. To do.
塗布液が塗布されるガラス板は、好ましくは大寸法のガラス板から所定の形状に切断されて得られる。切断されたガラス板の端部には、端面に微細な割れやカケが存在するためガラス板は割れやすく、さらに端面の角部は鋭利な状態となっているため、端面を研磨(シーミング)し、特には形状を略半円状に加工する等して、鋭利な状態をなくしている。この研磨方法としては、ダイヤモンドホイールや研磨ベルトやサンドペーパーなどを用いて機械もしくは手で研磨する方法、あるいは、それらの併用などの各種研磨方法が適宜採用し得る。 The glass plate to which the coating solution is applied is preferably obtained by cutting a large-size glass plate into a predetermined shape. At the end of the cut glass plate, there are fine cracks and chips on the end surface, so the glass plate is easily broken, and the corners of the end surface are sharp, so the end surface is polished (seamed). In particular, the sharp shape is eliminated by processing the shape into a substantially semicircular shape. As this polishing method, various polishing methods such as a method of polishing with a machine or hand using a diamond wheel, a polishing belt, a sandpaper or the like, or a combination thereof can be appropriately employed.
次いで、主面にゾルゲル膜を形成するための主面用塗布液、あるいは、端面にゾルゲル膜を形成するための端面用塗布液を保持材に保持させ、保持材をガラス板の主面、あるいは、端面に接触させることによって主面用塗布液、あるいは、端面用塗布液を塗布する(以降、主面用塗布液と端面用塗布液の両方を指すときに「塗布液」と記載することがある)。該保持材を基材に接触させる手段、塗布液を引き延ばす手段は、人手によるもの、ロボットや機械などによるものなどがある。保持材に塗布液を保持させる方法としては、保持材をガラス板に接触させる前に保持材に塗布液を保持させる方法だけでなく、ガラス板の表面に塗布液を給液して、次いで保持材をガラス板に接触させて保持材に塗布液を染み込ませながら塗布液をガラス板に塗り広げる方法、塗布液を保持材に給液しながら保持材をガラス板に接触させる方法、あるいは、それらの組合せがある。ただし、ガラス板の端面に端面用塗布液を給液するのは難しいので、端面を塗布する場合は、ガラス板に接触させる前に保持材に端面用塗布液を保持させる方法、端面用塗布液を保持材に給液しながら保持材をガラス板に接触させる方法が好ましい。 Next, the main surface coating liquid for forming the sol-gel film on the main surface, or the end surface coating liquid for forming the sol-gel film on the end surface is held by the holding material, and the holding material is held on the main surface of the glass plate, or The main surface coating solution or the end surface coating solution is applied by contacting the end surface (hereinafter referred to as “coating solution” when referring to both the main surface coating solution and the end surface coating solution). is there). The means for bringing the holding material into contact with the substrate and the means for extending the coating solution include those by hand, those by robots and machines, and the like. As a method of holding the coating solution on the holding material, not only the method of holding the coating solution on the holding material before bringing the holding material into contact with the glass plate, but also supplying the coating solution to the surface of the glass plate and then holding it. A method of spreading the coating liquid on the glass plate while allowing the coating material to come into contact with the glass plate and supplying the coating liquid to the holding material, or a method of bringing the holding material into contact with the glass plate while supplying the coating liquid to the holding material, or There are combinations. However, since it is difficult to feed the end surface coating solution to the end surface of the glass plate, when applying the end surface, a method of holding the end surface coating solution on the holding material before contacting the glass plate, the end surface coating solution A method of bringing the holding material into contact with the glass plate while supplying a liquid to the holding material is preferred.
主面用塗布液を保持する部材としては、布、紙、不織布、刷毛、ブラシ、ガーゼ、スポンジ、フェルトなどが挙げられる。 Examples of the member for holding the main surface coating liquid include cloth, paper, non-woven fabric, brush, brush, gauze, sponge and felt.
一方、端面用塗布液を保持する部材としては、布、紙、不織布、ガーゼ、スポンジ、フェルトなどが挙げられる。刷毛やブラシは、端面を塗布するときに塗布液を塗布する主面とは反対側の主面に塗布液が塗り広がり易いので好ましくない。また、端面と接触したときに、端面が保持材に深く沈み込んでしまうような保持材を用いると、塗布液を塗布する主面とは反対側の主面に塗布液が塗り広がる可能性が高くなるので好ましくない。例えば、端面と接触させる面を上にした状態で保持材を固い台の上に置き、該保持材の上に200g/cm2の荷重となる重石を置いたときに、重石の沈み込む量が10mm以下のものであれば、塗布液を塗布する主面とは反対側の主面に塗布液が塗り広がる可能性が低いので好ましい。 On the other hand, examples of the member for holding the end surface coating liquid include cloth, paper, non-woven fabric, gauze, sponge, and felt. Brushes and brushes are not preferable because the coating liquid is likely to spread on the main surface opposite to the main surface to which the coating liquid is applied when the end surface is applied. In addition, when a holding material is used, the end surface sinks deeply into the holding material when it comes into contact with the end surface, the coating liquid may spread on the main surface opposite to the main surface to which the coating liquid is applied. Since it becomes high, it is not preferable. For example, when the holding material is placed on a hard table with the surface to be brought into contact with the end face up, and the weight of 200 g / cm 2 is placed on the holding material, the amount of weight sinking can be reduced. If it is 10 mm or less, the possibility that the coating liquid spreads and spreads on the main surface opposite to the main surface to which the coating liquid is applied is preferable.
また、ゾルゲル膜を得るための塗布液は、固形分と溶媒を有し、該固形分はアルコキシシランを酸性水溶液中で加水分解及び重縮合することで得られる酸化ケイ素オリゴマーを含むことが好ましい。アルコキシシランとしては、トリアルコキシシラン及びテトラアルコキシシランから選ばれる少なくとも1種を用いることができる。アルコキシシランのアルコキシ基は、加水分解および重縮合反応によって強固なシロキサン結合を形成する。テトラアルコキシシランは、ケイ素原子に結合する4つの官能基が全てアルコキシ基であり、加水分解および重縮合反応によって緻密なシロキサンネットワークを形成するため、膜強度を向上させることに奏功する。また、トリアルコキシシランから形成される固形分は、シロキサンネットワークが密に形成されず柔軟性に優れたものとなるので、膜形成時の乾燥過程で生じる応力が上手く緩和でき、クラックの発生を抑制することに奏功する。そして、実用上十分な膜の耐摩耗性を有し、さらに膜厚が0.1μm、特には0.5μmを超えるようなものを得る場合には、トリアルコキシシラン及びテトラアルコキシシランを使うことが好ましい。 The coating solution for obtaining the sol-gel film preferably has a solid content and a solvent, and the solid content preferably contains a silicon oxide oligomer obtained by hydrolysis and polycondensation of alkoxysilane in an acidic aqueous solution. As the alkoxysilane, at least one selected from trialkoxysilane and tetraalkoxysilane can be used. The alkoxy group of alkoxysilane forms a strong siloxane bond by hydrolysis and polycondensation reaction. In tetraalkoxysilane, all four functional groups bonded to the silicon atom are alkoxy groups, and a dense siloxane network is formed by hydrolysis and polycondensation reaction, so that the film strength is improved. In addition, since the solid content formed from trialkoxysilane is excellent in flexibility because the siloxane network is not densely formed, the stress generated during the drying process during film formation can be relieved well, and the generation of cracks is suppressed. To be successful. In order to obtain a practically sufficient film abrasion resistance and to obtain a film having a film thickness exceeding 0.1 μm, particularly exceeding 0.5 μm, trialkoxysilane and tetraalkoxysilane may be used. preferable.
トリアルコキシシランには、メチルトリメトキシシラン、エチルトリメトキシシラン、プロピルトリメトキシシラン、イソプロピルトリメトキシシラン、ブチルトリメトキシシラン、イソブチルトリメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、エチルトリエトキシシラン、プロピルトリエトキシシラン、イソプロピルトリエトキシシラン、ブチルトリエトキシシラン、イソブチルトリエトキシシラン、フェニルトリエトキシシラン、メチルトリプロポキシシラン、エチルトリプロポキシシラン、プロピルトリプロポキシシラン、イソプロピルトリプロポキシシラン、ブチルトリプロポキシシラン、イソブチルトリプロポキシシラン、フェニルトリプロポキシシラン、メチルトリイソプロポキシシラン、エチルトリイソプロポキシシラン、プロピルトリイソプロポキシシラン、イソプロピルトリイソプロポキシシラン、ブチルトリイソプロポキシシラン、イソブチルトリイソプロポキシシラン、フェニルトリイソプロポキシシラン等の炭化水素基を持つトリアルコキシシラン、あるいは、3−グリシドキシプロピルトリメトキシシラン、3−グリシドキシプロピルトリエトキシシラン、5、6−エポキシヘキシルトリエトキシシラン、5、6−エポキシヘキシルトリエトキシシラン、2−(3、4エポキシシクロヘキシル)エチルトリメトキシシラン、2−(3、4エポキシシクロヘキシル)エチルトリエトキシシラン、3−オキセタニルプロピルトリエトキシシラン等の反応性有機基を有するトリアルコキシシラン、が使用できる。 For trialkoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane , Propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, propyltripropoxysilane, isopropyltripropoxysilane, butyltripropoxysilane , Isobutyl tripropoxy silane, phenyl tripropoxy silane, methyl triisopropoxy silane, ethyl Trialkoxysilane having a hydrocarbon group such as lyisopropoxysilane, propyltriisopropoxysilane, isopropyltriisopropoxysilane, butyltriisopropoxysilane, isobutyltriisopropoxysilane, phenyltriisopropoxysilane, or 3-glycol Sidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 5,6-epoxyhexyltriethoxysilane, 2- (3,4epoxycyclohexyl) ethyltrimethoxysilane , Trialkoxysilane having a reactive organic group such as 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and 3-oxetanylpropyltriethoxysilane.
前記テトラアルコキシシランには、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシランなどを使用することが可能である。そして、前記トリ及びテトラアルコキシシランは、それぞれ単独種の化合物を使用してもよいし、複種の化合物を使用してもよい。 As the tetraalkoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, or the like can be used. And as for the said tri and tetraalkoxysilane, a single kind of compound may be used, respectively, and a multiple kind of compound may be used.
また、塗布液の固形分として、微粒子を含ませても良い。このとき、微粒子が塗布液中で凝集することなく、均一に分散していることが好ましい。前記微粒子は、あらかじめ分散媒に分散させて分散液を形成した後、塗布液と混合させても良いし、また塗布液中で分散を行っても良い。微粒子の分散には、ボールミル、ジェットミル、ビーズミル、サンドミル、超音波分散法などの方法を用いる事ができる。 Moreover, you may include microparticles | fine-particles as solid content of a coating liquid. At this time, it is preferable that the fine particles are uniformly dispersed without aggregating in the coating solution. The fine particles may be dispersed in a dispersion medium in advance to form a dispersion, and then mixed with the coating liquid, or may be dispersed in the coating liquid. For dispersion of the fine particles, methods such as a ball mill, a jet mill, a bead mill, a sand mill, and an ultrasonic dispersion method can be used.
さらにまた、塗布液に含まれる溶媒は、酸性水溶液と有機溶媒を有する。酸性水溶液は、用いられるアルコキシシランのアルコキシ基の加水分解速度に応じて、塩酸、硫酸、硝酸などの無機酸、酢酸、フタル酸、コハク酸などの有機酸等の酸触媒を有する水溶液が選択できる。そして、アルコキシシランの加水分解及び重縮合時の溶液、すなわち、酸化ケイ素オリゴマーを有する溶液中でのpH値が1乃至5となるように酸触媒が添加されることが好ましい。 Furthermore, the solvent contained in the coating solution has an acidic aqueous solution and an organic solvent. As the acidic aqueous solution, an aqueous solution having an acid catalyst such as an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid, phthalic acid or succinic acid can be selected according to the hydrolysis rate of the alkoxy group of the alkoxysilane used. . And it is preferable that an acid catalyst is added so that the pH value in the solution at the time of hydrolysis and polycondensation of alkoxysilane, that is, the solution having a silicon oxide oligomer, becomes 1 to 5.
また、アルコキシシランの加水分解は、十分な量の水と酸触媒を添加し行うことができ、その反応は十分に進行させる必要がある。一方、加水分解反応が起こると同時に、加水分解物は脱水反応である重縮合反応を起こす。塗布液の粘度や膜の耐摩耗性の観点から、重縮合反応の進行は好ましくないため、加水分解反応は進行するが、重縮合反応は進行しにくいように、反応開始前に水をアルコキシシランの5モル倍以上、好ましくは7モル倍以上とすることが望ましい。 Further, hydrolysis of alkoxysilane can be performed by adding a sufficient amount of water and an acid catalyst, and the reaction needs to proceed sufficiently. On the other hand, simultaneously with the hydrolysis reaction, the hydrolyzate causes a polycondensation reaction which is a dehydration reaction. From the viewpoint of the viscosity of the coating solution and the abrasion resistance of the film, the progress of the polycondensation reaction is not preferable, so that the hydrolysis reaction proceeds, but the polycondensation reaction is difficult to proceed. 5 mol times or more, preferably 7 mol times or more.
ここで、2種以上のアルコキシシランを用いた場合、加水分解反応は別々に行い、後で混合しても良いし、一緒に行っても良い。なお、他の加水分解反応をさせる方法としては、上記のようなアルコキシシランを溶媒で希釈したものと、溶媒で希釈した酸性水溶液を徐々に混合する方法がる。この例は、急激な反応を避けることができ、より均質な反応が得られやすい。 Here, when two or more types of alkoxysilanes are used, the hydrolysis reaction may be performed separately and mixed later or together. In addition, as another method of performing the hydrolysis reaction, there is a method of gradually mixing an alkoxy silane diluted with a solvent and an acidic aqueous solution diluted with a solvent. In this example, a rapid reaction can be avoided, and a more homogeneous reaction can be easily obtained.
前記有機溶媒は、沸点が100℃以上、粘度が3.5mPa・s以下のものからなることが好ましい。そのような例としては、2−メトキシエタノール、2−エトキシエタノール、2−イソプロポキシエタノール、2−ブトキシエタノール、ジエチレングリコールモノメチルエーテル、1−メトキシ−2−プロパノール、1−エトキシ−2−プロパノール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジアセトンアルコール、2−メトキシエチルアセテート、2−エトキシエチルアセテート、2−ブトキシエチルアセテート、ジエチレングリコールモノエチルエーテルアセテートが挙げられる。 The organic solvent preferably has a boiling point of 100 ° C. or higher and a viscosity of 3.5 mPa · s or lower. Examples thereof include 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol, diethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene Examples include glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetone alcohol, 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, and diethylene glycol monoethyl ether acetate.
さらに、塗布液に加える酸性水溶液と良く混ざり合うため、前記有機溶媒は水との相溶性が高ければ好ましく、水への溶解性が無限大の溶媒であればより好ましい。沸点が100℃以上、粘度が3.5mPa・s以下、かつ水への溶解性が無限大の溶媒の例として、2−メトキシエタノール、2−エトキシエタノール、2−イソプロポキシエタノール、2−ブトキシエタノール、ジエチレングリコールモノメチルエーテル、1−メトキシ−2−プロパノール、1−エトキシ−2−プロパノール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジアセトンアルコール、2−メトキシエチルアセテート、ジエチレングリコールモノエチルエーテルアセテートが挙げられる。 Furthermore, since the organic solvent is well mixed with the acidic aqueous solution added to the coating solution, it is preferable that the organic solvent has high compatibility with water, and more preferable that the solvent has infinite solubility in water. Examples of solvents having a boiling point of 100 ° C. or more, a viscosity of 3.5 mPa · s or less, and an infinite solubility in water include 2-methoxyethanol, 2-ethoxyethanol, 2-isopropoxyethanol, 2-butoxyethanol. , Diethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diacetone alcohol, 2-methoxyethyl acetate, diethylene glycol monoethyl ether acetate Can be mentioned.
さらにまた、前記酸化ケイ素オリゴマーを、テトラアルコキシシランとトリアルコキシシランの加水分解および重縮合によって形成される酸化ケイ素オリゴマーとする場合、テトラアルコキシシランから形成される固形分とトリアルコキシシランから形成される固形分の重量比が55:45〜85:15とすることが好ましい。テトラアルコキシシランから形成される固形分が55重量%未満の場合、ゾルゲル膜の機械的強度が低くなる傾向があり、キズが生じやすくなる。一方、85重量%超の場合、ゾルゲル膜にクラックが生じやすくなる。 Furthermore, when the silicon oxide oligomer is a silicon oxide oligomer formed by hydrolysis and polycondensation of tetraalkoxysilane and trialkoxysilane, it is formed from a solid content formed from tetraalkoxysilane and trialkoxysilane. The weight ratio of the solid content is preferably 55:45 to 85:15. When the solid content formed from tetraalkoxysilane is less than 55% by weight, the mechanical strength of the sol-gel film tends to be low, and scratches are likely to occur. On the other hand, if it exceeds 85% by weight, cracks are likely to occur in the sol-gel film.
さらにまた、前記固形分に、微粒子を含ませることによってゾルゲル膜に機能を付与することができる。そのような微粒子として、酸化ケイ素、酸化チタン、酸化アルミニウム、酸化ジルコニウム、酸化亜鉛、ITO、ATOなどの酸化物微粒子、あるいは、鉄、金、銀、銅などの金属微粒子などが使用できる。また、その平均粒径は200nmであれば、ゾルゲル膜の透明性は低下しないので好ましい。ただし、10nm未満になると微粒子の比表面積が大きくなって耐久性が低下するため好ましくない。なお、ここで言う微粒子の平均粒径とは、動的光散乱法により、液体中の数平均の粒子径を測定することで得られる。 Furthermore, a function can be provided to the sol-gel film by including fine particles in the solid content. As such fine particles, fine oxide particles such as silicon oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, ITO and ATO, or fine metal particles such as iron, gold, silver and copper can be used. Moreover, if the average particle diameter is 200 nm, since the transparency of a sol-gel film does not fall, it is preferable. However, if the thickness is less than 10 nm, the specific surface area of the fine particles is increased and the durability is lowered, which is not preferable. The average particle diameter of the fine particles referred to here is obtained by measuring the number average particle diameter in the liquid by a dynamic light scattering method.
特に、微粒子の中でもITOは波長が1000nm以上の近赤外線を効率的に遮蔽するため有用である。このとき、該錫ドープ酸化インジウム微粒子と前記ケイ素オリゴマーの固形分との重量比は35:65〜70:30とすることが好ましい。該錫ドープ酸化インジウム微粒子が35重量%未満であれば、十分な赤外線遮蔽性能が得られず、さらに70重量%超であれば、バインダー量が少なくなって導電性酸化物微粒子を十分強固に保持できなくなり、結果、膜強度が低下するので好ましくない。 In particular, among fine particles, ITO is useful because it effectively blocks near infrared rays having a wavelength of 1000 nm or more. At this time, the weight ratio between the tin-doped indium oxide fine particles and the solid content of the silicon oligomer is preferably 35:65 to 70:30. If the tin-doped indium oxide fine particles are less than 35% by weight, sufficient infrared shielding performance cannot be obtained. If the tin-doped indium oxide fine particles are more than 70% by weight, the amount of the binder is reduced and the conductive oxide fine particles are sufficiently strong. As a result, the film strength decreases, which is not preferable.
また、本発明において、ガラス板の端面にゾルゲル膜を形成させるのは、端面の凹凸を小さくして白濁感を軽減させることが目的であり、赤外線遮蔽性能は必要としない。錫ドープ酸化インジウムは非常に高価な材料であることから、端面用塗布液は錫ドープ酸化インジウム微粒子を含まないものを用いることがコスト的には好ましい。 In the present invention, the purpose of forming the sol-gel film on the end face of the glass plate is to reduce the unevenness of the end face to reduce the cloudiness, and does not require infrared shielding performance. Since tin-doped indium oxide is a very expensive material, it is preferable in terms of cost to use a coating solution for end face that does not contain tin-doped indium oxide fine particles.
そして、本発明の塗布液の被塗布対象である車両用窓ガラスは、特に限定されるものではないが、例えば、フロ−ト板ガラス又はロ−ルアウト法で製造されたソーダ石灰ガラス、無アルカリガラス等無機質の透明性がある板ガラスを使用できる。当該板ガラスには、無色のもの、着色のもの共に使用可能で、他の機能性膜との組み合わせ、ガラスの形状等に特に限定されるものではない。 And the window glass for vehicles which is the application target of the coating liquid of the present invention is not particularly limited. For example, soda-lime glass or alkali-free glass produced by a float plate glass or a roll-out method. It is possible to use a plate glass having an inorganic transparency. The plate glass can be used both colorless and colored, and is not particularly limited to the combination with other functional films, the shape of the glass, and the like.
基材の形状は、平板、曲げ板を問わず、さらには、風冷強化ガラス、化学強化ガラス等の各種強化ガラスの他に網入りガラスや合せガラスも使用できる。さらには、ホウケイ酸塩ガラス、低膨張ガラス、ゼロ膨張ガラス、低膨張結晶化ガラス、ゼロ膨張結晶化ガラス等の各種ガラス基材を用いることができる。 The shape of the substrate is not limited to a flat plate or a bent plate, and in addition to various tempered glasses such as air-cooled tempered glass and chemically tempered glass, netted glass and laminated glass can also be used. Furthermore, various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, and zero expansion crystallized glass can be used.
また、ポリエチレンテレフタレート樹脂、ポリカーボネート樹脂、ポリカーボネート樹脂、ポリ塩化ビニール樹脂、ポリエチレン樹脂等の樹脂基材を使用してもよい。 Moreover, you may use resin base materials, such as a polyethylene terephthalate resin, a polycarbonate resin, a polycarbonate resin, a polyvinyl chloride resin, a polyethylene resin.
そして、調製された塗布液をガラス板に塗布し、乾燥する。乾燥雰囲気は、室温で乾燥してもよいが、により高い耐摩耗性や硬さが必要であれば、50〜300℃で熱処理すればゾルゲル膜の機械的郷強度が向上するので好ましい。 Then, the prepared coating solution is applied to a glass plate and dried. The drying atmosphere may be dried at room temperature, but if higher wear resistance and hardness are required, heat treatment at 50 to 300 ° C. is preferable because the mechanical strength of the sol-gel film is improved.
以下に本発明の実施例について説明する。
〔塗布液の評価方法〕
(1)塗布液A
テトラエトキシシラン(TEOS):7.28g、メチルトリエトキシシラン(MTES):2.39g、1−エトキシ2−プロパノール(1E2P):4.23g、0.5N酢酸:6.10gを混合し、30℃で16時間攪拌して、塗布液Aを得た。塗布液Aの酸化ケイ素オリゴマー成分量は15重量%、粘度は5.6mPa・sであった。
Examples of the present invention will be described below.
[Evaluation method of coating solution]
(1) Coating liquid A
Tetraethoxysilane (TEOS): 7.28 g, Methyltriethoxysilane (MTES): 2.39 g, 1-Ethoxy-2-propanol (1E2P): 4.23 g, 0.5N acetic acid: 6.10 g were mixed, and 30 The mixture was stirred at 0 ° C. for 16 hours to obtain a coating solution A. The coating solution A had a silicon oxide oligomer content of 15% by weight and a viscosity of 5.6 mPa · s.
(2)塗布液B
塗布液A:10gと平均粒径60nmのITO微粒子が分散された溶液(ITO超微粒子の含有量30重量%、溶媒:イソプロピルアルコール;三菱マテリアル社製):5gとを混合して塗布液Bを得た。塗布液の酸化ケイ素オリゴマー成分量は10重量%、粘度は5.4mPa・sであった。
(2) Coating liquid B
Coating solution A: 10 g and a solution in which ITO fine particles having an average particle size of 60 nm are dispersed (content of ITO ultrafine particles 30% by weight, solvent: isopropyl alcohol; manufactured by Mitsubishi Materials Corporation): 5 g are mixed to form coating solution B. Obtained. The coating solution had a silicon oxide oligomer component content of 10% by weight and a viscosity of 5.4 mPa · s.
〔車両用窓ガラスの準備〕
矩形ガラスから所定の形状に切断し、端面の全てを研磨し、曲げ強化加工を行って作製した車両用のフロントドアガラス(UVグリーンガラス)の車内面(面積0.5m2)を研磨液で研磨し、水洗及び乾燥し、ガラス板とした。なお、ここで用いた研磨液は、ガラス用研磨剤ミレークA(T)(三井金属鉱業製)を水に混合した2重量%のセリア懸濁液である。
[Preparation of vehicle window glass]
The vehicle inner surface (area 0.5 m 2 ) of the vehicle front door glass (UV green glass) produced by cutting the rectangular glass into a predetermined shape, polishing all of the end faces, and performing bending strengthening processing with a polishing liquid Polished, washed with water and dried to obtain a glass plate. In addition, the polishing liquid used here is a 2% by weight ceria suspension obtained by mixing a glass abrasive Milleak A (T) (manufactured by Mitsui Metal Mining) with water.
実施例1
車両用窓ガラス板の車内面に塗布液A:9gを給液し、手作業で不織布(商品名:ベンコット、品番:AZ−8、メーカー:小津産業株式会社製)をガラス板に接触させて、塗布液を該窓ガラスの主面全面に引き延ばした。さらに塗布液A:1gを別の不織布(ベンコット)に染み込ませて端面塗布用の塗布材を得た。次に、端面塗布用の塗布材をガラス板の端面に接触させ、全周囲を払拭して、塗布液を端面に塗布した。このとき、主面と端面の塗布に用いた2つの塗布材には、面積で約1/3の部分に塗布液が染み込んでいた。その後、200℃で10分間焼成し、室温まで冷却させてゾルゲル膜が形成された車両用窓ガラスを得た。本実施例では、塗布液Aを主面用塗布液と端面用塗布液の両方に用い、主面を塗布後に端面を塗布した。得られた車両用窓ガラスの端面は、全面が黒く、良好な外観であった。
Example 1
The coating liquid A: 9 g is supplied to the inner surface of the vehicle window glass plate, and the nonwoven fabric (trade name: Bencott, product number: AZ-8, manufacturer: Ozu Sangyo Co., Ltd.) is brought into contact with the glass plate by hand. The coating liquid was stretched over the entire main surface of the window glass. Furthermore, 1 g of coating solution A was soaked into another nonwoven fabric (Bencot) to obtain a coating material for end face coating. Next, the coating material for end face application was brought into contact with the end face of the glass plate, the entire periphery was wiped off, and the coating liquid was applied to the end face. At this time, the coating liquid soaked into about 1/3 of the area of the two coating materials used for coating the main surface and the end surface. Then, it baked at 200 degreeC for 10 minute (s), it was made to cool to room temperature, and the window glass for vehicles in which the sol gel film was formed was obtained. In this example, the coating liquid A was used for both the main surface coating liquid and the end surface coating liquid, and the end surface was applied after the main surface was applied. The end surface of the obtained vehicle window glass was black on the entire surface and had a good appearance.
実施例2
塗布液B:1gを不織布(ベンコット)に染み込ませ、さらに車両用窓ガラスの車内面(主面)に塗布液B:10gを給液し、手作業で不織布(ベンコット)をガラス板に接触させて、塗布液を該窓ガラスの主面全面に引き延ばした。次に、塗布液A:1gを不織布(ベンコット)に染み込ませ、不織布を窓ガラス板の端面に接触させ、全周囲を払拭して、塗布液を端面に塗布した。その後、200℃で10分間焼成し、室温まで冷却させてゾルゲル膜が形成された車両用窓ガラスを得た。すなわち、本実施例では、塗布液Bを主面用塗布液、塗布液Aを端面用塗布液に用い、主面を塗布後に端面を塗布した。得られた車両用窓ガラスの端面は、全面が黒く、良好な外観であった。
Example 2
Coating solution B: 1 g of the nonwoven fabric (Bencot) is soaked, and further, 10 g of coating solution B is supplied to the inner surface (main surface) of the vehicle window glass, and the nonwoven fabric (Bencot) is brought into contact with the glass plate by hand. Then, the coating solution was stretched over the entire main surface of the window glass. Next, 1 g of coating liquid A was impregnated into the nonwoven fabric (Bencot), the nonwoven fabric was brought into contact with the end face of the window glass plate, the entire periphery was wiped off, and the coating liquid was applied to the end face. Then, it baked at 200 degreeC for 10 minute (s), it was made to cool to room temperature, and the window glass for vehicles in which the sol gel film was formed was obtained. That is, in this example, the coating liquid B was used as the main surface coating liquid, and the coating liquid A was used as the end surface coating liquid. The end surface of the obtained vehicle window glass was black on the entire surface and had a good appearance.
実施例3
塗布液A:1gを不織布(ベンコット)に染み込ませ、不織布(ベンコット)をガラス板の端面に接触させ、全周囲を払拭して、塗布液を端面に塗布した。次に、塗布液B:1gを不織布(ベンコット)に染み込ませ、さらに車両用窓ガラスの車内面(主面)に塗布液B:9gを給液し、手作業で不織布(ベンコット)基材に接触させて、塗布液を該窓ガラスの主面全面に引き延ばした。その後、200℃で10分間焼成し、室温まで冷却させてゾルゲル膜が形成された車両用窓ガラスを得た。すなわち、本実施例では、塗布液Bを主面用塗布液、塗布液Aを端面用塗布液に用い、端面を塗布後に主面を塗布した。得られた車両用窓ガラスの端面は、全面が黒く、良好な外観であった。
Example 3
The coating liquid A: 1 g was impregnated into the nonwoven fabric (Bencot), the nonwoven fabric (Bencot) was brought into contact with the end face of the glass plate, and the entire periphery was wiped off to apply the coating liquid to the end face. Next, 1 g of coating liquid B is impregnated into the nonwoven fabric (Bencot), and further, 9 g of coating liquid B is supplied to the inner surface (main surface) of the window glass for the vehicle, and manually applied to the nonwoven fabric (Bencot) substrate. It was made to contact and the coating liquid was extended over the main surface of this window glass. Then, it baked at 200 degreeC for 10 minute (s), it was made to cool to room temperature, and the window glass for vehicles in which the sol gel film was formed was obtained. That is, in this example, the coating liquid B was used as the main surface coating liquid, the coating liquid A was used as the end surface coating liquid, and the main surface was applied after the end surfaces were applied. The end surface of the obtained vehicle window glass was black on the entire surface and had a good appearance.
比較例
実施例1乃至3において、端面塗布のための材を用意せず、主面に塗布液を塗りひろげる塗布を端面への塗布にまで拡張した以外は、各実施例と同様の手順を実施し、車両用窓ガラスを得た。結果、各例とも、該主面の反対側面にまで塗布液が廻り込み外観品質が低下した。
Comparative Example In Examples 1 to 3, the same procedure as in each example was performed, except that the material for applying the end face was not prepared and the application for spreading the coating liquid on the main surface was extended to the application to the end face. And the window glass for vehicles was obtained. As a result, in each of the examples, the coating solution turned around to the opposite side of the main surface and the appearance quality deteriorated.
Claims (4)
端面が研磨されたガラス板を準備する工程、
該ガラス板の主面及び研磨された端面の少なくとも可視化可能な端面にゾルゲル膜を形成する工程
を有し、ゾルゲル膜を形成する工程は、ゾルゲル膜を形成するための塗布液を保持した保持材をガラス板に接触させて塗布する工程を有し、保持材からの塗布液の吐出状態を、主面への塗布と端面への塗布とで異なったものとなるように調整することを特徴とする車両用窓ガラスの製造方法。 A method of manufacturing a window glass for a vehicle having an end face that can be visualized.
A step of preparing a glass plate whose end face is polished;
A step of forming a sol-gel film on at least a visible end surface of the main surface and the polished end surface of the glass plate, and the step of forming the sol-gel film includes a holding material that holds a coating solution for forming the sol-gel film Characterized by adjusting the discharge state of the coating liquid from the holding material to be different between the application to the main surface and the application to the end surface. A method of manufacturing a vehicle window glass.
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JP2000264679A (en) * | 1999-03-17 | 2000-09-26 | Central Glass Co Ltd | Green coated glass base plate and its production |
JP2002012024A (en) * | 2000-06-30 | 2002-01-15 | Asahi Glass Co Ltd | Window glass for vehicle |
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JP2000264679A (en) * | 1999-03-17 | 2000-09-26 | Central Glass Co Ltd | Green coated glass base plate and its production |
JP2002012024A (en) * | 2000-06-30 | 2002-01-15 | Asahi Glass Co Ltd | Window glass for vehicle |
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JP2012131668A (en) * | 2010-12-22 | 2012-07-12 | Bridgestone Corp | Heat ray shielding glass and layered glass using the same |
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