JP6826285B2 - Manufacturing method of base material with coating film and base material with coating film - Google Patents
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Description
本発明は、塗布膜付基材、特に自動車の窓ガラスに適した塗布膜付基材、及びその製法に関する。 The present invention relates to a base material with a coating film, particularly a base material with a coating film suitable for window glass of an automobile, and a method for producing the same.
ガラス板等の基材、特に自動車用窓ガラスの表面には、紫外線遮蔽、赤外線遮蔽、撥水性、防曇性の付与を目的に塗布膜が設けられる。このような塗布膜として、上下方向に保持した板状の基材の上縁にノズルを介して塗布液を流し出すフローコート法により基材に塗布液を塗布し、乾燥することにより塗布膜を形成する方法がとられている（例えば、特許文献１〜４）。 A coating film is provided on the surface of a base material such as a glass plate, particularly an automobile window glass, for the purpose of imparting ultraviolet ray shielding, infrared ray shielding, water repellency, and antifogging property. As such a coating film, the coating film is applied to the base material by a flow coating method in which the coating liquid is poured out through a nozzle onto the upper edge of a plate-shaped base material held in the vertical direction, and dried to form the coating film. A method of forming is adopted (for example, Patent Documents 1 to 4).
上述のようなフローコート法、すなわち、塗布対象の板状の基材を傾けるか、垂直にした状態で基材を上下方向に保持し、前記基材の少なくとも一方の主面上の上辺側で、塗布膜を形成するための塗布液を吐出する主ノズルを水平方向又は略水平方向等横方向に基材に対して相対移動させながら、前記主ノズルから前記塗布液を前記基材の主面上に吐出する工程を備える塗布膜付基材の製法では、塗布液が基材の上辺側から下辺側へと流れていくので、塗布膜の膜厚分布は、上辺側から下辺側に向けて漸次膜厚が厚くなるものとなりやすい。 The flow coating method as described above, that is, the plate-shaped base material to be coated is held in the vertical direction in a state of being tilted or vertical, and on the upper side side on at least one main surface of the base material. , While moving the main nozzle for discharging the coating liquid for forming the coating film relative to the base material in the horizontal direction or the lateral direction such as substantially horizontal direction, the coating liquid is discharged from the main surface of the base material. In the manufacturing method of the base material with a coating film including the step of discharging upward, the coating liquid flows from the upper side to the lower side of the base material, so that the film thickness distribution of the coating film is from the upper side to the lower side. The film thickness tends to increase gradually.
基材を上下方向に保持したフローコート法にあっては、塗布液の流下方向で、膜厚が漸次厚くなる。さらには、下辺側は、基材の主面上を流動する塗布液の縁となることから、塗布液の液溜りが生じやすくなる。この塗布方法では、下辺側の膜厚が厚いものとなりやすいので、塗布液の乾燥、固化の過程で、塗布膜の下辺側でクラックが生じやすくなる。下辺側にクラックが生じると、そのクラックを起点にして、塗布膜全体にわたって、ヒビや割れが生じやすくなる。 In the flow coating method in which the base material is held in the vertical direction, the film thickness gradually increases in the flow direction of the coating liquid. Further, since the lower side serves as an edge of the coating liquid flowing on the main surface of the base material, the coating liquid tends to collect. In this coating method, the film thickness on the lower side tends to be thick, so that cracks are likely to occur on the lower side of the coating film in the process of drying and solidifying the coating liquid. When a crack is generated on the lower side, cracks or cracks are likely to occur over the entire coating film starting from the crack.
本発明は、板状の基材を上下方向に保持したフローコート法による基材への塗布膜の形成であっても、塗布液の流下方向の縁となる下辺側で、塗布膜の膜厚を薄くすることが可能な塗布方法、ひいては、自動車のドアの開閉可能な窓ガラスに適した塗布膜付基材を提供することを課題とする。 In the present invention, even when the coating film is formed on the substrate by the flow coating method in which the plate-shaped substrate is held in the vertical direction, the film thickness of the coating film is on the lower side which is the edge in the flow direction of the coating liquid. It is an object of the present invention to provide a coating method capable of thinning the coating film, and by extension, a substrate with a coating film suitable for a window glass that can be opened and closed of an automobile door.
本発明の塗布膜付基材の製法は、塗布対象の基材を傾けるか、垂直にした状態で基材を保持し、前記基材の少なくとも一方の主面上の上辺側で、“塗布膜を形成するための塗布液（以下、「主塗布液」と表記）”を吐出する主ノズルを略水平方向に相対移動させながら、前記主ノズルから前記塗布液を前記基材の主面上に吐出する工程を備えるものであり、
前記主塗布液が、前記主塗布液の吐出位置から前記基材の主面上の下辺側に渡って、液膜として保持された状態で、主面上の下辺側に、前記主塗布液に対して希釈性のある第二の溶剤（以下、「第二副塗布液」と表記）を塗布する工程を備えることを特徴とする。
本発明の塗布膜付基材の製法の要旨は、フローコート法による塗布で形成された、主塗布液による液膜が基材の主面に保持された状態で、下辺側に第二副塗布液を塗布し、下辺側での主塗布液による液膜の厚みを薄くすることで、形成される塗布液の下辺側の厚みを薄くするというものである。下辺側は、基材の主面上を流動する主塗布液の縁となることから、塗布液の液溜りが生じやすいものとはなるが、第二副塗布液を下辺側に塗布することで、液溜りによる問題を回避しやすくなる。その結果、塗布膜の下辺側では、クラックが生じにくいものとなり、ひいては、塗布膜の外観品質の向上につながるという効果が生じる。尚、本発明における「少なくとも一方の主面」の「主面」とは、基材の面全体のことで、「少なくとも一方」とは、基材の片側だけでも、両面でもよい、ということを意味している。
In the method for producing a base material with a coating film of the present invention, the base material to be coated is held in a tilted or vertical state, and "coating film" is formed on the upper side of at least one main surface of the base material. The coating liquid is transferred from the main nozzle onto the main surface of the base material while the main nozzle for discharging the coating liquid (hereinafter referred to as “main coating liquid”) for forming the coating liquid (hereinafter referred to as “main coating liquid”) is relatively moved in a substantially horizontal direction. It is equipped with a discharge process.
In a state where the main coating liquid is held as a liquid film from the discharge position of the main coating liquid to the lower side on the main surface of the base material, the main coating liquid is applied to the lower side on the main surface. On the other hand, it is characterized by comprising a step of applying a second dilutable solvent (hereinafter, referred to as "second subcoating liquid").
The gist of the method for producing a base material with a coating film of the present invention is that a liquid film formed by coating by the flow coating method is held on the main surface of the base material, and a second secondary coating is applied to the lower side. By applying the liquid and reducing the thickness of the liquid film formed by the main coating liquid on the lower side, the thickness of the formed coating liquid on the lower side is reduced. Since the lower side is the edge of the main coating liquid that flows on the main surface of the base material, it is easy for the coating liquid to collect, but by applying the second secondary coating liquid to the lower side, , It becomes easier to avoid the problem caused by the liquid pool. As a result, cracks are less likely to occur on the lower side of the coating film, which in turn leads to an effect of improving the appearance quality of the coating film. In the present invention, the "main surface" of the "at least one main surface" means the entire surface of the base material, and the "at least one" means that the base material may be on only one side or both sides. Means.
また、本発明の塗布膜付基材の製法は、さらには、主塗布液を前記基材の主面上に吐出する前に、“主塗布液に対して希釈性のある第一の溶剤（以下、「第一副塗布液」と表記）”を吐出する副ノズルを、前記副ノズルを略水平方向に相対移動させながら、前記副ノズルから前記第一副塗布液を前記基材の主面上に吐出する工程を備えるものとし、前記主ノズルから前記塗布液を前記基材の主面上に吐出する工程は、前記主面上に前記溶剤による液膜が保持された状態で行うものとすることが好ましい。 Further, in the method for producing a base material with a coating film of the present invention, before discharging the main coating liquid onto the main surface of the base material, "a first solvent dilutable with respect to the main coating liquid (1) Hereinafter, the sub-nozzle for discharging "first sub-coating liquid") "is moved relative to the sub-nozzle in a substantially horizontal direction, and the first sub-coating liquid is transferred from the sub-nozzle to the main surface of the base material. A step of discharging the coating liquid from the main nozzle onto the main surface of the base material shall be provided, and the step of discharging the coating liquid from the main nozzle onto the main surface of the base material shall be performed in a state where the liquid film of the solvent is held on the main surface. It is preferable to do so.
この好ましい態様では、第一副塗布液をフローコート法で塗布にして、“第一副塗布液による液膜（以下、「下地液膜」と表記）”を基材に形成し、下地液膜上に主塗布液をフローコート法で塗布して、主塗布液による液膜が形成される。下地液膜も、塗布を始める上辺側から下辺側に向けて漸次膜厚が厚くなる。この下地液膜は、この上に塗布される主塗布液を希釈していくことになるので、主塗布液を塗布した後は、基材上の塗布液中の固形分濃度は、塗布を始める上辺側から下辺側に向けて漸次減少する。 In this preferred embodiment, the first subcoating liquid is applied by the flow coating method to form a "liquid film with the first subcoating liquid (hereinafter referred to as" base liquid film ")" on the substrate, and the base liquid film is formed. The main coating liquid is applied onto the surface by the flow coating method to form a liquid film formed by the main coating liquid. The film thickness of the base liquid film also gradually increases from the upper side to the lower side where coating is started. Since the liquid film dilutes the main coating liquid applied on it, the solid content concentration in the coating liquid on the base material after the main coating liquid is applied is the upper side where the coating is started. It gradually decreases from to the lower side.
結果、基材に塗布された塗布液を乾燥及び固化させた後に形成される塗布膜の膜厚は上辺側から下辺側に向けて漸次膜厚が厚くなるものとはならず、比較的フラットな膜厚分布を有する塗布膜を形成できるようになる。また、下辺側において、塗布膜の膜厚が厚くなるのを抑制しやすいものとなる。 As a result, the film thickness of the coating film formed after drying and solidifying the coating liquid applied to the base material does not gradually increase from the upper side to the lower side, and is relatively flat. It becomes possible to form a coating film having a film thickness distribution. Further, it becomes easy to suppress the thickening of the coating film on the lower side.
さらには、主ノズルの吐出位置を調整することで、塗布膜付基材の非塗布領域を、副ノズルの吐出位置を調整することで、塗布膜の膜厚徐変部（塗布を始める上辺側から下辺側に向けて膜厚が漸次厚くなる領域）と、塗布膜の膜厚分布が比較的フラットな部位とを任意に設定することができる。また、下地液膜上に塗布された主塗布液は、下地液膜が形成された領域だけに塗り広がるので、基材上に形成される下地液膜の形成領域を、主塗布液の塗布領域とすることができる。例えば、基材の主面上の側辺側に下地液膜を形成しなかった場合、下地液膜を形成しなかった主面の側辺側領域を塗布膜の非塗布領域とすることができる。 Furthermore, by adjusting the discharge position of the main nozzle, the non-coating area of the base material with the coating film can be adjusted, and by adjusting the discharge position of the sub nozzle, the film thickness gradual change portion of the coating film (upper side where coating starts). A region where the film thickness gradually increases from the lower side to the lower side) and a portion where the film thickness distribution of the coating film is relatively flat can be arbitrarily set. Further, since the main coating liquid applied on the base liquid film spreads only in the region where the base liquid film is formed, the formation region of the base liquid film formed on the base material is the coating region of the main coating liquid. Can be. For example, when the base liquid film is not formed on the side surface side on the main surface of the base material, the side side region of the main surface on which the base liquid film is not formed can be used as the non-coating region of the coating film. ..
本発明の塗布膜付基材は、前記の方法で製造することができ、自動車のドアの開閉可能な窓ガラスとして使用されるものであり、前記ドアの上部フレームの収納部内に前記基材が収納される領域は、塗布膜が非塗布領域となっている塗布膜付基材において、
前記塗布膜は、塗布膜を形成するための塗布液を吐出するノズルを基材に対して相対移動させながら前記ノズルから前記塗布液を前記基材の主面上に吐出する工程を経て形成されたものであり、
前記塗布膜は、塗布膜の上辺側周縁部において、前記非塗布領域に向かって、膜厚が徐々に小さくなる第一膜厚徐変部を有し、前記膜厚徐変部の開始位置は、塗布膜の上辺側周縁部から鉛直方向に、５〜２００ｍｍの範囲にあって、塗布膜の上辺側周縁部と膜厚徐変部の開始位置とは略平行な関係にあり、
さらには、前記塗布膜は、塗布膜の下辺側において、下辺側に向って、膜厚が徐々に小さくなる第二膜厚徐変部と、第二膜厚徐変部と下辺との間に下辺側平坦部とを有することを特徴とする。
The base material with a coating film of the present invention can be produced by the above method and is used as a window glass that can be opened and closed of an automobile door, and the base material is contained in a storage portion of an upper frame of the door. The area to be stored is the base material with a coating film in which the coating film is a non-coating area.
The coating film is formed through a step of discharging the coating liquid from the nozzle onto the main surface of the base material while moving the nozzle for discharging the coating liquid for forming the coating film relative to the base material. Nozzle
The coating film has a first film thickness gradual change portion in which the film thickness gradually decreases toward the non-coating region at the upper peripheral edge portion of the coating film, and the start position of the film thickness gradual change portion is In the vertical direction from the upper peripheral edge of the coating film in the range of 5 to 200 mm, the upper peripheral edge of the coating film and the start position of the film thickness gradual change portion are in a substantially parallel relationship.
Further, the coating film is formed between the second film thickness gradual change portion and the second film thickness gradual change portion and the lower side, where the film thickness gradually decreases toward the lower side on the lower side of the coating film. It is characterized by having a flat portion on the lower side.
塗布膜の機能性を発揮させるためには、塗布膜のほとんどの領域では、一定の膜厚があることが好ましい。しかしながら、非塗布領域近くの塗布膜は、光学的な歪を抑制するために、膜厚が分布していることが好ましい。具体的には、塗布膜の上辺側周縁部において、前記非塗布領域に向かって、膜厚が徐々に小さくなる第一膜厚徐変部を有しているものとしている。また、この塗布膜付基材は、塗布膜の下辺側を、第二膜厚徐変部と、第二膜厚徐変部と下辺との間に下辺側平坦部とすることで、下辺側周縁部での塗布膜の膜厚を薄いものとしている。そのため、下辺側で、クラックが発生し難くなり、ひいては、塗布膜の外観品質を向上せしめる。 In order to exert the functionality of the coating film, it is preferable that most regions of the coating film have a constant film thickness. However, it is preferable that the coating film near the non-coated region has a distributed film thickness in order to suppress optical distortion. Specifically, it is assumed that the upper peripheral edge portion of the coating film has a first film thickness gradual change portion in which the film thickness gradually decreases toward the non-coating region. Further, in this base material with a coating film, the lower side of the coating film is formed as a lower side flat portion between the second film thickness gradual change portion and the second film thickness gradual change portion and the lower side. The film thickness of the coating film at the peripheral portion is thin. Therefore, cracks are less likely to occur on the lower side, which in turn improves the appearance quality of the coating film.
前記の方法では、基材下辺側にあっては、塗布された主塗布液の大部分が、第二副塗布液によって押し流されて基材から除去される。基材上には、除去しきれなかった主塗布液が残り、これに起因して概略平坦な膜厚分布を有する下辺側平坦部が形成されることになる。そして、主塗布液と第二副塗布液とによる液膜の表面張力によって、前記下辺側平坦部と、膜厚を薄くする処理をされなかった塗布膜領域との膜厚を調整するように、第二膜厚徐変部が形成されるようになる。 In the above method, on the lower side of the base material, most of the applied main coating liquid is washed away by the second sub coating liquid and removed from the base material. The main coating liquid that could not be completely removed remains on the base material, and as a result, a flat portion on the lower side having a substantially flat film thickness distribution is formed. Then, the film thickness of the lower flat portion and the coating film region that has not been thinned is adjusted by the surface tension of the liquid film formed by the main coating liquid and the second secondary coating liquid. A second film thickness gradual change portion is formed.
第一膜厚徐変部の開始位置は、塗布膜の上辺側周縁部から鉛直方向に、好ましくは５〜１５０ｍｍ、より好ましくは５〜５０ｍｍの範囲にあって、塗布膜の上辺側周縁部と膜厚徐変部の開始位置とは略平行な関係とする。２００ｍｍ超では、膜の性能を確保する範囲が狭くなってしまうという傾向がある。 The starting position of the first film thickness gradual change portion is in the range of 5 to 150 mm, more preferably 5 to 50 mm in the vertical direction from the upper peripheral edge of the coating film, and is equal to the upper peripheral edge of the coating film. The relationship is substantially parallel to the start position of the film thickness gradual change portion. If it exceeds 200 mm, the range for ensuring the performance of the film tends to be narrowed.
また、基材の主面と第一膜厚徐変部の塗布膜と成す角を、０．０００５〜０．０２°、さらには０．０００５〜０．０１５°、またさらには０．００１５〜０．００２°とすることが好ましい。０．０００５°未満では、膜厚が薄く性能が低下する傾向があるし、０．０２°超では、膜厚が厚くなるため、膜とガラス面との境界でひっかかりが生じやすくなることや、膜歪みが生じやすくなる、という傾向がある。 Further, the angle formed by the main surface of the base material and the coating film of the first film thickness gradual change portion is 0.0005 to 0.02 °, further 0.0005 to 0.015 °, and further 0.0015 to. It is preferably 0.002 °. If it is less than 0.0005 °, the film thickness tends to be thin and the performance tends to deteriorate, and if it exceeds 0.02 °, the film thickness becomes thick, so that the boundary between the film and the glass surface is likely to be caught. There is a tendency for film thickness distortion to occur easily.
本発明の塗布膜付基材の製法は、自動車のドアの開閉可能な窓ガラスとして使用される塗布膜付基材において下辺側の塗布膜の膜厚が厚くなるのを抑制できるので、クラックの発生を抑制しやすく、塗布膜の外観品質の向上に奏功する。また、前記塗布膜の形成を、片側とする場合、自動車用途にあっては、塗布膜の形成は、車内側面とすることが、特に有用である。 The method for producing a base material with a coating film of the present invention can prevent the coating film on the lower side from becoming thicker in the base material with a coating film used as a window glass that can be opened and closed of an automobile door. It is easy to suppress the occurrence and is effective in improving the appearance quality of the coating film. Further, when the coating film is formed on one side, it is particularly useful that the coating film is formed on the inner surface of the vehicle in an automobile application.
本発明の具体的な実施態様を以下に詳述する。
１．塗布膜付基材の製法に使用される材料例
＜基材例＞
本発明の塗布膜付基材の製法に使用される板状の基材は、例えば、ガラス基材の場合には、建築用や車両用の窓や鏡に使用されているフロ−ト法、又は、ロ−ルアウト法で製造されたソーダ石灰ケイ酸塩ガラス、表示装置のカバーガラスや基板ガラスに使用されているソーダ石灰ケイ酸塩ガラス、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。当前記板ガラスには、無色のもの、着色のもの共に使用可能である。
Specific embodiments of the present invention will be described in detail below.
1. 1. Example of material used in the method of manufacturing a base material with a coating film <Example of base material>
The plate-shaped base material used in the method for producing a base material with a coating film of the present invention is, for example, in the case of a glass base material, the float method used for windows and mirrors for construction and vehicles. Alternatively, use inorganic transparent flat glass such as soda lime silicate glass manufactured by the roll-out method, soda lime silicate glass used for the cover glass and substrate glass of display devices, and non-alkali glass. it can. Both colorless and colored glass plates can be used.
板状の基材の形状は、特に限定されるものではないが、上辺２ａ、側辺２ｂ、２ｃ、下辺２ｄを備えるものが好適に使用される。各辺は、より大きな基材から切断されて形成された切断面であり、その切断面は、研削や研磨が施されていてもよい。また、基材として、平板も、湾曲している板も、どちらも使用することができる。湾曲している基材の場合、塗布膜の形成は、凸面側としてもよいが、当該基材が自動車用の窓ガラスとして使用されるときは、凹面側が室内側面となるので、塗布膜の形成は、凹面側面とすることが好ましいものとなる。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、ＴＦＴ用ガラス、ＰＤＰ用ガラス、光学フィルター用基材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 plate-shaped base material is not particularly limited, but one having an upper side 2a, a side side 2b, 2c, and a lower side 2d is preferably used. Each side is a cut surface formed by cutting from a larger substrate, and the cut surface may be ground or polished. Further, as the base material, either a flat plate or a curved plate can be used. In the case of a curved base material, the coating film may be formed on the convex side, but when the base material is used as a window glass for an automobile, the concave side is the indoor side surface, so that the coating film is formed. Is preferably a concave side surface. Furthermore, in addition to various tempered glasses such as air-cooled tempered glass and chemically tempered glass, wire-reinforced glass can also be used. Furthermore, various glass substrates such as borosilicate glass, low expansion glass, zero expansion glass, low expansion crystallized glass, zero expansion crystallized glass, TFT glass, PDP glass, and optical filter base glass are used. be able to.
また、ガラス板基材以外に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板基材を使用してもよい。 In addition to the glass plate base material, a resin plate base material such as polyethylene terephthalate resin, polycarbonate resin, polycarbonate resin, polyvinyl chloride resin, or polyethylene resin may be used.
＜主塗布液例＞
主塗布液は、基材への塗布後に、乾燥及び固化させることで塗布膜が形成せしめるものであり、塗布膜となる固形分または硬化性化合物と溶媒とを備えるものであれば限定されるものではない。
<Example of main coating liquid>
The main coating liquid is one in which a coating film is formed by drying and solidifying after coating on a substrate, and is limited as long as it contains a solid content or a curable compound to be a coating film and a solvent. is not it.
主塗布液としては、例えば、自動車用の被膜形成で一般的に用いられるアルコキシド化合物を加水分解及び重縮合反応させてオリゴマーを有する塗布液やポリシラザンなどの酸化ケイ素を主成分とする被膜を形成するものなどが用いられる。その他にもエポキシやウレタンなどの被膜を形成する塗布液が挙げられる。 As the main coating liquid, for example, an alkoxide compound generally used in film formation for automobiles is hydrolyzed and polycondensed to form a coating liquid having an oligomer or a film containing silicon oxide as a main component such as polysilazane. Things are used. In addition, a coating liquid that forms a film such as epoxy or urethane can be mentioned.
＜第一副塗布液、第二副塗布液＞
第一、第二副塗布液は、主塗布液を希釈する機能を有するものであり、主塗布液の種類により選択される。第一、第二副塗布液は、前記主塗布液を硬化または相分離させることなく希釈できる溶媒で、且つ前記基材との濡れ性が高い、即ち接触角が３０°以下のものが好ましく用いられる。尚、前記接触角は、ＪＩＳ Ｒ ３２５７（１９９９年）の静滴法に準拠した方法によって求めることができる。
<First secondary coating liquid, second secondary coating liquid>
The first and second secondary coating liquids have a function of diluting the main coating liquid, and are selected according to the type of the main coating liquid. The first and second secondary coating liquids are preferably solvents that can be diluted without curing or phase-separating the main coating liquid and have high wettability with the base material, that is, having a contact angle of 30 ° or less. Be done. The contact angle can be determined by a method based on the static drip method of JIS R 3257 (1999).
主塗布液の溶媒と、第一、第二副塗布液とは、それぞれの溶解度パラメーター（ＳＰ値）が近いほど好ましい。主塗布液と第一副塗布液とのＳＰ値の差、及び主塗布液と第二副塗布液とのＳＰ値の差、それぞれとも、１．５（ｃａｌ／ｃｍ３）１／２未満であることが好ましい。このＳＰ値の差が１．５（ｃａｌ／ｃｍ３）１／２以上の場合、主塗布液中の固形分が溶解できなくなって、固形分の析出または、液の相分離が生じやすくなる。前記ＳＰ値の差は、好ましくは１．０（ｃａｌ／ｃｍ３）１／２以下、より好ましくは０．５（ｃａｌ／ｃｍ３）１／２以下が望ましい。主塗布液の溶媒と第一、第二副塗布液は同一の物質であってもよい。 The closer the solubility parameters (SP values) of the solvent of the main coating liquid and the first and second secondary coating liquids are, the more preferable. The difference in SP value between the main coating liquid and the first sub coating liquid, and the difference in SP value between the main coating liquid and the second sub coating liquid, both are less than 1.5 (cal / cm 3 ) 1/2 . It is preferable to have. When the difference in SP value is 1.5 (cal / cm 3 ) 1/2 or more, the solid content in the main coating liquid cannot be dissolved, and the solid content is likely to precipitate or the liquid phase is separated easily. The difference in SP values is preferably 1.0 (cal / cm 3 ) 1/2 or less, and more preferably 0.5 (cal / cm 3 ) 1/2 or less. The solvent of the main coating liquid and the first and second secondary coating liquids may be the same substance.
なお、ＳＰ値は、一般的に知られる溶解度パラメーターで、溶解性や相溶性の指標となる。ＳＰ値は、液体の蒸発熱から計算する方法や、分子構造に基づいて算出するＨａｎｓｅｎ法やＨｏｙ法、Ｓｍａｌｌ法、Ｆｅｄｏｒの推算法等が知られている。本発明においては、例えばＲ．Ｆ．Ｆｅｄｏｒｓ：Ｐｏｌｙｍ．Ｅｎｇ．Ｓｃｉ．，１４（２），１４７−１５４（１９７４）に記載されている、分子構造から算出するＦｅｄｏｒの推算法を用いた。なお、本発明に関して規定しているＳＰ値は２５℃の測定条件で求めた値である。 The SP value is a generally known solubility parameter and serves as an index of solubility and compatibility. Known methods include a method of calculating the SP value from the heat of vaporization of a liquid, a Hansen method, a Hoy method, a Small method, and a Fedor estimation method, which are calculated based on the molecular structure. In the present invention, for example, R. F. Fedors: Polym. Eng. Sci. , 14 (2), 147-154 (1974), Fedor's estimation method calculated from the molecular structure was used. The SP value specified for the present invention is a value obtained under measurement conditions of 25 ° C.
第一、第二副塗布液は、基材との濡れ性が高いものが好ましい。基材の濡れ性は、基材に対す接触角が３０°以下が好ましい。さらには２０°以下が好ましい。接触角が大きい場合、副塗布液の液膜が***し易く、塗布液を大量に要するため、好ましくない。 The first and second secondary coating liquids preferably have high wettability with the base material. The wettability of the base material is preferably such that the contact angle with respect to the base material is 30 ° or less. Further, 20 ° or less is preferable. When the contact angle is large, the liquid film of the subcoating liquid is easily split and a large amount of coating liquid is required, which is not preferable.
第一、第二副塗布液は、主塗布液の種類により選択される。例えば、主塗布液がポリシラザン（メルクパフォーマンスマテリアルズ製ＮＰ１１０）の場合、主塗布液中の溶媒としてキシレン（ＳＰ値：９．１（ｃａｌ／ｃｍ３）１／２）を用いており、副塗布液として、ＳＰ値が等しいキシレン（ＳＰ値：９．１（ｃａｌ／ｃｍ３）１／２）やｎ−ヘキサン（ＳＰ値：７．２（ｃａｌ／ｃｍ３）１／２）、シクロヘキサノン（ＳＰ値：９．８（ｃａｌ／ｃｍ３）１／２）、２−ヘプタン（ＳＰ値：８．５（ｃａｌ／ｃｍ３）１／２）などが好ましい。 The first and second secondary coating liquids are selected according to the type of main coating liquid. For example, when the main coating liquid is polysilazane (NP110 manufactured by Merck Performance Materials), xylene (SP value: 9.1 (cal / cm 3 ) 1/2 ) is used as the solvent in the main coating liquid, and the secondary coating is used. As a liquid, xylene (SP value: 9.1 (cal / cm 3 ) 1/2 ), n-hexane (SP value: 7.2 (cal / cm 3 ) 1/2 ), cyclohexanone (SP) having the same SP value Values: 9.8 (cal / cm 3 ) 1/2 ), 2-heptane (SP value: 8.5 (cal / cm 3 ) 1/2 ) and the like are preferable.
２．塗布膜の形成
＜主ノズル、副ノズルについて＞
主ノズルおよび副ノズルに使用されるノズルは、主塗布液、第一副塗布液を吐出できるものであれば、特に制限されるものではない。単数のノズル、複数本のノズルが並列された複合ノズル、幅が広いスリット状の吐出口を有するスリットノズル等が使用される。主、副ノズル径は、０．５ｍｍφ〜５ｍｍφが好ましく、１ｍｍφ〜２ｍｍφがより好ましい。副塗布液を塗布する場合、液割れを生じさせてはならないため、副ノズルのノズル径は主ノズルよりも太い方が好ましい。
2. 2. Formation of coating film <Main nozzle and sub nozzle>
The nozzles used for the main nozzle and the sub-nozzle are not particularly limited as long as they can discharge the main coating liquid and the first sub-coating liquid. A single nozzle, a composite nozzle in which a plurality of nozzles are arranged in parallel, a slit nozzle having a wide slit-shaped discharge port, and the like are used. The main and sub nozzle diameters are preferably 0.5 mmφ to 5 mmφ, more preferably 1 mmφ to 2 mmφ. When applying the sub-coating liquid, the nozzle diameter of the sub-nozzle is preferably larger than that of the main nozzle because liquid cracking must not occur.
＜ノズルの操作と塗布液の基材への塗布＞
主ノズル、副ノズルを用いた、基材への主塗布液、第一副塗布液への塗布について、図面を用いて説明する。図１は、上辺２ａ、側辺２ｂ、側辺２ｃ、下辺２ｄを有する自動車の窓ガラスとして用いられる基材２に対して、主ノズル５０、副ノズル６０を横方向に基材２の主面の傾斜した上辺２ａの略平行に相対移動させなら、主塗布液、第一副塗布液を吐出する状態を模式的に表したものである。この図では基材２が上下方向に保持され静置された状態で主ノズル５０、主ノズル５０の下方の位置の副ノズル６０が横方向に相対移動された状態を表している。主ノズル５０、及び副ノズル６０を基材２に対して相対移動させる際は、ノズルの吐出口が対向する辺（図１の場合は、上辺２ａ）から間隔を塗布液が吐出されない領域として空け、且つ対向する辺に略平行に沿うように基材に対して相対移動させることで、塗布膜の非塗布領域を形成することがきる。
<Nozzle operation and application of coating liquid to the base material>
The application to the main coating liquid and the first auxiliary coating liquid to the base material using the main nozzle and the sub nozzle will be described with reference to the drawings. FIG. 1 shows the main surface of the base material 2 in which the main nozzle 50 and the sub nozzle 60 are laterally arranged with respect to the base material 2 used as a window glass of an automobile having an upper side 2a, a side side 2b, a side side 2c, and a lower side 2d. When the main coating liquid and the first secondary coating liquid are discharged relative to each other in substantially parallel to the inclined upper side 2a of the above, the state of discharging is schematically represented. In this figure, the main nozzle 50 and the sub-nozzle 60 located below the main nozzle 50 are relatively moved in the lateral direction while the base material 2 is held in the vertical direction and left to stand. When moving the main nozzle 50 and the sub-nozzle 60 relative to the base material 2, leave a space between the side where the nozzle discharge port faces (upper side 2a in the case of FIG. 1) as a region where the coating liquid is not discharged. In addition, a non-coated region of the coating film can be formed by moving the coating film relative to the base material so as to be substantially parallel to the opposite sides.
尚、基材２が正方形、長方形等矩形の場合は、ひとつの辺を上辺側として基材を上下方向に保持し、主ノズル５０、副ノズル６０を上辺側とした辺に対して、水平方向又は略水平方向に相対移動させる。この態様は、塗布膜付基材が、表示装置用の基材や、建材として使用される場合に有効となる。 When the base material 2 is a rectangle such as a square or a rectangle, the base material is held in the vertical direction with one side as the upper side, and the main nozzle 50 and the sub nozzle 60 are in the horizontal direction with respect to the upper side. Or move relative to each other in a substantially horizontal direction. This aspect is effective when the base material with a coating film is used as a base material for a display device or a building material.
図２は、基材２を側辺２ｂ側から観察したもので、主ノズル５０、副ノズルを基材２に対して相対移動させるときの各ノズルの配置位置を模式的に表したものである。図３は、基材２を側辺２ｂ側から観察したもので、下地液膜６２上に、主塗布液による液膜５２を形成したときの状態を模式的に表したものである。 FIG. 2 is an observation of the base material 2 from the side 2b side, and schematically shows the arrangement position of each nozzle when the main nozzle 50 and the sub nozzle are moved relative to the base material 2. .. FIG. 3 is an observation of the base material 2 from the side 2b side, and schematically shows a state when the liquid film 52 of the main coating liquid is formed on the base liquid film 62.
図１〜図３に示すように、上下方向に保持された板状の基材の上面（基材２の主面の上辺２ａ側の領域）にて、副ノズル６０を、基材２に対して、相対移動させながら、すなわち、下地液膜６２の最上辺６１（膜厚徐変部の最下辺６１）に沿って副ノズル６０を横方向に相対移動しながら、副塗布液を吐出する。副塗布液は重力によってガラス主面を基材２の下辺２ｄ側に流れていく。この際に生じる下地液膜の膜厚は、下方ほど、厚くなる。下地液膜６２の最上辺６１（図１に破線で示す）は、塗布膜の膜厚分布が比較的フラットな部位の始点となる位置であり、塗布膜の見栄えからすると、基材２の上辺２ａとは、略平行の関係とすることが好ましい。 As shown in FIGS. 1 to 3, the sub-nozzle 60 is attached to the base material 2 on the upper surface of the plate-shaped base material (the region on the upper side 2a side of the main surface of the base material 2) held in the vertical direction. The sub-coating liquid is discharged while moving relative to each other, that is, while moving the sub-nozzle 60 laterally along the uppermost side 61 of the base liquid film 62 (the lowermost side 61 of the film thickness gradual change portion). The subcoating liquid flows on the main surface of the glass to the lower side 2d side of the base material 2 by gravity. The film thickness of the base liquid film formed at this time becomes thicker toward the bottom. The uppermost side 61 (indicated by a broken line in FIG. 1) of the base liquid film 62 is a position where the film thickness distribution of the coating film becomes a starting point of a relatively flat portion, and from the appearance of the coating film, the upper side of the base material 2 It is preferable that the relationship with 2a is substantially parallel.
下地液膜６２が基材２に保持された状態で、主ノズル５０を、基材２に対して、相対移動させながら、すなわち、膜厚徐変部の最上辺５１（図１に実線で示す）に沿って主ノズル６０を横方向に相対移動しながら、主塗布液を吐出する。この際、主ノズル５０からの主塗布液の吐出を、副塗布液を塗布した領域外、例えば、主ノズル５０を相対移動させる位置を、下地膜６２が形成されていない領域（最上辺６１と上辺２ａとの間）で行えば、塗布膜の最上辺の部位（図面にあっては、膜厚徐変部の最上辺５１に相当する。）の形状（見切り形状とも呼ばれる）が滑らか線形状とすることができ、塗布膜付基材の見栄えを向上できる。 With the base liquid film 62 held by the base material 2, the main nozzle 50 is relatively moved with respect to the base material 2, that is, the uppermost side 51 of the film thickness gradual change portion (shown by a solid line in FIG. 1). ), While the main nozzle 60 is relatively moved in the lateral direction, the main coating liquid is discharged. At this time, the discharge of the main coating liquid from the main nozzle 50 is outside the region where the sub coating liquid is applied, for example, the position where the main nozzle 50 is relatively moved is the region where the base film 62 is not formed (the uppermost side 61). If it is performed between the upper side 2a), the shape (also called the parting shape) of the uppermost part of the coating film (corresponding to the uppermost side 51 of the film thickness gradual change portion in the drawing) is a smooth line shape. The appearance of the base material with a coating film can be improved.
主塗布液は、重力によってガラス主面を基材２の下辺２ｄ側に流れていく。この際に生じる主塗布液の液膜５２の膜厚は、下方ほど、厚くなる。下地液膜６２と、主塗布液の液膜５２は混ざり合うので、塗布膜を形成するための塗布液中の固形分の濃度は、下方ほど薄くなる。その結果、膜厚徐変部の最上辺５１と膜厚徐変部の最下辺６１との間にある膜の膜厚分布（「第１の膜厚分布」とする）と、膜厚徐変部の最下辺６１から、基材の下辺２ｄ側にある膜の膜厚分布（第２の膜厚分布）とする）は異なるものとなる。尚、図１に示す通り、基材の上辺２ａと膜厚徐変部の最上辺５１との間は、塗布膜が形成されない非塗布領域４となる。 The main coating liquid flows on the glass main surface to the lower side 2d side of the base material 2 by gravity. The film thickness of the liquid film 52 of the main coating liquid generated at this time becomes thicker toward the bottom. Since the base liquid film 62 and the liquid film 52 of the main coating liquid are mixed, the concentration of the solid content in the coating liquid for forming the coating film becomes thinner toward the bottom. As a result, the film thickness distribution (referred to as "first film thickness distribution") between the uppermost side 51 of the film thickness gradual change portion and the lowermost side 61 of the film thickness gradual change portion, and the film thickness gradual change. The film thickness distribution (the second film thickness distribution) of the film on the lower side 2d side of the base material is different from the lowermost side 61 of the portion. As shown in FIG. 1, the space between the upper side 2a of the base material and the uppermost side 51 of the film thickness gradual change portion is a non-coating region 4 in which a coating film is not formed.
各ノズルの基材２に対する相対移動、及び各塗布液の吐出は、基材の上辺２ａ側だけでもよいし、図６〜図８に示すように、主ノズル５０及び副ノズル６０からなる群から選ばれる少なくとも一つを基材２に対して縦方向に相対移動させる工程を含む方法としても良い。それらの相対移動の軌跡は、図６〜図８の各図で示す、破線、実線の矢印で示したようになる。 The relative movement of each nozzle to the base material 2 and the discharge of each coating liquid may be performed only on the upper side 2a side of the base material, or as shown in FIGS. 6 to 8, from the group consisting of the main nozzle 50 and the sub nozzle 60. The method may include a step of moving at least one selected relative to the base material 2 in the vertical direction. The loci of these relative movements are as shown by the broken lines and solid arrows shown in the respective figures of FIGS. 6 to 8.
例えば、図６は、基材の主面上の側辺側にも塗膜の非塗布領域を形成する場合の、主ノズル５０、副ノズル６０の基材２に対して相対移動させながら主塗布液、副塗布液を吐出する状態を模式的に表したものである。副ノズル６０を、側辺２ｃから任意の間隔を副塗布液が吐出されない領域として空けて、基材２の下辺側から側辺２ｃに沿うように基材２に対して相対移動させながら副塗布液を吐出する。その後、基材の上辺２ａ側から任意の間隔を副塗布液が吐出されない領域として空けて、上辺２ａに沿うように副ノズル６０を基材２に対して相対移動ささながら副塗布液を吐出し、さらに、側辺２ｂから任意の間隔を副塗布液が吐出されない領域として空けて、基材２の上辺側から側辺２ｂに沿うように基材２に対して相対移動させながら副塗布液を吐出して、下地液膜を形成する。下地液膜が形成された後、主ノズル５０を基材の上辺２ａ側から任意の間隔を主塗布液が吐出されない領域として空けて、上辺２ａに沿うように主ノズル５０を基材２に対して相対移動ささながら主塗布液を吐出する。このような塗布方法とすることで側辺２ｂ、２ｃ側に非塗布領域４を形成することできる。ここでの任意の間隔は、塗布膜付基材１が、膜厚徐変部３１、非塗布領域４が所定の領域を形成するように設けられる。これらの所定の領域の大きさ等は、塗布膜付基材１が説明される箇所にて説明される。 For example, FIG. 6 shows the main coating while relatively moving the main nozzle 50 and the sub nozzle 60 with respect to the base material 2 when a non-coating region of the coating film is formed on the side side of the main surface of the base material. It schematically shows the state of discharging the liquid and the subcoating liquid. The sub-nozzle 60 is left at an arbitrary interval from the side 2c as a region where the sub-coating liquid is not discharged, and the sub-nozzle 60 is sub-coated while being relatively moved from the lower side of the base material 2 along the side 2c along the side 2c. Discharge the liquid. After that, an arbitrary interval is left from the upper side 2a side of the base material as a region where the sub-coating liquid is not discharged, and the sub-coating liquid is discharged while the sub-nozzle 60 is relatively moved with respect to the base material 2 along the upper side 2a. Further, an arbitrary interval is left as a region where the subcoating liquid is not discharged from the side side 2b, and the subcoating liquid is moved relative to the base material 2 from the upper side of the base material 2 along the side side 2b. Discharge to form a base liquid film. After the base liquid film is formed, the main nozzle 50 is left at an arbitrary interval from the upper side 2a side of the base material as a region where the main coating liquid is not discharged, and the main nozzle 50 is placed on the base material 2 along the upper side 2a. The main coating liquid is discharged just like the relative movement. By adopting such a coating method, the non-coated region 4 can be formed on the side sides 2b and 2c. Here, the base material 1 with a coating film is provided so that the film thickness gradual change portion 31 and the non-coating region 4 form a predetermined region. The size and the like of these predetermined regions will be described in the places where the base material 1 with a coating film is described.
基材の主面上の側辺側にも塗膜の非塗布領域を形成する場合の態様として、図７に示すように主ノズル５０を副ノズル６０と同様の軌跡で基材２に対して相対移動させる態様としてもよいし、図８に示すように側辺２ｂ側、側辺２ｃ側にて各ノズルを基材２に対して縦方向に相対移動させて基材の側辺２ｂ、２ｃ側に液を吐出した後に、基材の上辺２ａ側にて各ノズルを基材２に対して横方向に相対移動させて基材に液を吐出する方法としても良い。下地液膜上に塗布された主塗布液は、下地液膜が形成された領域だけに塗り広がるので、側辺２ｂ、２ｃ側に非塗布領域４を有する塗布膜付基材を効率良く製造するためには、図６に示す方法がより好ましい。 As an embodiment in which a non-coated region of the coating film is formed on the side surface side of the main surface of the base material, as shown in FIG. 7, the main nozzle 50 is placed on the base material 2 in the same locus as the sub nozzle 60. It may be a mode of relative movement, or as shown in FIG. 8, each nozzle is moved relative to the base material 2 in the vertical direction on the side 2b side and the side side 2c side to move the side sides 2b, 2c of the base material. After discharging the liquid to the side, each nozzle may be moved relative to the base material 2 in the lateral direction on the upper side 2a side of the base material to discharge the liquid to the base material. Since the main coating liquid applied on the base liquid film spreads only in the region where the base liquid film is formed, a base material with a coating film having a non-coating region 4 on the side 2b and 2c sides is efficiently manufactured. For this purpose, the method shown in FIG. 6 is more preferable.
各塗布液の吐出時において、各ノズルが側辺２ｂ、２ｃに近い位置にあるとき（例えば、側辺から垂直方向に０〜１０ｍｍの位置にあるとき）は、各ノズルの向きを、基材の内側方向に向ける等の操作を行って、各ノズルからの液の吐出方向を基材２の内側方向となるように傾きを設けることが好ましい。こうすることにより、主塗布液、副塗布液の塗布対象面の裏側に液が回りこむことを防止しやすくなる。 When each nozzle is located close to the side sides 2b and 2c at the time of discharging each coating liquid (for example, when the position is 0 to 10 mm in the vertical direction from the side side), the orientation of each nozzle is set to the base material. It is preferable to perform an operation such as directing the liquid toward the inside of the base material 2 so that the discharge direction of the liquid from each nozzle is toward the inside of the base material 2. By doing so, it becomes easy to prevent the liquid from sneaking into the back side of the coating target surface of the main coating liquid and the sub coating liquid.
各ノズルの相対移動のスピード、基材２に対する各塗布液の吐出角度、基材２と各ノズルの吐出口との距離、液の吐出圧は、吐出される液の粘度、各ノズルからの液の吐出量、基材２の設置角度、液塗布時の液割れの発生度合い、形成される塗布膜の光学的な歪み、膜厚などを考慮して適宜決定される。 The relative movement speed of each nozzle, the discharge angle of each coating liquid with respect to the base material 2, the distance between the base material 2 and the discharge port of each nozzle, the discharge pressure of the liquid are the viscosity of the discharged liquid and the liquid from each nozzle. It is appropriately determined in consideration of the discharge amount of the base material 2, the installation angle of the base material 2, the degree of occurrence of liquid cracking at the time of liquid coating, the optical distortion of the formed coating film, the film thickness, and the like.
尚、塗布液を塗布するときは、板状の基材２は、図１、６、７、８に示したように基材２の側辺２ｃ、２ｄが水平方向を示す基準線７に対して垂直となる状態（基準線７１に沿うような状態）で保持されることが好ましい。このように保持することで、塗布液の塗布面から反対側の面に塗布液が回り込むことを防止しやすくなる。また、板状の基材２が湾曲している場合、図２、図３に示したように基材２の側辺２ｃ、２ｄの上部が水平方向を示す基準線７に対して垂直になる状態で基材を保持することが好ましい。このように保持することで、塗布液のスムーズな流下が生じ、塗布効率が上がる。尚、図１、２、３、６、７、８には、水平方向を示す基準線７に対して垂直な方向を示す補助線７１も合わせて示している。 When the coating liquid is applied, the plate-shaped base material 2 has a reference line 7 in which the side sides 2c and 2d of the base material 2 indicate the horizontal direction as shown in FIGS. 1, 6, 7, and 8. It is preferable to hold it in a vertical state (a state along the reference line 71). By holding in this way, it becomes easy to prevent the coating liquid from wrapping around from the coating surface to the opposite surface of the coating liquid. Further, when the plate-shaped base material 2 is curved, the upper portions of the side sides 2c and 2d of the base material 2 are perpendicular to the reference line 7 indicating the horizontal direction as shown in FIGS. 2 and 3. It is preferable to hold the base material in the state. By holding in this way, a smooth flow of the coating liquid occurs, and the coating efficiency is improved. In addition, in FIGS. 1, 2, 3, 6, 7, and 8, an auxiliary line 71 indicating a direction perpendicular to the reference line 7 indicating the horizontal direction is also shown.
以上では、主塗布膜を塗布する前に、第一副塗布液を用いて下地液膜を形成する方法を述べた。比較的フラットな膜厚分布を有する塗布膜を形成するためには、この方法とすることが好ましいことは言うまでもない。しかしながら、第一副塗布液を用いて下地液膜を形成することなしに、主塗布液を基材２に塗布する方法としてもよい。この場合、主塗布液の吐出位置、すなわち最上辺５１から下辺２ｄに向って漸次膜厚が厚くなる膜構造、すなわち第一膜厚徐変部３１が、第二膜厚徐変部の開始位置まで広がる構造となる。 In the above, the method of forming the undercoat liquid film using the first subcoating liquid before applying the main coating film has been described. Needless to say, this method is preferable in order to form a coating film having a relatively flat film thickness distribution. However, a method of applying the main coating liquid to the base material 2 may be used without forming the base liquid film using the first secondary coating liquid. In this case, the discharge position of the main coating liquid, that is, the film structure in which the film thickness gradually increases from the uppermost side 51 to the lower side 2d, that is, the first film thickness gradual change portion 31, is the start position of the second film thickness gradual change portion. It becomes a structure that extends to.
＜下辺２ｄ側の基材２主面周縁部への第二副塗布液の塗布＞
主塗布液による液膜５２が、主塗布液の吐出位置、すなわち最上辺５１から、基材２の主面上の下辺２ｄ側の縁に渡って保持された状態で、主面上の下辺側に、第二副塗布液を塗布する。第二副塗布液が塗布された領域では、液膜５２の大部分が基材から除去され、前項で説明したとおり、第二膜厚徐変部と、第二膜厚徐変部と下辺との間に下辺側膜厚平坦部が形成される。第二副塗布液は、主塗布液、第一副塗布液の塗布と同様に、ノズルから吐出することで、塗布エリアに塗布することができる。第二塗布液の基材２への塗布は、第二塗布液を吐出するためのノズルを下辺２ｄと略平行に相対移動させながら、第二塗布液を基材に吐出する方法とすることが好ましい。第二塗布液を吐出するためのノズルは 主ノズル５０、副ノズル６０と同様の構造のものとしてよい。またその他の方法として、第二副塗布液がしみ込んだ布を基材２の塗布エリアに払拭させる方法としてもよい。
<Applying the second secondary coating liquid to the peripheral edge of the main surface of the base material 2 on the lower side 2d side>
The liquid film 52 by the main coating liquid is held from the discharge position of the main coating liquid, that is, the uppermost side 51 to the edge on the lower side 2d side on the main surface of the base material 2, and is held on the lower side side on the main surface. The second secondary coating liquid is applied to. In the region where the second subcoating liquid was applied, most of the liquid film 52 was removed from the base material, and as explained in the previous section, the second film thickness gradual change portion, the second film thickness gradual change portion, and the lower side. A flat portion with a film thickness on the lower side is formed between the two. The second sub-coating liquid can be applied to the coating area by discharging from the nozzle in the same manner as the application of the main coating liquid and the first sub-coating liquid. The second coating liquid may be applied to the base material 2 by discharging the second coating liquid onto the base material while moving the nozzle for discharging the second coating liquid relative to the lower side 2d. preferable. The nozzle for discharging the second coating liquid may have the same structure as the main nozzle 50 and the sub nozzle 60. Further, as another method, a method of wiping the coating area of the base material 2 with the cloth soaked with the second secondary coating liquid may be used.
図１２に、図４に示した塗布膜付機材１のＸＹ断面の形状につき、下辺側を模式的に表したものを示す。塗布膜付基材１は、下辺２ｄ側に、第二膜厚徐変部の開始位置６３を備える第二膜厚徐変部３３、下辺側膜厚平坦部の開始位置６４（第二膜厚徐変部の終点部でもある）から、下辺２ｄの縁に渡って、膜厚分布が概略平坦な下辺側平坦部３４を備えている。下辺側平坦部３４の膜厚は、０．１μｍ〜２μｍであることが好ましい。膜厚が０．１μｍ未満の下辺側平坦部３４を形成することが難しく、他方、膜厚が１．５μｍ超の膜厚平坦部３４を得ようとすると、塗布膜の形成過程で下辺２ｄ側で液溜りが生じることがあり、膜厚平坦部３４の平滑性が悪くなることがある。これらを考慮すると、下辺側平坦部３４の膜厚は、０．３μｍ〜１．５μｍとしてもよい。 FIG. 12 shows a schematic representation of the lower side of the shape of the XY cross section of the equipment 1 with the coating film shown in FIG. The base material 1 with a coating film has a second film thickness gradual change portion 33 having a start position 63 of the second film thickness gradual change portion on the lower side 2d side, and a start position 64 (second film thickness) of the lower side film thickness flat portion. A lower side flat portion 34 having a substantially flat film thickness distribution is provided from (which is also the end point portion of the gradual change portion) to the edge of the lower side 2d. The film thickness of the lower flat portion 34 is preferably 0.1 μm to 2 μm. It is difficult to form the lower side flat portion 34 having a film thickness of less than 0.1 μm, while when trying to obtain a film thickness flat portion 34 having a film thickness of more than 1.5 μm, the lower side 2d side is formed in the process of forming the coating film. May cause liquid pooling, and the smoothness of the film thickness flat portion 34 may deteriorate. Considering these, the film thickness of the lower side flat portion 34 may be 0.3 μm to 1.5 μm.
また、第二膜厚徐変部３３の開始位置６３は、第二副塗布液の塗布領域に依存する。開始位置６３は、基材の下辺２ｄ（図１２の場合、基材２の主面と下辺２ｄとの境界、すなわち主面の縁を基点に考える）から鉛直方向に、１〜６０ｍｍの範囲になるように、第二副塗布液が塗布されることが好ましい。開始位置６３が、下辺２ｄから鉛直方向に１ｍｍ未満となるようにすることが難しいものであり、他方、開始位置６３が、下辺２ｄから鉛直方向に６０ｍｍ超の場合、塗布膜３が本来発揮すべき機能を奏する領域が狭いものとなりやすい。これらを考慮すると、開始位置６３は、基材の下辺２ｄから鉛直方向に、好ましくは３〜５７ｍｍ、さらに好ましくは５〜５５ｍｍの範囲になるように、第二副塗布液が塗布されることが好ましい。 Further, the start position 63 of the second film thickness gradual change portion 33 depends on the coating region of the second secondary coating liquid. The start position 63 is in the range of 1 to 60 mm in the vertical direction from the lower side 2d of the base material (in the case of FIG. 12, the boundary between the main surface and the lower side 2d of the base material 2, that is, the edge of the main surface is considered as the base point). It is preferable that the second subcoating liquid is applied so as to be. It is difficult to make the start position 63 less than 1 mm in the vertical direction from the lower side 2d, while the coating film 3 originally exhibits when the start position 63 is more than 60 mm in the vertical direction from the lower side 2d. The area where the function to be performed tends to be narrow. In consideration of these, the second subcoating liquid may be applied so that the starting position 63 is in the range of preferably 3 to 57 mm, more preferably 5 to 55 mm in the vertical direction from the lower side 2d of the base material. preferable.
主塗布液と第二副塗布液とによる液膜の表面張力によって、前記下辺側平坦部と、膜厚を薄くする処理をされなかった塗布膜領域との膜厚を調整するように、第二膜厚徐変部が形成されるようになることから、下辺側膜厚平坦部の開始位置６４は、開始位置６３の位置と、「主塗布液の溶媒と、第二副塗布液とのＳＰ値の差」とに依存することになる。開始位置６４は、開始位置６３から下辺２ｄに向って鉛直方向に好ましくは０．１〜５５ｍｍ、より好ましくは０．５〜５０ｍｍ、さらに好ましくは１〜２０ｍｍの位置とされる。 The film thickness of the lower flat portion and the coating film region that has not been thinned is adjusted by the surface tension of the liquid film formed by the main coating liquid and the second secondary coating liquid. Since the film thickness gradual change portion is formed, the start position 64 of the film thickness flat portion on the lower side is the position of the start position 63 and the SP of "the solvent of the main coating liquid and the second secondary coating liquid". It will depend on the "difference in value". The start position 64 is preferably a position of 0.1 to 55 mm, more preferably 0.5 to 50 mm, still more preferably 1 to 20 mm in the vertical direction from the start position 63 toward the lower side 2d.
＜塗布後の工程＞
主塗布液の基材２への塗布後は、副塗布液の溶剤、主塗布液の溶媒を蒸発させる乾燥工程、基材２に塗布された塗布液を塗布膜とするための固化工程が行われる。これら工程の前に基材２に塗布された塗布液の均質性を向上させるためのレベリング工程を設けてもよい。レベリング工程では、基材２を水平または傾けて、一定時間保持（例えば、室温で１〜２０分間程度）される。
<Process after application>
After the main coating liquid is applied to the base material 2, a drying step of evaporating the solvent of the sub-coating liquid and the solvent of the main coating liquid, and a solidification step for forming the coating liquid applied to the base material 2 into a coating film are performed. It is said. A leveling step for improving the homogeneity of the coating liquid applied to the base material 2 may be provided before these steps. In the leveling step, the base material 2 is horizontally or tilted and held for a certain period of time (for example, about 1 to 20 minutes at room temperature).
前記乾燥工程は、基材２の室温保持や、基材２に塗布された塗布液を加熱することで行ってもよいし、前記固化工程と同時に行ってもよい。前記固化工程は、前記固形分の種類に応じて、加熱、ＵＶ照射、過熱水蒸気の付与等が適宜選択される。 The drying step may be performed by keeping the base material 2 at room temperature or heating the coating liquid applied to the base material 2, or may be performed at the same time as the solidification step. In the solidification step, heating, UV irradiation, application of superheated steam, etc. are appropriately selected according to the type of the solid content.
３．塗布膜付基材の構成について
本発明の塗布膜付基材の製法によると、基材の主面上に塗布膜の非塗布領域を備える塗布膜付形成基材をしやすい。このような塗布膜付形成基材は、自動車のドアの開閉可能な窓ガラス（例えば、自動車のサイドドアに設置される上下にスライド可能な窓ガラス）として好適に使用できる。このようなドアには、窓ガラスのフレームがあり、ドア上方には、窓ガラスを収納するための収納部８（ランチャンネル）がある。窓ガラスが収納される領域は、塗布膜が非塗布領域となっていることが好ましい。以下に本発明の塗布膜付基材を、図面を用いて説明する。図４は、塗布膜付基材を塗布膜が形成された主面側から観察したときの模式図である。図５は、塗布膜付基材１をＸＹに切断したときの断面要部を模式的に表したものである。
3. 3. Regarding the configuration of the base material with a coating film According to the method for producing a base material with a coating film of the present invention, it is easy to form a base material with a coating film having a non-coating region of the coating film on the main surface of the base material. Such a formed base material with a coating film can be suitably used as a window glass that can be opened and closed of an automobile door (for example, a window glass that can be slid up and down installed on a side door of an automobile). Such a door has a window glass frame, and above the door, there is a storage unit 8 (run channel) for storing the window glass. It is preferable that the coating film is a non-coating region in the region where the window glass is housed. The substrate with a coating film of the present invention will be described below with reference to the drawings. FIG. 4 is a schematic view of the base material with a coating film when observed from the main surface side on which the coating film is formed. FIG. 5 schematically shows a cross-sectional main part when the base material 1 with a coating film is cut into XY.
塗布膜３において、第１の膜厚分布を形成する部位は、塗布膜の上辺２ａ側周縁部において、非塗布領域４に向かって、膜厚が徐々に小さくなる第一膜厚徐変部３１に相当する。第一膜厚徐変部３１の開始位置は、塗布膜の上辺側周縁部から鉛直方向に、５〜２００ｍｍの範囲にあって、短ければ短い程好ましい。０〜５ｍｍ未満の場合、基材の主面と膜厚徐変部の塗布膜と成す角が大きくなり、膜厚徐変部の光学歪みが生じやすく、塗膜の見栄えが悪くなる傾向がある。また、塗布膜の上辺側周縁部と膜厚徐変部の開始位置とは略平行な関係とし、基材の主面と膜厚徐変部の塗布膜と成す角が０．０００５〜０．０２°にあることが好ましい。基材の主面と膜厚徐変部の塗布膜と成す角は、表面粗さ測定機（小坂研究所製サーフコーダーＥＴ４０００Ａ等）を用いて、膜厚徐変部の種々位置での膜厚を測定し、膜厚徐変部の最上辺５１からの距離と膜厚との関係から角度を求めることができる。 In the coating film 3, the portion forming the first film thickness distribution is the first film thickness gradual change portion 31 in which the film thickness gradually decreases toward the non-coating region 4 in the peripheral portion on the upper side 2a side of the coating film. Corresponds to. The starting position of the first film thickness gradual change portion 31 is in the range of 5 to 200 mm in the vertical direction from the upper peripheral edge portion of the coating film, and the shorter it is, the more preferable. If it is less than 0 to 5 mm, the angle formed by the main surface of the base material and the coating film in the film thickness gradual change portion becomes large, optical distortion in the film thickness gradual change portion tends to occur, and the appearance of the coating film tends to deteriorate. .. Further, the upper peripheral edge of the coating film and the start position of the film thickness gradual change portion are in a substantially parallel relationship, and the angle formed by the main surface of the base material and the coating film of the film thickness gradual change portion is 0.0005-0. It is preferably at 02 °. The angle formed by the main surface of the base material and the coating film of the film thickness gradual change part is the film thickness at various positions of the film thickness gradual change part using a surface roughness measuring machine (Surfcoder ET4000A manufactured by Kosaka Laboratory). Can be measured, and the angle can be obtained from the relationship between the film thickness and the distance from the uppermost side 51 of the film thickness gradual change portion.
塗布膜３において、膜厚徐変部以外、すなわち、膜厚上辺部の最下辺６１より下部の領域（図５中の破線よりも下の領域）を膜主部３２とする。この膜主部３２において、その膜厚は、好ましくは、２．５〜５．５μｍ、より好ましくは、３．５〜５．０μｍとされる。２．５μｍ未満では、塗布膜の機能に膜厚依存性がある場合に、所望の性能を得にくくなり、５．５μｍ超では塗布膜３に光学的な歪みや、クラックが生じやすくなる。また、膜主部３２の膜厚の標準偏差は、好ましくは０．５以下、より好ましくは、０．３以下とされる。０．５を超えると光学的な歪みが生じやすくなる為、日本工業規格ＪＩＳ Ｒ３２１１（１９９８年改正版）の透視歪み試験および二重像試験を満足しないという傾向があるからである。 In the coating film 3, a region other than the film thickness gradual change portion, that is, a region below the lowermost side 61 of the film thickness upper side portion (a region below the broken line in FIG. 5) is defined as the film main portion 32. The film thickness of the film main portion 32 is preferably 2.5 to 5.5 μm, more preferably 3.5 to 5.0 μm. If it is less than 2.5 μm, it becomes difficult to obtain the desired performance when the function of the coating film depends on the film thickness, and if it exceeds 5.5 μm, the coating film 3 is likely to be optically distorted or cracked. The standard deviation of the film thickness of the film main portion 32 is preferably 0.5 or less, more preferably 0.3 or less. This is because if it exceeds 0.5, optical distortion is likely to occur, and therefore, there is a tendency that the fluoroscopic distortion test and the double image test of the Japanese Industrial Standard JIS R3211 (revised 1998) are not satisfied.
尚、本発明において、膜厚徐変部の開始位置、すなわち、膜厚徐変部の最下辺６１位置は、第一膜厚徐変部３１と非塗布領域４との境界域から鉛直方向に、距離と膜厚との関係をグラフ化した後、膜厚主部３２の中央部における切片と、第一膜厚徐変部３１における切片とが交わる位置として定義づけることができる。また、膜厚の標準偏差は、膜厚主部３２の任意の１０箇所（各任意点は近接しすぎないように選択する）の膜厚を測定し、標準偏差の公式を用いて求めることができる。 In the present invention, the start position of the film thickness gradual change portion, that is, the lowermost side 61 position of the film thickness gradual change portion is in the vertical direction from the boundary region between the first film thickness gradual change portion 31 and the non-coated region 4. After graphing the relationship between the distance and the film thickness, it can be defined as the position where the section in the central portion of the film thickness main portion 32 and the section in the first film thickness gradual change portion 31 intersect. The standard deviation of the film thickness can be obtained by measuring the film thickness at any 10 points of the film thickness main portion 32 (selecting the arbitrary points so that they are not too close to each other) and using the standard deviation formula. it can.
塗布膜付基材１が、自動車のドアの開閉可能な窓ガラスとして使用される場合、非塗布領域４は、図１０に示すようにドアの上部フレームの収納部（ランチャンネル）８に収納される領域となる。図１０は、塗布膜付基材１がドアの上部フレームの収納部内に収納される際の構造の要部を概略的に示す図で、前記ランチャンネル８は、断面略コ字状の構造を備えている。図１０に示される塗布膜付基材１の端面は、図４に示したＸＹに基材１を切断した場合に現れる断面を表したものである。 When the base material 1 with a coating film is used as a window glass that can be opened and closed of an automobile door, the non-coating region 4 is housed in a storage portion (run channel) 8 of the upper frame of the door as shown in FIG. Area. FIG. 10 is a diagram schematically showing a main part of the structure when the base material 1 with a coating film is stored in the storage portion of the upper frame of the door, and the run channel 8 has a substantially U-shaped cross section. I have. The end face of the base material 1 with a coating film shown in FIG. 10 represents a cross section that appears when the base material 1 is cut into XY shown in FIG.
基材１の厚さ方向両側から摺動可能に挟持する一対のシールリップ８１と外側リップ８２とを有し、シールリップ８１は非塗布領域４と接する構造となっている。図１０では、第一膜厚徐変部３１がランチャンネル８に収納されない構造を示したが、第一膜厚徐変部３１の一部も、ドアの上部フレームの収納部内に収納される領域となってもよい。その場合、第一膜厚徐変部３１の一部でドアの上部フレームに収納される領域は、第一膜厚徐変部３１開始位置から、０（超）〜１０ｍｍが好ましく、０（超）〜５ｍｍがより好ましい。この構成とすれば、第２の膜厚分布を形成する部位を多めに設定することができる。 塗布膜付基材１は、ドアの側辺フレームの収納部内に前記基材が収納される領域にも塗布膜の非塗布領域を備えるものであってもよい。 It has a pair of seal lips 81 and an outer lip 82 that are slidably sandwiched from both sides in the thickness direction of the base material 1, and the seal lips 81 have a structure in contact with the non-coated region 4. FIG. 10 shows a structure in which the first film thickness gradual change portion 31 is not housed in the run channel 8, but a part of the first film thickness gradual change part 31 is also housed in the storage part of the upper frame of the door. May be. In that case, the region of a part of the first film thickness gradual change portion 31 to be housed in the upper frame of the door is preferably 0 (super) to 10 mm from the start position of the first film thickness gradual change portion 31, and is preferably 0 (super). ) ~ 5 mm is more preferable. With this configuration, it is possible to set a large number of portions that form the second film thickness distribution. The base material 1 with a coating film may also include a non-coating region of the coating film in a region where the base material is stored in the storage portion of the side frame of the door.
さらに、図４に示した塗布膜付基材１の別の態様である、側辺２ｂ、２ｃ側に非塗布領域４を有する塗布膜付基材１を説明する。図９は、該塗布膜付基材１を塗布膜が形成された主面側から観察したときの模式図を示すものである。塗布膜付基材１が自動車のドアの開閉可能な窓ガラスとして使用される場合、側辺２ｂ、２ｃ側の非塗布領域４は、ドアの側部フレームの収納部（ランチャンネル）８に収納される領域となる。図１１は、塗布膜付基材１がドアの側部フレームの収納部内に収納される際の構造の要部を概略的に示す図で、前記ランチャンネル８は、断面略コ字状の構造を備えている。そして、基材１の厚さ方向両側から摺動可能に挟持する一対のシールリップ８１と外側リップ８２とを有し、シールリップ８１は非塗布領域４と接する構造となっている。尚、図１１に示される塗布膜付基材１の端面は、図９に示したｖｗに基材１を切断した場合に現れる断面を表したものである。 Further, another aspect of the base material 1 with a coating film shown in FIG. 4, which is a base material 1 with a coating film having a non-coating region 4 on the side sides 2b and 2c, will be described. FIG. 9 shows a schematic view of the base material 1 with a coating film when observed from the main surface side on which the coating film is formed. When the base material 1 with a coating film is used as a window glass that can be opened and closed of an automobile door, the non-coating region 4 on the side 2b and 2c sides is stored in the storage portion (run channel) 8 of the side frame of the door. It becomes the area to be done. FIG. 11 is a diagram schematically showing a main part of the structure when the base material 1 with a coating film is stored in the storage portion of the side frame of the door, and the run channel 8 has a substantially U-shaped cross section. It has. The base material 1 has a pair of seal lips 81 and an outer lip 82 slidably sandwiched from both sides in the thickness direction, and the seal lips 81 have a structure in contact with the non-coated region 4. The end face of the base material 1 with a coating film shown in FIG. 11 represents a cross section that appears when the base material 1 is cut into vw shown in FIG.
自動車のドア内を上下方向に移動させて基材（ガラス）の開閉を行う仕様においては、塗布膜付基材の側辺部は、上辺部よりも当業者には懸念されてこなかった。なぜなら、塗布膜付基材においてシールリップ８１と接する部位に関しては、側辺領域にある塗布膜３は、塗布膜が基材２から剥離することのない程度の強度を有していれば、塗布膜３の当該部位に傷がついたとしても、その傷は車両の使用者に視認されることはないからである。しかしながら、塗布膜３の表面は、基材表面よりも滑り性が劣るので、塗布膜付基材１のスムーズな昇降を求めた場合、側辺２ｂ、２ｃ側に非塗布領域４を有する塗布膜付基材１は好ましい構造のものとなる。 In the specification of opening and closing the base material (glass) by moving the inside of the door of the automobile in the vertical direction, the side portion of the base material with the coating film has not been of concern to those skilled in the art more than the upper side portion. This is because, with respect to the portion of the base material with a coating film that comes into contact with the seal lip 81, the coating film 3 in the side region is coated as long as the coating film has a strength that does not peel off from the base material 2. This is because even if the portion of the film 3 is scratched, the scratch is not visible to the user of the vehicle. However, since the surface of the coating film 3 is inferior in slipperiness to the surface of the base material, when the base material 1 with the coating film is required to move up and down smoothly, the coating film having the non-coating region 4 on the side 2b and 2c sides. The attached base material 1 has a preferable structure.
以下、実施例及び比較例を示して本発明を詳細に説明する。ただし、本発明は以下の記載によっては限定されない。実施例および比較例で得られた塗布膜付基材については、次の＜１＞、＜２＞の評価を行った。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the following description. The following <1> and <2> were evaluated for the base materials with a coating film obtained in Examples and Comparative Examples.
＜１＞塗布膜の膜厚および膜厚分布の測定
小坂研究所製サーフコーダーＥＴ４０００Ａを用いて、塗布膜付基材の塗膜の膜厚を測定した。
<1> Measurement of film thickness and film thickness distribution of the coating film The film thickness of the coating film of the base material with the coating film was measured using a surf coder ET4000A manufactured by Kosaka Laboratory.
＜２＞塗布膜時基材の光学的歪み、クラックの有無の確認
目視観察にて、塗布膜付基材の塗膜にクラックや歪みや着色や白濁（塗布膜中で紫外線吸収剤が凝集等により均一に分散されていない）等の外観上の不具合がないかどうか確認した。
<2> Optical distortion of the base material at the time of coating film, confirmation of the presence or absence of cracks By visual observation, the coating film of the base material with coating film is cracked, distorted, colored or cloudy (ultraviolet absorber aggregates in the coating film, etc.) It was confirmed whether there were any external defects such as (not evenly dispersed).
実施例１
１）基材の準備
厚み３．１ｍｍ、サイズ９４３ｍｍ×５１２ｍｍ、曲げ率２５００Ｒの湾曲した自動車ドアガラスとして使用されるガラスを基材２とした。
Example 1
1) Preparation of base material The base material 2 was glass used as a curved automobile door glass having a thickness of 3.1 mm, a size of 943 mm × 512 mm, and a bending ratio of 2500R.
２）主塗布液の準備
トリアジン系紫外線吸収剤TINUVIN４６０（ＢＡＳＦ社製）を２．２ｇ、TINUVIN４７７を０．６ｇ、TINUVIN２９２を０．６ｇ、溶媒として２−ヘプタノンを１９．４ｇ、メチ
ルエチルケトンを１９．４ｇ混合し、３０分間攪拌し、攪拌したものにスリップ剤（信越化学工業株式会社製 KP１０９）を０．２ｇ、３−メトキシ−３−メチル−１−ブタノール（以下、ＭＭＢ）で希釈されたＳｉ−Ｏ−Ｂ結合を含むエポキシ樹脂組成物（ニットーボーメディカル株式会社製）を４８．５ｇ、ＭＭＢで希釈された固形分２０ｗｔ％のスズドープ酸化インジウム（ITO）分散剤（三菱マテリアル株式会社製）を９．１ｇ混合し、３０分間攪拌し、紫外線・赤外線吸収塗布液を得、これを主塗布液とした。
2) Preparation of main coating solution 2.2 g of triazine-based ultraviolet absorber TINUVIN460 (manufactured by BASF), 0.6 g of TINUVIN477, 0.6 g of TINUVIN292, 19.4 g of 2-heptanone as a solvent, and 19.4 g of methyl ethyl ketone. Mix, stir for 30 minutes, and add 0.2 g of a slip agent (KP109 manufactured by Shinetsu Chemical Industry Co., Ltd.) to the stirred product, and Si- diluted with 3-methoxy-3-methyl-1-butanol (hereinafter, MMB). 9. Epoxy resin composition containing OB bond (manufactured by Nittobo Medical Co., Ltd.) and tin-doped indium oxide (ITO) dispersant (manufactured by Mitsubishi Materials Co., Ltd.) diluted with MMB and having a solid content of 20 wt%. 1 g was mixed and stirred for 30 minutes to obtain an ultraviolet / infrared absorbing coating solution, which was used as the main coating solution.
３）第一副塗布液、第二副塗布液の準備
第一副塗布液、第二副塗布液として、主塗布液の溶媒と同一の２−ヘプタノンを用いた。この液は、第一副塗布液として基材に塗布しても、主塗布液を塗布するまでに揮発はせず、液割れも生じないものであった。
3) Preparation of the first sub-coating liquid and the second sub-coating liquid As the first sub-coating liquid and the second sub-coating liquid, 2-heptanone, which is the same as the solvent of the main coating liquid, was used. Even if this liquid was applied to the base material as the first secondary coating liquid, it did not volatilize by the time the main coating liquid was applied, and liquid cracking did not occur.
４）第一副塗布液および主塗布液の基材への塗布
基材を研磨し洗浄し乾燥させた後、図１に示したように基材２の側辺２ｃ、２ｄが水平方向を示す基準線７に対して垂直となる状態、加えて、図２、図３に示したように基材２の側辺２ｃ、２ｄの上部が水平方向を示す基準線７に対して垂直となる状態（基準線７１に沿うような状態）で基材を立てかけて保持し、副ノズル６０を基材の上辺２ａから鉛直方向に１５ｍｍ下方で、上辺２ａの形状に略平行に沿うように１００ｍｍ/秒の速度で相対移動をし、２ｍｍφの吐出口を備える副ノズル６０から流量を５ｇ／秒として第一副塗布液を吐出し、基材に第一副塗布液を塗布した。
4) Application of the first subcoating liquid and the main coating liquid to the base material After the base material is polished, washed and dried, the side sides 2c and 2d of the base material 2 indicate the horizontal direction as shown in FIG. A state of being perpendicular to the reference line 7, and a state in which the upper portions of the side surfaces 2c and 2d of the base material 2 are perpendicular to the reference line 7 indicating the horizontal direction as shown in FIGS. 2 and 3. Hold the base material upright (in a state along the reference line 71), and hold the sub-nozzle 60 15 mm below the upper side 2a of the base material in the vertical direction and 100 mm / sec so as to be substantially parallel to the shape of the upper side 2a. The first sub-coating liquid was discharged from the sub-nozzle 60 provided with a discharge port of 2 mmφ at a speed of 5 g / sec, and the first sub-coating liquid was applied to the base material.
基材２に第一副塗布液が保持された状態で、主ノズル５０を基材の上辺２ａから鉛直方向に１０ｍｍ下方で、上辺２ａの形状に略平行に沿うように１００ｍｍ/秒の速度で相対移動をし、２ｍｍφの吐出口を備える主ノズル５０から流量を２ｇ／秒として主塗布液を吐出し、基材に主塗布液を塗布した。 With the first secondary coating liquid held on the base material 2, the main nozzle 50 is positioned 10 mm downward in the vertical direction from the upper side 2a of the base material and at a speed of 100 mm / sec so as to be substantially parallel to the shape of the upper side 2a. The main coating liquid was discharged from the main nozzle 50 provided with a discharge port of 2 mmφ at a flow rate of 2 g / sec, and the main coating liquid was applied to the base material.
主塗布液による液膜５２が、主塗布液の吐出位置、すなわち最上辺５１から、基材２の主面上の下辺２ｄ側の縁に渡って保持された状態で、５分間静置後、主面上の下辺２ｄから鉛直方向に５ｍｍ上方に副ノズル６０を設置し、下辺２ｄの形状に略平行に沿うように２５０ｍｍ／秒の速度で相対移動をし、吐出口から、流量を２．５ｇ／秒にて、第二副塗布液を吐出し、基材に第二副塗布液を塗布した。 After allowing the liquid film 52 of the main coating liquid to stand for 5 minutes while being held from the discharge position of the main coating liquid, that is, from the uppermost side 51 to the edge on the main surface of the base material 2 on the lower side 2d side, The sub-nozzle 60 is installed 5 mm above the lower side 2d on the main surface in the vertical direction, and moves relative to each other at a speed of 250 mm / sec so as to be substantially parallel to the shape of the lower side 2d, and the flow rate from the discharge port is 2. The second subcoating liquid was discharged at 5 g / sec, and the second subcoating liquid was applied to the substrate.
５）塗布された塗布液のレベリング工程、および乾燥工程と固化工程
塗布工程の後、下辺側の側辺が垂直になる状態で基材を立てかけて保持し、２０分間レベリングさせた後に、上記基材の表面温度を１８０℃まで５分間予備加熱する。予備加熱工程の後に、１８０℃で１０分間上記基材を過熱水蒸気に曝すことにより上記塗膜を硬化させ、塗布膜を形成し、塗布膜付基材を得た。
5) Leveling step of the applied coating liquid, and drying step and solidification step After the coating step, the base material is held upright with the lower side side vertical, and after leveling for 20 minutes, the above base is used. Preheat the surface temperature of the material to 180 ° C. for 5 minutes. After the preheating step, the coating film was cured by exposing the substrate to superheated steam at 180 ° C. for 10 minutes to form a coating film, and a substrate with a coating film was obtained.
得られた塗布膜付基材１は、上辺２ａ側に非塗布領域４が形成され、見切り形状（膜厚徐変部の最上辺５１に相当）が滑らかな曲線状で見栄えの良いものであった。また、主ノズル５０と副ノズル６０を相対移動させた間は、膜厚徐変部となり、基材２の主面と第一膜厚徐変部の塗布膜と成す角が０．００１°、下辺側平坦部の膜厚は、０．８μｍ（開始位置６３は、下辺２ｄから鉛直方向に５ｍｍの位置、開始位置６４は、開始位置６３から下辺２ｄに向って鉛直方向に１ｍｍの位置）であった。また、その他の塗布膜形成領域の膜厚は、３．５〜４．５μｍで、比較的フラットな膜形状で、膜厚の標準偏差は０．１９であった。また、塗布膜は、クラック、歪み、着色、白濁が目視では発見しづらく、見栄えの良いものであった。 In the obtained base material 1 with a coating film, the non-coating region 4 is formed on the upper side 2a side, and the parting shape (corresponding to the uppermost side 51 of the film thickness gradual change portion) is a smooth curved shape and has a good appearance. It was. Further, while the main nozzle 50 and the sub nozzle 60 are relatively moved, the film thickness gradually changes, and the angle formed by the main surface of the base material 2 and the coating film of the first film thickness gradually changes is 0.001 °. The film thickness of the flat portion on the lower side is 0.8 μm (the start position 63 is a position 5 mm in the vertical direction from the lower side 2d, and the start position 64 is a position 1 mm in the vertical direction from the start position 63 toward the lower side 2d). there were. The film thickness of the other coating film forming region was 3.5 to 4.5 μm, the film shape was relatively flat, and the standard deviation of the film thickness was 0.19. In addition, cracks, distortions, colorings, and cloudiness of the coating film were difficult to detect visually, and the coating film had a good appearance.
実施例２
第一副塗布液を基材２に塗布しない以外は、実施例１と同様の操作をし、塗布膜付基材１を得た。塗布膜３は、最上辺５１から開始位置６３に向って漸次膜厚が上昇するものとなった（最上辺５１から開始位置６３までが第一膜厚徐変部となる）。基材２の主面と第一膜厚徐変部の塗布膜と成す角が０．００１°、下辺側平坦部の膜厚は、０．８μｍ（開始位置６３は、下辺２ｄから鉛直方向に５ｍｍの位置、開始位置６４は、開始位置６３から下辺２ｄに向って鉛直方向に１ｍｍの位置）であった。塗布膜は、クラック、歪み、着色、白濁が目視では発見しづらく、見栄えの良いものであった。
Example 2
The same operation as in Example 1 was performed except that the first subcoating liquid was not applied to the base material 2, to obtain a base material 1 with a coating film. The film thickness of the coating film 3 gradually increases from the uppermost side 51 toward the start position 63 (the first film thickness gradually changes from the uppermost side 51 to the start position 63). The angle formed by the main surface of the base material 2 and the coating film of the first film thickness gradual change portion is 0.001 °, and the film thickness of the flat portion on the lower side is 0.8 μm (the start position 63 is in the vertical direction from the lower side 2d). The position of 5 mm and the start position 64 were positions 1 mm in the vertical direction from the start position 63 toward the lower side 2d). The coating film had good appearance because cracks, distortions, colorings, and cloudiness were difficult to detect visually.
比較例１
第二副塗布液を塗布しなかった以外は、実施例２と同様の操作をし、塗布膜付基材１を得た。塗布膜の下辺２ｄ側でクラックが観測された。
Comparative Example 1
The same operation as in Example 2 was performed except that the second secondary coating liquid was not applied, to obtain a substrate 1 with a coating film. Cracks were observed on the lower 2d side of the coating film.
１ 塗布膜付基材
２ 基材
３ 塗布膜
３１ 第一膜厚徐変部
３２ 膜主部
３３ 第二膜厚徐変部
４ 非塗布領域
５０ 主ノズル
５１ 膜厚徐変部の最上辺
５２ 主塗布液による液膜
６０ 副ノズル
６１ 膜厚徐変部の最下辺
６２ 副塗布液
６３ 第二膜厚徐変部の開始位置
６４ 下辺側膜厚平坦部の開始位置
７ 水平方向を示す基準線
1 Base material with coating film 2 Base material 3 Coating film 31 First film thickness gradual change part 32 Film main part 33 Second film thickness gradual change part 4 Non-coating area 50 Main nozzle
51 Top side of film thickness gradual change part 52 Liquid film by main coating liquid 60 Sub-nozzle 61 Bottom side of film thickness gradual change part 62 Sub-coating liquid 63 Start position of second film thickness gradual change part 64 Lower side film thickness flat part Start position 7 Reference line indicating the horizontal direction
Claims (16)
前記主塗布液による液膜が、前記主塗布液の吐出位置から前記基材の主面上の下辺側に渡って保持された状態で、主面上の下辺側に、前記主塗布液の希釈用溶剤を第二副塗布液として塗布する工程とを備え、
前記主塗布液を前記基材の主面上に吐出する前に、前記主塗布液の希釈用溶剤を第一副塗布液として吐出する副ノズルを用い、前記副ノズルを横方向に基材に対して相対移動させながら、前記副ノズルから前記第一副塗布液を前記基材の主面上に吐出する工程を備え、前記主ノズルから前記主塗布液を前記基材の主面上に吐出する工程は、前記主面上に前記第一副塗布液による液膜が保持された状態で行い、
前記主ノズルからの前記主塗布液の吐出を、前記副塗布液を塗布した領域外で行うことを特徴とする塗布膜付基材の製法。 A plate-shaped base material to be coated is held in the vertical direction, and a main nozzle for discharging a coating liquid for forming a coating film is laterally placed on the upper side of at least one main surface of the base material. In the method for producing a base material with a coating film, which comprises a step of discharging the coating liquid from the main nozzle as the main coating liquid onto the main surface of the base material while moving relative to the main surface.
The liquid film formed by the main coating liquid is held from the discharge position of the main coating liquid to the lower side on the main surface of the base material, and the main coating liquid is diluted on the lower side on the main surface. It is equipped with a process of applying the solvent as a second secondary coating liquid .
Before discharging the main coating liquid onto the main surface of the base material, a sub-nozzle that discharges a solvent for diluting the main coating liquid as the first sub-coating liquid is used, and the sub-nozzle is laterally mounted on the base material. A step of discharging the first sub-coating liquid from the sub-nozzle onto the main surface of the base material while moving relative to the main surface is provided, and the main coating liquid is discharged from the main nozzle onto the main surface of the base material. The step is performed with the liquid film of the first subcoating liquid held on the main surface.
A method for producing a base material with a coating film, which comprises discharging the main coating liquid from the main nozzle outside the area where the sub coating liquid is applied.
主ノズルの吐出口を、塗布液が吐出されない領域として基材の上辺から間隔を空け、且つ対向する上辺に沿うように基材に対して相対移動させながら主塗布液を基材の主面に吐出する工程とを備えることで、基材の上辺側と側辺側とに塗布膜の非塗布領域を形成することを特徴とする請求項１に記載の塗布膜付基材の製法。 The sub-nozzle discharge port is set as a region where the coating liquid is not discharged, and the sub-coating liquid is applied while keeping a space from the side and upper sides of the base material and moving the three sides relative to the base material along the opposite sides. The process of discharging to the main surface of the base material and the discharge port of the main nozzle are moved relative to the base material so as to be a region where the coating liquid is not discharged, at intervals from the upper side of the base material, and along the opposite upper side. The first aspect of the present invention is characterized in that a non-coating region of the coating film is formed on the upper side and the side side of the base material by providing the step of discharging the main coating liquid onto the main surface of the base material. Manufacturing method of base material with coating film.
前記主塗布液による液膜が、前記主塗布液の吐出位置から前記基材の主面上の下辺側に渡って保持された状態で、主面上の下辺側に、前記主塗布液の希釈用溶剤を第二副塗布液として塗布する工程とを備え、The liquid film formed by the main coating liquid is held from the discharge position of the main coating liquid to the lower side on the main surface of the base material, and the main coating liquid is diluted on the lower side on the main surface. It is equipped with a process of applying the solvent as a second secondary coating liquid.
前記主塗布液を前記基材の主面上に吐出する前に、前記主塗布液の希釈用溶剤を第一副塗布液として吐出する副ノズルを用い、前記副ノズルを横方向に基材に対して相対移動させながら、前記副ノズルから前記第一副塗布液を前記基材の主面上に吐出する工程を備え、前記主ノズルから前記主塗布液を前記基材の主面上に吐出する工程は、前記主面上に前記第一副塗布液による液膜が保持された状態で行い、Before discharging the main coating liquid onto the main surface of the base material, a sub-nozzle that discharges a solvent for diluting the main coating liquid as the first sub-coating liquid is used, and the sub-nozzle is laterally mounted on the base material. A step of discharging the first sub-coating liquid from the sub-nozzle onto the main surface of the base material while moving relative to the main surface is provided, and the main coating liquid is discharged from the main nozzle onto the main surface of the base material. The step is performed with the liquid film of the first subcoating liquid held on the main surface.
副ノズルの吐出口を、塗布液が吐出されない領域として基材の側辺及び上辺から間隔を空け、且つ対向する辺に沿うように３辺を基材に対して相対移動させながら副塗布液を基材の主面に吐出する工程、とThe sub-nozzle discharge port is set as a region where the coating liquid is not discharged, and the sub-coating liquid is applied while keeping a space from the side and upper sides of the base material and moving the three sides relative to the base material along the opposite sides. The process of discharging to the main surface of the base material,
主ノズルの吐出口を、塗布液が吐出されない領域として基材の上辺から間隔を空け、且つ対向する上辺に沿うように基材に対して相対移動させながら主塗布液を基材の主面に吐出する工程とを備えることで、基材の上辺側と側辺側とに塗布膜の非塗布領域を形成することを特徴とする塗布膜付基材の製法。The main coating liquid is applied to the main surface of the base material while the discharge port of the main nozzle is spaced from the upper side of the base material as a region where the coating liquid is not discharged and is relatively moved with respect to the base material along the opposite upper side. A method for producing a base material with a coating film, which comprises forming a non-coating region of the coating film on the upper side side and the side side side of the base material by providing a step of discharging.
前記塗布膜は、塗布膜の上辺側周縁部において、前記非塗布領域に向かって、膜厚が徐々に小さくなる第一膜厚徐変部を有し、前記膜厚徐変部の開始位置は、塗布膜の上辺側周縁部から鉛直方向に、５〜２００ｍｍの範囲にあって、塗布膜の上辺側周縁部と膜厚徐変部の開始位置とは略平行な関係にあり、
さらには、前記塗布膜は、塗布膜の下辺側において、下辺側に向って、膜厚が徐々に小さくなる第二膜厚徐変部と、第二膜厚徐変部と下辺との間に下辺側平坦部とを有することを特徴とする塗布膜付基材。 In a base material with a coating film used as a window glass that can be opened and closed of an automobile door, the coating film is a non-coating region in the area where the base material is stored in the storage portion of the upper frame of the door.
The coating film has a first film thickness gradual change portion in which the film thickness gradually decreases toward the non-coating region at the upper peripheral edge portion of the coating film, and the start position of the film thickness gradual change portion is In the vertical direction from the upper peripheral edge of the coating film in the range of 5 to 200 mm, the upper peripheral edge of the coating film and the start position of the film thickness gradual change portion are in a substantially parallel relationship.
Further, the coating film is formed between the second film thickness gradual change portion and the second film thickness gradual change portion and the lower side, where the film thickness gradually decreases toward the lower side on the lower side of the coating film. A base material with a coating film, which has a flat portion on the lower side.
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| JP5733197B2 (en) * | 2011-12-22 | 2015-06-10 | 旭硝子株式会社 | Automotive window glass with coating film and method for producing the same |
| JP2014200730A (en) * | 2013-04-03 | 2014-10-27 | 東京応化工業株式会社 | Coating applicator and application method |
| JP6273980B2 (en) * | 2013-07-11 | 2018-02-07 | セントラル硝子株式会社 | Plate glass with ultraviolet shielding film, method for producing the same, and coating solution for coating film of sheet glass with ultraviolet shielding film |
| US20160085944A1 (en) * | 2014-09-18 | 2016-03-24 | Enki Technology, Inc. | Glass coating specification library |
| WO2017002592A1 (en) * | 2015-06-30 | 2017-01-05 | セントラル硝子株式会社 | Method for producing substrate provided with coating film, and substrate provided with coating film |
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