JP4047991B2 - Mirror edge coating composition and mirror - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、鏡切断端面に対する付着性に優れた防腐食性鏡縁用塗料組成物及びこの塗料を塗布することによって製造された鏡に関する。
【０００２】
【従来の技術】
鏡は、通常、ガラス基板の表面に、銀鏡面膜、銅（めっき）保護膜、裏止め塗膜などが順次塗装されるため、鏡の切断端面には、ガラス基板、銀鏡面膜、銅保護膜、裏止め塗膜等の端面が共存し、露出している。特に金属皮膜は、湿気や、炭酸ガス、亜硫酸ガス等に曝されると、腐食し易く、腐食は、鏡の切断端面から、金属皮膜間又は金属皮膜と裏止め塗膜との間に内部に向かって進行する。
従って、従来より、切断端面を被覆保護するための各種の塗料が考案されている。特に、鏡保護用の塗料としては、これらの端面に対する付着性に優れたものが必要であるが、銀鏡面膜、銅保護膜、裏止め塗膜への付着性を重視すると、ガラス基板端面への付着性が劣り、逆にガラス基板端面への付着性を重視すると、銀鏡面膜、銅保護膜への付着性が劣ることとなり、これまで、付着性に優れた防腐食性鏡縁部保護効果を有する塗料は存在しなかった。
【０００３】
【発明が解決しようとする課題】
従って、本発明は、鏡縁部全ての切断端面への付着性が向上した防腐食性鏡縁用塗料組成物及び該鏡縁用塗料組成物を切断端面に塗布した鏡を提供することを目的とする。
【０００４】
【課題を解決するための手段】
本発明の鏡縁用塗料組成物は、ビスフェノール型エポキシ樹脂と、該ビスフェノール型エポキシ樹脂中のエポキシ基と反応性を有するアミノ基含有硬化剤、及びシランカップリング剤からなることを特徴とする。
【０００５】
【発明の実施の形態】
以下、本発明について詳細に説明する。
まず、図面により本発明を説明すると、図１は、本発明に係る鏡の一具体例を示したものであり、１は、ガラス基板、２は、ガラス基板上に形成された銀鏡面膜、３は、銀鏡面膜２の化学的耐久性を高めるために銀鏡面上に形成された銅保護膜、４は、銀鏡面膜及び銅保護膜を保護し、更に、耐アルカリ性、耐酸性、耐久性を向上させるために銅保護膜上に形成された裏止め塗膜を示す。
上記した鏡において、銀鏡面膜としては、無電解メッキ法によりガラス基板面に膜状に析出させて形成される膜が通常使用されるが、必ずしもこれに限定されることはなく、真空蒸着法や、スパッター法、その他各種の被膜形成法により形成される銀膜も鏡面膜として使用できる。かかる銀鏡面膜は、鏡として要求される反射率が充分得られ、かつ耐久性に優れた銀鏡面膜が得られるように、例えば、0.５〜２ｇ／ｍ2 、好ましくは、0.８〜1.３ｇ／ｍ2 の膜厚が適当である。
【０００６】
銅保護膜は、化学的に変質しやすい銀鏡面膜の化学的耐久性を高める保護膜として形成されるものであり、そのために、例えば、０．１〜１ｇ／ｍ2 、好ましくは、0.３〜0.６ｇ／ｍ2 の膜厚が適当である。
銀鏡面膜及び銅保護膜の形成された鏡の代表的な製造方法は、表面が平滑で、かつ表面欠点のないガラス板を用意し、このガラス板を充分に洗浄した後、銀鏡面膜の形成される面を活性化処理し、その表面に無電解メッキ法、例えば所謂銀鏡反応によって銀を析出する銀メッキ液をスプレーして銀鏡面膜を形成し、次いで銀鏡膜上に無電解メッキ法により銅メッキ液をスプレーして銅保護膜を形成し、次いで洗浄、乾燥する方法が挙げられるが、その他各種方法によっても製造することが出来る。
【０００７】
本発明においては、上記銅保護膜上には、銀鏡面膜及び銅保護膜の耐アルカリ性、耐酸性、耐食性、機械的耐久性を高めるために、裏止め塗膜が形成される。裏止め塗膜としては、従来より公知の組成のものが適宜使用することができる。
裏止め塗膜の厚みは、例えば、５０〜７０μm 、好ましくは、５５〜６０μm であることが適当である。
本発明においては、図１で図示されるように、上記各塗膜の切断端面に対して、鏡縁用塗料組成物が適用される。
本発明の鏡縁用塗料組成物は、（１）ビスフェノール型エポキシ樹脂、（２）該ビスフェノール型エポキシ樹脂中のエポキシ基と反応するアミノ基含有硬化剤、及び（３）シランカップリング剤を含む。
【０００８】
本発明で用いられるビスフェノール型エポキシ樹脂としては、例えば、エポキシ当量が、３５０〜５，０００、好ましくは、４００〜４，０００の常温で固形である、ビスフェノール型エポキシ樹脂が好ましい。このようなビスフェノール型エポキシ樹脂としては、例えば、エピクロン４０５０や、エピクロン４０５５、エピクロン７０５０、エピクロン９０５５、ベッコゾールＰ−７９１−５０［大日本インキ化学工業株式会社製商品名］、エピコート１００４、エピコート１００７、エピコート１００９、エピコート１０１０［油化シェルエポキシ株式会社製商品名］等が、好ましく使用される。これらは一種もしくは二種以上の混合物として使用可能である。
【０００９】
本発明で用いられるアミノ基含有硬化剤は、好ましくは、１分子中に、上記エポキシ樹脂中のエポキシ基と反応する活性水素基を有する少なくとも２個の窒素原子を有する硬化剤である。１つの窒素原子には、活性水素が少なくとも１つ存在することが必要である。１つの窒素原子に、２個の活性水素原子が存在してもよい。
このようなアミノ基含有硬化剤としては、従来より、エポキシ樹脂用硬化剤として使用されているアミノ基含有硬化剤又はアミノ系硬化剤を使用することができる。このようなアミノ基含有硬化剤としては、例えば、メタキシレンジアミンや、イソホロンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ジアミノジフェニルメタン等の脂肪族ポリアミン類、脂環族ポリアミン類、芳香族ポリアミン類；ポリアミンのエポキシ樹脂アダクト物、ポリアミドアミン類、ポリアミド樹脂、アミノ樹脂、ポリイソシアネート、ブロックポリイソシアネートなどが好適に使用される。
【００１０】
本発明で用いられるシランカップリング剤としては、無機材料（ガラス、銀、銅等）に対して反応性又は親和性を有する官能基と、有機材料（裏止め塗膜に使用される樹脂等）に対して反応性又は親和性を有する官能基とを有するシランカップリング剤が好適に挙げられる。
無機材料に対して反応性又は親和性を有する官能基としては、例えば、直鎖又は分岐鎖を有するメトキシ基、エトキシ基等のアルコキシ基や、シラノール基などが挙げられる。有機材料に対して反応性又は親和性を有する官能基としては、例えば、ビニル基や、ハロゲン原子、エポキシ基、メタクリル基、アミノ基、メルカプト基などが好適に挙げられる。
このようなシランカップリング剤としては、具体的には、例えば、β−（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や、γ−メルカプトプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、Ｎ−β−（アミノエチル）−γ−アミノプロピルトリメトキシシラン、γ−クロロプロピルトリメトキシシランなどが挙げられる。
【００１１】
本発明の塗料組成物においては、ビスフェノール型エポキシ樹脂（１）及びアミノ基含有硬化剤（２）からなる混合物（結合剤）の重量に基づいて、ビスフェノール型エポキシ樹脂（１）は、例えば、６０〜９５重量％、好ましくは、６５〜８５重量％の量で使用することが適当である。従って、結合剤の重量に基づいて、アミノ基含有硬化剤は、例えば、５〜４０重量％、好ましくは、１５〜３５重量％の量で使用することが適当である。
本発明の塗料組成物は、ビスフェノール型エポキシ樹脂（１）及びアミノ基含有硬化剤（２）からなる結合剤１００重量部（固形分）に対して、シランカップリング剤（３）を０．３〜２０重量部、更に好ましくは、５〜２０重量部の量で配合することが適当である。シランカップリング剤の配合量が、０．３重量部未満の場合、付着性が大幅に劣り易く、温水、硫化水素、塩酸性が低下し易い。逆に、シランカップリング剤の配合量が２０重量％を越えると、付着性は問題無いが、他の塗膜性能は全て不良となり易くなる。
【００１２】
本発明の塗料組成物は、通常、溶媒を含む。溶媒としては、トルエン、キシレン等の芳香族炭化水素、ヘプタン、ヘキサン、ペンタン等の脂肪族炭化水素、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル等のエーテル類等が好適に挙げられる。
本発明の塗料組成物には、必要により、更に、増粘剤や、沈澱防止剤、硬化促進剤、抗菌剤等の添加剤などを配合することも可能である。
かくして得られた塗料組成物は、鏡の切断端面へ、刷毛や、ローラー、浸漬等の方法で、乾燥膜厚８０〜２５０μｍ、好ましくは、８０〜１２０μｍになるように塗布することが適当である。次いで、常温もしくは強制乾燥により、８０℃×３時間程度に加熱乾燥し、仕上げられる。
【００１３】
【実施例】
＜実施例１〜１２及び比較例１〜２＞
充分に洗浄されたガラス基板（サイズ７２ｍｍ×３６ｍｍ×５ｍｍ）面上に銀鏡反応によって銀を析出する硝酸銀を含む溶液と銀を還元させる還元液との銀メッキ液をスプレーし、１ｇ／ｍ2 厚の銀鏡面膜を形成し、この膜面を水洗した後、無電解メッキ法によって銅を析出する硫酸銅を含む溶液と銅を還元させる還元液との銅メッキ液をスプレーし、０．３ｇ／ｍ2 厚の銅からなる銅保護膜を形成し、次いで水洗した後乾燥した。
この銀鏡面膜及び銅保護膜の形成されたガラス板の上記銅保護膜上に、エポキシ樹脂及び硬化剤を８５重量部、ロジン樹脂を１５重量部のバインダー（Ｂ）と顔料（Ｐ）とが重量比でＰ／Ｂ＝１．０〜４６であり、かつ顔料組成物中５〜１５重量％の硫酸鉛を含有する裏止め塗料組成物をそれぞれフローコーター法により塗布し、ガラス板温８０℃にて５分間焼付して、乾燥膜厚６５μｍの被膜を形成せしめ、更に、ガラス板温１２０℃にて３分間焼付を行った。
【００１４】
次に、表１に記載の各種鏡縁用塗料組成物を、モータによって駆動される駆動側プーリと一部が塗料浴に浸漬された従動側プーリとの間に丸ベルトを張設し、丸ベルトが従動側プーリから離間する位置で半円状切欠きを持ちその切欠き部の中央に凹部を形成したドクターナイフと半円状切欠きを持つドクターナイフとを相対峙させて丸ベルト通過用の空間を画成し、且つ該丸ベルトの移送方向に対して傾斜面取りしたガラス板を載置する作業台を直角に配置するようガラス板を載置する作業台を設けた鏡面取り部用塗工機（実公昭６４−４４５９号公報参照）を用いて傾斜面側面の銀鏡面膜、銅保護膜、裏止め塗膜の露出端面を覆って塗布し、ガラス板温８０℃にて３時間焼付して乾燥膜厚１００〜２００μｍの被膜を形成せしめ、各種試験片を得た。
【００１５】
表１において、以下の試験方法に定めた条件下で合格、不合格を示した。但し、試験片の４辺は事前に４５°の角度に面取り加工されており、前記組成物を４辺とも塗布した状態で試験を行った。
表１において、エポキシ樹脂としては、固形ビスフェノール型エポキシ樹脂（エポキシ当量４５０〜５００、不揮発分重量１００％（表１中の注１）を使用した。また、硬化剤としては、トーマイド４１０−Ｎ［富士化成工業株式会社製：ポリエチレンポリアミン・重合脂肪酸・重縮合物、分子量（ＧＰＣによる測定値）１，０００、アミン価６５］（表１中の注２）、サンマイド３２８Ａ［三和化学工業株式会社製：ポリエチレンポリアミン・重合脂肪酸・重縮合物、分子量（ＧＰＣによる測定値）６，２００、アミン価３５０］（表１中の注３）を使用した。更に、シランカップリング剤としては、エポキシシラン系：β−（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、メルカプトシラン系：γ−メルカプトプロピルトリメトキシシラン、アミノシラン系：Ｎ−β−（アミノエチル）γ−アミノプロピルトリメトキシシラン、クロロピリシラン系：γ−クロロプロピルトリメトキシシランを使用した。
表１における評価は、以下の試験方法に定めた条件下で合格（○）、不合格（×）を示した。
【００１６】
［１．付着試験］
鏡縁用塗料組成物が塗布された部分に２ｍｍ間隔で、カッターナイフでカットを入れ、セロテープ剥離を行い、塗膜の剥離有無の確認。
評価；剥離面積を確認、剥離面積％は１５％以内で合格とする。
［２．温水浸漬］
純粋６０℃に２４０時間浸漬し取り出したとき、塗膜の白化、剥離、端面よりの銀鏡面膜の変色、腐食がないこと。
［３．硫化水素ガス試験］
硫化水素ガスを飽和したデシケーター中にて、２０℃に４８時間曝露した後、取り出したときに、塗膜の剥離、端面よりの銀鏡面膜の変色、腐食がないこと。
［４．塩酸浸漬］
１０重量％塩酸（試薬１級）水に２０℃で７２時間浸漬した後、取り出したときに、塗膜の剥離、端面より銀鏡面膜に異常を認めないこと。
［５．カセイソーダ水浸漬］
４重量％カセイソーダ（試薬１級）水に２０℃で９６時間浸漬した後、取り出したときに、塗膜の剥離、端面より銀鏡面膜に異常を認めないこと。
［６．アンモニア水浸漬］
アンモニア水（試薬１級）５０重量部と純水５０重量部とを混ぜた混合液に２０℃で９６時間浸漬した後、取り出したときに、塗膜の剥離、端面より銀鏡面膜に異常を認めないこと。
［７．ホルマリン浸漬］
ホルマリン（試薬１級）に２０℃で３１２時間浸漬した後、取り出したときに、端面より銀鏡面膜に異常を認めないこと。
［８．漂白剤浸漬］
ライオン（株）製品「キッチンブライト」に２０℃で９６時間浸漬した後、取り出したときに、塗膜の剥離、端面より銀鏡面に異常を認めないこと。
［９．洗剤浸漬］
ライオン（株）製品「サンポール」（特許番号１２４９７１９）に２０℃で４８時間浸漬し取り出したとき、塗膜の剥離、端面よりの銀鏡面膜に異常を認めないこと。
［１０．塩水噴霧試験］
ＪＩＳ Ｚ ２３７１による塩水噴霧試験を、３６０時間行ったときに塗膜の剥離、端面より銀鏡面膜に異常を認めないこと。
［１１．促進耐候試験］
ＪＩＳ Ｋ ５４００ ６．１７による促進耐候試験を２４０時間行ったときに、塗膜の剥離、塗面より銀鏡面膜に異常を認めず、白亜化の程度が小さいこと。
［１２．沸騰水浸漬］
純水１００℃に１８時間浸漬した後、取り出したときに、塗膜の剥離、端面より銀鏡面膜に異常を認めないこと。
【００１７】
【表１】
【表２】
【発明の効果】
本発明による鏡は、従来の鏡に比較し、切断端面に対する付着性に優れるとともに、耐アルカリ性、耐酸性、耐触性、耐久性などにおいて格段に優れ、厳しい使用条件の環境下においても充分使用に耐えうるものである。
【図面の簡単な説明】
【図１】 本発明の一具体例に係る鏡の縦断面図。
【符号の説明】
１．ガラス基板
２．銀鏡面膜
３．銅保護膜
４．裏止め塗膜
５．鏡縁塗面[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a coating composition for anticorrosive mirror edges having excellent adhesion to a mirror cut end face, and a mirror produced by applying this paint.
[0002]
[Prior art]
The mirror is usually coated with a silver mirror surface film, a copper (plating) protective film, a back coating film, etc. in order on the surface of the glass substrate, so the glass substrate, silver mirror surface film, copper protective film, The end faces of the back coating film etc. coexist and are exposed. In particular, the metal film is easily corroded when exposed to moisture, carbon dioxide gas, sulfurous acid gas, etc., and the corrosion is caused from the cut end surface of the mirror to the inside between the metal film or between the metal film and the backing film. Proceed toward.
Therefore, various kinds of paints have been devised conventionally for covering and protecting the cut end face. In particular, the coating material for mirror protection needs to have excellent adhesion to these end surfaces. However, if importance is attached to the silver mirror surface film, the copper protective film, and the back coating film, Adhesion is inferior, and conversely, if importance is attached to the glass substrate end face, adhesion to silver mirror film and copper protective film will be inferior, and so far, it has an anticorrosive mirror edge protection effect with excellent adhesion There was no paint.
[0003]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide an anticorrosive mirror edge coating composition having improved adhesion to the cut end face of all mirror edges and a mirror coated with the mirror edge paint composition on the cut end face. To do.
[0004]
[Means for Solving the Problems]
The coating composition for mirror edges of the present invention comprises a bisphenol-type epoxy resin, an amino group-containing curing agent having reactivity with the epoxy group in the bisphenol-type epoxy resin, and a silane coupling agent.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
First, the present invention will be described with reference to the drawings. FIG. 1 shows a specific example of a mirror according to the present invention, where 1 is a glass substrate, 2 is a silver mirror film formed on the glass substrate, 3 Is a copper protective film formed on the silver mirror surface to enhance the chemical durability of the silver
In the mirror described above, as the silver mirror film, a film formed by depositing a film on the glass substrate surface by an electroless plating method is usually used, but the film is not necessarily limited to this. A silver film formed by sputtering, other various film forming methods can also be used as a mirror film. Such a silver mirror film is, for example, 0.5 to 2 g / m 2 , and preferably 0.8 to 1 so that the mirror mirror film having sufficient durability required for a mirror and having excellent durability can be obtained. A film thickness of 0.3 g / m 2 is suitable.
[0006]
The copper protective film is formed as a protective film that enhances the chemical durability of the silver mirror film that is easily chemically altered. For this purpose, for example, 0.1 to 1 g / m 2 , preferably 0.3 is used. thickness of ~0.6g / m 2 are suitable.
A typical method for manufacturing a mirror having a silver mirror film and a copper protective film is to prepare a glass plate having a smooth surface and having no surface defects, and after the glass plate is sufficiently washed, a silver mirror film is formed. The surface is activated and electroless plating is performed on the surface, for example, a silver plating solution that deposits silver by a so-called silver mirror reaction is sprayed to form a silver mirror film, and then copper plating is performed on the silver mirror film by electroless plating. A method of spraying a liquid to form a copper protective film, followed by washing and drying can be mentioned, but it can also be produced by various other methods.
[0007]
In the present invention, a backing coating film is formed on the copper protective film in order to increase the alkali resistance, acid resistance, corrosion resistance, and mechanical durability of the silver mirror film and the copper protective film. As the back coating film, those having a conventionally known composition can be appropriately used.
The thickness of the backing coating film is, for example, 50 to 70 μm, preferably 55 to 60 μm.
In the present invention, as shown in FIG. 1, the mirror edge coating composition is applied to the cut end face of each coating film.
The mirror edge coating composition of the present invention includes (1) a bisphenol type epoxy resin, (2) an amino group-containing curing agent that reacts with an epoxy group in the bisphenol type epoxy resin, and (3) a silane coupling agent. .
[0008]
As the bisphenol type epoxy resin used in the present invention, for example, a bisphenol type epoxy resin having an epoxy equivalent of 350 to 5,000, preferably 400 to 4,000, which is solid at room temperature is preferable. Examples of such bisphenol-type epoxy resins include Epicron 4050, Epicron 4055, Epicron 7050, Epicron 9055, Beccosol P-791-50 [trade names manufactured by Dainippon Ink and Chemicals, Inc.], Epicoat 1004, Epicoat 1007, Epicoat 1009, Epicoat 1010 [trade name of Yuka Shell Epoxy Co., Ltd.] and the like are preferably used. These can be used as one kind or a mixture of two or more kinds.
[0009]
The amino group-containing curing agent used in the present invention is preferably a curing agent having at least two nitrogen atoms having an active hydrogen group that reacts with the epoxy group in the epoxy resin in one molecule. One nitrogen atom needs to have at least one active hydrogen. Two active hydrogen atoms may exist in one nitrogen atom.
As such an amino group-containing curing agent, an amino group-containing curing agent or an amino curing agent that has been conventionally used as a curing agent for epoxy resins can be used. Examples of such an amino group-containing curing agent include metaxylenediamine, isophoronediamine, diethylenetriamine, triethylenetetramine, diaminodiphenylmethane and other aliphatic polyamines, alicyclic polyamines, aromatic polyamines; polyamine epoxy Resin adducts, polyamide amines, polyamide resins, amino resins, polyisocyanates, block polyisocyanates and the like are preferably used.
[0010]
As the silane coupling agent used in the present invention, functional groups having reactivity or affinity for inorganic materials (glass, silver, copper, etc.) and organic materials (resins used for backing coatings, etc.) A silane coupling agent having a functional group having reactivity or affinity with respect to is preferable.
Examples of functional groups having reactivity or affinity for inorganic materials include linear or branched alkoxy groups such as methoxy groups and ethoxy groups, and silanol groups. Preferable examples of the functional group having reactivity or affinity for the organic material include a vinyl group, a halogen atom, an epoxy group, a methacryl group, an amino group, and a mercapto group.
Specific examples of such silane coupling agents include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-glycidoxypropyltrimethoxysilane. , Γ-glycidoxypropylmethyldiethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like.
[0011]
In the coating composition of the present invention, based on the weight of the mixture (binder) comprising the bisphenol type epoxy resin (1) and the amino group-containing curing agent (2), the bisphenol type epoxy resin (1) is, for example, 60 It is suitable to use in an amount of -95% by weight, preferably 65-85% by weight. Accordingly, it is appropriate to use the amino group-containing curing agent in an amount of, for example, 5 to 40% by weight, preferably 15 to 35% by weight, based on the weight of the binder.
The coating composition of the present invention comprises 0.3 parts of the silane coupling agent (3) with respect to 100 parts by weight (solid content) of the binder comprising the bisphenol type epoxy resin (1) and the amino group-containing curing agent (2). It is appropriate to blend in an amount of -20 parts by weight, more preferably 5-20 parts by weight. When the compounding quantity of a silane coupling agent is less than 0.3 weight part, adhesiveness tends to be inferior remarkably, and warm water, hydrogen sulfide, and hydrochloric acid property fall easily. On the contrary, when the amount of the silane coupling agent exceeds 20% by weight, there is no problem in adhesion, but all other coating film performances are likely to be poor.
[0012]
The coating composition of the present invention usually contains a solvent. Solvents include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as heptane, hexane and pentane, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether and propylene glycol monomethyl ether. Preferred examples include ethers such as
If necessary, the coating composition of the present invention may further contain additives such as thickeners, precipitation inhibitors, curing accelerators, and antibacterial agents.
The coating composition thus obtained is applied to the cut end surface of the mirror by a method such as brush, roller, or dipping so that the dry film thickness is 80 to 250 μm, preferably 80 to 120 μm. . Next, it is dried by heating at 80 ° C. for about 3 hours at room temperature or forced drying.
[0013]
【Example】
<Examples 1-12 and Comparative Examples 1-2>
A silver plating solution of a solution containing silver nitrate that precipitates silver by a silver mirror reaction and a reducing solution that reduces silver is sprayed onto a sufficiently cleaned glass substrate (size 72 mm × 36 mm × 5 mm) surface, and the thickness is 1 g / m 2. After the silver mirror surface film is formed and this film surface is washed with water, a copper plating solution of a solution containing copper sulfate for depositing copper and a reducing solution for reducing copper is sprayed by an electroless plating method, and 0.3 g / m A copper protective film made of two- thick copper was formed, then washed with water and dried.
On the copper protective film of the glass plate on which the silver mirror film and the copper protective film are formed, 85 parts by weight of epoxy resin and curing agent and 15 parts by weight of rosin resin are binder (B) and pigment (P) by weight. A back coating composition containing P / B = 1.0 to 46 in a ratio and containing 5 to 15% by weight of lead sulfate in the pigment composition was applied by a flow coater method, and the glass plate temperature was set to 80 ° C. The film was baked for 5 minutes to form a film having a dry film thickness of 65 μm, and further baked at a glass plate temperature of 120 ° C. for 3 minutes.
[0014]
Next, various mirror edge coating compositions shown in Table 1 were formed by stretching a round belt between a driving pulley driven by a motor and a driven pulley partially immersed in a coating bath. For passing the round belt by making the doctor knife with a semi-circular notch at the position where the belt separates from the driven pulley and forming a recess at the center of the notch and the doctor knife with the semi-circular notch relatively A mirror chamfered portion provided with a work table on which the glass plate is placed so that a work table on which the glass plate inclined with respect to the transfer direction of the round belt is placed is placed at a right angle. Using a machine tool (see Japanese Utility Model Publication No. 64-4459), coat the silver mirror surface film on the side of the inclined surface, the copper protective film, and the exposed end face of the backing film, and baked at a glass plate temperature of 80 ° C for 3 hours. To form a film with a dry film thickness of 100 to 200 μm, and various tests It was obtained.
[0015]
In Table 1, pass / fail was shown under the conditions defined in the following test methods. However, the four sides of the test piece were chamfered at an angle of 45 ° in advance, and the test was performed in a state where all the four sides of the composition were applied.
In Table 1, a solid bisphenol type epoxy resin (epoxy equivalent 450-500, nonvolatile content weight 100% (Note 1 in Table 1) was used as an epoxy resin. Further, as a curing agent, tomide 410-N [ Made by Fuji Chemical Industry Co., Ltd .: Polyethylene polyamine, polymerized fatty acid, polycondensate, molecular weight (measured by GPC) 1,000, amine value 65] (Note 2 in Table 1), sunmide 328A [Sanwa Chemical Industry Co., Ltd. Manufactured by: Polyethylene polyamine / polymerized fatty acid / polycondensate, molecular weight (measured by GPC) 6,200, amine value 350] (Note 3 in Table 1) Further, epoxy silane as the silane coupling agent System: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercaptosilane System: γ-mercaptopropyl Limethoxysilane, aminosilane type: N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, chloropyrisilane type: γ-chloropropyltrimethoxysilane were used.
The evaluation in Table 1 showed a pass (◯) and a failure (x) under the conditions defined in the following test methods.
[0016]
[1. Adhesion test]
Cut with a cutter knife at intervals of 2 mm at the part where the mirror edge coating composition was applied, and peel off the cellophane to confirm the presence or absence of peeling of the coating film.
Evaluation : The peeled area is confirmed, and the peeled area% is acceptable within 15%.
[2. Hot water immersion]
When immersed in pure 60 ° C. for 240 hours and taken out, there should be no whitening, peeling, discoloration or corrosion of the silver mirror film from the end face.
[3. Hydrogen sulfide gas test]
When exposed to 20 ° C. for 48 hours in a desiccator saturated with hydrogen sulfide gas, when taken out, there should be no peeling of the coating film, discoloration of the silver mirror film from the end face, or corrosion.
[4. Hydrochloric acid immersion]
When immersed in 10% by weight hydrochloric acid (reagent grade 1) water at 20 ° C. for 72 hours and then removed, the coating film is peeled off and no abnormality is observed in the silver mirror film from the end face.
[5. Caustic soda soaked in water]
When immersed in 4% by weight caustic soda (reagent grade 1) water at 20 ° C. for 96 hours and then taken out, the coating film should be peeled off, and no abnormality should be observed in the silver mirror film from the end face.
[6. Ammonia water immersion]
When immersed in a mixed solution of 50 parts by weight of ammonia water (reagent grade 1) and 50 parts by weight of pure water at 20 ° C. for 96 hours and then removed, the coating film was peeled off, and an abnormality was observed in the silver mirror film from the end face. Not there.
[7. Formalin immersion]
When immersed in formalin (reagent grade 1) at 20 ° C. for 312 hours and then removed, no abnormality is observed in the silver mirror film from the end face.
[8. Bleach immersion]
When immersed in Lion Kitchen's “Kitchen Bright” at 20 ° C. for 96 hours and then removed, the coating film will not peel off, and no abnormalities will be observed on the silver mirror surface from the edge.
[9. Detergent soaking]
When immersed in Lion's product “Sun Paul” (patent No. 1249719) at 20 ° C. for 48 hours, the coating film should not peel off, and the silver mirror film from the end face should not be abnormal.
[10. Salt spray test]
When the salt spray test according to JIS Z 2371 is conducted for 360 hours, the coating film is peeled off and no abnormality is observed in the silver mirror film from the end face.
[11. Accelerated weathering test]
When the accelerated weathering test according to JIS K 5400 6.17 is conducted for 240 hours, no abnormality is observed in the silver mirror film from the coating film and the coated surface is not chalked.
[12. Boiling water immersion]
When immersed in pure water at 100 ° C. for 18 hours and then taken out, there should be no abnormality in the silver mirror film from the peeling of the coating film or from the end face.
[0017]
[Table 1]
[Table 2]
【The invention's effect】
Compared with conventional mirrors, the mirror according to the present invention has excellent adhesion to the cut end face, and is remarkably superior in alkali resistance, acid resistance, touch resistance, durability, etc., and can be used sufficiently even under severe operating conditions. It can endure.
[Brief description of the drawings]
FIG. 1 is a longitudinal sectional view of a mirror according to a specific example of the present invention.
[Explanation of symbols]
1. 1.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37220398A JP4047991B2 (en) | 1998-12-28 | 1998-12-28 | Mirror edge coating composition and mirror |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP37220398A JP4047991B2 (en) | 1998-12-28 | 1998-12-28 | Mirror edge coating composition and mirror |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000191978A JP2000191978A (en) | 2000-07-11 |
| JP4047991B2 true JP4047991B2 (en) | 2008-02-13 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP37220398A Expired - Fee Related JP4047991B2 (en) | 1998-12-28 | 1998-12-28 | Mirror edge coating composition and mirror |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4776254B2 (en) * | 2004-03-24 | 2011-09-21 | セントラル硝子株式会社 | Mirror coating liquid and mirror coated with the coating liquid |
| CN100345921C (en) * | 2004-03-24 | 2007-10-31 | 中央硝子株式会社 | Coating material and mirror coated therewith |
| IN2012DN01796A (en) * | 2009-08-31 | 2015-06-05 | Asahi Glass Co Ltd | |
| EP2940089A4 (en) * | 2012-12-27 | 2016-08-03 | Asahi Glass Co Ltd | Back coating composition and mirror |
| JP6253966B2 (en) * | 2013-12-10 | 2017-12-27 | 株式会社栗本鐵工所 | Coating composition for metal tube and metal tube formed by applying the same |
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1998
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| JP2000191978A (en) | 2000-07-11 |
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