JP3897175B2 - Rust-proof paint and mirror using it - Google Patents
Rust-proof paint and mirror using it Download PDFInfo
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Description
本発明は鉛を含まない防錆塗料とそれを用いた鏡に関する。 The present invention relates to a rust preventive paint containing no lead and a mirror using the same.
鏡は、例えば図１で示したように、透明なガラス基材１の裏面に、まず銀膜２を鏡面膜として成膜し、この銀鏡面膜の化学的耐久性を確保するために、ついで銅の保護膜３を成膜し、そして、この銅保護膜３に防錆塗料を塗布したのちそれを乾燥または焼き付けることにより、裏止め塗膜４を成膜して製造されている。
そして、鏡の設置に際しては、工場で製造された大板サイズの鏡板を所定の寸法に切断する切り離し作業を行い、ついでその切断面を研削する面取り作業を行ったのち、所定の場所に設置する。
For example, as shown in FIG. 1, a mirror is formed by first forming a
When installing the mirror, a large plate manufactured at the factory is cut into a predetermined size, and then the cut surface is ground and then the cut surface is ground, and then the mirror is installed at a predetermined location. .
このようなことから、鏡における裏止め塗膜には次のようなことが要求されている。
まず、鏡の設置環境下に置いたとき、鏡が環境中の水蒸気や腐食性ガスなどに曝されても、銀鏡面膜や銅保護膜が変質することがなく、また剥離したりすることがないように、鏡の耐食性を確保する機能である。
また、適当な硬さを備えていて、鏡板の切り離し作業時にあってもその切断作業性の低下を招かないことや、更には、銅保護膜との密着性が良好で、例えば、切断面の面取り作業時に剥離しないことも必要とされる。剥離すれば、鏡の端面から内部に向かって銀や銅の発錆が進行するからである。
For this reason, the following is required for the back coating film in the mirror.
First, when placed in a mirror installation environment, even if the mirror is exposed to water vapor or corrosive gas in the environment, the silver mirror film and copper protective film will not be altered or peeled off. Thus, it is a function which ensures the corrosion resistance of a mirror.
In addition, it has appropriate hardness and does not cause a decrease in the cutting workability even when the end plate is cut off, and also has good adhesion with the copper protective film. It is also necessary not to peel off during the chamfering operation. This is because rusting of silver and copper progresses from the end face of the mirror to the inside if peeled off.
このようなことが要求されている裏止め塗膜の形成に用いる防錆塗料は、通常、結合材として機能する各種の樹脂と、鏡の耐食性を確保するための防錆顔料と、鏡板の切り離し性を確保するためにタルク、硫酸バリウム、マイカのような体質顔料の混合物を、溶剤で希釈して構成されている（特許文献１を参照）。
そして必要に応じては、更に、酸化チタン、酸化鉄、カーボンブラックのような着色顔料や、ナフテン酸コバルト、ナフテン酸ジルコニウムのような乾燥剤が添加されている。
Rust preventive paint used for the formation of a backing coating that requires this is usually a variety of resins that function as binders, anticorrosive pigments to ensure the corrosion resistance of the mirror, and the separation of the end plate In order to ensure the properties, a mixture of extender pigments such as talc, barium sulfate, and mica is diluted with a solvent (see Patent Document 1).
If necessary, color pigments such as titanium oxide, iron oxide, and carbon black, and desiccants such as cobalt naphthenate and zirconium naphthenate are further added.
このような防錆塗料における、防錆顔料としては、鏡の耐食性の確保にとって優れた効果を発現するという点で、従来から鉛丹、鉛白、硫酸鉛、鉛酸カルシウム、シアナミド鉛のような鉛化合物が広く用いられている。 In such anti-corrosion paints, as anti-corrosion pigments, in the past, such as red lead, lead white, lead sulfate, calcium lead acid, cyanamide lead, etc., in terms of expressing an excellent effect for ensuring the corrosion resistance of the mirror Lead compounds are widely used.
しかしながら、鉛化合物は人体や環境にとって有害な物質として規制の対象になっているので、鏡の耐食性確保の点では有用であってもその使用はひかえるべきである。
例えば、切り離し作業後における切断面の研削時には、裏止め塗膜の研削屑も発生するが、それには有害な鉛化合物が含まれているので、その廃棄に際しては特別の処理が必要となるからである。
However, since lead compounds are regulated as substances harmful to the human body and the environment, their use should be avoided even if they are useful in terms of ensuring the corrosion resistance of mirrors.
For example, when grinding the cut surface after detachment, grinding scraps from the back coating film are also generated, but since it contains harmful lead compounds, special treatment is required for its disposal. is there.
本発明は、上記した観点に立って開発された防錆塗料とそれを用いた鏡であって、防錆顔料として鉛化合物を用いた防錆塗料と比較しても遜色のない鏡への耐食性を付与することができ、また鏡板の切り離し性、密着性も良好である無鉛防錆塗料とそれを用いた鏡の提供を目的とする。 The present invention is a rust preventive paint developed from the above viewpoint and a mirror using the same, and the corrosion resistance to a mirror comparable to a rust preventive paint using a lead compound as a rust preventive pigment An object is to provide a lead-free rust-proof paint having a good separation and adhesion of the end plate and a mirror using the same.
上記した目的を達成するために、本発明においては、アルキド樹脂６０〜８０質量％、メラミン樹脂５〜１５質量％、およびエポキシ樹脂１０〜２５質量％を混合して成る混合樹脂１００質量部に対し、体質顔料４０〜６０質量部、塩基性シアナミド亜鉛カルシウム１０〜２５質量部、および溶剤４０〜６０質量部を必須成分として含有することを特徴とする防錆塗料が提供される。 In order to achieve the above-described object, in the present invention, with respect to 100 parts by mass of a mixed resin obtained by mixing 60 to 80% by mass of alkyd resin, 5 to 15% by mass of melamine resin, and 10 to 25% by mass of epoxy resin. The present invention provides a rust-preventing paint comprising 40 to 60 parts by mass of an extender pigment, 10 to 25 parts by mass of basic cyanamide zinc calcium, and 40 to 60 parts by mass of a solvent as essential components.
また、本発明においては、ガラス基材の片面に、銀鏡膜、銅保護膜、および裏止め塗膜がこの順序で形成されている鏡において、
前記裏止め塗膜が、上記した防錆塗料を用いた塗膜であることを特徴とする鏡が提供される。
Further, in the present invention, a mirror in which a silver mirror film, a copper protective film, and a back coating film are formed in this order on one side of a glass substrate,
There is provided a mirror characterized in that the backing coating film is a coating film using the above-mentioned rust preventive paint.
この防錆塗料とそれを用いて裏止め塗膜が形成されている鏡は、鉛化合物を全く含有していないので、人体への危害や環境汚染を引き起こす心配はない。
また、この防錆塗料で形成した裏止め塗膜とガラス基材との密着性は良好で、また塗膜の耐食性も優れている。
更には、適量の体質顔料が含まれているので、鏡板の切り離し加工時の作業性は良好で、また塗膜の密着性が良好であるため、切断面の研削作業時に当該塗膜の剥離も起こりづらく、銀鏡面膜や銅保護膜の保護機能も消失しない。
Since this anti-corrosion paint and the mirror on which the back coating film is formed do not contain any lead compound, there is no fear of causing harm to the human body or environmental pollution.
Further, the adhesion between the backing coating film formed with this rust-proof coating and the glass substrate is good, and the corrosion resistance of the coating film is also excellent.
Furthermore, since an appropriate amount of extender pigment is included, the workability at the time of cutting off the end plate is good and the adhesion of the coating film is good, so that the coating film can be peeled off during the grinding operation of the cut surface. It is hard to occur and the protective function of the silver mirror film and the copper protective film is not lost.
最初に、本発明の防錆塗料について説明する。
この防錆塗料は、後述する混合樹脂と、体質顔料と、塩基性シアナミド亜鉛カルシウムと、溶剤とを必須成分として調製されている。
混合樹脂は、目的とする裏止め塗膜の骨格を構成する成分であり、しかも、前記塗膜は塗料塗布層の乾燥または焼付けで形成されるので、基本的には各種の熱硬化性樹脂を混合して用いることができる。
First, the rust preventive paint of the present invention will be described.
This rust preventive paint is prepared by using a mixed resin, which will be described later, extender pigments, basic cyanamide zinc calcium, and a solvent as essential components.
The mixed resin is a component that constitutes the skeleton of the desired backing coating film, and since the coating film is formed by drying or baking the paint coating layer, basically various thermosetting resins are used. It can be used by mixing.
本発明では、アルキド樹脂、メラミン樹脂、エポキシ樹脂を混合して成る混合樹脂が使用される。
この混合樹脂において、アルキド樹脂がベース樹脂になっているが、エポキシ樹脂の混合割合が多くなりすぎると、製造した鏡の耐食性は低下するようになり、また少なすぎると塗膜の密着性が悪くなり、メラミン樹脂の混合割合が多くなりすぎると、鏡の耐食性の低下と塗膜の密着性の低下を招くようになり、また少なすぎても塗膜の密着性が低下する。
In the present invention, a mixed resin obtained by mixing an alkyd resin, a melamine resin, and an epoxy resin is used.
In this mixed resin, the alkyd resin is the base resin, but if the mixing ratio of the epoxy resin is too large, the corrosion resistance of the manufactured mirror will be lowered, and if it is too small, the adhesion of the coating will be poor. When the mixing ratio of the melamine resin is too large, the corrosion resistance of the mirror and the adhesiveness of the coating film are reduced. If the mixing ratio is too small, the adhesiveness of the coating film is decreased.
このようなことから、各樹脂の混合割合は、アルキド樹脂６０〜８０質量％、メラミン樹脂５〜１５質量％、エポキシ樹脂１０〜２５質量％に設定する。
体質顔料は、形成した塗膜内に分散して鏡板の切り離し加工時における切り離し作業性を確保するために配合される成分である。
体質顔料としては、従来から使用されているものであれば何であってもよく格別限定されるものではない。例えば、タルク、硫酸バリウム、マイカ、炭酸カルシウムなどをあげることができる。
For this reason, the mixing ratio of each resin is set to 60 to 80% by mass of alkyd resin, 5 to 15% by mass of melamine resin, and 10 to 25% by mass of epoxy resin.
The extender pigment is a component that is mixed in the formed coating film and is blended in order to ensure the detachment workability at the time of detachment processing of the end plate.
Any extender may be used as long as it is conventionally used, and it is not particularly limited. For example, talc, barium sulfate, mica, calcium carbonate and the like can be mentioned.
この体質顔料の配合量は、前記した混合樹脂１００質量部に対し、４０〜６０質量部に設定される。
この配合量を６０質量部より多くすると、塗料製造の分散時における増粘、形成された塗膜の強度低下、密着性の低下などが起こり、また４０質量部よりも少なくすると、鏡板の切り離し性が悪くなって切断作業性が低下する。
The amount of the extender is set to 40 to 60 parts by mass with respect to 100 parts by mass of the mixed resin.
If the blending amount is more than 60 parts by mass, thickening at the time of dispersion of the paint production, strength reduction of the formed coating film, decrease in adhesion, etc. occur, and if it is less than 40 parts by mass, the detachability of the end plate will occur. As a result, cutting workability decreases.
塩基性シアナミド亜鉛カルシウムは、式：ＺｎＯ・ＣａＣＮ2で示されるアルカリ性の無鉛防錆顔料（白色微粉末）である。
この成分は、形成された裏止め塗膜中に分散し、鏡の設置環境から塗膜内に拡散してくる例えば酸性の腐食物質を中和して塗膜環境を塩基性に保持することにより、鏡の耐食性の確保に寄与する。
Basic cyanamide zinc calcium is an alkaline lead-free rust preventive pigment (white fine powder) represented by the formula: ZnO.CaCN 2 .
This component is dispersed in the formed backing coating film, and neutralizes, for example, acidic corrosive substances that diffuse into the coating film from the installation environment of the mirror to keep the coating film environment basic. Contributes to ensuring the corrosion resistance of mirrors.
この塩基性シアナミド亜鉛カルシウムとしては、例えば、ＬＦボーセイＺＫ−Ｓ２（商品名、キクチカラー（株）製）をあげることができる。
この防錆顔料の配合量は、混合樹脂１００質量部に対し、１０〜２５質量部に設定される。
配合量を２５質量部より多くすると、形成された塗膜それ自体の耐食性は向上するものの、他方では塗膜の強度低下や密着性が低下してしまい、結局は総体として鏡の耐食性が低下する。また、配合量を１０質量部より少なくすると、この防錆顔料の上記した効果の発揮は不充分となって鏡の耐食性が低下する。
Examples of this basic cyanamide zinc calcium include LF Bosei ZK-S2 (trade name, manufactured by Kikuchi Color Co., Ltd.).
The compounding quantity of this antirust pigment is set to 10-25 mass parts with respect to 100 mass parts of mixed resin.
When the blending amount is more than 25 parts by mass, the corrosion resistance of the formed coating film itself is improved, but on the other hand, the strength and adhesion of the coating film are reduced, and eventually the overall corrosion resistance of the mirror is lowered. . On the other hand, if the blending amount is less than 10 parts by mass, the effect of the anticorrosive pigment described above is insufficient and the corrosion resistance of the mirror is lowered.
溶剤としては、混合樹脂に対して溶解能を有するものであれば何であってもよいが、例えば、キシレン、トルエン、ブチルアルコール、ブチルセロソルブ、酢酸エチル、酢酸ブチルなどをあげることができる。これらは単独で用いてもよく、また２種以上を混合して用いてもよい。
溶剤の配合量は、混合樹脂１００質量部に対し、４０〜６０質量部に設定される。
Any solvent can be used as long as it has solubility in the mixed resin. Examples thereof include xylene, toluene, butyl alcohol, butyl cellosolve, ethyl acetate, and butyl acetate. These may be used alone or in combination of two or more.
The compounding quantity of a solvent is set to 40-60 mass parts with respect to 100 mass parts of mixed resin.
この配合量を６０質量部より多くすると、塗料の粘性が低下して流動性を増すので、所望厚みの塗料塗布層の形成に難をきたすとともに、前記した防錆顔料（比重３程度）が沈殿するようになって塗料塗布層内における均一分散が阻害される。また、配合量を４０質量部より少なくすると、塗料の粘性が増大して塗布作業が困難になる。
本発明の防錆塗料は上記した成分を必須成分とするが、更には着色顔料や乾燥剤などを含有していてもよい。
If the blending amount is more than 60 parts by mass, the viscosity of the paint is lowered and the fluidity is increased, so that it is difficult to form a paint coating layer having a desired thickness and the rust preventive pigment (specific gravity of about 3) is precipitated. As a result, uniform dispersion in the coating layer is hindered. On the other hand, if the blending amount is less than 40 parts by mass, the viscosity of the paint increases and the coating operation becomes difficult.
The anticorrosive paint of the present invention contains the above-described components as essential components, but may further contain a color pigment, a desiccant, and the like.
着色顔料としては、従来から使用されているものであれば何であってもよく、例えば、酸化チタン（白色）、カーボンブラック（黒色）、酸化第二鉄（赤色〜黄土色）などをあげることができる。また、これらを適当に混合して、塗膜を所望する色調にしてもよい。
この着色顔料の配合量が過度に多くなると、塗膜の強度低下や密着性の低下が起こるようになるので、配合する場合には、混合樹脂１００質量部に対し、１０質量部以下に規制することが好ましい。
Any pigment may be used as long as it is conventionally used. Examples thereof include titanium oxide (white), carbon black (black), and ferric oxide (red to ocher). it can. Moreover, you may mix these suitably and may make the coating film into the desired color tone.
If the blending amount of the coloring pigment is excessively large, the strength of the coating film and the adhesiveness are lowered. Therefore, when blending, the amount is limited to 10 parts by mass or less with respect to 100 parts by mass of the mixed resin. It is preferable.
乾燥剤を配合することにより、塗料塗布層の乾燥と塗膜化が迅速に進んで鏡の生産性が向上する。しかし、あまり多量に配合すると、塗料保管中に増粘、皮張り等の不具合を生じる、また塗料の塗布膜が不均一な塗膜を形成する、乾燥性が速くなりすぎて塗膜自体が硬くなって密着性が低下するなどの問題が発生してくるので、配合する場合には、混合樹脂１００質量部に対し、５質量部以下に規制することが好ましい。 By blending the desiccant, drying and coating of the paint coating layer proceed rapidly, and the productivity of the mirror is improved. However, if it is added too much, problems such as thickening and skinning occur during storage of the paint, and the coating film of the paint forms a non-uniform coating film. The drying property becomes too fast and the coating film itself is hard. This causes problems such as a decrease in adhesiveness. Therefore, when blended, it is preferable to regulate the amount to 5 parts by mass or less with respect to 100 parts by mass of the mixed resin.
乾燥剤としては、例えば、ナフテン酸コバルト、ナフテン酸ジルコニウム、ナフテン酸カルシウム、ナフテン酸亜鉛、オクチル酸ジルコニウムなどを用いることができる。
次に、本発明の鏡について説明する。
本発明の鏡は、ガラス基材の片面に、厚み７０〜１２０nm程度の銀鏡面膜、厚み２０〜５０nm程度の銅保護膜を順次成膜し、更に銅保護膜を被覆して前記した防錆顔料を塗布したのち、乾燥または焼付けを行うことにより塗料塗布層を塗膜に転化して製造される。
As the desiccant, for example, cobalt naphthenate, zirconium naphthenate, calcium naphthenate, zinc naphthenate, zirconium octylate and the like can be used.
Next, the mirror of the present invention will be described.
In the mirror of the present invention, a silver mirror surface film having a thickness of about 70 to 120 nm and a copper protective film having a thickness of about 20 to 50 nm are sequentially formed on one side of a glass substrate, and further coated with the copper protective film, and the anticorrosive pigment described above. After coating, the coating layer is produced by converting the coating layer into a coating film by drying or baking.
銀鏡面膜や銅保護膜の成膜に関しては、従来から実施されている公知の方法を適用することができる。例えば、無電解めっき法、真空蒸着法、スパッタ法などを適用することができる。
とくに、銀鏡面膜の成膜に関しては、表面を清浄化したガラス基材を第１塩化すず水溶液に浸漬し、水洗後、更に塩化パラジウムの希塩酸酸性水溶液に浸漬したのち、銀鏡反応を実施する方法で成膜すると、銀鏡面膜とガラス基材との密着性が非常に向上するので好適である。
With respect to the film formation of the silver mirror film and the copper protective film, conventionally known methods can be applied. For example, an electroless plating method, a vacuum evaporation method, a sputtering method, or the like can be applied.
In particular, with respect to the film formation of the silver mirror surface film, the glass substrate whose surface has been cleaned is immersed in a first tin chloride aqueous solution, washed with water, and further immersed in a dilute hydrochloric acid aqueous solution of palladium chloride, followed by a silver mirror reaction. The film formation is preferable because the adhesion between the silver mirror film and the glass substrate is greatly improved.
防錆塗料の塗布に関しては、例えば刷毛塗り、スプレー塗装、ロールコータ塗装、カーテンフローコータ塗装などの方法で行えばよい。このとき、乾燥厚みが３０〜４０μｍ程度になるように塗料塗布層を形成すればよい。
塗布終了後、全体を例えば温度１３０〜１８０℃で５〜１０分間程度加熱することにより、目的とする裏止め塗膜が形成される。
The application of the rust preventive paint may be performed by a method such as brush painting, spray coating, roll coater coating, curtain flow coater coating, or the like. At this time, the paint coating layer may be formed so that the dry thickness is about 30 to 40 μm.
After the application is completed, the entire back coating film is formed by heating the whole at, for example, a temperature of 130 to 180 ° C. for about 5 to 10 minutes.
実施例１〜３、比較例１〜１２
表１〜３で示した組成の各種の防錆塗料を調製した。
Examples 1-3, Comparative Examples 1-12
Various antirust paints having the compositions shown in Tables 1 to 3 were prepared.
一方、長さ２００mm、幅１００mm、厚み２mmのガラス基材の片面に、表１〜３で示した各防錆塗料を乾燥厚みが３５μｍとなるように塗布したのち、熱風乾燥機を用いて、温度１８０℃で５分間の焼き付けを行った。
各塗膜を室温下の大気中に２４時間放置し、それぞれに付き、下記の仕様で光沢、鉛筆硬度、ガラス基材との密着性を調べた。
On the other hand, after applying each rust preventive paint shown in Tables 1 to 3 to one side of a glass substrate having a length of 200 mm, a width of 100 mm, and a thickness of 2 mm so that the dry thickness becomes 35 μm, using a hot air dryer, Baking was performed at a temperature of 180 ° C. for 5 minutes.
Each coating film was allowed to stand in the atmosphere at room temperature for 24 hours, attached to each, and examined for gloss, pencil hardness, and adhesion to a glass substrate according to the following specifications.
光沢：ＪＩＳ Ｋ ５６００−４−７に準拠して６０度鏡面光沢を測定。この値が大きい塗膜ほど表面凹凸が少ない。
鉛筆硬度：ＪＩＳ Ｋ ５６００−５−４に準拠して鉛筆ひっかき値で評価。塗膜の硬度としては、Ｈ以上で合格とする。
密着性：ＪＩＳ Ｋ ５６００−５−６に準拠して、１mm碁盤目に対するセロテープ試験時における剥離状態で評価。
Gloss: 60 degree specular gloss is measured in accordance with JIS K 5600-4-7. The coating film having a larger value has less surface unevenness.
Pencil hardness: evaluated with a pencil scratch value in accordance with JIS K 5600-5-4. The hardness of the coating film is H or more and is considered acceptable.
Adhesion: Based on JIS K 5600-5-6, evaluated in a peeled state at the time of a cellophane test for a 1 mm grid.
そのときの評価基準は、６段階分類で行い、カット部の碁盤目に剥離がないが場合を０点と評価し、部分的な剥離があり、クロスカット部で影響を受けるのは１５％を超えるが３５％を上まわることはない場合を３点と評価し、全面剥離の場合を５点と評価した。
一方、銀鏡面膜と銅保護膜を成膜した鏡を、ダイヤモンドカッタで切断して、長さ２００mm、幅２５mm、厚み２mmの鏡片を作製し、銅保護膜の上に表１〜３で示した各防錆塗料を塗布したのち、熱風乾燥機を用いて温度１８０℃で５分間の焼付けを行った。
The evaluation criteria at that time are classified into 6 stages, and the case where there is no peeling on the grid of the cut part is evaluated as 0 point, there is partial peeling, and 15% is affected by the cross cut part. In the case of exceeding 35%, it was evaluated as 3 points, and in the case of full peeling, it was evaluated as 5 points.
On the other hand, the mirror on which the silver mirror surface film and the copper protective film were formed was cut with a diamond cutter to produce a mirror piece having a length of 200 mm, a width of 25 mm, and a thickness of 2 mm, and shown in Tables 1 to 3 on the copper protective film. After applying each rust preventive paint, baking was performed at a temperature of 180 ° C. for 5 minutes using a hot air dryer.
そして、室温下の大気中に２４時間放置して、下記仕様の耐食評価試験を行った。
塩水噴霧試験：各試験片の塗膜に１mm基盤目のクロスカットを入れた状態で、５％ＮａＣｌ水溶液（液温３５℃）を各試験片に噴霧し、１４日経過後に取出し、クロスカット部の剥離状態を目視観察。塗膜の外観に異常なしの場合を○、塗膜に若干の剥離が認められる場合を△、塗膜が剥離していた場合を×と評価した。
Then, it was left in the atmosphere at room temperature for 24 hours, and a corrosion resistance evaluation test having the following specifications was performed.
Salt spray test: A 1% base cross-cut was put on the coating film of each test piece, and a 5% NaCl aqueous solution (liquid temperature 35 ° C.) was sprayed on each test piece. Visual observation of the peeled state. The case where there was no abnormality in the appearance of the coating film was evaluated as ◯, the case where slight peeling was observed in the coating film was evaluated as Δ, and the case where the coating film was peeled was evaluated as ×.
塩水浸漬試験：各試験片の塗膜に１mm碁盤目のクロスカットを入れた状態で３％ＮａＣｌ水溶液（液温５０℃）に各試験片を浸漬し、１４日経過後に取出し、クロスカット部の剥離状を目視観察。塗膜の外観に異常なしの場合を○、塗膜に若干の剥離が認められる場合を△、塗膜が剥離していた場合を×と評価した。
以上の結果を一括して表４に示した。
Salt water immersion test: Each test piece was immersed in a 3% NaCl aqueous solution (liquid temperature 50 ° C.) with a 1 mm cross cut in the coating film of each test piece, taken out after 14 days, Visual observation of peeling. The case where there was no abnormality in the appearance of the coating film was evaluated as ◯, the case where slight peeling was observed in the coating film was evaluated as Δ, and the case where the coating film was peeled was evaluated as ×.
The results are collectively shown in Table 4.
表１〜３と表４から次のことが明らかである。
（１）実施例３と比較例４を対比して明らかなように、無鉛の防錆塗料を用いた本発明の鏡は、鉛化合物を用いた比較例４の鏡と塗膜の密着性、耐食性が同等である。
（２）実施例１〜３と比較例１〜３を対比して明らかなように、これらはいずれも無鉛の防錆顔料を用いているが、比較例１〜３は、実施例１〜３に比べて密着性と耐食性のいずれにおいても劣っている。このことから、塩基性シアナミド亜鉛カルシウムを防錆顔料として含む本発明の防錆塗料の有用性は極めて明らかである。
From Tables 1 to 3 and Table 4, the following is clear.
(1) As apparent from the comparison between Example 3 and Comparative Example 4, the mirror of the present invention using a lead-free anticorrosive paint is the adhesion between the mirror of Comparative Example 4 using a lead compound and the coating film, Corrosion resistance is equivalent.
(2) As is clear by comparing Examples 1 to 3 and Comparative Examples 1 to 3, these all use lead-free rust preventive pigments, but Comparative Examples 1 to 3 are Examples 1 to 3. Compared to, both adhesion and corrosion resistance are inferior. From this, the usefulness of the rust preventive coating material of the present invention containing basic cyanamide zinc calcium as a rust preventive pigment is very clear.
（３）その場合、塩基性シアナミド亜鉛カルシウムの含有量が８.２質量部と少ない比較例９の場合は、耐食性がやや劣っている。したがって、塩基性シアナミド亜鉛カルシウムの含有量は、切り離しのことも考慮に入れて、１０〜２５質量部にすべきであると考えてよい。
（４）一方、混合樹脂においてメラミン樹脂を混合していない比較例５の場合は、耐食性の劣化が認められ、エポキシ樹脂を混合していない比較例８の場合は、密着性と耐食性の双方の劣化が認められる。このようなことから、混合樹脂は３つの樹脂を混合して構成すべきであることがわかる。
(3) In that case, in the case of Comparative Example 9 in which the content of basic cyanamide zinc calcium is as low as 8.2 parts by mass, the corrosion resistance is slightly inferior. Therefore, it may be considered that the content of basic cyanamide zinc calcium should be 10 to 25 parts by mass in consideration of separation.
(4) On the other hand, in the case of Comparative Example 5 in which no melamine resin is mixed in the mixed resin, deterioration of corrosion resistance is recognized, and in the case of Comparative Example 8 in which no epoxy resin is mixed, both adhesion and corrosion resistance are observed. Deterioration is observed. From this, it is understood that the mixed resin should be constituted by mixing three resins.
その場合、メラミン樹脂の混合割合が少ない比較例６、エポキシ樹脂が少ない比較例７の場合、密着性は１点で、塩水試験で若干の剥離が認められる程度であることを考えると、混合樹脂におけるメラミン樹脂は５〜１５質量％、エポキシ樹脂は１０〜２５質量％にすればよいことになる。
また、アルキド樹脂の混合割合が少ない比較例１１、アルキド樹脂の混合割合が多い比較例１２は、いずれも鉛筆硬度がＦになってしまい、塗膜の硬度が不合格になる。このようなことから、アルキド樹脂の混合割合は、６０〜８０質量％にすべきであることがわかる。
In that case, in the case of Comparative Example 6 where the mixing ratio of the melamine resin is low and Comparative Example 7 where the epoxy resin is low, the adhesiveness is 1 point, and considering that the slight peeling is recognized in the salt water test, the mixed resin The melamine resin may be 5 to 15% by mass, and the epoxy resin may be 10 to 25% by mass.
Further, in Comparative Example 11 in which the mixing ratio of the alkyd resin is small and Comparative Example 12 in which the mixing ratio of the alkyd resin is large, the pencil hardness becomes F, and the hardness of the coating film is rejected. From this, it can be seen that the mixing ratio of the alkyd resin should be 60 to 80% by mass.
本発明の防錆塗料は無鉛である。しかも、それを用いた塗膜はガラス基材との密着性に優れ、耐食性も優れている。したがって、この防錆塗料を用いた裏止め塗膜が形成されている鏡は、環境や人体に対して無害である。 The anticorrosive paint of the present invention is lead-free. And the coating film using it is excellent in adhesiveness with a glass base material, and is excellent also in corrosion resistance. Therefore, the mirror in which the back coating film using this rust preventive paint is formed is harmless to the environment and the human body.
１ ガラス基材
２ 銀鏡面膜
３ 銅保護膜
４ 裏止め塗膜
DESCRIPTION OF SYMBOLS 1
Claims (3)
前記裏止め塗膜が、請求項１または２の防錆塗料を用いた塗膜であることを特徴とする鏡。
In a mirror in which a silver mirror surface film, a copper protective film, and a back coating film are formed in this order on one side of a glass substrate,
A mirror characterized in that the backing coating film is a coating film using the rust preventive paint according to claim 1 or 2.
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| JP4703311B2 (en) * | 2005-08-05 | 2011-06-15 | セントラル硝子株式会社 | Composition for backing film and anticorrosion mirror using the same |
| JP4883957B2 (en) * | 2005-08-05 | 2012-02-22 | セントラル硝子株式会社 | Composition for backing film and anticorrosion mirror using the same |
| JP4703317B2 (en) * | 2005-08-16 | 2011-06-15 | セントラル硝子株式会社 | Mirror backing film and mirror using the same |
| US20090153988A1 (en) * | 2006-06-16 | 2009-06-18 | Agc Flat Glass Europe Sa | Mirror |
| KR101860988B1 (en) * | 2015-12-30 | 2018-05-25 | 주식회사 케이씨씨 | Water soluble anti-corrosive paint composition using acrylic modified epoxy ester resin |
| TWI762785B (en) * | 2019-05-31 | 2022-05-01 | 高鼎實業股份有限公司 | Mirror back coating composition without copper process and method for forming the same |
| CN110229595A (en) * | 2019-07-12 | 2019-09-13 | 广西民族大学 | A kind of preparation method of the abietyl short oil-ity alcohol acid resin corrosive enamel of high pitting potential |
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