JP2514566B2 - Improved mirror - Google Patents
Improved mirrorInfo
- Publication number
- JP2514566B2 JP2514566B2 JP5082582A JP8258293A JP2514566B2 JP 2514566 B2 JP2514566 B2 JP 2514566B2 JP 5082582 A JP5082582 A JP 5082582A JP 8258293 A JP8258293 A JP 8258293A JP 2514566 B2 JP2514566 B2 JP 2514566B2
- Authority
- JP
- Japan
- Prior art keywords
- mirror
- silver
- film
- aminotriazole
- lead
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Mirrors, Picture Frames, Photograph Stands, And Related Fastening Devices (AREA)
- Epoxy Resins (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、改良鏡、さらに詳しく
は鉛含有率を低くするか或いは鉛含有分フリーで且つ耐
蝕性、加工性の優れた改良鏡に関する。FIELD OF THE INVENTION The present invention relates to an improved mirror, and more particularly to a lead content lowering or a lead content-free and durable.
The present invention relates to an improved mirror having excellent corrosion resistance and workability .
【０００２】[0002]
【従来の技術】従来、鏡としては、硝子基材の少なくと
も片面に銀鏡面膜を、該基材の銀鏡面膜上には金属保護
層が形成されているが、たとえば米国では鏡に対するア
メリカ環境保護局の新しい法律が制定され、この法律は
土壌及び水源を汚染させないことを目的としており、有
害重金属、有害化学物質を含む数多くの廃棄物の放棄が
禁止されるもので、これらには鉛、銀、銅等も含まれて
いる。2. Description of the Related Art Conventionally, as a mirror, a silver mirror surface film is formed on at least one side of a glass base material, and a metal protective layer is formed on the silver mirror surface film of the base material. A new law has been enacted that aims to prevent pollution of soil and water sources and prohibits the abandonment of numerous wastes containing hazardous heavy metals and hazardous chemicals, including lead, silver and Copper, etc. are also included.
【０００３】[0003]
【発明が解決しようとする課題】例えば、廃棄物を処理
している業者は、この法律が特に定める方法により、そ
の廃棄物を認定を受けた、検査期間で検査して貰わなけ
ればならず、この検査については各々の化学物質につい
ての基準が設定されている。鉛に関しては許容基準は、
鏡材１００Ｇ中，５ＭＧ／Ｌとなっている。また銀、及
び銅もリストに載っており、法律の許容最高値は５ＭＧ
／Ｌであるが、ＴＣＬＰと呼ばれる検査機関の検査で
は、１ＭＧ／Ｌ以下、普通は０．２ＭＧ／Ｌとなってお
り、銅は常に１ＭＧ／Ｌである。そして、米国での鏡業
界にとって問題となるのは、鏡のカレット或いは加工し
た場合に出るスクラップであり、これらの鏡屑が月に１
００ＫＧを超えた場合、前記の法律が適用されるといわ
れている。このため出来るだけ鉛の含有率を下げる為、
鏡は厚い程良い。何故なら１００Ｇの検査サンプルはガ
ラスの重さも含むからであり、当然３ＭＭのガラスより
６ＭＭのガラスの方が相対的にペイント、即ち鉛の含有
率が低くなるからである。上記は米国での鏡業界での事
情であるが、我が国でも近年環境保護の動きが胎動して
おり当業界の関心事であることに変わりない。たとえ
ば、上記ＴＣＬＰの検査は、５ＭＧ／Ｌであるが、各州
は独自にこの値を低く設定できることになっており、い
ずれにしても５ＭＧ／Ｌより高くはできず、例えばノー
ス カロライナ州の許容値は０．５ＭＧ／Ｌであるとい
われている。このような鏡業界を取り巻く事情に鑑み、
本発明者等は、耐蝕性、切断、面取り等の加工性と共
に、鉛含有率が低い裏面用塗料組成物を塗布し硬化して
なる裏止め塗膜層を形成した構成について検討し種々検
討の結果、本発明に到達した。本発明は、硝子基材の少
なくとも片面に銀鏡面膜を、該基材の銀鏡面膜上に金属
保護層を形成した鏡材において、前記金属保護層の上に
エポキシ系樹脂と硬化剤アミノトリアゾールを含有する
塗料組成物を塗布し硬化してなる裏止め被膜層を形成し
たことを特徴とする改良鏡を目的とするものである。ま
た本発明の第二の目的は鏡材の耐蝕性、耐久性及び加工
性に優れると共に、鉛分含有率が低いか若しくは鉛含有
分フリーの鏡材を工業的有利に得ることにある。For example, a trader who treats waste must have the waste inspected in a certified inspection period by the method specified by this law. Standards for each chemical are set for this inspection. For lead, the acceptance criteria are
It is 5 MG / L in 100 G of the mirror material. Also, silver and copper are on the list, and the maximum legal value allowed is 5 MG.
/ L, but in the inspection by the inspection organization called TCLP, it is 1 MG / L or less, usually 0.2 MG / L, and copper is always 1 MG / L. The problem for the mirror industry in the United States is the cullet of the mirror or the scrap produced when it is processed.
It is said that the above law will be applied when the number exceeds 00KG. Therefore, in order to reduce the lead content as much as possible,
The thicker the mirror, the better. This is because the inspection sample of 100 G also includes the weight of glass, and naturally, the glass of 6 MM has a relatively lower paint, that is, the lead content, than the glass of 3 MM. The above is the situation in the mirror industry in the United States, but in Japan as well, the movement to protect the environment has recently been moving, and it remains the concern of the industry. For example, the above TCLP inspection is 5 MG / L, but each state can set this value low independently, and in any case it cannot be higher than 5 MG / L. For example, the allowable value in North Carolina Is said to be 0.5 MG / L. Considering the circumstances surrounding the mirror industry,
The inventors of the present invention have investigated various structures of corrosion resistance, cutting, processability such as chamfering, and studying the constitution of a backing coating film layer formed by applying and curing a backside coating composition having a low lead content. As a result, the present invention has been reached. The present invention provides a mirror material in which a silver mirror surface film is formed on at least one surface of a glass substrate, and a metal protective layer is formed on the silver mirror surface film of the substrate, and an epoxy resin and a curing agent aminotriazole are contained on the metal protective layer. An improved mirror is characterized in that a backing coating layer formed by applying and curing the coating composition is formed. A second object of the present invention is to industrially obtain a mirror material which is excellent in corrosion resistance, durability and workability of the mirror material and has a low lead content or a lead-free content.
【０００４】[0004]
【課題を解決するための手段】これらの問題点を解決す
る手段として、本発明者等は硝子基材の少なくとも片面
に銀鏡面膜を、該膜上の金属保護層の上にエポキシ系樹
脂と硬化剤アミノトリアゾールを含有する塗料組成物を
塗布し硬化した裏止め被膜層を形成することにより、鉛
含有率を低く或いは鉛含有分フリーとし、また銀鏡及び
裏止め被膜層の腐食を防止した改良鏡を提供するもので
ある。As a means for solving these problems, the present inventors have found that a glass mirror substrate has a silver mirror surface film on at least one surface thereof, and an epoxy resin and a resin are cured on the metal protective layer on the film. Improved coating with a low lead content or a lead-free content by applying a coating composition containing a coating agent aminotriazole to form a cured backing coating layer and preventing corrosion of the silver mirror and backing coating layer Is provided.
【０００５】以下、本発明をさらに詳細に説明する。第
１図は、本発明に係る改良鏡の一実施例を示す断面図で
あり、本発明に係る改良鏡本体１において、２は硝子基
材、３は硝子基材に形成された銀鏡面膜、４は銀鏡面膜
３の耐久性のために形成された金属保護層、５は銀鏡面
膜３および金属保護層４を保護し、さらに耐食性、耐久
性を図るために金属保護層上に形成された裏止め被膜層
を示す。本発明に係る改良鏡本体１で、硝子基材２に形
成する銀鏡面膜３はその方法に特に限定なく、真空蒸着
法、スパッター法などの常法を使用することができる。
また、金属保護層４は化学的に変質し易い銀鏡面膜の化
学的耐久性を高める保護膜として形成され、銀面膜３と
の密着性が良く、化学的安定性が高いことが好ましく、
一層であってもよいし二層以上としてもよく、十分な化
学的耐久性の効果と併せて銀面膜との密着性を保持する
ため、２０〜４０ｍμの膜厚とするのが適当である。The present invention will be described in more detail below. FIG. 1 is a cross-sectional view showing an embodiment of an improved mirror according to the present invention. In the improved mirror body 1 according to the present invention, 2 is a glass base material, 3 is a silver mirror surface film formed on the glass base material, 4 is a metal protective layer formed for the durability of the silver mirror surface film 3, 5 is a backing layer formed on the metal protective layer for protecting the silver mirror surface film 3 and the metal protective layer 4, and further for corrosion resistance and durability. A stop coat layer is shown. In the improved mirror body 1 according to the present invention, the silver mirror surface film 3 formed on the glass substrate 2 is not particularly limited in its method, and a conventional method such as a vacuum deposition method or a sputtering method can be used.
Further, the metal protective layer 4 is formed as a protective film that enhances the chemical durability of the silver mirror surface film that is easily chemically deteriorated, and it is preferable that the metal protective layer 4 has good adhesion to the silver surface film 3 and high chemical stability.
The thickness may be one layer or two or more layers, and a thickness of 20 to 40 mμ is appropriate in order to maintain sufficient adhesiveness to the silver surface film in addition to the effect of chemical durability.
【０００６】次に、本発明においては、上記金属保護層
４上に銀鏡面膜３及び金属保護層４の耐蝕性、耐久性を
高めるために、下記のような組成からなる塗料組成物を
用いて塗布し、硬化処理されて裏止め被膜層５が形成さ
れる。本発明に使用される塗料組成物の配合の代表的な
ものとしては次が挙げられる。エポキシ系樹脂２０．０
０、硬化剤アミノトリアゾール１．００、体積顔料（タ
ルク，硫酸バリウム）３６．００、着色顔料（カーボ
ン，酸化鉄）３．５０鉛顔料（鉛白）０．００又は０．
４０、溶剤（ｎ−ブタノール，キシレン，ブチルセロソ
ルブ）３８．７０〜３９．１０、添加剤（シリコーン）
０．３０、硬化促進剤（２−メチルイミダゾール）０．
１０の配合比からなるものであり、上記塗料特性として
は、つぶ２５μ，粘度４２秒（ザーンカップ＃３）／２
５℃、比重１．４／２０℃であり、また鏡１００Ｇ中の
鉛分は、上記の鉛顔料（鉛白）０．４０を添加配合の場
合、５ＭＭの硝子で３．０ＭＧ／Ｌであり、無添加では
０ＭＧ／Ｌである。本発明においては、エポキシ系樹脂
とその硬化剤にアミノトリアゾールを使用することを特
長とするものであり、本発明に使用されるアミノトリア
ゾール化１は、シアナミドが二分子重合してアミノトリ
アゾールを生成する反応により得られるものである。Next, in the present invention, a coating composition having the following composition is used on the metal protective layer 4 in order to enhance the corrosion resistance and durability of the silver mirror surface film 3 and the metal protective layer 4. It is applied and cured to form a backing coating layer 5. Typical examples of the composition of the coating composition used in the present invention are as follows. Epoxy resin 20.0
0, curing agent aminotriazole 1.00, volume pigment (talc, barium sulfate) 36.00, coloring pigment (carbon, iron oxide) 3.50 lead pigment (lead white) 0.00 or 0.
40, solvent (n-butanol, xylene, butyl cellosolve) 38.70 to 39.10, additive (silicone)
0.30, curing accelerator (2-methylimidazole) 0.
The paint composition has a composition ratio of 10 and has the following paint characteristics of 25 μ in a crushed state and a viscosity of 42 seconds (Zahn cup # 3) / 2.
5 ° C., specific gravity 1.4 / 20 ° C., and the lead content in the mirror 100G is 3.0 MG / L with 5 MM glass when the lead pigment (lead white) 0.40 is added and compounded. , And 0MG / L without addition. The present invention is characterized by using an aminotriazole as an epoxy resin and a curing agent therefor. The aminotriazole compound 1 used in the present invention is a bimolecular polymerization of cyanamide to produce aminotriazole. Is obtained by the reaction.
【０００７】[0007]
【化１】 Embedded image
【０００８】エポキシ系樹脂の硬化のための配合は、エ
ポキシ樹脂１ｇ当量に対してアミノトリアゾールを０．
２〜０．２５モル使用するのが最低必要であるが、添加
量が余り多すぎると該アミノトリアゾール自体の親水性
の為防蝕効果が阻害される。また、前記裏止め被膜層を
形成する塗料組成物におけるエポキシ系樹脂としては、
エポキシ当量４５０〜３３００の樹脂が適当であり、た
とえば一般に市販されている三井石油化学，エポミック
Ｒ３０１，同３０２，同３０４，同３０７．旭化成，
Ａ．Ｅ．Ｒ．＃６６１，同６６２，同６６４，同６６
７，同６６９．旭電化，アデカレジンＥＰ−５１００，
同５４００，同５７００，同５９００．油化シエルエポ
キシ，エピコート−１００１，同１００２，同１００
４，同１００７，同１００９．日本チバガイギー，アラ
ルダイトＣＹ−６０７１，７０７２，同６０８４，同６
０９７，同６０９９等から選ぶことができる。本発明に
おいて、塗料組成物中のエポキシ系樹脂（固形分）１０
〜５０％，好ましくは１５〜３０％，及び硬化剤アミノ
トリアゾールを１〜１０ＰＨＲ，好ましくは１〜３ＰＨ
Ｒ、顔料体積濃度（ＰＶＣ）を２０〜５０％，好ましく
は３０〜４０％の配合、顔料体積濃度（ＰＶＣ）を２０
〜５０％，好ましくは３０〜４０％の配合からなり、ま
たその他顔料および充填剤等の添加量ならびに添加方法
により異なるが、上記のとおり該アミノトリアゾールの
添加量はエポキシ系樹脂に対して１〜１０ＰＨＲ，好ま
しくは１〜３ＰＨＲの範囲である。The composition for curing the epoxy resin is such that 1 g of the epoxy resin is mixed with aminotriazole in an amount of 0.
It is necessary to use at least 2 to 0.25 mol, but if the amount added is too large, the anticorrosion effect is hindered due to the hydrophilicity of the aminotriazole itself. Further, as the epoxy resin in the coating composition forming the backing coating layer,
A resin having an epoxy equivalent of 450 to 3300 is suitable, for example, commercially available Mitsui Petrochemical, Epomic R301, 302, 304, 307. Asahi Kasei,
A. E. FIG. R. # 661, 662, 664, 66
7, the same 669. Asahi Denka, ADEKA RESIN EP-5100,
5400, 5700, 5900. Oiled shell epoxy, Epicoat-1001, 1002, 100
4, the same 1007, the same 1009. Japan Ciba Geigy, Araldite CY-6071, 7072, 6084, 6
097, 6099, etc. can be selected. In the present invention, the epoxy resin (solid content) 10 in the coating composition
-50%, preferably 15-30%, and the curing agent aminotriazole 1-10 PHR, preferably 1-3 PH
R, the pigment volume concentration (PVC) is 20 to 50%, preferably 30 to 40%, and the pigment volume concentration (PVC) is 20.
The amount of the aminotriazole added is 1 to 50% by weight, preferably 30 to 40%, and depending on the addition amount of other pigments and fillers and the addition method. It is in the range of 10 PHR, preferably 1 to 3 PHR.
【０００９】[0009]
【作用】本発明において、鏡裏面用塗料組成物として、
エポキシ系樹脂並びにその硬化剤にアミノトリアゾール
を使用するが、これによって該エポキシ系樹脂とアミノ
トリアゾールが熱によって架橋し親水性のアミノトリア
ゾールがフリーで残らない為、塗膜の耐水性、耐機械的
強度が高まる。この架橋したエポキシ系樹脂は、常にア
ルカリ性を呈して銀膜と銅膜を保護する。また、硬化剤
アミノトリアゾールは銅と反応し、水や多くの有機溶媒
に不溶のキレート化合物をつくり、種々の腐食環境を遮
断して銀膜と銅膜を保護する。従来の鉛顔料の作用、す
なわち銀膜、銅膜に対してアルカリ性の状態をもたら
し、不動態化状態を保つと同時に腐蝕を防止するもので
あるといわれているが、本発明はこのような従来の鉛顔
料に代替するものであり、鉛含有量を低くするか或いは
鉛含有分フリーの鏡材が得られると共に、かつ銀面膜お
よび金属保護層の腐蝕を防止し得るように働く。In the present invention, as the coating composition for the back surface of the mirror,
Aminotriazole is used for the epoxy resin and its curing agent. Due to this, the epoxy resin and aminotriazole are crosslinked by heat and the hydrophilic aminotriazole does not remain free, so the water resistance and mechanical resistance of the coating film Strength increases. The crosslinked epoxy resin always exhibits alkalinity to protect the silver film and the copper film. Further, the curing agent aminotriazole reacts with copper to form a chelate compound which is insoluble in water and many organic solvents and blocks various corrosive environments to protect the silver film and the copper film. It is said that the conventional action of the lead pigment, that is, that it brings an alkaline state to the silver film and the copper film, keeps the passivated state and at the same time prevents corrosion, the present invention It is a substitute for the lead pigment of No. 1, and serves to reduce the lead content or obtain a lead-free mirror material and prevent corrosion of the silver surface film and the metal protective layer.
【００１０】[0010]
【実施例】次に本発明の実施例を示す。硝子基材（日本
板硝子製，サイズ１８３０ｍｍ×９１５ｍｍ×５ｍｍ）
を用いて、十分にブラッシング洗滌し水切り乾燥を行っ
た後、該硝子基材の面上に銀鏡反応によって銀を折出す
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９０ｍμ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
をスプレー３０ｍμ厚の銅からなる金属保護膜を形成
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硝子基材の上記銅保護膜上に、下記
表１記載の硬化剤アミノトリアゾールを使用した塗料配
合の塗料組成物，実施例１及び実施例２を作製し、フロ
ーコーター法により乾燥膜厚５０μｍとなるよう塗布
し、硝子基材の板温１８０℃にて、１０分間焼付けし
て、実施例１及び実施例２の試料片を作製した。EXAMPLES Examples of the present invention will be described below. Glass substrate (manufactured by Nippon Sheet Glass, size 1830 mm × 915 mm × 5 mm)
After thoroughly washing by brushing, draining and drying, spray a silver plating solution of a solution containing silver nitrate that causes silver to stick out by a silver mirror reaction and a reducing solution that reduces silver on the surface of the glass substrate. After forming a silver mirror surface film with a thickness of 90 mμ, washing this film surface with water, spraying copper plating with a solution containing copper sulfate that deposits copper and a reducing solution for reducing copper by electroless plating A metal protective film was formed, washed with water, and then dried. On the above-mentioned copper protective film of the glass base material on which the silver mirror surface film and the copper protective film were formed, a coating composition of a coating composition using the curing agent aminotriazole shown in Table 1 below, Example 1 and Example 2 were prepared. Then, it was applied by a flow coater method so as to have a dry film thickness of 50 μm, and baked at a plate temperature of the glass substrate of 180 ° C. for 10 minutes to prepare the sample pieces of Example 1 and Example 2.
【００１１】[0011]
【表１】 [Table 1]
【００１２】これら各試料片について、各種性能試験を
行った結果を表２に示す。その結果鏡１００Ｇ中の鉛含
有量は、実施例１の場合、３．５ＭＧ／Ｌ、実施例２で
は、０ＭＧ／Ｌであった。Table 2 shows the results of various performance tests performed on each of these sample pieces. As a result, the lead content in the mirror 100G was 3.5 MG / L in Example 1 and 0 MG / L in Example 2.
【００１３】[0013]
【表２】 [Table 2]
【００１４】また、比較例１は表３に記載の塗料組成物
による塗布を行ったものとしたが、鏡１００Ｇ中の鉛成
分は２３０ＭＧ／Ｌであった。Further, in Comparative Example 1, the coating composition shown in Table 3 was applied, but the lead component in the mirror 100G was 230 MG / L.
【００１５】[0015]
【表３】 [Table 3]
【００１６】[0016]
【発明の効果】本発明の改良鏡においては、従来鏡裏面
用の塗料組成物に含まれる鉛成分の含有率を低くするこ
とができると共に、併せて鏡材の耐蝕性、耐久性及び加
工性のいずれにおいても優れた効果が得られる。In the improved mirror of the present invention, the content of the lead component contained in the coating composition for the back surface of the conventional mirror can be reduced, and at the same time, the corrosion resistance, durability and workability of the mirror material can be reduced. In any of the above cases, excellent effects can be obtained.
【図１】本発明に係る改良鏡の１実施例を示す断面図で
ある。FIG. 1 is a sectional view showing one embodiment of an improved mirror according to the present invention.
１ 改良鏡本体 ２ 硝子基材 ３ 銀鏡面膜 ４ 金属保護層 ５ 裏止め被膜層 1 Improved mirror body 2 Glass base material 3 Silver mirror surface film 4 Metal protective layer 5 Backing coating layer
Claims (1)
を、該基材の銀鏡面膜上に金属保護層を形成した鏡材に
おいて、前記金属保護層の上にエポキシ系樹脂１０〜５
０％および硬化剤アミノトリアゾールが１〜１０ＰＨ
Ｒ、顔料体積濃度２０〜５０％からなる塗料組成物を塗
布し硬化してなる裏止め被膜層を形成したことを特徴と
する改良鏡。1. A mirror material in which a silver mirror surface film is formed on at least one surface of a glass base material and a metal protective layer is formed on the silver mirror surface film of the base material, and epoxy resins 10 to 5 are provided on the metal protective layer.
0% and 1-10 PH of curing agent aminotriazole
An improved mirror comprising a backing coating layer formed by applying a coating composition comprising R and a pigment volume concentration of 20 to 50% and curing the coating composition .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5082582A JP2514566B2 (en) | 1992-07-17 | 1993-03-16 | Improved mirror |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-213344 | 1992-07-17 | ||
| JP21334492 | 1992-07-17 | ||
| JP5082582A JP2514566B2 (en) | 1992-07-17 | 1993-03-16 | Improved mirror |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06253963A JPH06253963A (en) | 1994-09-13 |
| JP2514566B2 true JP2514566B2 (en) | 1996-07-10 |
Family
ID=26423619
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5082582A Expired - Lifetime JP2514566B2 (en) | 1992-07-17 | 1993-03-16 | Improved mirror |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2514566B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012193340A (en) * | 2011-02-28 | 2012-10-11 | Fujifilm Corp | Thermosetting composition, adhesive film, and multilayer printed circuit board |
| JP5927688B2 (en) * | 2011-04-01 | 2016-06-01 | 大日本塗料株式会社 | Mirror and manufacturing method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0749015B2 (en) * | 1989-08-18 | 1995-05-31 | 旭硝子株式会社 | Improved mirror |
-
1993
- 1993-03-16 JP JP5082582A patent/JP2514566B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| 垣内弘編、（株）昭晃堂、（昭６０．５．１０）、Ｐ．２２５ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06253963A (en) | 1994-09-13 |
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