JPH02209548A - Roof plate material of cu or cu alloy early forming patina - Google Patents
Roof plate material of cu or cu alloy early forming patinaInfo
- Publication number
- JPH02209548A JPH02209548A JP2801489A JP2801489A JPH02209548A JP H02209548 A JPH02209548 A JP H02209548A JP 2801489 A JP2801489 A JP 2801489A JP 2801489 A JP2801489 A JP 2801489A JP H02209548 A JPH02209548 A JP H02209548A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- patina
- copper
- alloy
- plate material
- 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.)
- Granted
Links
- 241001311547 Patina Species 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 20
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 31
- 238000007747 plating Methods 0.000 claims abstract description 30
- 230000003746 surface roughness Effects 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 238000000576 coating method Methods 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 3
- 229910001651 emery Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000001007 puffing effect Effects 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Roof Covering Using Slabs Or Stiff Sheets (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は建築用として用いられるＣｕまたはＣｕ合金の
屋根板材に関し、特に早期に緑青が形成するものである
。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a Cu or Cu alloy roof sheet material used for construction, and in particular, patina forms early.
神社、仏閣、住宅等の建築物の屋根やエフステリヤある
いは美術装飾品の多くは銅または銅合金を用いて製作さ
れ、もしくは表面に銅メッキが施されている。これは銅
が耐候性に優れていて腐食されにくく、長期間の使用に
耐えることもあるが、殊に銅は表面に緑青が生じてこれ
が銅製品に重厚で落ち着いた感じを与えるので、この点
が建築物の屋根材や美術品として銅が好まれている理由
である。Many of the roofs, efsteria, and artistic decorations of buildings such as shrines, temples, and residences are made of copper or copper alloys, or their surfaces are plated with copper. This is because copper has excellent weather resistance, is resistant to corrosion, and can withstand long-term use, but copper in particular develops a patina on its surface, which gives copper products a solid and calm feel. This is the reason why copper is preferred as roofing material for buildings and works of art.
ところで緑青は銅製品を大気中に曝（、ておくことによ
って自然に発生するが、その成長速度は極めて遅く所望
の被膜が形成されるまでには数年もしくはそれ以上の長
時間を要するのが一般的である。By the way, patina occurs naturally when copper products are exposed to the atmosphere, but its growth rate is extremely slow and it takes several years or more for the desired coating to form. Common.
このため従来は銅製品に硫酸、硝酸あるいは塩酸等の無
機酸を滌ぎかけてその表面を一時的に浸食した後、炭酸
ナトリウムその他でこれを処理することによって緑青を
人工的に発生させる方法が試みられた。しかしながらこ
の方法で生成した緑青被膜は極めて薄く、かっ色ムラが
生じるうえ生産性が低く、しかも大規模な廃水設備を要
する等の欠点があった。For this reason, conventional methods have been used to artificially generate patina by dousing copper products with inorganic acids such as sulfuric acid, nitric acid, or hydrochloric acid to temporarily erode the surface, and then treating the surface with sodium carbonate or other substances. Attempted. However, the verdigris film produced by this method is extremely thin and has brownish unevenness, has low productivity, and has drawbacks such as requiring large-scale wastewater facilities.
そこでこのような欠点を除去する方策として緑青に代え
て塩基性炭酸銅、硫化銅または酸化銅等の銅化合物を顔
料とした塗料を銅製品の表面に塗布する方法も試みられ
た。ところがこの方法は上記の表面処理方法に比べれば
生産性は格段に高いが、反面これらの塗膜は耐候性が非
常に低く、例えばこれを銅葺き屋根などに使用すると一
年も経過しないうちに塗装が剥がれてしまい外観が著し
く醜くなる欠点があった。Therefore, as a measure to eliminate such defects, attempts have been made to apply a paint containing a copper compound such as basic copper carbonate, copper sulfide, or copper oxide as a pigment to the surface of copper products instead of patina. However, although this method has much higher productivity than the above-mentioned surface treatment methods, on the other hand, these coatings have very low weather resistance, and if used on copper roofs, for example, they will wear out within a year. The problem was that the paint peeled off, making the exterior look extremely ugly.
本発明はこれに鑑み種々検討の結果、銅または銅合金の
表面に発生する緑青の成長速度を加速して短期的に緑青
が自然に発生ずる早期に緑青を形成するＣｕまたはＣｕ
合金屋根板材を開発したものである。In view of this, as a result of various studies, the present invention has developed Cu or Cu, which accelerates the growth rate of patina generated on the surface of copper or copper alloy and forms patina at an early stage when patina naturally occurs in the short term.
This is a developed alloy roofing sheet material.
即ち本発明は、ＣｕまたはＣｕ合金からなる屋根板材の
少なくとも片面の表面粗度（Ｒａ）をｏ、 １０４以上
と腰さらにこの面にＣｕメッキを施したことを特徴とす
るものである。That is, the present invention is characterized in that the surface roughness (Ra) of at least one side of the roofing board material made of Cu or Cu alloy is o, 104 or more, and that this surface is further plated with Cu.
そしてＣｕメッキとしてはいわゆるヤケメッキがよく、
またＣｕメッキのメッキ厚はｏ、 ｏｏｉ〜１Ｍが良好
である。And so-called burnt plating is good for Cu plating.
Moreover, the plating thickness of Cu plating is preferably o, ooi to 1M.
自然界において緑青が生成する過程は、降雨時や多湿時
に上記銅製の屋根板表面で結露する結露水中に大気中の
ＣＯ，，３０２等が溶は込んで銅を腐食させるため緑青
が発生ずるものである。The process by which patina is produced in nature is that CO, 302, etc. from the atmosphere dissolves into the condensed water that condenses on the surface of the copper roofing board during rain or high humidity, corroding the copper and causing patina. be.
この結露水が屋根板表面に付着する際に、その表面が平
滑であると降雨水等がトラップされにくくなって速やか
に流れ落ちたり、短時間で蒸発乾燥してしまうので、銅
が腐食環墳に置かれている時間が短（なり、従って腐食
反応の進行が遅くなり、自然状態のままでは緑青発生ま
でに非常に長期間を必要とすることになる。When this condensation water adheres to the surface of the roof board, if the surface is smooth, it becomes difficult for the rain water to be trapped and quickly runs off, or it evaporates and dries in a short period of time, causing copper to corrode. The time it is left in place is short, so the corrosion reaction progresses slowly, and in its natural state it would take a very long time to develop a patina.
そこで本発明は屋根板材の表面粗度を０゜ｌＯ１！ｙＲ
以上とし、さらにこの表面にＣｕメッキを施すことによ
り、この荒れた屋根板材表面であれば降雨水や結露水等
が流れ落ちるのを妨げることができ、さらに粗化された
表面に形成される無数の微小な溝内での毛管現象により
上記水分の平衡蒸気圧が低下するため、表面が水に濡れ
ている時間を長く保つことができる。Therefore, the present invention reduces the surface roughness of roofing board materials to 0°lO1! yR
In addition to the above, by applying Cu plating to this surface, it is possible to prevent rain water, dew water, etc. from flowing down on this rough roof board surface, and furthermore, by applying Cu plating to this surface, it is possible to prevent rain water, dew water, etc. Since the equilibrium vapor pressure of the water is lowered by capillary action within the minute grooves, the surface can be kept wet for a longer period of time.
このように屋根板材表面の水濡れ時間が長期化すること
により、この水分中に溶は込んでいる大気中のｓｏ２．
ｃｏｔがＣｕを腐食する時間が長くなり、従って緑青の
発生が早期化されることになる。As the surface of the roofing board is exposed to water for a long period of time, the SO2 in the atmosphere that is dissolved in this moisture increases.
The time for cot to corrode Cu becomes longer, and therefore the occurrence of patina is accelerated.
次に表面の粗化の方法としては、一般の乾式パフ、湿式
パフ、ショツトブラスト、乾式ブラシまたは湿式ブラシ
等いずれの方法であってもよい。そして表面粗度（Ｒａ
）を０．１０Ｑ以上としたのは、Ｒａ＜０．１０−では
実質的に緑青の発生が加速されないからである。Next, as a method for roughening the surface, any method such as general dry puffing, wet puffing, shot blasting, dry brushing, or wet brushing may be used. and surface roughness (Ra
) is set to 0.10Q or more because the generation of patina is not substantially accelerated when Ra<0.10-.
またＣｕメッキは硫酸銅浴、青化浴、ビロリン酸浴また
はホウフッ化浴等いずれの浴を利用するものであっても
よい。そしてメ・ツキ膜厚を０．００１〜１．０ｔｒＩ
ｌ としたのは、膜厚が０．００１ｘ未満では緑青発
生の加速性がなく、１．０−を超えるとメッキコストが
増大し、かつ形成した緑青の外観にムラが生じたり剥離
が生じたりするからである。Further, Cu plating may be performed using any bath such as a copper sulfate bath, a cyanizing bath, a birophosphoric acid bath, or a borofluoride bath. Then, set the film thickness to 0.001 to 1.0trI.
l is selected because if the film thickness is less than 0.001x, the formation of patina will not be accelerated, and if it exceeds 1.0, the plating cost will increase, and the formed patina will have an uneven appearance or peeling. Because it does.
さらにメッキとしてはいわゆるヤケメッキが効果が大き
い。なおいわゆるヤケメ・ツキとは、例えばＣｕＳＯ４
浴でのメッキの際にＣＯ−が過剰や過少または電流密度
が過大であったことによりメッキ表面に光沢がなく、表
面のレベリングの悪いメッキをいい、またはＣｕ箔と樹
脂との接着を強めるためにＣｕ箔に施す粗化処理をいう
。Furthermore, as plating, so-called discolored plating is highly effective. In addition, the so-called "Yakeme Tsuki" is, for example, CuSO4
This refers to plating with poor surface leveling and lack of luster on the plating surface due to excessive or insufficient CO- or excessive current density during plating in a bath, or to strengthen the adhesion between Cu foil and resin. This refers to the roughening treatment applied to Cu foil.
次に本発明の実施例を示すが、本発明はこれに限定され
るものではない。Next, examples of the present invention will be shown, but the present invention is not limited thereto.
先ず以下に示すような銅製の本発明屋根板材Ｎｏ、 ｌ
〜Ｎｏ、 ３を製作した。First, copper roofing sheet materials No. 1 of the present invention as shown below.
～No. 3 was made.
く本発明屋根板材Ｎｏ、 １ ＞
板厚０．４５ｍｍで表面粗度がＲａ＝０．０４／／ｌｌ
＋のリン脱酸銅板の表面を、＃２８０のエメリー紙にて
湿式回転研磨を１５分間行い、表面粗度をＲ＆・０．１
２雇とした。その後この銅板に以下のようなメッキ浴お
よびメッキ条件でＣｕメッキを施し、表面に０．０１４
のメッキ被膜を形成した。Roofing board material No. 1 of the present invention > Board thickness 0.45mm and surface roughness Ra = 0.04//ll
The surface of the + phosphorus deoxidized copper plate was wet-rotated with #280 emery paper for 15 minutes to achieve a surface roughness of R&-0.1.
Two employees were employed. After that, this copper plate was plated with Cu using the following plating bath and plating conditions, and the surface was coated with 0.014
A plating film was formed.
ＣｕＳＯ４・５Ｈ２０ Ｈ２ＳＯ。CuSO4・5H20 H2SO.
ＣＱ“イオン
温 度
電流密度
く本発明屋根板材Ｎｏ、 ２ ＞
板厚０．４５ａ＋ｍで表面粗度がＲａ−０，０４４のリ
ン脱酸銅板の表面を、＃２８０のエメリー紙にて湿式回
転研磨を１５分間行い、表面粗度をＲａ・０．１２１ｎ
１とした。その後この銅板に以下のようなメッキ浴およ
びメッキ条件でＣｏメッキを施し、表面に０．０１−の
メッキ被膜を形成した。CQ "Ion Temperature Current Density Invention Roofing Sheet Material No. 2 > The surface of a phosphorus-deoxidized copper plate with a thickness of 0.45a+m and a surface roughness of Ra-0,044 was wet-rotated with #280 emery paper. was carried out for 15 minutes, and the surface roughness was Ra・0.121n.
It was set to 1. Thereafter, Co plating was applied to this copper plate using the following plating bath and plating conditions to form a 0.01-coating film on the surface.
ＣｕＳ ０４ ・５ Ｈｚｏ ２００ ｇ／ ｉ！
Ｈｉｓ Ｏａ ５０ ｇ／１２００ｇ／
ｉ？
５０ｇ／１
５０ｍｇ／ ｉ？
３０ ℃
３Ａ／ｄａｉ”
ＣＯ−イオン ２５０１Ｉ１ｇ／ｌ温 度
３０ ℃電流密度 ８
Ａ／ｄが
く本発明屋根板材Ｎｏ−３＞
板厚０．４５ｍｍで表面粗塵がＲａ＝０．０４Ｉ１１１
のリン脱酸銅板の表面を、＃２８０のエメリー紙にて湿
式回転研磨を１５分間行い、表面粗度をＲａ・０．１２
−とした。その後この銅板に以下のようなメッキ浴およ
びメッキ条件でＣｏメッキを施し、表面に１、 ｏｌｌ
ＩＩのメッキ被膜を形成した。CuS 04 ・5 Hz 200 g/i!
His Oa 50g/1200g/
i? 50g/1 50mg/i? 30°C 3A/dai” CO- ion 2501I1g/l Temperature 30°C Current density 8
A/d: Invention roofing board material No. 3> Plate thickness: 0.45mm, surface roughness Ra = 0.04I111
The surface of the phosphorus-deoxidized copper plate was wet-rotated for 15 minutes with #280 emery paper, and the surface roughness was Ra.0.12.
−. After that, Co plating was applied to this copper plate using the following plating bath and plating conditions, and the surface was coated with 1, oll.
A plating film II was formed.
ＣｕＳ ０４ ・５ Ｈｔｏ ２００ ｇ／ １２
ＨｚＳＯ４５ｏｇ＃
ＣＯ−イオン ２５０ｍｇ／ （！温 度
３０ ℃電流密度
８Ａ／ｄａ”
なお上記メッキの内、ＣＱ−イオン濃度および電流密度
の大きい本発明屋根板材Ｎｏ、２とＮｏ、 ３の表面は
いわゆるヤケメッキとなっていた。CuS 04 ・5 Hto 200 g/ 12
HzSO45og# CO- ion 250mg/ (!Temperature 30℃Current density
8A/da'' Among the above-mentioned platings, the surfaces of roofing sheet materials No. 2 and No. 3 of the present invention, which had high CQ-ion concentrations and high current densities, were so-called burnt plating.
次に上記の屋根板材を、これらの処理を施さない板厚０
．４５ｍａ＋で表面粗度がＲ＆・ｏ、ｏｉｔ４のリン脱
酸銅板からなる比較屋根板材Ｎｏ、 ４と共に、海岸地
帯および山岳地帯に曝露して緑青の発生状況を調査し、
その結果を第１表に示した。Next, the above-mentioned roof sheet material is made into a sheet with a thickness of 0 without these treatments.
．． Comparative roofing sheet material No. 4, which is made of phosphorus-deoxidized copper sheeting with a surface roughness of 45ma+ and a surface roughness of R&O and oit4, was exposed to coastal areas and mountainous areas to investigate the occurrence of patina.
The results are shown in Table 1.
ある。be.
第１表
第１表から明らかなように、本発明屋根板材Ｎｏ、 １
−Ｎｏ、 ３はいずれも表面粗度の小さい比較屋根板材
Ｎｏ、 ４より緑青の発生が早く、かつ均一であった。Table 1 As is clear from Table 1, the roof sheet material No. 1 of the present invention
- No. 3 developed patina earlier and more uniformly than comparison roof sheet materials No. 4, which had a smaller surface roughness.
Claims (3)
も片面の表面粗度（Ｒａ）を０．１０μｍ以上とし、さ
らにこの面にＣｕメッキを施したことを特徴とする早期
に緑青を形成するＣｕまたはＣｕ合金の屋根板材。(1) The surface roughness (Ra) of at least one side of a roofing sheet material made of Cu or Cu alloy is 0.10 μm or more, and this surface is further plated with Cu. Cu alloy roofing board material.
１）記載の早期に緑青を形成するＣｕまたはＣｕ合金の
屋根板材。(2) Claim that the Cu plating is so-called burnt plating (
1) Roofing sheets of Cu or Cu alloys that form a patina at an early stage as described.
る請求項（１）または（２）記載の早期に緑青を形成す
るＣｕまたはＣｕ合金の屋根板材。(3) The roof sheet material of Cu or Cu alloy that forms a patina at an early stage according to claim 1 or 2, wherein the thickness of the Cu plating is 0.001 to 1 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028014A JP2662014B2 (en) | 1989-02-07 | 1989-02-07 | Cu or Cu alloy roofing sheet material that forms patina early |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1028014A JP2662014B2 (en) | 1989-02-07 | 1989-02-07 | Cu or Cu alloy roofing sheet material that forms patina early |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02209548A true JPH02209548A (en) | 1990-08-21 |
| JP2662014B2 JP2662014B2 (en) | 1997-10-08 |
Family
ID=12236914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1028014A Expired - Lifetime JP2662014B2 (en) | 1989-02-07 | 1989-02-07 | Cu or Cu alloy roofing sheet material that forms patina early |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2662014B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5752425A (en) * | 1980-09-11 | 1982-03-27 | Hitachi Netsu Kigu Kk | Self-cleaning type coating layer for heat cooker |
| JPS6357500A (en) * | 1986-08-27 | 1988-03-12 | 日立建機株式会社 | Multi-joint arm machine |
-
1989
- 1989-02-07 JP JP1028014A patent/JP2662014B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5752425A (en) * | 1980-09-11 | 1982-03-27 | Hitachi Netsu Kigu Kk | Self-cleaning type coating layer for heat cooker |
| JPS6357500A (en) * | 1986-08-27 | 1988-03-12 | 日立建機株式会社 | Multi-joint arm machine |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2662014B2 (en) | 1997-10-08 |
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