JPH01188680A - Base material having black film and formation of black film - Google Patents
Base material having black film and formation of black filmInfo
- Publication number
- JPH01188680A JPH01188680A JP62283878A JP28387887A JPH01188680A JP H01188680 A JPH01188680 A JP H01188680A JP 62283878 A JP62283878 A JP 62283878A JP 28387887 A JP28387887 A JP 28387887A JP H01188680 A JPH01188680 A JP H01188680A
- Authority
- JP
- Japan
- Prior art keywords
- film
- oxidation treatment
- black
- alloy plating
- black film
- 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
- 239000000463 material Substances 0.000 title claims abstract description 22
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 230000003647 oxidation Effects 0.000 claims abstract description 28
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 28
- 238000007747 plating Methods 0.000 claims abstract description 25
- 229910001096 P alloy Inorganic materials 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 claims description 15
- 229910000990 Ni alloy Inorganic materials 0.000 claims 2
- 239000007864 aqueous solution Substances 0.000 abstract description 10
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011521 glass Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 4
- 238000007654 immersion Methods 0.000 abstract description 3
- 235000010344 sodium nitrate Nutrition 0.000 abstract description 3
- 238000007772 electroless plating Methods 0.000 abstract description 2
- -1 NaNO3 Chemical compound 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003287 optical effect Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 241000252229 Carassius auratus Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Laminated Bodies (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、金属又はセラミック、ガラス、プラスチック
等の基材表面に黒色皮膜を形成する方法に関し、特に、
光カロリーメータの受光素子等に利用ｙれる光吸収量が
極めて高い超黒色皮膜を形成する方法に関するものであ
る。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for forming a black film on the surface of a base material such as metal, ceramic, glass, plastic, etc.
The present invention relates to a method for forming an ultra-black film with extremely high light absorption that can be used in light-receiving elements of optical calorimeters, etc.
［従来の技術］
従来、黒色皮膜を形成する方法として１よ、黒色塗料を
用いた塗膜、黒色の表面耐化物、金属化合物の皮膜、電
気めっき法による黒色クロメート、黒色クロム、黒色ニ
ンケル皮膜及び陽極酸化法により生成した多孔質皮膜に
黒色染料を入れる黒染処理法等があった。しかし、これ
らの黒色皮膜は一般に全反射率が３〜１０％程度あり、
かつ、波長依存性も高いという問題があり、光パワーの
測定等の光吸収体として用いるには不満足であった。[Prior art] Conventionally, methods for forming a black film include 1, a film using a black paint, a black surface-resistant material, a film of a metal compound, a black chromate film by electroplating, a black chromium film, a black nickel film, and There was a black dyeing treatment method in which black dye was added to a porous film produced by anodizing. However, these black films generally have a total reflectance of about 3 to 10%,
In addition, there is a problem of high wavelength dependence, making it unsatisfactory for use as a light absorber for measurements of optical power, etc.
光吸収体として、上記皮膜よりも全反射率の低いものに
、合焦があり、合焦の皮膜は全反射率が約０．５％で上
記黒色塗料等に比べて一段と低く、光パワー測定の受光
体としても利用されている。As a light absorber, there is a focus that has a lower total reflectance than the above film, and the focus film has a total reflectance of about 0.5%, which is much lower than the above black paint, etc., and the optical power measurement It is also used as a photoreceptor.
また、米国特許第４２３３１０７号明細書（対応特開昭
５７−１１４６５５）には、ニッケルφリンめっき皮膜
を硝酸水溶液で酸化処理して得られる黒色皮膜が開示さ
れている。Further, US Pat. No. 4,233,107 (corresponding to JP-A-57-114655) discloses a black film obtained by oxidizing a nickel φ phosphorus plating film with an aqueous nitric acid solution.
［発明が解決しようとする問題点］
従来光パワー測定に用いられている金魚は、その全反射
率が小さく、超黒色の受光体として利用されているが、
機械的振動や摩擦などで簡単にはげ落ち、高温度条件下
では水分を吸収して反射率が増加し、乾燥によっても元
の反射率を回復しないという問題があり、実用上難点が
多い。[Problems to be solved by the invention] Goldfish, which have been conventionally used for optical power measurement, have a low total reflectance and are used as ultra-black photoreceptors;
It easily flakes off due to mechanical vibration or friction, absorbs moisture under high temperature conditions and increases its reflectance, and does not recover its original reflectance even when dried, which poses many practical problems.
また、米国特許第４２３３１０７号明細書に開示されて
いる黒色皮膜は、全反射率が１．０％以下で、かつ、皮
膜強度が高い点で実用性が高いが、反射率に波長依存性
があり、０．４〜２．０ ＩＬｍという広い波長帯域で
高精度で光パワーを測定する受光体として用いるにはな
お問題がある。In addition, the black film disclosed in U.S. Pat. No. 4,233,107 has a total reflectance of 1.0% or less and is highly practical in that it has high film strength, but the reflectance has wavelength dependence. However, there are still problems in using it as a photoreceptor for measuring optical power with high precision in a wide wavelength band of 0.4 to 2.0 ILm.
本発明の目的は、金属、セラミック、カラス、プラスチ
ック等の基材表面に、光吸収量が極めて高く、波長依存
性が少なく、さらに機械的強度、耐温性の優れた超黒色
皮膜の形成された光吸収材料及びそのための黒色皮膜形
成方法を提供することにある。The purpose of the present invention is to form an ultra-black film on the surface of metal, ceramic, glass, plastic, etc. substrates, which has extremely high light absorption, little wavelength dependence, and excellent mechanical strength and temperature resistance. An object of the present invention is to provide a light-absorbing material and a method for forming a black film therefor.
［問題点を解決するための手段］
すなわち本発明は、基材上のニッケル・リン合金皮膜が
、蜂の巣状に隣接する無数の凹穴からなり、かつ、該凹
穴の壁面に更に微細な凹凸を有する表面構造であること
を特徴とする黒色皮膜を有する基材を提供するものであ
る。[Means for Solving the Problems] In other words, the present invention provides a method in which the nickel-phosphorus alloy film on the base material is composed of numerous concave holes adjacent to each other in a honeycomb shape, and the wall surface of the concave holes has fine irregularities. The present invention provides a base material having a black film characterized by a surface structure having a black film.
また、本発明は、ニッケル・リン合金めつき液により、
ニッケル・リン合金めっき皮膜を形成し、該ニッケル・
リン合金皮膜を硝酸水溶液で一次醇化処理し、次いで硫
酸を含有する硝酸塩水溶液で二次酸化処理することによ
り、無数の微細な穴を有し、かつ、該無数の微細穴の壁
面に更に微細な凹凸が形成された表面構造を有する皮膜
が形成されることを特徴とする黒色皮膜形成方法を提供
するものである。In addition, the present invention uses a nickel-phosphorus alloy plating solution to
A nickel-phosphorus alloy plating film is formed, and the nickel
By subjecting the phosphorus alloy film to primary oxidation treatment with a nitric acid aqueous solution and then secondary oxidation treatment with a nitrate aqueous solution containing sulfuric acid, it has countless fine holes, and even finer holes are formed on the walls of the countless fine holes. The present invention provides a method for forming a black film, characterized in that a film having a surface structure with unevenness is formed.
本発明において、黒色皮膜の形成される基材としては、
金属、ガラス、セラミックス、プラスチックス等が用い
られる。In the present invention, the base material on which the black film is formed is as follows:
Metals, glass, ceramics, plastics, etc. are used.
基材には先ずニッケル・リン合金めつ５液によりニッケ
ル・リン合金めっき皮膜が施Ｓれる。First, a nickel-phosphorus alloy plating film is applied to the base material using nickel-phosphorus alloy plating solution 5.
このめっきは通常行なわれている無電解めっき法が用い
られる。基材が金属の場合はアルカリ液で脱脂した後酸
洗し、次いでニッケルストライクめっきを行ない、無電
解ニッケル・リン合金めっき液に浸漬して基材表面にリ
ン濃度６〜８ｚ程度のニッケル・リン合金めっき皮膜を
形成せしめる。A commonly used electroless plating method is used for this plating. If the base material is metal, it is degreased with an alkaline solution and then pickled, followed by nickel strike plating, and immersed in an electroless nickel-phosphorus alloy plating solution to coat the surface of the base material with nickel-phosphorus with a phosphorus concentration of about 6-8z. Forms an alloy plating film.
基材がガラス、セラミックス、プラスチックスのような
電気の不導体の場合には、塩化錫溶液及び塩化パラジウ
ム溶液で表面の活性化処理を行なった後無電解ニッケル
・リンめっき液によるニッケル・リン合金皮膜形成が行
なわれる。When the base material is an electrically nonconducting material such as glass, ceramics, or plastics, the surface is activated with a tin chloride solution and a palladium chloride solution, and then a nickel-phosphorus alloy is coated with an electroless nickel-phosphorus plating solution. Film formation takes place.
無電解ニッケル・リンめっき液は市販のものが使用でき
、通常８０〜４５°Ｃの液温で６０分〜５時間浸漬され
る。ニッケル・リン合金皮膜の厚さは少なくとも３０ル
ｍ、好ましくは７０〜８０ｇｍである。A commercially available electroless nickel/phosphorous plating solution can be used, and the plating solution is usually immersed at a solution temperature of 80 to 45°C for 60 minutes to 5 hours. The thickness of the nickel-phosphorous alloy coating is at least 30 gm, preferably 70-80 gm.
ニッケル・リン合金めっき皮膜の形成された基材は、水
洗乾燥した後黒色化のために酸化処理される。The base material on which the nickel-phosphorous alloy plating film has been formed is washed with water, dried, and then oxidized for blackening.
本発明の方法において、この酸化処理は硝酸水溶液によ
る第一次酸化処理と、硫酸を含有する硝酸塩水溶液によ
る第二次酸化処理の２工程からなっている。In the method of the present invention, this oxidation treatment consists of two steps: a first oxidation treatment using an aqueous nitric acid solution and a second oxidation treatment using an aqueous nitrate solution containing sulfuric acid.
第一次酸化処理で基材が浸漬される硝酸の濃度は、硝酸
：水＝１：５から濃硝酸までの範囲の濃度で、液温は２
０〜１００°Ｃ，浸漬時間は５秒〜５分である。ニッケ
ル・リン合金皮膜が黒色化される時間は皮膜のリン含量
、硝酸液の濃度及び液温によるが、通常５０°Ｃの １
＝１硝酸を用いて５〜３０秒である。皮膜が黒色化され
た基材は水洗後、乾燥せずに第二次酸化処理される。The concentration of nitric acid in which the substrate is immersed in the primary oxidation treatment ranges from nitric acid:water = 1:5 to concentrated nitric acid, and the liquid temperature is 2.
The temperature is 0 to 100°C, and the immersion time is 5 seconds to 5 minutes. The time it takes for the nickel-phosphorus alloy film to turn black depends on the phosphorus content of the film, the concentration of the nitric acid solution, and the temperature of the solution, but it is usually heated at 50°C.
= 5 to 30 seconds using 1 nitric acid. After washing the base material with a blackened film, it is subjected to a secondary oxidation treatment without drying.
第二次酸化処理で用いられる硝酸塩は、通常硝酸ナトリ
ウムであり、その濃度は２００〜４５０ｇ／ｆ２、好ま
しくは３００〜４００ｇ／ｆｆで、添加される硫酸の濃
度は３００〜７００ ｇＩＱ、好ましくは４００〜Ｂｏ
ｏ ｇ／Ｄ、である。液温３θ〜８０°Ｃ１浸漬時間５
秒〜５分で処理されるが、これらの濃度、液温、時間は
第一次酸化処理によるニッケル・リン合金めっき皮膜の
状態との関係で最適のものが選択される。The nitrate used in the secondary oxidation treatment is usually sodium nitrate, and its concentration is 200 to 450 g/f2, preferably 300 to 400 g/ff, and the concentration of sulfuric acid added is 300 to 700 gIQ, preferably 400 g/ff. ~Bo
o g/D. Liquid temperature 3θ~80°C 1 Immersion time 5
The treatment takes seconds to 5 minutes, but the optimum concentration, liquid temperature, and time are selected in relation to the condition of the nickel-phosphorous alloy plating film obtained by the primary oxidation treatment.
第二次酸化処理の後、水洗乾燥して得られた基材の黒色
皮膜は、極めて安定で、機械的にも、耐湿性においても
優れており、その全反射率は、０４〜２．０ ｇｍの波
長域において、０．３％以下であり、かつ、波長依存性
が極めて小さかった。After the secondary oxidation treatment, the black film on the base material obtained by washing with water and drying is extremely stable and has excellent mechanical and moisture resistance, and its total reflectance is 0.4 to 2.0. In the gm wavelength range, it was 0.3% or less, and the wavelength dependence was extremely small.
走査電子顕微鏡による観察によれば、本発明の方法によ
り得られた黒色皮膜の表面には、無数の凹穴が蜂の巣状
に隣接しており、該凹穴の内壁は微小な凹凸が形成され
ている。この微小凹凸がさらに全反射率を低下させてい
るものと考えられる。According to observation using a scanning electron microscope, the surface of the black film obtained by the method of the present invention has numerous concave holes adjacent to each other in a honeycomb pattern, and the inner walls of the concave holes are formed with minute irregularities. There is. It is thought that these minute irregularities further reduce the total reflectance.
［実施例］
実施例１
直径８ｍｍ厚さ ｍｌ１１の銅板の基材をアルカリ脱脂
液浴温５０〜６０°Ｃで脱脂処理し、水洗後１：１の塩
酸により酸洗いし、次いでニッケルストライクめっき（
電気めっき）を行なった後、浴温９０°Ｃの無電解ニッ
ケル・リンめっき液に３時間浸漬し、基材表面にニッケ
ル・リン合金めっき皮膜を約７０〜８゜ｐ、、ＩＩ＋析
出させた。[Example] Example 1 A copper plate base material with a diameter of 8 mm and a thickness of 11 ml was degreased in an alkaline degreasing solution bath temperature of 50 to 60°C, washed with water, pickled with 1:1 hydrochloric acid, and then nickel strike plated (
After electroplating), it was immersed in an electroless nickel-phosphorus plating solution at a bath temperature of 90°C for 3 hours to deposit a nickel-phosphorus alloy plating film on the surface of the substrate at a thickness of approximately 70-8°p. .
このようにしてニッケル・リン合金めっき皮膜の形成さ
れた銅の基材を水洗した後、第一次酸化処理として浴温
５０℃の１＝１硝酸水溶液で３０秒処理した。After washing the copper base material on which the nickel-phosphorous alloy plating film was formed in this way with water, it was treated with a 1=1 nitric acid aqueous solution at a bath temperature of 50° C. for 30 seconds as a primary oxidation treatment.
第一次の酸化処理された基材を水洗し、乾燥せずに第二
次の酸化処理として硝酸ナトリウ４００ｇ１０．、硫酸
５５２ ｇＩＱ含む水溶液１００社中に３０秒浸漬し、
取出して水洗乾燥した。The base material subjected to the first oxidation treatment was washed with water, and the second oxidation treatment was performed without drying with 400 g of sodium nitrate10. , immersed for 30 seconds in an aqueous solution containing 552 gIQ of sulfuric acid,
It was taken out, washed with water and dried.
銅の基材表面に形成された黒色の皮膜は極めて安定で、
機械的振動及び摩擦、耐湿性に対し優れていた。The black film formed on the surface of the copper base material is extremely stable.
Excellent resistance to mechanical vibration, friction, and moisture.
第１図は得られた黒色皮膜の０．４〜２．０ ルｍの波
長域での全反射率を積分球分光光度計で測定した結果を
示す。実線がその測定値で、全波長域にわたって０．２
％以下であり、波長による反射率の変化は極めて小さい
。この皮膜を８５°Ｃで相対湿度８５％ＲＨの環境に２
００時間及び５００時間暴露したのちに測定した全反射
率を、それぞれ破線及び鎖線で示す。全反射率の若干の
増加が見られるが、なお全波長域で０．２ｚ前後であり
、波長依存性は殆ど見られない。FIG. 1 shows the results of measuring the total reflectance of the obtained black film in the wavelength range of 0.4 to 2.0 lumen using an integrating sphere spectrophotometer. The solid line is the measured value, which is 0.2 over the entire wavelength range.
% or less, and the change in reflectance depending on wavelength is extremely small. This film was exposed to an environment of 85°C and relative humidity of 85% RH for 2 hours.
The total reflectance measured after 00 and 500 hours of exposure is shown by the dashed line and the chain line, respectively. Although a slight increase in total reflectance is observed, it is still around 0.2z in the entire wavelength range, and almost no wavelength dependence is observed.
第２図はＡが本実施例で得られた本発明の黒色皮膜の全
反射率測定値で、Ｂは本実施例において第一次酸化処理
のみで得られた黒色皮膜についての測定値である。この
Ｂは米国特許第４２３３１０７号明細書に開示されてい
る黒色皮膜に相当し、Ａの第二次酸化処理皮膜に比して
、全反射率レベルが高く、かつ、波長依存性が見られる
。Ｃは金魚皮膜についての測定値である。In Figure 2, A is the measured total reflectance of the black film of the present invention obtained in this example, and B is the measured value of the black film obtained only by the primary oxidation treatment in this example. . This B corresponds to the black film disclosed in US Pat. No. 4,233,107, and has a higher total reflectance level than the secondary oxidation treated film of A, and shows wavelength dependence. C is the measured value for goldfish film.
第二次酸化処理による表面状態の変化は第３図及び第４
図に示される。第３図は第一次酸化処理のみで水洗乾燥
した黒色皮膜Ｂの表面構造を示す走査電子顕微鏡写真で
、第４図は第二次酸化処理によって得られた本発明の黒
色皮膜Ａについての同様な写真である。第４図において
は凹穴の壁面に微小な凹凸が形成されていることが観察
される。Changes in surface condition due to secondary oxidation treatment are shown in Figures 3 and 4.
As shown in the figure. FIG. 3 is a scanning electron micrograph showing the surface structure of black film B which was washed and dried with water after only the first oxidation treatment, and FIG. 4 is a similar photograph of the black film A of the present invention obtained by the second oxidation treatment. This is a great photo. In FIG. 4, it is observed that minute irregularities are formed on the wall surface of the recessed hole.
実施例２〜６
実施例１において、第二次酸化処理に用いた硝酸ナトリ
ウム及び硫酸の法度を変更して他は実施例１と同様にし
て黒色皮膜を得た。これらの黒色皮膜の全反射率測定結
果を第５図〜第９図に示す。Examples 2 to 6 A black film was obtained in the same manner as in Example 1 except that the amounts of sodium nitrate and sulfuric acid used in the secondary oxidation treatment were changed. The results of measuring the total reflectance of these black films are shown in FIGS. 5 to 9.
［発明の効果］
本発明は、基材の種類を問わず、６〜９ｚリン含有ニッ
ケルリン合金めっきめっき液から析出させたニッケルリ
ン合金めっきめっき皮膜を硝酸水溶液及び硫酸を含有し
た硝酸塩水溶液の２段階酸化処理で黒色化したことによ
り、０．４〜２．０ ｐ、ｍの波長範囲において波長依
存性が少なく、機械的振動及び摩擦に強く、耐湿性に対
しても安定し、全反射率が０．１６〜０．２駕と極めて
低い反射率を有する皮膜が形成される。得られた皮膜は
精密な光パワー絶対値測定用の光吸収体として極めて有
用であり、また、太陽光集熱板、光学機器内部反射防止
材等に利用することができる。[Effects of the Invention] Regardless of the type of substrate, the present invention can coat a nickel phosphorus alloy plating film precipitated from a 6-9z phosphorus-containing nickel phosphorus alloy plating solution with a nitric acid aqueous solution and a nitrate aqueous solution containing sulfuric acid. Due to its blackening through step oxidation treatment, it has little wavelength dependence in the wavelength range of 0.4 to 2.0 p, m, is resistant to mechanical vibration and friction, is stable against moisture resistance, and has a high total reflectance. A film having an extremely low reflectance of 0.16 to 0.2 is formed. The obtained film is extremely useful as a light absorber for precise absolute value measurement of optical power, and can also be used for solar heat collecting plates, anti-reflection materials inside optical equipment, etc.
第１図は本発明の黒色皮膜の全反射率の湿度変化を示す
グラフであり、第２図は本発明の方法による第−吹酸化
処理皮膜及び金魚の全反射率な木明の第二次酸化処理皮
膜と比較したグラフである。
第３図は第一次酸化処理のみで水洗乾燥した黒色皮膜Ｂ
の表面構造を示す走査電子顕微鏡写真で、第４図は第二
次酸化処理によって得られた本発明の黒色皮膜Ａについ
ての同様な写真である。
第５図〜第９図は本発明で第二次酸化処理液の組成を変
更した他の実施例により得られた黒色皮膜の全反射率の
測定結果を示す。FIG. 1 is a graph showing humidity changes in the total reflectance of the black coating of the present invention, and FIG. This is a graph comparing it with an oxidized film. Figure 3 shows black film B after washing and drying with only primary oxidation treatment.
FIG. 4 is a scanning electron micrograph showing the surface structure of the black film A of the present invention obtained by secondary oxidation treatment. FIGS. 5 to 9 show the measurement results of the total reflectance of black films obtained in other examples of the present invention in which the composition of the secondary oxidation treatment solution was changed.
Claims (2)
隣接する無数の凹穴からなり、かつ、該凹穴の壁面に更
に微細な凹凸を有する表面構造であることを特徴とする
黒色皮膜を有する基材。(1) A black color characterized in that the nickel-phosphorus alloy film on the base material has a surface structure consisting of numerous concave holes adjacent to each other in a honeycomb shape, and further has fine irregularities on the wall surface of the concave holes. Base material with a film.
リン合金めっき皮膜を形成し、該ニッケル・リン合金皮
膜を硝酸水溶液で一次酸化処理し、次いで硫酸を含有す
る硝酸塩水溶液で二次酸化処理することにより、無数の
微細な穴を有し、かつ、該無数の微細穴の壁面に更に微
細な凹凸が形成された表面構造を有する皮膜が形成され
ることを特徴とする黒色皮膜形成方法。(2) Nickel and phosphorus alloy plating solution
A phosphorus alloy plating film is formed, and the nickel/phosphorus alloy film is subjected to a primary oxidation treatment with an aqueous nitric acid solution, and then a secondary oxidation treatment with an aqueous nitrate solution containing sulfuric acid, so that it has countless fine holes, and A method for forming a black film, characterized in that a film having a surface structure in which fine irregularities are formed on the walls of the countless microscopic holes is formed.
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62283878A JPH01188680A (en) | 1987-11-10 | 1987-11-10 | Base material having black film and formation of black film |
| US07/268,509 US4984855A (en) | 1987-11-10 | 1988-11-08 | Ultra-black film and method of manufacturing the same |
| EP88118758A EP0317838B1 (en) | 1987-11-10 | 1988-11-10 | Ultra-Black film and method of manufacturing the same |
| DE3887832T DE3887832T2 (en) | 1987-11-10 | 1988-11-10 | Deep black coating and process for its production. |
| US07/595,608 US5074957A (en) | 1987-11-10 | 1990-10-11 | Method of manufacturing ultra-black film |
| US07/595,607 US5079643A (en) | 1987-11-10 | 1990-10-11 | Ultra-black film and method of manufacturing the same |
| US07/595,561 US5096300A (en) | 1987-11-10 | 1990-10-11 | Ultra-black film and method of manufacturing the same |
| US07/595,606 US5111335A (en) | 1987-11-10 | 1990-10-11 | Ultra-black film and method of manufacturing the same |
| US07/595,593 US5083222A (en) | 1987-11-10 | 1990-10-11 | Ultra-black film and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62283878A JPH01188680A (en) | 1987-11-10 | 1987-11-10 | Base material having black film and formation of black film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01188680A true JPH01188680A (en) | 1989-07-27 |
| JPH0431024B2 JPH0431024B2 (en) | 1992-05-25 |
Family
ID=17671347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62283878A Granted JPH01188680A (en) | 1987-11-10 | 1987-11-10 | Base material having black film and formation of black film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01188680A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03117856U (en) * | 1990-03-19 | 1991-12-05 | ||
| JP2010222704A (en) * | 2009-03-20 | 2010-10-07 | Universo Sa | Electrochemical deposition method |
-
1987
- 1987-11-10 JP JP62283878A patent/JPH01188680A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03117856U (en) * | 1990-03-19 | 1991-12-05 | ||
| JP2010222704A (en) * | 2009-03-20 | 2010-10-07 | Universo Sa | Electrochemical deposition method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0431024B2 (en) | 1992-05-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0317838B1 (en) | Ultra-Black film and method of manufacturing the same | |
| US5853897A (en) | Substrate coated with highly diffusive metal surface layer | |
| AU529399B2 (en) | Black coatings on substrates | |
| US4361630A (en) | Ultra-black coating due to surface morphology | |
| US3210220A (en) | Process for coating stainless steel | |
| JPH01188680A (en) | Base material having black film and formation of black film | |
| JP2661983B2 (en) | Substrate having black body film and method for producing this substrate with black body film | |
| US4082898A (en) | Electroless deposition of electrically nonconductive copper-boron coatings on nonmetallic substrates | |
| NO144365B (en) | SELECTIVE ABSORPTION SURFACE, FOR SOLAR COLLECTOR, AND PROCEDURES IN THE PREPARATION OF THIS | |
| EP0067567A2 (en) | Selective solar surfaces | |
| JPH0520516B2 (en) | ||
| JP3194064B2 (en) | Solar heat absorber | |
| US3963528A (en) | Oxidation of chromium surfaces | |
| CA1045909A (en) | Processes and products of sensitizing substrates | |
| JPS6138783B2 (en) | ||
| JPH03115583A (en) | Light absorber and production thereof | |
| JPH0280581A (en) | Base material having black body film and production of base material fitted with black body film thereof | |
| JPS5953458B2 (en) | solar heat absorber | |
| JPH01178829A (en) | Optical calorimeter photodetector | |
| SU1067081A1 (en) | Method for producing local copper coatings on insulators | |
| JPS621513B2 (en) | ||
| JPH02200218A (en) | Mirror | |
| JPS6138784B2 (en) | ||
| JPS6323461B2 (en) | ||
| JPS6359065B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313532 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080525 Year of fee payment: 16 |