JP3192815B2 - Low-gloss black steel sheet and method for producing the same - Google Patents
Low-gloss black steel sheet and method for producing the sameInfo
- Publication number
- JP3192815B2 JP3192815B2 JP07148093A JP7148093A JP3192815B2 JP 3192815 B2 JP3192815 B2 JP 3192815B2 JP 07148093 A JP07148093 A JP 07148093A JP 7148093 A JP7148093 A JP 7148093A JP 3192815 B2 JP3192815 B2 JP 3192815B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- steel sheet
- weight
- low
- value
- 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 - Fee Related
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/24—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds
- C23C22/26—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing hexavalent chromium compounds containing also organic compounds
- C23C22/28—Macromolecular compounds
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- 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)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、建材・家電・自動車等
の分野に適した外観均一で低光沢な黒色化処理鋼板に関
するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a blackened steel sheet having a uniform appearance and a low gloss, which is suitable for fields such as building materials, home appliances and automobiles.
【０００２】[0002]
【従来の技術】現在、表面を黒化処理した鋼板が家電、
複写機、情報通信機、自動車部品、内装建材等にひろく
利用されている。この黒色鋼板の製造方法としては
（１）黒色塗装、（２）化学処理法、（３）黒色クロメ
ート法、（４）陽極処理法、（５）陰極処理法等があ
る。2. Description of the Related Art At present, home appliances,
It is widely used in copiers, information and communication equipment, automobile parts, interior building materials, and the like. As a method for producing this black steel sheet, there are (1) black coating, (2) chemical treatment, (3) black chromate, (4) anodizing, and (5) cathodic treatment.
【０００３】中でも、陽極処理法は工業的な製造方法と
して特公昭61−60915 号公報、特公昭63−46158 号公
報、特公昭63−46159 号公報に開示されており、Zn−Ni
合金電気めっきした鋼板を各種水溶液中で陽極酸化処理
して、表面を黒色化するものである。そして、このよう
にして製造された黒色鋼板は、黒色度を安定させるとと
もに着色被膜を保護するため透明な有機樹脂被膜を数μ
ｍ施す。また、耐食性を得るために、樹脂塗布前にクロ
メート処理したり、樹脂中にクロム酸を含有させてい
る。[0003] Above all, the anodizing method is disclosed in Japanese Patent Publication No. 61-60915, Japanese Patent Publication No. 63-46158 and Japanese Patent Publication No. 63-46159 as industrial production methods.
Anodizing is performed on a steel plate electroplated with an alloy in various aqueous solutions to blacken the surface. Then, the black steel sheet manufactured in this manner has a transparent organic resin film having a thickness of several μm to stabilize the blackness and protect the colored film.
m. Further, in order to obtain corrosion resistance, chromate treatment is performed before resin application, or chromic acid is contained in the resin.
【０００４】しかしながら、従来の有機樹脂被覆施した
黒色鋼板は、樹脂塗布前はその光沢度（JIS Z8741によ
る60°鏡面光沢度で以下Ｇ値と言う）が５以下と光の反
射の少ない鋼板であるにもかかわらず、めっきの不均一
や陽極処理の不均一がわずかでもあると、均一美麗な黒
色外観を呈せず、樹脂を約１μｍ程度その上に塗布する
と、外観が均一美麗にはなるものの光が反射しやすくＧ
値が20〜35のてかてかした外観を呈する黒色鋼板とな
る。特に、このような黒色化した鋼板を光学機器や複写
機等の装置内部に使用する場合には、単に色が黒いだけ
でなく、光を反射しないことが望ましい。また個人的な
好みにもよるが、光沢のない重厚な外観を好ましいと思
う用途も多い。However, the conventional black steel sheet coated with an organic resin is a steel sheet having low light reflection, having a gloss (below G value at 60 ° mirror gloss according to JIS Z8741) of 5 or less before resin coating. Nevertheless, if the plating is not uniform or the anodization is slight, it does not exhibit a uniform beautiful black appearance, and if the resin is applied on it about 1 μm, the appearance becomes uniform and beautiful. G is easy to reflect light
The value is 20-35, which is a black steel plate with a prominent appearance. In particular, when such a blackened steel sheet is used in an apparatus such as an optical device or a copying machine, it is desirable that the color be not only black but also not reflect light. Also, depending on personal preference, there are many applications in which a dull and solid appearance is preferable.
【０００５】[0005]
【発明が解決しようとする課題】従来の黒色化鋼板は、
このような要求に十分答えるものではなかった。そこで
本発明は、前記問題点を解決し、Ｇ値が１〜10、Ｌ値
（ＣＩＥ着色系）が10〜15の低光沢黒色鋼板およびその
製造方法を提案することを目的とするものである。The conventional blackened steel sheet is
It did not fully answer such a request. Accordingly, an object of the present invention is to solve the above problems and propose a low-gloss black steel sheet having a G value of 1 to 10 and an L value (CIE color system) of 10 to 15 and a method of manufacturing the same. .
【０００６】[0006]
【課題を解決するための手段】本発明は、陽極黒色化電
解処理されたZn−Ni合金めっき鋼板の表面にアクリル樹
脂 100重量部に対し平均一次粒子径７〜40nmのフューム
ドシリカを３〜30重量部とクロム酸 0.2〜1.0 重量部を
含有してなる有機樹脂複合皮膜を 0.5〜２μｍ厚有し、
Ｇ値（ JIS Z8741 による60°鏡面光沢度）が１〜10、
Ｌ値が10〜15であることを特徴とする低光沢黒色鋼板で
あり、またZn−Ni合金めっき鋼板を陽極電解処理により
黒色化したのち、その表面に、水分散型アクリル樹脂不
揮発分 100重量部に対して、平均一次粒子径が７〜40nm
のフュームドシリカを３〜30重量部とクロム酸を 0.2〜
1.0 重量部添加した溶液を塗布し、到達板温 100〜150
℃で乾燥処理することを特徴とする低光沢黒色鋼板の製
造方法である。According to the present invention, a fumed silica having an average primary particle diameter of 7 to 40 nm per 100 parts by weight of an acrylic resin is coated on the surface of a Zn—Ni alloy-plated steel sheet which has been subjected to anodizing and blackening electrolysis. An organic resin composite film containing 30 parts by weight and chromic acid 0.2 to 1.0 parts by weight having a thickness of 0.5 to 2 μm,
G value (60 ° specular gloss according to JIS Z8741) is 1 to 10,
A low-gloss black steel sheet characterized by an L value of 10 to 15, and a Zn-Ni alloy-plated steel sheet blackened by anodic electrolysis treatment, and then, on the surface thereof, a water-dispersed acrylic resin nonvolatile content of 100 wt. Parts, the average primary particle diameter is 7 to 40 nm
3 to 30 parts by weight of fumed silica and 0.2 to chromic acid
1.0 part by weight of the added solution was applied and the plate temperature reached 100-150
It is a method for producing a low-gloss black steel sheet, which is characterized by performing a drying treatment at ℃.
【０００７】なお、Ｌ値はＣＩＡ着色系で測定した値
で、その数値が大きい程、明度が高い即ち明るいことを
示す。また、本発明におけるZn−Ni合金めっきはNiを７
〜20重量％、好ましくは10〜14重量％含有するZn−Ni合
金めっきであり、通常電気めっきによって製造される。
このZn−Ni合金めっき鋼板を陽極処理して黒色化する。
陽極処理は硝酸や塩素酸等の酸化剤を加えた酸性水溶液
中でZn−Niめっき鋼板を陽極として電解処理することに
よって行うもので、通常行われている方法でよい。[0007] The L value is a value measured in a CIA coloring system, and the larger the value, the higher the brightness, that is, the brighter. Further, the Zn—Ni alloy plating in the present invention is
It is a Zn-Ni alloy plating containing -20% by weight, preferably 10-14% by weight, and is usually produced by electroplating.
The Zn—Ni alloy plated steel sheet is anodized to blacken.
The anodic treatment is performed by subjecting a Zn-Ni plated steel sheet to an electrolytic treatment in an acidic aqueous solution to which an oxidizing agent such as nitric acid or chloric acid is added, and may be a commonly used method.
【０００８】[0008]
【作用】本発明は、このようにして得られた黒色化処理
鋼板にアクリル樹脂を主体とする有機樹脂性合皮膜を形
成するが、とりわけ樹脂中にフュームドシリカを添加す
ることにより低光沢な表面性状を達成したことに特徴が
ある。フュームドシリカの平均一次粒子径を７〜40nmに
限定したのは、７nm未満では低光沢化に効果がなく、Ｇ
値が10を越えてしまう。また、40nmを越えると水分散性
が悪くなったり、沈降しやすくなるので製造する上で好
ましくない。添加量はベース樹脂固形分 100部に対し３
〜30部である。３部未満では低光沢化に効果がなく、30
部を越えると粘性が増し、扱いが難しくなり樹脂も固く
なり加工成形時に樹脂が剥離するので好ましくない。According to the present invention, an organic resin composite film mainly composed of an acrylic resin is formed on the blackened steel sheet obtained as described above, and in particular, low gloss is obtained by adding fumed silica to the resin. Characterized by achieving surface properties. The reason why the average primary particle diameter of the fumed silica is limited to 7 to 40 nm is that when the average primary particle diameter is less than 7 nm, there is no effect in lowering the gloss,
The value exceeds 10. On the other hand, if it exceeds 40 nm, water dispersibility deteriorates and sedimentation tends to occur, which is not preferable for production. Addition amount is 3 per 100 parts of base resin solids
~ 30 parts. Less than 3 parts has no effect on low gloss,
Beyond the portion, the viscosity increases, handling becomes difficult, the resin becomes hard, and the resin peels off during processing and molding, which is not preferable.
【０００９】ベース樹脂の水分散型アクリル樹脂は特に
指定されるものではないが、乳化剤が塗装後の耐食性に
悪影響を及ぼさないようあるいは、クロム酸を添加した
場合樹脂が固化したり、膜はりなどの悪影響がないもの
を選ぶ必要がある。本発明ではさらにクロム酸を0.2 〜
1.0 部添加する。0.2 部未満では耐食性が不足し、1.0
部を越えると導電性がなくなりスポット溶接ができなく
なったり、アース性がなくなるなどの不都合が生じるの
で好ましくない。The water-dispersible acrylic resin as the base resin is not particularly specified. However, the emulsifier does not adversely affect the corrosion resistance after coating, or when chromic acid is added, the resin is solidified or the film is stuck. It is necessary to select one that does not have the adverse effect of In the present invention, chromic acid is further added at 0.2 to
Add 1.0 part. If less than 0.2 parts, corrosion resistance is insufficient, and 1.0
Exceeding the portion is not preferable because it causes inconveniences such as loss of conductivity and spot welding and loss of grounding.
【００１０】以上の組成の溶液を、陽極電解処理後のZn
−Niめっき鋼板上にロールコーター等で塗布し、到達板
温 100〜150 ℃で乾燥する。 100℃未満では乾燥が不充
分で膜がはがれ落ちたりする。また、 150℃超では、樹
脂の劣化が早まるので好ましくない。このような樹脂皮
膜を乾燥膜厚で 0.5〜２μ形成する。 0.5μ未満ではＬ
値が10未満となり美麗な外観に仕上げるのが難しい。ま
た、２μを越えるとＧ値が10を越え低光沢を実現できな
くなるので好ましくない。The solution having the above composition is treated with Zn after anodic electrolytic treatment.
-Apply on a Ni-plated steel sheet with a roll coater or the like, and dry at an ultimate sheet temperature of 100 to 150 ° C. If the temperature is lower than 100 ° C., drying is insufficient and the film may peel off. On the other hand, if the temperature exceeds 150 ° C., deterioration of the resin is accelerated, which is not preferable. Such a resin film is formed in a dry film thickness of 0.5 to 2 μm. L is less than 0.5μ
The value is less than 10, making it difficult to finish the appearance beautifully. On the other hand, if it exceeds 2 μm, the G value exceeds 10, and low gloss cannot be realized.
【００１１】なお、本発明でＧ値を１〜10に限定した理
由は、１未満では外観が美麗な鋼板の実現が困難であ
り、樹脂膜厚を 0.5μ未満の領域で実施しても耐食性が
劣り好ましくないからであり、10超では反射光による光
沢感がでて、黒色の重厚感が失なわれるからである。ま
たＬ値を10〜15に限定した理由は、10未満では外観が美
麗な鋼板の実現が困難であり、樹脂膜厚を 0.5μ未満の
領域で実施しても耐食性が劣り好ましくないからであ
り、15超では黒色の重厚感が失なわれ、良好な黒色外観
が得られないからである。The reason why the G value is limited to 1 to 10 in the present invention is that if it is less than 1, it is difficult to realize a steel sheet having a beautiful appearance. If it exceeds 10, glossiness due to reflected light appears and black solid feeling is lost. The reason why the L value is limited to 10 to 15 is that if it is less than 10, it is difficult to realize a steel plate with a beautiful appearance, and even if the resin film thickness is less than 0.5 μm, the corrosion resistance is poor and it is not preferable. If it exceeds 15, the profound feeling of black is lost and a good black appearance cannot be obtained.
【００１２】次に実施例に基づいて本発明をより詳細に
説明する。Next, the present invention will be described in more detail based on embodiments.
【００１３】[0013]
１．黒色化処理方法 Zn−Ni合金めっき鋼板（付着量20ｇ／ｍ2 、Ni含有率12
％、下地鋼板SPCC相当板厚0.7mm ）を用い NaClO3 50ｇ
／ｌ、Na2SO4 100ｇ／ｌ、pH 1.5、50℃の黒化処理液で
75Ａ／dm2 、 150Ｃ／dm2 の条件で陽極電解を行い、黒
化させたものを樹脂被覆に供した。因みに樹脂被覆前の
Ｌ値＝８、Ｇ値＝0.5 であった。1. Blackening treatment Zn-Ni alloy plated steel sheet (adhesion amount 20g / m 2 , Ni content 12
%, Base steel sheet SPCC equivalent sheet thickness 0.7mm) NaClO 3 50g
/ L, 100 g / l of Na 2 SO 4 , pH 1.5, with blackening treatment solution at 50 ° C
Anodic electrolysis was performed under the conditions of 75 A / dm 2 and 150 C / dm 2 , and the blackened one was subjected to resin coating. Incidentally, the L value before resin coating was 8, and the G value was 0.5.
【００１４】２．樹脂被覆方法 水分散型アクリル系樹脂として、日本パーカライジング
（株）製の3966ＡＸ（商品名）を使用した。フュームド
シリカは日本アエロジル社製のものを使用した。表１に
実施例および評価方法を示した。2. Resin coating method 3966AX (trade name) manufactured by Nippon Parkerizing Co., Ltd. was used as the water-dispersed acrylic resin. Fumed silica manufactured by Nippon Aerosil Co., Ltd. was used. Table 1 shows examples and evaluation methods.
【００１５】Ｌ値（国際照明委員会ＣＩＥによる1976年
のＣＩＥＬＡＢ表面系による明度指数）、Ｇ値は、スガ
試験機製のカラーコンピューターにより測定した。耐食
性は、塩水噴霧試験（ JIS Z2371 ）により行い、 200
時間後の白錆発生状況により判定した。加工性は、ＯＴ
折り曲げ試験後セロハンテープ剥離を行い、樹脂の密着
性により評価した。The L value (brightness index based on the CIELAB surface system in 1976 by the International Commission on Illumination) and the G value were measured by a color computer manufactured by Suga Test Instruments. Corrosion resistance was determined by salt spray test (JIS Z2371).
Judgment was made based on the state of white rust occurrence after a lapse of time. Workability is OT
After the bending test, the cellophane tape was peeled off and evaluated by the adhesiveness of the resin.
【００１６】溶接性は、加圧力150kg 、40ＲのＲ型Cu−
Cr電極で7.5KA の電流を流したときに、通電されてナゲ
ットとが形成されたが否かにより評価した。なお、耐食
性、溶接性および加工性の評価において、○は良好、△
はやや良好、×は不良である。The weldability is as follows: 150 kg, 40 R, R-type Cu-
When a current of 7.5 KA was passed through the Cr electrode, the current was passed to form a nugget. In the evaluation of corrosion resistance, weldability and workability, ○ indicates good, and △ indicates
Slightly good, x is bad.
【００１７】[0017]
【表１】 [Table 1]
【００１８】[0018]
【発明の効果】本発明により、光の反射をきらう家電製
品や産業用装置の内板として有用な低光沢鋼板の安定し
た提供が可能となった。また、黒い外観がいかされる、
家電製品や室内外装飾用途にも効果的に用いることがで
きるようになった。According to the present invention, it has become possible to stably provide a low-gloss steel sheet which is useful as an inner plate of home electric appliances and industrial equipment which are less reflective of light. In addition, black appearance is used,
It can also be used effectively for home appliances and interior and exterior decoration applications.
フロントページの続き (56)参考文献 特開 平１−147096（ＪＰ，Ａ) 特開 平１−316259（ＪＰ，Ａ) 特開 昭61−227179（ＪＰ，Ａ) 特開 平３−131371（ＪＰ，Ａ) 特開 平３−24278（ＪＰ，Ａ) 特開 昭62−33781（ＪＰ，Ａ) 特開 昭55−91993（ＪＰ，Ａ) 特開 昭61−143594（ＪＰ，Ａ) 特開 平１−56881（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B32B 15/00 - 15/20 C23C 22/00 - 22/86 Continuation of the front page (56) References JP-A-1-147096 (JP, A) JP-A-1-316259 (JP, A) JP-A-61-227179 (JP, A) JP-A-3-131371 (JP) JP-A-3-24278 (JP, A) JP-A-62-33781 (JP, A) JP-A-55-91993 (JP, A) JP-A-61-143594 (JP, A) 1-56881 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) B32B 15/00-15/20 C23C 22/00-22/86
Claims (2)
っき鋼板の表面にアクリル樹脂 100重量部に対し平均一
次粒子径７〜40nmのフュームドシリカを３〜30重量部と
クロム酸 0.2〜1.0 重量部を含有してなる有機樹脂複合
皮膜を 0.5〜２μｍ厚有し、Ｇ値（ JIS Z8741 による
60°鏡面光沢度）が１〜10、Ｌ値が10〜15であることを
特徴とする低光沢黒色鋼板。An anodic blackening electrolytically treated Zn—Ni alloy-plated steel sheet is provided with 3 to 30 parts by weight of fumed silica having an average primary particle diameter of 7 to 40 nm and chromic acid of 0.2 to 100 parts by weight based on 100 parts by weight of an acrylic resin. The organic resin composite film containing 1.0 parts by weight has a thickness of 0.5 to 2 μm, and has a G value (according to JIS Z8741).
A low-gloss black steel sheet having a 60 ° specular glossiness of 1 to 10 and an L value of 10 to 15.
より黒色化したのち、その表面に、水分散型アクリル樹
脂不揮発分 100重量部に対して、平均一次粒子径が７〜
40nmのフュームドシリカを３〜30重量部とクロム酸を
0.2〜1.0 重量部添加した溶液を塗布し、到達板温 100
〜150 ℃で乾燥処理することを特徴とする低光沢黒色鋼
板の製造方法。2. After the Zn—Ni alloy-plated steel sheet is blackened by anodic electrolysis treatment, the average primary particle diameter is 7 to 10 parts by weight based on 100 parts by weight of a water-dispersible acrylic resin nonvolatile component.
40 to 3 to 30 parts by weight of fumed silica and chromic acid
Apply the solution containing 0.2 to 1.0 parts by weight, and reach the plate temperature of 100
A method for producing a low-gloss black steel sheet, comprising drying at -150 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07148093A JP3192815B2 (en) | 1993-03-30 | 1993-03-30 | Low-gloss black steel sheet and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07148093A JP3192815B2 (en) | 1993-03-30 | 1993-03-30 | Low-gloss black steel sheet and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06278245A JPH06278245A (en) | 1994-10-04 |
| JP3192815B2 true JP3192815B2 (en) | 2001-07-30 |
Family
ID=13461849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP07148093A Expired - Fee Related JP3192815B2 (en) | 1993-03-30 | 1993-03-30 | Low-gloss black steel sheet and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3192815B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI220128B (en) * | 1998-07-17 | 2004-08-11 | Toyo Kohan Co Ltd | Resin coated steel plate, patrone cap and patrone body portion made thereof |
| JP5058519B2 (en) * | 2006-06-13 | 2012-10-24 | 新日本製鐵株式会社 | Resin-coated Ni-plated steel sheet and method for producing the same |
| JP7531880B2 (en) * | 2020-03-19 | 2024-08-13 | シーバイエス株式会社 | Aqueous matte coating composition |
-
1993
- 1993-03-30 JP JP07148093A patent/JP3192815B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06278245A (en) | 1994-10-04 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |