JP3464816B2 - Painted steel sheet with excellent moisture and corrosion resistance - Google Patents
Painted steel sheet with excellent moisture and corrosion resistanceInfo
- Publication number
- JP3464816B2 JP3464816B2 JP34341693A JP34341693A JP3464816B2 JP 3464816 B2 JP3464816 B2 JP 3464816B2 JP 34341693 A JP34341693 A JP 34341693A JP 34341693 A JP34341693 A JP 34341693A JP 3464816 B2 JP3464816 B2 JP 3464816B2
- Authority
- JP
- Japan
- Prior art keywords
- steel sheet
- film
- added
- corrosion resistance
- coating
- 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
Links
- 229910000831 Steel Inorganic materials 0.000 title claims description 12
- 230000007797 corrosion Effects 0.000 title claims description 12
- 238000005260 corrosion Methods 0.000 title claims description 12
- 239000010959 steel Substances 0.000 title claims description 10
- 239000003973 paint Substances 0.000 claims description 19
- -1 chromic acid compound Chemical class 0.000 claims description 16
- 239000000049 pigment Substances 0.000 claims description 12
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 11
- 230000003449 preventive effect Effects 0.000 claims description 11
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 7
- 229910001335 Galvanized steel Inorganic materials 0.000 claims description 4
- 239000008397 galvanized steel Substances 0.000 claims description 4
- 229920000137 polyphosphoric acid Polymers 0.000 claims 1
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- 229920000388 Polyphosphate Polymers 0.000 description 13
- 239000001205 polyphosphate Substances 0.000 description 13
- 235000011176 polyphosphates Nutrition 0.000 description 13
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 229920001225 polyester resin Polymers 0.000 description 5
- 239000004645 polyester resin Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000007739 conversion coating Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- LFYJSSARVMHQJB-QIXNEVBVSA-N bakuchiol Chemical compound CC(C)=CCC[C@@](C)(C=C)\C=C\C1=CC=C(O)C=C1 LFYJSSARVMHQJB-QIXNEVBVSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000003204 osmotic effect Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- DHAHRLDIUIPTCJ-UHFFFAOYSA-K aluminium metaphosphate Chemical compound [Al+3].[O-]P(=O)=O.[O-]P(=O)=O.[O-]P(=O)=O DHAHRLDIUIPTCJ-UHFFFAOYSA-K 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は、耐湿性、耐食性に優れ
た塗装鋼板に関する。
【０００２】
【従来技術】亜鉛めっき鋼板を塗装原板とする通常の塗
装鋼板は、塗装原板に化成処理皮膜を形成し、その上に
下塗り塗膜、上塗り塗膜を順次形成している。ここで、
化成処理皮膜としては、クロメ−ト皮膜やリン酸塩皮膜
などが一般的であるが、湿潤雰囲気で使用する場合は化
成処理皮膜をクロメ−ト皮膜にしている。また、下塗り
塗膜には、クロム酸ストロンチウム、クロム酸亜鉛など
のクロム酸化合物系防錆顔料を塗料不揮発分に対して２
０〜３０重量％添加して、耐食性を付与し、塗膜厚を３
〜１０μｍにしている。
【０００３】しかしながら、化成処理皮膜をクロメ−ト
皮膜にしても、耐食性向上のために下塗り塗膜のクロム
酸化合物系防錆顔料を４０〜５０重量％に増量すると、
高温多湿環境にさらされた場合、平坦部塗膜に湿潤フク
レが発生する。この湿潤フクレはクロム酸化合物系防錆
顔料の添加量が多い程短時間に発生するため、クロム酸
化合物系防錆顔料添加による浸透圧上昇が原因であると
考えられている。
【０００４】しかし、現時点では、クロム酸化合物系防
錆顔料以外にこれに匹敵する防錆顔料は見当たらないた
め、耐食性と耐湿性を調和させるのが難しいという問題
があった。
【０００５】
【発明が解決しようとする課題】本発明は、かかる問題
を解決した塗装鋼板を提供するものである。
【０００６】
【課題を解決するための手段】本発明は、クロム酸化合
物系防錆顔料を塗料不揮発分に対して４０〜５０重量％
にするとともに、下塗り塗膜にメタリン酸化合物または
ポリリン酸化合物を塗料不揮発分に対して０.５〜１５
重量％添加した。
【０００７】
【作用】本発明者らは、クロム酸化合物系防錆顔料以外
の防錆物質で、添加量を増大させても、耐湿性を低下さ
せないものについて種々検討した結果、メタリン酸化合
物またはポリリン酸化合物が適していることを見いだし
た。これらの化合物を添加すると、耐食性、耐湿性が向
上する理由は明確ではないが、メタリン酸化合物、ポリ
リン酸化合物は水に難溶性で、過剰に溶出しないため、
浸透圧を高めず、しかも、僅かでも溶出すると、亜鉛め
っき鋼板の表面に緻密な不動態皮膜を形成して、腐食を
抑制するためであると考えられる。
【０００８】メタリン酸化合物またはポリリン酸化合物
の添加量は、塗料不揮発分に対して０.５重量％未満で
あると、湿潤フクレ発生を抑制できず、１５重量％を超
えると、クロム酸化合物系防錆顔料添加量が多くても、
耐食性が低下するので、０.５〜１５重量％にする。メ
タリン酸化合物としては、メタリン酸アルミニウム、メ
タリン酸モリブデン、メタリン酸マンガンなどが挙げら
れ、また、ポリリン酸化合物としては、ポリリン酸アル
ミニウム、ポリリン酸マンガン、ポリリン酸マグネシウ
ムなどが挙げられる。
【０００９】下塗り塗膜にメタリン酸化合物またはポリ
リン酸化合物を添加しても、クロメ−ト処理や下塗り塗
膜の樹脂を従来と変更する必要がない。すなわち、クロ
メ−ト皮膜はクロム付着量が５mg/ｍ2未満であると、耐
食性が劣り、１２０mg/ｍ2を超えると、塗膜密着性が安
定しないので、クロム付着量を５〜１２０mg/ｍ2にする
のが好ましい。下塗り塗膜の樹脂は従来より使用されて
いるポリエステル樹脂系、エポキシ樹脂系、エポキシ／
ウレタン樹脂系などでよい。
【００１０】
【実施例】実施例１〜５
めっき付着量が６０ｇ/ｍ2の溶融亜鉛めっき鋼板に塗布
型クロメ−ト処理液で全クロム付着量が４０mg/ｍ2のク
ロメ−ト皮膜を形成した後、その上にクロム酸ストロン
チウムとポリリン酸アルミニウムを含有するポリエステ
ル樹脂系下塗り塗料を乾燥塗膜厚で５μｍになるように
塗装し、焼き付け乾燥した。その後ポリエステル樹脂系
の上塗り塗料を乾燥塗膜厚で２０μｍになるように塗装
し、焼き付け乾燥した。なお、下塗り塗料としては、ク
ロム酸ストロンチウムとポリリン酸アルミニウムが塗料
不揮発分に対して前者（重量％）/後者（重量％）＝４
５/０.５、４５/５、４５/１０、４５/１５、５０/５添
加したものを用いた。
【００１１】実施例６〜８
実施例１において、下塗り塗料として、塗料不揮発分に
対してクロム酸ストロンチウム４５重量％およびポリリ
ン酸アルミニウム５重量％を含有するエポキシ樹脂系塗
料、エポキシ−ウレタン樹脂系塗料およびアクリル樹脂
系塗料を塗装した。
【００１２】比較例１〜４
実施例１において、下塗り塗料として、クロム酸ストロ
ンチウムおよびポリリン酸アルミニウムが塗料不揮発分
に対して前者（重量％）/後者（重量％）＝５/５、６０
/５、４５/０.３ 、４５/１７添加したポリエステル樹
脂系のものを塗装した。
【００１３】比較例５
実施例１において、下塗り塗料として、クロム酸ストロ
ンチウムだけを塗料不揮発分に対して４５重量％を含有
するポリエステル樹脂系塗料を塗装した。
【００１４】以上のようにして得られた塗装鋼板に対し
て塗膜密着性、耐湿性および耐食性の各試験を次の要領
で実施した。その結果を表１に示す。
（１）塗膜密着性試験
ＪＩＳ Ｇ ３３１２の１２.２.２に準拠して、試験片を
１８０度折り曲げ（２Ｔ、４Ｔ）後、セロハンテ−プで
剥離し、剥離状態を次の基準で評価した。
【００１５】塗膜剥離状態
記号 評価基準
５ 塗膜剥離なし
４ １〜２０％塗膜剥離
３ ２１〜４０％塗膜剥離
２ ４１〜６０％塗膜剥離
１ ６１〜１００％塗膜剥離
【００１６】（２）耐湿性試験
ＪＩＳ Ｚ ０２３６に準拠して湿潤試験を５００時間実
施した後、湿潤フクレの発生状態を目視で観察して、湿
潤フクレの発生しないものを○、発生したものを×とし
て評価した。
【００１７】（３）耐食性試験
ＪＩＳ Ｚ ２３７１に準拠して塩水噴霧試験を５００時
間実施した後、切断端面のエッジクリ−プ最大幅を測定
した。
【００１８】
【表１】【００１９】
【発明の効果】以上のように、本発明の塗装鋼板は、ク
ロム酸化合物系防錆顔料の下塗り塗膜への添加量を増大
させても耐湿性を向上させることができる。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coated steel sheet having excellent moisture resistance and corrosion resistance. 2. Description of the Related Art An ordinary coated steel sheet using a galvanized steel sheet as a coating base sheet is formed by forming a chemical conversion coating on the coating base sheet, and subsequently forming an undercoating film and an overcoating film thereon. here,
As the chemical conversion coating, a chromate coating or a phosphate coating is generally used, but when used in a wet atmosphere, the chemical conversion coating is a chromate coating. In addition, a chromate compound-based rust preventive pigment such as strontium chromate or zinc chromate is applied to the undercoating film in an amount of 2% based on the nonvolatile content of the paint.
0 to 30% by weight is added to impart corrosion resistance, and the coating thickness is 3
To 10 μm. [0003] However, even when the chemical conversion coating is a chromate coating, if the chromic acid compound-based rust-preventive pigment of the undercoat coating is increased to 40 to 50% by weight to improve corrosion resistance,
When exposed to a high-temperature and high-humidity environment, wet blisters occur on the coating film on the flat portion. This wet blister is generated in a shorter time as the amount of the chromic acid compound-based rust preventive pigment is added, and is considered to be caused by an increase in osmotic pressure due to the addition of the chromic acid compound-based rust preventive pigment. However, at present, there is no comparable rust preventive pigment other than the chromic acid compound-based rust preventive pigment, so that there is a problem that it is difficult to balance corrosion resistance and moisture resistance. [0005] The present invention is to provide a coated steel sheet which solves such a problem. According to the present invention, a chromic acid compound-based rust-preventive pigment is used in an amount of 40 to 50% by weight based on a nonvolatile content of a paint.
And a metaphosphate compound or a polyphosphate compound is added to the undercoating film in an amount of 0.5 to 15 with respect to the non-volatile content of the paint.
% By weight. The present inventors have conducted various studies on rust preventive substances other than chromic acid compound-based rust preventive pigments, which do not decrease the moisture resistance even if the added amount is increased. Polyphosphate compounds have been found to be suitable. When these compounds are added, it is not clear why the corrosion resistance and moisture resistance are improved, but the metaphosphate compound and the polyphosphate compound are hardly soluble in water and do not elute excessively.
This is considered to be because, if the osmotic pressure is not increased and a small amount is eluted, a dense passive film is formed on the surface of the galvanized steel sheet to suppress corrosion. If the amount of the metaphosphate compound or the polyphosphate compound is less than 0.5% by weight based on the nonvolatile content of the paint, the occurrence of wet blisters cannot be suppressed. Even if the amount of rust preventive pigment added is large,
Since corrosion resistance is reduced, the content is made 0.5 to 15% by weight. Examples of the metaphosphate compound include aluminum metaphosphate, molybdenum metaphosphate, and manganese metaphosphate, and examples of the polyphosphate compound include aluminum polyphosphate, manganese polyphosphate, and magnesium polyphosphate. Even if a metaphosphate compound or a polyphosphate compound is added to the undercoat film, it is not necessary to perform a chromate treatment or to change the resin of the undercoat film from the conventional one. That is, if the amount of chromium is less than 5 mg / m 2 , the corrosion resistance is poor. If the amount of chromium exceeds 120 mg / m 2 , the adhesion of the film is not stable. Preferably it is 2 . The resin of the undercoat coating is a polyester resin, epoxy resin, epoxy /
A urethane resin type or the like may be used. Examples 1 to 5 A chromate film having a total chromium deposit of 40 mg / m 2 was formed on a hot-dip galvanized steel sheet having a plating deposit of 60 g / m 2 using a coating type chromate treatment solution. After that, a polyester resin-based undercoat containing strontium chromate and aluminum polyphosphate was applied thereon to a dry film thickness of 5 μm, and baked and dried. Thereafter, a polyester resin-based top coat was applied to a dry film thickness of 20 μm, and baked and dried. As the undercoat paint, strontium chromate and aluminum polyphosphate were the former (weight%) / the latter (weight%) = 4 based on the nonvolatile matter of the paint.
Those added with 5 / 0.5, 45/5 , 45/10 , 45/15 , 50/5 were used. Examples 6 to 8 In Example 1, an epoxy resin paint containing 45% by weight of strontium chromate and 5% by weight of aluminum polyphosphate, based on the nonvolatile matter of the paint, as an undercoat paint, an epoxy-urethane resin paint And an acrylic resin paint. Comparative Examples 1 to 4 In Example 1, strontium chromate and aluminum polyphosphate were used as undercoat paints in terms of the former (wt%) / the latter (wt%) = 5/5, 60
/ 5, 45 / 0.3 and 45/17 were coated with polyester resin. Comparative Example 5 In Example 1, a polyester resin-based paint containing only strontium chromate and containing 45% by weight based on the nonvolatile content of the paint was applied as the undercoat paint. Each of the coated steel sheets obtained as described above was subjected to the following tests in terms of coating film adhesion, moisture resistance and corrosion resistance. Table 1 shows the results. (1) Coating film adhesion test According to JIS G 3312 12.2.2, the test piece was bent 180 degrees (2T, 4T), peeled off with a cellophane tape, and the peeled state was evaluated according to the following criteria. did. Coating peeling state symbol Evaluation criteria 5 No coating peeling 4 1 to 20% coating removal 3 21 to 40% coating removal 2 41 to 60% coating removal 1 61 to 100% coating removal (2) Moisture resistance test After a wet test was performed for 500 hours in accordance with JIS Z 0236, the state of occurrence of wet swelling was visually observed, and evaluation was made as "O" when no wet swelling was generated and "X" when it was generated. did. (3) Corrosion resistance test A salt spray test was carried out for 500 hours in accordance with JIS Z 2371, and then the maximum edge creep width of the cut end face was measured. [Table 1] As described above, the coated steel sheet of the present invention can improve the moisture resistance even when the amount of the chromic acid compound-based rust preventive pigment added to the undercoat film is increased.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 上川 英泰 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社 鉄鋼研究所 塗覆装研究 部内 (72)発明者 坂井 哲男 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社 鉄鋼研究所 塗覆装研究 部内 (72)発明者 福本 博光 千葉県市川市高谷新町７番地の１ 日新 製鋼株式会社 鉄鋼研究所 塗覆装研究 部内 (56)参考文献 特開 平３−69351（ＪＰ，Ａ) 特開 平４−215873（ＪＰ，Ａ) 特開 平４−221085（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B05D 7/14 B05D 3/10 B05D 7/24 303 B32B 15/08 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideyasu Uekawa 7th, Takayashinmachi, Ichikawa-shi, Chiba Pref. 7-in-1 Shinmachi, Nisshin Steel Co., Ltd. Steel Research Laboratory, Paint Coating Research Department (72) Inventor Hiromitsu Fukumoto 7-in-1 Nisshin Steel Co., Ltd. Steel Research Laboratory, Paint Coating Research Department at Takamachi Shinmachi, Ichikawa-shi, Chiba (56 References JP-A-3-69351 (JP, A) JP-A-4-215873 (JP, A) JP-A-4-2211085 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB B05D 7/14 B05D 3/10 B05D 7/24 303 B32B 15/08
Claims (1)
クロム酸化合物系防錆顔料を添加した下塗り塗膜および
上塗り塗膜を順次形成した塗装鋼板において、クロム酸
化合物系防錆顔料を塗料不揮発分に対して４０〜５０重
量％にするとともに、下塗り塗膜にメタリン酸化合物ま
たはポリリン酸化合物を塗料不揮発分に対して０.５〜
１５重量％添加したことを特徴とする耐湿性、耐食性に
優れた塗装鋼板。(57) [Claims] [Claim 1] A chromate film on a galvanized steel sheet surface,
In a coated steel sheet in which an undercoating film and an overcoating film to which a chromic acid compound-based rust preventive pigment is added are sequentially formed, the chromic acid compound-based rust preventive pigment is added in an amount of 40 to 50% by weight based on the nonvolatile content of the paint. Metaphosphoric acid compound or polyphosphoric acid compound is added to the film in an amount of 0.5 to 0.5% of the paint non-volatile content.
A coated steel sheet excellent in moisture resistance and corrosion resistance characterized by being added by 15% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34341693A JP3464816B2 (en) | 1993-12-16 | 1993-12-16 | Painted steel sheet with excellent moisture and corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34341693A JP3464816B2 (en) | 1993-12-16 | 1993-12-16 | Painted steel sheet with excellent moisture and corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07171495A JPH07171495A (en) | 1995-07-11 |
| JP3464816B2 true JP3464816B2 (en) | 2003-11-10 |
Family
ID=18361350
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34341693A Expired - Fee Related JP3464816B2 (en) | 1993-12-16 | 1993-12-16 | Painted steel sheet with excellent moisture and corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3464816B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100762465B1 (en) * | 2006-08-02 | 2007-10-04 | 주식회사 포스코 | Coating composition for forming insulating film with excellent corrosion resistance after chromium-free corrosion resistance and stress relief annealing and method for forming insulating film of non-oriented electrical steel sheet using the same |
-
1993
- 1993-12-16 JP JP34341693A patent/JP3464816B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07171495A (en) | 1995-07-11 |
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