JPH0433844A - Organic/inorganic composite steel plate having excellent thermal resistance, heat resisting discoloration, and corrosion resistance - Google Patents
Organic/inorganic composite steel plate having excellent thermal resistance, heat resisting discoloration, and corrosion resistanceInfo
- Publication number
- JPH0433844A JPH0433844A JP13826490A JP13826490A JPH0433844A JP H0433844 A JPH0433844 A JP H0433844A JP 13826490 A JP13826490 A JP 13826490A JP 13826490 A JP13826490 A JP 13826490A JP H0433844 A JPH0433844 A JP H0433844A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- organic
- weight
- parts
- steel plate
- 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
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 104
- 239000010959 steel Substances 0.000 title claims abstract description 104
- 230000007797 corrosion Effects 0.000 title claims abstract description 41
- 238000005260 corrosion Methods 0.000 title claims abstract description 41
- 238000002845 discoloration Methods 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims abstract description 41
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 40
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 28
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000006185 dispersion Substances 0.000 claims abstract description 24
- -1 polyethylene Polymers 0.000 claims abstract description 20
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000004698 Polyethylene Substances 0.000 claims abstract description 9
- 239000004111 Potassium silicate Substances 0.000 claims abstract description 9
- 229920000573 polyethylene Polymers 0.000 claims abstract description 9
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052913 potassium silicate Inorganic materials 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 84
- 239000007787 solid Substances 0.000 claims description 39
- 238000007747 plating Methods 0.000 claims description 29
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 22
- 239000008158 vegetable oil Substances 0.000 claims description 22
- 239000011247 coating layer Substances 0.000 claims description 21
- 239000010775 animal oil Substances 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 229920002125 Sokalan® Polymers 0.000 claims description 13
- 239000004584 polyacrylic acid Substances 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- 239000002344 surface layer Substances 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 239000002480 mineral oil Substances 0.000 claims description 7
- 235000010446 mineral oil Nutrition 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- PHIQPXBZDGYJOG-UHFFFAOYSA-N sodium silicate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-][Si]([O-])=O PHIQPXBZDGYJOG-UHFFFAOYSA-N 0.000 claims description 6
- 235000019794 sodium silicate Nutrition 0.000 claims description 5
- AZUZXOSWBOBCJY-UHFFFAOYSA-N Polyethylene, oxidized Polymers OC(=O)CCC(=O)C(C)C(O)CCCCC=O AZUZXOSWBOBCJY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052681 coesite Inorganic materials 0.000 abstract description 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000377 silicon dioxide Substances 0.000 abstract description 3
- 229910052682 stishovite Inorganic materials 0.000 abstract description 3
- 229910052905 tridymite Inorganic materials 0.000 abstract description 3
- 239000011343 solid material Substances 0.000 abstract 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract 1
- 238000005187 foaming Methods 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 20
- 229910045601 alloy Inorganic materials 0.000 description 17
- 239000000956 alloy Substances 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 9
- 229910007567 Zn-Ni Inorganic materials 0.000 description 9
- 229910007614 Zn—Ni Inorganic materials 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- 230000007423 decrease Effects 0.000 description 9
- 229920006026 co-polymeric resin Polymers 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 239000008234 soft water Substances 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910018605 Ni—Zn Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229920006127 amorphous resin Polymers 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004690 nonahydrates Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、耐熱性、耐加熱変色性及び１ｉ１１に性に優
れた有機／無機複合鋼板に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an organic/inorganic composite steel sheet having excellent heat resistance, heat discoloration resistance, and 1i11 properties.
［従来の技術］
これまでに電気亜鉛めっき鋼板や溶融めっき鋼板あるい
は各種合金めっき鋼板が製造され、家電、自動車、建材
などに広く使用されている。[Prior Art] Electrogalvanized steel sheets, hot-dip galvanized steel sheets, and various alloy-plated steel sheets have been manufactured so far and are widely used in home appliances, automobiles, building materials, and the like.
従来、耐蝕性に優れた鋼板として、亜鉛系めっき鋼板の
クロメート材に特殊樹脂を塗布したいわゆる簡易プレコ
ート鋼板（以後有機複合鋼板とよぶ）、亜鉛系めっき鋼
板のクロメート材に顔料添加によって着色された樹脂を
塗布したいわゆる着色塗装鋼板が開発され、一部市販さ
れている。Conventionally, steel sheets with excellent corrosion resistance have been manufactured using so-called simple pre-coated steel sheets (hereinafter referred to as organic composite steel sheets), which are made by applying a special resin to the chromate material of zinc-based plated steel sheets, and those colored by adding pigments to the chromate material of zinc-based plated steel sheets. So-called colored painted steel sheets coated with resin have been developed, and some are commercially available.
前者の有機複合鋼板の例としては、特公昭６１−３６５
８７号公報、特開昭６０−１４９７８６号公報、特開昭
５８−２１０１９２号公報、特開昭５８−２１０１９０
号公報、特開昭５９−１１６３９７号公報等の発明をあ
げることができ、後者の着色塗装鋼板の例としては、特
開昭６３−１２８９３５号公報の発明をあげることがで
きる。An example of the former organic composite steel sheet is the Japanese Patent Publication No. 61-365
87, JP 60-149786, JP 58-210192, JP 58-210190
JP-A-59-116397, etc., and an example of the latter colored painted steel sheet is the invention of JP-A-63-128935.
特公昭６１−３６５８７号公報は、電気亜鉛めっき鋼板
にクロム付着量が１０〜６０ｍｇ／ｍ２となるようにク
ロメート被膜を形成し、ポリエチレン系樹脂ディスバー
ジョンの固形分１００重量部に対しコロイダルシリカを
固形分でｌＯ〜６Ｃ１量部混合し量水混合を０．３〜４
ｇ／ｍ’（固形分）となるように塗布することを特徴と
する発明を開示するものである。Japanese Patent Publication No. 61-36587 discloses that a chromate film is formed on an electrogalvanized steel sheet so that the amount of chromium deposited is 10 to 60 mg/m2, and colloidal silica is added in solid form to 100 parts by weight of the solid content of polyethylene resin dispersion. Mix 1 part of lO~6C in minutes and mix with 0.3~4 parts of water.
This invention discloses an invention characterized in that the coating is applied so as to have a solid content of g/m' (solid content).
特開昭６０−１４９７８６号公報は、亜鉛系合金電気め
っき鋼板にクロム付着量が２〜６０ ｍｇ／ ｍ’とな
るようにクロメート被膜を形成し、ポリエチレン系樹脂
ディスバージョンの固形分１００重量部に対し水溶性メ
ラミン樹脂を固形分として１０〜３０重量部、コロイダ
ルシリカを固形分でｌＯ〜６０重量部混合した水性液を
０．３〜５ｇ／ｒｒ？（固形分）塗布することを特徴と
する発明を開示するものである。JP-A-60-149786 discloses that a chromate film is formed on a zinc-based alloy electroplated steel sheet so that the amount of chromium deposited is 2 to 60 mg/m', and the solid content of polyethylene resin dispersion is 100 parts by weight. On the other hand, 0.3 to 5 g/rr? This invention discloses an invention characterized in that (solid content) is applied.
特開昭５８−２１０１９２号公報及び特開昭５８−２１
０１９０号公報は、γ相単相からなるＮｉ−Ｚｎ合金め
っき層或いはＦｅ−Ｚｎ合金めっき層をもつめっき鋼板
をクロメート処理し、その上に導電性物質を含有する塗
料、例えばエポキシ樹脂にＺｎ粉末を混入した塗料を塗
布したものを開示するものである。JP-A-58-210192 and JP-A-58-21
Publication No. 0190 discloses that a plated steel sheet having a Ni-Zn alloy plating layer or a Fe-Zn alloy plating layer consisting of a single γ phase is treated with chromate, and then a paint containing a conductive substance, such as an epoxy resin containing Zn powder, is treated with chromate. This disclosure discloses a product coated with a paint mixed with.
特開昭５９−１１６３９７号公報は、鋼板の一方の面に
は第１層として高耐蝕性電気めっき層を有し、その上に
第２層として薄電気めっき層を有し、他方の面には第１
層として高耐蝕性電気めっき層を有し、その上に第２層
として導電性顔料を含むエポキシ樹脂あるいはポリエス
テル樹脂を３〜１０Ｌ１塗布するか、導電性顔料を含ま
ないエポキシ樹脂あるいはポリエステル樹脂を３〜１０
μ塗布するものを開示するものである。JP-A-59-116397 discloses that a steel plate has a highly corrosion-resistant electroplated layer as a first layer on one side, a thin electroplated layer as a second layer thereon, and a steel plate on the other side. is the first
It has a highly corrosion-resistant electroplated layer as a layer, and on top of that, 3 to 10 L1 of epoxy resin or polyester resin containing a conductive pigment is applied as a second layer, or 3 to 10 L1 of an epoxy resin or polyester resin containing no conductive pigment is applied. ~10
This disclosure discloses a product that is coated with μ.
特開昭６３−１２８９３５号公報は、鋼板表面上に、最
内層として亜鉛又は亜鉛合金めっき層、中間層としてク
ロメート被膜層、表層として顔料がン呑加されたアルキ
ッド樹脂、アミノアルキッド樹脂、アものである。JP-A No. 63-128935 discloses that on the surface of a steel sheet, a zinc or zinc alloy plating layer is used as the innermost layer, a chromate coating layer is used as the intermediate layer, and a pigment-incorporated alkyd resin, amino alkyd resin, or amorphous resin is added as the surface layer. It is.
これらの有機複合鋼板あるいは着色塗装鋼板は、表層に
形成された特殊樹脂層あるいは着色塗装層によって特に
裸耐蝕性はかなり改善される。These organic composite steel plates or colored coated steel plates have a special resin layer or a colored coating layer formed on the surface layer, which significantly improves their corrosion resistance.
［発明が解決しようとする課ＮＭ］
しかし、これら鋼板はｉｉ１熱性がほとんどなく、２５
０℃以上になると樹脂は分解するため、使用する場合の
温度はたかだか２００℃以下である。そのため加熱時直
ちに下地鋼接は変色し、また酸化物が形成していく、ま
た、加熱すると樹脂はほとんど分解するため、加熱後の
耐蝕性は確保出来ない。[Problem to be solved by the invention NM] However, these steel plates have almost no heat resistance, and 25
Since the resin decomposes at temperatures above 0°C, the temperature at which it is used should be at most 200°C or below. As a result, the base steel immediately changes color when heated, and oxides begin to form.Furthermore, the resin almost decomposes when heated, so corrosion resistance cannot be ensured after heating.
これに対し、最近の傾向として特に家電業界ではｔｉ１
熱性に優れ、加熱時に変色しない、すなわち耐加熱変色
性に優れ、かつ加熱後価れた耐蝕性を確保できる鋼板を
要求している。 １ｉｉｌｌえば、電気ストーブや石油
ストーブあるいはトースター等に使用される素材は２５
０〜４００°Ｃで長時間使用されても変色しないととも
に酸化されず、かつ優れた耐蝕性を有する必要がある。On the other hand, as a recent trend, especially in the home appliance industry, ti1
There is a need for a steel plate that has excellent thermal properties and does not change color when heated, that is, has excellent heat discoloration resistance and can ensure good corrosion resistance after heating. 1iill, the materials used in electric stoves, kerosene stoves, toasters, etc. are 25
It must not discolor or oxidize even when used for a long time at 0 to 400°C, and must have excellent corrosion resistance.
また、テレビジョンに使用されているブラウン管のシュ
リンクバンドに使用される素材の多くは最近ではクロメ
ート被覆黒色めっき鋼板の上に有機樹脂皮膜を形成した
有機複合鋼板であり、製造時６００〜７００℃の高温に
加熱されるが、素材の黒色の色調が加熱時に変色せず、
かつ加熱後優れた耐蝕性を有する必要がある。その他各
種加熱を伴う家電製品に対し、耐熱性、 ｉ耐加熱変色
性及び加熱後の耐蝕性に優れた鋼板への要求が益々強く
なってきた。In addition, most of the materials used for the shrink bands of cathode ray tubes used in televisions are now organic composite steel sheets, which are made by forming an organic resin film on a chromate-coated black plated steel sheet. Although it is heated to high temperatures, the black color of the material does not change color during heating.
It also needs to have excellent corrosion resistance after heating. For various other home appliances that require heating, there is an increasing demand for steel sheets with excellent heat resistance, heat discoloration resistance, and corrosion resistance after heating.
しかし、前述したように優れた耐熱性、耐加熱変色性及
び耐蝕性をかねそえた皮膜を有する有得複合鋼板あるい
は着色塗装鋼板は皆無といってよい。However, as mentioned above, it can be said that there are no composite steel sheets or colored coated steel sheets that have a coating that has excellent heat resistance, heat discoloration resistance, and corrosion resistance.
これに対し、本発明は優れた耐熱性、耐加熱変色性及び
加熱後のｉｉ１蝕性を兼ねそえた有機／無機の混合皮膜
を有する有機／無機複合銅板を提供することを目的とす
るものであり、詳しくはクロメート皮膜を有するめっき
鋼板あるいはさらにその上に着色塗装層を有する着色塗
装鋼板の表面に特殊組成からなる有機／無機混合皮膜を
形成させることによって耐熱性、耐加熱変色性に優れ、
かつ加熱後の耐蝕性に優れた有機／無機複合鋼板を提供
するものである。In contrast, the present invention aims to provide an organic/inorganic composite copper plate having an organic/inorganic mixed film that has excellent heat resistance, heat discoloration resistance, and corrosion resistance after heating. More specifically, by forming an organic/inorganic mixed film with a special composition on the surface of a plated steel sheet with a chromate film or a colored painted steel sheet with a colored paint layer thereon, it has excellent heat resistance and heat discoloration resistance.
The present invention also provides an organic/inorganic composite steel sheet that has excellent corrosion resistance after heating.
［課題を解決するための手段］ 本発明の要旨は次の通りである。[Means to solve the problem] The gist of the invention is as follows.
（１）鋼板表面に第１層としてめっき層を有し、第２層
として１０〜１５０ ｍｇ／ ｒｎ’のクロメート皮膜
層を有し、第３Ｎとしてポリエチレン、酸化ポリエチレ
ン、ポリプロピレン、鉱物油、植物油９合成動物油９合
成植物油１合成動植物油、エチレン／アクリル酸共重合
体樹脂、ポリアクリル酸及びその共重合体、ポリアクリ
ル酸エステル及びその共重合体の水系分散体から選ばれ
た１種又は２種以上の混合物の固形分１００重量部に対
し、ＳｉＯｚ、 ＣｒｚＯｘ、 Ｆｅｚｅｌ、 Ｆｅ５
０４． ＭｇＯ，ＺｒＯ２，５ｎＯｚ。(1) It has a plating layer as the first layer on the steel plate surface, a chromate film layer of 10 to 150 mg/rn' as the second layer, and polyethylene, oxidized polyethylene, polypropylene, mineral oil, vegetable oil 9 as the tertiary N. Synthetic animal oil 9 Synthetic vegetable oil 1 Synthetic animal and vegetable oil, one or two selected from aqueous dispersions of ethylene/acrylic acid copolymer resin, polyacrylic acid and its copolymer, polyacrylic acid ester and its copolymer SiOz, CrzOx, Fezel, Fe5 based on 100 parts by weight of the solid content of the above mixture.
04. MgO, ZrO2, 5nOz.
ＡＱ２０３． Ｓｂ、０．のゾルの１種又は２種以上を
固形分５０〜６００重量部含有し、かつ、ケイ酸カリ。AQ203. Sb, 0. containing 50 to 600 parts by weight of solid content of one or more of the sols, and containing potassium silicate.
ケイ酸ソーダ、水ガラス、粉末状水ガラス、メタケイ酸
ナトリウム９水塩の１種又は２種以上を固形分で５０〜
６００重量部混合した水性液を塗布。One or more of sodium silicate, water glass, powdered water glass, and sodium metasilicate nonahydrate in a solid content of 50~
Apply a mixed aqueous solution of 600 parts by weight.
乾燥させた０、２〜５．０ ｇ／ｒｒ？の有機／無機皮
膜層を有することを特徴とする耐熱性、耐加熱変色性及
び耐蝕性に優れた有機／無機複合鋼板。Dried 0.2~5.0 g/rr? An organic/inorganic composite steel sheet having excellent heat resistance, heat discoloration resistance, and corrosion resistance, characterized by having an organic/inorganic film layer of
（２）鋼板表面に第１層としてめっき層を有し、第２層
として１０〜１５０ｍｇ／ｍ２のクロメート皮膜層を有
し、第３層として着色塗装層を有し、第４層としてポリ
エチレン、酸化ポリニチレン、ポリプロピレン、鉱物油
、植物油１合成動物油１合成植物油１合成動植物油、エ
チレン／アクリル酸共重合体樹脂、ポリアクリル酸及び
その共重合体。(2) It has a plating layer as the first layer on the surface of the steel plate, a chromate film layer of 10 to 150 mg/m2 as the second layer, a colored coating layer as the third layer, polyethylene as the fourth layer, Polynytylene oxide, polypropylene, mineral oil, vegetable oil, 1 synthetic animal oil, 1 synthetic vegetable oil, 1 synthetic animal and vegetable oil, ethylene/acrylic acid copolymer resin, polyacrylic acid and its copolymer.
ポリアクリル酸エステル及びその共重合体の水系分散体
から選ばれた１種又は２種以上の混合物の固形分１００
重量部に対し、５ｉ０２． Ｃｒ２Ｏ５，Ｆｅ２ｅｓ。Solid content of one or a mixture of two or more selected from aqueous dispersions of polyacrylic esters and their copolymers: 100
By weight parts: 5i02. Cr2O5, Fe2es.
Ｆｅ５ｒ４． ＭｇＯ，Ｚｒ０ｉ、 ５ｎＯｚ、＋ｌ
ｚＬ、 ＳｂｚＯｇのゾルの１種又は２種以上を固形分
５０〜６００重量部含有し、かつ、ケイ酸カリ、ケイ酸
ソーダ、水ガラス、粉末状水ガラス、メタケイ酸ナトリ
ウム９水塩のＩＩ！！又は２種以上を固形分で５０〜６
００重量部混合した水性液を塗布、乾燥させた０、２〜
５０ｇ ／ ｒｎ’の有機／無機皮膜層を有することを
特徴とする耐熱性、ｉｉ’１７１Ｄ熱変色性及び耐蝕性
に優れた有機／無機複合鋼板。Fe5r4. MgO, Zr0i, 5nOz, +l
zL, contains one or more sol of SbzOg in a solid content of 50 to 600 parts by weight, and contains potassium silicate, sodium silicate, water glass, powdered water glass, and sodium metasilicate nonahydrate II! ! Or two or more types in solid content of 50 to 6
0,2~ by coating and drying an aqueous solution mixed with 00 parts by weight
An organic/inorganic composite steel sheet with excellent heat resistance, II'171D thermochromic property and corrosion resistance, characterized by having an organic/inorganic film layer of 50 g/rn'.
（３）めっき層の表層または全層が着色されていること
を特徴とする前記（１）または（２）記載のｆｉ＋熱性
、 ｉ耐加熱変色性及び耐蝕性に性に優れた有機／無機
複合鋼板。(3) The organic/inorganic composite excellent in fi + heat resistance, i heat discoloration resistance, and corrosion resistance as described in (1) or (2) above, characterized in that the surface layer or all layers of the plating layer are colored. steel plate.
［イ乍 用］
本発明は、クロメート皮膜ｔを有するめっき鋼板あるい
はクロメート被覆めっき鋼板の上にさらに着色塗装層を
有する着色塗装鋼板にｔｉｊ熱性、 ｉｉＩ加熱変色性
及び耐蝕性の極めて優れた有機／無機の混合皮膜を形成
させ、商品価値を著しく高めるものである。ここで言う
めっき鋼板とは、電気めっき鋼板、溶融めっき鋼板及び
着色めっき鋼板を指す、電気めっき鋼板とは、鋼板上に
亜鉛、２、ズ１銅、クロム、ニッケルを単独めっきする
か、あるいはこれら１種または２種以上の金属を含有し
た合金めっき鋼板であり、溶融めっき鋼板とは、亜鉛、
アルミニウム、スズ、マグネシララム、Ｅ。[For use] The present invention provides a coated steel plate with a chromate coating or a colored coated steel plate with a colored coating layer on top of the chromate coated plated steel plate. It forms an inorganic mixed film and significantly increases commercial value. The plated steel sheet referred to here refers to electroplated steel sheet, hot-dipped steel sheet, and colored plated steel sheet. Electroplated steel sheet refers to a steel sheet plated with zinc, copper, chromium, or nickel alone, or It is an alloy-plated steel sheet containing one or more metals, and hot-dip galvanized steel sheet refers to zinc,
Aluminum, tin, magnesillarum, E.
クロム、ニッケルを単独めっきするか、あるいはこれら
１種または２種以上の金属を含有した合金めっき鋼板で
ある。また、着色めっき鋼板とは、めっき層表層が着色
化されているものでもよいし、めっき層全体が着色化さ
れているものでもよい。例えば、Ｚｎ−Ｎｉ合金めっき
鋼板に硝酸系の薬剤を塗布し、表層を黒色化したもの（
以降黒色めっき鋼板とよぶ）、Ａ、ｅめっき鋼板などに
薬剤処理をし表層を着色化したもの、また、電気めっき
時のめっき層に酸化物系のものを共析させたり、溶融め
っき時Ｚｎ浴にＴｉなどを添加し、溶融めっき後熱処理
し、酸化状態によってめっき層全体を着色化しためっき
鋼板などいずれでもよい。また、着色塗装鋼板の着色塗
装層とは、顔料によって着色された有機樹脂層であり、
顔料が添加された水溶性または水分散性の有機樹脂、あ
るいは溶剤で溶かした有機樹脂を塗布することによって
形成されるものである。It is a steel plate plated with chromium or nickel alone, or an alloy plated steel plate containing one or more of these metals. Furthermore, the colored plated steel sheet may be one in which the surface layer of the plating layer is colored, or one in which the entire plating layer is colored. For example, a Zn-Ni alloy plated steel plate is coated with a nitric acid-based chemical to blacken the surface layer (
(hereinafter referred to as black-plated steel sheets), A, E-plated steel sheets, etc., which are treated with chemicals to color the surface layer, and oxide-based materials are eutectoided in the plating layer during electroplating, or Zn is added during hot-dip plating. Any plated steel sheet may be used, such as a plated steel sheet in which Ti or the like is added to a bath, heat-treated after hot-dip plating, and the entire plated layer is colored depending on the oxidation state. In addition, the colored coating layer of a colored painted steel sheet is an organic resin layer colored with a pigment,
It is formed by applying a water-soluble or water-dispersible organic resin to which a pigment has been added, or an organic resin dissolved in a solvent.
以下本発明について詳細に説明する。The present invention will be explained in detail below.
本発明はクロメート被覆めっき鋼板、あるいはその上に
さらに着色塗装層を有する塗装鋼板に下記■〜■の３者
の混合水性液を塗布することにより得られる極めて優れ
たｉｉ１熱性と加熱後の耐蝕性に優れた皮膜を有する有
機／無機複合鋼板である。The present invention provides extremely excellent thermal resistance and corrosion resistance after heating, which can be obtained by applying a mixed aqueous solution of the following three to a chromate-coated plated steel plate or a coated steel plate having a colored coating layer thereon. This is an organic/inorganic composite steel sheet with an excellent coating.
第１図及び第２図は本発明による有機／無機複合！ｇ板
の断面構造の１例を示す、第１図は鋼板１の上層にめっ
き層２ 、 １０〜１５０ ｍｇ／ ｒｎ’のクロメー
ト皮膜層３を形成した表面処理鋼板上に、下記■〜■の
３者を特定比率で混合した特定厚の有機／無機混合皮膜
層４を形成させたものである。Figures 1 and 2 are organic/inorganic composites according to the present invention! Figure 1, which shows an example of the cross-sectional structure of a g-plate, shows a surface-treated steel plate in which a plating layer 2 and a chromate film layer 3 of 10 to 150 mg/rn' are formed on the upper layer of a steel plate 1. An organic/inorganic mixed film layer 4 having a specific thickness is formed by mixing the three in a specific ratio.
第１図は鋼板の両面にめっき層２．クロメート皮膜層３
．有機／無機混合皮膜層４が形成されている場合を示し
たが、めっき層２．クロメート皮膜層３．有機／無機混
合皮月莫層４が鋼板の片面に存在する場合も本発明に含
まれる。第２図は鋼板１の上層にめっき層２ 、 Ｉ
０−１５（ｌ ｍｇ／ｍ２のクロメート皮膜層３を形
成し、さらにその上に着色塗装層５を形成した表面処理
鋼板上に、下記■〜■の３者を特定比率で混合した特定
厚の有機／無機混合皮膜層４を形成させたものである。Figure 1 shows two plating layers on both sides of a steel plate. Chromate film layer 3
．． Although the case where the organic/inorganic mixed film layer 4 is formed is shown, the plating layer 2. Chromate film layer 3. A case where the organic/inorganic mixed skin layer 4 is present on one side of the steel sheet is also included in the present invention. Figure 2 shows a plating layer 2, I on the upper layer of the steel plate 1.
On a surface-treated steel sheet on which a chromate film layer 3 of 0-15 (l mg/m2) was formed, and a colored coating layer 5 was further formed thereon, a coating of a specific thickness obtained by mixing the following three materials (■ to ■) in a specific ratio was applied. An organic/inorganic mixed film layer 4 is formed.
第２図は鋼板の両面にめっき層２．クロメート皮膜層３
゜着色塗装層５．有機／無機混合皮膜層４が形成されて
いる場合を示したが、めっき層２．クロメート皮膜層３
．＠色塗装層５、有機／無機混合皮膜層４が鋼板の片面
に存在する場合も本発明に含まれる。また、第１図また
は第２図のめっき層２が、めっき層の表層または全層が
着色された着色めっき層である場合も本発明に含まれる
。Figure 2 shows two plating layers on both sides of the steel plate. Chromate film layer 3
゜Colored coating layer 5. Although the case where the organic/inorganic mixed film layer 4 is formed is shown, the plating layer 2. Chromate film layer 3
．． The present invention also includes cases where the colored coating layer 5 and the organic/inorganic mixed coating layer 4 are present on one side of the steel plate. Further, the present invention also includes a case where the plating layer 2 in FIG. 1 or 2 is a colored plating layer in which the surface layer or the entire layer of the plating layer is colored.
■ ポリエチレン、酸化ポリエチレン、ポリプロピレン
、鉱物油、植物油１合成動物油。■ Polyethylene, polyethylene oxide, polypropylene, mineral oil, vegetable oil 1 synthetic animal oil.
合成植物油１合成動植物油、エチレン／アクリル酸共重
合体樹脂、ポリアクリル酸及びその共重合体、ポリアク
リル酸エステル及びその共重合体の水系分散体から選ば
れ・た１種又は２種以上の混合物
■＋ ５ＬＯｘ、 ＣｒｘＣｈ、 Ｆｅ＊Ｏｓ、
Ｆｅ５Ｃｈ、 Ｍｇ０． ２ｒＯｚ。Synthetic vegetable oil 1 One or more types selected from synthetic animal and vegetable oils, ethylene/acrylic acid copolymer resins, polyacrylic acid and its copolymers, polyacrylic esters and aqueous dispersions of their copolymers. Mixture ■+ 5LOx, CrxCh, Fe*Os,
Fe5Ch, Mg0. 2rOz.
ＳｎＯ，、Ａｊ２．０．、 Ｓｂ、Ｏｓのゾルの１種又
は２種以上の混合物
■：ケイ酸カリ、ケイ酸ソーダ、水ガラス、粉末状水ガ
ラス、メタケイ酸ナトリウム９水塩の１種又は２ ｆ１
以上の混合物
本発明の耐熱性、耐加熱変色性及びｉｉｌ蝕性成性皮膜
鋼板れた特性は、上記■〜■の３者を混合して形成され
た有機／無機混合皮膜層に起因１−るものである０本発
明のｉＩｉイ熱性、 ｉ１加Ｕ変色性及び耐蝕性皮膜鋼
板は、上記■〜■を特定比率で混合した特定厚の有機／
無機混合皮膜層をクロメート皮膜層上あるいは着色塗装
層上に形成させることにより製造できるが、上記■〜■
の混合比率および有機／無機混合皮膜層厚について以下
に述べる。SnO,,Aj2.0. , Sb, Os, or a mixture of two or more sol: one or two of potassium silicate, sodium silicate, water glass, powdered water glass, and sodium metasilicate nonahydrate f1
The properties of the heat resistance, heat discoloration resistance, and corrosion-resistant coating steel sheet of the above mixture of the present invention are due to the organic/inorganic mixed coating layer formed by mixing the above three materials. The steel sheet with heat resistance, heat resistance, and corrosion resistance of the present invention has a specific thickness of organic/
It can be produced by forming an inorganic mixed film layer on a chromate film layer or a colored coating layer, but the above
The mixing ratio and the organic/inorganic mixed film layer thickness will be described below.
上記■に示す水系分散体樹脂の１ ｆｉ！あるいは２種
以上の混合物を１００部（固形分重量部）に対し■に示
す各種酸化物のゾルの１種あるいは２種以上の固形分を
５０〜６００部（固形分重量部）混合し、かつ■に示す
ケイ酸化合物の１種あるいは２種以上を５０〜６００部
（固形分重量部）混合した水性液を０．２ｇ／ｍ２ （
固形分） Ｌ、を十となるように塗布すると耐熱性及び
加熱後のｉｉ１蝕性に極めて優れた皮膜が形成され、優
れた有機／無機複合鋼板を製造できることを確認した。1 fi! of the aqueous dispersion resin shown in ■ above! Alternatively, 50 to 600 parts (parts by weight of solids) of one or more of the various oxide sols shown in ■ are mixed with 100 parts (parts by weight of solids) of the mixture of two or more kinds, and 0.2 g/m2 (
It was confirmed that when the solid content (solid content) L was applied to 10, a film with extremely excellent heat resistance and ii1 corrosion resistance after heating was formed, and an excellent organic/inorganic composite steel sheet could be manufactured.
第３図、第４図、第５図は、クロム付着量が６５ｍｇ／
ｍ２となるようにクロメート処理したＺｎ−Ｎｉ系合金
めっき鋼板の上に、
酸化ポリエチレンの水系分散体・５ｉ０２ゾル＝１００
・３００（固形分重量比） 、となるように固定し、
粉末状水ガラスの添加量をかえた水性液を乾燥後の皮膜
が１．０ｇ／ｍ２となるように塗布し、耐熱性、耐加熱
変色性及び加熱後の耐蝕性がどのように変化するかを示
したものである。Figures 3, 4, and 5 show that the amount of chromium deposited is 65mg/
Aqueous dispersion of polyethylene oxide 5i02 sol = 100 on a Zn-Ni alloy plated steel sheet that has been chromated so that the
・Fix it to 300 (solid content weight ratio),
Aqueous solutions with different amounts of powdered water glass added are applied so that the film after drying is 1.0 g/m2, and how the heat resistance, heat discoloration resistance, and corrosion resistance after heating change. This is what is shown.
ここで耐熱性は６００°Ｃに６０分均熱しく試料温度）
、試料の酸化による重量増を測定し評価した。Here, heat resistance is measured by soaking the sample at 600°C for 60 minutes)
The weight increase due to oxidation of the sample was measured and evaluated.
０ 全く重量変化無
００〜０．１ ｇ／ｒｒｆ重量増加
△： ０．１〜０５ｇ／ｒ！１′重量増加ｘ ： ０
．５〜１．０ ｇ／ｍ２重量増加ＸＸ： １．ｏｇ／
ｍ”以上重量増力［１耐加熱変色性は６００°Ｃに６０
分均熱しく試料温度）、試１表面の変色性を調査し、０
．○、△。0 No weight change at all 00~0.1 g/rrf Weight increase △: 0.1~05 g/r! 1′ weight increase x: 0
．． 5-1.0 g/m2 Weight increase XX: 1. og/
m” or more weight increase [1 Heat discoloration resistance is 60°C at 600°C
The sample temperature was soaked for 1 minute), and the discoloration of the surface of sample 1 was investigated.
．． ○、△.
×、××の５段階で評価したものであり、０が最良であ
る。It is evaluated on a five-point scale of × and ××, with 0 being the best.
０・全（変色無
○：わずかに変色有り
△・一部変色有り
× ブルーイング
××：かなり黒色化あるいは灰暗色
また、加熱後の耐蝕性は ６００°Ｃて６０秒加熱後、
ＪＩＳ−２−２３７１規格に準拠した塩水噴ｉｘ式験に
より（食塩水濃度５％、槽内温度３５°Ｃ１噴ｎ圧力２
０ ｐｓｉ ） ５００時間後の発錆状況を調査し、０
゜○、△、Ｘ、ＸＸの５段階で評価したものであり、０
が最良である。0・Complete (No discoloration ○: Slight discoloration △・Partial discoloration × Blueing XX: Significantly blackened or grayish color Also, the corrosion resistance after heating is as follows: After heating at 600°C for 60 seconds,
Based on the salt water injection test in accordance with the JIS-2-2371 standard (salt water concentration 5%, tank temperature 35°C, injection pressure 2
0 psi) The rusting situation after 500 hours was investigated and 0
゜It is evaluated in 5 stages: ○, △, X, XX, and 0
is the best.
０：赤錆発生 ０％
○： 〃 ０〜１％
△ ・ 〃 １〜ｌＯ％
Ｘ：／／ １０〜５０％
× Ｘ ツノ ５０％ふるＬ上第
３図から明らかなように粉末状水ガラスの添加量によっ
てｉｉ′ｌ１４Ｉ！性は変化し、粉末状水ガラスが５０
部に満たないと皮膜の１ｉＬＵ性は低下し、酸化されて
重量は増加する。また、 ６００部を超えると次第に耐
熱性は低下する。これに対し、５０〜６ｆ）０部の領域
では皮膜は極めて優れた耐熱性を示し、重量変化は全く
認められない。0: Red rust generation 0% ○: 〃 0~1% △ ・ 〃 1~1O% X: // 10~50% × Depending on the amount ii′l14I! The nature changes, powdered water glass is 50
If the amount is less than 10%, the 1iLU properties of the film will decrease, and the weight will increase due to oxidation. Moreover, when the amount exceeds 600 parts, the heat resistance gradually decreases. On the other hand, in the range of 50 to 6f)0 parts, the film exhibits extremely excellent heat resistance and no weight change is observed.
第４図から明らかなように粉末状水ガラスの添加量によ
って耐加熱変色性も変化し、粉末状水ガラスが５０部に
満たないと耐加熱変色性はかなり低下する。また、 ６
００部を超えると耐加熱変色性はやや低下する傾向にあ
る。As is clear from FIG. 4, the heat discoloration resistance changes depending on the amount of powdered water glass added, and if the amount of powdered water glass is less than 50 parts, the heat discoloration resistance decreases considerably. Also, 6
If the amount exceeds 0.00 parts, heat discoloration resistance tends to decrease somewhat.
また、第５図から明らかなように粉末状水ガラスの添加
量によって加熱後の耐蝕性も変化し、粉末軟水ガラスが
５０部に満たないとｆｉｔ蝕性はかなり低下する。また
、 ６００部を超えると加熱後の耐蝕性はやや低下する
傾向にある。Furthermore, as is clear from FIG. 5, the corrosion resistance after heating changes depending on the amount of powdered water glass added, and if the amount of powdered soft water glass is less than 50 parts, the fit corrosion resistance is considerably reduced. Moreover, if it exceeds 600 parts, the corrosion resistance after heating tends to decrease somewhat.
以上の結果は、粉末状水ガラスのかわりにケイ酸カリ、
ケイ酸ソーダ、水ガラス、メタケイ酸プトリウム９水塩
を用いても、あるいはこれらのうち２種以上を同時に使
用してもほぼ同様の結果が得られた。The above results showed that potassium silicate was used instead of powdered water glass.
Almost the same results were obtained even when sodium silicate, water glass, and putrium metasilicate nonahydrate were used, or when two or more of these were used simultaneously.
次に第６図、第７図、第８図は、同じくクロム付着量が
６５ｍｇ／ｍ２となるようにクロメート処理したＺｎ−
Ｎｉ系合金めっき鋼板の上に、酸化ポリエチレンの水系
分散体
粉末状水ガラス＝ １００：３５０ （固形分重量比
）となるように固定し、５ｉ０２ゾルの添加ｍをかえた
水性液を乾燥後の皮膜が］、 Ｏｇ ／ｍ’となるよう
に塗布し、４１熱性、耐加熱変色性及び加熱後の帽を飯
性がどのように変化するかを示したものである。Next, Figures 6, 7, and 8 show Zn-
An aqueous dispersion of polyethylene oxide powdered water glass was fixed on a Ni-based alloy plated steel plate at a ratio of 100:350 (solid content weight ratio), and an aqueous solution with different addition m of 5i02 sol was dried. The figure shows how the heat resistance, heat discoloration resistance, and texture of the cap after heating change when the film is applied so that the film is 0g/m'.
第６図から明らかなように３１０２ゾルの添加■によっ
て耐熱性は変化し、ＳｉＯ２ゾルが５０部に満たないと
耐熱性は低下し、酸化され重量増加しゃすくなる。また
、 ６００部を超えると皮膜の造膜性を失い、かなり酸
化されやすくなる。これに対し、５０〜６００部の領域
ではまったく酸化されず、優れた耐熱性を示す、一方、
５ｔ０２ゾルの添加量は耐加熱変色性にも大きな影響
を与＾、第７図から明らかなように５ｉ０２ゾルが５０
部に満たないと耐加熱変色性はやや低下し、一部変色し
、 ６００部を超えるとｉｉｊ加熱変色性は大幅に低下
する。また、５ｉ０２ゾルの添加量は加熱後の耐蝕性に
も大きな影響を与え、第８図から明らかなように５ｉ０
２ゾルが５０部に満たないと加熱後の耐蝕性はやや低下
し、 ６００部を超えると加熱後のｉｉ′１１！ｉＩ性
と大幅に低下する。これに対し、５０〜６００部の領域
では安定して優れた耐蝕性が得られる。As is clear from FIG. 6, the heat resistance changes with the addition of 3102 sol, and if the amount of SiO2 sol is less than 50 parts, the heat resistance decreases and the weight increases due to oxidation. Moreover, if the amount exceeds 600 parts, the film will lose its film-forming properties and will be considerably susceptible to oxidation. On the other hand, in the range of 50 to 600 parts, it is not oxidized at all and exhibits excellent heat resistance.
The amount of 5t02 sol added has a large effect on heat discoloration resistance, and as is clear from Figure 7, the amount of 5i02 sol added is 50%.
If the amount is less than 600 parts, the heat discoloration resistance will be slightly reduced and some parts will change color, and if it exceeds 600 parts, the heat discoloration resistance will be significantly reduced. In addition, the amount of 5i02 sol added has a great effect on the corrosion resistance after heating, and as is clear from Figure 8, the amount of 5i02 sol added
If the amount of 2 sol is less than 50 parts, the corrosion resistance after heating will decrease slightly, and if it exceeds 600 parts, the ii'11! The iI property is significantly reduced. On the other hand, in the range of 50 to 600 parts, excellent corrosion resistance can be stably obtained.
以上の結果は、ＳｉＯ□ゾルのかわりにＣｒｔＯｓ。The above results show that CrtOs is used instead of SiO□ sol.
Ｆｅ２０ｓ、 Ｆｅ５０４． ＭｇＯ、ＺｒＯ２、Ｓｎ
Ｏ２、Ａｌ２Ｏ３、Ｓｂ２Ｏ ５ｎＯｚ、Ａ ９ｚＯｓ
、 ５ｂｚＯ＊のゾルを用いても、あるいはこれらのう
ち２種以上を同時に使用してもほぼ同様の結果が得られ
た。Fe20s, Fe504. MgO, ZrO2, Sn
O2, Al2O3, Sb2O 5nOz, A 9zOs
, 5bzO* or when two or more of these were used simultaneously, almost the same results were obtained.
また、上記第３〜８図の結果は酸化ポリエチレンの水分
散体を用いたが、酸化ポリエチレンのかわりにポリエチ
レン、ポリプロピレン、鉱物油。Furthermore, although the results shown in Figures 3 to 8 above used an aqueous dispersion of polyethylene oxide, polyethylene, polypropylene, and mineral oil were used instead of polyethylene oxide.
植物油１合成動物油５合成植物油９合成動植物油、エチ
レン／アクリル酸共重合体樹脂、ポリアクリル酸及びそ
の共重合体樹脂、ポリアクリル酸エステル及びその共重
合体樹脂、ポリメタクリル酸及びその共重合体樹脂、ポ
リメタクリル酸エステル及びその共重合体樹脂の水分散
体を用いても同様の結果が得られた。Vegetable oil 1 Synthetic animal oil 5 Synthetic vegetable oil 9 Synthetic animal and vegetable oil, ethylene/acrylic acid copolymer resin, polyacrylic acid and its copolymer resin, polyacrylic acid ester and its copolymer resin, polymethacrylic acid and its copolymer resin Similar results were obtained using an aqueous dispersion of resin, polymethacrylate ester, and its copolymer resin.
次に第９図、第１０図、第１１図は、クロム付着量が６
５ｍｇ／ｍ２となるようにクロメート処理したＺｎ−Ｎ
ｉ系合金めっき鋼板の上に、
酸化ポリエチレンの水系分散体・ＳｉＯ２ゾル粉末秋水
ガラス＝ １００：３００：３５０（固形分重量比）
となるように固定し、水性液を塗布し乾燥後の皮膜厚を
かえ、耐熱性、 ｉｔ加熱変色性及び加熱後の耐蝕性が
どのように変化するかを示したものである。Next, in Figures 9, 10, and 11, the amount of chromium deposited is 6.
Zn-N treated with chromate to be 5 mg/m2
The aqueous dispersion of polyethylene oxide/SiO2 sol powder Shusui Glass was fixed on an i-based alloy plated steel plate at a ratio of 100:300:350 (solid weight ratio), and an aqueous liquid was applied and the film thickness after drying was determined. This figure shows how heat resistance, heat discoloration, and corrosion resistance after heating change.
第９図、第１Ｏ図、第１１図から明らかなように、皮膜
厚によって耐熱性、耐加熱変色性、加熱後の耐蝕性は変
化し、 ０．２ｇ／ｍ２未満ではそれら特性が低下し、
これに対して０．２ｇ／ｍ’以上では優れた耐熱性、
ｉｉ１加熱変色性、加熱後のｉｉｔ蝕性を示す。As is clear from Fig. 9, Fig. 1O, and Fig. 11, the heat resistance, heat discoloration resistance, and corrosion resistance after heating change depending on the film thickness, and below 0.2 g/m2, these properties decrease.
On the other hand, when it is 0.2 g/m' or more, it has excellent heat resistance.
ii1 indicates heat discoloration, and IIT shows corrosion properties after heating.
上記第１〜１１図の結果はめっき鋼板のＣｒ付着量が６
５ｍｇ／ばの場合であるが、第１２図にＺｎ−Ｎｉ系合
金めっき鋼板の上にクロム付着量をかえ、水系分散体酸
化ポリエチレン１００部（固形分重量部）に５ｉＯｚゾ
ル３００部（固形分重量部）、粉末状水ガラス３５０部
（固形分重量部）混合した水性液を１．Ｏｇ／ｍ２ （
固形分）塗布した場合の皮膜の重着性を示す。The results shown in Figures 1 to 11 above show that the amount of Cr deposited on the plated steel sheet is 6.
In the case of 5 mg/ba, Fig. 12 shows that the amount of chromium deposited on a Zn-Ni alloy plated steel sheet was changed, and 300 parts of 5iOz sol (solid content) was added to 100 parts (solid content) of aqueous polyethylene oxide dispersion. (parts by weight) and 350 parts of powdered water glass (parts by weight of solids) were mixed into 1. Og/m2 (
Solid content) indicates the adhesion of the film when applied.
皮膜の密着性試験は上記塗布した試験片を３０分沸騰し
、その後２ｍｍゴバン目に皮膜をカットしテープ剥離し
、剥離面積で評価した。To test the adhesion of the film, the coated test piece was boiled for 30 minutes, then the film was cut into 2 mm squares and peeled off with a tape, and the peeled area was evaluated.
０ ： ！ＩＩ離面積 ０％
○・ 〃 ０〜１％
△ 〃 １〜ｌＯ％
×・ 〃ｌＯ〜５０％
ＸＸ： ｌ） ５Ｏ％以上
第１２区から明らかなようにＣｒ（を着量が１゜ｍｇ／
ｍ’未満、あるいは１５０ｍｇ／ｍ２超では皮膜の密着
性は低下する。0:! II separation area 0% ○・〃 0~1% △〃 1~lO% ×・〃lO~50% XX: l) More than 50% As is clear from Section 12, the amount of Cr (applied 1゜mg/
If it is less than m' or more than 150 mg/m2, the adhesion of the film will decrease.
上記第９〜１１図の結果および第１２図の結果は、
酸化ポリエチレンの水系分散体： ５ｉＯｚゾル粉末秋
水ガラス＝ １００：３００：３５０（固形分Ｍ量比）
となるように固定したものであるが、ＳｉＯ□ゾルを５
０〜６００部、粉末状水ガラスを５０〜６００部に変更
してもほぼ同様な結果が得られた。The results shown in Figures 9 to 11 above and the results shown in Figure 12 are obtained by fixing polyethylene oxide aqueous dispersion: 5iOz sol powder Shusui Glass = 100:300:350 (solid content M ratio). However, the SiO□ sol is 5
Almost similar results were obtained even when the amount of powdered water glass was changed from 0 to 600 parts and from 50 to 600 parts.
また、Ｓｉｎ、ゾルのかわりにＣｒｚＯｉ、 ＦｅｚＯ
ｘ。Also, instead of Sin and sol, CrzOi, FezO
x.
ＦｅＪ＜、 ＭｇＯ，ＺｒＯｘ、 ５ｎＯｉ、Ａｊ’！
ｘｉｓ、 ５ｂｔＯｓのゾルを用いても、あるいはこ
れらのうち２種以上を同時に使用してもほぼ同様の結果
が得られた。FeJ<, MgO, ZrOx, 5nOi, Aj'!
Almost the same results were obtained even when the sols of 5btOs and 5btOs were used, or when two or more of these were used simultaneously.
また、粉末状水ガラスのがわりにケイ酸カリ。Also, potassium silicate is used instead of powdered water glass.
ケイ酸ソーダ、水ガラス、メタケイ酸ナトリウム９水塩
を用いても、あるいはこれらのうち２種以上を同時に使
用してもほぼ同様の結果が得られた。Almost the same results were obtained even when sodium silicate, water glass, and sodium metasilicate nonahydrate were used, or when two or more of these were used simultaneously.
また、酸化ポリエチレンのかわりにボリエヂレン、ポリ
プロピレン、鉱物油、植物油１合成動物油１合成植物油
１合成動植物油、エチレン／アクリル酸共重合体樹脂、
ポリアクリル酸及びその共重合体樹脂、ポリアクリル酸
エステル及びその共重合体樹脂、ポリメタクリル酸及び
その共重合体樹脂、ポリメタクリル酸エステル及びその
共重合体樹脂の水系分散体を用いても同様の結果が得ら
れた６
以上の結果より、第２層のクロメート皮膜層のクロムイ
１＠量を１０〜１５０ｍｇ／ｍ２に限定するものであり
、第３層の有機／無機皮膜層の上記■〜■の有機／無機
混合比率を、■の固形分１００重量部に対して、■を固
形分で５０〜６００重量部、■を固形分で５０〜６００
重量部に限定し、皮膜層の下限を０．２ｇ／ｍ２に限定
するものである。なお、皮膜層の上限については経済的
なし点より ５０ｇ ／ ｒｒ？に限定するものである
。In addition, instead of polyethylene oxide, polyethylene, polypropylene, mineral oil, vegetable oil 1 synthetic animal oil 1 synthetic vegetable oil 1 synthetic animal and vegetable oil, ethylene/acrylic acid copolymer resin,
The same effect can be obtained by using an aqueous dispersion of polyacrylic acid and its copolymer resin, polyacrylic acid ester and its copolymer resin, polymethacrylic acid and its copolymer resin, polymethacrylic acid ester and its copolymer resin. 6 Based on the above results, the amount of chromium 1 in the second chromate film layer is limited to 10 to 150 mg/m2, and the amount of chromium 1 in the third organic/inorganic film layer is limited to The organic/inorganic mixing ratio of
The lower limit of the film layer is limited to 0.2 g/m2. In addition, the upper limit of the film layer is 50g/rr from an economic point of view. It is limited to.
ここで、本発明による有機／無機複合皮膜によって極め
て優れた耐熱性、耐加熱変色性及び耐蝕性が得られるメ
カニズムについてはかならずしも明確ではないが、おお
よそ次のように考えられる。すなわち、本発明で用いる
樹脂は比軸的高温域まで安定であり、且つ分解速度が遅
い。したがって、加熱により急激な燃焼や、分解が起き
にくく、徐々に分解されるため塗布された皮膜の状態は
そのまま維持される。また、それと平行してその温度に
応じてケイ酸化合物とゾルが反応し、緻密な皮膜を形成
する。このようにして得られた皮膜は半無定形なため極
めて緻密であり、ｕ、素の拡散を遮断するため酸化物は
形成されずｉｉ１熱性に優れ、また同時に第１層のめっ
き層、第２層のクロメート層の酸化を防止することによ
り変色することを防ぐとともに、自身も透明皮膜のまま
変化しないため耐加熱変色性にも優れている。また、こ
のようにして形成された皮膜は柔軟性に冨むため、加工
に追従し、かつ緻密であることがら、腐食環境下で１（
２０やＣρ−の拡散を押さえ価れたｉｉｌめっき鋼板に
処理した場合について述べたが、クロメート処理して１
０〜１５０ｍｇ／ｍ２のクロメート皮膜層を形成しため
っき鋼板にさらに着色塗装層を有する着色塗装鋼板に、
上記有機／無機混合皮膜を塗布しても同様の効果かえら
れる。すなわち、着色塗装層は顔料を含有する有機樹脂
で形成されているので上層の有機／無機混合庄原との密
着性は充分に確保されると共に、上記有機／無機混合皮
膜は加熱時反応して極めて緻密な皮膜に改質するため、
外部から拡散してくる酸素を遮断し、着色塗装層を形成
する顔料や有機樹脂の酸化を押さえるため、顔料や有機
樹脂の変色を防止し、優れた耐加熱変色性を示す、あわ
せて上記有機／無機混合皮膜は加熱時反応して軟化点が
高く、かつ緻密で柔軟性にも冨んでいるため、優れた耐
熱性と加熱後優れた耐蝕性も付与される。The mechanism by which the organic/inorganic composite film of the present invention provides extremely excellent heat resistance, heat discoloration resistance, and corrosion resistance is not necessarily clear, but it is thought to be roughly as follows. That is, the resin used in the present invention is stable up to a specific axial high temperature range and has a slow decomposition rate. Therefore, rapid combustion or decomposition due to heating is unlikely to occur, and since the coating is gradually decomposed, the state of the coated film is maintained as it is. In addition, in parallel with this, the silicic acid compound and the sol react depending on the temperature, forming a dense film. The film obtained in this way is semi-amorphous and extremely dense, and because it blocks the diffusion of u and elements, no oxides are formed, and ii1 it has excellent thermal properties. It prevents discoloration by preventing oxidation of the chromate layer, and it also has excellent heat discoloration resistance because it remains a transparent film and does not change. In addition, the film formed in this way is highly flexible, so it follows processing and is dense, so it can withstand 1 (1) in a corrosive environment.
We have described the case where the IIL-plated steel sheet is treated to suppress the diffusion of 20 and Cρ-.
A colored coated steel plate having a colored coating layer on a plated steel plate on which a chromate film layer of 0 to 150 mg/m2 is formed,
A similar effect can be obtained by applying the above-mentioned organic/inorganic mixed film. In other words, since the colored coating layer is formed of an organic resin containing pigment, sufficient adhesion with the upper layer organic/inorganic mixed Shobara is ensured, and the organic/inorganic mixed film reacts when heated and is extremely To reform into a dense film,
In order to block oxygen diffusing from the outside and suppress oxidation of the pigments and organic resins that form the colored coating layer, it prevents discoloration of the pigments and organic resins and exhibits excellent heat discoloration resistance. /The inorganic mixed film reacts when heated, has a high softening point, is dense, and has plenty of flexibility, so it also provides excellent heat resistance and excellent corrosion resistance after heating.
なお、着色塗装鋼板におけるクロメート皮膜層のクロメ
ート付着量を１０ ＝ １５０ ｍｇ／ ｍ″に限定す
るのは、周知のように着色塗装層とのに着性を確保する
ためである。The reason why the amount of chromate deposited in the chromate coating layer on the colored painted steel sheet is limited to 10 = 150 mg/m'' is to ensure adhesion to the colored coating layer, as is well known.
［実施例］
（実施例１）
めっき付着量が２０ｇ／ｍ２のＺ ｎ −Ｎ ｉ系合金
めっき鋼板（Ｎ ｉ ： １１．０％）に、Ｃｒ付Ｗｌ
が６５ｍｇ／ｍ２となるようにクロメート処理し、水系
分散体酸化ポリエチレン ＳｉＯ□ゾル粉末状水ガラス
−１００：３５０：３００（固形分重量部）
となるように調整した水性液をその上に塗布し、乾燥し
て １．０ｇ／ｍ２となるように皮膜を形成した。[Example] (Example 1) Cr-coated Wl was applied to a Zn-Ni alloy coated steel sheet (Ni: 11.0%) with a coating weight of 20 g/m2.
Aqueous dispersion polyethylene oxide SiO□ sol powdered water glass - 100:350:300 (solids weight parts) was applied with an aqueous solution adjusted to have a chromate treatment of 65 mg/m2. , to form a film with a drying weight of 1.0 g/m2.
（実施例２） めっき付着量が２０ ｇ／ｍ’のＺｎ−Ｎ１−Ｃ。(Example 2) Zn-N1-C with a coating weight of 20 g/m'.
系合金めっき鋼板（Ｎ ｉ ： １１．０％、Ｃｏ＝０
．５％）に、Ｃｒ（４着塁が９０ｍｇ／ばとなるように
クロメ−［・処理し、
水系分散体ポリエチレン・ＣｒｚＯｉゾルケイ酸カリ＝
１００・２００・４００（固形分重量部）となるように
調整した水性液をその上に塗布し、乾燥して １．２ｇ
／ｒｒ？どなるように皮膜を形成した。alloy-plated steel sheet (N i: 11.0%, Co=0
．． 5%), Cr (treated with chromate so that 4 bases reach 90 mg/ba, aqueous dispersion polyethylene CrzOi sol potassium silicate =
An aqueous solution adjusted to 100, 200, and 400 (solids weight parts) was applied on top of it, dried, and weighed 1.2g.
/rr? A film formed like a roar.
（実施例′、３）
めっき付着量が２０ｇ／ｍ２のＺｎ−Ｆｅ系合金めっき
鋼板（Ｆ ｅ ： １１．５％）に、Ｃｒ付着量が１２
０ｍｇ／ｍ２となるようにクロメート処理し、水系分散
体動植物油 Ｆｅｚｅ３ゾル
ケイ酸ソーダ＝ １００：４００：３５０（固形分重量
部）
となるように調整した水性液をその上に塗布し、乾燥し
て １．８ｇ／ｍ２となるように皮膜を形成した。(Example ', 3) A Zn-Fe alloy plated steel sheet (Fe: 11.5%) with a coating weight of 20 g/m2 was coated with a Cr coating weight of 12 g/m2.
Aqueous dispersion animal and vegetable oil Feze3 sol Sodium silicate = 100:400:350 (parts by weight of solid content) was applied on top of the aqueous solution, which was chromated to a concentration of 0 mg/m2, and then dried. A film was formed so that the weight was 1.8 g/m2.
（実施例４）
めっき付＠量が２０ ｇ ／ ｍ’のＺｎ−Ｎｉ−Ｃｒ
系合金めっき鋼ｆｆｊ （Ｎ ｉ ： １２．５％、Ｃ
ｒ＝１．５％）に、Ｃｒ付着量が４０ｍｇ／ｍ２となる
ようにクロメート処理し、
エチレン／アクリル酸共重合体樹脂
Ａ４□０３ゾル・水ガラス＝１００・１００：５００（
固形分重量部）
となるように調整した水性液をその上に塗布し、乾燥し
て ２．１ｇ／ｌｎ’となるように皮膜を形成した。(Example 4) Zn-Ni-Cr with plating @ amount of 20 g/m'
alloy plated steel ffj (N i: 12.5%, C
r = 1.5%) was treated with chromate so that the Cr adhesion amount was 40 mg/m2, and ethylene/acrylic acid copolymer resin A4□03 sol/water glass = 100/100:500 (
An aqueous solution adjusted to have a solid content of 2.1 g/ln' was applied thereon and dried to form a film having a solid content of 2.1 g/ln'.
（実施例５）
めっき付着量が２０ｇ／ｍ’のＺｎ−Ｍｎ系合金めっき
鋼板（Ｍｎ・７５５％）に、Ｃｒ付着量が５５ｍｇ／ｍ
２となるようにクロメート処理し、ポリアクリル酸 ｓ
ｂ、ｏ、ゾル：扮末状水ガラス＝ １００：５００：５
００ （固形分重量部）となるように調整した水性液を
その上に塗布し、乾燥して０．９ｇ／ｍ２となるように
皮膜を形成した。(Example 5) A Zn-Mn alloy plated steel sheet (Mn 755%) with a coating weight of 20 g/m' and a Cr coating weight of 55 mg/m
Chromate treatment to give polyacrylic acid s
b, o, sol: powdered water glass = 100:500:5
An aqueous solution adjusted to have a solid content of 0.00 (parts by weight of solids) was applied thereon and dried to form a film having a concentration of 0.9 g/m2.
（実施例６）
めっき付着量が２０ｇ／ｍ２のＺｎ−Ｎｉ系合金めっき
鋼板（Ｎｉ・１１．５％）に、Ｃｒ付着量が６５ ｍｇ
／ ｍ”となるようにクロメート処理し、水系分散体酸
化ポリエチレン・ＳｉＯ□ゾルメクケイ酸ナトリウム９
水塩＝ １００：３５０：３５０（固形分重量部）
となるように調整した水性液をその上に塗布し、乾燥し
て １．０ｇ／ｍ２となるように皮膜を形成した。(Example 6) A Zn-Ni alloy plated steel sheet (Ni 11.5%) with a coating weight of 20 g/m2 and a Cr coating weight of 65 mg
/m”, aqueous dispersion of polyethylene oxide/SiO□solmek sodium silicate 9
An aqueous solution adjusted to have an aqueous salt ratio of 100:350:350 (parts by weight of solid content) was applied thereon and dried to form a film with a concentration of 1.0 g/m2.
（実施例７）
めっき付着量が２０ｇ／ｍ２のＺｎ−Ｎｉ系合金めっき
１岡１反（Ｎ ｉ ： １２．０％）（こ、石肖酸と硫
酸の混合液をスプレー塗布し、めっき屡の表面を黒色化
した後、Ｃｒ付付量量９５ｍｇ／ｍ２となるようにクロ
メ−１−処理し
エチしン／アクリル酸共重合体１６１脂５ｉ０２ゾル・
メクケイ酸すｌ−リウム９水塩＝ｌＯＯ：４００：３０
０ （固形分重量部）となるように調整した水性液を
その上に塗布し、乾燥して １．２ｇ／ｍ’となるよう
に皮膜を形成した。(Example 7) Zn-Ni alloy plating with a coating weight of 20 g/m2 (Ni: 12.0%). After blackening the surface, it was treated with chromate-1 so that the amount of Cr applied was 95 mg/m2, and then the ethicine/acrylic acid copolymer 161 fat 5i02 sol.
Sl-lium silicate nonahydrate = lOO: 400:30
An aqueous solution adjusted to have a solid content of 0 (parts by weight by weight) was applied thereon and dried to form a film having a solid content of 1.2 g/m'.
（実施例８）
めっき（付着量が２０ｇ／ｍ２のＺｎめっき１岡１尺の
表面に、付着量が４５ ｍｇ／ ｍ’となるようにクロ
メ−１〜処理し、その上に着色頷料を含む水濡性樹脂を
ｌｏｕ塗布した塗装綱桜の上に
水系分散体エチレン／アクリル酸共重合体樹脂ＺｒＬゾ
ル 粉末状本ガラス＝ ＋００：３５０：３５０となる
ように調整した水性液を塗布し、乾燥して１５ｇ／醒と
なるように皮膜を形成した。(Example 8) Plating (The surface of Zn plating with an adhesion amount of 20 g/m2 and 1 square inch was treated with chrome-1 to chromate so that the adhesion amount was 45 mg/m', and a coloring agent was applied on top of it. Aqueous dispersion ethylene/acrylic acid copolymer resin ZrL sol Powdered real glass = +00:350:350 Aqueous liquid adjusted to be applied is applied to the painted rope cherry tree coated with a water-wettable resin containing lou, and dried. A film was formed at a weight of 15 g/ml.
（比較例１）
めっき付着量が２０ｇ／ｍ２のＺｎ−Ｎｉ系合金めっき
鋼板（Ｎ ｉ ： １１．５％）を用いた。(Comparative Example 1) A Zn-Ni alloy plated steel sheet (N i : 11.5%) with a coating weight of 20 g/m 2 was used.
（比較例２）
めっき付着量が２０ｇ／ｍ２のＺｎ−Ｎｉ系合金めっき
鋼板（Ｎ ｉ ： １１．５％）に、Ｃｒ付着量が８０
ｍｇ／ｍ２となるようにクロメート処理した鋼板を用い
た。(Comparative Example 2) A Zn-Ni alloy plated steel sheet (Ni: 11.5%) with a coating weight of 20 g/m2 was coated with a Cr coating weight of 80 g/m2.
A steel plate was used that was chromate-treated to give a concentration of mg/m2.
（比較例３）
めっき付着量が２０ｇ／ｍ′のＺｎ−Ｎｉ系合金めっき
鋼板（Ｎ ｉ ： １１．５％）に、Ｃｒ付付量量８０
ｍｇ／ｍ２となるようにクロメート処理し、その上にエ
ポキシ樹脂を塗布し、乾燥して１．６ｇ／ｍ２となるよ
うに皮膜を形成した。(Comparative Example 3) A Zn-Ni alloy coated steel sheet (N i : 11.5%) with a coating weight of 20 g/m' was coated with Cr at a coating weight of 80 g/m'.
Chromate treatment was carried out to give a concentration of mg/m2, and an epoxy resin was applied thereon and dried to form a film having a concentration of 1.6 g/m2.
実施例１〜８ならびに比較例１〜３で得られた表面処理
鋼板について各種試験を行った結果を第１表に示す。Table 1 shows the results of various tests conducted on the surface-treated steel sheets obtained in Examples 1 to 8 and Comparative Examples 1 to 3.
各種試験条件は次の通りである。Various test conditions are as follows.
（ａ）ｉｉ１熱性
第３図、第６図、第９図と同じ条件で実施し、評価も同
じ基準で実施した。(a) ii1 Fever The test was carried out under the same conditions as in Figs. 3, 6, and 9, and the evaluation was also carried out using the same criteria.
Ｆｂ］ ｉｉ１加熱変色性
第４区、第７図、第１０図と同し条件で実施し、評価も
同じ基準で実施した。Fb] ii1 Heating discoloration The test was carried out under the same conditions as in Section 4, Figs. 7 and 10, and the evaluation was also carried out using the same criteria.
（ｃｌ Ｍ触性
第５図、第８図、第１１図と同じ条件で実施し、 ６０
０°Ｃで６０秒加熱後ＪＩＳ−２−２３７１規格に準拠
した塩水噴霧試験により、 ５００ｈ後の白錆発生率（
％）及び１ｏｏｏｈ後の赤錆発生率（％）を求めた。(Cl M tactility was carried out under the same conditions as in Figures 5, 8 and 11,
After heating at 0°C for 60 seconds, a salt spray test based on the JIS-2-2371 standard was conducted to determine the white rust incidence after 500 hours (
%) and the incidence of red rust (%) after 1oooh.
［発明の効果Ｊ
従来、耐熱性、耐加熱変色性及び加熱後の１ＩｉＩ独性
を同時に充分満足する有機／無機複合皮膜を有する表面
処理鋼板は存在しなかったが、本発明によればきわめて
優れた耐熱性、１１加熱変色性及び加熱後の耐蝕性に優
れた皮膜が得られる。従って、例えば本発明による有機
複合鋼板を、加工時或いは組立時に熱履歴を受けたり、
あるいは製品として使用する際、長時間熱を受ける家１
！製品の各種部品や、建材など多くの用途に使用するこ
とにより素材は酸化されず、また着色めっき層および／
または着色塗装層は変色せずいつまでも軒やかな色調を
維持し、かつ優れた１ｔｉｔ蝕性を確保できることから
１本発明の経済的効果は極めて大なるものである。[Effect of the Invention J Conventionally, there has been no surface-treated steel sheet with an organic/inorganic composite film that fully satisfies heat resistance, heat discoloration resistance, and 1IiI uniqueness after heating, but according to the present invention, an extremely excellent A film with excellent heat resistance, heat discoloration property, and corrosion resistance after heating can be obtained. Therefore, for example, if the organic composite steel sheet according to the present invention is subjected to thermal history during processing or assembly,
Or a house that receives heat for a long time when used as a product1
! By using the material in many applications such as various parts of products and building materials, the material will not be oxidized, and the colored plating layer and/or
Moreover, the colored coating layer does not change color and maintains a bright color tone forever, and also ensures excellent 1-tit corrosion resistance, so that the economic effects of the present invention are extremely large.
第１図、第２図は本発明による有機／無機複合鋼板の断
面概要図、
第３図、第４図、第５図はクロメート処理したＺｎ−Ｎ
ｉ系合金めっき鋼板の上に水系分散体の酸化ポリエチレ
ンとコロイダルシリカの配合を固定し、粉末状水ガラス
の添加量をかえた水性液を塗布し、組ｊ熱性、１ｊ加熱
変色性及び加ｐハ後の釦Ｉ貫λ性がどのように変化する
かを示した図、０′Ｘｔ”＋ Ｉ看Ｉ、第７図、第８図
（」同しくクロメ−Ｉ−処理したＺｎ−Ｎｉ系合金めっ
きＩＷＩｔＦｊの上に水系分Ｎ＋Ｈの酸化ポリエチレン
と粉末軟水ガラスの配合を固定し、コロイダルシリカの
添加量をかえた水性液を塗布し、４１熱性と加熱後の耐
蝕性がどのように変化づるか示した図、
第９図、第１Ｏ図、第１１図はクロメート処理したＺｎ
−Ｎｉ系合金めっき鋼板の上に水系分散体の酸化ポリエ
チレンとコロイダルシリカと粉末状水ガラスの配合を固
定した水性液を塗布し、乾燥後の皮膜厚をか＾、ｉ′ｉ
Ｉρハ牲、 ｉ耐加熱変色性及び加熱後の耐蝕性がどの
ように変化するかを示した図、
第１２図はＺｎ−Ｎｉ系合金めっき鋼板の上にクロム付
着量をかえ、水系分散体酸化ポリエチレンとコロイダル
シリカ及び粉末状水ガラスを混合した水性液を塗布した
場合の皮膜の密着性を示す図である。
１ ・鋼板、２・・めっき層、３・・クロメート皮膜層
、４・・有ｊＪ！／無機混合皮膜層、５・着色塗装層。
代理人 弁理士 秋 沢 政 光
信１名
第１図
才２図
梃普俵四づFigures 1 and 2 are cross-sectional schematic diagrams of an organic/inorganic composite steel sheet according to the present invention, and Figures 3, 4, and 5 are chromate-treated Zn-N.
The composition of the aqueous dispersion of polyethylene oxide and colloidal silica was fixed on the I-based alloy plated steel sheet, and the aqueous liquid with the added amount of powdered water glass was applied. Figures 7 and 8 show how the button I penetration properties change after 0' On alloy plating IWItFj, we fixed the composition of aqueous N+H polyethylene oxide and powdered soft water glass, and applied aqueous liquids with varying amounts of colloidal silica to determine how the 41 thermal properties and corrosion resistance after heating changed. Figures 9, 1O, and 11 show chromate-treated Zn.
- Apply an aqueous solution with a fixed composition of aqueous dispersion of polyethylene oxide, colloidal silica, and powdered water glass onto a Ni-based alloy-plated steel sheet, and measure the film thickness after drying.
Figure 12 shows how the heat discoloration resistance and corrosion resistance after heating change. FIG. 3 is a diagram showing the adhesion of a film when an aqueous solution containing a mixture of polyethylene oxide, colloidal silica, and powdered water glass is applied. 1. Steel plate, 2. Plating layer, 3. Chromate film layer, 4. Yes! /Inorganic mixed film layer, 5. Colored coating layer. Agent: Patent Attorney Masaaki Akizawa Mitsunobu (1 figure, 2 figures, 2 figures, 4 figures)
Claims (3)
として１０〜１５０ｍｇ／ｍ＾２のクロメート皮膜層を
有し、第３層としてポリエチレン、酸化ポリエチレン、
ポリプロピレン、鉱物油、植物油、合成動物油、合成植
物油、合成動植物油、エチレン／アクリル酸共重合体樹
脂、ポリアクリル酸及びその共重合体、ポリアクリル酸
エステル及びその共重合体の水系分散体から選ばれた１
種又は２種以上の混合物の固形分１００重量部に対し、
ＳｉＯ＿２、Ｃｒ＿２Ｏ＿３、Ｆｅ＿２Ｏ＿３、Ｆｅ＿
２Ｏ＿４、ＭｇＯ、ＺｒＯ＿２、ＳｎＯ＿２、Ａｌ＿２
Ｏ＿２、Ｓｂ＿２Ｏ＿５のゾルの１種又は２種以上を固
形分５０〜６００重量部含有し、かつ、ケイ酸カリ、ケ
イ酸ソーダ、水ガラス、粉末状水ガラス、メタケイ酸ナ
トリウム９水塩の１種又は２種以上を固形分で５０〜６
００重量部混合した水性液を塗布、乾燥させた０．２〜
５．０ｇ／ｍ＾２の有機／無機皮膜層を有することを特
徴とする耐熱性、耐加熱変色性及び耐蝕性に優れた有機
／無機複合鋼板。(1) It has a plating layer as the first layer on the surface of the steel plate, a chromate film layer of 10 to 150 mg/m^2 as the second layer, and polyethylene, oxidized polyethylene,
Selected from aqueous dispersions of polypropylene, mineral oil, vegetable oil, synthetic animal oil, synthetic vegetable oil, synthetic animal and vegetable oil, ethylene/acrylic acid copolymer resin, polyacrylic acid and its copolymer, polyacrylic acid ester and its copolymer 1
For 100 parts by weight of solid content of seeds or a mixture of two or more,
SiO_2, Cr_2O_3, Fe_2O_3, Fe_
2O_4, MgO, ZrO_2, SnO_2, Al_2
Contains 50 to 600 parts by weight of one or more sol of O_2, Sb_2O_5 in solid content, and one of potassium silicate, sodium silicate, water glass, powdered water glass, and sodium metasilicate nonahydrate. Or two or more types in solid content of 50 to 6
0.2 to 0.0 parts by weight mixed aqueous liquid was applied and dried.
An organic/inorganic composite steel sheet with excellent heat resistance, heat discoloration resistance, and corrosion resistance, characterized by having an organic/inorganic film layer of 5.0 g/m^2.
として１０〜１５０ｍｇ／ｍ＾２のクロメート皮膜層を
有し、第３層として着色塗装層を有し、第４層としてポ
リエチレン、酸化ポリエチレン、ポリプロピレン、鉱物
油、植物油、合成動物油、合成植物油、合成動植物油、
エチレン／アクリル酸共重合体樹脂、ポリアクリル酸及
びその共重合体、ポリアクリル酸エステル及びその共重
合体の水系分散体から選ばれた１種又は２種以上の混合
物の固形分１００重量部に対し、ＳｉＯ＿２、Ｃｒ＿２
Ｏ＿３、Ｆｅ＿２Ｏ＿３、Ｆｅ＿３Ｏ＿４、ＭｇＯ、Ｚ
ｒＯ＿２、ＳｎＯ＿２、Ａｌ＿２Ｏ＿３、Ｓｂ＿２Ｏ＿
５のゾルの１種又は２種以上を固形分５０〜６００重量
部含有し、かつ、ケイ酸カリ、ケイ酸ソーダ、水ガラス
、粉末状水ガラス、メタケイ酸ナトリウム９水塩の１種
又は２種以上を固形分で５０〜６００重量部混合した水
性液を塗布、乾燥させた０．２〜５．０ｇ／ｍ＾２の有
機／無機皮膜層を有することを特徴とする耐熱性、耐加
熱変色性及び耐蝕性に優れた有機／無機複合鋼板。(2) It has a plating layer as the first layer on the surface of the steel plate, a chromate film layer of 10 to 150 mg/m^2 as the second layer, a colored coating layer as the third layer, and a colored coating layer as the fourth layer. Polyethylene, polyethylene oxide, polypropylene, mineral oil, vegetable oil, synthetic animal oil, synthetic vegetable oil, synthetic animal and vegetable oil,
100 parts by weight of solid content of one or more mixtures selected from aqueous dispersions of ethylene/acrylic acid copolymer resin, polyacrylic acid and its copolymer, polyacrylic acid ester and its copolymer On the other hand, SiO_2, Cr_2
O_3, Fe_2O_3, Fe_3O_4, MgO, Z
rO_2, SnO_2, Al_2O_3, Sb_2O_
Containing 50 to 600 parts by weight of one or more of the sols listed in No. 5 above, and one or two of potassium silicate, sodium silicate, water glass, powdered water glass, and sodium metasilicate nonahydrate. Heat resistant, heat resistant, characterized by having an organic/inorganic film layer of 0.2 to 5.0 g/m^2, which is obtained by coating and drying an aqueous solution containing 50 to 600 parts by weight of solids of 50 to 600 parts by weight of seeds or more. Organic/inorganic composite steel sheet with excellent discoloration and corrosion resistance.
を特徴とする請求項１または２記載の耐熱性、耐加熱変
色性及び耐蝕性に優れた有機／無機複合鋼板。(3) The organic/inorganic composite steel sheet having excellent heat resistance, heat discoloration resistance, and corrosion resistance according to claim 1 or 2, wherein the surface layer or all layers of the plating layer are colored.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2138264A JPH062389B2 (en) | 1990-05-30 | 1990-05-30 | Organic / inorganic composite steel sheet with excellent heat resistance, heat discoloration resistance, and corrosion resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2138264A JPH062389B2 (en) | 1990-05-30 | 1990-05-30 | Organic / inorganic composite steel sheet with excellent heat resistance, heat discoloration resistance, and corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0433844A true JPH0433844A (en) | 1992-02-05 |
| JPH062389B2 JPH062389B2 (en) | 1994-01-12 |
Family
ID=15217871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2138264A Expired - Fee Related JPH062389B2 (en) | 1990-05-30 | 1990-05-30 | Organic / inorganic composite steel sheet with excellent heat resistance, heat discoloration resistance, and corrosion resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH062389B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011189705A (en) * | 2010-03-16 | 2011-09-29 | Kobe Steel Ltd | Pre-coated aluminum sheet |
| JP2012192582A (en) * | 2011-03-16 | 2012-10-11 | Kobe Steel Ltd | Precoated aluminum sheet |
| JP2013067037A (en) * | 2011-09-21 | 2013-04-18 | Kobe Steel Ltd | Precoated metal sheet |
| JP2013208916A (en) * | 2013-07-01 | 2013-10-10 | Kobe Steel Ltd | Precoated aluminum plate |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5413429A (en) * | 1977-07-04 | 1979-01-31 | Nippon Kokan Kk <Nkk> | Surface treating method for zinc-plated steel material |
| JPS62152578A (en) * | 1985-12-25 | 1987-07-07 | Kawasaki Steel Corp | Manufacture of alloy plated steel of zn or zn family superb in corrosion resistance, paintability and weldability |
| JPS62180080A (en) * | 1986-01-31 | 1987-08-07 | Kobe Steel Ltd | Production of protective film for black galvanized steel sheet |
| JPS63123472A (en) * | 1986-11-12 | 1988-05-27 | Nippon Steel Corp | Surface treatment of steel plate |
| JPH01148369A (en) * | 1987-12-04 | 1989-06-09 | Kobe Steel Ltd | Surface treatment of galvanized steel sheet |
-
1990
- 1990-05-30 JP JP2138264A patent/JPH062389B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5413429A (en) * | 1977-07-04 | 1979-01-31 | Nippon Kokan Kk <Nkk> | Surface treating method for zinc-plated steel material |
| JPS62152578A (en) * | 1985-12-25 | 1987-07-07 | Kawasaki Steel Corp | Manufacture of alloy plated steel of zn or zn family superb in corrosion resistance, paintability and weldability |
| JPS62180080A (en) * | 1986-01-31 | 1987-08-07 | Kobe Steel Ltd | Production of protective film for black galvanized steel sheet |
| JPS63123472A (en) * | 1986-11-12 | 1988-05-27 | Nippon Steel Corp | Surface treatment of steel plate |
| JPH01148369A (en) * | 1987-12-04 | 1989-06-09 | Kobe Steel Ltd | Surface treatment of galvanized steel sheet |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011189705A (en) * | 2010-03-16 | 2011-09-29 | Kobe Steel Ltd | Pre-coated aluminum sheet |
| JP2012192582A (en) * | 2011-03-16 | 2012-10-11 | Kobe Steel Ltd | Precoated aluminum sheet |
| JP2013067037A (en) * | 2011-09-21 | 2013-04-18 | Kobe Steel Ltd | Precoated metal sheet |
| JP2013208916A (en) * | 2013-07-01 | 2013-10-10 | Kobe Steel Ltd | Precoated aluminum plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH062389B2 (en) | 1994-01-12 |
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